Synthesis, Characterization and Microstructure of New Liquid Poly(methylhydrosiloxanes) Containing Branching Units SiO4/2
Identifieur interne : 001125 ( Pmc/Corpus ); précédent : 001124; suivant : 001126Synthesis, Characterization and Microstructure of New Liquid Poly(methylhydrosiloxanes) Containing Branching Units SiO4/2
Auteurs : Jerzy J. Chru Ciel ; Marzena Fejdy ; Witold FortuniakSource :
- Polymers [ 2073-4360 ] ; 2018.
Abstract
Six liquid branched poly(methylhydrosiloxanes) of new random structures (PMHS-Q), containing quadruple branching units SiO4/2 (Q), both MeHSiO (DH) and Me2SiO (D) chain building units (or only mers MeHSiO), and terminal groups Me3SiO0.5 (M) were prepared by a hydrolytic polycondensation method of appropriate organic chlorosilanes and tetraethyl ortosilicate (TEOS), in diethyl ether medium at temperature below 0 °C. Volatile low molecular weight siloxanes were removed by a vacuum distillation at 150–155 °C. Yields of PMHS-Q reached from 55–69 wt%. Their dynamic viscosities were measured in the Brookfield HBDV+IIcP cone-plate viscometer and ranged from 10.7–13.1 cP. Molecular weights (MW) of PMHS-Q (Mn = 2440–6310 g/mol, Mw = 5750–10,350 g/mol) and polydispersities of MW (Mw/Mn = 2.0–2.8) were determined by a size exclusion chromatography (SEC). All polymers were characterized by FTIR, 1H- and 29Si-NMR, and an elemental analysis. A microstructure of siloxane chains was proposed on a basis of 29Si-NMR results and compared with literature data.
Url:
DOI: 10.3390/polym10050484
PubMed: 30966518
PubMed Central: 6415389
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<record><TEI><teiHeader><fileDesc><titleStmt><title xml:lang="en">Synthesis, Characterization and Microstructure of New Liquid Poly(methylhydrosiloxanes) Containing Branching Units SiO<sub>4/2</sub></title><author><name sortKey="Chru Ciel, Jerzy J" sort="Chru Ciel, Jerzy J" uniqKey="Chru Ciel J" first="Jerzy J." last="Chru Ciel">Jerzy J. Chru Ciel</name><affiliation><nlm:aff id="af1-polymers-10-00484">Textile Research Institute, Brzezińska Str. 5/15, 92-103 Łódź, Poland</nlm:aff></affiliation></author><author><name sortKey="Fejdy, Marzena" sort="Fejdy, Marzena" uniqKey="Fejdy M" first="Marzena" last="Fejdy">Marzena Fejdy</name><affiliation><nlm:aff id="af2-polymers-10-00484">The Institute of Security Technologies “MORATEX”, Marii Skłodowskiej-Curie Str. 3, 90-505 Łódź, Poland;<email>mfejdys@moratex.eu</email></nlm:aff></affiliation></author><author><name sortKey="Fortuniak, Witold" sort="Fortuniak, Witold" uniqKey="Fortuniak W" first="Witold" last="Fortuniak">Witold Fortuniak</name><affiliation><nlm:aff id="af3-polymers-10-00484">Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza Str. 112, 90-363 Łódź, Poland;<email>wfortuni@cbmm.lodz.pl</email></nlm:aff></affiliation></author></titleStmt><publicationStmt><idno type="wicri:source">PMC</idno><idno type="pmid">30966518</idno><idno type="pmc">6415389</idno><idno type="url">http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6415389</idno><idno type="RBID">PMC:6415389</idno><idno type="doi">10.3390/polym10050484</idno><date when="2018">2018</date><idno type="wicri:Area/Pmc/Corpus">001125</idno><idno type="wicri:explorRef" wicri:stream="Pmc" wicri:step="Corpus" wicri:corpus="PMC">001125</idno></publicationStmt><sourceDesc><biblStruct><analytic><title xml:lang="en" level="a" type="main">Synthesis, Characterization and Microstructure of New Liquid Poly(methylhydrosiloxanes) Containing Branching Units SiO<sub>4/2</sub></title><author><name sortKey="Chru Ciel, Jerzy J" sort="Chru Ciel, Jerzy J" uniqKey="Chru Ciel J" first="Jerzy J." last="Chru Ciel">Jerzy J. Chru Ciel</name><affiliation><nlm:aff id="af1-polymers-10-00484">Textile Research Institute, Brzezińska Str. 5/15, 92-103 Łódź, Poland</nlm:aff></affiliation></author><author><name sortKey="Fejdy, Marzena" sort="Fejdy, Marzena" uniqKey="Fejdy M" first="Marzena" last="Fejdy">Marzena Fejdy</name><affiliation><nlm:aff id="af2-polymers-10-00484">The Institute of Security Technologies “MORATEX”, Marii Skłodowskiej-Curie Str. 3, 90-505 Łódź, Poland;<email>mfejdys@moratex.eu</email></nlm:aff></affiliation></author><author><name sortKey="Fortuniak, Witold" sort="Fortuniak, Witold" uniqKey="Fortuniak W" first="Witold" last="Fortuniak">Witold Fortuniak</name><affiliation><nlm:aff id="af3-polymers-10-00484">Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza Str. 112, 90-363 Łódź, Poland;<email>wfortuni@cbmm.lodz.pl</email></nlm:aff></affiliation></author></analytic><series><title level="j">Polymers</title><idno type="eISSN">2073-4360</idno><imprint><date when="2018">2018</date></imprint></series></biblStruct></sourceDesc></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en"><p>Six liquid branched poly(methylhydrosiloxanes) of new random structures (PMHS-Q), containing quadruple branching units SiO<sub>4/2</sub> (Q), both MeHSiO (D<sup>H</sup>) and Me<sub>2</sub>SiO (D) chain building units (or only mers MeHSiO), and terminal groups Me<sub>3</sub>SiO<sub>0.5</sub> (M) were prepared by a hydrolytic polycondensation method of appropriate organic chlorosilanes and tetraethyl ortosilicate (TEOS), in diethyl ether medium at temperature below 0 °C. Volatile low molecular weight siloxanes were removed by a vacuum distillation at 150–155 °C. Yields of PMHS-Q reached from 55–69 wt%. Their dynamic viscosities were measured in the Brookfield HBDV+IIcP cone-plate viscometer and ranged from 10.7–13.1 cP. Molecular weights (MW) of PMHS-Q (M<sub>n</sub> = 2440–6310 g/mol, M<sub>w</sub> = 5750–10,350 g/mol) and polydispersities of MW (M<sub>w</sub>/M<sub>n</sub> = 2.0–2.8) were determined by a size exclusion chromatography (SEC). All polymers were characterized by FTIR, <sup>1</sup>H- and <sup>29</sup>Si-NMR, and an elemental analysis. A microstructure of siloxane chains was proposed on a basis of <sup>29</sup>Si-NMR results and compared with literature data.</p></div></front><back><div1 type="bibliography"><listBibl><biblStruct><analytic><author><name sortKey="Eaborn, C" uniqKey="Eaborn C">C. Eaborn</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Noll, W" uniqKey="Noll W">W. Noll</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Hardman, B" uniqKey="Hardman B">B. Hardman</name></author><author><name sortKey="Torkelson, A" uniqKey="Torkelson A">A. Torkelson</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Ro Ciszewski, P" uniqKey="Ro Ciszewski P">P. Rościszewski</name></author><author><name sortKey="Zielecka, M" uniqKey="Zielecka M">M. Zielecka</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Chauhan, B P S" uniqKey="Chauhan B">B.P.S. Chauhan</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Kricheldorf, H R" uniqKey="Kricheldorf H">H.R. Kricheldorf</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Brook, M A" uniqKey="Brook M">M.A. Brook</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Chru Ciel, J" uniqKey="Chru Ciel J">J. Chruściel</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Chru Ciel, J" uniqKey="Chru Ciel J">J. Chruściel</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Chru Ciel, J" uniqKey="Chru Ciel J">J. Chruściel</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Devimille, L" uniqKey="Devimille L">L. Devimille</name></author><author><name sortKey="Bresson, B" uniqKey="Bresson B">B. Bresson</name></author><author><name sortKey="Bokobza, L" uniqKey="Bokobza L">L. Bokobza</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Fejdy, M" uniqKey="Fejdy M">M. Fejdyś</name></author><author><name sortKey="Chru Ciel, J" uniqKey="Chru Ciel J">J. Chruściel</name></author><author><name sortKey="Miazga, A" uniqKey="Miazga A">A. Miazga</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Jia, L" uniqKey="Jia L">L. Jia</name></author><author><name sortKey="Du, Z" uniqKey="Du Z">Z. Du</name></author><author><name sortKey="Zhang, C" uniqKey="Zhang C">C. Zhang</name></author><author><name sortKey="Liu, C" uniqKey="Liu C">C. Liu</name></author><author><name sortKey="Li, H" uniqKey="Li H">H. Li</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Urayama, K" uniqKey="Urayama K">K. Urayama</name></author><author><name sortKey="Kawamura, T" uniqKey="Kawamura T">T. Kawamura</name></author><author><name sortKey="Kohjiya, S" uniqKey="Kohjiya S">S. Kohjiya</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Chru Ciel, J" uniqKey="Chru Ciel J">J. Chruściel</name></author><author><name sortKey="Le Niak, E" uniqKey="Le Niak E">E. Leśniak</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Hager, R" uniqKey="Hager R">R. Hager</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Hager, R" uniqKey="Hager R">R. Hager</name></author><author><name sortKey="Schneider, O" uniqKey="Schneider O">O. Schneider</name></author><author><name sortKey="Schuster, J" uniqKey="Schuster J">J. Schuster</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Razzano, J S" uniqKey="Razzano J">J.S. Razzano</name></author><author><name sortKey="Anderson, P P" uniqKey="Anderson P">P.P. Anderson</name></author><author><name sortKey="Perry, R J" uniqKey="Perry R">R.J. Perry</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Nye, S A" uniqKey="Nye S">S.A. Nye</name></author><author><name sortKey="Riccio, D A" uniqKey="Riccio D">D.A. Riccio</name></author><author><name sortKey="Wutzer, B S" uniqKey="Wutzer B">B.S. Wutzer</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Liao, W P" uniqKey="Liao W">W.P. Liao</name></author><author><name sortKey="Nye, S A" uniqKey="Nye S">S.A. Nye</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Palaprat, G" uniqKey="Palaprat G">G. Palaprat</name></author><author><name sortKey="Ganachaud, F" uniqKey="Ganachaud F">F. Ganachaud</name></author><author><name sortKey="Mauzac, M" uniqKey="Mauzac M">M. Mauzac</name></author><author><name sortKey="Hemery, P" uniqKey="Hemery P">P. Hemery</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Maisonnier, S" uniqKey="Maisonnier S">S. Maisonnier</name></author><author><name sortKey="Favier, J C" uniqKey="Favier J">J.C. Favier</name></author><author><name sortKey="Masure, M" uniqKey="Masure M">M. Masure</name></author><author><name sortKey="Hemery, P" uniqKey="Hemery P">P. Hemery</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Paulasaari, J K" uniqKey="Paulasaari J">J.K. Paulasaari</name></author><author><name sortKey="Weber, W P" uniqKey="Weber W">W.P. Weber</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Agaskar, P A" uniqKey="Agaskar P">P.A. Agaskar</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Chru Ciel, J" uniqKey="Chru Ciel J">J. Chruściel</name></author><author><name sortKey="Kulpi Ski, J" uniqKey="Kulpi Ski J">J. Kulpiński</name></author><author><name sortKey="Romanowski, Z" uniqKey="Romanowski Z">Z. Romanowski</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Agaskar, P A" uniqKey="Agaskar P">P.A. Agaskar</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Bassindale, A R" uniqKey="Bassindale A">A.R. Bassindale</name></author><author><name sortKey="Gentle, T E" uniqKey="Gentle T">T.E. Gentle</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Crivello, J V" uniqKey="Crivello J">J.V. Crivello</name></author><author><name sortKey="Malik, R" uniqKey="Malik R">R. Malik</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Tsuchida, A" uniqKey="Tsuchida A">A. Tsuchida</name></author><author><name sortKey="Bolin, C" uniqKey="Bolin C">C. Bolin</name></author><author><name sortKey="Sernetz, F G" uniqKey="Sernetz F">F.G. Sernetz</name></author><author><name sortKey="Frey, H" uniqKey="Frey H">H. Frey</name></author><author><name sortKey="Mulhaupt, R" uniqKey="Mulhaupt R">R. Mülhaupt</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Zhang, C" uniqKey="Zhang C">C. Zhang</name></author><author><name sortKey="Babonneau, F" uniqKey="Babonneau F">F. Babonneau</name></author><author><name sortKey="Laine, R M" uniqKey="Laine R">R.M. Laine</name></author><author><name sortKey="Soles, C L" uniqKey="Soles C">C.L. Soles</name></author><author><name sortKey="Hristov, H A" uniqKey="Hristov H">H.A. Hristov</name></author><author><name sortKey="Yee, A F" uniqKey="Yee A">A.F. Yee</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Zhang, C" uniqKey="Zhang C">C. Zhang</name></author><author><name sortKey="Laine, R M" uniqKey="Laine R">R.M. Laine</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Constantopoulos, K" uniqKey="Constantopoulos K">K. Constantopoulos</name></author><author><name sortKey="Clarke, D" uniqKey="Clarke D">D. Clarke</name></author><author><name sortKey="Markovic, E" uniqKey="Markovic E">E. Markovic</name></author><author><name sortKey="Uhrig, D" uniqKey="Uhrig D">D. Uhrig</name></author><author><name sortKey="Clarke, S" uniqKey="Clarke S">S. Clarke</name></author><author><name sortKey="Matisons, J G" uniqKey="Matisons J">J.G. Matisons</name></author><author><name sortKey="Simon, G" uniqKey="Simon G">G. Simon</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Frye, C" uniqKey="Frye C">C. Frye</name></author><author><name sortKey="Collins, W T" uniqKey="Collins W">W.T. Collins</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Agaskar, P A" uniqKey="Agaskar P">P.A. Agaskar</name></author><author><name sortKey="Day, V W" uniqKey="Day V">V.W. Day</name></author><author><name sortKey="Klemperer, W G" uniqKey="Klemperer W">W.G. Klemperer</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Hasegawa, I" uniqKey="Hasegawa I">I. Hasegawa</name></author><author><name sortKey="Motojima, D" uniqKey="Motojima D">D. Motojima</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Majoros, I" uniqKey="Majoros I">I. Majoros</name></author><author><name sortKey="Marsylko, T M" uniqKey="Marsylko T">T.M. Marsylko</name></author><author><name sortKey="Kennedy, J P" uniqKey="Kennedy J">J.P. Kennedy</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Provatas, A" uniqKey="Provatas A">A. Provatas</name></author><author><name sortKey="Luft, M" uniqKey="Luft M">M. Luft</name></author><author><name sortKey="Mu, J C" uniqKey="Mu J">J.C. Mu</name></author><author><name sortKey="White, A H" uniqKey="White A">A.H. White</name></author><author><name sortKey="Matisons, J G" uniqKey="Matisons J">J.G. Matisons</name></author><author><name sortKey="Skelton, B W" uniqKey="Skelton B">B.W. Skelton</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Perrin, F X" uniqKey="Perrin F">F.X. Perrin</name></author><author><name sortKey="Nguyen, T B V" uniqKey="Nguyen T">T.B.V. Nguyen</name></author><author><name sortKey="Margaillan, A" uniqKey="Margaillan A">A. Margaillan</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Dutkiewicz, M" uniqKey="Dutkiewicz M">M. Dutkiewicz</name></author><author><name sortKey="Maciejewski, H" uniqKey="Maciejewski H">H. Maciejewski</name></author><author><name sortKey="Marciniec, B" uniqKey="Marciniec B">B. Marciniec</name></author><author><name sortKey="Karasiewicz, J" uniqKey="Karasiewicz J">J. Karasiewicz</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Hasegawa, I" uniqKey="Hasegawa I">I. Hasegawa</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Moran, M" uniqKey="Moran M">M. Moran</name></author><author><name sortKey="Casado, C M" uniqKey="Casado C">C.M. Casado</name></author><author><name sortKey="Cuadrado, I" uniqKey="Cuadrado I">I. Cuadrado</name></author><author><name sortKey="Losada, J" uniqKey="Losada J">J. Losada</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Sellinger, A" uniqKey="Sellinger A">A. Sellinger</name></author><author><name sortKey="Laine, R M" uniqKey="Laine R">R.M. Laine</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Laine, R M" uniqKey="Laine R">R.M. Laine</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Hasegawa, I" uniqKey="Hasegawa I">I. Hasegawa</name></author><author><name sortKey="Ino, K" uniqKey="Ino K">K. Ino</name></author><author><name sortKey="Onishi, H" uniqKey="Onishi H">H. Onishi</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Soh, M S" uniqKey="Soh M">M.S. Soh</name></author><author><name sortKey="Yap, A U J" uniqKey="Yap A">A.U.J. Yap</name></author><author><name sortKey="Sellinger, A" uniqKey="Sellinger A">A. Sellinger</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Hessel, C M" uniqKey="Hessel C">C.M. Hessel</name></author><author><name sortKey="Henderson, E J" uniqKey="Henderson E">E.J. Henderson</name></author><author><name sortKey="Veinot, J G C" uniqKey="Veinot J">J.G.C. Veinot</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Gunji, T" uniqKey="Gunji T">T. Gunji</name></author><author><name sortKey="Shioda, T" uniqKey="Shioda T">T. Shioda</name></author><author><name sortKey="Tsuchihira, K" uniqKey="Tsuchihira K">K. Tsuchihira</name></author><author><name sortKey="Seki, H" uniqKey="Seki H">H. Seki</name></author><author><name sortKey="Kajiwara, T" uniqKey="Kajiwara T">T. Kajiwara</name></author><author><name sortKey="Abe, Y" uniqKey="Abe Y">Y. Abe</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Shioda, T" uniqKey="Shioda T">T. Shioda</name></author><author><name sortKey="Gunji, T" uniqKey="Gunji T">T. Gunji</name></author><author><name sortKey="Abe, N" uniqKey="Abe N">N. Abe</name></author><author><name sortKey="Abe, Y" uniqKey="Abe Y">Y. Abe</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Handke, M" uniqKey="Handke M">M. Handke</name></author><author><name sortKey="Kowalewska, A" uniqKey="Kowalewska A">A. Kowalewska</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Cai, G" uniqKey="Cai G">G. Cai</name></author><author><name sortKey="Weber, W P" uniqKey="Weber W">W.P. Weber</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Grunlan, M A" uniqKey="Grunlan M">M.A. Grunlan</name></author><author><name sortKey="Lee, N S" uniqKey="Lee N">N.S. Lee</name></author><author><name sortKey="Mansfeld, F" uniqKey="Mansfeld F">F. Mansfeld</name></author><author><name sortKey="Kus, E" uniqKey="Kus E">E. Kus</name></author><author><name sortKey="Finlay, J A" uniqKey="Finlay J">J.A. Finlay</name></author><author><name sortKey="Callow, J A" uniqKey="Callow J">J.A. Callow</name></author><author><name sortKey="Callow, M E" uniqKey="Callow M">M.E. Callow</name></author><author><name sortKey="Weber, W P" uniqKey="Weber W">W.P. Weber</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Sargent, J R" uniqKey="Sargent J">J.R. Sargent</name></author><author><name sortKey="Weber, W P" uniqKey="Weber W">W.P. Weber</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Cai, G" uniqKey="Cai G">G. Cai</name></author><author><name sortKey="Sargent, J R" uniqKey="Sargent J">J.R. Sargent</name></author><author><name sortKey="Weber, W P" uniqKey="Weber W">W.P. Weber</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Saxena, K" uniqKey="Saxena K">K. Saxena</name></author><author><name sortKey="Bisaria, C S" uniqKey="Bisaria C">C.S. Bisaria</name></author><author><name sortKey="Saxena, A K" uniqKey="Saxena A">A.K. Saxena</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Zhang, R" uniqKey="Zhang R">R. Zhang</name></author><author><name sortKey="Dai, D" uniqKey="Dai D">D. Dai</name></author><author><name sortKey="Cui, L" uniqKey="Cui L">L. Cui</name></author><author><name sortKey="Xu, H" uniqKey="Xu H">H. Xu</name></author><author><name sortKey="Liu, C" uniqKey="Liu C">C. Liu</name></author><author><name sortKey="Xie, P" uniqKey="Xie P">P. Xie</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Wan, Y" uniqKey="Wan Y">Y. Wan</name></author><author><name sortKey="Xu, L" uniqKey="Xu L">L. Xu</name></author><author><name sortKey="Ren, L" uniqKey="Ren L">L. Ren</name></author><author><name sortKey="Zhang, L" uniqKey="Zhang L">L. Zhang</name></author><author><name sortKey="Xie, P" uniqKey="Xie P">P. Xie</name></author><author><name sortKey="Liu, Y" uniqKey="Liu Y">Y. Liu</name></author><author><name sortKey="Zhang, R" uniqKey="Zhang R">R. Zhang</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Cao, M" uniqKey="Cao M">M. Cao</name></author><author><name sortKey="Li, Z" uniqKey="Li Z">Z. Li</name></author><author><name sortKey="Zhang, Y" uniqKey="Zhang Y">Y. Zhang</name></author><author><name sortKey="Xie, P" uniqKey="Xie P">P. Xie</name></author><author><name sortKey="Dai, D" uniqKey="Dai D">D. Dai</name></author><author><name sortKey="Zhang, R" uniqKey="Zhang R">R. Zhang</name></author><author><name sortKey="Lin, Y" uniqKey="Lin Y">Y. Lin</name></author><author><name sortKey="Chung, N T" uniqKey="Chung N">N.T. Chung</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Uchida, H" uniqKey="Uchida H">H. Uchida</name></author><author><name sortKey="Kabe, Y" uniqKey="Kabe Y">Y. Kabe</name></author><author><name sortKey="Yoshino, K" uniqKey="Yoshino K">K. Yoshino</name></author><author><name sortKey="Kawamata, A" uniqKey="Kawamata A">A. Kawamata</name></author><author><name sortKey="Tsumuraya, T" uniqKey="Tsumuraya T">T. Tsumuraya</name></author><author><name sortKey="Masamune, S" uniqKey="Masamune S">S. Masamune</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Zhao, S" uniqKey="Zhao S">S. Zhao</name></author><author><name sortKey="Feng, S" uniqKey="Feng S">S. Feng</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Su, H W" uniqKey="Su H">H.W. Su</name></author><author><name sortKey="Chen, W C" uniqKey="Chen W">W.C. Chen</name></author><author><name sortKey="Lee, W C" uniqKey="Lee W">W.C. Lee</name></author><author><name sortKey="King, J S" uniqKey="King J">J.S. King</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Seino, M" uniqKey="Seino M">M. Seino</name></author><author><name sortKey="Hayakawa, T" uniqKey="Hayakawa T">T. Hayakawa</name></author><author><name sortKey="Ishida, Y" uniqKey="Ishida Y">Y. Ishida</name></author><author><name sortKey="Kakimoto, M" uniqKey="Kakimoto M">M. Kakimoto</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Soraru, G D" uniqKey="Soraru G">G.D. Soraru</name></author><author><name sortKey="D Ndrea, G" uniqKey="D Ndrea G">G. D’Andrea</name></author><author><name sortKey="Campostrini, R" uniqKey="Campostrini R">R. Campostrini</name></author><author><name sortKey="Baboneau, F" uniqKey="Baboneau F">F. Baboneau</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Campostrini, R" uniqKey="Campostrini R">R. Campostrini</name></author><author><name sortKey="D Ndrea, G" uniqKey="D Ndrea G">G. D’Andrea</name></author><author><name sortKey="Carturan, G" uniqKey="Carturan G">G. Carturan</name></author><author><name sortKey="Ceccato, R" uniqKey="Ceccato R">R. Ceccato</name></author><author><name sortKey="Soraru, G D" uniqKey="Soraru G">G.D. Soraru</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Bazant, V" uniqKey="Bazant V">V. Bažant</name></author><author><name sortKey="Chvalovsk, V" uniqKey="Chvalovsk V">V. Chvalovský</name></author><author><name sortKey="Rathousk, I" uniqKey="Rathousk I">I. Rathouský</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Morikawa, A" uniqKey="Morikawa A">A. Morikawa</name></author><author><name sortKey="Kakimoto, M" uniqKey="Kakimoto M">M. Kakimoto</name></author><author><name sortKey="Imai, Y" uniqKey="Imai Y">Y. Imai</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Chang, H T" uniqKey="Chang H">H.T. Chang</name></author><author><name sortKey="Frechet, J M J" uniqKey="Frechet J">J.M.J. Frechet</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Innoue, K" uniqKey="Innoue K">K. Innoue</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Paulasaari, J K" uniqKey="Paulasaari J">J.K. Paulasaari</name></author><author><name sortKey="Weber, W P" uniqKey="Weber W">W.P. Weber</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Paulasaari, J K" uniqKey="Paulasaari J">J.K. Paulasaari</name></author><author><name sortKey="Weber, W P" uniqKey="Weber W">W.P. Weber</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Jikei, M" uniqKey="Jikei M">M. Jikei</name></author><author><name sortKey="Kakimoto, M" uniqKey="Kakimoto M">M. Kakimoto</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Servaty, S" uniqKey="Servaty S">S. Servaty</name></author><author><name sortKey="Kohler, W" uniqKey="Kohler W">W. Köhler</name></author><author><name sortKey="Meyer, W H" uniqKey="Meyer W">W.H. Meyer</name></author><author><name sortKey="Rosenauer, C" uniqKey="Rosenauer C">C. Rosenauer</name></author><author><name sortKey="Spickermann, J" uniqKey="Spickermann J">J. Spickermann</name></author><author><name sortKey="R Der, H J" uniqKey="R Der H">H.J. Räder</name></author><author><name sortKey="Wegner, G" uniqKey="Wegner G">G. Wegner</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Silverstein, R M" uniqKey="Silverstein R">R.M. Silverstein</name></author><author><name sortKey="Bassler, G C" uniqKey="Bassler G">G.C. Bassler</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Glaser, R H" uniqKey="Glaser R">R.H. Glaser</name></author><author><name sortKey="Wilkes, G L" uniqKey="Wilkes G">G.L. Wilkes</name></author><author><name sortKey="Bronnimann, C E" uniqKey="Bronnimann C">C.E. Bronnimann</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Harris, R K" uniqKey="Harris R">R.K. Harris</name></author><author><name sortKey="Kimber, B J" uniqKey="Kimber B">B.J. Kimber</name></author></analytic></biblStruct></listBibl></div1></back></TEI><pmc article-type="research-article"><pmc-dir>properties open_access</pmc-dir>
<front><journal-meta><journal-id journal-id-type="nlm-ta">Polymers (Basel)</journal-id><journal-id journal-id-type="iso-abbrev">Polymers (Basel)</journal-id><journal-id journal-id-type="publisher-id">polymers</journal-id><journal-title-group><journal-title>Polymers</journal-title></journal-title-group><issn pub-type="epub">2073-4360</issn><publisher><publisher-name>MDPI</publisher-name></publisher></journal-meta><article-meta><article-id pub-id-type="pmid">30966518</article-id><article-id pub-id-type="pmc">6415389</article-id><article-id pub-id-type="doi">10.3390/polym10050484</article-id><article-id pub-id-type="publisher-id">polymers-10-00484</article-id><article-categories><subj-group subj-group-type="heading"><subject>Article</subject></subj-group></article-categories><title-group><article-title>Synthesis, Characterization and Microstructure of New Liquid Poly(methylhydrosiloxanes) Containing Branching Units SiO<sub>4/2</sub></article-title></title-group><contrib-group><contrib contrib-type="author"><contrib-id contrib-id-type="orcid" authenticated="true">https://orcid.org/0000-0002-6227-9428</contrib-id><name><surname>Chruściel</surname><given-names>Jerzy J.</given-names></name><xref ref-type="aff" rid="af1-polymers-10-00484">1</xref><xref rid="c1-polymers-10-00484" ref-type="corresp">*</xref></contrib><contrib contrib-type="author"><name><surname>Fejdyś</surname><given-names>Marzena</given-names></name><xref ref-type="aff" rid="af2-polymers-10-00484">2</xref></contrib><contrib contrib-type="author"><contrib-id contrib-id-type="orcid" authenticated="true">https://orcid.org/0000-0002-4064-6944</contrib-id><name><surname>Fortuniak</surname><given-names>Witold</given-names></name><xref ref-type="aff" rid="af3-polymers-10-00484">3</xref></contrib></contrib-group><aff id="af1-polymers-10-00484"><label>1</label>Textile Research Institute, Brzezińska Str. 5/15, 92-103 Łódź, Poland</aff><aff id="af2-polymers-10-00484"><label>2</label>The Institute of Security Technologies “MORATEX”, Marii Skłodowskiej-Curie Str. 3, 90-505 Łódź, Poland;<email>mfejdys@moratex.eu</email></aff><aff id="af3-polymers-10-00484"><label>3</label>Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza Str. 112, 90-363 Łódź, Poland;<email>wfortuni@cbmm.lodz.pl</email></aff><author-notes><corresp id="c1-polymers-10-00484"><label>*</label>Correspondence: <email>jchrusci@p.lodz.pl</email> or <email>jchrusciel@iw.lodz.pl</email>; Tel.: +48-42-61-63-187; Fax: +48-42-67-92-638</corresp></author-notes><pub-date pub-type="epub"><day>28</day><month>4</month><year>2018</year></pub-date><pub-date pub-type="collection"><month>5</month><year>2018</year></pub-date><volume>10</volume><issue>5</issue><elocation-id>484</elocation-id><history><date date-type="received"><day>28</day><month>3</month><year>2018</year></date><date date-type="accepted"><day>25</day><month>4</month><year>2018</year></date></history><permissions><copyright-statement>© 2018 by the authors.</copyright-statement><copyright-year>2018</copyright-year><license license-type="open-access"><license-p>Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (<ext-link ext-link-type="uri" xlink:href="http://creativecommons.org/licenses/by/4.0/">http://creativecommons.org/licenses/by/4.0/</ext-link>).</license-p></license></permissions><abstract><p>Six liquid branched poly(methylhydrosiloxanes) of new random structures (PMHS-Q), containing quadruple branching units SiO<sub>4/2</sub> (Q), both MeHSiO (D<sup>H</sup>) and Me<sub>2</sub>SiO (D) chain building units (or only mers MeHSiO), and terminal groups Me<sub>3</sub>SiO<sub>0.5</sub> (M) were prepared by a hydrolytic polycondensation method of appropriate organic chlorosilanes and tetraethyl ortosilicate (TEOS), in diethyl ether medium at temperature below 0 °C. Volatile low molecular weight siloxanes were removed by a vacuum distillation at 150–155 °C. Yields of PMHS-Q reached from 55–69 wt%. Their dynamic viscosities were measured in the Brookfield HBDV+IIcP cone-plate viscometer and ranged from 10.7–13.1 cP. Molecular weights (MW) of PMHS-Q (M<sub>n</sub> = 2440–6310 g/mol, M<sub>w</sub> = 5750–10,350 g/mol) and polydispersities of MW (M<sub>w</sub>/M<sub>n</sub> = 2.0–2.8) were determined by a size exclusion chromatography (SEC). All polymers were characterized by FTIR, <sup>1</sup>H- and <sup>29</sup>Si-NMR, and an elemental analysis. A microstructure of siloxane chains was proposed on a basis of <sup>29</sup>Si-NMR results and compared with literature data.</p></abstract><kwd-group><kwd>hyperbranched poly(methylhydrosiloxanes)</kwd><kwd>hydrolytic polycondensation</kwd><kwd><sup>29</sup>Si-NMR</kwd><kwd>topology of polysiloxane chains</kwd></kwd-group></article-meta></front><body><sec sec-type="intro" id="sec1-polymers-10-00484"><title>1. Introduction</title><p>Poly(methylhydrosiloxanes) (PMHS) are inorganic–organic hybrid polymers with inorganic backbone, composed of alternatively bound silicon and oxygen atoms. Hydrogen atoms and methyl groups are the main substituents of silicon atoms in PMHS; however, other organic groups may be attached to silicon atoms in their structures as well. Most PMHS are colorless oils, though some of them are solids [<xref rid="B1-polymers-10-00484" ref-type="bibr">1</xref>,<xref rid="B2-polymers-10-00484" ref-type="bibr">2</xref>,<xref rid="B3-polymers-10-00484" ref-type="bibr">3</xref>,<xref rid="B4-polymers-10-00484" ref-type="bibr">4</xref>,<xref rid="B5-polymers-10-00484" ref-type="bibr">5</xref>,<xref rid="B6-polymers-10-00484" ref-type="bibr">6</xref>,<xref rid="B7-polymers-10-00484" ref-type="bibr">7</xref>,<xref rid="B8-polymers-10-00484" ref-type="bibr">8</xref>,<xref rid="B9-polymers-10-00484" ref-type="bibr">9</xref>]. Linear, star, hyperbranched and dendritic poly(methylhydrosiloxanes), as well as spherical hydrosilicates, are important classes of functional silicones. Many methods of their preparation were described in our previous publication, concerning synthesis and characterization of branched PMHS containing triple branching units MeSiO<sub>1.5</sub> (T) [<xref rid="B9-polymers-10-00484" ref-type="bibr">9</xref>]. PMHS find numerous practical applications. Most often they are used as cross-linking agents in a technology of silicone elastomers [<xref rid="B9-polymers-10-00484" ref-type="bibr">9</xref>,<xref rid="B10-polymers-10-00484" ref-type="bibr">10</xref>,<xref rid="B11-polymers-10-00484" ref-type="bibr">11</xref>,<xref rid="B12-polymers-10-00484" ref-type="bibr">12</xref>,<xref rid="B13-polymers-10-00484" ref-type="bibr">13</xref>,<xref rid="B14-polymers-10-00484" ref-type="bibr">14</xref>,<xref rid="B15-polymers-10-00484" ref-type="bibr">15</xref>].</p><p>One of the newer synthetic methods used for the preparation of poly(dimethylsiloxanes- -<italic>co</italic>-methylhydrosiloxanes) (PDMS-<italic>co</italic>-PMHS) is based on an equilibration polymerization of poly(dimethylsiloxanes) with linear hydrosiloxane polymer and hexamethyldisiloxane Me<sub>3</sub>SiOSiMe<sub>3</sub>, towards phosphonitrile catalyst [Cl<sub>3</sub>P(NPCl<sub>2</sub>)<sub>2</sub>PCl<sub>3</sub>]<sup>+</sup>PCl<sub>6</sub><sup>−</sup> at elevated temperature [<xref rid="B16-polymers-10-00484" ref-type="bibr">16</xref>,<xref rid="B17-polymers-10-00484" ref-type="bibr">17</xref>,<xref rid="B18-polymers-10-00484" ref-type="bibr">18</xref>,<xref rid="B19-polymers-10-00484" ref-type="bibr">19</xref>,<xref rid="B20-polymers-10-00484" ref-type="bibr">20</xref>].</p><p>A polymerization of 1,3,5,7-tetramethylcyclotetrasiloxane (D<sup>H</sup><sub>4</sub>) [D<sup>H</sup> = H(CH<sub>3</sub>)SiO] was carried out in the presence of the non-ionic emulgator C<sub>12</sub>H<sub>25</sub>(OCH<sub>2</sub>CH<sub>2</sub>)<sub>23</sub>OH and dodecylbenzene- sulphonic acid and it was accelerated by ultrasounds [<xref rid="B21-polymers-10-00484" ref-type="bibr">21</xref>,<xref rid="B22-polymers-10-00484" ref-type="bibr">22</xref>].</p><p>Weber and Paulasaari obtained poly(1-hydro-1,3,3,5,5-pentamethyltrisiloxane) with a regular chain structure by the polymerization of a new monomer, pentamethylcyclotrisiloxane c-(Me<sub>2</sub>SiO)<sub>2</sub>(MeHSiO) [c-D<sub>2</sub>D<sup>H</sup>; D = (CH<sub>3</sub>)<sub>2</sub>SiO] in tetrahydrofurane (THF), in the presence of Ph<sub>2</sub>Si(OLi)<sub>2</sub>, at −79 °C [<xref rid="B23-polymers-10-00484" ref-type="bibr">23</xref>]. The starting monomer c-D<sub>2</sub>D<sup>H</sup> was prepared by heterocondensation of MeHSiCl<sub>2</sub> with HO(Me<sub>2</sub>SiO)<sub>2</sub>H (yield: 49%). At the same time was elaborated a new sequential polycondensation method (“one-pot”) leading to three homological series of new PDMS-<italic>b</italic>-PMHS with a general formula:<disp-formula>RMe<sub>2</sub>SiO[(Me<sub>2</sub>SiO)<sub>m</sub>(MeHSiO)<sub>k</sub>]<sub>n</sub>(Me<sub>2</sub>SiO)<sub>m</sub>SiMe<sub>2</sub>R,<label>(1)</label></disp-formula>(where: R = –OH or –Me; m = 2, 6, 10, 14, ~50; k = 1–4; n = 5, 10, 15, 20), containing single or multiple MeHSiO units in macromolecules [<xref rid="B9-polymers-10-00484" ref-type="bibr">9</xref>,<xref rid="B24-polymers-10-00484" ref-type="bibr">24</xref>]. This synthetic method is based on a non-stoichiometric polycondensation of appropriate dimethylsiloxane-α,ω-diols HO(Me<sub>2</sub>SiO)<sub>m</sub>H with siloxane oligomers of a general formula Cl(MeHSiO)<sub>k-1</sub>SiHMeCl, having chloro(hydro)silyl functionalities, followed by termination reactions with chlorotrimethylsilane Me<sub>3</sub>SiCl, when PDMS-<italic>b</italic>-PMHS chains were blocked with (CH<sub>3</sub>)<sub>3</sub>SiO<sub>0.5</sub> (M) groups. An isolation and characterization of many model H-siloxanes helped us to establish the regular microstructure of prepared PDMS-<italic>b</italic>-PMHS, which was further confirmed by <sup>1</sup>H- and <sup>29</sup>Si-NMR studies [<xref rid="B9-polymers-10-00484" ref-type="bibr">9</xref>,<xref rid="B25-polymers-10-00484" ref-type="bibr">25</xref>].</p><p>In recent years a growing interest has been observed in the field of syntheses of star, highly branched, and dendritic poly(methylhydrosiloxanes). Cage silsesquioxanes (“spherosiloxanes”): T<sup>H</sup><sub>8</sub>, T<sup>H</sup><sub>10</sub>, T<sup>H</sup><sub>12</sub>, T<sup>H</sup><sub>14</sub>, and T<sup>H</sup><sub>16</sub> (T<sup>H</sup> = HSiO<sub>1.5</sub>) are solids, which can be prepared by the hydrolytic polycondensation of: (a) trichlorosilane HSiCl<sub>3</sub>, carried out in the presence of FeCl<sub>3</sub> in methanol medium [<xref rid="B24-polymers-10-00484" ref-type="bibr">24</xref>,<xref rid="B26-polymers-10-00484" ref-type="bibr">26</xref>,<xref rid="B27-polymers-10-00484" ref-type="bibr">27</xref>,<xref rid="B28-polymers-10-00484" ref-type="bibr">28</xref>], or (b) trimethoxysilane HSi(OCH<sub>3</sub>)<sub>3</sub>, saturated with anhydrous HCl, in acetic acid solution [<xref rid="B29-polymers-10-00484" ref-type="bibr">29</xref>,<xref rid="B30-polymers-10-00484" ref-type="bibr">30</xref>,<xref rid="B31-polymers-10-00484" ref-type="bibr">31</xref>,<xref rid="B32-polymers-10-00484" ref-type="bibr">32</xref>], or in the presence of concentrated H<sub>2</sub>SO<sub>4</sub> [<xref rid="B33-polymers-10-00484" ref-type="bibr">33</xref>,<xref rid="B34-polymers-10-00484" ref-type="bibr">34</xref>]. Octakis(dimethylsiloxy)- octasilsesquioxane [(HMe<sub>2</sub>SiO)SiO<sub>1.5</sub>]<sub>8</sub> [Q<sub>8</sub>M<sup>H</sup><sub>8</sub>, Q = SiO<sub>4/2</sub>, M<sup>H</sup> = H(CH<sub>3</sub>)<sub>2</sub>SiO<sub>0.5</sub>] can be prepared with high yields in reaction of octakis(tetramethylammonium)octasilsesquioxane with ClSiMe<sub>2</sub>H [<xref rid="B35-polymers-10-00484" ref-type="bibr">35</xref>,<xref rid="B36-polymers-10-00484" ref-type="bibr">36</xref>,<xref rid="B37-polymers-10-00484" ref-type="bibr">37</xref>], up to 85–91% yield [<xref rid="B38-polymers-10-00484" ref-type="bibr">38</xref>,<xref rid="B39-polymers-10-00484" ref-type="bibr">39</xref>]. Currently a low molecular mass star tetrakis(dimethylsiloxy)silane Si[OSi(CH<sub>3</sub>)<sub>2</sub>H]<sub>4</sub>, octahydrosilsesquioxane (T<sup>H</sup><sub>8</sub>) and cubic Q<sub>8</sub>M<sup>H</sup><sub>8</sub> are commercially available [<xref rid="B35-polymers-10-00484" ref-type="bibr">35</xref>,<xref rid="B40-polymers-10-00484" ref-type="bibr">40</xref>,<xref rid="B41-polymers-10-00484" ref-type="bibr">41</xref>,<xref rid="B42-polymers-10-00484" ref-type="bibr">42</xref>,<xref rid="B43-polymers-10-00484" ref-type="bibr">43</xref>,<xref rid="B44-polymers-10-00484" ref-type="bibr">44</xref>,<xref rid="B45-polymers-10-00484" ref-type="bibr">45</xref>,<xref rid="B46-polymers-10-00484" ref-type="bibr">46</xref>].</p><p>Recently siloxane-polyhedral silsesquioxane copolymers (soluble in THF) were prepared by the dehydrogenative condensation of T<sup>H</sup><sub>8</sub> with diphenylsilanediol, tetraphenyldisiloxane diol or oligodimethylsiloxane-α,ω-diols in the presence of diethylhydroxylamine, followed by trimethyl- silylation [<xref rid="B47-polymers-10-00484" ref-type="bibr">47</xref>,<xref rid="B48-polymers-10-00484" ref-type="bibr">48</xref>]. T<sup>H</sup><sub>8</sub> was also applied as a precursor of mezoporous silica, which was prepared without using any template or surfactant [<xref rid="B49-polymers-10-00484" ref-type="bibr">49</xref>].</p><p>An equilibration of octamethylcyclotetrasiloxane [(Me<sub>2</sub>SiO)<sub>4</sub>, D<sub>4</sub>] with Si[OSi(CH<sub>3</sub>)<sub>2</sub>H]<sub>4</sub> and trifluoromethanesulphonic acid led to tetraarm star polysiloxane Si{[OSi(CH<sub>3</sub>)<sub>2</sub>]<sub>n</sub>OSi(CH<sub>3</sub>)<sub>2</sub>H}<sub>4</sub> [<xref rid="B50-polymers-10-00484" ref-type="bibr">50</xref>,<xref rid="B51-polymers-10-00484" ref-type="bibr">51</xref>]. Six- and eight-membered silicates: hexakis(dimethylsiloxy)cyclotrisiloxane [(HMe<sub>2</sub>SiO)<sub>2</sub>SiO]<sub>3</sub> and octakis(dimethylsiloxy)cyclotetrasiloxane [(HMe<sub>2</sub>SiO)<sub>2</sub>SiO]<sub>4</sub> were synthesized with low yields, from reactions of pyrolysis products of wollastonite. [(HMe<sub>2</sub>SiO)<sub>2</sub>SiO]<sub>3</sub> was prepared in reaction of chlorodimethylsilane HMe<sub>2</sub>SiCl with pseudowollastonite Ca<sub>3</sub>Si<sub>3</sub>O<sub>9</sub>Cl<sub>6</sub>, while [(HMe<sub>2</sub>SiO)<sub>2</sub>SiO]<sub>4</sub> was prepared by heating octakis(trimethylsiloxy)cyclotetrasiloxane [(Me<sub>3</sub>SiO)<sub>2</sub>SiO]<sub>4</sub> with 1,1,3,3- -tetramethyldisiloxane HMe<sub>2</sub>SiOSiMe<sub>2</sub>H in the presence of trifluoromethanesulphonic acid [<xref rid="B52-polymers-10-00484" ref-type="bibr">52</xref>,<xref rid="B53-polymers-10-00484" ref-type="bibr">53</xref>]. The equilibration of [(HMe<sub>2</sub>SiO)<sub>2</sub>SiO]<sub>3</sub> with D<sub>4</sub> and triflic acid gave PMHS of the following branched structure: –{–OSi[(OSiMe<sub>2</sub>O)<sub>n</sub>SiMe<sub>2</sub>H]<sub>2</sub>–}<sub>6</sub>– [<xref rid="B52-polymers-10-00484" ref-type="bibr">52</xref>]. The Si–H terminated multifunctional silicone dendrimer, i.e., tetrakis(dimethylsiloxy)silane, was prepared with 69% yield by the reaction of TEOS and dimethoxysilane [<xref rid="B54-polymers-10-00484" ref-type="bibr">54</xref>].</p><p>Zhang et al. synthesized polysilsesquioxanes of a ladder structure, containing units HSiO<sub>1.5</sub> and MeSiO<sub>1.5</sub>, by hydrolysis of byproducts prepared through condensation of HSiCl<sub>3</sub> and MeSiCl<sub>3</sub> with <italic>p</italic>-phenylenediamine or ethylenediamine [<xref rid="B55-polymers-10-00484" ref-type="bibr">55</xref>,<xref rid="B56-polymers-10-00484" ref-type="bibr">56</xref>,<xref rid="B57-polymers-10-00484" ref-type="bibr">57</xref>].</p><p>A silicone dendrimer of a third generation with symmetrical structure and the general formula (CH<sub>3</sub>SiO<sub>1.5</sub>)<sub>22</sub>[(CH<sub>3</sub>)<sub>2</sub>SiO)]<sub>162</sub>[H(CH<sub>3</sub>)<sub>2</sub>SiO<sub>0.5</sub>]<sub>24</sub> was prepared by Masamune et al. [<xref rid="B58-polymers-10-00484" ref-type="bibr">58</xref>] in a multistep synthesis from siloxane oligomers containing functional groups: Si-H, Si-Cl, Si-Br and Si-OH. It had 24 terminal functional Si-H groups “on the surface”. Branched resins, containing 10–14 Si-H functional groups in macromolecules were synthesized by the hydrolytic polycondensation of methyldichlorosilane with dimethyldichlorosilane, trimethylchlorosilane and methyltriethoxy)- silane or phenyl(triethoxy)silane. These resins were used as crosslinking agents for addition of cured silicone elastomers [<xref rid="B59-polymers-10-00484" ref-type="bibr">59</xref>]. Condensation of (triethoxy)silane HSi(OC<sub>2</sub>H<sub>5</sub>)<sub>3</sub>, towards HCl solution, in the mixture of THF and methylisobutyl ketone (MIBK), led to soluble multifunctional poly- (hydrogensilsesquioxanes) (PHSSQ) of combined cage-like and network-like structures [<xref rid="B60-polymers-10-00484" ref-type="bibr">60</xref>]. A solid four-membered silsesquioxane ring compound (PhSiO<sub>1.5</sub>)<sub>8</sub>(MeHSiO)<sub>2</sub>, so-called ”double-decker- shaped-silsesquioxane”, was prepared from reaction of MeHSiCl<sub>2</sub> with a byproduct, which was obtained via a condensation of phenyl(trimethoxy)silane and NaOH with 20% yield [<xref rid="B61-polymers-10-00484" ref-type="bibr">61</xref>].</p><p>Twelve new liquid branched poly(methylhydrosiloxanes) with statistical structures (b-r-PMHS), containing triple branching units MeSiO<sub>1.5</sub> (T), both Me<sub>2</sub>SiO (D) and MeHSiO (D<sup>H</sup>) chain building units (or only mers MeHSiO), and two b-r-PMHS containing five different structural units: D, D<sup>H</sup>, T and T<sup>H</sup> and trimethylsiloxy end groups Me<sub>3</sub>SiO<sub>0.5</sub> (M) were prepared by the hydrolytic poly- condensation method of appropriate chlorosilanes in diethyl ether medium at temperature <0 °C. Yields of b-r-PMHS ranged from 57–84 wt% (after removal of low molecular weight oligosiloxanes by a vacuum distillation at 125–150 °C). All polymeric products were characterized by FTIR, <sup>1</sup>H- and <sup>29</sup>Si-NMR, and elemental analysis. Their dynamic viscosities were very low and usually ranged from ~8–30 cP, which presumably resulted from their globular structure [<xref rid="B9-polymers-10-00484" ref-type="bibr">9</xref>].</p><p>Methyl-substituted silica gels with Si-H functionalities were prepared by hydrolysis and condensation reactions of triethoxysilane and methyldiethoxysilane, used in various molar ratios [<xref rid="B62-polymers-10-00484" ref-type="bibr">62</xref>]. They gave higher ceramic residue after pyrolysis than gels based only on MeSiO<sub>1.5</sub> branching units [<xref rid="B63-polymers-10-00484" ref-type="bibr">63</xref>].</p><p>In the present work, we describe the hydrolytic polycondensation synthetic route to new liquid branched poly(methylhydrosiloxanes) of random structures (PMHS-Q), containing both MeHSiO (D<sup>H</sup>) and Me<sub>2</sub>SiO (D) chain building units (or only mers MeHSiO), quadruple branching units SiO<sub>4/2</sub> (Q), and terminal groups Me<sub>3</sub>SiO<sub>0.5</sub>, from appropriate organic chlorosilanes and tetraethoxysilane.</p></sec><sec id="sec2-polymers-10-00484"><title>2. Materials and Methods</title><p>Dichloromethylsilane MeHSiCl<sub>2</sub> (MDS, 99%, b.p. 41 °C), dichlorodimethylsilane Me<sub>2</sub>SiCl<sub>2</sub> (DDS, b.p. 70–71 °C), tetraethoxysilane Si(OC<sub>2</sub>H<sub>5</sub>)<sub>4</sub> (b.p. 168 °C), (4-dimetylamino)pyridine (DMAP, 99%) were all sourced from Aldrich Chemical Company Inc., USA. Chlorotrimethylsilane Me<sub>3</sub>SiCl was obtained from Fluka, Seelze, Germany (TMCS, >99%, b.p. 57 °C). Tetraethoxysilane Si(OEt)<sub>4</sub> was obtained from Unisil, Tarnów, Poland (TEOS, 99%, b.p. 168 °C). Triethylamine (>99%, Fluka) was dried with anhydrous KOH, decanted, and distilled over P<sub>2</sub>O<sub>5</sub>. Diethyl ether was purified and dried with anhydrous KOH, and distilled over CaH<sub>2</sub>.</p><p>All products were analyzed by a nuclear magnetic resonance (NMR), infrared spectroscopy (FTIR) and gel chromatography (SEC). FTIR spectra (neat) were done on spectrophotometer IR Bio-Rad 175 C (American Laboratory Trading, East Lyme, CT 06333, USA) for samples placed between NaCI plates. <sup>1</sup>H-NMR and <sup>29</sup>Si-NMR (INEPT) spectra were recorded on Bruker DRX 500 machine (Bruker Physik AG, Karlsruhe, Germany) at CBMM PAN in Łódź. Hexamethyldisiloxane Me<sub>3</sub>SiOSiMe<sub>3</sub> was used as an external standard in <sup>29</sup>Si-NMR (δ = 6.98 ppm, in CDCl<sub>3</sub>).</p><p>An elementary analysis (% C and % H) was performed at the Centre of Molecular and Macromolecular Studies of the Polish Academy of Sciences in Łódź (CBMM PAN). The content of Si-H groups was calculated from an integration ratio of their signals to CH<sub>3</sub> signals in <sup>1</sup>H-NMR spectra, and compared to theoretical integration ratios of Si-H and CH<sub>3</sub> signals. The content of Si was determined by the gravimetric method with H<sub>2</sub>SO<sub>4</sub> (p.a.) [<xref rid="B64-polymers-10-00484" ref-type="bibr">64</xref>].</p><p>Dynamic viscosities (η<sup>25</sup>) of polysiloxanes were measured at 25.0 °C in a Brookfield cone-plate reoviscometer HBDV-II+cP (Brookfield Engineering Laboratories, Inc., Middleboro, MA 02346, USA), using a cone cP40.</p><p>The molecular masses and molecular mass distribution of polysiloxanes were analyzed by a size exclusion chromatography (SEC) in toluene solution, using LDC analytical chromatograph (Artisan Technology Group, Champaign, IL 61822, USA) equipped with refractoMonitor and a battery of two phenogel columns covering the MW range 10<sup>2</sup>–10<sup>5</sup> g∙mol<sup>−1</sup>. Calibration was made with polystyrene Ultrastyrogel standards with MWs: 10<sup>2</sup>, 10<sup>3</sup>, and 10<sup>4</sup> g∙mol<sup>−1</sup>.</p><sec><title>Synthesis of Branched Polymethylhydrosiloxanes (PMHS-Q)</title><p>Branched polymethylhydrosiloxanes, containing only units D<sup>H</sup> and Q, terminated with Me<sub>3</sub>SiO<sub>0.5</sub> groups, with structures described by a general formula:<disp-formula>(SiO<sub>4/2</sub>)<sub>y</sub>[CH<sub>3</sub>(H)SiO]<sub>n</sub>[(CH<sub>3</sub>)<sub>3</sub>SiO<sub>0.5</sub>]<sub>p</sub><label>(2)</label></disp-formula>(where: y = 1–3, n = 48–50, p = 2y + 2), and branched poly(dimethyl-<italic>co</italic>-methylhydro)siloxanes, containing both mers D, as well mers D<sup>H</sup>, units Q and end Me<sub>3</sub>SiO<sub>0.5</sub> groups, of a general formula:<disp-formula>(SiO<sub>4/2</sub>)<sub>y</sub>[(CH<sub>3</sub>)<sub>2</sub>SiO]<sub>m</sub>[CH<sub>3</sub>(H)SiO]<sub>n</sub>[(CH<sub>3</sub>)<sub>3</sub>SiO<sub>0.5</sub>]<sub>p</sub><label>(3)</label></disp-formula>(where: y = 1–3, m = n = 49–52, p = 2y + 2), were synthesized by the hydrolytic polycondensation of mixtures of tetraethoxysilane Si(OEt)<sub>4</sub> and appropriate chlorosilanes: dichloromethylsilane MeHSiCl<sub>2</sub>, dichlorodimethylsilane Me<sub>2</sub>SiCl<sub>2</sub>, and chlorotrimethylsilane Me<sub>3</sub>SiCl, in the medium of diethyl ether and water, at temperature ranged from −10–0 °C, within 3–5 h. Molar ratios of chlorosilanes were changed, depending on expected molecular formula of polysiloxane. Amounts of substrates used in syntheses of branched PMHS-Q and times of additions of chlorosilanes are presented in <xref rid="polymers-10-00484-t001" ref-type="table">Table 1</xref>. In the hydrolytic polycondensation reactions were used such amounts of distilled water, which were sufficient for a formation of hydrochloric acid with a final concentration about 20 wt%.</p><p>Reaction mixture was allowed to warm to room temperature within 120–170 min, acid layer was separated, and organosilicon layer was washed with water until neutral, transferred to an Erlenmayer flask, and dried at ~4 °C with anhydrous magnesium sulfate overnight. Magnesium sulfate was filtered through Schott funnel G-3 and washed with ether. Alternatively, instead of drying with anhydrous MgSO<sub>4</sub> traces of water were removed from products by cooling their ether solution in a refrigerator overnight, warming up the content of the flask to room temperature, and the ether solution of products was decanted from drops of water. The solvent was distilled off. In order to remove volatile cyclic and linear low molecular weight siloxane oligomers, the prepared products were heated at temperature 150–155 °C under reduced pressure (16–21 mm Hg, 2128–2793 Pa), and subsequently under a vacuum (3–5 mm Hg, 400–665 Pa).</p><p>In a second step of syntheses of <bold>Q<sub>3</sub>D<sup>H</sup><sub>50</sub>M<sub>8</sub></bold> and other poly(dimethyl-<italic>co</italic>-methylhydro)siloxanes, containing both mers D and D<sup>H</sup>, with a general formula:<disp-formula>(SiO<sub>4/2</sub>)<sub>y</sub>[(CH<sub>3</sub>)<sub>2</sub>SiO]<sub>m</sub>[CH<sub>3</sub>(H)SiO]<sub>n</sub>[(CH<sub>3</sub>)<sub>3</sub>SiO<sub>0.5</sub>]<sub>p</sub><label>(3)</label></disp-formula>(where: y = 1–3, m = n = 49–52, p = 2y + 2), so called “extra blocking” of unreacted silanol groups Si-OH was applied: in reactions with (chloro)trimethylsilane, in the presence of triethylamine, which was used as an acceptor of hydrogen chloride with ~5% excess with respect to a stoichiometric amount. (4-Dimethylamino)pyridine (DMAP) was used as a nucleophilic catalyst in 1:10 mole ratio with respect to Et<sub>3</sub>N. Products untreated with extra amounts of TMCS and DMAP/Et<sub>3</sub>N showed increase of their viscosity after few months and a presence of small drops of water from a homo- condensation reaction of residual Si-OH groups.</p><p>The “extra blocking” reactions of silanol groups were carried out after drying step of ether solutions of products of the hydrolytic polycondensation, at room temperature within few hours. Precipitates of amines hydrochlorides were dissolved in diluted solution (5–10 wt%) of hydrochloric acid, a water layers were discarded and washed with distilled water until neutral, dried with anhydrous MgSO<sub>4</sub>, and filtered. Ether was distilled off under atmospheric pressure and final products were evacuated under vacuum at temperature 150–155 °C (<xref rid="polymers-10-00484-t002" ref-type="table">Table 2</xref>). A chemical composition of volatile siloxanes was not analyzed.</p></sec></sec><sec sec-type="results" id="sec3-polymers-10-00484"><title>3. Results and Discussion</title><sec id="sec3dot1-polymers-10-00484"><title>3.1. Synthesis of Branched Polymethylhydrosiloxanes (PMHS-Q)</title><p>Syntheses of poly(methylhydrosiloxanes) with statistical and branched structures containing quadruple branching points SiO<sub>4/2</sub> were carried out in the medium of diethyl ether at temperature below 0 °C. Solutions of chlorosilanes and Si(OEt)<sub>4</sub> in dry ether were added dropwise to water. In all syntheses were used such amounts of water which were necessary for hydrolysis reactions and dissolution of HCl, allowing to obtain hydrochloric acid with concentrations approximately 20 wt%.</p><p>Applying the hydrolytic polycondensation of mixtures of appropriate amounts of (tetraethoxy)-silane Si(OEt)<sub>4</sub> and chlorosilanes: MeHSiCl<sub>2</sub>, Me<sub>2</sub>SiCl<sub>2</sub>, and Me<sub>3</sub>SiCl, with water, at temperature from −10–0 °C, within 3–5 h, were prepared branched poly(methylhydrosiloxanes) with SiO<sub>4/2</sub> branching points and the general formula:<disp-formula>[SiO<sub>4/2</sub>]<sub>y</sub>[CH<sub>3</sub>(H)SiO]<sub>n</sub>[(CH<sub>3</sub>)<sub>3</sub>SiO<sub>0.5</sub>]<sub>p</sub><label>(2)</label></disp-formula>(where: y = 1–3, n = 48–50, p = 2y + 2), containing quadruple branching points SiO<sub>4/2</sub> (Q), mers D<sup>H</sup> and terminal groups Me<sub>3</sub>SiO<sub>0.5</sub>. Similarly, branched poly(dimethyl-<italic>co</italic>-methylhydro)siloxanescontaining branching units Q, linear building blocks D, and D<sup>H</sup>, and terminal groups M, were synthesized with the general formula:<disp-formula>[SiO<sub>4/2</sub>]<sub>y</sub>[(CH<sub>3</sub>)<sub>2</sub>SiO]<sub>m</sub>[CH<sub>3</sub>(H)SiO]<sub>n</sub>[(CH<sub>3</sub>)<sub>3</sub>SiO<sub>0.5</sub>]<sub>p</sub><label>(3)</label></disp-formula>where y = 1–3, m = n = 49–52, p = 2y + 2. After addition of substrates stirring of obtained reaction mixtures was continued within next 2–3 h, in order to reach full conversion of substrates and full hydrolysis of Si-Cl and Si-OC<sub>2</sub>H<sub>5</sub> groups. In the case of syntheses of <bold>Q3</bold>, <bold>Q1D</bold>, <bold>Q2D</bold>, and <bold>Q3D</bold> termination reactions (so called “extra blocking” reactions) of unreacted silanol groups Si-OH in reactions with (chloro)trimethylsilane were applied, in the presence of: (1) triethylamine as the acceptor of hydrogen chloride (used with ~5–10% excess with respect to stoichiometric amounts); and (2) (4-dimethylamino)pyridine (DMAP) as the nucleophilic catalyst (used in 1:10 mole ratio with respect to Et<sub>3</sub>N).</p><p>Products not treated with additional amounts of TMCS and DMAP/Et<sub>3</sub>N showed increase of their viscosity after few months and a presence of traces of water, which could originate from the homocondensation reaction of residual Si-OH groups. However, in the case of syntheses of <bold>Q1</bold> and <bold>Q2</bold> “extra blocking” was not applied, and no increase of their viscosity was observed during longer storage of these PMHS-Q. Ether solutions of products <bold>Q1</bold>, <bold>Q2</bold>, and <bold>Q3</bold> were dried with anhydrous MgSO<sub>4</sub>, while polymers <bold>Q1D</bold>, <bold>Q2D</bold>, and <bold>Q3D</bold> were dried by freezing traces of water in the refrigerator overnight. Yields of prepared PMHS-Q ranged from 55–69 wt% (<xref rid="polymers-10-00484-t002" ref-type="table">Table 2</xref>). The highest yield was obtained for <bold>Q3</bold>.</p><p>The chemical structures of all PMHS-Q were confirmed by spectroscopic methods: FTIR and NMR (<sup>1</sup>H and <sup>29</sup>Si) and the elemental analysis (% C, % H, and % Si) (see <xref rid="polymers-10-00484-t003" ref-type="table">Table 3</xref>).</p><p>Dynamic viscosities (η<sup>25</sup>) of PMHS-Q containing quadruple branching points SiO<sub>4/2</sub>, were very low and ranged from 10.7–13.1 cP. Low viscosities of PMHS-Q in comparison with linear polysiloxanes having similar molecular weights presumably may result from a globular structure of hyperbranched macromolecules. It is commonly known from a literature that dendrimers and hyperbranched polymers in solution and in melt have low viscosities. Their viscosities and molecular weights are much lower than those for linear analogs and depend on a degree of branching, a polarity of a solvent, a kind of functional group on their “surface”, and also on pH of a polymer solution. Dendritic and hyperbranched polymers have a variable hydrodynamic radii depending on the property of solvents; they are smaller than those of their linear analogs with the same molar mass.</p><p>The values of molecular weights of prepared PMHS-Q determined by SEC method were lower than calculated values for predicted molecular formulas: QD<sub>52</sub>D<sup>H</sup><sub>52</sub>M<sub>4</sub>, Q<sub>2</sub>D<sub>49</sub>D<sup>H</sup><sub>49</sub>M<sub>6</sub>, and Q<sub>3</sub>D<sub>50</sub>D<sup>H</sup><sub>50</sub>M<sub>8.</sub> A polydispersity of molecular weights of PMHS-Q ranged from 2.0 to 2.8. The molecular weights of dendrimers and hyperbranched polymers determined by SEC using polystyrene standards are regarded with some scepticism. The hydrodynamic radii were also susceptible to the polarity of functional groups on the periphery [<xref rid="B65-polymers-10-00484" ref-type="bibr">65</xref>,<xref rid="B66-polymers-10-00484" ref-type="bibr">66</xref>,<xref rid="B67-polymers-10-00484" ref-type="bibr">67</xref>]. Values of M<sub>n</sub> and M<sub>w</sub> determined by SEC method with polystyrene standards for hyperbranched polysiloxanes were much lower than MW obtained with application of MALLS detectors [<xref rid="B68-polymers-10-00484" ref-type="bibr">68</xref>,<xref rid="B69-polymers-10-00484" ref-type="bibr">69</xref>,<xref rid="B70-polymers-10-00484" ref-type="bibr">70</xref>].</p><p>Köhler et al. used the SEC, <sup>1</sup>H- and <sup>29</sup>Si NMR, and MALDI-TOF-MS methods for characterization of a linear poly(dimethylsiloxane)-<italic>co</italic>-poly(hydromethysiloxane) (PDMS-<italic>co</italic>-PHMS) copolymer with respect to chain length distribution, heterogeneity of chemical composition, and sequence distribution [<xref rid="B71-polymers-10-00484" ref-type="bibr">71</xref>].</p></sec><sec id="sec3dot2-polymers-10-00484"><title>3.2. Characterization of PMHS-Q by FTIR</title><p>In all FTIR spectra of studied PMHS-Q containing quadruple branching points Q were present absorption bands in the range 2160 cm<sup>−1</sup>, corresponding to stretching vibrations of Si-H bonds, and also absorption bands of the remaining groups of atoms: Si-CH<sub>3</sub> (2960, 2890, 1440, 1400, 1255, and 830–700 cm<sup>−1</sup>), Si-O-Si (1010–1110 cm<sup>−1</sup>), and Si(CH<sub>3</sub>)<sub>3</sub> (750, 690 cm<sup>−1</sup>) (see data in <xref rid="polymers-10-00484-t004" ref-type="table">Table 4</xref>). Examples of the FTIR spectra of branched poly(methylhydrosiloxanes) are presented in <xref ref-type="fig" rid="polymers-10-00484-f001">Figure 1</xref>, <xref ref-type="fig" rid="polymers-10-00484-f002">Figure 2</xref> and <xref ref-type="fig" rid="polymers-10-00484-f003">Figure 3</xref>.</p></sec><sec id="sec3dot3-polymers-10-00484"><title>3.3. Characterization of PMHS-Q by NMR</title><p>In <sup>1</sup>H–NMR spectra of copolymers, <bold>QD<sup>H</sup><sub>48</sub>M<sub>4</sub></bold>, <bold>Q<sub>2</sub>D<sup>H</sup><sub>49</sub>M<sub>6</sub></bold> and <bold>Q<sub>3</sub>D<sup>H</sup><sub>50</sub>M<sub>8</sub></bold> were present signals at δ 0.01–0.22 ppm, corresponding to hydrogen atoms of Si-CH<sub>3</sub> groups and signals at δ about five parts per million, characteristic for hydrosilane groups Si-H. In the <sup>1</sup>H-NMR spectra of copolymers: <bold>QD<sub>52</sub>D<sup>H</sup><sub>52</sub>M<sub>4</sub></bold>, <bold>Q<sub>2</sub>D<sub>49</sub>D<sup>H</sup><sub>49</sub>M<sub>6</sub></bold>, and <bold>Q<sub>3</sub>D<sub>50</sub>D<sup>H</sup><sub>50</sub>M<sub>8</sub></bold> were present signals at δ 0.0–0.30 ppm, corresponding to hydrogen atoms of Si–CH<sub>3</sub> groups and signals at δ about five parts per million, characteristic for Si-H groups. Examples of the <sup>1</sup>H-NMR and <sup>29</sup>Si-NMR spectra of branched poly(methylhydrosiloxanes) are presented in <xref ref-type="fig" rid="polymers-10-00484-f004">Figure 4</xref>, <xref ref-type="fig" rid="polymers-10-00484-f005">Figure 5</xref>, <xref ref-type="fig" rid="polymers-10-00484-f006">Figure 6</xref> and <xref ref-type="fig" rid="polymers-10-00484-f007">Figure 7</xref>.</p><p>In <sup>29</sup>Si-NMR INEPT spectra of copolymers <bold>QD<sup>H</sup><sub>48</sub>M<sub>4</sub></bold>, <bold>Q<sub>2</sub>D<sup>H</sup><sub>49</sub>M<sub>6</sub></bold> and <bold>Q<sub>3</sub>D<sup>H</sup><sub>50</sub>M<sub>8</sub></bold> were present signals at δ −31.62–−39.97 ppm corresponding to silicon atoms of units D<sup>H</sup> [<xref rid="B8-polymers-10-00484" ref-type="bibr">8</xref>,<xref rid="B9-polymers-10-00484" ref-type="bibr">9</xref>,<xref rid="B54-polymers-10-00484" ref-type="bibr">54</xref>] and at δ 9.40–11.25 ppm corresponding to silicon atoms of end groups Me<sub>3</sub>SiO<sub>0.5</sub> (M). In the range of δ −63–−68 ppm in INEPT <sup>29</sup>Si-NMR spectra were present signals of a very low intensity, from Si atoms of branching units MeSiO<sub>1,5</sub>, which could be formed during trace hydrolysis of Si-H bonds. In the INEPT NMR spectra of copolymers <bold>QD<sub>52</sub>D<sup>H</sup><sub>52</sub>M<sub>4</sub></bold> (<bold>Q1D</bold>), <bold>Q<sub>2</sub>D<sub>49</sub>D<sup>H</sup><sub>49</sub>M<sub>6</sub></bold> (<bold>Q2D</bold>), and <bold>Q<sub>3</sub>D<sub>50</sub>D<sup>H</sup><sub>50</sub>M<sub>8</sub></bold> (<bold>Q3D</bold>) existed signals at δ 7.27–9.92 ppm, corresponding to silicon atoms of end groups Me<sub>3</sub>SiO<sub>0.5</sub> and at δ −34.61 to −38.87 ppm, characteristic for mers MeHSiO (D<sup>H</sup>), and also at δ −18.77–−21.85 ppm from silicon atoms of units Me<sub>2</sub>SiO (D) [<xref rid="B8-polymers-10-00484" ref-type="bibr">8</xref>,<xref rid="B9-polymers-10-00484" ref-type="bibr">9</xref>,<xref rid="B52-polymers-10-00484" ref-type="bibr">52</xref>]. It was impossible to observe signals of quadruple silicon atoms of units SiO<sub>4/2</sub> in <sup>29</sup>Si-NMR spectra, which were registered by the INEPT technique, so it was necessary to run <sup>29</sup>Si–NMR spectra with application of the INVGATE program. A summary of chemical shifts data in the <sup>1</sup>H- and <sup>29</sup>Si-NMR (INEPT and INVGATE) spectra of all PMHS-Q is presented in <xref rid="polymers-10-00484-t005" ref-type="table">Table 5</xref>.</p><p>In the <sup>29</sup>Si-NMR INVGATE spectra of branched random PMHS were present signals of silicon atoms corresponding to linear mers:
<array orientation="portrait"><tbody><tr><td align="right" valign="middle" rowspan="1" colspan="1">CH<sub>3</sub>(H)SiO</td><td align="left" valign="middle" rowspan="1" colspan="1">at δ −34.0–−36.0 ppm (for Q1, Q2, and Q3),</td></tr><tr><td align="right" valign="middle" rowspan="1" colspan="1"></td><td align="left" valign="middle" rowspan="1" colspan="1">at δ −34.0–−37.5 ppm (for Q1D, Q2D, and Q3D),</td></tr><tr><td align="right" valign="middle" rowspan="1" colspan="1">(CH<sub>3</sub>)<sub>2</sub>SiO</td><td align="left" valign="middle" rowspan="1" colspan="1">at δ −16.5–−22.0 ppm (for Q1D, Q2D, and Q3D),</td></tr></tbody></array>and terminal groups (CH<sub>3</sub>)<sub>3</sub>SiO<sub>1/2</sub>:<disp-formula>at δ 9.5–11.3 ppm (for Q1, Q2, and Q3),</disp-formula><disp-formula>at δ 7.3–7.9 and 9.8–10.0 ppm (for Q1D, Q2D, and Q3D).</disp-formula>Resonance signals of Si atoms of branching units Q were present in the range of δ:<disp-formula>−100.3–−112.4 ppm,</disp-formula>and they overlapped with very strong <sup>29</sup>Si signals of a borosilicate glass.</p><p>In the <sup>29</sup>Si-NMR INVGATE spectra of copolymers: <bold>QD<sup>H</sup><sub>48</sub>M<sub>4</sub></bold>, <bold>Q<sub>2</sub>D<sup>H</sup><sub>49</sub>M<sub>6</sub></bold> and <bold>Q<sub>3</sub>D<sup>H</sup><sub>50</sub>M<sub>8</sub></bold> were present signals at: δ 9.40–11.25 ppm, corresponding to the terminal groups Me<sub>3</sub>SiO<sub>0.5</sub>, at δ −31.81–−36.25 ppm, characteristic for units MeHSiO (D<sup>H</sup>), and also resonance signals in the range of δ −100.3–−112.3 ppm for Si atoms from units <bold>Q</bold>. According to data in the literature [<xref rid="B73-polymers-10-00484" ref-type="bibr">73</xref>] chemical shifts of Si atoms from units Q exist in the range of δ −100–−106 ppm.</p><p>Chemical shifts at δ 9–11 ppm have been assigned to resonances of Si atoms of Me<sub>3</sub>SiO<sub>0.5</sub> (M) groups in the following sequences of the siloxane chain ends: <bold><underline>M</underline></bold>D<sup>H</sup>D<sup>H</sup>D<sup>H</sup>, <bold><underline>M</underline></bold>D<sup>H</sup>D<sup>H</sup>D, <bold><underline>M</underline></bold>D<sup>H</sup>DD<sup>H</sup>, <bold><underline>M</underline></bold>D<sup>H</sup>DD, <bold><underline>M</underline></bold>D<sup>H</sup>D<sup>H</sup>Q, <bold><underline>M</underline></bold>D<sup>H</sup>QD<sup>H</sup>, <bold><underline>M</underline></bold>D<sup>H</sup>DQ, and<bold><underline> M</underline></bold>D<sup>H</sup>QD, while chemical shifts at δ 7–8 ppm belong to resonances of Si atoms of end groups M in the sequences: <bold><underline>M</underline></bold>DDD, <bold><underline>M</underline></bold>DDD<sup>H</sup>, <bold><underline>M</underline></bold>DD<sup>H</sup>D, <bold><underline>M</underline></bold>DD<sup>H</sup>D<sup>H</sup>, <bold><underline>M</underline></bold>DDQ, <bold><underline>M</underline></bold>DQD, <bold><underline>M</underline></bold>QDD, and <bold><underline>M</underline></bold>QDD<sup>H</sup>. Chemical shifts of middle silicon atoms of units D change in pentades, and magnetic interactions are shifted through four bonds in chain ends.</p><p>The sequences of dimethylsiloxane linkages in polymethylhydrosiloxane copolymers might be the following: DD<sup>H</sup><bold><underline>D</underline></bold>D<sup>H</sup>D, DD<sup>H</sup><bold><underline>D</underline></bold>D<sup>H</sup>D<sup>H</sup>, D<sup>H</sup>D<sup>H</sup><bold><underline>D</underline></bold>D<sup>H</sup>D<sup>H</sup>, QD<sup>H</sup><bold><underline>D</underline></bold>D<sup>H</sup>Q, MD<sup>H</sup><bold><underline>D</underline></bold>D<sup>H</sup>D, MD<sup>H</sup><bold><underline>D</underline></bold>D<sup>H</sup>D<sup>H</sup>, MD<sup>H</sup><bold><underline>D</underline></bold>D<sup>H</sup>Q, MD<sup>H</sup><bold><underline>D</underline></bold>D<sup>H</sup>D (δ of middle silicon atoms of units <bold><underline>D</underline></bold>: −20–−22 ppm), and: D<sup>H</sup>D<bold><underline>D</underline></bold>D<sup>H</sup>D<sup>H</sup>, D<sup>H</sup>D<bold><underline>D</underline></bold>D<sup>H</sup>D, DD<bold><underline>D</underline></bold>D<sup>H</sup>D<sup>H</sup>, DD<bold><underline>D</underline></bold>D<sup>H</sup>D (δ of middle silicon atoms of units <bold><underline>D</underline></bold>: −18–−19.7 ppm).</p><p>In the <sup>29</sup>Si-NMR spectra (recorded by INEPT and INVGATE techniques) in the range of δ −33–−37 ppm exist signals of middle silicon atoms of units <bold>D<sup>H</sup></bold>, which undergo changes in pentades (<xref rid="polymers-10-00484-t005" ref-type="table">Table 5</xref>). Signals of silicon atoms in the range of δ −102 to −109 ppm, presumably correspond to Si atoms in the central units <bold><underline>Q</underline></bold>, in the following sequences of siloxane structures:</p><p><graphic xlink:href="polymers-10-00484-i001.jpg" position="float" orientation="portrait"></graphic></p><p>Chemical shifts in the range of 7–11 ppm in the <sup>29</sup>Si-NMR spectra (INEPT and INVGATE) correspond to silicon atoms of the end groups M and change in tetrads (<xref rid="polymers-10-00484-t005" ref-type="table">Table 5</xref>) [<xref rid="B8-polymers-10-00484" ref-type="bibr">8</xref>,<xref rid="B9-polymers-10-00484" ref-type="bibr">9</xref>,<xref rid="B74-polymers-10-00484" ref-type="bibr">74</xref>].</p><p>Signals at δ −64 ppm of a very low intensity, registered both in INVGATE and INEPT <sup>29</sup>Si-NMR spectra of these three copolymers, probably come from Si atoms of units MeSiO<sub>1.5</sub> (T), which were formed during syntheses of PMHS-Q from trace hydrolysis of Si-H bonds [<xref rid="B74-polymers-10-00484" ref-type="bibr">74</xref>].</p><p>Assignments of all <sup>29</sup>Si-NMR signals resulting from the microstructure of siloxane chain of branched polymethylhydrosiloxanes are summarized in <xref rid="polymers-10-00484-t006" ref-type="table">Table 6</xref>.</p></sec></sec></body><back><ack><title>Acknowledgments</title><p>The authors would like to acknowledge the Ministry of Science and Higher Education (Poland), for a financial support through a grant 3 T08E 053 30. We are also very grateful to a Management of the Institute of Polymers and Dye Technology, Lodz University of Technology, and especially to Director Professor Marian Zaborski, for providing laboratories.</p></ack><notes><title>Author Contributions</title><p>Syntheses and characterization of branched PMHS were carried out by J.J. Chruściel and M. Fejdyś. Moreover, J.J. Chruściel measured dynamic viscosities of PMHS, M. Fejdyś (35% total contribution) recorded FT-IR spectra, and W. Fortuniak (10% contribution) performed measurements of molecular weights of PMHS by the SEC method. A manuscript has been written by J.J. Chruściel (55% total contribution).</p></notes><notes notes-type="COI-statement"><title>Conflicts of Interest</title><p>The authors declare no conflict of interest.</p></notes><ref-list><title>References</title><ref id="B1-polymers-10-00484"><label>1.</label><element-citation publication-type="book"><person-group person-group-type="author"><name><surname>Eaborn</surname><given-names>C.</given-names></name></person-group><source>Organosilicon Compounds</source><publisher-name>Butterworth Scientific Publications</publisher-name><publisher-loc>London, UK</publisher-loc><year>1960</year></element-citation></ref><ref id="B2-polymers-10-00484"><label>2.</label><element-citation publication-type="book"><person-group person-group-type="author"><name><surname>Noll</surname><given-names>W.</given-names></name></person-group><source>Chemie und Technologie der Silikone</source><comment>2 Auflage</comment><publisher-name>Verlag Chemie</publisher-name><publisher-loc>Weinheim Germany</publisher-loc><publisher-name>GmbH</publisher-name><publisher-loc>Weinheim Germany</publisher-loc><year>1968</year></element-citation></ref><ref id="B3-polymers-10-00484"><label>3.</label><element-citation publication-type="book"><person-group person-group-type="author"><name><surname>Hardman</surname><given-names>B.</given-names></name><name><surname>Torkelson</surname><given-names>A.</given-names></name></person-group><article-title>Chapter Silicones</article-title><source>Encyclopedia of Polymer Science and Engineering</source><edition>2nd ed.</edition><person-group person-group-type="editor"><name><surname>Mark</surname><given-names>F.</given-names></name><name><surname>Gaylord</surname><given-names>N.G.</given-names></name><name><surname>Bikales</surname><given-names>N.M.</given-names></name></person-group><publisher-name>J. Wiley & Sons</publisher-name><publisher-loc>New York, NY, USA</publisher-loc><year>1989</year><volume>Volume 15</volume><fpage>271</fpage><lpage>289</lpage></element-citation></ref><ref id="B4-polymers-10-00484"><label>4.</label><element-citation publication-type="book"><person-group person-group-type="author"><name><surname>Rościszewski</surname><given-names>P.</given-names></name><name><surname>Zielecka</surname><given-names>M.</given-names></name></person-group><source>Silikony, Właściwości i Zastosowanie</source><publisher-name>WNT</publisher-name><publisher-loc>Warsaw, Poland</publisher-loc><year>2002</year><fpage>26</fpage><lpage>38</lpage><page-range>26–30, 38</page-range></element-citation></ref><ref id="B5-polymers-10-00484"><label>5.</label><element-citation publication-type="book"><person-group person-group-type="editor"><name><surname>Chauhan</surname><given-names>B.P.S.</given-names></name></person-group><source>Hybrid Nanomaterials Synthesis, Characterization, and Applications</source><publisher-name>Wiley-VCH</publisher-name><publisher-loc>Weinheim, Germany</publisher-loc><year>2011</year></element-citation></ref><ref id="B6-polymers-10-00484"><label>6.</label><element-citation publication-type="book"><person-group person-group-type="editor"><name><surname>Kricheldorf</surname><given-names>H.R.</given-names></name></person-group><source>Silicon in Polymer Synthesis</source><publisher-name>Springer</publisher-name><publisher-loc>Berlin/Heidelberg, Germany</publisher-loc><publisher-loc>New York, NY, USA</publisher-loc><year>1996</year></element-citation></ref><ref id="B7-polymers-10-00484"><label>7.</label><element-citation publication-type="book"><person-group person-group-type="author"><name><surname>Brook</surname><given-names>M.A.</given-names></name></person-group><source>Silicon in Organic, Organometallic and Polymer Chemistry</source><publisher-name>J Wiley & Sons</publisher-name><publisher-loc>New York, NY, USA</publisher-loc><publisher-loc>Chichester, UK</publisher-loc><publisher-loc>Weinheim, Germany</publisher-loc><publisher-loc>Brisbane, Australia</publisher-loc><publisher-loc>Singapore</publisher-loc><publisher-loc>Toronto, Japan</publisher-loc><year>2000</year><isbn>0-471-19658-4</isbn></element-citation></ref><ref id="B8-polymers-10-00484"><label>8.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Chruściel</surname><given-names>J.</given-names></name></person-group><article-title>Progress in chemistry of polymethylhydrosiloxanes</article-title><source>Polimery</source><year>1999</year><volume>44</volume><fpage>462</fpage><lpage>474</lpage></element-citation></ref><ref id="B9-polymers-10-00484"><label>9.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Chruściel</surname><given-names>J.</given-names></name></person-group><article-title>Synthesis and characterization of new liquid, branched and random poly(methyl-hydrosiloxanes)</article-title><source>e-Polymers</source><year>2008</year><volume>8</volume><fpage>1</fpage><lpage>23</lpage><pub-id pub-id-type="doi">10.1515/epoly.2008.8.1.621</pub-id></element-citation></ref><ref id="B10-polymers-10-00484"><label>10.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Chruściel</surname><given-names>J.</given-names></name></person-group><article-title>Crosslinking of polydimethylsiloxane-α,ω-diols with polymethylhydrosiloxanes and some properties of prepared silicone elastomers</article-title><source>Polimery</source><year>1999</year><volume>44</volume><fpage>586</fpage><lpage>596</lpage></element-citation></ref><ref id="B11-polymers-10-00484"><label>11.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Devimille</surname><given-names>L.</given-names></name><name><surname>Bresson</surname><given-names>B.</given-names></name><name><surname>Bokobza</surname><given-names>L.</given-names></name></person-group><article-title>Synthesis, structure and morphology of poly(dimethyl-siloxane) networks filled with in situ generated silica particles</article-title><source>Polymer</source><year>2005</year><volume>46</volume><fpage>4135</fpage><lpage>4143</lpage><pub-id pub-id-type="doi">10.1016/j.polymer.2005.02.049</pub-id></element-citation></ref><ref id="B12-polymers-10-00484"><label>12.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Fejdyś</surname><given-names>M.</given-names></name><name><surname>Chruściel</surname><given-names>J.</given-names></name><name><surname>Miazga</surname><given-names>A.</given-names></name></person-group><article-title>Mechanical properties of silicone vulcanizates crosslinked with polymethylhydrosiloxanes containing silica and calcium carbonate</article-title><source>Polimery</source><year>2006</year><volume>51</volume><fpage>48</fpage><lpage>57</lpage></element-citation></ref><ref id="B13-polymers-10-00484"><label>13.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Jia</surname><given-names>L.</given-names></name><name><surname>Du</surname><given-names>Z.</given-names></name><name><surname>Zhang</surname><given-names>C.</given-names></name><name><surname>Liu</surname><given-names>C.</given-names></name><name><surname>Li</surname><given-names>H.</given-names></name></person-group><article-title>Reinforcement of polydimethylsiloxane through formation of inorganic–organic hybrid network</article-title><source>Polym. Eng. Sci.</source><year>2008</year><volume>48</volume><fpage>74</fpage><lpage>79</lpage><pub-id pub-id-type="doi">10.1002/pen.20856</pub-id></element-citation></ref><ref id="B14-polymers-10-00484"><label>14.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Urayama</surname><given-names>K.</given-names></name><name><surname>Kawamura</surname><given-names>T.</given-names></name><name><surname>Kohjiya</surname><given-names>S.</given-names></name></person-group><article-title>Structure–mechanical property correlations of model siloxane elastomers with controlled network topology</article-title><source>Polymer</source><year>2009</year><volume>50</volume><fpage>347</fpage><lpage>356</lpage><pub-id pub-id-type="doi">10.1016/j.polymer.2008.10.027</pub-id></element-citation></ref><ref id="B15-polymers-10-00484"><label>15.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Chruściel</surname><given-names>J.</given-names></name><name><surname>Leśniak</surname><given-names>E.</given-names></name></person-group><article-title>Preparation of flexible, self-extinguishing silicone foams</article-title><source>J. Appl. Polym. Sci.</source><year>2011</year><volume>119</volume><fpage>1696</fpage><lpage>1703</lpage><pub-id pub-id-type="doi">10.1002/app.32852</pub-id></element-citation></ref><ref id="B16-polymers-10-00484"><label>16.</label><element-citation publication-type="confproc"><person-group person-group-type="author"><name><surname>Hager</surname><given-names>R.</given-names></name></person-group><article-title>Phosphazene catalysis—Basic technology in silicone production</article-title><source>Proceedings of the XI International Symposium on Organosilicon Chemistry</source><conf-loc>Montpellier, France</conf-loc><conf-date>1–6 September 1996</conf-date><publisher-name>Universite Montpellier II</publisher-name><publisher-loc>Montpellier, France</publisher-loc><year>1996</year><comment>Abstracts, LD5</comment></element-citation></ref><ref id="B17-polymers-10-00484"><label>17.</label><element-citation publication-type="patent"><person-group person-group-type="author"><name><surname>Hager</surname><given-names>R.</given-names></name><name><surname>Schneider</surname><given-names>O.</given-names></name><name><surname>Schuster</surname><given-names>J.</given-names></name></person-group><article-title>Process for the Condensation and/or Equilibration of Organosilicon Compounds</article-title><source>U.S. Patent</source><patent>5,380,902</patent><year>1995</year></element-citation></ref><ref id="B18-polymers-10-00484"><label>18.</label><element-citation publication-type="patent"><person-group person-group-type="author"><name><surname>Razzano</surname><given-names>J.S.</given-names></name><name><surname>Anderson</surname><given-names>P.P.</given-names></name><name><surname>Perry</surname><given-names>R.J.</given-names></name></person-group><article-title>Production of Low Molecular Weight Linear Hydrogen Siloxanes</article-title><source>U.S. Patent</source><patent>5,670,596</patent><day>23</day><month>9</month><year>1997</year></element-citation></ref><ref id="B19-polymers-10-00484"><label>19.</label><element-citation publication-type="patent"><person-group person-group-type="author"><name><surname>Nye</surname><given-names>S.A.</given-names></name><name><surname>Riccio</surname><given-names>D.A.</given-names></name><name><surname>Wutzer</surname><given-names>B.S.</given-names></name></person-group><article-title>Process for Preparing Hydrogen Siloxane Copolymers</article-title><source>U.S. Patent</source><patent>5,698,654</patent><year>1997</year></element-citation></ref><ref id="B20-polymers-10-00484"><label>20.</label><element-citation publication-type="patent"><person-group person-group-type="author"><name><surname>Liao</surname><given-names>W.P.</given-names></name><name><surname>Nye</surname><given-names>S.A.</given-names></name></person-group><article-title>Process for Preparing Self-Curable Alkenyl Hydride Siloxane Copolymers and Coating Composition</article-title><source>European Patent</source><patent>EP 0838547 B1</patent><year>1998</year></element-citation></ref><ref id="B21-polymers-10-00484"><label>21.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Palaprat</surname><given-names>G.</given-names></name><name><surname>Ganachaud</surname><given-names>F.</given-names></name><name><surname>Mauzac</surname><given-names>M.</given-names></name><name><surname>Hemery</surname><given-names>P.</given-names></name></person-group><article-title>Cationic polymerization of 2,4,6,8-tetramethylcyclotetrasiloxane processed by tuning the pH of the miniemulsion</article-title><source>Polymer</source><year>2005</year><volume>46</volume><fpage>11213</fpage><lpage>11218</lpage><pub-id pub-id-type="doi">10.1016/j.polymer.2005.10.044</pub-id></element-citation></ref><ref id="B22-polymers-10-00484"><label>22.</label><element-citation publication-type="confproc"><person-group person-group-type="author"><name><surname>Maisonnier</surname><given-names>S.</given-names></name><name><surname>Favier</surname><given-names>J.C.</given-names></name><name><surname>Masure</surname><given-names>M.</given-names></name><name><surname>Hemery</surname><given-names>P.</given-names></name></person-group><article-title>Poly(methylhydrosiloxane) synthesis in anionic aqueous emulsion</article-title><source>Proceedings of the XI International Symposium on Organosilicon Chemistry</source><conf-loc>Montpellier, France</conf-loc><conf-date>1–6 September 1996</conf-date><publisher-name>Universite Montpellier II</publisher-name><publisher-loc>Montpellier, France</publisher-loc><year>1996</year><comment>Abstracts, PB84</comment></element-citation></ref><ref id="B23-polymers-10-00484"><label>23.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Paulasaari</surname><given-names>J.K.</given-names></name><name><surname>Weber</surname><given-names>W.P.</given-names></name></person-group><article-title>Preparation of Highly Regular Poly(1-hydrido-1,3,3,5,5- -pentamethyltrisiloxane) and Its Chemical Modification by Hydrosilylation</article-title><source>Macromolecules</source><year>1999</year><volume>32</volume><fpage>6574</fpage><lpage>6577</lpage><pub-id pub-id-type="doi">10.1021/ma991201u</pub-id></element-citation></ref><ref id="B24-polymers-10-00484"><label>24.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Agaskar</surname><given-names>P.A.</given-names></name></person-group><article-title>Facile, High-Yield Synthesis of Functionalized Spherosilicates: Precursors of Novel Organolithic Macromolecular Materials</article-title><source>Inorg. Chem.</source><year>1990</year><volume>29</volume><fpage>1603</fpage><pub-id pub-id-type="doi">10.1021/ic00334a005</pub-id></element-citation></ref><ref id="B25-polymers-10-00484"><label>25.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Chruściel</surname><given-names>J.</given-names></name><name><surname>Kulpiński</surname><given-names>J.</given-names></name><name><surname>Romanowski</surname><given-names>Z.</given-names></name></person-group><article-title>Synthesis of Some Block Polymethylhydrosiloxanes</article-title><source>Zeszyty Naukowe Politechniki Śląskiej Seria Chemia</source><year>1999</year><volume>140</volume><fpage>109</fpage><lpage>114</lpage></element-citation></ref><ref id="B26-polymers-10-00484"><label>26.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Agaskar</surname><given-names>P.A.</given-names></name></person-group><article-title>New Synthetic Route to the Hydridospherosiloxanes <italic>O<sub>h</sub></italic>-HSi<sub>8</sub>0<sub>12</sub> and <italic>D</italic><sub>5<italic>h</italic></sub>-H<sub>10</sub>Si<sub>10</sub>O<sub>15</sub></article-title><source>Inorg. Chem.</source><year>1991</year><volume>30</volume><fpage>2707</fpage><lpage>2708</lpage><pub-id pub-id-type="doi">10.1021/ic00013a002</pub-id></element-citation></ref><ref id="B27-polymers-10-00484"><label>27.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Bassindale</surname><given-names>A.R.</given-names></name><name><surname>Gentle</surname><given-names>T.E.</given-names></name></person-group><article-title>Siloxane and Hydrocarbon Octopus Molecules with Silsesquioxane Cores</article-title><source>J. Mater. Chem.</source><year>1993</year><volume>3</volume><fpage>1319</fpage><lpage>1325</lpage><pub-id pub-id-type="doi">10.1039/jm9930301319</pub-id></element-citation></ref><ref id="B28-polymers-10-00484"><label>28.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Crivello</surname><given-names>J.V.</given-names></name><name><surname>Malik</surname><given-names>R.</given-names></name></person-group><article-title>Synthesis and Photoinitiated Cationic Polymerization of Monomers with the Silsesquioxane Core</article-title><source>J. Polym. Sci. Part A Polym. Chem.</source><year>1997</year><volume>35</volume><fpage>407</fpage><lpage>425</lpage><pub-id pub-id-type="doi">10.1002/(SICI)1099-0518(199702)35:3<407::AID-POLA3>3.0.CO;2-P</pub-id></element-citation></ref><ref id="B29-polymers-10-00484"><label>29.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Tsuchida</surname><given-names>A.</given-names></name><name><surname>Bolin</surname><given-names>C.</given-names></name><name><surname>Sernetz</surname><given-names>F.G.</given-names></name><name><surname>Frey</surname><given-names>H.</given-names></name><name><surname>Mülhaupt</surname><given-names>R.</given-names></name></person-group><article-title>Ethene and Propene Copolymers Containing Silsesquioxane Side Groups</article-title><source>Macromolecules</source><year>1997</year><volume>30</volume><fpage>2818</fpage><lpage>2824</lpage><pub-id pub-id-type="doi">10.1021/ma960846g</pub-id></element-citation></ref><ref id="B30-polymers-10-00484"><label>30.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Zhang</surname><given-names>C.</given-names></name><name><surname>Babonneau</surname><given-names>F.</given-names></name><name><surname>Laine</surname><given-names>R.M.</given-names></name><name><surname>Soles</surname><given-names>C.L.</given-names></name><name><surname>Hristov</surname><given-names>H.A.</given-names></name><name><surname>Yee</surname><given-names>A.F.</given-names></name></person-group><article-title>Highly Porous Polyhedral Silsesquioxane Polymers. Synthesis and Characterization</article-title><source>J. Am. Chem. Soc.</source><year>1998</year><volume>120</volume><fpage>8380</fpage><lpage>8391</lpage><pub-id pub-id-type="doi">10.1021/ja9808853</pub-id></element-citation></ref><ref id="B31-polymers-10-00484"><label>31.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Zhang</surname><given-names>C.</given-names></name><name><surname>Laine</surname><given-names>R.M.</given-names></name></person-group><article-title>Hydrosilylation of Allyl Alcohol with [HSiMe<sub>2</sub>OSiO<sub>1.5</sub>]<sub>8</sub>: Octa(3-hydroxypropyldimethylsiloxy)octasilsesquioxane and Its Octamethacrylate Derivative as Potential Precursors to Hybrid Nanocomposites</article-title><source>J. Am. Chem. Soc.</source><year>2000</year><volume>122</volume><fpage>6979</fpage><lpage>6988</lpage><pub-id pub-id-type="doi">10.1021/ja000318r</pub-id></element-citation></ref><ref id="B32-polymers-10-00484"><label>32.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Constantopoulos</surname><given-names>K.</given-names></name><name><surname>Clarke</surname><given-names>D.</given-names></name><name><surname>Markovic</surname><given-names>E.</given-names></name><name><surname>Uhrig</surname><given-names>D.</given-names></name><name><surname>Clarke</surname><given-names>S.</given-names></name><name><surname>Matisons</surname><given-names>J.G.</given-names></name><name><surname>Simon</surname><given-names>G.</given-names></name></person-group><article-title>A new family of POSS monomers suitable for forming urethane polymerizable nanocomposite coatings</article-title><source>Polym. Prepr.</source><year>2004</year><volume>45</volume><fpage>668</fpage></element-citation></ref><ref id="B33-polymers-10-00484"><label>33.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Frye</surname><given-names>C.</given-names></name><name><surname>Collins</surname><given-names>W.T.</given-names></name></person-group><article-title>The Oligomeric Silsesquioxanes, (HSiO<sub>3/2</sub>)<sub>n</sub></article-title><source>J. Am. Chem. Soc.</source><year>1970</year><volume>92</volume><fpage>5586</fpage><lpage>5588</lpage><pub-id pub-id-type="doi">10.1021/ja00722a009</pub-id></element-citation></ref><ref id="B34-polymers-10-00484"><label>34.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Agaskar</surname><given-names>P.A.</given-names></name><name><surname>Day</surname><given-names>V.W.</given-names></name><name><surname>Klemperer</surname><given-names>W.G.</given-names></name></person-group><article-title>A New Route to Trimnethylsilylated Spherosilicates: Synthesis and Structure of [Si<sub>12</sub>0<sub>18</sub>](OSiMe<sub>3</sub>)<sub>12</sub>, <italic>D</italic><sub>3<italic>h</italic></sub>-[Si<sub>14</sub>O<sub>21</sub>](OSiMe<sub>3</sub>)<sub>14</sub>, and <italic>C</italic><sub>2<italic>v</italic></sub>-[Si<sub>14</sub>O<sub>21</sub>](OSiMe<sub>3</sub>)<sub>14</sub></article-title><source>J. Am. Chem. Soc.</source><year>1987</year><volume>109</volume><fpage>5554</fpage><lpage>5556</lpage><pub-id pub-id-type="doi">10.1021/ja00252a058</pub-id></element-citation></ref><ref id="B35-polymers-10-00484"><label>35.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Hasegawa</surname><given-names>I.</given-names></name><name><surname>Motojima</surname><given-names>D.</given-names></name></person-group><article-title>Dimethylvinylsilylation of Si<sub>8</sub>O<sub>20</sub><sup>8-</sup> silicate anion in methanol solutions of tetramethylammonium silicate</article-title><source>J. Organomet. Chem.</source><year>1992</year><volume>441</volume><fpage>373</fpage><lpage>380</lpage><pub-id pub-id-type="doi">10.1016/0022-328X(92)80168-W</pub-id></element-citation></ref><ref id="B36-polymers-10-00484"><label>36.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Majoros</surname><given-names>I.</given-names></name><name><surname>Marsylko</surname><given-names>T.M.</given-names></name><name><surname>Kennedy</surname><given-names>J.P.</given-names></name></person-group><article-title>Synthesis and characterization of novel well-defined stars consisting of eight polyisobutylene arms emanating from an octa(dimethylsiloxy)octasilsesquioxane core</article-title><source>Polym. Bull.</source><year>1997</year><volume>38</volume><fpage>15</fpage><lpage>22</lpage><pub-id pub-id-type="doi">10.1007/s002890050013</pub-id></element-citation></ref><ref id="B37-polymers-10-00484"><label>37.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Provatas</surname><given-names>A.</given-names></name><name><surname>Luft</surname><given-names>M.</given-names></name><name><surname>Mu</surname><given-names>J.C.</given-names></name><name><surname>White</surname><given-names>A.H.</given-names></name><name><surname>Matisons</surname><given-names>J.G.</given-names></name><name><surname>Skelton</surname><given-names>B.W.</given-names></name></person-group><article-title>Silsesquioxanes: Part I: A key intermediate in the building of molecular composite materials</article-title><source>J. Organomet. Chem.</source><year>1998</year><volume>565</volume><fpage>159</fpage><lpage>164</lpage><pub-id pub-id-type="doi">10.1016/S0022-328X(98)00450-1</pub-id></element-citation></ref><ref id="B38-polymers-10-00484"><label>38.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Perrin</surname><given-names>F.X.</given-names></name><name><surname>Nguyen</surname><given-names>T.B.V.</given-names></name><name><surname>Margaillan</surname><given-names>A.</given-names></name></person-group><article-title>Linear and branched alkyl substituted octakis(dimethylsiloxy)octasilsesquioxanes: WAXS and thermal properties</article-title><source>Eur. Polym. J.</source><year>2011</year><volume>47</volume><fpage>1370</fpage><lpage>1382</lpage><pub-id pub-id-type="doi">10.1016/j.eurpolymj.2011.04.004</pub-id></element-citation></ref><ref id="B39-polymers-10-00484"><label>39.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Dutkiewicz</surname><given-names>M.</given-names></name><name><surname>Maciejewski</surname><given-names>H.</given-names></name><name><surname>Marciniec</surname><given-names>B.</given-names></name><name><surname>Karasiewicz</surname><given-names>J.</given-names></name></person-group><article-title>New Fluorocarbofunctional Spherosilicates: Synthesis and Characterization</article-title><source>Organometallics</source><year>2011</year><volume>30</volume><fpage>2149</fpage><lpage>2153</lpage><pub-id pub-id-type="doi">10.1021/om1010337</pub-id></element-citation></ref><ref id="B40-polymers-10-00484"><label>40.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Hasegawa</surname><given-names>I.</given-names></name></person-group><article-title>Co-hydrolysis products of tetraethoxysilane and methyltriethoxysilane in the presence of tetramethylammonium ions</article-title><source>J. Sol-Gel Sci. Technol.</source><year>1993</year><volume>1</volume><fpage>57</fpage><lpage>63</lpage><pub-id pub-id-type="doi">10.1007/BF00486429</pub-id></element-citation></ref><ref id="B41-polymers-10-00484"><label>41.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Moran</surname><given-names>M.</given-names></name><name><surname>Casado</surname><given-names>C.M.</given-names></name><name><surname>Cuadrado</surname><given-names>I.</given-names></name><name><surname>Losada</surname><given-names>J.</given-names></name></person-group><article-title>Ferrocenyl Substituted Octakis- (dimethylsiloxy)octasilsesquioxanes: A New Class of Supramolecular Organometallic Compounds. Synthesis, Characterization, and Electrochemistry</article-title><source>Organometallics</source><year>1993</year><volume>12</volume><fpage>4327</fpage><lpage>4333</lpage><pub-id pub-id-type="doi">10.1021/om00035a018</pub-id></element-citation></ref><ref id="B42-polymers-10-00484"><label>42.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Sellinger</surname><given-names>A.</given-names></name><name><surname>Laine</surname><given-names>R.M.</given-names></name></person-group><article-title>Silsesquioxanes as Synthetic Platforms. 3. Photocurable, Liquid Epoxides as Inorganic/Organic Hybrid Precursors</article-title><source>Chem. Mater.</source><year>1996</year><volume>8</volume><fpage>1592</fpage><lpage>1593</lpage><pub-id pub-id-type="doi">10.1021/cm9601493</pub-id></element-citation></ref><ref id="B43-polymers-10-00484"><label>43.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Laine</surname><given-names>R.M.</given-names></name></person-group><article-title>Nanobuilding blocks based on the [OSiO<sub>1.5</sub>]<sub>x</sub> (x = 6, 8, 10) Octasilsesquioxanes</article-title><source>J. Mater. Chem.</source><year>2005</year><volume>15</volume><fpage>3725</fpage><lpage>3744</lpage><pub-id pub-id-type="doi">10.1039/b506815k</pub-id></element-citation></ref><ref id="B44-polymers-10-00484"><label>44.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Hasegawa</surname><given-names>I.</given-names></name><name><surname>Ino</surname><given-names>K.</given-names></name><name><surname>Onishi</surname><given-names>H.</given-names></name></person-group><article-title>An improved procedure for syntheses of silyl derivatives of the cubeoctameric silicate anion</article-title><source>Appl. Organomet. Chem.</source><year>2003</year><volume>17</volume><fpage>287</fpage><lpage>290</lpage><pub-id pub-id-type="doi">10.1002/aoc.453</pub-id></element-citation></ref><ref id="B45-polymers-10-00484"><label>45.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Soh</surname><given-names>M.S.</given-names></name><name><surname>Yap</surname><given-names>A.U.J.</given-names></name><name><surname>Sellinger</surname><given-names>A.</given-names></name></person-group><article-title>Methacrylate and epoxy functionalized nanocomposites based on silsesquioxane cores for use in dental applications</article-title><source>Eur. Polym. J.</source><year>2007</year><volume>43</volume><fpage>315</fpage><lpage>327</lpage><pub-id pub-id-type="doi">10.1016/j.eurpolymj.2006.11.020</pub-id></element-citation></ref><ref id="B46-polymers-10-00484"><label>46.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Hessel</surname><given-names>C.M.</given-names></name><name><surname>Henderson</surname><given-names>E.J.</given-names></name><name><surname>Veinot</surname><given-names>J.G.C.</given-names></name></person-group><article-title>Hydrogen Silsesquioxane: A Molecular Precursor for Nanocrystalline Si-SiO<sub>2</sub> Composites and Freestanding Hydride-Surface-Terminated Silicon Nano-particles</article-title><source>Chem. Mater.</source><year>2006</year><volume>18</volume><fpage>6139</fpage><lpage>6146</lpage><pub-id pub-id-type="doi">10.1021/cm0602803</pub-id></element-citation></ref><ref id="B47-polymers-10-00484"><label>47.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Gunji</surname><given-names>T.</given-names></name><name><surname>Shioda</surname><given-names>T.</given-names></name><name><surname>Tsuchihira</surname><given-names>K.</given-names></name><name><surname>Seki</surname><given-names>H.</given-names></name><name><surname>Kajiwara</surname><given-names>T.</given-names></name><name><surname>Abe</surname><given-names>Y.</given-names></name></person-group><article-title>Preparation and properties of polyhedral oligomeric silsesquioxane–polysiloxane copolymers</article-title><source>Appl. Organomet. Chem.</source><year>2010</year><volume>24</volume><fpage>545</fpage><lpage>550</lpage><pub-id pub-id-type="doi">10.1002/aoc.1562</pub-id></element-citation></ref><ref id="B48-polymers-10-00484"><label>48.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Shioda</surname><given-names>T.</given-names></name><name><surname>Gunji</surname><given-names>T.</given-names></name><name><surname>Abe</surname><given-names>N.</given-names></name><name><surname>Abe</surname><given-names>Y.</given-names></name></person-group><article-title>Preparation and properties of polyhedral oligomeric silsesquioxane polymers</article-title><source>Appl. Organomet. Chem.</source><year>2011</year><volume>25</volume><fpage>661</fpage><lpage>664</lpage><pub-id pub-id-type="doi">10.1002/aoc.1820</pub-id></element-citation></ref><ref id="B49-polymers-10-00484"><label>49.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Handke</surname><given-names>M.</given-names></name><name><surname>Kowalewska</surname><given-names>A.</given-names></name></person-group><article-title>Siloxane and silsesquioxane molecules—Precursors for silicate materials</article-title><source>Spectrochim. Acta Part A</source><year>2011</year><volume>79</volume><fpage>749</fpage><lpage>757</lpage><pub-id pub-id-type="doi">10.1016/j.saa.2010.08.049</pub-id><pub-id pub-id-type="pmid">21030292</pub-id></element-citation></ref><ref id="B50-polymers-10-00484"><label>50.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Cai</surname><given-names>G.</given-names></name><name><surname>Weber</surname><given-names>W.P.</given-names></name></person-group><article-title>Synthesis of terminal Si–H irregular tetra-branched star polysiloxanes. Pt-catalyzed hydrosilylation with unsaturated epoxides. Polysiloxane films by photo-acid catalyzed crosslinking</article-title><source>Polymer</source><year>2004</year><volume>45</volume><fpage>2941</fpage><lpage>2948</lpage><pub-id pub-id-type="doi">10.1016/j.polymer.2004.02.057</pub-id></element-citation></ref><ref id="B51-polymers-10-00484"><label>51.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Grunlan</surname><given-names>M.A.</given-names></name><name><surname>Lee</surname><given-names>N.S.</given-names></name><name><surname>Mansfeld</surname><given-names>F.</given-names></name><name><surname>Kus</surname><given-names>E.</given-names></name><name><surname>Finlay</surname><given-names>J.A.</given-names></name><name><surname>Callow</surname><given-names>J.A.</given-names></name><name><surname>Callow</surname><given-names>M.E.</given-names></name><name><surname>Weber</surname><given-names>W.P.</given-names></name></person-group><article-title>Minimally Adhesive Polymer Surfaces Prepared from Star Oligosiloxanes and Star Oligofluorosiloxanes</article-title><source>J. Polym. Sci. Part A Polym. Chem.</source><year>2006</year><volume>44</volume><fpage>2551</fpage><lpage>2566</lpage><pub-id pub-id-type="doi">10.1002/pola.21362</pub-id></element-citation></ref><ref id="B52-polymers-10-00484"><label>52.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Sargent</surname><given-names>J.R.</given-names></name><name><surname>Weber</surname><given-names>W.P.</given-names></name></person-group><article-title>Telechelic 4 and 6 branch star siloxanes by acid catalyzed incorporation of D4 units into the Si-O-Si bonds of tetra(dimethylsiloxy)silane and hexa(dimethylsiloxy)-cyclotrisiloxane</article-title><source>Polym. Prepr.</source><year>2000</year><volume>41</volume><fpage>604</fpage></element-citation></ref><ref id="B53-polymers-10-00484"><label>53.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Cai</surname><given-names>G.</given-names></name><name><surname>Sargent</surname><given-names>J.R.</given-names></name><name><surname>Weber</surname><given-names>W.P.</given-names></name></person-group><article-title>Preparation and reactivity of polyfunctional six- and eight-membered cyclic silicates</article-title><source>J. Organomet. Chem.</source><year>2004</year><volume>689</volume><fpage>689</fpage><lpage>693</lpage><pub-id pub-id-type="doi">10.1016/j.jorganchem.2003.11.001</pub-id></element-citation></ref><ref id="B54-polymers-10-00484"><label>54.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Saxena</surname><given-names>K.</given-names></name><name><surname>Bisaria</surname><given-names>C.S.</given-names></name><name><surname>Saxena</surname><given-names>A.K.</given-names></name></person-group><article-title>Studies on the synthesis and thermal properties of alkoxysilane-terminated organosilicone dendrimers</article-title><source>Appl. Organomet. Chem.</source><year>2010</year><volume>24</volume><fpage>251</fpage><lpage>256</lpage><pub-id pub-id-type="doi">10.1002/aoc.1615</pub-id></element-citation></ref><ref id="B55-polymers-10-00484"><label>55.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Zhang</surname><given-names>R.</given-names></name><name><surname>Dai</surname><given-names>D.</given-names></name><name><surname>Cui</surname><given-names>L.</given-names></name><name><surname>Xu</surname><given-names>H.</given-names></name><name><surname>Liu</surname><given-names>C.</given-names></name><name><surname>Xie</surname><given-names>P.</given-names></name></person-group><article-title>A glance at the relation of stepwise coupling polymerization to supramolecular chemistry</article-title><source>Mater. Sci. Eng. C</source><year>1999</year><volume>10</volume><fpage>13</fpage><lpage>18</lpage><pub-id pub-id-type="doi">10.1016/S0928-4931(99)00099-5</pub-id></element-citation></ref><ref id="B56-polymers-10-00484"><label>56.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Wan</surname><given-names>Y.</given-names></name><name><surname>Xu</surname><given-names>L.</given-names></name><name><surname>Ren</surname><given-names>L.</given-names></name><name><surname>Zhang</surname><given-names>L.</given-names></name><name><surname>Xie</surname><given-names>P.</given-names></name><name><surname>Liu</surname><given-names>Y.</given-names></name><name><surname>Zhang</surname><given-names>R.</given-names></name></person-group><article-title>Synthesis and mesomorphic properties of fishbone-like liquid crystalline polysilsesquioxanes V. Pd-coordinating, fishbone-like azo-based liquid crystalline polysilsesquioxanes</article-title><source>Liquid Cryst.</source><year>1998</year><volume>24</volume><fpage>871</fpage><lpage>876</lpage><pub-id pub-id-type="doi">10.1080/026782998206696</pub-id></element-citation></ref><ref id="B57-polymers-10-00484"><label>57.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Cao</surname><given-names>M.</given-names></name><name><surname>Li</surname><given-names>Z.</given-names></name><name><surname>Zhang</surname><given-names>Y.</given-names></name><name><surname>Xie</surname><given-names>P.</given-names></name><name><surname>Dai</surname><given-names>D.</given-names></name><name><surname>Zhang</surname><given-names>R.</given-names></name><name><surname>Lin</surname><given-names>Y.</given-names></name><name><surname>Chung</surname><given-names>N.T.</given-names></name></person-group><article-title>Synthesis and characterization of ladder-like copolymethyl-epoxysilsesquioxane</article-title><source>React. Funct. Polym.</source><year>2000</year><volume>45</volume><fpage>119</fpage><lpage>130</lpage><pub-id pub-id-type="doi">10.1016/S1381-5148(00)00018-3</pub-id></element-citation></ref><ref id="B58-polymers-10-00484"><label>58.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Uchida</surname><given-names>H.</given-names></name><name><surname>Kabe</surname><given-names>Y.</given-names></name><name><surname>Yoshino</surname><given-names>K.</given-names></name><name><surname>Kawamata</surname><given-names>A.</given-names></name><name><surname>Tsumuraya</surname><given-names>T.</given-names></name><name><surname>Masamune</surname><given-names>S.</given-names></name></person-group><article-title>General Strategy for the Systematic Synthesis of Oligosiloxanes. Silicone Dendrimers</article-title><source>J. Am. Chem. Soc.</source><year>1990</year><volume>112</volume><fpage>7077</fpage><lpage>7079</lpage><pub-id pub-id-type="doi">10.1021/ja00175a062</pub-id></element-citation></ref><ref id="B59-polymers-10-00484"><label>59.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Zhao</surname><given-names>S.</given-names></name><name><surname>Feng</surname><given-names>S.</given-names></name></person-group><article-title>Hydrogen-Containing Silicone Resin as the Crosslinking Agent of Heat-Curable Silicone Rubber</article-title><source>J. Appl. Polym. Sci.</source><year>2003</year><volume>88</volume><fpage>3066</fpage><lpage>3069</lpage><pub-id pub-id-type="doi">10.1002/app.11912</pub-id></element-citation></ref><ref id="B60-polymers-10-00484"><label>60.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Su</surname><given-names>H.W.</given-names></name><name><surname>Chen</surname><given-names>W.C.</given-names></name><name><surname>Lee</surname><given-names>W.C.</given-names></name><name><surname>King</surname><given-names>J.S.</given-names></name></person-group><article-title>New Photocurable Acrylic/Silsesquioxane Hybrid Optical Materials: Synthesis, Properties, and Patterning</article-title><source>Macromol. Mater. Eng.</source><year>2007</year><volume>292</volume><fpage>666</fpage><lpage>673</lpage><pub-id pub-id-type="doi">10.1002/mame.200600442</pub-id></element-citation></ref><ref id="B61-polymers-10-00484"><label>61.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Seino</surname><given-names>M.</given-names></name><name><surname>Hayakawa</surname><given-names>T.</given-names></name><name><surname>Ishida</surname><given-names>Y.</given-names></name><name><surname>Kakimoto</surname><given-names>M.</given-names></name></person-group><article-title>Hydrosilylation Polymerization of Double-Decker-Shaped Silsesquioxane Having Hydrosilane with Diynes</article-title><source>Macromolecules</source><year>2006</year><volume>39</volume><fpage>3473</fpage><lpage>3475</lpage><pub-id pub-id-type="doi">10.1021/ma052631p</pub-id></element-citation></ref><ref id="B62-polymers-10-00484"><label>62.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Soraru</surname><given-names>G.D.</given-names></name><name><surname>D’Andrea</surname><given-names>G.</given-names></name><name><surname>Campostrini</surname><given-names>R.</given-names></name><name><surname>Baboneau</surname><given-names>F.</given-names></name></person-group><article-title>Characterization of Methyl-substituted Silica Gels with Si-H Functionalities</article-title><source>J. Mater. Chem.</source><year>1995</year><volume>5</volume><fpage>1363</fpage><lpage>1374</lpage><pub-id pub-id-type="doi">10.1039/JM9950501363</pub-id></element-citation></ref><ref id="B63-polymers-10-00484"><label>63.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Campostrini</surname><given-names>R.</given-names></name><name><surname>D’Andrea</surname><given-names>G.</given-names></name><name><surname>Carturan</surname><given-names>G.</given-names></name><name><surname>Ceccato</surname><given-names>R.</given-names></name><name><surname>Soraru</surname><given-names>G.D.</given-names></name></person-group><article-title>Pyrolysis study of methyl-substituted Si-H containing gels as precursors for oxycarbide glasses, by combined thermo-gravimetry, gas chromatographic and mass spectrometric analysis</article-title><source>J. Mater. Chem.</source><year>1996</year><volume>6</volume><fpage>585</fpage><lpage>594</lpage><pub-id pub-id-type="doi">10.1039/JM9960600585</pub-id></element-citation></ref><ref id="B64-polymers-10-00484"><label>64.</label><element-citation publication-type="book"><person-group person-group-type="author"><name><surname>Bažant</surname><given-names>V.</given-names></name><name><surname>Chvalovský</surname><given-names>V.</given-names></name><name><surname>Rathouský</surname><given-names>I.</given-names></name></person-group><source>Silikony</source><publisher-name>PWT</publisher-name><publisher-loc>Warsaw, Poland</publisher-loc><year>1955</year><fpage>153</fpage></element-citation></ref><ref id="B65-polymers-10-00484"><label>65.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Morikawa</surname><given-names>A.</given-names></name><name><surname>Kakimoto</surname><given-names>M.</given-names></name><name><surname>Imai</surname><given-names>Y.</given-names></name></person-group><article-title>Synthesis and Characterization of New Polysiloxane Starburst Polymers</article-title><source>Macromolecules</source><year>1991</year><volume>24</volume><fpage>3469</fpage><lpage>3474</lpage><pub-id pub-id-type="doi">10.1021/ma00012a001</pub-id></element-citation></ref><ref id="B66-polymers-10-00484"><label>66.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Chang</surname><given-names>H.T.</given-names></name><name><surname>Frechet</surname><given-names>J.M.J.</given-names></name></person-group><article-title>Proton-Transfer Polymerization: A New Approach to Hyperbranched Polymers</article-title><source>J. Am. Chem. Soc.</source><year>1999</year><volume>121</volume><fpage>2313</fpage><lpage>2314</lpage><pub-id pub-id-type="doi">10.1021/ja983797r</pub-id></element-citation></ref><ref id="B67-polymers-10-00484"><label>67.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Innoue</surname><given-names>K.</given-names></name></person-group><article-title>Functional dendrimers, hyperbranched and star polymers</article-title><source>Prog. Polym. Sci.</source><year>2000</year><volume>25</volume><fpage>453</fpage><lpage>571</lpage><pub-id pub-id-type="doi">10.1016/S0079-6700(00)00011-3</pub-id></element-citation></ref><ref id="B68-polymers-10-00484"><label>68.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Paulasaari</surname><given-names>J.K.</given-names></name><name><surname>Weber</surname><given-names>W.P.</given-names></name></person-group><article-title>Synthesis of Hyperbranched Polysiloxanes by Base-Catalyzed Proton-Transfer Polymerization. Comparison of Hyperbranched Polymer Microstructure and Properties to Those of Linear Analogues Prepared by Cationic or Anionic Ring-Opening Polymerization</article-title><source>Macromolecules</source><year>2000</year><volume>33</volume><fpage>2005</fpage><lpage>2010</lpage><pub-id pub-id-type="doi">10.1021/ma991755x</pub-id></element-citation></ref><ref id="B69-polymers-10-00484"><label>69.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Paulasaari</surname><given-names>J.K.</given-names></name><name><surname>Weber</surname><given-names>W.P.</given-names></name></person-group><article-title>Base catalyzed proton transfer polymerization of 1-hydroxy- pentamethylcyclotrisiloxane. Comparison of hyperbranched polymer microstructure and properties to those of highly regular linear analogs</article-title><source>Macromol. Chem. Phys.</source><year>2000</year><volume>201</volume><fpage>1585</fpage><lpage>1592</lpage><pub-id pub-id-type="doi">10.1002/1521-3935(20000901)201:14<1585::AID-MACP1585>3.0.CO;2-3</pub-id></element-citation></ref><ref id="B70-polymers-10-00484"><label>70.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Jikei</surname><given-names>M.</given-names></name><name><surname>Kakimoto</surname><given-names>M.</given-names></name></person-group><article-title>Hyperbranched polymers: A promising new class of materials</article-title><source>Prog. Polym. Sci.</source><year>2001</year><volume>26</volume><fpage>1233</fpage><lpage>1285</lpage><pub-id pub-id-type="doi">10.1016/S0079-6700(01)00018-1</pub-id></element-citation></ref><ref id="B71-polymers-10-00484"><label>71.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Servaty</surname><given-names>S.</given-names></name><name><surname>Köhler</surname><given-names>W.</given-names></name><name><surname>Meyer</surname><given-names>W.H.</given-names></name><name><surname>Rosenauer</surname><given-names>C.</given-names></name><name><surname>Spickermann</surname><given-names>J.</given-names></name><name><surname>Räder</surname><given-names>H.J.</given-names></name><name><surname>Wegner</surname><given-names>G.</given-names></name></person-group><article-title>MALDI-TOF-MS Copolymer Analysis: Characterization of a Poly(dimethylsiloxane)- -<italic>co</italic>-Poly(hydromethylsiloxane) as a Precursor of a Functionalized Silicone Graft Copolymer</article-title><source>Macromolecules</source><year>1998</year><volume>31</volume><fpage>2468</fpage><lpage>2474</lpage><pub-id pub-id-type="doi">10.1021/ma970710y</pub-id></element-citation></ref><ref id="B72-polymers-10-00484"><label>72.</label><element-citation publication-type="book"><person-group person-group-type="author"><name><surname>Silverstein</surname><given-names>R.M.</given-names></name><name><surname>Bassler</surname><given-names>G.C.</given-names></name></person-group><source>Spektroskopowe Metody Identyfikacji Związków Organicznych</source><publisher-name>PWN</publisher-name><publisher-loc>Warsaw, Poland</publisher-loc><year>1969</year><fpage>72</fpage><lpage>118</lpage></element-citation></ref><ref id="B73-polymers-10-00484"><label>73.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Glaser</surname><given-names>R.H.</given-names></name><name><surname>Wilkes</surname><given-names>G.L.</given-names></name><name><surname>Bronnimann</surname><given-names>C.E.</given-names></name></person-group><article-title><italic>Solid</italic>-state <sup>29</sup>Si NMR of TEOS-based multifunctional sol-gel materials</article-title><source>J. Non-Cryst. Solids</source><year>1989</year><volume>113</volume><fpage>73</fpage><lpage>87</lpage><pub-id pub-id-type="doi">10.1016/0022-3093(89)90320-7</pub-id></element-citation></ref><ref id="B74-polymers-10-00484"><label>74.</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Harris</surname><given-names>R.K.</given-names></name><name><surname>Kimber</surname><given-names>B.J.</given-names></name></person-group><article-title><sup>29</sup>Si nuclear magnetic resonance studies of some oligo- and polymeric siloxanes</article-title><source>J. Organomet. Chem.</source><year>1974</year><volume>70</volume><fpage>43</fpage><lpage>49</lpage><pub-id pub-id-type="doi">10.1016/S0022-328X(00)88243-1</pub-id></element-citation></ref></ref-list></back><floats-group><fig id="polymers-10-00484-f001" orientation="portrait" position="float"><label>Figure 1</label><caption><p>FTIR spectrum of Q<sub>2</sub>D<sup>H</sup><sub>49</sub>M<sub>6</sub>.</p></caption><graphic xlink:href="polymers-10-00484-g001"></graphic></fig><fig id="polymers-10-00484-f002" orientation="portrait" position="float"><label>Figure 2</label><caption><p>FTIR spectrum of Q<sub>3</sub>D<sup>H</sup><sub>50</sub>M<sub>8</sub>.</p></caption><graphic xlink:href="polymers-10-00484-g002"></graphic></fig><fig id="polymers-10-00484-f003" orientation="portrait" position="float"><label>Figure 3</label><caption><p>FTIR spectrum of Q<sub>2</sub>D<sub>49</sub>D<sup>H</sup><sub>49</sub>M<sub>6</sub>.</p></caption><graphic xlink:href="polymers-10-00484-g003"></graphic></fig><fig id="polymers-10-00484-f004" orientation="portrait" position="float"><label>Figure 4</label><caption><p><sup>1</sup>H-NMR spectrum (in C<sub>6</sub>D<sub>6</sub>) of polymethylhydrosiloxane Q<sub>3</sub>D<sup>H</sup><sub>50</sub>M<sub>8</sub>.</p></caption><graphic xlink:href="polymers-10-00484-g004"></graphic></fig><fig id="polymers-10-00484-f005" orientation="portrait" position="float"><label>Figure 5</label><caption><p><sup>29</sup>Si-NMR spectrum (INVGATE, in C<sub>6</sub>D<sub>6</sub>) of polymethylhydrosiloxane Q<sub>3</sub>D<sup>H</sup><sub>50</sub>M<sub>8</sub>.</p></caption><graphic xlink:href="polymers-10-00484-g005"></graphic></fig><fig id="polymers-10-00484-f006" orientation="portrait" position="float"><label>Figure 6</label><caption><p><sup>1</sup>H-NMR spectrum (in C<sub>6</sub>D<sub>6</sub>) of polymethylhydrosiloxane Q<sub>2</sub>D<sub>49</sub>D<sup>H</sup><sub>49</sub>M<sub>6</sub>.</p></caption><graphic xlink:href="polymers-10-00484-g006"></graphic></fig><fig id="polymers-10-00484-f007" orientation="portrait" position="float"><label>Figure 7</label><caption><p><sup>29</sup>Si-NMR spectra (in C<sub>6</sub>D<sub>6</sub>) of polymethylhydrosiloxane Q<sub>2</sub>D<sub>49</sub>D<sup>H</sup><sub>49</sub>M<sub>6</sub>: (<bold>a</bold>) INEPT, (<bold>b</bold>) INVGATE.</p></caption><graphic xlink:href="polymers-10-00484-g007"></graphic></fig><table-wrap id="polymers-10-00484-t001" orientation="portrait" position="float"><object-id pub-id-type="pii">polymers-10-00484-t001_Table 1</object-id><label>Table 1</label><caption><p>Amounts of substrates and a solvent, reaction time in syntheses of branched PMHS containing quadruple branching points, and methods of drying of products solutions.</p></caption><table frame="hsides" rules="groups"><thead><tr><th rowspan="3" colspan="2" align="center" valign="middle" style="border-top:solid thin;border-bottom:solid thin">Substrates, solvent, and reaction conditions</th><th colspan="6" align="center" valign="middle" style="border-top:solid thin;border-bottom:solid thin" rowspan="1">Predicted molecular formulas of PMHS-Q *</th></tr><tr><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">QD<sup>H</sup><sub>48</sub>M<sub>4</sub></th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">Q<sub>2</sub>D<sup>H</sup><sub>49</sub>M<sub>6</sub></th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">Q<sub>3</sub>D<sup>H</sup><sub>50</sub>M<sub>8</sub></th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">QD<sub>52</sub>D<sup>H</sup><sub>52</sub>M<sub>4</sub></th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">Q<sub>2</sub>D<sub>49</sub>D<sup>H</sup><sub>49</sub>M<sub>6</sub></th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">Q<sub>3</sub>D<sub>50</sub>D<sup>H</sup><sub>50</sub>M<sub>8</sub></th></tr><tr><th colspan="6" align="center" valign="middle" style="border-bottom:solid thin" rowspan="1">Amounts of reagents and a solvent</th></tr></thead><tbody><tr><td rowspan="2" align="center" valign="middle" colspan="1"><bold>Si(OEt)<sub>4</sub></bold></td><td align="center" valign="middle" rowspan="1" colspan="1">(mol)</td><td align="center" valign="middle" rowspan="1" colspan="1">0.01</td><td align="center" valign="middle" rowspan="1" colspan="1">0.04</td><td align="center" valign="middle" rowspan="1" colspan="1">0.06</td><td align="center" valign="middle" rowspan="1" colspan="1">0.01</td><td align="center" valign="middle" rowspan="1" colspan="1">0.02</td><td align="center" valign="middle" rowspan="1" colspan="1">0.03</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1">(cm<sup>3</sup>)</td><td align="center" valign="middle" rowspan="1" colspan="1">2.2</td><td align="center" valign="middle" rowspan="1" colspan="1">8.9</td><td align="center" valign="middle" rowspan="1" colspan="1">13.4</td><td align="center" valign="middle" rowspan="1" colspan="1">2.2</td><td align="center" valign="middle" rowspan="1" colspan="1">4.6</td><td align="center" valign="middle" rowspan="1" colspan="1">6.7</td></tr><tr><td rowspan="2" align="center" valign="middle" colspan="1"><bold>MeHSiCl<sub>2</sub> (MDS)</bold></td><td align="center" valign="middle" rowspan="1" colspan="1">(mol)</td><td align="center" valign="middle" rowspan="1" colspan="1">0.48</td><td align="center" valign="middle" rowspan="1" colspan="1">0.98</td><td align="center" valign="middle" rowspan="1" colspan="1">1.0</td><td align="center" valign="middle" rowspan="1" colspan="1">0.52</td><td align="center" valign="middle" rowspan="1" colspan="1">0.49</td><td align="center" valign="middle" rowspan="1" colspan="1">0.50</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1">(cm<sup>3</sup>)</td><td align="center" valign="middle" rowspan="1" colspan="1">50.0</td><td align="center" valign="middle" rowspan="1" colspan="1">102.0</td><td align="center" valign="middle" rowspan="1" colspan="1">104.1</td><td align="center" valign="middle" rowspan="1" colspan="1">54.1</td><td align="center" valign="middle" rowspan="1" colspan="1">51.5</td><td align="center" valign="middle" rowspan="1" colspan="1">52.1</td></tr><tr><td rowspan="2" align="center" valign="middle" colspan="1"><bold>Me<sub>2</sub>SiCl<sub>2</sub> (DDS)</bold></td><td align="center" valign="middle" rowspan="1" colspan="1">(mol)</td><td align="center" valign="middle" rowspan="1" colspan="1">-</td><td align="center" valign="middle" rowspan="1" colspan="1">-</td><td align="center" valign="middle" rowspan="1" colspan="1">-</td><td align="center" valign="middle" rowspan="1" colspan="1">0.52</td><td align="center" valign="middle" rowspan="1" colspan="1">0.49</td><td align="center" valign="middle" rowspan="1" colspan="1">0.50</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1">(cm<sup>3</sup>)</td><td align="center" valign="middle" rowspan="1" colspan="1">-</td><td align="center" valign="middle" rowspan="1" colspan="1">-</td><td align="center" valign="middle" rowspan="1" colspan="1">-</td><td align="center" valign="middle" rowspan="1" colspan="1">63.1</td><td align="center" valign="middle" rowspan="1" colspan="1">59.8</td><td align="center" valign="middle" rowspan="1" colspan="1">60.6</td></tr><tr><td rowspan="2" align="center" valign="middle" colspan="1"><bold>Me<sub>3</sub>SiCl (TMCS)</bold></td><td align="center" valign="middle" rowspan="1" colspan="1">(mol)</td><td align="center" valign="middle" rowspan="1" colspan="1">0.04</td><td align="center" valign="middle" rowspan="1" colspan="1">0.12</td><td align="center" valign="middle" rowspan="1" colspan="1">0.16</td><td align="center" valign="middle" rowspan="1" colspan="1">0.04</td><td align="center" valign="middle" rowspan="1" colspan="1">0.06</td><td align="center" valign="middle" rowspan="1" colspan="1">0.08</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1">(cm<sup>3</sup>)</td><td align="center" valign="middle" rowspan="1" colspan="1">5.1</td><td align="center" valign="middle" rowspan="1" colspan="1">15.2</td><td align="center" valign="middle" rowspan="1" colspan="1">20.3</td><td align="center" valign="middle" rowspan="1" colspan="1">5.1</td><td align="center" valign="middle" rowspan="1" colspan="1">7.6</td><td align="center" valign="middle" rowspan="1" colspan="1">10.2</td></tr><tr><td rowspan="2" align="center" valign="middle" colspan="1"><bold>H<sub>2</sub>O</bold></td><td align="center" valign="middle" rowspan="1" colspan="1">(mol)</td><td align="center" valign="middle" rowspan="1" colspan="1">9.11</td><td align="center" valign="middle" rowspan="1" colspan="1">18.94</td><td align="center" valign="middle" rowspan="1" colspan="1">19.66</td><td align="center" valign="middle" rowspan="1" colspan="1">19.33</td><td align="center" valign="middle" rowspan="1" colspan="1">18.38</td><td align="center" valign="middle" rowspan="1" colspan="1">18.94</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1">(cm<sup>3</sup>)</td><td align="center" valign="middle" rowspan="1" colspan="1">164</td><td align="center" valign="middle" rowspan="1" colspan="1">341</td><td align="center" valign="middle" rowspan="1" colspan="1">354</td><td align="center" valign="middle" rowspan="1" colspan="1">348</td><td align="center" valign="middle" rowspan="1" colspan="1">331</td><td align="center" valign="middle" rowspan="1" colspan="1">341</td></tr><tr><td rowspan="2" align="center" valign="middle" colspan="1"><bold>(4-dimethylamino)-pyridine (DMAP)</bold></td><td align="center" valign="middle" rowspan="1" colspan="1">(mol)</td><td align="center" valign="middle" rowspan="1" colspan="1">-</td><td align="center" valign="middle" rowspan="1" colspan="1">-</td><td align="center" valign="middle" rowspan="1" colspan="1">0.003</td><td align="center" valign="middle" rowspan="1" colspan="1">0.0109</td><td align="center" valign="middle" rowspan="1" colspan="1">0.0108</td><td align="center" valign="middle" rowspan="1" colspan="1">0.01</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1">(g)</td><td align="center" valign="middle" rowspan="1" colspan="1">-</td><td align="center" valign="middle" rowspan="1" colspan="1">-</td><td align="center" valign="middle" rowspan="1" colspan="1">0.3665</td><td align="center" valign="middle" rowspan="1" colspan="1">1.3316</td><td align="center" valign="middle" rowspan="1" colspan="1">1.3194</td><td align="center" valign="middle" rowspan="1" colspan="1">1.2217</td></tr><tr><td rowspan="2" align="center" valign="middle" colspan="1"><bold>Et<sub>3</sub>N</bold></td><td align="center" valign="middle" rowspan="1" colspan="1">(mol)</td><td align="center" valign="middle" rowspan="1" colspan="1">-</td><td align="center" valign="middle" rowspan="1" colspan="1">-</td><td align="center" valign="middle" rowspan="1" colspan="1">0.03</td><td align="center" valign="middle" rowspan="1" colspan="1">0.109</td><td align="center" valign="middle" rowspan="1" colspan="1">0.108</td><td align="center" valign="middle" rowspan="1" colspan="1">0.10</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1">(cm<sup>3</sup>)</td><td align="center" valign="middle" rowspan="1" colspan="1">-</td><td align="center" valign="middle" rowspan="1" colspan="1">-</td><td align="center" valign="middle" rowspan="1" colspan="1">4.2</td><td align="center" valign="middle" rowspan="1" colspan="1">101.2</td><td align="center" valign="middle" rowspan="1" colspan="1">15.1</td><td align="center" valign="middle" rowspan="1" colspan="1">13.9</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1">Diethyl ether</td><td align="center" valign="middle" rowspan="1" colspan="1">(cm<sup>3</sup>)</td><td align="center" valign="middle" rowspan="1" colspan="1">50</td><td align="center" valign="middle" rowspan="1" colspan="1">80</td><td align="center" valign="middle" rowspan="1" colspan="1">60</td><td align="center" valign="middle" rowspan="1" colspan="1">100</td><td align="center" valign="middle" rowspan="1" colspan="1">80</td><td align="center" valign="middle" rowspan="1" colspan="1">90</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1">Addition time of chlorosilanes and Si(OEt)<sub>4</sub></td><td align="center" valign="middle" rowspan="1" colspan="1">(min)</td><td align="center" valign="middle" rowspan="1" colspan="1">50</td><td align="center" valign="middle" rowspan="1" colspan="1">60</td><td align="center" valign="middle" rowspan="1" colspan="1">95</td><td align="center" valign="middle" rowspan="1" colspan="1">80</td><td align="center" valign="middle" rowspan="1" colspan="1">55</td><td align="center" valign="middle" rowspan="1" colspan="1">95</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1">Temperature during addition of chlorosilanes and Si(OEt)<sub>4</sub></td><td align="center" valign="middle" rowspan="1" colspan="1">(°C)</td><td align="center" valign="middle" rowspan="1" colspan="1">−4–−2</td><td align="center" valign="middle" rowspan="1" colspan="1">−1–3</td><td align="center" valign="middle" rowspan="1" colspan="1">−1–3</td><td align="center" valign="middle" rowspan="1" colspan="1">−1–3</td><td align="center" valign="middle" rowspan="1" colspan="1">−1–6</td><td align="center" valign="middle" rowspan="1" colspan="1">−2–2</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1">Stirring time after addition of chlorosilanes and Si(OEt)<sub>4</sub></td><td align="center" valign="middle" rowspan="1" colspan="1">(min)</td><td align="center" valign="middle" rowspan="1" colspan="1">170</td><td align="center" valign="middle" rowspan="1" colspan="1">130</td><td align="center" valign="middle" rowspan="1" colspan="1">130</td><td align="center" valign="middle" rowspan="1" colspan="1">130</td><td align="center" valign="middle" rowspan="1" colspan="1">120</td><td align="center" valign="middle" rowspan="1" colspan="1">120</td></tr><tr><td colspan="2" align="center" valign="middle" style="border-bottom:solid thin" rowspan="1">Drying of products:</td><td colspan="3" align="center" valign="middle" style="border-bottom:solid thin" rowspan="1">with anhydrous MgSO<sub>4</sub></td><td colspan="3" align="center" valign="middle" style="border-bottom:solid thin" rowspan="1">by cooling in a fridge</td></tr></tbody></table><table-wrap-foot><fn><p>* Average molecular composition of polymers, based on a stoichiometry of monomers. PMHS-Q: liquid branched poly(methylhydrosiloxanes) of random structures.</p></fn></table-wrap-foot></table-wrap><table-wrap id="polymers-10-00484-t002" orientation="portrait" position="float"><object-id pub-id-type="pii">polymers-10-00484-t002_Table 2</object-id><label>Table 2</label><caption><p>Yields of PMHS-Q, conditions of removal of volatile products, and results of measurements of dynamic viscosity of branched PMHS, containing quadruple branching units Q.</p></caption><table frame="hsides" rules="groups"><thead><tr><th colspan="3" align="center" valign="middle" style="border-top:solid thin;border-bottom:solid thin" rowspan="1">PMHS-Q</th><th rowspan="2" align="center" valign="middle" style="border-top:solid thin;border-bottom:solid thin" colspan="1">Dynamic viscosity</th><th colspan="2" align="center" valign="middle" style="border-top:solid thin;border-bottom:solid thin" rowspan="1">Evacuation conditions</th><th colspan="2" align="center" valign="middle" style="border-top:solid thin;border-bottom:solid thin" rowspan="1">Volatile products</th></tr><tr><th rowspan="2" align="center" valign="middle" style="border-bottom:solid thin" colspan="1">Predicted molecular formula (polymer abreviation)</th><th colspan="2" align="center" valign="middle" style="border-bottom:solid thin" rowspan="1">Yield</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">Bath temp. </th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">Time</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">B.p./pressure</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">Mass</th></tr><tr><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">(g)</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">(wt%)</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">(cP)</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">(°C)</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">(min)</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">(°C/mm Hg)</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">(g)</th></tr></thead><tbody><tr><td align="left" valign="middle" rowspan="1" colspan="1"><bold>QD<sup>H</sup><sub>48</sub>M<sub>4</sub> (Q1)</bold></td><td align="center" valign="middle" rowspan="1" colspan="1">20.14</td><td align="center" valign="middle" rowspan="1" colspan="1">62</td><td align="center" valign="middle" rowspan="1" colspan="1">12.8</td><td align="center" valign="middle" rowspan="1" colspan="1">152</td><td align="center" valign="middle" rowspan="1" colspan="1">190</td><td align="center" valign="middle" rowspan="1" colspan="1">24/16–79/3.5</td><td align="center" valign="middle" rowspan="1" colspan="1">9.27</td></tr><tr><td align="left" valign="middle" rowspan="1" colspan="1"><bold>Q<sub>2</sub>D<sup>H</sup><sub>49</sub>M<sub>6</sub> (Q2)</bold></td><td align="center" valign="middle" rowspan="1" colspan="1">48.70</td><td align="center" valign="middle" rowspan="1" colspan="1">68</td><td align="center" valign="middle" rowspan="1" colspan="1">11.0</td><td align="center" valign="middle" rowspan="1" colspan="1">154</td><td align="center" valign="middle" rowspan="1" colspan="1">200</td><td align="center" valign="middle" rowspan="1" colspan="1">23/16–77/3.5</td><td align="center" valign="middle" rowspan="1" colspan="1">18.14</td></tr><tr><td align="left" valign="middle" rowspan="1" colspan="1"><bold>Q<sub>3</sub>D<sup>H</sup><sub>50</sub>M<sub>8</sub> (Q3)</bold></td><td align="center" valign="middle" rowspan="1" colspan="1">52.82</td><td align="center" valign="middle" rowspan="1" colspan="1">69</td><td align="center" valign="middle" rowspan="1" colspan="1">13.1</td><td align="center" valign="middle" rowspan="1" colspan="1">155</td><td align="center" valign="middle" rowspan="1" colspan="1">190</td><td align="center" valign="middle" rowspan="1" colspan="1">23/18–70/3.5</td><td align="center" valign="middle" rowspan="1" colspan="1">16.71</td></tr><tr><td align="left" valign="middle" rowspan="1" colspan="1"><bold>QD<sub>52</sub>D<sup>H</sup><sub>52</sub>M<sub>4</sub> (Q1D)</bold></td><td align="center" valign="middle" rowspan="1" colspan="1">40.29</td><td align="center" valign="middle" rowspan="1" colspan="1">55</td><td align="center" valign="middle" rowspan="1" colspan="1">12.5</td><td align="center" valign="middle" rowspan="1" colspan="1">150</td><td align="center" valign="middle" rowspan="1" colspan="1">210</td><td align="center" valign="middle" rowspan="1" colspan="1">21/21–80/5</td><td align="center" valign="middle" rowspan="1" colspan="1">34.84</td></tr><tr><td align="left" valign="middle" rowspan="1" colspan="1"><bold>Q<sub>2</sub>D<sub>49</sub>D<sup>H</sup><sub>49</sub>M<sub>6</sub> (Q2D)</bold></td><td align="center" valign="middle" rowspan="1" colspan="1">40.49</td><td align="center" valign="middle" rowspan="1" colspan="1">56</td><td align="center" valign="middle" rowspan="1" colspan="1">11.8</td><td align="center" valign="middle" rowspan="1" colspan="1">155</td><td align="center" valign="middle" rowspan="1" colspan="1">200</td><td align="center" valign="middle" rowspan="1" colspan="1">27/19–78/4</td><td align="center" valign="middle" rowspan="1" colspan="1">31.06</td></tr><tr><td align="left" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1"><bold>Q<sub>3</sub>D<sub>50</sub>D<sup>H</sup><sub>50</sub>M<sub>8</sub> (Q3D)</bold></td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">43.77</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">58</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">10.7</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">155</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">190</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">21/16–74/4.5</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">28.22</td></tr></tbody></table></table-wrap><table-wrap id="polymers-10-00484-t003" orientation="portrait" position="float"><object-id pub-id-type="pii">polymers-10-00484-t003_Table 3</object-id><label>Table 3</label><caption><p>Characteristics of polymethylhydrosiloxanes with branched, random structure of siloxane chains, containing branching units Q.</p></caption><table frame="hsides" rules="groups"><thead><tr><th rowspan="2" align="center" valign="middle" style="border-top:solid thin;border-bottom:solid thin" colspan="1">PMHS-Q</th><th rowspan="2" align="center" valign="middle" style="border-top:solid thin;border-bottom:solid thin" colspan="1">M<sub>n</sub> (calc.)</th><th rowspan="2" align="center" valign="middle" style="border-top:solid thin;border-bottom:solid thin" colspan="1">M<sub>n</sub></th><th rowspan="2" align="center" valign="middle" style="border-top:solid thin;border-bottom:solid thin" colspan="1">M<sub>w</sub></th><th rowspan="2" align="center" valign="middle" style="border-top:solid thin;border-bottom:solid thin" colspan="1">M<sub>w</sub>/M<sub>n</sub></th><th colspan="2" align="center" valign="middle" style="border-top:solid thin;border-bottom:solid thin" rowspan="1">% C</th><th colspan="2" align="center" valign="middle" style="border-top:solid thin;border-bottom:solid thin" rowspan="1">% H</th><th colspan="2" align="center" valign="middle" style="border-top:solid thin;border-bottom:solid thin" rowspan="1">% Si</th></tr><tr><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">calc.</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">found</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">calc.</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">found</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">calc.</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">found</th></tr></thead><tbody><tr><td align="center" valign="middle" rowspan="1" colspan="1"><bold>QD<sup>H</sup><sub>48</sub>M<sub>4</sub></bold></td><td align="center" valign="middle" rowspan="1" colspan="1">3271</td><td align="center" valign="middle" rowspan="1" colspan="1">6310</td><td align="center" valign="middle" rowspan="1" colspan="1">17,750</td><td align="center" valign="middle" rowspan="1" colspan="1">2.81</td><td align="center" valign="middle" rowspan="1" colspan="1">22.03</td><td align="center" valign="middle" rowspan="1" colspan="1">21.51<break></break>21.76</td><td align="center" valign="middle" rowspan="1" colspan="1">7.03</td><td align="center" valign="middle" rowspan="1" colspan="1">6.61<break></break>6.90</td><td align="center" valign="middle" rowspan="1" colspan="1">45.50</td><td align="center" valign="middle" rowspan="1" colspan="1">44.87</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1"><bold>Q<sub>2</sub>D<sup>H</sup><sub>49</sub>M<sub>6</sub></bold></td><td align="center" valign="middle" rowspan="1" colspan="1">3554</td><td align="center" valign="middle" rowspan="1" colspan="1">3220</td><td align="center" valign="middle" rowspan="1" colspan="1">8330</td><td align="center" valign="middle" rowspan="1" colspan="1">2.59</td><td align="center" valign="middle" rowspan="1" colspan="1">22.64</td><td align="center" valign="middle" rowspan="1" colspan="1">22.01<break></break>22.11</td><td align="center" valign="middle" rowspan="1" colspan="1">7.09</td><td align="center" valign="middle" rowspan="1" colspan="1">6.92<break></break>7.01</td><td align="center" valign="middle" rowspan="1" colspan="1">45.05</td><td align="center" valign="middle" rowspan="1" colspan="1">45.15</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1"><bold>Q<sub>3</sub>D<sup>H</sup><sub>50</sub>M<sub>8</sub></bold></td><td align="center" valign="middle" rowspan="1" colspan="1">3836</td><td align="center" valign="middle" rowspan="1" colspan="1">3840</td><td align="center" valign="middle" rowspan="1" colspan="1">10,350</td><td align="center" valign="middle" rowspan="1" colspan="1">2.69</td><td align="center" valign="middle" rowspan="1" colspan="1">23.16</td><td align="center" valign="middle" rowspan="1" colspan="1">22.03<break></break>22.14</td><td align="center" valign="middle" rowspan="1" colspan="1">7.14</td><td align="center" valign="middle" rowspan="1" colspan="1">7.02<break></break>6.85</td><td align="center" valign="middle" rowspan="1" colspan="1">44.65</td><td align="center" valign="middle" rowspan="1" colspan="1">43.81</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1"><bold>QD<sub>52</sub>D<sup>H</sup><sub>52</sub>M<sub>4</sub></bold></td><td align="center" valign="middle" rowspan="1" colspan="1">7367</td><td align="center" valign="middle" rowspan="1" colspan="1">2650</td><td align="center" valign="middle" rowspan="1" colspan="1">6280</td><td align="center" valign="middle" rowspan="1" colspan="1">2.36</td><td align="center" valign="middle" rowspan="1" colspan="1">27.39</td><td align="center" valign="middle" rowspan="1" colspan="1">28.89<break></break>28.70</td><td align="center" valign="middle" rowspan="1" colspan="1">7.60</td><td align="center" valign="middle" rowspan="1" colspan="1">7.89<break></break>8.03</td><td align="center" valign="middle" rowspan="1" colspan="1">41.55</td><td align="center" valign="middle" rowspan="1" colspan="1">41.54</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1"><bold>Q<sub>2</sub>D<sub>49</sub>D<sup>H</sup><sub>49</sub>M<sub>6</sub></bold></td><td align="center" valign="middle" rowspan="1" colspan="1">7187</td><td align="center" valign="middle" rowspan="1" colspan="1">2440</td><td align="center" valign="middle" rowspan="1" colspan="1">5750</td><td align="center" valign="middle" rowspan="1" colspan="1">2.35</td><td align="center" valign="middle" rowspan="1" colspan="1">27.57</td><td align="center" valign="middle" rowspan="1" colspan="1">28.15<break></break>28.40</td><td align="center" valign="middle" rowspan="1" colspan="1">7.63</td><td align="center" valign="middle" rowspan="1" colspan="1">7.69<break></break>7.88</td><td align="center" valign="middle" rowspan="1" colspan="1">41.42</td><td align="center" valign="middle" rowspan="1" colspan="1">41.40</td></tr><tr><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1"><bold>Q<sub>3</sub>D<sub>50</sub>D<sup>H</sup><sub>50</sub>M<sub>8</sub></bold></td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">7544</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">5100</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">10,210</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">2.00</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">27.07</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">27.78<break></break>27.92</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">7.65</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">8.35<break></break>7.98</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">41.32</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">41.30</td></tr></tbody></table></table-wrap><table-wrap id="polymers-10-00484-t004" orientation="portrait" position="float"><object-id pub-id-type="pii">polymers-10-00484-t004_Table 4</object-id><label>Table 4</label><caption><p>Characteristic absorption bands in FTIR spectra of Q<sub>2</sub>D<sub>49</sub>D<sup>H</sup><sub>49</sub>M<sub>6</sub>.</p></caption><table frame="hsides" rules="groups"><thead><tr><th colspan="2" align="center" valign="middle" style="border-top:solid thin;border-bottom:solid thin" rowspan="1">Wave number [cm<sup>−1</sup>]</th><th align="center" valign="middle" style="border-top:solid thin;border-bottom:solid thin" rowspan="1" colspan="1">Group or bond</th><th align="center" valign="middle" style="border-top:solid thin;border-bottom:solid thin" rowspan="1" colspan="1">Vibration</th></tr></thead><tbody><tr><td align="center" valign="middle" rowspan="1" colspan="1">found</td><td align="center" valign="middle" rowspan="1" colspan="1">literature data [<xref rid="B72-polymers-10-00484" ref-type="bibr">72</xref>] </td><td align="center" valign="middle" rowspan="1" colspan="1"></td><td align="center" valign="middle" rowspan="1" colspan="1"></td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1">2965</td><td align="center" valign="middle" rowspan="1" colspan="1">2975–2950</td><td align="center" valign="middle" rowspan="1" colspan="1">CH<sub>3</sub></td><td align="center" valign="middle" rowspan="1" colspan="1">ν <sub>asym</sub> C-H</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1">2878</td><td align="center" valign="middle" rowspan="1" colspan="1">2885–2860</td><td align="center" valign="middle" rowspan="1" colspan="1">CH<sub>3</sub></td><td align="center" valign="middle" rowspan="1" colspan="1">ν <sub>sym</sub> C-H</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1">2164</td><td align="center" valign="middle" rowspan="1" colspan="1">2300–2100</td><td align="center" valign="middle" rowspan="1" colspan="1">Si-H</td><td align="center" valign="middle" rowspan="1" colspan="1">ν Si-H</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1">1450</td><td align="center" valign="middle" rowspan="1" colspan="1">1470–1420</td><td align="center" valign="middle" rowspan="1" colspan="1">CH<sub>3</sub></td><td align="center" valign="middle" rowspan="1" colspan="1">δ <sub>asym</sub> C-H</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1">1410</td><td align="center" valign="middle" rowspan="1" colspan="1">1390–1365</td><td align="center" valign="middle" rowspan="1" colspan="1">CH<sub>3</sub></td><td align="center" valign="middle" rowspan="1" colspan="1">δ <sub>sym</sub> C-H</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1">1260</td><td align="center" valign="middle" rowspan="1" colspan="1">1265–1250</td><td align="center" valign="middle" rowspan="1" colspan="1">Si-CH<sub>3</sub></td><td align="center" valign="middle" rowspan="1" colspan="1">δ <sub>asym</sub> Si-C</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1">1115–1027</td><td align="center" valign="middle" rowspan="1" colspan="1">1100–1000</td><td align="center" valign="middle" rowspan="1" colspan="1">Si-O-Si</td><td align="center" valign="middle" rowspan="1" colspan="1">ν <sub>asym</sub> Si-O</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1">910</td><td align="center" valign="middle" rowspan="1" colspan="1">950–800</td><td align="center" valign="middle" rowspan="1" colspan="1">Si-H</td><td align="center" valign="middle" rowspan="1" colspan="1">δ Si-H</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1">864</td><td align="center" valign="middle" rowspan="1" colspan="1">860–750</td><td align="center" valign="middle" rowspan="1" colspan="1">Si-CH<sub>3</sub></td><td align="center" valign="middle" rowspan="1" colspan="1">ν <sub>asym</sub> Si-C</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1">830</td><td align="center" valign="middle" rowspan="1" colspan="1">910–830</td><td align="center" valign="middle" rowspan="1" colspan="1">Si-O</td><td align="center" valign="middle" rowspan="1" colspan="1">ν <sub>asym</sub> Si-O</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1">800</td><td align="center" valign="middle" rowspan="1" colspan="1">800</td><td align="center" valign="middle" rowspan="1" colspan="1">Si-CH<sub>3</sub></td><td align="center" valign="middle" rowspan="1" colspan="1">δ <sub>sym</sub> Si-C</td></tr><tr><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">759</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">755</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">Si-(CH<sub>3</sub>)<sub>3</sub></td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">δ <sub>asym</sub> Si-C</td></tr></tbody></table></table-wrap><table-wrap id="polymers-10-00484-t005" orientation="portrait" position="float"><object-id pub-id-type="pii">polymers-10-00484-t005_Table 5</object-id><label>Table 5</label><caption><p>Chemical shifts of PMHS-Q in their <sup>1</sup>H- and <sup>29</sup>Si-NMR spectra (in C6D6).</p></caption><table frame="hsides" rules="groups"><thead><tr><th rowspan="4" align="center" valign="middle" style="border-top:solid thin;border-bottom:solid thin" colspan="1">PMHS-Q</th><th colspan="11" align="center" valign="middle" style="border-top:solid thin;border-bottom:solid thin" rowspan="1">δ (ppm)</th></tr><tr><th rowspan="2" colspan="2" align="center" valign="middle" style="border-bottom:solid thin"><sup>1</sup>H-NMR</th><th colspan="9" align="center" valign="middle" style="border-bottom:solid thin" rowspan="1"><sup>29</sup>Si-NMR</th></tr><tr><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">INEPT</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">INVGATE</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">INEPT</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">INVGATE</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">INEPT</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">INVGATE</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">INEPT</th><th colspan="2" align="center" valign="middle" style="border-bottom:solid thin" rowspan="1">INVGATE</th></tr><tr><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">Si–H</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">Si–CH<sub>3</sub></th><th colspan="2" align="center" valign="middle" style="border-bottom:solid thin" rowspan="1">Me<sub>3</sub>SiO<sub>0.5</sub></th><th colspan="2" align="center" valign="middle" style="border-bottom:solid thin" rowspan="1">Me<sub>2</sub>SiO</th><th colspan="2" align="center" valign="middle" style="border-bottom:solid thin" rowspan="1">MeHSiO</th><th colspan="2" align="center" valign="middle" style="border-bottom:solid thin" rowspan="1">MeSiO<sub>3/2</sub></th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">SiO<sub>4/2</sub></th></tr></thead><tbody><tr><td align="center" valign="middle" rowspan="1" colspan="1"><bold>QD<sup>H</sup><sub>48</sub>M<sub>4</sub></bold></td><td align="center" valign="middle" rowspan="1" colspan="1">4.90</td><td align="center" valign="middle" rowspan="1" colspan="1">0.01–0.22</td><td align="center" valign="middle" rowspan="1" colspan="1">9.75–11.03</td><td align="center" valign="middle" rowspan="1" colspan="1">9.98–10.96</td><td align="center" valign="middle" rowspan="1" colspan="1">-</td><td align="center" valign="middle" rowspan="1" colspan="1">-</td><td align="center" valign="middle" rowspan="1" colspan="1">−31.51–−37.42</td><td align="center" valign="middle" rowspan="1" colspan="1">−31.85–−35.90</td><td align="center" valign="middle" rowspan="1" colspan="1">−64.51</td><td align="center" valign="middle" rowspan="1" colspan="1">−64.58</td><td align="center" valign="middle" rowspan="1" colspan="1">−101.40–−108.13</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1"><bold>Q<sub>2</sub>D<sup>H</sup><sub>49</sub>M<sub>6</sub></bold></td><td align="center" valign="middle" rowspan="1" colspan="1">4.80</td><td align="center" valign="middle" rowspan="1" colspan="1">0.01–0.12</td><td align="center" valign="middle" rowspan="1" colspan="1">9.40–11.24</td><td align="center" valign="middle" rowspan="1" colspan="1">9.70–10.32</td><td align="center" valign="middle" rowspan="1" colspan="1">-</td><td align="center" valign="middle" rowspan="1" colspan="1">-</td><td align="center" valign="middle" rowspan="1" colspan="1">−31.62–−39.97</td><td align="center" valign="middle" rowspan="1" colspan="1">−31.83–−36.25</td><td align="center" valign="middle" rowspan="1" colspan="1">−62.60–−64.61</td><td align="center" valign="middle" rowspan="1" colspan="1">-</td><td align="center" valign="middle" rowspan="1" colspan="1">−101.37–−112.33</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1"><bold>Q<sub>3</sub>D<sup>H</sup><sub>50</sub>M<sub>8</sub></bold></td><td align="center" valign="middle" rowspan="1" colspan="1">4.80</td><td align="center" valign="middle" rowspan="1" colspan="1">0.01–0.12</td><td align="center" valign="middle" rowspan="1" colspan="1">9.40–11.25</td><td align="center" valign="middle" rowspan="1" colspan="1">9.42–11.28</td><td align="center" valign="middle" rowspan="1" colspan="1">-</td><td align="center" valign="middle" rowspan="1" colspan="1">-</td><td align="center" valign="middle" rowspan="1" colspan="1">−37.46–−31.16</td><td align="center" valign="middle" rowspan="1" colspan="1">−32.16–−35.87</td><td align="center" valign="middle" rowspan="1" colspan="1">−62.97–−64.56</td><td align="center" valign="middle" rowspan="1" colspan="1">−64.54</td><td align="center" valign="middle" rowspan="1" colspan="1">−100.31–−110.20</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1"><bold>QD<sub>52</sub>D<sup>H</sup><sub>52</sub>M<sub>4</sub></bold></td><td align="center" valign="middle" rowspan="1" colspan="1">4.92</td><td align="center" valign="middle" rowspan="1" colspan="1">0.05–0.22</td><td align="center" valign="middle" rowspan="1" colspan="1">9.92–7.27</td><td align="center" valign="middle" rowspan="1" colspan="1">7.30–9.96</td><td align="center" valign="middle" rowspan="1" colspan="1">−18.48–−21.74</td><td align="center" valign="middle" rowspan="1" colspan="1">−18.67–−21.44</td><td align="center" valign="middle" rowspan="1" colspan="1">−33.27–−38.87</td><td align="center" valign="middle" rowspan="1" colspan="1">−34.56–−37.30</td><td align="center" valign="middle" rowspan="1" colspan="1">−63.12–−65.39</td><td align="center" valign="middle" rowspan="1" colspan="1">−63.72–−65.89</td><td align="center" valign="middle" rowspan="1" colspan="1">−102.92–−109.92</td></tr><tr><td align="center" valign="middle" rowspan="1" colspan="1"><bold>Q<sub>2</sub>D<sub>49</sub>D<sup>H</sup><sub>49</sub>M<sub>6</sub></bold></td><td align="center" valign="middle" rowspan="1" colspan="1">4.92</td><td align="center" valign="middle" rowspan="1" colspan="1">0.01–0.30</td><td align="center" valign="middle" rowspan="1" colspan="1">9.92–7.26</td><td align="center" valign="middle" rowspan="1" colspan="1">7.32–9.98</td><td align="center" valign="middle" rowspan="1" colspan="1">−18.43–−21.85</td><td align="center" valign="middle" rowspan="1" colspan="1">−18.70–−21.69</td><td align="center" valign="middle" rowspan="1" colspan="1">−34.54–−37.33</td><td align="center" valign="middle" rowspan="1" colspan="1">−34.61–−37.03</td><td align="center" valign="middle" rowspan="1" colspan="1">−62.95–−65.26</td><td align="center" valign="middle" rowspan="1" colspan="1">−62.35–−66.16</td><td align="center" valign="middle" rowspan="1" colspan="1">−101.81–−109.71</td></tr><tr><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1"><bold>Q<sub>3</sub>D<sub>50</sub>D<sup>H</sup><sub>50</sub>M<sub>8</sub></bold></td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">4.83</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">0.01–0.23</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">9.91–7.27</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">7.32–9.98</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">−18.77–−21.75</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">−18.72–−21.29</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">−34.61–−37.57</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">−34.54–−36.10</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">−64.73</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">−63.35–−65.16</td><td align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">−102.84–−109.61</td></tr></tbody></table></table-wrap><table-wrap id="polymers-10-00484-t006" orientation="portrait" position="float"><object-id pub-id-type="pii">polymers-10-00484-t006_Table 6</object-id><label>Table 6</label><caption><p>The microstructure of siloxane chains in PMHS-Q, containing quadruple branching units Q (all possible sequences among tetrads of terminal groups, and linear and star pentads); values of δ concern Si atoms in structural units denoted as bold and underlined.</p></caption><table frame="hsides" rules="groups"><thead><tr><th colspan="6" align="center" valign="middle" style="border-top:solid thin;border-bottom:solid thin" rowspan="1">δ <sup>29</sup>Si-NMR (ppm)</th></tr><tr><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">9–11</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">7–8</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">−18–−19</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">−20–−22</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">−33–−37</th><th align="center" valign="middle" style="border-bottom:solid thin" rowspan="1" colspan="1">−101–−109</th></tr></thead><tbody><tr><td align="center" valign="top" style="border-bottom:solid thin" rowspan="1" colspan="1"><bold><underline>M</underline></bold>D<sup>H</sup>D<sup>H</sup>D<sup>H</sup><break></break><break></break><bold><underline>M</underline></bold>D<sup>H</sup>D<sup>H</sup>Q<break></break><break></break><bold><underline>M</underline></bold>D<sup>H</sup>QD<sup>H</sup><break></break><break></break><bold><underline>M</underline></bold>D<sup>H</sup>D<sup>H</sup>D<break></break><break></break><bold><underline>M</underline></bold>D<sup>H</sup>D<sup>H</sup>D<sup>H</sup><break></break><break></break><bold><underline>M</underline></bold>D<sup>H</sup>DD<sup>H</sup><break></break><break></break><bold><underline>M</underline></bold>D<sup>H</sup>DD</td><td align="center" valign="top" style="border-bottom:solid thin" rowspan="1" colspan="1"><bold><underline>M</underline></bold>DDD<break></break><break></break><bold><underline>M</underline></bold>DDD<sup>H</sup><break></break><break></break><bold><underline>M</underline></bold>DD<sup>H</sup>D<break></break><break></break><bold><underline>M</underline></bold>DD<sup>H</sup>D<sup>H</sup><break></break><break></break><bold><underline>M</underline></bold>DDQ<break></break><break></break><bold><underline>M</underline></bold>DQD<break></break><break></break><bold><underline>M</underline></bold>QDD<break></break><bold><underline>M</underline></bold>QDD<sup>H</sup></td><td align="center" valign="top" style="border-bottom:solid thin" rowspan="1" colspan="1">DD<sup>H</sup><bold><underline>D</underline></bold>D<sup>H</sup>D<break></break><break></break>DD<sup>H</sup><bold><underline>D</underline></bold>D<sup>H</sup>D<sup>H</sup><break></break><break></break>D<sup>H</sup>D<sup>H</sup><bold><underline>D</underline></bold>D<sup>H</sup>D<sup>H</sup><break></break><break></break>DD<sup>H</sup><bold><underline>D</underline></bold>D<sup>H</sup>Q<break></break><break></break>QD<sup>H</sup><bold><underline>D</underline></bold>D<sup>H</sup>Q<break></break><break></break>MD<sup>H</sup><bold><underline>D</underline></bold>D<sup>H</sup>D<break></break><break></break>MD<sup>H</sup><bold><underline>D</underline></bold>D<sup>H</sup>D<sup>H</sup><break></break><break></break>MD<sup>H</sup><bold><underline>D</underline></bold>D<sup>H</sup>Q<break></break><break></break>MD<sup>H</sup><bold><underline>D</underline></bold>D<sup>H</sup>D</td><td align="center" valign="top" style="border-bottom:solid thin" rowspan="1" colspan="1">D<sup>H</sup>D<bold><underline>D</underline></bold>D<sup>H</sup>D<sup>H</sup><break></break>D<sup>H</sup>D<bold><underline>D</underline></bold>D<sup>H</sup>D<break></break>DD<bold><underline>D</underline></bold>D<sup>H</sup>D<sup>H</sup><break></break>DD<bold><underline>D</underline></bold>D<sup>H</sup>D<break></break>D<sup>H</sup>D<bold><underline>D</underline></bold>DQ<break></break>D<sup>H</sup>D<bold><underline>D</underline></bold>QD<break></break>DD<sup>H</sup><bold><underline>D</underline></bold>DQ<break></break>DD<sup>H</sup><bold><underline>D</underline></bold>QD<break></break>DD<bold><underline>D</underline></bold>DQ<break></break>DD<bold><underline>D</underline></bold>QD<break></break>QD<bold><underline>D</underline></bold>DQ<break></break>QD<bold><underline>D</underline></bold>QD<break></break>DQ<bold><underline>D</underline></bold>QD<break></break>DQ<bold><underline>D</underline></bold>DQ<break></break>MD<bold><underline>D</underline></bold>DQ<break></break>MD<bold><underline>D</underline></bold>QD<break></break>MQ<bold><underline>D</underline></bold>DD<break></break>MD<bold><underline>D</underline></bold>DQ<break></break>MQ<bold><underline>D</underline></bold>QD</td><td align="center" valign="top" style="border-bottom:solid thin" rowspan="1" colspan="1">D<sup>H</sup>D<sup>H</sup><bold><underline>D<sup>H</sup></underline></bold>D<sup>H</sup>D<sup>H</sup><break></break>DD<sup>H</sup><bold><underline>D<sup>H</sup></underline></bold>D<sup>H</sup>D<sup>H</sup><break></break>D<sup>H</sup>D<bold><underline>D<sup>H</sup></underline></bold>D<sup>H</sup>D<sup>H</sup><break></break>DD<sup>H</sup><bold><underline>D<sup>H</sup></underline></bold>D<sup>H</sup>D <break></break>DD<sup>H</sup><bold><underline>D<sup>H</sup></underline></bold>DD<sup>H</sup><break></break>D<sup>H</sup>D<bold><underline>D<sup>H</sup></underline></bold>D D<sup>H</sup><break></break>D<sup>H</sup>D<bold><underline>D<sup>H</sup></underline></bold>D<sup>H</sup>Q <break></break>D<sup>H</sup>D<sup>H</sup><bold><underline>D<sup>H</sup></underline></bold>QD<sup>H</sup><break></break>DD<sup>H</sup><bold><underline>D<sup>H</sup></underline></bold>D<sup>H</sup>Q<break></break>D<sup>H</sup>D<bold><underline>D<sup>H</sup></underline></bold>D<sup>H</sup>Q <break></break>D<sup>H</sup>D<bold><underline>D<sup>H</sup></underline></bold>QD<sup>H</sup><break></break>DD<sup>H</sup><bold><underline>D<sup>H</sup></underline></bold><sup>H</sup>QD<sup>H</sup><break></break>DD<bold><underline>D<sup>H</sup></underline></bold>QD<sup>H</sup><break></break>D<sup>H</sup>D<sup>H</sup><bold><underline>D<sup>H</sup></underline></bold>DQ <break></break>D<sup>H</sup>D<sup>H</sup><bold><underline>D<sup>H</sup></underline></bold>QD<break></break>DD<sup>H</sup><bold><underline>D<sup>H</sup></underline></bold>DQ<break></break>DD<sup>H</sup><bold><underline>D<sup>H</sup></underline></bold>QD<break></break>D<sup>H</sup>D<bold><underline>D<sup>H</sup></underline></bold>DQ<break></break>D<sup>H</sup>D<bold><underline>D<sup>H</sup></underline></bold>QD<break></break>DD<bold><underline>D<sup>H</sup></underline></bold>D<sup>H</sup>Q<break></break>DD<bold><underline>D<sup>H</sup></underline></bold>DQ<break></break>MD<sup>H</sup><bold><underline>D<sup>H</sup></underline></bold>D<sup>H</sup>D<sup>H</sup><break></break>MD<sup>H</sup><bold><underline>D<sup>H</sup></underline></bold>D<sup>H</sup> 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