Microstructure characterization of acetylenic polymers by Curie-point pyrolysis/capillary gas chromatography/mass spectrometry
Identifieur interne : 001474 ( Istex/Corpus ); précédent : 001473; suivant : 001475Microstructure characterization of acetylenic polymers by Curie-point pyrolysis/capillary gas chromatography/mass spectrometry
Auteurs : Sandrine Duc ; Alain PetitSource :
- Journal of Analytical and Applied Pyrolysis [ 0165-2370 ] ; 1997.
English descriptors
- KwdEn :
- Anal, Appl, Boundary effect, Boundary effect theory, Catalyst systems, Chain microstructures, Chem, Chemical inversions, Copolymer, Copolymer chain, Copolymer chains, Copolymer composition, Cyclic trimers, Cyclotrimer, Cyclotrimers, Degradation, Degradation behaviour, Different products, Homogeneous cyclotrimers, Homogeneous trimers, Hybrid, Hybrid trimers, Inversed monomer linkages, Linkage, Marcel dekker, Mass spectrometry, Metathesis, Metathesis catalyst, Metathesis initiator, Microstructure, Molar, Molar amounts, Molar fraction, Monomer, Monomer placement, Neighbouring monomer units, Open points, Other hand, Polym, Polymer, Polymer chain, Polymeric systems, Present work, Probability constants, Pyrograms, Pyrolysis, Quantitative treatment, Random copolymers, Reactivity ratios, Relative abundance, Sequence distributions, Solid points, Thermal degradation, Thermal scission, Transition metal, Triad, Triad concentrations, Triad distributions, Trimer, Tsuge, Various compositions.
- Teeft :
- Anal, Appl, Boundary effect, Boundary effect theory, Catalyst systems, Chain microstructures, Chem, Chemical inversions, Copolymer, Copolymer chain, Copolymer chains, Copolymer composition, Cyclic trimers, Cyclotrimer, Cyclotrimers, Degradation, Degradation behaviour, Different products, Homogeneous cyclotrimers, Homogeneous trimers, Hybrid, Hybrid trimers, Inversed monomer linkages, Linkage, Marcel dekker, Mass spectrometry, Metathesis, Metathesis catalyst, Metathesis initiator, Microstructure, Molar, Molar amounts, Molar fraction, Monomer, Monomer placement, Neighbouring monomer units, Open points, Other hand, Polym, Polymer, Polymer chain, Polymeric systems, Present work, Probability constants, Pyrograms, Pyrolysis, Quantitative treatment, Random copolymers, Reactivity ratios, Relative abundance, Sequence distributions, Solid points, Thermal degradation, Thermal scission, Transition metal, Triad, Triad concentrations, Triad distributions, Trimer, Tsuge, Various compositions.
Abstract
Abstract: The degradation of homo- and copolymers of 1-hexyne and phenylacetylene synthesized with a Ziegler-Natta initiating system and a metathesis catalyst have been investigated by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) in order to describe the monomer arrangement in the macromolecular chains. The experiments were performed at 500°C using a Curie-point pyrolyzer and the products were separated by means of a capillary column GC. The most characteristic pyrolysis products were identified by Py-GC/MS coupling and by comparison with the retention data of anticipated degradation compounds. After discussion of the respective thermal degradation behaviour of poly(1-hexyne), polyphenylacetylene, blends of these polymers and copolymers of various compositions, the chain microstructures were studied through the quantitative treatment of the characteristic homogeneous trimers and hybrid trimers of the 1,2,4- and 1,3,5-trisubstituted benzene type formed during the pyrolysis. The relative yields of 1,2,4- and 1,3,5-cyclotrimers were quantitatively related to the corresponding head-to-head (or tail-to-tail) and head-to-tail monomer linkages in the homo- and copolymer chains. Furthermore, by applying the ‘both-side boundary effect’ theory to the molar amounts of the various cyclotrimers which depend both upon copolymer compositions and pentad sequence distributions, the relative values of the trimer formation probability constants were calculated. Then, the run number of each pyrolyzed sample was evaluated using these parameters. The analytical data thus obtained are in good agreement with those predicted by the usual theory of copolymerization.
Url:
DOI: 10.1016/S0165-2370(97)00029-6
Links to Exploration step
ISTEX:3F1FE07FC4736BFA26BB438BC63115EC84E4AA33Le document en format XML
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Alain" uniqKey="Petit A" first="Alain" last="Petit">Alain Petit</name><affiliation><mods:affiliation>Laboratoire de Chimie-Physique Macromoléculaire, CNRS-URA 494, ENSIC-INPL, 1, rue Grandville, BP 451, 54001 Nancy cedex, France</mods:affiliation></affiliation></author></analytic><monogr></monogr><series><title level="j">Journal of Analytical and Applied Pyrolysis</title><title level="j" type="abbrev">JAAP</title><idno type="ISSN">0165-2370</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="1997">1997</date><biblScope unit="volume">40–41</biblScope><biblScope unit="supplement">C</biblScope><biblScope unit="page" from="55">55</biblScope><biblScope unit="page" to="68">68</biblScope></imprint><idno type="ISSN">0165-2370</idno></series></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0165-2370</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Anal</term><term>Appl</term><term>Boundary 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composition</term><term>Cyclic trimers</term><term>Cyclotrimer</term><term>Cyclotrimers</term><term>Degradation</term><term>Degradation behaviour</term><term>Different products</term><term>Homogeneous cyclotrimers</term><term>Homogeneous trimers</term><term>Hybrid</term><term>Hybrid trimers</term><term>Inversed monomer linkages</term><term>Linkage</term><term>Marcel dekker</term><term>Mass spectrometry</term><term>Metathesis</term><term>Metathesis catalyst</term><term>Metathesis initiator</term><term>Microstructure</term><term>Molar</term><term>Molar amounts</term><term>Molar fraction</term><term>Monomer</term><term>Monomer placement</term><term>Neighbouring monomer units</term><term>Open points</term><term>Other hand</term><term>Polym</term><term>Polymer</term><term>Polymer chain</term><term>Polymeric systems</term><term>Present work</term><term>Probability constants</term><term>Pyrograms</term><term>Pyrolysis</term><term>Quantitative treatment</term><term>Random copolymers</term><term>Reactivity ratios</term><term>Relative abundance</term><term>Sequence distributions</term><term>Solid points</term><term>Thermal degradation</term><term>Thermal scission</term><term>Transition metal</term><term>Triad</term><term>Triad concentrations</term><term>Triad distributions</term><term>Trimer</term><term>Tsuge</term><term>Various compositions</term></keywords></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">Abstract: The degradation of homo- and copolymers of 1-hexyne and phenylacetylene synthesized with a Ziegler-Natta initiating system and a metathesis catalyst have been investigated by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) in order to describe the monomer arrangement in the macromolecular chains. The experiments were performed at 500°C using a Curie-point pyrolyzer and the products were separated by means of a capillary column GC. The most characteristic pyrolysis products were identified by Py-GC/MS coupling and by comparison with the retention data of anticipated degradation compounds. After discussion of the respective thermal degradation behaviour of poly(1-hexyne), polyphenylacetylene, blends of these polymers and copolymers of various compositions, the chain microstructures were studied through the quantitative treatment of the characteristic homogeneous trimers and hybrid trimers of the 1,2,4- and 1,3,5-trisubstituted benzene type formed during the pyrolysis. The relative yields of 1,2,4- and 1,3,5-cyclotrimers were quantitatively related to the corresponding head-to-head (or tail-to-tail) and head-to-tail monomer linkages in the homo- and copolymer chains. Furthermore, by applying the ‘both-side boundary effect’ theory to the molar amounts of the various cyclotrimers which depend both upon copolymer compositions and pentad sequence distributions, the relative values of the trimer formation probability constants were calculated. Then, the run number of each pyrolyzed sample was evaluated using these parameters. The analytical data thus obtained are in good agreement with those predicted by the usual theory of copolymerization.</div></front></TEI><istex><corpusName>elsevier</corpusName><keywords><teeft><json:string>copolymer</json:string><json:string>pyrolysis</json:string><json:string>trimer</json:string><json:string>appl</json:string><json:string>anal</json:string><json:string>tsuge</json:string><json:string>triad</json:string><json:string>microstructure</json:string><json:string>cyclotrimer</json:string><json:string>metathesis</json:string><json:string>chem</json:string><json:string>pyrograms</json:string><json:string>polym</json:string><json:string>molar fraction</json:string><json:string>cyclotrimers</json:string><json:string>molar</json:string><json:string>monomer</json:string><json:string>polymer</json:string><json:string>triad distributions</json:string><json:string>other hand</json:string><json:string>chemical inversions</json:string><json:string>triad concentrations</json:string><json:string>hybrid</json:string><json:string>monomer placement</json:string><json:string>copolymer chains</json:string><json:string>inversed monomer linkages</json:string><json:string>copolymer composition</json:string><json:string>quantitative treatment</json:string><json:string>solid points</json:string><json:string>marcel dekker</json:string><json:string>molar amounts</json:string><json:string>present work</json:string><json:string>sequence distributions</json:string><json:string>various compositions</json:string><json:string>hybrid trimers</json:string><json:string>random copolymers</json:string><json:string>homogeneous trimers</json:string><json:string>chain microstructures</json:string><json:string>mass spectrometry</json:string><json:string>metathesis initiator</json:string><json:string>degradation behaviour</json:string><json:string>polymeric systems</json:string><json:string>thermal degradation</json:string><json:string>reactivity ratios</json:string><json:string>boundary effect</json:string><json:string>neighbouring monomer units</json:string><json:string>different products</json:string><json:string>cyclic trimers</json:string><json:string>transition metal</json:string><json:string>thermal scission</json:string><json:string>relative abundance</json:string><json:string>homogeneous cyclotrimers</json:string><json:string>catalyst systems</json:string><json:string>polymer chain</json:string><json:string>copolymer chain</json:string><json:string>boundary effect theory</json:string><json:string>probability constants</json:string><json:string>open points</json:string><json:string>metathesis catalyst</json:string><json:string>linkage</json:string><json:string>degradation</json:string></teeft></keywords><author><json:item><name>Sandrine Duc</name><affiliations><json:string>Laboratoire de Chimie-Physique Macromoléculaire, CNRS-URA 494, ENSIC-INPL, 1, rue Grandville, BP 451, 54001 Nancy cedex, France</json:string></affiliations></json:item><json:item><name>Alain Petit</name><affiliations><json:string>Laboratoire de Chimie-Physique Macromoléculaire, CNRS-URA 494, ENSIC-INPL, 1, rue Grandville, BP 451, 54001 Nancy cedex, France</json:string></affiliations></json:item></author><language><json:string>eng</json:string></language><originalGenre><json:string>Full-length article</json:string></originalGenre><abstract>The degradation of homo- and copolymers of 1-hexyne and phenylacetylene synthesized with a Ziegler-Natta initiating system and a metathesis catalyst have been investigated by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) in order to describe the monomer arrangement in the macromolecular chains. The experiments were performed at 500°C using a Curie-point pyrolyzer and the products were separated by means of a capillary column GC. The most characteristic pyrolysis products were identified by Py-GC/MS coupling and by comparison with the retention data of anticipated degradation compounds. After discussion of the respective thermal degradation behaviour of poly(1-hexyne), polyphenylacetylene, blends of these polymers and copolymers of various compositions, the chain microstructures were studied through the quantitative treatment of the characteristic homogeneous trimers and hybrid trimers of the 1,2,4- and 1,3,5-trisubstituted benzene type formed during the pyrolysis. The relative yields of 1,2,4- and 1,3,5-cyclotrimers were quantitatively related to the corresponding head-to-head (or tail-to-tail) and head-to-tail monomer linkages in the homo- and copolymer chains. Furthermore, by applying the ‘both-side boundary effect’ theory to the molar amounts of the various cyclotrimers which depend both upon copolymer compositions and pentad sequence distributions, the relative values of the trimer formation probability constants were calculated. Then, the run number of each pyrolyzed sample was evaluated using these parameters. 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Audisio</persName></editor><imprint><publisher>ELSEVIER</publisher><date type="published" when="1997"></date><biblScope unit="volume">40–41</biblScope><biblScope unit="supplement">C</biblScope><biblScope unit="page" from="55">55</biblScope><biblScope unit="page" to="68">68</biblScope></imprint></monogr></biblStruct></sourceDesc></fileDesc><profileDesc><creation><date>1997</date></creation><langUsage><language ident="en">en</language></langUsage><abstract xml:lang="en"><p>The degradation of homo- and copolymers of 1-hexyne and phenylacetylene synthesized with a Ziegler-Natta initiating system and a metathesis catalyst have been investigated by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) in order to describe the monomer arrangement in the macromolecular chains. The experiments were performed at 500°C using a Curie-point pyrolyzer and the products were separated by means of a capillary column GC. The most characteristic pyrolysis products were identified by Py-GC/MS coupling and by comparison with the retention data of anticipated degradation compounds. After discussion of the respective thermal degradation behaviour of poly(1-hexyne), polyphenylacetylene, blends of these polymers and copolymers of various compositions, the chain microstructures were studied through the quantitative treatment of the characteristic homogeneous trimers and hybrid trimers of the 1,2,4- and 1,3,5-trisubstituted benzene type formed during the pyrolysis. The relative yields of 1,2,4- and 1,3,5-cyclotrimers were quantitatively related to the corresponding head-to-head (or tail-to-tail) and head-to-tail monomer linkages in the homo- and copolymer chains. Furthermore, by applying the ‘both-side boundary effect’ theory to the molar amounts of the various cyclotrimers which depend both upon copolymer compositions and pentad sequence distributions, the relative values of the trimer formation probability constants were calculated. Then, the run number of each pyrolyzed sample was evaluated using these parameters. The analytical data thus obtained are in good agreement with those predicted by the usual theory of copolymerization.</p></abstract></profileDesc><revisionDesc><change when="1997">Published</change></revisionDesc></teiHeader></istex:fulltextTEI><json:item><extension>txt</extension><original>false</original><mimetype>text/plain</mimetype><uri>https://api.istex.fr/document/3F1FE07FC4736BFA26BB438BC63115EC84E4AA33/fulltext/txt</uri></json:item></fulltext><metadata><istex:metadataXml wicri:clean="Elsevier, elements deleted: tail"><istex:xmlDeclaration>version="1.0" encoding="utf-8"</istex:xmlDeclaration><istex:docType PUBLIC="-//ES//DTD journal article DTD version 4.5.2//EN//XML" URI="art452.dtd" name="istex:docType"></istex:docType><istex:document><converted-article version="4.5.2" docsubtype="fla"><item-info><jid>JAAP</jid><aid>97000296</aid><ce:pii>S0165-2370(97)00029-6</ce:pii><ce:doi>10.1016/S0165-2370(97)00029-6</ce:doi><ce:copyright type="unknown" year="1997"></ce:copyright></item-info><head><ce:title>Microstructure characterization of acetylenic polymers by Curie-point pyrolysis/capillary gas chromatography/mass spectrometry</ce:title><ce:author-group><ce:author><ce:given-name>Sandrine</ce:given-name><ce:surname>Duc</ce:surname></ce:author><ce:author><ce:given-name>Alain</ce:given-name><ce:surname>Petit</ce:surname><ce:cross-ref refid="COR1"><ce:sup>∗</ce:sup></ce:cross-ref></ce:author><ce:affiliation><ce:textfn>Laboratoire de Chimie-Physique Macromoléculaire, CNRS-URA 494, ENSIC-INPL, 1, rue Grandville, BP 451, 54001 Nancy cedex, France</ce:textfn></ce:affiliation><ce:correspondence id="COR1"><ce:label>∗</ce:label><ce:text>Corresponding author.</ce:text></ce:correspondence></ce:author-group><ce:date-received day="18" month="10" year="1996"></ce:date-received><ce:date-accepted day="28" month="1" year="1997"></ce:date-accepted><ce:abstract><ce:section-title>Abstract</ce:section-title><ce:abstract-sec><ce:simple-para>The degradation of homo- and copolymers of 1-hexyne and phenylacetylene synthesized with a Ziegler-Natta initiating system and a metathesis catalyst have been investigated by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) in order to describe the monomer arrangement in the macromolecular chains. The experiments were performed at 500°C using a Curie-point pyrolyzer and the products were separated by means of a capillary column GC. The most characteristic pyrolysis products were identified by Py-GC/MS coupling and by comparison with the retention data of anticipated degradation compounds. After discussion of the respective thermal degradation behaviour of poly(1-hexyne), polyphenylacetylene, blends of these polymers and copolymers of various compositions, the chain microstructures were studied through the quantitative treatment of the characteristic homogeneous trimers and hybrid trimers of the 1,2,4- and 1,3,5-trisubstituted benzene type formed during the pyrolysis. The relative yields of 1,2,4- and 1,3,5-cyclotrimers were quantitatively related to the corresponding head-to-head (or tail-to-tail) and head-to-tail monomer linkages in the homo- and copolymer chains. Furthermore, by applying the ‘both-side boundary effect’ theory to the molar amounts of the various cyclotrimers which depend both upon copolymer compositions and pentad sequence distributions, the relative values of the trimer formation probability constants were calculated. Then, the run number of each pyrolyzed sample was evaluated using these parameters. The analytical data thus obtained are in good agreement with those predicted by the usual theory of copolymerization.</ce:simple-para></ce:abstract-sec></ce:abstract></head></converted-article></istex:document></istex:metadataXml><mods version="3.6"><titleInfo><title>Microstructure characterization of acetylenic polymers by Curie-point pyrolysis/capillary gas chromatography/mass spectrometry</title></titleInfo><titleInfo type="alternative" contentType="CDATA"><title>Microstructure characterization of acetylenic polymers by Curie-point pyrolysis/capillary gas chromatography/mass spectrometry</title></titleInfo><name type="personal"><namePart type="given">Sandrine</namePart><namePart type="family">Duc</namePart><affiliation>Laboratoire de Chimie-Physique Macromoléculaire, CNRS-URA 494, ENSIC-INPL, 1, rue Grandville, BP 451, 54001 Nancy cedex, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Alain</namePart><namePart type="family">Petit</namePart><affiliation>Laboratoire de Chimie-Physique Macromoléculaire, CNRS-URA 494, ENSIC-INPL, 1, rue Grandville, BP 451, 54001 Nancy cedex, France</affiliation><description>Corresponding author.</description><role><roleTerm type="text">author</roleTerm></role></name><typeOfResource>text</typeOfResource><genre type="research-article" displayLabel="Full-length article" authority="ISTEX" authorityURI="https://content-type.data.istex.fr" valueURI="https://content-type.data.istex.fr/ark:/67375/XTP-1JC4F85T-7">research-article</genre><originInfo><publisher>ELSEVIER</publisher><dateIssued encoding="w3cdtf">1997</dateIssued><copyrightDate encoding="w3cdtf">1997</copyrightDate></originInfo><language><languageTerm type="code" authority="iso639-2b">eng</languageTerm><languageTerm type="code" authority="rfc3066">en</languageTerm></language><abstract lang="en">Abstract: The degradation of homo- and copolymers of 1-hexyne and phenylacetylene synthesized with a Ziegler-Natta initiating system and a metathesis catalyst have been investigated by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) in order to describe the monomer arrangement in the macromolecular chains. The experiments were performed at 500°C using a Curie-point pyrolyzer and the products were separated by means of a capillary column GC. The most characteristic pyrolysis products were identified by Py-GC/MS coupling and by comparison with the retention data of anticipated degradation compounds. After discussion of the respective thermal degradation behaviour of poly(1-hexyne), polyphenylacetylene, blends of these polymers and copolymers of various compositions, the chain microstructures were studied through the quantitative treatment of the characteristic homogeneous trimers and hybrid trimers of the 1,2,4- and 1,3,5-trisubstituted benzene type formed during the pyrolysis. The relative yields of 1,2,4- and 1,3,5-cyclotrimers were quantitatively related to the corresponding head-to-head (or tail-to-tail) and head-to-tail monomer linkages in the homo- and copolymer chains. Furthermore, by applying the ‘both-side boundary effect’ theory to the molar amounts of the various cyclotrimers which depend both upon copolymer compositions and pentad sequence distributions, the relative values of the trimer formation probability constants were calculated. Then, the run number of each pyrolyzed sample was evaluated using these parameters. The analytical data thus obtained are in good agreement with those predicted by the usual theory of copolymerization.</abstract><relatedItem type="host"><titleInfo><title>Journal of Analytical and Applied Pyrolysis</title></titleInfo><titleInfo type="abbreviated"><title>JAAP</title></titleInfo><name type="conference"><namePart>PYROLYSIS '96, Venice, Italy</namePart><namePart type="date">19961014</namePart><namePart type="date">19961018</namePart></name><name type="personal"><namePart>G. Audisio</namePart><role><roleTerm type="text">editor</roleTerm></role></name><genre type="journal" authority="ISTEX" authorityURI="https://publication-type.data.istex.fr" valueURI="https://publication-type.data.istex.fr/ark:/67375/JMC-0GLKJH51-B">journal</genre><originInfo><publisher>ELSEVIER</publisher><dateIssued encoding="w3cdtf">199705</dateIssued></originInfo><identifier type="ISSN">0165-2370</identifier><identifier type="PII">S0165-2370(00)X0017-4</identifier><part><date>199705</date><detail type="issue"><title>PYROLYSIS '96, Venice, Italy</title></detail><detail type="volume"><number>40–41</number><caption>vol.</caption></detail><detail type="supplement"><number>C</number><caption>Suppl.</caption></detail><extent unit="issue-pages"><start>1</start><end>620</end></extent><extent unit="pages"><start>55</start><end>68</end></extent></part></relatedItem><identifier type="istex">3F1FE07FC4736BFA26BB438BC63115EC84E4AA33</identifier><identifier type="ark">ark:/67375/6H6-GX74BXD4-8</identifier><identifier type="DOI">10.1016/S0165-2370(97)00029-6</identifier><identifier type="PII">S0165-2370(97)00029-6</identifier><recordInfo><recordContentSource authority="ISTEX" authorityURI="https://loaded-corpus.data.istex.fr" valueURI="https://loaded-corpus.data.istex.fr/ark:/67375/XBH-HKKZVM7B-M">elsevier</recordContentSource></recordInfo></mods><json:item><extension>json</extension><original>false</original><mimetype>application/json</mimetype><uri>https://api.istex.fr/document/3F1FE07FC4736BFA26BB438BC63115EC84E4AA33/metadata/json</uri></json:item></metadata></istex></record>Pour manipuler ce document sous Unix (Dilib)
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