Pub Date : 1994-12-01DOI: 10.1002/APMC.1994.052230109
H. Cherdron, M.‐J. Brekner, F. Osan
Investigation of the polymerization process and property modification of metallocene-based cycloolefin (COC) shows that this monomer-catalyst combination enables synthesis of a new class of transparent thermoplastic polymers. Metallocene catalysis offers much opportunity to vary the composition and microstructure of the copolymers. The breadth of the polymer spectrum which can be further widened by polymer modification enables many applications for this new class of thermoplastics. The key parameters that control structure and properties in the COC family are discussed in this paper
{"title":"Cycloolefin-copolymere: Eine neue klasse transparenter thermoplaste†","authors":"H. Cherdron, M.‐J. Brekner, F. Osan","doi":"10.1002/APMC.1994.052230109","DOIUrl":"https://doi.org/10.1002/APMC.1994.052230109","url":null,"abstract":"Investigation of the polymerization process and property modification of metallocene-based cycloolefin (COC) shows that this monomer-catalyst combination enables synthesis of a new class of transparent thermoplastic polymers. Metallocene catalysis offers much opportunity to vary the composition and microstructure of the copolymers. The breadth of the polymer spectrum which can be further widened by polymer modification enables many applications for this new class of thermoplastics. The key parameters that control structure and properties in the COC family are discussed in this paper","PeriodicalId":7808,"journal":{"name":"Angewandte Makromolekulare Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1994-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73481602","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1994-12-01DOI: 10.1002/APMC.1994.052230102
B. Voit, S. Turner
Dendritic polymers are highly branched structures with globular shape and high number of functionalities. In a divergent stepwise synthesis perfect macromolecules with controlled size and architecture are obtained. From the broad variety of dendrimer structures some examples are given and the properties of these unusual polymers are illustrated. For comparison the hyperbranched polymers, dentritic structures with defects made in a one-pot polycondensation reaction, are discussed. Differences and conformities of properties like molecular weight distributions, functionalities, solubility, viscosity behavior and glass transition temperatures for both globular polymer structures are explained
{"title":"Dendritische und “hyperbranched” Polymere. Beispiele für die Beeinflussung von Polymereigenschaften durch gezielte Synthese von dreidimensionalen Strukturen†","authors":"B. Voit, S. Turner","doi":"10.1002/APMC.1994.052230102","DOIUrl":"https://doi.org/10.1002/APMC.1994.052230102","url":null,"abstract":"Dendritic polymers are highly branched structures with globular shape and high number of functionalities. In a divergent stepwise synthesis perfect macromolecules with controlled size and architecture are obtained. From the broad variety of dendrimer structures some examples are given and the properties of these unusual polymers are illustrated. For comparison the hyperbranched polymers, dentritic structures with defects made in a one-pot polycondensation reaction, are discussed. Differences and conformities of properties like molecular weight distributions, functionalities, solubility, viscosity behavior and glass transition temperatures for both globular polymer structures are explained","PeriodicalId":7808,"journal":{"name":"Angewandte Makromolekulare Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1994-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82536414","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1994-12-01DOI: 10.1002/APMC.1994.052230107
C. Eisenbach, Wolfgang Lieberth, B. Sperlich
The free radical copolymerization and multipolymerization of olefins with acrylic monomers in the presence of acids has been studied. It was found that Bronsted acids are as suitable complexing agents for the acrylic comonomer as the up to now exclusively used Lewis acids. The effectiveness of the Bronsted acids, e.g. carboxylic acids, for obtaining alternating copolymers increased with the pKs value, and trifluoroacetic acid turned out to be the acid of choice. The variation of the Lewis acid-type complexation agents was extended by the zinc chloride diethylether complex which is advantageous over ZnCl 2 or other Lewis acids because of its good solubility and recycling practically, which is also a feature of the Bronsted acids
{"title":"Copolymers with periodic comonomer sequences","authors":"C. Eisenbach, Wolfgang Lieberth, B. Sperlich","doi":"10.1002/APMC.1994.052230107","DOIUrl":"https://doi.org/10.1002/APMC.1994.052230107","url":null,"abstract":"The free radical copolymerization and multipolymerization of olefins with acrylic monomers in the presence of acids has been studied. It was found that Bronsted acids are as suitable complexing agents for the acrylic comonomer as the up to now exclusively used Lewis acids. The effectiveness of the Bronsted acids, e.g. carboxylic acids, for obtaining alternating copolymers increased with the pKs value, and trifluoroacetic acid turned out to be the acid of choice. The variation of the Lewis acid-type complexation agents was extended by the zinc chloride diethylether complex which is advantageous over ZnCl 2 or other Lewis acids because of its good solubility and recycling practically, which is also a feature of the Bronsted acids","PeriodicalId":7808,"journal":{"name":"Angewandte Makromolekulare Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1994-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77498030","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1994-12-01DOI: 10.1002/APMC.1994.052230105
R. Kopp, Gerhard Dr. Grögler, Heinrich Dr Hes, E. Prolingheuer, H. Casselmann
engStorage-stable polyurethane one-pack systems are usually cured either by moisture from the environment or by splitting off a blocking agent. The curing characteristics of moisture-curing isocyanate-prepolymers are strongly dependent on humidity and temperature whilst in the case of blocked isocyanate systems special care has to be taken to avoid air pollution. New heterogeneous systems on the basis of usual isocyanate-reactive compounds and solid polyisocyanate particles, which are surrounded by a diffusion-barrier-layer, are highly storage-stable und cure even in thick layers without the need of humidity and without formation of volatile blocking agents or by-products
{"title":"Neuartige Einkomponenten-Reaktiv-Systeme auf basis von festen Polyisocyanaten","authors":"R. Kopp, Gerhard Dr. Grögler, Heinrich Dr Hes, E. Prolingheuer, H. Casselmann","doi":"10.1002/APMC.1994.052230105","DOIUrl":"https://doi.org/10.1002/APMC.1994.052230105","url":null,"abstract":"engStorage-stable polyurethane one-pack systems are usually cured either by moisture from the environment or by splitting off a blocking agent. The curing characteristics of moisture-curing isocyanate-prepolymers are strongly dependent on humidity and temperature whilst in the case of blocked isocyanate systems special care has to be taken to avoid air pollution. New heterogeneous systems on the basis of usual isocyanate-reactive compounds and solid polyisocyanate particles, which are surrounded by a diffusion-barrier-layer, are highly storage-stable und cure even in thick layers without the need of humidity and without formation of volatile blocking agents or by-products","PeriodicalId":7808,"journal":{"name":"Angewandte Makromolekulare Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1994-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81496813","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1994-12-01DOI: 10.1002/APMC.1994.052230103
O. Nuyken
New developments in the synthesis of telechelics, macromonomers, block- and graft copolymers are presented. Synthetic strategies for them are demonstrated with examples from different fields such as polycondensation, radical, anionic, and cationic polymerization, chain cleavage and criss-cross-cycloaddition
{"title":"Massgeschneiderte Polymere : Synthesestrategien für Telechele, Makromonomere, Block- und Pfropfcopolymere","authors":"O. Nuyken","doi":"10.1002/APMC.1994.052230103","DOIUrl":"https://doi.org/10.1002/APMC.1994.052230103","url":null,"abstract":"New developments in the synthesis of telechelics, macromonomers, block- and graft copolymers are presented. Synthetic strategies for them are demonstrated with examples from different fields such as polycondensation, radical, anionic, and cationic polymerization, chain cleavage and criss-cross-cycloaddition","PeriodicalId":7808,"journal":{"name":"Angewandte Makromolekulare Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1994-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73944991","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1994-12-01DOI: 10.1002/APMC.1994.052230114
E. Klemm, Nils Kottner, Gamil Alhakimi
New polymers with an alternating sequence of aliphatic chains and coronands were synthesized via Diels-Alder addition polymerization of bis(2-pyrones) with bismaleimides. The chemical structures of these polymers 6 are supported by NMR spectra, model reactions and crystal X-ray structure analysis.
{"title":"Hochmolekulare lösliche polymere mit coronandenstruktur‐synthese und eigenschaften","authors":"E. Klemm, Nils Kottner, Gamil Alhakimi","doi":"10.1002/APMC.1994.052230114","DOIUrl":"https://doi.org/10.1002/APMC.1994.052230114","url":null,"abstract":"New polymers with an alternating sequence of aliphatic chains and coronands were synthesized via Diels-Alder addition polymerization of bis(2-pyrones) with bismaleimides. The chemical structures of these polymers 6 are supported by NMR spectra, model reactions and crystal X-ray structure analysis.","PeriodicalId":7808,"journal":{"name":"Angewandte Makromolekulare Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1994-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74656837","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1994-12-01DOI: 10.1002/APMC.1994.052230115
Michael Geck, Bernward Deubzer, J. Weis
Intramolecularly crosslinked poly(organosiloxane) particles are prepared by means of emulsion polycondensation or emulsion polymerization of alkoxysilanes or cyclic organic siloxanes. Starting from these intramolecularly crosslinked poly(organosiloxane) particles, graft copolymers are obtained by free-radical emulsion polymerization of unsaturated olefinic monomers (e.g. acrylates, styrene) in the presence of (functionalized) organosiloxanes. Intramolecularly crosslinked poly(siloxane) particles and their graft copolymers are characterized by means of light scattering (in dispersion), electron microscopy and thermal analyses (DSC, DMTA)
{"title":"Intramolekular vernetzte poly(organosiloxan)partikel","authors":"Michael Geck, Bernward Deubzer, J. Weis","doi":"10.1002/APMC.1994.052230115","DOIUrl":"https://doi.org/10.1002/APMC.1994.052230115","url":null,"abstract":"Intramolecularly crosslinked poly(organosiloxane) particles are prepared by means of emulsion polycondensation or emulsion polymerization of alkoxysilanes or cyclic organic siloxanes. Starting from these intramolecularly crosslinked poly(organosiloxane) particles, graft copolymers are obtained by free-radical emulsion polymerization of unsaturated olefinic monomers (e.g. acrylates, styrene) in the presence of (functionalized) organosiloxanes. Intramolecularly crosslinked poly(siloxane) particles and their graft copolymers are characterized by means of light scattering (in dispersion), electron microscopy and thermal analyses (DSC, DMTA)","PeriodicalId":7808,"journal":{"name":"Angewandte Makromolekulare Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1994-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83770319","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1994-12-01DOI: 10.1002/APMC.1994.052230101
E. Goethals, P. Caeter, J. Geeraert, F. D. Prez
After a general classification of the cationic ring-opening polymerizations (CROP's) according to their polymerization mechanism, a number of examples of tailored polymers based on CROP are presented. The monomers used for the synthesis of these tailored structures are tetrahydrofuran (THF), N-tert-butyl aziridine (TBA), 2-methyl-1,3-oxazoline (MeOX) and 1,3-dioxolane (DXL). The polymer structures include different block and graft copolymers, macromonomers, star-shaped polymers, polymer networks and interpenetrating polymer networks (IPNs)
{"title":"Tailored polymers by cationic ring‐opening polymerization","authors":"E. Goethals, P. Caeter, J. Geeraert, F. D. Prez","doi":"10.1002/APMC.1994.052230101","DOIUrl":"https://doi.org/10.1002/APMC.1994.052230101","url":null,"abstract":"After a general classification of the cationic ring-opening polymerizations (CROP's) according to their polymerization mechanism, a number of examples of tailored polymers based on CROP are presented. The monomers used for the synthesis of these tailored structures are tetrahydrofuran (THF), N-tert-butyl aziridine (TBA), 2-methyl-1,3-oxazoline (MeOX) and 1,3-dioxolane (DXL). The polymer structures include different block and graft copolymers, macromonomers, star-shaped polymers, polymer networks and interpenetrating polymer networks (IPNs)","PeriodicalId":7808,"journal":{"name":"Angewandte Makromolekulare Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1994-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80668413","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1994-12-01DOI: 10.1002/APMC.1994.052230110
W. Heitz
While metal-catalysed polymerizations are chain reactions with constant valence of the metal, metal-catalysed polycondensations are step polymerizations with changing valence of the metal. Taking as examples the Pd-catalysed vinyl polymerization of norbornene, the alternating copolymerization of ethylene and carbon monoxide, and the Heck reaction, the essential structural prerequisites of the catalyst to control those reactions are presented. Metal-catalysed polycondensations may occur as one- or two-electron processes. The oxidative polymerization of 2,6-dimethylphenol, and the Ni-catalysed polyphenylene synthesis are discussed
{"title":"Übergangsmetall‐katalysierte kondensations‐ und polykondensationsreaktionen","authors":"W. Heitz","doi":"10.1002/APMC.1994.052230110","DOIUrl":"https://doi.org/10.1002/APMC.1994.052230110","url":null,"abstract":"While metal-catalysed polymerizations are chain reactions with constant valence of the metal, metal-catalysed polycondensations are step polymerizations with changing valence of the metal. Taking as examples the Pd-catalysed vinyl polymerization of norbornene, the alternating copolymerization of ethylene and carbon monoxide, and the Heck reaction, the essential structural prerequisites of the catalyst to control those reactions are presented. Metal-catalysed polycondensations may occur as one- or two-electron processes. The oxidative polymerization of 2,6-dimethylphenol, and the Ni-catalysed polyphenylene synthesis are discussed","PeriodicalId":7808,"journal":{"name":"Angewandte Makromolekulare Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1994-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90869674","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1994-12-01DOI: 10.1002/APMC.1994.052230112
H. Ritter
The present paper deals with the synthesis and modification of functionalized polymers characterized by a special molecular architecture. The reactivity of a functionalized polymer with comb-like structure can be controlled in a significant manner by the crystalline order of the side chains. In contrast, photocrosslinking of comb-like polymers containing cinnamic components in the side chains influences the crystallization process. The air drying process of a modified polybutadiene system with comb-like structure was shown to depend sensitivity on the side chain order
{"title":"Funktionalisierte Kammpolymere: Synthesen, modifizierung und anwendungen","authors":"H. Ritter","doi":"10.1002/APMC.1994.052230112","DOIUrl":"https://doi.org/10.1002/APMC.1994.052230112","url":null,"abstract":"The present paper deals with the synthesis and modification of functionalized polymers characterized by a special molecular architecture. The reactivity of a functionalized polymer with comb-like structure can be controlled in a significant manner by the crystalline order of the side chains. In contrast, photocrosslinking of comb-like polymers containing cinnamic components in the side chains influences the crystallization process. The air drying process of a modified polybutadiene system with comb-like structure was shown to depend sensitivity on the side chain order","PeriodicalId":7808,"journal":{"name":"Angewandte Makromolekulare Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1994-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73273257","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}