Pub Date : 1998-03-01DOI: 10.1002/(SICI)1522-9505(19980301)255:1<67::AID-APMC67>3.0.CO;2-#
T. Schulze, E. Klemm
The crosslinking copolymerization of two 9-substituted 4-methylene-3,5,8,10-tetraoxabicyclo[5.3.0]decanes (1 and 2) with 3,9-dimethylene-2,4,8,10-tetraoxa-spiro[5.5]undecane (3) or ethylene glycol dimethacrylate (4) was investigated. Dependent on the amount of bifunctional agent added, the material properties can be controlled and change from highly viscous to mechanically hard, as the extent of crosslinking increases. Combined with bicyclic monomers, the influence of the crosslinkers on the polymerization shrinkage is low.
{"title":"Crosslinking copolymerization of cyclic ketenacetals","authors":"T. Schulze, E. Klemm","doi":"10.1002/(SICI)1522-9505(19980301)255:1<67::AID-APMC67>3.0.CO;2-#","DOIUrl":"https://doi.org/10.1002/(SICI)1522-9505(19980301)255:1<67::AID-APMC67>3.0.CO;2-#","url":null,"abstract":"The crosslinking copolymerization of two 9-substituted 4-methylene-3,5,8,10-tetraoxabicyclo[5.3.0]decanes (1 and 2) with 3,9-dimethylene-2,4,8,10-tetraoxa-spiro[5.5]undecane (3) or ethylene glycol dimethacrylate (4) was investigated. Dependent on the amount of bifunctional agent added, the material properties can be controlled and change from highly viscous to mechanically hard, as the extent of crosslinking increases. Combined with bicyclic monomers, the influence of the crosslinkers on the polymerization shrinkage is low.","PeriodicalId":7808,"journal":{"name":"Angewandte Makromolekulare Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1998-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87412368","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 : 1996-12-01DOI: 10.1002/APMC.1996.052430102
J. Fleischhauer, G. Schmidt-Naake, D. Scheller
Fur die radikalischen Copolymerisationen von α-Methylstyrol (MS) mit Methacrylnitril (MAN) sowie MS mit Acrylnitril (AN) wurden Untersuchungen zur Prufung der in der Literatur postulierten kinetischen Modelle des „sequenzlangenunabhangigen” bzw. „sequenzlangenabhangigen” Terminalmodells mit Depolymerisationsschritten durchgefuhrt. Sie basieren auf Analysen der Sequenzverteilungen aus 13C-NMR-Spektren. Resultate von 13C-NMR-Untersuchungen an MS/MAN-Polymeren variabler Zusammensetzung werden vorgestellt. Reaktionsparameter und Gleichgewichtskonstanten wurden direkt aus den Informationen der 13C-NMR-Spektren fur das Terminalmodell mit Depolymerisationsschritten in Abhangigkeit von der Reaktionstemperatur der Polymeren bestimmt. Hieraus konnten die Polymerisationsenthalpie ΔH = 26,5 ± 0,5 kJ mol−1, die Polymerisationsentropie ΔS = 95 ± 5 J mol−1 K−1 sowie die Ceilingtemperatur Tceiling = 65 ± 1°C fur MS bestimmt werden. Es wurde nachgewiesen, das im Rahmen der Terminalnaherung auch mit Berucksichtigung von Depolymerisationseinflussen keine adaquate Beschreibung des Copolymerisationsverhaltens im Falle der untersuchten Systeme moglich ist. Vielmehr konnten als Ergebnis der Untersuchungen sowohl in Copolymeren von MS mit AN als auch mit MAN signifikante Penultimate-Effekte nachgewiesen werden. Aufbauend auf diesen Ergebnissen wird die Anwendung eines auf einer Penultimate-Naherung basierenden Modells, welches auch das Gleichgewicht in den Wachstumsreaktionen von MS berucksichtigt, zur theoretischen Vorhersage des Copolymerisationsverhaltens vorgeschlagen. For radical copolymerizations of α-methylstyrene (MS) with methacrylonitrile (MAN) and of MS with acrylonitrile (AN) studies were carried out to examine postulations of kinetic models known from literature, in particular the terminal model with chain-length-independent and chain-length-dependent depolymerization steps. The results of investigations were based on measurements of the sequence length distributions from 13C-NMR spectra. Analyses of MS/MAN copolymers with various compositions were carried out. Reaction parameters and depolymerization constants depending on temperature were calculated. The values of enthalpy and entropy of polymerization and the ceiling temperature were computed for MS to ΔH = 26,5 ± 0,5 kJ mol−1, ΔS = 95 ± 5 J mol−1 K−1, Tceiling = 65 ± 1°C. The terminal model with depolymerization steps turned out to be wrong for the accurate description of the polymerization behaviour in case of the tested systems. Results clearly show important penultimate effects. At the point of knowledge, the description of the polymerization behaviour in terms of a penultimate model with depolymerization steps are suggested.
够给radikalischen Copolymerisationen的α-Methylstyrol (m) Methacrylnitril (MAN)及m与Acrylnitril(的)被调查结果对Prufung文学中印象. sequenzlangenunabhangigen的动态模型和“sequenzlangenabhangigen”Terminalmodells Depolymerisationsschritten durchgefuhrt .它们依赖于13c ncd光谱的断层分布分析。提出了13c nmri测试m和人聚合物组成的结果。反应参数与平衡常数直接来源于13c nmri所使用的与终端模调频相关信息以及与聚合物共同化过程的交替。的人员可以PolymerisationsenthalpieΔH =含有7±0.5 kJ小馬−1,PolymerisationsentropieΔS = 95±5 J小馬−1 K−1以及Ceilingtemperatur Tceiling = 65±1°C指定为m .研究结果表明，在定期工作中可能没有考虑露水运动员产生的工作邀请，因此不能考虑对被调查的系统进行组合处理行为的考虑。结果表明，在MS中全身都会有明显的尾部效应，也有明显的尾部效应。在这一结果的基础上，基于天平拉动的模型被提出为理论预测铜化的预测。这一模型使用的是一种基于天平拉动的模型，它关注了MS的增长反应平衡。For radical copolymerizations ofα-methylstyrene (m)和methacrylonitrile(人们)与带acrylonitrile of m()研究中心的地方carried out to examine postulations是非从literature of kinetic模,particular们在终端模特和chain-length-independent chain-length-dependent depolymerization张开.根据13c先生其它部门的员工生存参数测量和死亡控制温度下降是计算机跟踪The values of enthalpy and of polymerization收集and The亦无边temperature那时computed for m toΔH =含有7±0.5 kJ小馬−1,ΔS = 95±5 J小馬−1 K−1,Tceiling = 65±1°C .失败而失败的步骤最后可以预测到他们推出了丰功表演至少在知识的成熟阶段，即理解
{"title":"Untersuchungen zum Reaktionsverhalten beim Vorliegen von Depolymerisationsreaktionen: Untersuchung von Copolymerisationen des α-methylstyrols","authors":"J. Fleischhauer, G. Schmidt-Naake, D. Scheller","doi":"10.1002/APMC.1996.052430102","DOIUrl":"https://doi.org/10.1002/APMC.1996.052430102","url":null,"abstract":"Fur die radikalischen Copolymerisationen von α-Methylstyrol (MS) mit Methacrylnitril (MAN) sowie MS mit Acrylnitril (AN) wurden Untersuchungen zur Prufung der in der Literatur postulierten kinetischen Modelle des „sequenzlangenunabhangigen” bzw. „sequenzlangenabhangigen” Terminalmodells mit Depolymerisationsschritten durchgefuhrt. Sie basieren auf Analysen der Sequenzverteilungen aus 13C-NMR-Spektren. Resultate von 13C-NMR-Untersuchungen an MS/MAN-Polymeren variabler Zusammensetzung werden vorgestellt. Reaktionsparameter und Gleichgewichtskonstanten wurden direkt aus den Informationen der 13C-NMR-Spektren fur das Terminalmodell mit Depolymerisationsschritten in Abhangigkeit von der Reaktionstemperatur der Polymeren bestimmt. Hieraus konnten die Polymerisationsenthalpie ΔH = 26,5 ± 0,5 kJ mol−1, die Polymerisationsentropie ΔS = 95 ± 5 J mol−1 K−1 sowie die Ceilingtemperatur Tceiling = 65 ± 1°C fur MS bestimmt werden. Es wurde nachgewiesen, das im Rahmen der Terminalnaherung auch mit Berucksichtigung von Depolymerisationseinflussen keine adaquate Beschreibung des Copolymerisationsverhaltens im Falle der untersuchten Systeme moglich ist. Vielmehr konnten als Ergebnis der Untersuchungen sowohl in Copolymeren von MS mit AN als auch mit MAN signifikante Penultimate-Effekte nachgewiesen werden. Aufbauend auf diesen Ergebnissen wird die Anwendung eines auf einer Penultimate-Naherung basierenden Modells, welches auch das Gleichgewicht in den Wachstumsreaktionen von MS berucksichtigt, zur theoretischen Vorhersage des Copolymerisationsverhaltens vorgeschlagen. \u0000 \u0000 \u0000 \u0000For radical copolymerizations of α-methylstyrene (MS) with methacrylonitrile (MAN) and of MS with acrylonitrile (AN) studies were carried out to examine postulations of kinetic models known from literature, in particular the terminal model with chain-length-independent and chain-length-dependent depolymerization steps. The results of investigations were based on measurements of the sequence length distributions from 13C-NMR spectra. Analyses of MS/MAN copolymers with various compositions were carried out. Reaction parameters and depolymerization constants depending on temperature were calculated. The values of enthalpy and entropy of polymerization and the ceiling temperature were computed for MS to ΔH = 26,5 ± 0,5 kJ mol−1, ΔS = 95 ± 5 J mol−1 K−1, Tceiling = 65 ± 1°C. The terminal model with depolymerization steps turned out to be wrong for the accurate description of the polymerization behaviour in case of the tested systems. Results clearly show important penultimate effects. At the point of knowledge, the description of the polymerization behaviour in terms of a penultimate model with depolymerization steps are suggested.","PeriodicalId":7808,"journal":{"name":"Angewandte Makromolekulare Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1996-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84997522","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 : 1996-08-01DOI: 10.1002/APMC.1996.052400126
A. Matsumoto, A. Okamoto, S. Okuno, Hiroyuki Aota
The critical conditions in which the classical Flory-Stockmayer gelation theory (F-S theory) is applicable to monovinyl-divinyl copolymerizations were pursued in detail. The resulting prepolymers or precursors of ideal crosslinked-polymers were characterized as standard polymers for the discussion of network formation in free-radical monovinyl-divinyl copolymerizations. Methyl methacrylate was copolymerized with a small amount of ethylene dimethacrylate, butylene dimethacrylate or nonapropyleneglycol dimethacrylate in the presence of lauryl mercaptan, a chain transfer agent to reduce the occurrence of a thermodynamic excluded volume effect and intramolecular crosslinking as the primary and secondary factors, respectively, for the greatly delayed gelation in the free-radical monovinyl-divinyl copolymerizations and, moreover, to keep the primary chain length constant by inhibiting a get effect. The ratio of the actual get point to the theoretical one reached 1.1, supporting the validity of F-S theory. The resulting prepolymers were subjected to SEC-MALLS analysis to determine the molecular weights, the molecular-weight distributions and the radii of gyration ; the correlations of molecular weight vs. elution volume and radius of gyration vs. molecular weight were useful for the characterization of the precursors of ideal network-polymers.
{"title":"Ideal crosslinked‐polymers and their characterization in free‐radical monovinyl‐divinyl copolymerizations","authors":"A. Matsumoto, A. Okamoto, S. Okuno, Hiroyuki Aota","doi":"10.1002/APMC.1996.052400126","DOIUrl":"https://doi.org/10.1002/APMC.1996.052400126","url":null,"abstract":"The critical conditions in which the classical Flory-Stockmayer gelation theory (F-S theory) is applicable to monovinyl-divinyl copolymerizations were pursued in detail. The resulting prepolymers or precursors of ideal crosslinked-polymers were characterized as standard polymers for the discussion of network formation in free-radical monovinyl-divinyl copolymerizations. Methyl methacrylate was copolymerized with a small amount of ethylene dimethacrylate, butylene dimethacrylate or nonapropyleneglycol dimethacrylate in the presence of lauryl mercaptan, a chain transfer agent to reduce the occurrence of a thermodynamic excluded volume effect and intramolecular crosslinking as the primary and secondary factors, respectively, for the greatly delayed gelation in the free-radical monovinyl-divinyl copolymerizations and, moreover, to keep the primary chain length constant by inhibiting a get effect. The ratio of the actual get point to the theoretical one reached 1.1, supporting the validity of F-S theory. The resulting prepolymers were subjected to SEC-MALLS analysis to determine the molecular weights, the molecular-weight distributions and the radii of gyration ; the correlations of molecular weight vs. elution volume and radius of gyration vs. molecular weight were useful for the characterization of the precursors of ideal network-polymers.","PeriodicalId":7808,"journal":{"name":"Angewandte Makromolekulare Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1996-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86201318","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 : 1996-08-01DOI: 10.1002/APMC.1996.052400118
T. Takigawa, K. Urayama, S. Yamasaki, T. Masuda
Elastic properties of real elastomers were examined by using partial derivatives of the strain energy density function (W) with respect to the invariant (I i , i=1,2,3) of deformation tensor. The values of the derivatives at zero strain limit for styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR) and butadiene rubber (BR) were compared with those derived from the theory shown in the previous paper, where compressibility of the materials was taken into account. The asymptotic behavior of the derivatives for isoprene rubber (IR) and segmented polyurethaneurea (SPU) was also compared with those of the three types of rubbers. It was shown that the theoretical predictions for the limiting value agreed fairly well with the experimental values of the elastomers.
利用应变能密度函数(W)对变形张量的不变量(I I, I =1,2,3)的偏导数，研究了实际弹性体的弹性特性。将丁苯橡胶(SBR)、丁腈橡胶(NBR)和丁二烯橡胶(BR)在零应变极限下的导数值与考虑材料可压缩性的理论推导值进行了比较。对异戊二烯橡胶(IR)和分段聚氨酯(SPU)衍生物的渐近行为进行了比较。结果表明，理论预测的极限值与弹性体的实验值吻合较好。
{"title":"Elastic properties of real elastomers at small deformations","authors":"T. Takigawa, K. Urayama, S. Yamasaki, T. Masuda","doi":"10.1002/APMC.1996.052400118","DOIUrl":"https://doi.org/10.1002/APMC.1996.052400118","url":null,"abstract":"Elastic properties of real elastomers were examined by using partial derivatives of the strain energy density function (W) with respect to the invariant (I i , i=1,2,3) of deformation tensor. The values of the derivatives at zero strain limit for styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR) and butadiene rubber (BR) were compared with those derived from the theory shown in the previous paper, where compressibility of the materials was taken into account. The asymptotic behavior of the derivatives for isoprene rubber (IR) and segmented polyurethaneurea (SPU) was also compared with those of the three types of rubbers. It was shown that the theoretical predictions for the limiting value agreed fairly well with the experimental values of the elastomers.","PeriodicalId":7808,"journal":{"name":"Angewandte Makromolekulare Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1996-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86905500","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 : 1996-08-01DOI: 10.1002/APMC.1996.052400113
Teruo Sasaki
Seismic isolation was reconfirmed to be extremely efficient for the protection of buildings, and hence human life, on the occasion of the Great Hanshin Earthquake. Rubber bearings are placed under the buildings for isolation, and thus the type of rubber bearings is a dominant factor for efficient isolation. In this report, the performance of peripherally restraining type rubber bearing (PRB) was examined where its contracted model was found to simulate the performance of full scale PRB precisely. Damping ratio and vertical spring constant of PRB are as good as the existing ones. PRB showed lower critical shear strain, but it was concluded that no problems were found for the actual use of PRB.
{"title":"Peripherally restraining type rubber bearing","authors":"Teruo Sasaki","doi":"10.1002/APMC.1996.052400113","DOIUrl":"https://doi.org/10.1002/APMC.1996.052400113","url":null,"abstract":"Seismic isolation was reconfirmed to be extremely efficient for the protection of buildings, and hence human life, on the occasion of the Great Hanshin Earthquake. Rubber bearings are placed under the buildings for isolation, and thus the type of rubber bearings is a dominant factor for efficient isolation. In this report, the performance of peripherally restraining type rubber bearing (PRB) was examined where its contracted model was found to simulate the performance of full scale PRB precisely. Damping ratio and vertical spring constant of PRB are as good as the existing ones. PRB showed lower critical shear strain, but it was concluded that no problems were found for the actual use of PRB.","PeriodicalId":7808,"journal":{"name":"Angewandte Makromolekulare Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1996-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81405985","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 : 1996-07-01DOI: 10.1002/APMC.1996.052390113
J. Michalek, J. Vacík, Jana Kúdelková, N. Ježová
Macromonomers of various chain lengths with an average of three allyl double bonds per chain were prepared by anionic copolymerization of allyl methacrylate with methyl methacrylate. The macromonomers were characterized by gel permeation chromatography and nuclear magnetic resonance. The macromonomers were then copolymerized with 1-vinyl-2-pyrrolidone to form three-dimensional structures. Their optical, swelling and mechanical properties were studied and the crosslinking efficiency was determined. The copolymer properties are not greatly affected by macromonomer chain lengths up to 40-mers; above 50-mers there is a slight decrease in the equilibrium water content and a significant increase in the modulus of elasticity. The crosslinking efficiency depends on the macromonomer chain length; a marked increase was observed for the 50-mer because of a greater number of methyl-methyl interactions. Copolymers have favourable strength-strain properties and a low content of water-soluble extracts, in which the IR analysis demonstrated the presence of 1-vinyl-2-pyrrolidone homopolymers. In spite of the good results obtained for all the macromonomers described in this work, the 50-mer seems to be optimal for copolymerization with 1-vinyl-2-pyrrolidone. Durch anionische Copolymerisation von Allylmethacrylat und Methylmethacrylat wurden Makromonomere unterschiedlicher Kettenlange mit durchschnittlich drei Allyl-Doppelbindungen pro Kette hergestellt und mit NMR-Spektroskopie und Gelpermeationschromatographie charakterisiert. Durch Copolymerisation der Makromonomeren mit 1-Vinyl-2-pyrrolidon wurden dreidimensionale Strukturen erhalten. Die optischen und mechanischen Eigenschaften der Produkte wurden untersucht, und die Quellungseigenschaften und Vernetzungsgrade wurden bestimmt. Die Copolymereigenschaften wurden durch Makromonomere mit Kettenlangen bis 40 Einheiten nur wenig beeinflust. Bei Kettenlangen uber 50 Einheiten wurde eine leichte Abnahme der Wasseraufnahmefahigkeit und eine deutliche Erhahung des Elastizitatsmoduls beobachtet. Die Vernetzungsgrade hangen von der Makromonomer-Kettenlange ab; eine merkliche Erhohung aufgrund der grooseren Zahl an Methyl-Methyl-Wechselwirkungen wurde bei Kettenlangen uber 50 Einheiten festgestellt. Die Copolymeren zeigen gunstige Festigkeits-Dehnungs-Eigenschaften und einen geringen Gehalt an wasserloslichen Extrakten, in denen durch IR-Spektroskopie 1-Vinyl-2-pyrrolidon-Homopolymere identifiziert wurden. Obwohl mit allen untersuchten Makromonomeren gute Resultate erzielt wurden, scheint fur die Copolymerisation mit 1-Vinyl-2-pyrrolidon das Makromonomere mit 50 Einheiten am besten geeignet.
{"title":"Hydrogels for biomedical use based on 1‐vinyl‐2‐pyrrolidone crosslinked with macromonomers","authors":"J. Michalek, J. Vacík, Jana Kúdelková, N. Ježová","doi":"10.1002/APMC.1996.052390113","DOIUrl":"https://doi.org/10.1002/APMC.1996.052390113","url":null,"abstract":"Macromonomers of various chain lengths with an average of three allyl double bonds per chain were prepared by anionic copolymerization of allyl methacrylate with methyl methacrylate. The macromonomers were characterized by gel permeation chromatography and nuclear magnetic resonance. The macromonomers were then copolymerized with 1-vinyl-2-pyrrolidone to form three-dimensional structures. Their optical, swelling and mechanical properties were studied and the crosslinking efficiency was determined. The copolymer properties are not greatly affected by macromonomer chain lengths up to 40-mers; above 50-mers there is a slight decrease in the equilibrium water content and a significant increase in the modulus of elasticity. The crosslinking efficiency depends on the macromonomer chain length; a marked increase was observed for the 50-mer because of a greater number of methyl-methyl interactions. Copolymers have favourable strength-strain properties and a low content of water-soluble extracts, in which the IR analysis demonstrated the presence of 1-vinyl-2-pyrrolidone homopolymers. In spite of the good results obtained for all the macromonomers described in this work, the 50-mer seems to be optimal for copolymerization with 1-vinyl-2-pyrrolidone. \u0000 \u0000 \u0000 \u0000Durch anionische Copolymerisation von Allylmethacrylat und Methylmethacrylat wurden Makromonomere unterschiedlicher Kettenlange mit durchschnittlich drei Allyl-Doppelbindungen pro Kette hergestellt und mit NMR-Spektroskopie und Gelpermeationschromatographie charakterisiert. Durch Copolymerisation der Makromonomeren mit 1-Vinyl-2-pyrrolidon wurden dreidimensionale Strukturen erhalten. Die optischen und mechanischen Eigenschaften der Produkte wurden untersucht, und die Quellungseigenschaften und Vernetzungsgrade wurden bestimmt. Die Copolymereigenschaften wurden durch Makromonomere mit Kettenlangen bis 40 Einheiten nur wenig beeinflust. Bei Kettenlangen uber 50 Einheiten wurde eine leichte Abnahme der Wasseraufnahmefahigkeit und eine deutliche Erhahung des Elastizitatsmoduls beobachtet. Die Vernetzungsgrade hangen von der Makromonomer-Kettenlange ab; eine merkliche Erhohung aufgrund der grooseren Zahl an Methyl-Methyl-Wechselwirkungen wurde bei Kettenlangen uber 50 Einheiten festgestellt. Die Copolymeren zeigen gunstige Festigkeits-Dehnungs-Eigenschaften und einen geringen Gehalt an wasserloslichen Extrakten, in denen durch IR-Spektroskopie 1-Vinyl-2-pyrrolidon-Homopolymere identifiziert wurden. Obwohl mit allen untersuchten Makromonomeren gute Resultate erzielt wurden, scheint fur die Copolymerisation mit 1-Vinyl-2-pyrrolidon das Makromonomere mit 50 Einheiten am besten geeignet.","PeriodicalId":7808,"journal":{"name":"Angewandte Makromolekulare Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1996-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85045568","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 : 1996-07-01DOI: 10.1002/APMC.1996.052390110
R. Kaulbach, U. Gebauer, C. Mähner, M. Lechner, K. Gehrke
Fur die Copolymerisation von 1,3-Butadien mit Propylenoxid wurde nach dem Vergleich der drei Katalysatorsysteme Nd(Oct)3/Al2Cl3ET3/Al(i-But)3, Ni(Oct)2/ BF3OEt2/AlEt3 und Al(i-But)3/I2/TiCl4 das Titankatalysatorsystem eingesetzt. Neben dem Einflus der Monomerzusammensetzung auf den Umsatz, die Microstruktur, die Copolymerzusammensetzung, die Molmassen sowie die Molmassenverteilungen wurden auch die Polymerisationszeit und das Aluminium/Titan-Verhaltnis untersucht. Die Copolymerisationsparameter wurden nach Kelen-Tudős zu rButadien = 0,9 und rPropylenoxid = 3,9 bestimmt. Der Copolymernachweis erfolgte uber 13C-NMR-Spektroskopie und Extraktionsuntersuchungen in Verbindung mit 1H-NMR-Spektroskopie. After comparison of three catalyst systems, i.e. [Nd(Oct)3/Al2Cl3ET3/Al(i-But)3, Ni(Oct)2/BF3OEt2/AlEt3 and Al(i-But)3/I2/TiCl4] the titanium catalyst system was used for the copolymerization of 1,3-butadiene with propylene oxide. The effects of monomer ratio on copolymer composition, conversion, microstructure, molar mass and molar mass distribution as well as of time of polymerization and of the aluminium/titanium ratio were evaluted. The copolymerization parameters were determined according to Kelen-Tudős as rbutadiene = 0,9 and rpropylene oxide = 3,9. Copolymerization was confirmed by 13C NMR spectroscopy and extract evaluation combined with 1H NMR spectroscopy.
{"title":"Untersuchungen zur synthese von poly(butadien-co-propylenoxid) mit einem ziegler-natta-titankatalysatorsystem","authors":"R. Kaulbach, U. Gebauer, C. Mähner, M. Lechner, K. Gehrke","doi":"10.1002/APMC.1996.052390110","DOIUrl":"https://doi.org/10.1002/APMC.1996.052390110","url":null,"abstract":"Fur die Copolymerisation von 1,3-Butadien mit Propylenoxid wurde nach dem Vergleich der drei Katalysatorsysteme Nd(Oct)3/Al2Cl3ET3/Al(i-But)3, Ni(Oct)2/ BF3OEt2/AlEt3 und Al(i-But)3/I2/TiCl4 das Titankatalysatorsystem eingesetzt. Neben dem Einflus der Monomerzusammensetzung auf den Umsatz, die Microstruktur, die Copolymerzusammensetzung, die Molmassen sowie die Molmassenverteilungen wurden auch die Polymerisationszeit und das Aluminium/Titan-Verhaltnis untersucht. Die Copolymerisationsparameter wurden nach Kelen-Tudős zu rButadien = 0,9 und rPropylenoxid = 3,9 bestimmt. Der Copolymernachweis erfolgte uber 13C-NMR-Spektroskopie und Extraktionsuntersuchungen in Verbindung mit 1H-NMR-Spektroskopie. \u0000 \u0000 \u0000 \u0000After comparison of three catalyst systems, i.e. [Nd(Oct)3/Al2Cl3ET3/Al(i-But)3, Ni(Oct)2/BF3OEt2/AlEt3 and Al(i-But)3/I2/TiCl4] the titanium catalyst system was used for the copolymerization of 1,3-butadiene with propylene oxide. The effects of monomer ratio on copolymer composition, conversion, microstructure, molar mass and molar mass distribution as well as of time of polymerization and of the aluminium/titanium ratio were evaluted. The copolymerization parameters were determined according to Kelen-Tudős as rbutadiene = 0,9 and rpropylene oxide = 3,9. Copolymerization was confirmed by 13C NMR spectroscopy and extract evaluation combined with 1H NMR spectroscopy.","PeriodicalId":7808,"journal":{"name":"Angewandte Makromolekulare Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1996-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86701205","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 : 1996-07-01DOI: 10.1002/APMC.1996.052390111
I. Park, Jung-Mok Suh
A cyanomethylated styrene-divinylbenzene copolymer was prepared by the reaction of a chloromethylated styrene-divinylbenzene copolymer with sodium cyanide. A polystyrene-based macroreticular resin containing a pair of neighboring nitrile groups in each monomeric styrene unit was obtained from the reaction of the cyanomethylated copolymer with 3-chloropropionitrile under phase transfer conditions. The resin was reacted with hydroxylamine to afford a chelating resin containing a pair of neighboring amidoxime groups in each monomeric styrene unit. The chelating resin showed high adsorption capacity for uranyl ions. It was found that the resin was an effective adsorbent for other heavy metal ions such as Hg2+ and Pb2+. Durch Reaktion eines chlormethylierten Styrol/Divinylbenzol-Copolymeren mit Natriumcyanid wurde ein cyanmethyliertes Styrol/Divinylbenzol-Copolymeres hergestellt. Ein makroretikulares Harz auf Polystyrolbasis, das zwei benachbarte Nitrilgruppen pro Monomereinheit enthielt, wurde durch die Reaktion des cyanmethylierten Copolymeren mit 3-Chlorpropionitril unter Phasentransferbedingungen hergestellt. Durch Reaktion mit Hydroxylamin wurde ein Chelatharz mit zwei Amidoximgruppen pro Monomereinheit erhalten. Das Chelatharz zeigte hohes Adsorptionsvermogen fur Uranylionen. Es wurde festgestellt, das das Harz ein wirksames Adsorbens fur andere Schwermetallionen wie z. B. Hg2+ und Pb2+ ist.
以氯甲基化苯乙烯-二乙烯基苯共聚物与氰化钠为原料，制备了氰甲基化苯乙烯-二乙烯基苯共聚物。在相转移条件下，将氰甲基化共聚物与3-氯丙腈进行反应，得到了一种聚苯乙烯基大网状树脂，每个单体苯乙烯单元上含有一对相邻的腈基。该树脂与羟胺反应得到一种螯合树脂，在每个单体苯乙烯单元中含有一对相邻的偕胺肟基。螯合树脂对铀酰离子具有较高的吸附能力。结果表明，该树脂对Hg2+、Pb2+等重金属离子均有较好的吸附效果。氯甲基苯乙烯/二乙烯基苯-共聚物的化学反应in makrotikulares Harz auf polystyrol - basis, as zwei benachbarte nitr - gruppen pro monmeeinheit thielt, de durch die在相转移下与3-氯丙腈共聚物的反应。羟基胺蛋白在螯合酶中的反应与氨基肟组蛋白单体的反应。chchelatharz zeiget研究了稀土对铀的吸附。[2][2][3][1][3][1][3][1][3][1][3][1][4]。
{"title":"Preparation and uranyl ion adsorptivity of macroreticular chelating resins containing a pair of neighboring amidoxime groups in a monomeric styrene unit","authors":"I. Park, Jung-Mok Suh","doi":"10.1002/APMC.1996.052390111","DOIUrl":"https://doi.org/10.1002/APMC.1996.052390111","url":null,"abstract":"A cyanomethylated styrene-divinylbenzene copolymer was prepared by the reaction of a chloromethylated styrene-divinylbenzene copolymer with sodium cyanide. A polystyrene-based macroreticular resin containing a pair of neighboring nitrile groups in each monomeric styrene unit was obtained from the reaction of the cyanomethylated copolymer with 3-chloropropionitrile under phase transfer conditions. The resin was reacted with hydroxylamine to afford a chelating resin containing a pair of neighboring amidoxime groups in each monomeric styrene unit. The chelating resin showed high adsorption capacity for uranyl ions. It was found that the resin was an effective adsorbent for other heavy metal ions such as Hg2+ and Pb2+. \u0000 \u0000 \u0000 \u0000Durch Reaktion eines chlormethylierten Styrol/Divinylbenzol-Copolymeren mit Natriumcyanid wurde ein cyanmethyliertes Styrol/Divinylbenzol-Copolymeres hergestellt. Ein makroretikulares Harz auf Polystyrolbasis, das zwei benachbarte Nitrilgruppen pro Monomereinheit enthielt, wurde durch die Reaktion des cyanmethylierten Copolymeren mit 3-Chlorpropionitril unter Phasentransferbedingungen hergestellt. Durch Reaktion mit Hydroxylamin wurde ein Chelatharz mit zwei Amidoximgruppen pro Monomereinheit erhalten. Das Chelatharz zeigte hohes Adsorptionsvermogen fur Uranylionen. Es wurde festgestellt, das das Harz ein wirksames Adsorbens fur andere Schwermetallionen wie z. B. Hg2+ und Pb2+ ist.","PeriodicalId":7808,"journal":{"name":"Angewandte Makromolekulare Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1996-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86103327","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.1994.052230108
Werner Kaminsky
Metallocenes have gained widespread interest as catalysts for olefin polymerization due to their high activity and versatility. A large range of new polymers with narrow molecular weight distribution and different microstructures can be produced with these “single-site” catalysts. These highly active catalysts which are able to produce 40 tonnes of polyethylene per gram zirconium per hour are even capable of incorporating remarkable amounts of sterically demanding olefins and dienes in copolymerization with ethylene. Isotactic, syndiotactic, stereoblock and isoblock polyolefins are accessible by variation of the metallocene ligands. Similarly, the isotacticity and molecular weight of the generated polyolefins are influenced by the ligand structure. By heterogenization of the metallocene on metal powder or silica polymers with substantially higher molecular weight, higher melting points and other new properties may be attained. Cyclic olefins like cyclopentene, norbornene or dimethanooctahydronaphthalene polymerize without ring-opening to yield highly melting and poorly soluble polymers. By separation of the racemic catalyst into enantiomers, optically active alkanes and alkenes are accessi-ble. Trimers are obtained with ee of 95%. These results provide new insights into the mechanism of Ziegler-Natta catalysis.
{"title":"Olefinpolymerisation mittels Metallocenkatalysatoren","authors":"Werner Kaminsky","doi":"10.1002/APMC.1994.052230108","DOIUrl":"https://doi.org/10.1002/APMC.1994.052230108","url":null,"abstract":"Metallocenes have gained widespread interest as catalysts for olefin polymerization due to their high activity and versatility. A large range of new polymers with narrow molecular weight distribution and different microstructures can be produced with these “single-site” catalysts. These highly active catalysts which are able to produce 40 tonnes of polyethylene per gram zirconium per hour are even capable of incorporating remarkable amounts of sterically demanding olefins and dienes in copolymerization with ethylene. Isotactic, syndiotactic, stereoblock and isoblock polyolefins are accessible by variation of the metallocene ligands. Similarly, the isotacticity and molecular weight of the generated polyolefins are influenced by the ligand structure. By heterogenization of the metallocene on metal powder or silica polymers with substantially higher molecular weight, higher melting points and other new properties may be attained. Cyclic olefins like cyclopentene, norbornene or dimethanooctahydronaphthalene polymerize without ring-opening to yield highly melting and poorly soluble polymers. By separation of the racemic catalyst into enantiomers, optically active alkanes and alkenes are accessi-ble. Trimers are obtained with ee of 95%. These results provide new insights into the mechanism of Ziegler-Natta catalysis.","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":"90147758","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.1994.052230116
M. Beck, Paul Birnbrich, U. Eicken, H. Fischer, William E. Fristad, Brigitte Hase, H. Krause
A new, economic techniques was developed for the production of 2-alkyl-2-oxazolines with saturated, unsaturated or OH-functionalized alkylrests. In the process the fatty acids are changed into polymerizable monomers. The cationic polymerization of fattyalkyl-2-oxazolines was investigated in unpolar solvents and in bulk. It reacts in a living mechanism. The polymerization is remarkable inert against impurities like water or ethanolamide. A reaction enthalpy of ΔH= 85,9 kJ/mol was found for the bulk polymerization of 2-pentadecyl-2-oxazoline
{"title":"Polyoxazoline auf fettchemischer Basis","authors":"M. Beck, Paul Birnbrich, U. Eicken, H. Fischer, William E. Fristad, Brigitte Hase, H. Krause","doi":"10.1002/APMC.1994.052230116","DOIUrl":"https://doi.org/10.1002/APMC.1994.052230116","url":null,"abstract":"A new, economic techniques was developed for the production of 2-alkyl-2-oxazolines with saturated, unsaturated or OH-functionalized alkylrests. In the process the fatty acids are changed into polymerizable monomers. The cationic polymerization of fattyalkyl-2-oxazolines was investigated in unpolar solvents and in bulk. It reacts in a living mechanism. The polymerization is remarkable inert against impurities like water or ethanolamide. A reaction enthalpy of ΔH= 85,9 kJ/mol was found for the bulk polymerization of 2-pentadecyl-2-oxazoline","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":"79557239","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：