{"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":null,"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":"79 1","pages":"275-284"},"PeriodicalIF":0.0000,"publicationDate":"1996-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"24","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Angewandte Makromolekulare Chemie","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1002/APMC.1996.052400126","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 24
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.