{"title":"通过聚异戊二烯的乙烯裂解选择性合成作为大单体的 α-乙烯基-ω-亚乙烯基-醇基异戊二烯","authors":"Ryo Tanaka, Akane Shimmei, Riki Otsuka, Yuushou Nakayama, Takeshi Shiono","doi":"10.1038/s41428-023-00858-6","DOIUrl":null,"url":null,"abstract":"Oligoisoprene macromonomer, which bears a terminal vinyl group, was prepared by the metathesis degradation of high-molecular-weight polyisoprene with ethylene for coordination polymerization. The ethenolysis of polyisoprene using the 2nd-generation Grubbs catalyst (G2) at ambient pressure gave heterotelechelic (α-vinyl-ω-vinylidene) oligoisoprene, keeping the stereoregularity in high yield, whereas the 1st generation Grubbs catalyst was immediately deactivated. In such metathesis degradation, an intramolecular side reaction giving cyclic oligomers may be competitive, but ethenolysis proceeded with high selectivity, probably because of the least steric effect of ethylene. The ethenolysis is also applicable for the degradation of natural rubber-derived polyisoprene, although the catalytic activity decreased. The prepared oligoisoprene macromonomer was successfully copolymerized with ethylene using a phenoxyimine-ligated titanium catalyst, and the reactivity of the macromonomer was almost the same as that of 1-hexadecene. The oligoisoprene-grafted polyethylene showed a typical stress‒strain curve, of which the tensile modulus and yielding stress are comparable to those of linear low-density polyethylene. Oligoisoprene macromonomer, which bears a terminal vinyl group and cis-1,4 regularity, was prepared by the metathesis degradation of high-molecular-weight polyisoprene with ethylene in a high selectivity and yield. The ethenolysis is also applicable for the degradation of natural rubber-derived polyisoprene, although the catalytic activity decreased. The prepared oligoisoprene macromonomer was successfully copolymerized with ethylene similarly with 1-hexadecene using a phenoxyimine-ligated titanium catalyst. The oligoisoprene-grafted polyethylene showed a typical stress‒strain curve, of which the tensile modulus and yielding stress are comparable to those of linear low-density polyethylene.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":null,"pages":null},"PeriodicalIF":2.3000,"publicationDate":"2024-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-023-00858-6.pdf","citationCount":"0","resultStr":"{\"title\":\"Selective synthesis of α-vinyl-ω-vinylidene-oligoisoprene as a macromonomer via ethenolysis of polyisoprene\",\"authors\":\"Ryo Tanaka, Akane Shimmei, Riki Otsuka, Yuushou Nakayama, Takeshi Shiono\",\"doi\":\"10.1038/s41428-023-00858-6\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Oligoisoprene macromonomer, which bears a terminal vinyl group, was prepared by the metathesis degradation of high-molecular-weight polyisoprene with ethylene for coordination polymerization. The ethenolysis of polyisoprene using the 2nd-generation Grubbs catalyst (G2) at ambient pressure gave heterotelechelic (α-vinyl-ω-vinylidene) oligoisoprene, keeping the stereoregularity in high yield, whereas the 1st generation Grubbs catalyst was immediately deactivated. In such metathesis degradation, an intramolecular side reaction giving cyclic oligomers may be competitive, but ethenolysis proceeded with high selectivity, probably because of the least steric effect of ethylene. The ethenolysis is also applicable for the degradation of natural rubber-derived polyisoprene, although the catalytic activity decreased. The prepared oligoisoprene macromonomer was successfully copolymerized with ethylene using a phenoxyimine-ligated titanium catalyst, and the reactivity of the macromonomer was almost the same as that of 1-hexadecene. The oligoisoprene-grafted polyethylene showed a typical stress‒strain curve, of which the tensile modulus and yielding stress are comparable to those of linear low-density polyethylene. Oligoisoprene macromonomer, which bears a terminal vinyl group and cis-1,4 regularity, was prepared by the metathesis degradation of high-molecular-weight polyisoprene with ethylene in a high selectivity and yield. The ethenolysis is also applicable for the degradation of natural rubber-derived polyisoprene, although the catalytic activity decreased. The prepared oligoisoprene macromonomer was successfully copolymerized with ethylene similarly with 1-hexadecene using a phenoxyimine-ligated titanium catalyst. The oligoisoprene-grafted polyethylene showed a typical stress‒strain curve, of which the tensile modulus and yielding stress are comparable to those of linear low-density polyethylene.\",\"PeriodicalId\":20302,\"journal\":{\"name\":\"Polymer Journal\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.3000,\"publicationDate\":\"2024-01-11\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.nature.com/articles/s41428-023-00858-6.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Polymer Journal\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.nature.com/articles/s41428-023-00858-6\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Polymer Journal","FirstCategoryId":"92","ListUrlMain":"https://www.nature.com/articles/s41428-023-00858-6","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Selective synthesis of α-vinyl-ω-vinylidene-oligoisoprene as a macromonomer via ethenolysis of polyisoprene
Oligoisoprene macromonomer, which bears a terminal vinyl group, was prepared by the metathesis degradation of high-molecular-weight polyisoprene with ethylene for coordination polymerization. The ethenolysis of polyisoprene using the 2nd-generation Grubbs catalyst (G2) at ambient pressure gave heterotelechelic (α-vinyl-ω-vinylidene) oligoisoprene, keeping the stereoregularity in high yield, whereas the 1st generation Grubbs catalyst was immediately deactivated. In such metathesis degradation, an intramolecular side reaction giving cyclic oligomers may be competitive, but ethenolysis proceeded with high selectivity, probably because of the least steric effect of ethylene. The ethenolysis is also applicable for the degradation of natural rubber-derived polyisoprene, although the catalytic activity decreased. The prepared oligoisoprene macromonomer was successfully copolymerized with ethylene using a phenoxyimine-ligated titanium catalyst, and the reactivity of the macromonomer was almost the same as that of 1-hexadecene. The oligoisoprene-grafted polyethylene showed a typical stress‒strain curve, of which the tensile modulus and yielding stress are comparable to those of linear low-density polyethylene. Oligoisoprene macromonomer, which bears a terminal vinyl group and cis-1,4 regularity, was prepared by the metathesis degradation of high-molecular-weight polyisoprene with ethylene in a high selectivity and yield. The ethenolysis is also applicable for the degradation of natural rubber-derived polyisoprene, although the catalytic activity decreased. The prepared oligoisoprene macromonomer was successfully copolymerized with ethylene similarly with 1-hexadecene using a phenoxyimine-ligated titanium catalyst. The oligoisoprene-grafted polyethylene showed a typical stress‒strain curve, of which the tensile modulus and yielding stress are comparable to those of linear low-density polyethylene.
期刊介绍:
Polymer Journal promotes research from all aspects of polymer science from anywhere in the world and aims to provide an integrated platform for scientific communication that assists the advancement of polymer science and related fields. The journal publishes Original Articles, Notes, Short Communications and Reviews.
Subject areas and topics of particular interest within the journal''s scope include, but are not limited to, those listed below:
Polymer synthesis and reactions
Polymer structures
Physical properties of polymers
Polymer surface and interfaces
Functional polymers
Supramolecular polymers
Self-assembled materials
Biopolymers and bio-related polymer materials
Polymer engineering.