Selective synthesis of α-vinyl-ω-vinylidene-oligoisoprene as a macromonomer via ethenolysis of polyisoprene

IF 2.3 4区 化学 Q3 POLYMER SCIENCE Polymer Journal Pub Date : 2024-01-11 DOI:10.1038/s41428-023-00858-6
Ryo Tanaka, Akane Shimmei, Riki Otsuka, Yuushou Nakayama, Takeshi Shiono
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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.

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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
通过乙烯对高分子量聚异戊二烯的偏聚降解,制备了带有末端乙烯基的寡异戊二烯大单体,并进行了配位聚合。在常压下使用第二代格拉布斯催化剂(G2)对聚异戊二烯进行乙烯裂解,可得到异链烷基(α-乙烯基-ω-亚乙烯基)低聚异戊二烯,并保持高产率的立体规整性,而第一代格拉布斯催化剂则立即失活。在这种偏合成降解过程中,产生环状低聚物的分子内副反应可能是竞争性的,但乙烯裂解却具有很高的选择性,这可能是因为乙烯的立体效应最小。尽管催化活性降低,但乙烯醇解也适用于天然橡胶衍生的聚异戊二烯的降解。使用苯氧亚氨基配位钛催化剂成功地将制备的低聚异戊二烯大单体与乙烯共聚,大单体的反应活性与 1-十六碳烯几乎相同。低聚异戊二烯接枝聚乙烯呈现出典型的应力-应变曲线,其拉伸模量和屈服应力与线性低密度聚乙烯相当。
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来源期刊
Polymer Journal
Polymer Journal 化学-高分子科学
CiteScore
5.60
自引率
7.10%
发文量
131
审稿时长
2.5 months
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.
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