Multicomponent Polymerization of β-Propiolactone, Epoxides, Anhydrides, and CO2: Synthesizing Sustainable Materials with Widely Adjustable Properties,Macromolecules

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Multicomponent Polymerization of β-Propiolactone, Epoxides, Anhydrides, and CO2: Synthesizing Sustainable Materials with Widely Adjustable Properties
Macromolecules ( IF 5.1 ) Pub Date : 2024-09-06 , DOI: 10.1021/acs.macromol.4c01512
Bai-Hao Ren _{1,

2} , Jin-Ming Fu ₁ , Wen-Bing Li ₁ , Geoffrey W. Coates ₂ , Xiao-Bing Lu ₁

Affiliation

Multicomponent polymerization of three or more monomers can potentially introduce different subunits into a polymer chain with adjustable composition and sequence distribution to improve the material properties and leverage their respective advantages. This study presents multicomponent polymerization reactions of a mixed-monomer feedstock of epoxides, β-propiolactone (BPL), anhydrides, and CO₂ under mild conditions. The binary catalyst system consisting of (salcy)Co(III)OTs (salcy = N,N′-bis(3-tert-5-fluoro-butylsalicylidene)-1,2-diaminocyclohexane; OTs = p-toluenesulfonate) and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD) is capable of catalyzing the ring-opening polymerization of BPL, and the alternating copolymerization of epoxides and anhydrides or CO₂. Additionally, the versatile catalyst is very efficient in the terpolymerization of epoxides, BPL, and anhydrides, or CO₂. The cleavage of the alkyl C–O bond rather than the acyl C(═O)–O bond of BPL, through the nucleophilic attack of carboxylate or carbonate during polymerization, significantly prevents transesterification side reactions, thereby resulting in the terpolymerization proceeding in a controlled manner. The gradient or statistical distributions of two types of subunits could be observed in the resultant terpolymers. Notably, (salcy)Co(III)OTs/MTBD-mediated multicomponent polymerization of epoxides, BPL, phthalic anhydride (PA), and CO₂ afforded a novel diblock polymer constituting epoxide/PA/BPL and epoxide/CO₂/BPL terpolymer segments, while the quaternary polymerization involving the less reactive glutaric anhydride (GA) generated a random epoxide/GA/CO₂/BPL polymer. The controlled and random polymerization pathway offers a promising synthesis route to sustainable materials with a mixed-glass transition temperature that can be adjusted over a wide range.

中文翻译：

β-丙内酯、环氧化物、酸酐和二氧化碳的多组分聚合：合成具有广泛可调性能的可持续材料

三种或多种单体的多组分聚合可以潜在地将不同的亚基引入具有可调节组成和序列分布的聚合物链中，以改善材料性能并利用它们各自的优势。本研究介绍了环氧化物、β-丙内酯 (BPL)、酸酐和 CO ₂的混合单体原料在温和条件下的多组分聚合反应。二元催化剂体系由(salcy)Co(III)OTs（salcy = N,N'-双(3-叔-5-氟丁基水杨基)-1,2-二氨基环己烷；OTs = 对甲苯磺酸盐）和7-组成甲基-1,5,7-三氮杂双环[4.4.0]dec-5-ene (MTBD)能够催化BPL的开环聚合，以及环氧化物和酸酐或CO ₂的交替共聚。此外，这种多功能催化剂在环氧化物、BPL 和酸酐或 CO ₂的三聚反应中非常有效。通过聚合过程中羧酸酯或碳酸酯的亲核攻击，BPL 中的烷基 C-O 键而不是酰基 C(=O)-O 键断裂，显着防止了酯交换副反应，从而导致三聚在受控的条件下进行。方式。在所得三元共聚物中可以观察到两种类型亚基的梯度或统计分布。值得注意的是，(salcy)Co(III)OTs/MTBD介导的环氧化物、BPL、邻苯二甲酸酐(PA)和CO _{2 的}多组分聚合提供了一种新型二嵌段聚合物，由环氧化物/PA/BPL和环氧化物/CO ₂ /BPL三元共聚物链段组成，而涉及反应性较低的戊二酸酐（GA）的四元聚合生成无规环氧化物/GA/CO ₂ /BPL聚合物。受控和随机聚合途径为合成具有可在较宽范围内调节的混合玻璃化转变温度的可持续材料提供了一种有前途的合成途径。

更新日期：2024-09-06

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