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由α,ω-羟基遥爪聚(ε-己内酯)(HOPCLOH)衍生的大分子二醇和非嵌段聚(酯-聚氨酯)(PEU)的合成与表征:引发剂、聚合度和二异氰酸酯的影响

Synthesis and characterization of macrodiols and non-segmented poly(ester-urethanes) (PEUs) derived from α,ω-hydroxy telechelic poly(ε-caprolactone) (HOPCLOH): effect of initiator, degree of polymerization, and diisocyanate.

作者信息

Barrera-Nava Miriam P, Navarro Rodrigo, Marcos-Fernández Ángel, Báez José E

机构信息

Department of Chemistry, University of Guanajuato (UG) Noria Alta S/N 36050 Guanajuato Gto Mexico

Institute of Polymer Science and Technology, CSIC C/Juan de la Cierva No. 3 28006 Madrid Spain.

出版信息

RSC Adv. 2024 Aug 27;14(37):27241-27251. doi: 10.1039/d4ra03951c. eCollection 2024 Aug 22.

Abstract

Nine different macrodiols derived from α,ω-hydroxy telechelic poly(ε-caprolactone) (HOPCLOH) were prepared by ring-opening polymerization of ε-caprolactone (CL) using three linear aliphatic diols (HO-(CH) -OH, where = 4, 8, and 12) as initiators and catalyzed by ammonium decamolybdate (NH)[MoO]. The crystallization temperature ( ) and crystallinity ( ) were relatively high for HOPCLOH species with a long aliphatic chain [-(CH)-] in the oligoester. Also, HOPCLOH was the precursor of twenty-seven different poly(ester-urethanes) (PEUs) with various degrees of polymerization (DP) of HOPCLOH and three types of diisocyanates such as 1,6-hexamethylene diisocyanate (HDI), methylene diphenyl diisocyanate (MDI), and 4,4'-methylenebis (cyclohexyl isocyanate) (HMDI). HOPCLOH exhibited the melting temperature ( ) and crystallinity ( ) with a proportional dependency to the degree of polymerization (DP). PEUs showed significant thermal and mechanical properties, which had a direct correlation in terms of the type of DP and diisocyanate. PEUs derived from HDI MDI or HMDI exhibited an apparent effect where aliphatic diisocyanate (HDI) induced a significant with respect to aromatic and cyclic diisocyanate (MDI or HMDI). The profile of PEUs films according to mechanical properties is mainly a plastic behavior. The chemical nature and properties of HOPCLOH and PEUs were characterized by NMR, FT-IR, GPC, MALDI-TOF, DSC, and mechanical properties.

摘要

以三种直链脂肪族二醇(HO-(CH₂)ₙ-OH,其中n = 4、8和12)为引发剂,在十钼酸铵((NH₄)₂[Mo₁₀O₃₂])催化下,通过ε-己内酯(CL)的开环聚合反应制备了九种不同的源自α,ω-羟基遥爪聚(ε-己内酯)(HOPCLOH)的大分子二醇。对于在低聚酯中具有长脂肪链[-(CH₂)ₙ-]的HOPCLOH物种,其结晶温度(Tc)和结晶度(χc)相对较高。此外,HOPCLOH是二十七种不同聚合度(DP)的聚(酯-聚氨酯)(PEU)的前体,这些PEU由HOPCLOH与三种二异氰酸酯(如1,6-六亚甲基二异氰酸酯(HDI)、亚甲基二苯基二异氰酸酯(MDI)和4,4'-亚甲基双(环己基异氰酸酯)(HMDI))反应得到。HOPCLOH的熔点(Tm)和结晶度(χc)与聚合度(DP)呈正比关系。PEU表现出显著的热性能和机械性能,这些性能与DP类型和二异氰酸酯直接相关。源自HDI、MDI或HMDI的PEU表现出明显的效果,其中脂肪族二异氰酸酯(HDI)相对于芳香族和环状二异氰酸酯(MDI或HMDI)会导致显著更高的玻璃化转变温度(Tg)。根据机械性能,PEU薄膜的特性主要表现为塑性行为。通过核磁共振(NMR)、傅里叶变换红外光谱(FT-IR)、凝胶渗透色谱(GPC)、基质辅助激光解吸电离飞行时间质谱(MALDI-TOF)、差示扫描量热法(DSC)和机械性能对HOPCLOH和PEU的化学性质及性能进行了表征。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/55d0/11348852/6d8972e344a0/d4ra03951c-s1.jpg

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