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由α-环糊精与聚(乙二醇)单甲醚或十二烷醇部分之间的主客体相互作用驱动的自修复热固性聚氨酯。

Self-Healing Thermoset Polyurethanes Driven by Host-Guest Interactions Between α-Cyclodextrin and Poly(ethylene glycol) Monomethyl Ether or Dodecanol Moieties.

作者信息

Miyagawa Riku, Shibata Mitsuhiro

机构信息

Department of Applied Chemistry, Faculty of Engineering, Chiba Institute of Technology, 2-17-1, Tsudanuma, Narashino 275-0016, Chiba, Japan.

出版信息

Molecules. 2025 Apr 27;30(9):1941. doi: 10.3390/molecules30091941.

Abstract

Self-healing thermoset polymers have attracted significant attention because they contribute to resource and energy savings by extending their service life. The reactions between glycerol ethoxylate (GCE), -cyclodextrin (-CD), poly(ethylene glycol) monomethyl ether (MPEG), and hexamethylene diisocyanate (HDI) at molar ratios of GCE:-CD:MPEG = :: produced polyurethane networks (GCM-, = 311, 411, and 511) containing α-CD and MPEG as host and guest moieties, respectively. To compare this with GCM-411, 1-dodecanol (DN) was used instead of MPEG as a guest molecule to yield a polyurethane network (GCD-411). Dynamic mechanical analysis revealed the formation of a polymer network, and the loss tangent (tan ) peak temperature () and crosslinking density () decreased with increasing GCE fraction for GCMs, and the and values of GCD were slightly higher than those of GCM-411. The tensile strength of the GCMs decreased with increasing GCE fraction, and the tensile strength of GCD-411 was slightly higher than that of GCM-411. All cured films were healed at room temperature for 24 h, and the healing efficiency (), based on tensile strength, increased in the order of GCM-311 < GCM-411 < GCM-511 < GCD-411. When the healing temperature increased from room temperature to 80 °C, increased from 24-38% to 45-62%. GCM-411 and GCD-411 were self-healed thrice by treatment at 80 °C, and gradually decreased with each healing cycle.

摘要

自修复热固性聚合物因其通过延长使用寿命有助于节约资源和能源而备受关注。甘油乙氧基化物(GCE)、α-环糊精(α-CD)、聚乙二醇单甲醚(MPEG)和六亚甲基二异氰酸酯(HDI)以GCE:α-CD:MPEG = 3:1:1、4:1:1和5:1:1的摩尔比反应生成了分别含有α-CD和MPEG作为主体和客体部分的聚氨酯网络(GCM-,x = 311、411和511)。为了将其与GCM-411进行比较,使用1-十二醇(DN)代替MPEG作为客体分子以生成聚氨酯网络(GCD-411)。动态力学分析揭示了聚合物网络的形成,对于GCMs,损耗角正切(tanδ)峰值温度(T)和交联密度(ν)随着GCE比例的增加而降低,并且GCD的T和ν值略高于GCM-411。GCMs的拉伸强度随着GCE比例的增加而降低,并且GCD-411的拉伸强度略高于GCM-411。所有固化膜在室温下愈合24小时,基于拉伸强度的愈合效率(η)按GCM-311 < GCM-411 < GCM-511 < GCD-411的顺序增加。当愈合温度从室温升高到80°C时,η从24 - 38%增加到45 - 62%。GCM-411和GCD-411在80°C下处理三次后实现自修复,并且η随着每个愈合循环逐渐降低。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7767/12073313/aa988482a4f9/molecules-30-01941-sch001.jpg

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