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第 36 卷第 6 期 精 细 化 工 Vol.36, No.6
201 9 年 6 月 FINE CHEMICALS June 2019

皮革化学品
封闭型无溶剂聚氨酯的制备及其性能

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刘 帅，马兴元 ，丁 博，张铭芮，何远鑫，贺营花，吴晓珍
（陕西科技大学 轻工科学与工程学院，陕西 西安 710021）

摘要：以氢化苯基甲烷二异氰酸酯（H 12 MDI）和聚酯二元醇 2000 为主要原料，分别以甲乙酮肟（MEKO）和
己内酰胺为封闭剂，以二月桂酸二丁基锡（DBTD）为催化剂，采用预聚体封闭法制备封闭型无溶剂聚氨酯（SFPU）
膜。采用 TGA 和 DSC 考察了封闭型 SFPU 膜的解封温度和热性能；探究了不同封闭剂、流平剂用量、催化剂
用量、烘箱温度以及封闭率对封闭型 SFPU 的解封温度、封闭型 SFPU 的固化条件和成膜性能的影响。结果表
明：通过 DSC 测试，以 MEKO 作为封闭剂的 SFPU 的解封温度为 143.3 ℃，以己内酰胺为封闭剂的 SFPU 的解
封温度为 163.7 ℃。TGA 结果表明，在相同解封温度下，以 MEKO 作为封闭剂的 SFPU 的固化速度明显高于以
己内酰胺作为封闭剂的 SFPU。在烘箱温度为 143 ℃、流平剂质量分数为 5%、催化剂质量分数为 5‰的条件下，
封闭型 SFPU 能够很好地固化成膜，而且封闭型 SFPU 的封闭率越低、固化温度越高，其开始成膜时间和完
全固化时间越短；由 75%、80%、85%、90%、95%、100% 6 个封闭率可知，膜的力学性能随封闭率的升高而
升高。
关键词：封闭型 SFPU；封闭剂；封闭率；解封温度；固化条件；成膜性能；皮革化学品
中图分类号：TQ314.2；TS529.1 文献标识码：A 文章编号：1003-5214 (2019) 06-1191-07

Preparation and Properties of Blocked Solvent-free Polyurethanes

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LIU Shuai, MA Xing-yuan , DING Bo, ZHANG Ming-rui,
HE Yuan-xin, HE Ying-hua, WU Xiao-zhen
（College of Bioresources Chemical and Materials Engineering, Shaanxi University of Science & Technology, Xi'an
710021, Shaanxi, China）

Abstract: Blocked solvent-free polyurethanes were composed of hydrogenated phenylmethane diisocyanate
(H 12MDI) and polyester diol 2000 using dibutyltin dilaurate (DBTD) as catalyst, methyl ethyl ketone oxime
(MEKO) and caprolactam as blocking agents, respectively. The blocked solvent-free polyurethane (SFPU)
film was prepared by a prepolymer blocking method. The deblocking temperature and thermal properties of
the blocked SFPU films were investigated by TGA and DSC. The effects of different sealers, leveling
agents, catalyst dosage, oven temperature and blocking ratio on the deblocking temperature of the blocked
SFPU, the curing conditions of the blocked SFPU and the film forming properties were investigated. The
results showed that the deblocking temperature of the blocked SFPU with MEKO as blocking agent was
143.3 ℃ and that of the blocked SFPU with caprolactam asblocking agent was 163.7 ℃ by differential
scanning calorimetry (DSC). TGA analysis showed that at the same deblocking temperature, the blocking
speed of the blocked SFPU with MEKO as blocking agent was significantly higher than that of the blocked
SFPU with caprolactam as blocking agent. Under suitable curing conditions of oven temperature of 143 ℃,
leveling agent mass fraction of 5%, and catalyst mass fraction of 5‰, the blocked SFPU can be cured into a
film. And the lower the blocking ratio of the blocked SFPU, the higher the curing temperature, the shorter
the initial film forming time and the complete curing time of the blocked SFPU. From the six percentage
closure gradients of 75%, 80%, 85%, 90%, 95% and 100%, the mechanical properties of the film increased
with the increase of the blocking ratio.

收稿日期：2018-11-14; 定用日期：2019-02-25; DOI: 10.13550/j.jxhg.20180842
基金项目：国家 863 计划项目（2015AA033903）
作者简介：刘 帅（1994—），男，硕士生。联系人：马兴元（1972—），男，教授，E-mail：maleather@163.com。