CN105504209B - 力学性能改善的聚氨酯弹性体及其制备方法 - Google Patents

力学性能改善的聚氨酯弹性体及其制备方法 Download PDF

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CN105504209B
CN105504209B CN201511029988.5A CN201511029988A CN105504209B CN 105504209 B CN105504209 B CN 105504209B CN 201511029988 A CN201511029988 A CN 201511029988A CN 105504209 B CN105504209 B CN 105504209B
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陈伟
陈海良
刘兆阳
蒋东旭
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Abstract

本发明涉及一种力学性能改善的聚氨酯弹性体及其制备方法，属于聚氨酯弹性体改性技术领域。本发明所述的力学性能改善的聚氨酯弹性体，由A组分和B组分组成，A、B组分的重量比为100:12.5‑22.5，其中A组分为聚氨酯预聚物，由聚四氢呋喃醚二元醇、聚酯二元醇和二异氰酸酯制成；B组分为扩链剂。所述聚四氢呋喃醚二元醇数均分子量为650‑1000；所述聚酯二元醇由己二酸与1，4丁二醇制备而成，或由己二酸与乙二醇和1，4丁二醇制备而成，官能度为2，数均分子量为650‑1000。本发明所述的力学性能改善的聚氨酯弹性体，撕裂及拉伸性能得到提高；本发明同时提供了简单易行、节能环保的制备方法。

Description

力学性能改善的聚氨酯弹性体及其制备方法
技术领域
本发明涉及一种力学性能改善的聚氨酯弹性体及其制备方法，属于聚氨酯弹性体改性技术领域。
背景技术
聚氨酯弹性体是一种主链上含有较多的氨基甲酸酯基团的高分子嵌段聚合物，具有独特的软硬段嵌段共聚物的结构，其具有优良的综合力学性能尤其是耐磨性能。聚四氢呋喃型聚氨酯弹性体具有优异的回弹性、耐水解性、耐磨性、耐高温性能以及低温柔顺性，然而与聚醚型弹性体相同，由聚四氢呋喃醚多元醇制备的聚氨酯弹性体撕裂强度低，尤其是裤型撕裂强度。聚酯型聚氨酯弹性体由于分子链上酯键较大的极性从而赋予其更高的力学性能，尤其是裤型撕裂强度远优于聚醚型弹性体，但聚酯型弹性体由于存在酯基而易于水解。聚四氢呋喃醚多元醇和聚酯多元醇的极性相差太大难以互溶，然而通过实验发现小分子量的聚四氢呋喃醚多元醇(数均分子量小于1000)和数均分子量小于1000，同时采用己二酸和1,4丁二醇合成的聚酯多元醇能够互溶在一起，这也就为我们合成力学性能改善的聚氨酯弹性体成为一种可能。
发明内容
本发明的目的是提供一种力学性能改善的聚氨酯弹性体，其撕裂及拉伸性能得到提高；本发明同时提供了简单易行、节能环保的制备方法。
本发明所述的力学性能改善的聚氨酯弹性体，由A组分和B组分组成，A、B组分的重量比为100:12.5-22.5，其中：
(1)A组分为聚氨酯预聚物，由以下重量百分含量的原料制成：
聚四氢呋喃醚二元醇 41.2～66.0％
聚酯二元醇 7.7～31.08％
二异氰酸酯 22.3～31.4％；
(2)B组分为扩链剂；
所述聚四氢呋喃醚二元醇数均分子量为650-1000；
所述聚酯二元醇由己二酸与1，4丁二醇制备而成，或由己二酸与乙二醇和1，4丁二醇制备而成，官能度为2，数均分子量为650-1000。
所述二异氰酸酯为甲苯二异氰酸酯TDI-80或TDI-100中的一种或两种。
所述扩链剂为3,3’-二氯-4,4’-二氨基二苯基甲烷或3,5二甲硫基甲苯二胺。
所述的力学性能改善的聚氨酯弹性体的制备方法，包括以下步骤：
(1)制备A组分：将聚四氢呋喃醚二元醇、聚酯二元醇和二异氰酸酯在75～85℃反应2～3小时，得到异氰酸根含量为4.2～7.5％的聚氨酯预聚物；
(2)制备聚氨酯弹性体：将聚氨酯预聚物和B组分在75～85℃下混合，然后将混合物浇注到100～120℃的模具中，30～60分钟后脱模，将脱模后的制品在100～120℃下硫化12小时，得到力学性能改善的聚氨酯弹性体，其硬度为邵A 90～65D。
本发明在聚四氢呋喃聚氨酯弹性体的制备过程中，通过加入少部分可互溶的聚酯二元醇改善聚四氢呋喃型聚氨酯弹性体的拉伸撕裂等性能。
本发明具有以下有益效果：
制得的力学性能改善的聚氨酯弹性体，撕裂及拉伸性能得到提高；所述的力学性能改善的聚氨酯弹性体简单易行、节能环保。
具体实施方式
下面结合实施例对本发明作进一步的说明，但其并不限制本发明的实施。
实施例中所用材料如下：
PTMG1000：数均分子量1000，聚四氢呋喃醚二醇；
PTMG 650：数均分子量1000，聚四氢呋喃醚二醇；
PE-4010:数均分子量1000，由己二酸、1，4丁二醇制备而成；
PE-2410：数均分子量1000，由己二酸、1，4丁二醇及乙二醇制备而成；
PE4007：数均分子量650，由己二酸、1，4丁二醇制备而成；
TDI-100:2，6甲苯二异氰酸酯；
TDI-80：2，4-甲苯二异氰酸酯80％，2，6-甲苯二异氰酸酯20％；
MOCA：3，3ˊ-二氯-4,4ˊ-二氨基二苯基甲烷；
E-300：3，5－二甲硫基甲苯二胺。
以下用量均为质量百分含量。
实施例1
预聚物的制备：PTMG1000 46.6％，PE-4010 31.08％，TDI-80 22.32％，在85℃反应3小时，真空(－0.095MPa)脱除气泡，得到异氰酸根含量为4.2％的预聚体。
预聚物和扩链剂MOCA以100/12.5的质量比例混合反应，混合温度为80℃，浇注入模具，模具温度120℃，硫化60分钟脱模，制品再在100℃环境中后硫化12小时，得到硬度为邵A 90的聚氨酯弹性体制品。
实施例2
预聚物的制备：PTMG1000 66.0％，PE-4007 7.7％，TDI-100 26.3％，在80℃反应2.5小时，真空(－0.095MPa)脱除气泡，得到异氰酸根含量为6.2％的预聚体。
预聚物和扩链剂E-300以100/14.5的质量比例混合反应，混合温度为75℃，浇注入模具，模具温度115℃，硫化40分钟脱模，制品再在120℃环境中后硫化12小时，得到硬度为邵A95的聚氨酯弹性体制品。
实施例3
预聚物的制备：PTMG650 42.2％，PE-2410 27.4％，TDI-100 15.7％，TDI-8014.7％。在75℃反应2小时，真空(－0.095MPa)脱除气泡，得到异氰酸根含量为7.5％的预聚体。
预聚物和扩链剂MOCA以100/22.5的质量比例混合反应，混合温度为85℃，浇注入模具，模具温度100℃，硫化30分钟脱模，制品再在110℃环境中后硫化12小时，得到硬度为邵D65的聚氨酯弹性体制品。
对比例1
预聚物的制备：PTMG1000 73.7％，TDI-80 26.3％，在80℃反应2.5小时，真空(－0.095MPa)脱除气泡，得到异氰酸根含量为6.2％的预聚体。
预聚物和扩链剂E-300以100/14.5的比例混合反应，混合温度为75℃，浇注入模具，模具温度115℃，硫化40分钟脱模，制品再在100℃环境中后硫化12小时，得到硬度为邵A95的聚氨酯弹性体制品。
对以上实例制得的产品测试拉伸、撕裂、硬度及回弹等性能，测试结果见表1。
表1 制品的物理性能测试结果

Claims (6)

1.一种力学性能改善的聚氨酯弹性体，其特征在于：由A组分和B组分组成，A、B组分的重量比为100:12.5-22.5，其中：
(1)A组分为聚氨酯预聚物，由以下重量百分含量的原料制成：
聚四氢呋喃醚二元醇 41.2～66.0％
聚酯二元醇 7.7～31.08％
二异氰酸酯 22.3～31.4％；
(2)B组分为扩链剂；
所述聚四氢呋喃醚二元醇数均分子量为650-1000；
所述聚酯二元醇由己二酸与乙二醇和1，4丁二醇制备而成，官能度为2，数均分子量为650-1000。
2.根据权利要求1所述的力学性能改善的聚氨酯弹性体，其特征在于：二异氰酸酯为甲苯二异氰酸酯TDI-80或TDI-100中的一种或两种。
3.根据权利要求1所述的力学性能改善的聚氨酯弹性体，其特征在于：扩链剂为3,3’-二氯-4,4’-二氨基二苯基甲烷或3,5二甲硫基甲苯二胺。
4.一种权利要求1-3任一所述的力学性能改善的聚氨酯弹性体的制备方法，其特征在于包括以下步骤：
(1)制备A组分：将聚四氢呋喃醚二元醇、聚酯二元醇和二异氰酸酯在75～85℃反应2～3小时，得到聚氨酯预聚物；
(2)制备聚氨酯弹性体：将聚氨酯预聚物和B组分在75～85℃下混合，然后将混合物浇注到100～120℃的模具中，30～60分钟后脱模，将脱模后的制品在100～120℃下硫化12小时，得到力学性能改善的聚氨酯弹性体。
5.根据权利要求4所述的力学性能改善的聚氨酯弹性体的制备方法，其特征在于：聚氨酯预聚物的异氰酸根含量为4.2～7.5％。
6.根据权利要求4所述的力学性能改善的聚氨酯弹性体的制备方法，其特征在于：制得的耐低温聚氨酯弹性体的硬度为邵A90～65D。
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