CN110467713A - 热塑性有机硅聚氨酯弹性体材料及其制备方法 - Google Patents

热塑性有机硅聚氨酯弹性体材料及其制备方法 Download PDF

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CN110467713A
CN110467713A CN201910813328.8A CN201910813328A CN110467713A CN 110467713 A CN110467713 A CN 110467713A CN 201910813328 A CN201910813328 A CN 201910813328A CN 110467713 A CN110467713 A CN 110467713A
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polyurethane elastomer
elastomer material
thermoplastic silicone
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reaction kettle
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陈海良
宋小娜
陈淑海
刘凯良
贺宽宽
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Shandong Inov Polyurethane Co Ltd
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Abstract

本发明涉及聚氨酯弹性体技术领域,具体涉及一种热塑性有机硅聚氨酯弹性体材料及其制备方法。所述热塑性有机硅聚氨酯弹性体材料,由以下质量份数的原料组成:聚合物多元醇44‑79份,有机硅改性剂3‑15份,二异氰酸酯16‑33份,扩链剂4‑7.8份,偶联剂0.1‑1份,抗氧化剂0.2‑0.6份,催化剂0.02‑0.04份;所述有机硅改性剂为以羟烷基为端基官能团的硅氧烷‑聚酯化合物或以羟烷基为端基官能团的硅氧烷‑聚醚化合物。本发明的热塑性有机硅聚氨酯弹性体材料,提高了低温柔韧性、耐水性、滑爽性、耐撕拉等性能,同时避免了有机硅迁移的问题;本发明该提供其制备方法,工艺简单,操作简便。

Description

热塑性有机硅聚氨酯弹性体材料及其制备方法
技术领域
本发明涉及聚氨酯弹性体技术领域,具体涉及一种热塑性有机硅聚氨酯弹性体材料及其制备方法。
背景技术
热塑性聚氨酯弹性体简称TPU,是一种由低聚物多元醇软段与二异氰酸酯-扩链剂硬段构成的线性嵌段共聚物,机械强度高、韧性好、耐磨和耐油等性能优异。随着智能电子时代的来临,在可穿戴电子产品等与人体直接接触的材料领域,由于其耐候性差、耐老化性能不足,极大限制了其应用范围。有机硅材料具有耐低温性好,耐候性好,柔韧性强等许多优异的性能。通过有机硅对TPU进行改性,可获得两种材料的性能优点,具有卓越的耐磨性,低于TPU的表面摩擦系数,热空气老化后依然可以保持较高的物理机械性能,易于挤出和注塑成型,广泛应用于消费电子、化妆品、食品、汽车、运动休闲等各个行业。
专利CN 109135293 A中公开了一种动态硫化硅橡胶/热塑性聚氨酯弹性体及其制备方法,采用硅橡胶原料与热塑性聚氨酯弹性体进行动态硫化制备,制备过程分两步进行,操作复杂,涉及高温捏炼造粒及动态硫化,需要开发动态硫化专用设备、精确控制动态硫化工艺,在动态硫化过程中会出现橡胶不易剪切、破碎形成均匀微小的分散相颗粒,难以实现硅橡胶在TPU基体中的理想分散,导致硅橡胶聚氨酯热塑性硫化胶的微观形态不够精细,力学性能和弹性较差。
专利CN 108641057 A中公开了一种硅橡胶聚氨酯热塑性弹性体的制备方法,采用一步法反应挤出工艺,使多元醇与异氰酸酯、扩链剂反应生成聚氨酯与液态有机硅橡胶的固化在同时进行。双组份液态有机硅橡胶为液态甲基有机硅橡胶或液态苯基有机硅橡胶,有A、B两个组分,两个组分经浇注口混合后在挤出机螺杆中进行固化并剪切分散在聚氨酯反应相中。非极性硅橡胶和极性聚氨酯材料相容性差,两者液态时不互溶,同时聚氨酯固化和有机硅的固化难以匹配,不易形成相分离,获得理想性能。
专利CN201510740025X中公开了一种有机硅改性热塑性聚氨酯弹性体及其制备方法,采用大分子二元醇、端羟烷基封端聚二甲基硅氧烷、二异氰酸酯、小分子扩链剂、催化剂、抗氧化剂、紫外线吸收剂合成聚氨酯弹性体,增强了聚氨酯弹性体的耐高低温性能和疏水性;但是其未加相容剂,有机硅容易迁移。
发明内容
针对现有技术的不足,本发明的目的是提供一种热塑性有机硅聚氨酯弹性体材料,提高了聚氨酯弹性体材料的低温柔韧性、耐水性、滑爽性、耐撕拉等性能,同时避免了有机硅迁移的问题;本发明该提供其制备方法,工艺简单,操作简便。
本发明所述的热塑性有机硅聚氨酯弹性体材料,由以下质量份数的原料组成:
所述有机硅改性剂为反应型有机硅;优选为以羟烷基为端基官能团的硅氧烷-聚酯化合物或以羟烷基为端基官能团的硅氧烷-聚醚化合物,所述反应型有机硅包括双端双官能度、单端双官能度以及单端单官能度。
所述热塑性有机硅聚氨酯弹性体材料采用一步反应挤出工艺制备得到。
有机硅改性剂的分子量为1000-4000,硅氧烷质量含量为50-90%。
聚合物多元醇为聚己二酸乙二醇酯二醇、聚己二酸丁二醇酯二醇、聚己二酸乙二醇丁二醇酯二醇、聚己二酸己二醇酯二醇、聚己内酯二元醇或聚四亚甲基醚二醇中的一种或多种,聚合物多元醇的数均分子量为1000-4000。
二异氰酸酯为4,4'-二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯或苯二亚甲基二异氰酸酯中的一种或多种。
扩链剂为含有2-10个碳原子的直链小分子二醇;优选为乙二醇、1,4-丁二醇、1,2-丙二醇、1,6-己二醇、1,3-丙二醇、1,3-丁二醇中的一种或多种;进一步优选为1,4-丁二醇。
偶联剂为有机硅偶联剂;优选为硅烷偶联剂KH-550、KH560、KH560中的一种或多种。
抗氧化剂由主抗氧化剂和辅助氧化剂组成,主抗氧化剂为受阻酚或芳香族仲胺类抗氧剂,辅助催化剂为硫酯或亚磷酸酯类抗氧剂。
优选地,主抗氧化剂为3,5-二叔丁基-4-羟基苯基丙酸十八酯(1076)、四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(1010);辅助抗氧剂为亚磷酸三(2,4-二叔丁基苯基)酯(168)、β,β`-硫代二丙酸二月桂酯(DLTP)。
催化剂为有机铋催化剂;优选为异辛酸铋,月桂酸铋,新癸酸铋的一种或多种。
本发明所述的热塑性有机硅聚氨酯弹性体材料的制备方法,包括以下步骤:
将聚合物多元醇、有机硅改性剂、偶联剂和抗氧化剂加入反应釜A中,在95-105℃温度下搅拌;将二异氰酸酯加入反应釜B中,在60-75℃温度下搅拌;将扩链剂加入反应釜中C,保持温度为40-60℃;通过灌注系统,将反应釜A、反应釜B和反应釜C中的原料组分经高速旋转混合头混合,注入双螺杆挤出机,同时在双螺杆挤出机喂料口通过微量注射泵加入催化剂,混合物料在双螺杆筒体内均匀反应输送,塑化后经水造粒,即得热塑性有机硅聚氨酯弹性体材料。
原料组分体系的异氰酸酯指数为0.99-1.03。
与现有技术相比,本发明有以下有益效果:
(1)本发明采用端羟烷基改性的有机硅化合物作为有机硅改性剂,具有高反应活性,通过其与异氰酸酯的反应,可在聚氨酯材料原位合成中引入有机硅组分,与共混改性方法只能改进表面性能不同,可以提高聚氨酯材料的低温柔韧性、耐水性、滑爽性、耐撕拉等性能,同时避免了有机硅迁移的问题;
(2)本发明采用有机硅偶联剂,偶联剂上的氨基和烷氧基分别与多元醇的端羟基、聚硅氧烷的羟基进行反应生成嵌段结构,提高相容性,并降低体系的内应力,可以在两种物质界面起架桥作用,作为过渡相的方法来改善聚酯/聚醚多元醇与聚醚/聚酯硅氧烷化合物的相容性,杜绝由于混合不均匀出现的制品分层导致各项性能下降以及有机硅迁移的问题,从而增加硅氧烷化合物的用量,提高体系的各项性能;
(3)本发明采用一步法反应挤出工艺,使聚合物多元醇、端羟烷基改性的有机硅化合物与异氰酸酯、扩链剂反应,嵌入有机硅组分,生成原位聚合的热塑性有机硅聚氨酯弹性体,操作简单,生产效率高。
具体实施方式
以下结合实施例对本发明做进一步说明,但本发明的保护范围不仅限于此,该领域专业人员对本发明技术方案所作的改变,均应属于本发明的保护范围内。
实施例1
以质量份数计,将78.85份聚己二酸乙二醇丁二醇酯二醇(PEBA,M=3000),3份单端双官能团端羟烷基硅氧烷-聚酯化合物(分子量1000,硅氧烷含量为80%),0.8份硅烷偶联剂KH-550,0.4份主抗氧化剂1076,0.2份辅助抗氧化剂168,加入反应釜A中,保持温度为100℃;将15.96份MDI-100加入反应釜B中,保持温度为70℃;将3.75份1,4-丁二醇加入反应釜C中,保持温度为50℃;异氰酸酯指数控制在1.005。待各反应釜温度稳定,通过带有精确计量的灌注系统,将反应釜A、反应釜B和反应釜C中的原料组分经高速旋转混合头混合,注入双螺杆挤出机,同时在双螺杆挤出机喂料口通过微量注射泵加入0.04份异辛酸铋催化剂,混合物料在双螺杆筒体内均匀反应输送,塑化后经水下切粒机切成粒径均匀的椭圆形粒子,即得热塑性有机硅聚氨酯弹性体材料。
实施例2
以质量份数计,将59.39份聚己二酸丁二醇酯二醇(PBA,M=3000),5份双端双官能团端羟烷基硅氧烷-聚醚化合物(分子量4000,硅氧烷含量为95%),0.5份硅烷偶联剂KH-560,0.2份主抗氧化剂1010,0.2份辅助抗氧化剂168,加入反应釜A中,保持温度为100℃;将26.94份MDI-100加入反应釜B中,保持温度为70℃;将7.74份1,4-丁二醇加入反应釜C中,保持温度为50℃;异氰酸酯指数控制在1.005。待各反应釜温度稳定,通过带有精确计量的灌注系统,将反应釜A、反应釜B和反应釜C中的原料组分经高速旋转混合头混合,注入双螺杆挤出机,同时在双螺杆挤出机喂料口通过微量注射泵加入0.03份新癸酸铋催化剂,混合物料在双螺杆筒体内均匀反应输送,塑化后经水下切粒机切成粒径均匀的椭圆形粒子,即得热塑性有机硅聚氨酯弹性体材料。
实施例3
以质量份数计,将44.58份聚四亚甲基醚二醇(PTMG,M=1000),15份双端双官能团端羟烷基硅氧烷-聚醚化合物(分子量2000,硅氧烷含量为50%),0.2份硅烷偶联剂KH-560,0.2份主抗氧化剂1010,0.1份辅助抗氧化剂DLTP,加入反应釜A中,保持温度为100℃;将32.61份MDI-100加入反应釜B中,保持温度为70℃;将7.11份1,4-丁二醇加入反应釜C中,保持温度为50℃;异氰酸酯指数控制在1.005。待各反应釜温度稳定,通过带有精确计量的灌注系统,将反应釜A、反应釜B和反应釜C中的原料组分经高速旋转混合头混合,注入双螺杆挤出机,同时在双螺杆挤出机喂料口通过微量注射泵加入0.02份月桂酸铋催化剂,混合物料在双螺杆筒体内均匀反应输送,塑化后经水下切粒机切成粒径均匀的椭圆形粒子,即得热塑性有机硅聚氨酯弹性体材料。
对比例1
本对比例与实施例2相比,不同点仅在于未加有机硅改性剂及偶联剂,具体制备方法如下:
以质量份数计,将64.72份聚己二酸丁二醇酯二醇(PBA,M=3000),0.2份主抗氧化剂1010,0.2份辅助抗氧化剂168,加入反应釜A中,保持温度为100℃;将27.07份MDI-100加入反应釜B中,保持温度为70℃;将7.7份1,4-丁二醇加入反应釜C中,保持温度为50℃;异氰酸酯指数控制在1.005。待各反应釜温度稳定,通过带有精确计量的灌注系统,将反应釜A、反应釜B和反应釜C中的原料组分经高速旋转混合头混合,注入双螺杆挤出机,同时在双螺杆挤出机喂料口通过微量注射泵加入0.03份新癸酸铋催化剂,混合物料在双螺杆筒体内均匀反应输送,塑化后经水下切粒机切成粒径均匀的椭圆形粒子,即得热塑性聚氨酯弹性体材料。
对比例2
本对比例与实施例2相比,不同点仅在于未加偶联剂,具体制备方法如下:
以质量份数计,将59.72份聚己二酸丁二醇酯二醇(PBA,M=3000),5份双端双官能团端羟烷基硅氧烷-聚醚化合物(分子量4000,硅氧烷含量为95%),0.2份主抗氧化剂1010,0.2份辅助抗氧化剂168,加入反应釜A中,保持温度为100℃;将27.04份MDI-100加入反应釜B中,保持温度为70℃;将7.81份1,4-丁二醇加入反应釜C中,保持温度为50℃;异氰酸酯指数控制在1.005。待各反应釜温度稳定,通过带有精确计量的灌注系统,将反应釜A、反应釜B和反应釜C中的原料组分经高速旋转混合头混合,注入双螺杆挤出机,同时在双螺杆挤出机喂料口通过微量注射泵加入0.03份新癸酸铋催化剂,混合物料在双螺杆筒体内均匀反应输送,塑化后经水下切粒机切成粒径均匀的椭圆形粒子,即得热塑性有机硅聚氨酯弹性体材料。
将实施例1-3和对比例1-2的热塑性聚氨酯弹性体材料通过注塑热压成薄片,进行性能测试,测试方法如下:邵氏硬度测试执行GB/T531.2-2009标准;回弹测试执行GB/T1681-2009标准;拉伸强度测试执行GB/T528-2009标准;撕裂强度测试执行GB/T529-2008标准;磨耗测试执行GB/T9867-2008标准;玻璃化转变温度测试执行GB/T19466.2-2004标准。
测试结果如表1所示。
表1实施例1-3和对比例1的产品性能测试结果
从表1可以看出,与对比例1相比,本发明采用端羟烷基硅氧烷化合物,在热塑性聚氨酯弹性体材料中原位合成,引入有机硅组分,制品表面爽滑,手感好,提高了制品的弹性、力学性能、磨耗性能以及耐低温性能;同时,与对比例2相比,本发明由于偶联剂的加入,提高了有机硅与热塑性弹性体的相容性,杜绝由于混合不均匀出现的制品分层及各项性能下降。

Claims (10)

1.一种热塑性有机硅聚氨酯弹性体材料,其特征在于,由以下质量份数的原料组成:
所述有机硅改性剂为以羟烷基为端基官能团的硅氧烷-聚酯化合物或以羟烷基为端基官能团的硅氧烷-聚醚化合物;
所述热塑性有机硅聚氨酯弹性体材料采用一步反应挤出工艺制备得到。
2.根据权利要求1所述的热塑性有机硅聚氨酯弹性体材料,其特征在于:有机硅改性剂的分子量为1000-4000,硅氧烷质量含量为50-90%。
3.根据权利要求1所述的热塑性有机硅聚氨酯弹性体材料,其特征在于:聚合物多元醇为聚己二酸乙二醇酯二醇、聚己二酸丁二醇酯二醇、聚己二酸乙二醇丁二醇酯二醇、聚己二酸己二醇酯二醇、聚己内酯二元醇或聚四亚甲基醚二醇中的一种或多种,聚合物多元醇的数均分子量为1000-4000。
4.根据权利要求1所述的热塑性有机硅聚氨酯弹性体材料,其特征在于:二异氰酸酯为4,4'-二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯或苯二亚甲基二异氰酸酯中的一种或多种。
5.根据权利要求1所述的热塑性有机硅聚氨酯弹性体材料,其特征在于:扩链剂为含有2-10个碳原子的直链小分子二醇。
6.根据权利要求1所述的热塑性有机硅聚氨酯弹性体材料,其特征在于:偶联剂为有机硅偶联剂。
7.根据权利要求1所述的热塑性有机硅聚氨酯弹性体材料,其特征在于:抗氧化剂由主抗氧剂和辅助氧化剂组成,主抗氧剂为受阻酚或芳香族仲胺类抗氧剂,辅助催化剂为硫酯或亚磷酸酯类抗氧剂。
8.根据权利要求1所述的热塑性有机硅聚氨酯弹性体材料,其特征在于:催化剂为有机铋催化剂。
9.一种权利要求1-8任一项所述的热塑性有机硅聚氨酯弹性体材料的制备方法,其特征在于,包括以下步骤:
将聚合物多元醇、有机硅改性剂、偶联剂和抗氧化剂加入反应釜A中,在95-105℃温度下搅拌;将二异氰酸酯加入反应釜B中,在60-75℃温度下搅拌;将扩链剂加入反应釜中C,保持温度为40-60℃;通过灌注系统,将反应釜A、反应釜B和反应釜C中的原料组分经高速旋转混合头混合,注入双螺杆挤出机,同时在双螺杆挤出机喂料口通过微量注射泵加入催化剂,混合物料在双螺杆筒体内均匀反应输送,塑化后经水下造粒,即得热塑性有机硅聚氨酯弹性体材料。
10.根据权利要求9所述的热塑性有机硅聚氨酯弹性体材料的制备方法,其特征在于:原料组分体系的异氰酸酯指数为0.99-1.03。
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