CN107652412B - 聚醚硅酮共聚物改性热塑性聚氨酯弹性体及其制备方法 - Google Patents

聚醚硅酮共聚物改性热塑性聚氨酯弹性体及其制备方法 Download PDF

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CN107652412B
CN107652412B CN201711043907.6A CN201711043907A CN107652412B CN 107652412 B CN107652412 B CN 107652412B CN 201711043907 A CN201711043907 A CN 201711043907A CN 107652412 B CN107652412 B CN 107652412B
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陈淑海
肖培栋
张宁
张倩
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Shandong Dongda Inov Polyurethane Co Ltd
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Abstract

本发明属于高分子材料合成领域，具体涉及一种聚醚硅酮共聚物改性热塑性聚氨酯弹性体及其制备方法。由如下质量分数原料制成：聚酯型二醇40％～70％，二异氰酸酯15％～50％，扩链剂3％～14％，聚醚硅酮共聚物1％～5％，抗氧化剂0.1％～0.5％，光稳定剂0.1％～0.5％；催化剂0.005％～0.05％。本发明具有优异的抗水解性能，在解决耐水解性能的同时，具有优异的耐磨性能，并有效的降低了产品成本；本发明还提供其制备方法，生产加工简单易行。

Description

聚醚硅酮共聚物改性热塑性聚氨酯弹性体及其制备方法
技术领域
本发明属于高分子材料合成领域，具体涉及一种聚醚硅酮共聚物改性热塑性聚氨酯弹性体及其制备方法。
背景技术
热塑型聚氨酯弹性体(TPU)是一类加热可以塑化、溶剂可以溶解的聚氨酯材料，具有独特的软硬段嵌段共聚物结构，因其同时具有橡胶的弹性和塑料的可加工性，被广泛应用于诸多领域。聚酯型TPU具有优良的机械性能，高强度、高伸长和高弹性，其不足之处在于耐湿热性能不佳，长期在湿热环境中使用可导致TPU链段发生水解而降低其力学性能，大大限制了应用。通常用的耐水解型聚氨酯弹性体多为聚醚型，然而聚醚型聚氨酯弹性体拉伸强度和撕裂性能稍差，无法满足特殊条件下的使用要求，且聚醚型TPU的成本高，限制了其应用领域。对聚酯型聚氨酯弹性体通过添加适量的水解稳定剂，能够提高弹性体的水解稳定性，即使长期在湿热环境中使用也能保持较高的力学性能。通常添加的水解稳定剂为碳化二亚胺类，但目前碳化二亚胺类抗水解剂产品主要依赖进口，价格高昂，使其在产品应用中受到限制。
发明内容
针对现有技术的不足，本发明的目的是提供一种聚醚硅酮共聚物改性热塑性聚氨酯弹性体，具有优异的抗水解性能，在解决耐水解性能的同时，具有优异的耐磨性能，并有效的降低了产品成本；本发明还提供其制备方法，生产加工简单易行。
本发明所述的聚醚硅酮共聚物改性热塑性聚氨酯弹性体，由如下质量分数原料制成：
Figure BDA0001451830530000011
聚酯型二醇为聚己二酸乙二醇酯二醇、聚己二酸丁二醇酯二醇或聚己二酸己二醇酯二醇中的一种或几种以任意比例混合，聚酯型二醇分子量为1000-4000。
聚酯型二醇的羟值为28.5-75mgKOH/g。
二异氰酸酯为：4,4'-二苯基甲烷二异氰酸酯、亚苯基-1,4-二异氰酸酯、甲苯二异氰酸酯、1,4-环己基-二异氰酸酯或癸烷-1,10-二异氰酸酯中的一种；优选的是4,4'-二苯基甲烷二异氰酸酯(MDI-100)。添加量优选为20％～40％。
扩链剂为1,4-丁二醇、乙二醇、1,2-丙二醇、2-甲基-1,3-丙二醇或1,6-己二醇；优选丁二醇和/或己二醇。
聚醚硅酮共聚物为羟基封端、二官能度的聚醚与有机硅ABA型嵌段共聚物，优选为Dow
Figure BDA0001451830530000021
Q4-3667。
抗氧化剂为受阻酚类抗氧剂、亚磷酸酯类抗氧剂或含硫抗氧剂；优选1010、1076、168、626、DLTDP或DMTDP中的一种或几种的混合物。
光稳定剂为Tinuvin 770、Tinuvin234或Tinuvin571中的一种或几种以任意比例混合。
催化剂为有机铋、有机锡或钛酸酯类催化剂。
本发明所述的聚醚硅酮共聚物改性热塑性聚氨酯弹性体的制备方法，由聚酯型二醇、二异氰酸酯和扩链剂，在适量聚醚硅酮共聚物的存在下经一步法制成。具体包括以下步骤：
将聚酯型二醇、聚醚硅酮共聚物、抗氧化剂、光稳定剂和催化剂混合加热至100-115℃，充分混合均匀；二异氰酸酯加热至45-55℃；扩链剂加热至45-55℃；将加热后的各原料组分通过精确计量混合注入双螺杆反应机，混合物料在双螺杆反应机内反应塑化，经水下切粒后得到产品。
综上所述，本发明具有以下优点：
(1)本发明由于聚醚硅酮大分子本身较强的空间位阻作用及硅油链段的疏水性，可以保护并减少水分子对酯类基团的攻击，使得该聚氨酯弹性体具有优异的抗水解性能，且该聚醚硅酮产品成本较为低廉，可得到更为广泛的应用。另外，由于硅油链段的润滑性，有效提高了TPU的耐磨性能，效果显著。
(2)本发明能够抑制聚酯型TPU在湿热环境下发生的自降解行为，同时提高了制品的耐磨性能；水解测试拉伸强度维持率最高达到88％，展现了优异的耐磨性能。
(3)提供了一种新的聚酯型TPU产品耐水解解决方案，在80℃×95％RH/7d的条件下，弹性体的拉伸强度保留原强度百分比不低于80％，显示了良好的耐水解性能，并有效的降低了产品成本；在解决耐水解性能的同时，获得了更优的耐磨性能；
(4)本发明还提供其制备方法，生产加工简单易行，聚醚硅酮为无色透明低粘度液体物料，储存、添加方便，性质稳定，可直接添加到聚酯型二醇组分或采用侧添加方式，对产品外观、反应性无负面影响。
具体实施方式
下面结合实施例对本发明做进一步说明。
实施例1
一种聚醚硅酮共聚物改性热塑性聚氨酯弹性体，由以下重量百分数的原料制成：
Figure BDA0001451830530000031
制备工艺：将聚己二酸丁二醇酯二醇、Dow
Figure BDA0001451830530000032
Q4-3667、1010、770和T-9混合加热至100-115℃，充分混合均匀；MDI-100加热至45-55℃；1，6-己二醇加热至55-65℃；将加热后的各原料组分通过精确计量混合注入双螺杆反应机，混合物料在双螺杆反应机内反应塑化，经水下切粒后得到相关产品。
实施例2
一种聚醚硅酮共聚物改性热塑性聚氨酯弹性体，由以下重量百分数的原料制成：
Figure BDA0001451830530000033
制备工艺：将聚己二酸丁二醇酯二醇、Dow
Figure BDA0001451830530000034
Q4-3667、1010、770和T-9混合加热至100-115℃，充分混合均匀；MDI-100加热至45-55℃；BDO加热至45-55℃；将加热后的各原料组分通过精确计量混合注入双螺杆反应机，混合物料在双螺杆反应机内反应塑化，经水下切粒后得到相关产品。
实施例3：
一种聚醚硅酮共聚物改性热塑性聚氨酯弹性体，由以下重量百分数的原料制成：
Figure BDA0001451830530000041
制备工艺：将聚己二酸丁二醇酯二醇、Dow
Figure BDA0001451830530000042
Q4-3667、1010、770和T-9混合加热至100-115℃，充分混合均匀；MDI-100加热至45-55℃；BDO加热至45-55℃；将加热后的各原料组分通过精确计量混合注入双螺杆反应机，混合物料在双螺杆反应机内反应塑化，经水下切粒后得到相关产品。
实施例4：
一种聚醚硅酮共聚物改性热塑性聚氨酯弹性体，由以下重量百分数的原料制成：
Figure BDA0001451830530000043
制备工艺：将聚己二酸丁二醇酯二醇、Dow
Figure BDA0001451830530000044
Q4-3667、1010、770和T-9混合加热至100-115℃，充分混合均匀；MDI-100加热至45-55℃；BDO加热至45-55℃；将加热后的各原料组分通过精确计量混合注入双螺杆反应机，混合物料在双螺杆反应机内反应塑化，经水下切粒后得到相关产品。
对比例1
一种聚醚硅酮共聚物改性热塑性聚氨酯弹性体，由以下重量百分数的原料制成：
Figure BDA0001451830530000051
制备工艺：将聚己二酸丁二醇酯二醇、Dow
Figure BDA0001451830530000052
Q4-3667、1010、770和T-9混合加热至100-115℃，充分混合均匀；MDI-100加热至45-55℃；BDO加热至45-55℃；将加热后的各原料组分通过精确计量混合注入双螺杆反应机，混合物料在双螺杆反应机内反应塑化，经水下切粒后得到相关产品。
耐水解测试按照GE-08恒温恒湿测量方法，温度70℃，相对湿度为95％，测试周期为168h。
磨耗测试按照GB/T 9867-2008测定。
各实施例和对比例所制得聚氨酯弹性体制品性能如表1。
表1
Figure BDA0001451830530000053
从表中数据可以看出，本发明产品的耐水解性能和耐磨性能均有大幅提升，并且未对制品的力学强度造成不利影响。

Claims (7)

1.一种聚醚硅酮共聚物改性热塑性聚氨酯弹性体，其特征在于：由如下质量分数原料制成：
Figure FDA0002666105150000011
聚醚硅酮共聚物为Q4-3667；
聚酯型二醇为聚己二酸乙二醇酯二醇、聚己二酸丁二醇酯二醇或聚己二酸己二醇酯二醇中的一种或几种以任意比例混合，聚酯型二醇分子量为1000-4000；
聚酯型二醇的羟值为28.5-75mgKOH/g。
2.根据权利要求1所述的聚醚硅酮共聚物改性热塑性聚氨酯弹性体，其特征在于：二异氰酸酯为：4,4'-二苯基甲烷二异氰酸酯、亚苯基-1,4-二异氰酸酯、甲苯二异氰酸酯、1,4-环己基-二异氰酸酯或癸烷-1,10-二异氰酸酯中的一种。
3.根据权利要求1所述的聚醚硅酮共聚物改性热塑性聚氨酯弹性体，其特征在于：扩链剂为1,4-丁二醇、乙二醇、1,2-丙二醇、2-甲基-1,3-丙二醇或1,6-己二醇。
4.根据权利要求1所述的聚醚硅酮共聚物改性热塑性聚氨酯弹性体，其特征在于：抗氧化剂为受阻酚类抗氧剂、亚磷酸酯类抗氧剂或含硫抗氧剂。
5.根据权利要求1所述的聚醚硅酮共聚物改性热塑性聚氨酯弹性体，其特征在于：光稳定剂为Tinuvin770、Tinuvin234或Tinuvin571中的一种或几种以任意比例混合。
6.根据权利要求1所述的聚醚硅酮共聚物改性热塑性聚氨酯弹性体，其特征在于：催化剂为有机铋、有机锡或钛酸酯类催化剂。
7.一种权利要求1-6任一所述的聚醚硅酮共聚物改性热塑性聚氨酯弹性体的制备方法，其特征在于：包括以下步骤：
将聚酯型二醇、聚醚硅酮共聚物、抗氧化剂、光稳定剂和催化剂混合加热至100-115℃，充分混合均匀；二异氰酸酯加热至45-55℃；扩链剂加热至45-55℃；将加热后的各原料组分通过精确计量混合注入双螺杆反应机，混合物料在双螺杆反应机内反应塑化，经水下切粒后得到产品。
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