CN112358599B - 热塑性聚氨酯弹性体及其制备方法和应用 - Google Patents
热塑性聚氨酯弹性体及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种热塑性聚氨酯弹性体及其制备方法和应用，其特征在于，它主要是通过先合成特殊的封闭型聚氨酯树脂B；然后添加高反应活性扩链剂，真空干燥去除溶剂，冷却固化后造粒得到封闭型的热塑性聚氨酯粒料C；热塑性粒料C进行注塑加工，产品经后硫化制得。该热塑性聚氨酯弹性体注塑加工性能好、力学性能高及压缩永久变形小。
Description
技术领域
本发明涉及聚氨酯弹性体技术领域，更具体地说涉及一种易注塑的低压缩变形的热塑性聚氨酯弹性体。
背景技术
热塑性聚氨酯弹性体与热固性聚氨酯弹性体相比具有加工效率高的特点，但常规热塑性聚氨酯弹性体分子基本为线性结构，在注塑过程中，分子量会下降，导致弹性体性能下降。
同时由于常规热塑性聚氨酯弹性体交联密度太低，导致其压缩永久变形较大。为了改善热塑性聚氨酯弹性体压缩永久变形大的问题，很多人进行了大量的改性工作。主要方法是提高热塑性聚氨酯弹性体的交联密度。CN102532464A专利中公布了采用引入TMP或CAPA305等官能度大于2的扩链剂来增大交联密度；CN102311636A中通过引入含有不饱和键的TMPME，然后用过氧化物引发交联反应；“热塑性聚氨酯交联技术的研究进展”(橡塑技术与装备(塑料)，2016年第42卷)中提到采用辐射交联的方式提高热塑性聚氨酯弹性体的交联密度。上述方法对压缩永久变形的改善非常有限，同时注塑加工性严重下降。
发明内容
本发明的目的就是为了解决现有技术之不足而提供的一种热塑性聚氨酯弹性体，该热塑性聚氨酯弹性体注塑加工性能好、力学性能高及压缩永久变形小。
本发明的另一目的在于提供上述热塑性聚氨酯弹性体的制备方法。
本发明的再一目的在于提供上述热塑性聚氨酯弹性体的应用。
本发明是采用如下技术解决方案来实现上述目的：一种热塑性聚氨酯弹性体，其特征在于，它主要是通过先合成一种封闭型聚氨酯树脂B；然后添加高反应活性扩链剂，真空干燥去除溶剂，冷却固化后造粒得到封闭型的热塑性聚氨酯粒料C；热塑性粒料C进行注塑加工，产品经后硫化制得。
作为上述方案的进一步说明，所述封闭型的聚氨酯树脂B是先由低聚物多元醇和多异氰酸酯反应生成NCO基团封端的预聚体A，再加入催化剂及封闭剂和部分NCO基团反应，最后加入溶剂、小分子扩链剂反应至无残留NCO基团。
进一步地，所述低聚物多元醇，官能度为2的己二酸系聚酯二元醇、芳香族聚酯二元醇、聚碳酸酯二元醇、聚己内酯二元醇或聚四氢呋喃二元醇中的一种或几种。
所述低聚物多元醇的分子量为500-4000，优选分子量1000-3000。
所述多异氰酸酯是脂肪族异氰酸酯和芳香族异氰酸酯中的至少一种；优选芳香族异氰酸酯，更进一步的优选4,4’-二苯甲烷二异氰酸酯MDI。
所述催化剂为辛酸亚锡、二月桂酸二丁基锡、辛酸锌、辛酸铅、环烷酸锌、异辛酸铋、三亚乙基二胺中的至少一种，优选二月桂酸二丁基锡或三亚乙基二胺，用量为预聚体A总质量的0.05％-0.1％。
所述封闭剂是含有活性氢的小分子化合物，优选沸点高于200℃的单羟基小分子化合物，避免在注塑加工温度下，低沸点封闭剂气化产生气体，产品出现气泡缺陷进而影响产品性能；具体包括十八醇、二乙二醇单丁醚、壬基苯酚、对甲氧基苯酚、2,4,6-三氯苯酚、2-氯-4-硝基苯酚等中的至少一种。
所述封闭剂中OH基团与预聚体A中NCO基团物质的量比为0.8-0.9。
所述溶剂为四氢呋喃、N,N-二甲基甲酰胺和N,N-二甲基乙酰胺中的至少一种，用量一般为预聚体A总质量的40％-50％。
所述小分子扩链剂为二醇类扩链剂，包括乙二醇、二乙二醇、1，3-丙二醇，1，4-丁二醇、1，5-戊二醇、1，6-己二醇、1，4-环己醇、对苯二酚-双(β-羟乙基)醚和间苯二酚-双(β-羟乙基)醚中的至少一种。
所述小分子扩链剂中OH基团与预聚体A中NCO基团物质的量比为0.1-0.2；其中加入小分子扩链剂和端NCO基的预聚体进行扩链反应，通过配方设计，调节热塑性粒料C至合适的分子量，易于注塑加工；若小分子扩链剂含量过少，粒料分子量低，注塑时容易出现流延现象；小分子扩链剂含量过高，影响弹性体最终性能。
所述高反应活性扩链剂是胺类扩链剂，进一步优选4,4'-二氨基二苯甲烷MDA。
所述高反应活性扩链剂中NH基团与预聚体A中NCO基团的物质的量比为0.78-0.93。
一种热塑性聚氨酯弹性体的制备方法，其特征在于，它包括如下步骤：
a、将干燥的低聚物多元醇加入反应器中，加热至45-55℃，加入多异氰酸酯，在70-80℃下反应2.0-3.0h，得到聚氨酯预聚体A；
b、将计量好的催化剂及封闭剂加入上述聚氨酯预聚体A中，于80-90℃下反应2.0-3.0h，再加入相应的溶剂和小分子扩链剂，在80-90℃下反应40-60min，得到封闭型的聚氨酯树脂B；
c、将高反应活性扩链剂加入上述封闭型的聚氨酯树脂B中，在110-120℃下搅拌混合均匀，倒入涂有脱模剂的浅托盘里，在90-110℃下真空干燥16-20h去除溶剂，室温冷却脱模后得到薄片，将所得薄片破碎成颗粒，即为封闭型的热塑性聚氨酯注塑粒料C；
d、将所述注塑粒料C加入注塑机中注塑成型，制品放入100-120℃烘箱中后硫化20-24h，即得成品。
进一步地，在步骤d中，从进注塑机的料斗开始，注塑温度依次设置为：一段温度80-90℃，二段温度100-110℃，三段温度120-150℃，四段温度160-190℃。
本发明反应原理：通过在端NCO基的预聚体中添加可热解离的封闭剂和小分子扩链剂制得封闭型热塑性聚氨酯注塑粒料，注塑粒料在注塑机中螺杆高温下解封注塑，最后在模具中快速反应成型。
本发明采用上述技术解决方案所能达到的有益效果是：
1、本发明采用新思路，使得热塑性聚氨酯弹性体的分子量增长在模具中进行，规避了常规热塑性聚氨酯粒料在注塑过程中分子量下降这一风险，提高了热塑性聚氨酯弹性体的力学性能；制得特殊的封闭型热塑性聚氨酯注塑粒料，有效的降低了注塑成型温度，并且有很好的流动性，加工成型性能良好。
2、本发明制备得到热塑性聚氨酯弹性体因为加入了部分胺类扩链剂进行扩链反应，增强了弹性体中的两相分离程度，从而有效的改善了弹性体的力学性能和压缩永久变形性能。
3、本发明制备得到热塑性聚氨酯弹性体可应用于加工复杂的薄壁制品，或是需要高机械强度和低压缩永久变形的部件。
具体实施方式
以下结合具体实施例对本技术方案作详细的描述。
实施例1
本发明是一种热塑性聚氨酯弹性体，它的制备方法包括如下步骤：
(1)将500g干燥的PTMG3000加入反应器中，在55℃下加入171.58g MDI，70℃反应3.0h，得到聚氨酯预聚体A；
(2)将0.67g二月桂酸二丁基锡和224.89g十八醇加入聚氨酯预聚体A中，80℃反应3.0h，再加入268.62g N,N-二甲基甲酰胺和6.47g EG在80℃下反应60min，得到封闭型的聚氨酯树脂B；
(3)将80.38g MDA加入封闭型的聚氨酯树脂B中，在110℃下搅拌混合均匀，倒入涂有脱模剂的浅托盘里，在90℃下真空干燥20h去除溶剂，室温冷却脱模后得到薄片，将所得薄片破碎成颗粒，即为封闭型的热塑性聚氨酯注塑粒料C；
(4)将注塑粒料C加入注塑机中注塑成型，制品放入100℃烘箱中后硫化20h，即得成品。从进料斗开始，注塑温度依次设置为：一段温度80℃，二段温度100℃，三段温度120℃，四段温度160℃。
实施例2
本发明是一种热塑性聚氨酯弹性体，它的制备方法包括如下步骤：
(1)将500g干燥的PEA2000加入反应器中，在50℃下加入184.76g MDI，80℃反应2.0h，得到聚氨酯预聚体A；
(2)将0.55g二月桂酸二丁基锡及134.89g二乙二醇单丁醚加入聚氨酯预聚体A中，90℃反应2.0h，再加入308.14g N,N-二甲基甲酰胺和8.67g HDO在85℃下反应50min，得到封闭型的聚氨酯树脂B；
(3)将82.43g MDA加入封闭型的聚氨酯树脂B中，在115℃下搅拌混合均匀，倒入涂有脱模剂的浅托盘里，在100℃下真空干燥18h去除溶剂，室温冷却脱模后得到薄片，将所得薄片破碎成颗粒，即为封闭型的热塑性聚氨酯注塑粒料C；
(4)将注塑粒料C加入注塑机中注塑成型，制品放入110℃烘箱中后硫化22h，即得成品。从进料斗开始，注塑温度依次设置为：一段温度85℃，二段温度105℃，三段温度140℃，四段温度180℃。
实施例3：
本发明是一种热塑性聚氨酯弹性体，它的制备方法包括如下步骤：
(1)将500g干燥的PCDL1000加入反应器中，在50℃下，加入247.35g MDI，80℃下反应2.0h，得到聚氨酯预聚体A；
(2)将0.37g三亚乙基二胺及183.3g壬基苯酚加入聚氨酯预聚体中，90℃反应2.0h，再加入373.68g N,N-二甲基甲酰胺和8.66g HDO在85℃下反应40min，得到封闭型的聚氨酯树脂B；
(3)将82.48g MDA加入封闭型聚氨酯树脂B中，在120℃下搅拌混合均匀，倒入涂有脱模剂的浅托盘里，在110℃下真空干燥16h去除溶剂，室温冷却脱模后得到薄片，将所得薄片破碎成颗粒，即为封闭型的热塑性聚氨酯注塑粒料C；
(4)将注塑粒料C加入注塑机中注塑成型，制品放入120℃烘箱中后硫化24h，即得成品。从进料斗开始，注塑温度依次设置为：一段温度90℃，二段温度110℃，三段温度150℃，四段温度190℃。
实施例4
本发明是一种热塑性聚氨酯弹性体，它的制备方法包括如下步骤：
(1)将500g干燥的PCL2000加入反应器中，在45℃下加入190g MDI，75℃反应2.5h，得到聚氨酯预聚体A；
(2)将0.55g三亚乙基二胺和113.96g对甲氧基苯酚加入聚氨酯预聚体A中，85℃反应2.5h，再加入310.5g N,N-二甲基甲酰胺和4.6g BDO在85℃下反应40min，得到封闭型的聚氨酯树脂B；
(3)将93.92g MDA加入封闭型的聚氨酯树脂B中，在115℃下搅拌混合均匀，倒入涂有脱模剂的浅托盘里，在100℃下真空干燥18h去除溶剂，室温冷却脱模后得到薄片，将所得薄片破碎成颗粒，即为封闭型的热塑性聚氨酯注塑粒料C；
(4)将注塑粒料加入注塑机中注塑成型，制品放入120℃烘箱中后硫化22h，即得成品。从进料斗开始，注塑温度依次设置为：一段温度85℃，二段温度105℃，三段温度130℃，四段温度170℃。
对比例1：
本发明是一种热塑性聚氨酯弹性体，它的制备方法包括如下步骤：
(1)将500g干燥的PCL2000加入反应器中，在55℃下加入336.2g MDI，75℃下反应2.5h，得到聚氨酯预聚体A；
(2)预聚体A温度保持在60℃下，加入73.8g BDO搅拌混合均匀，倒入涂有脱模剂的浅托盘里，放入100℃烘箱中后硫化22h，脱模后得到薄片，将所得薄片破碎成为颗粒，即为热塑性聚氨酯注塑粒料D；
(3)将注塑粒料D加入注塑机中注塑成型，制品放入120℃烘箱中后硫化22h，即得成品。从进料斗开始，注塑温度依次设置为：一段温度200℃，二段温度210℃，三段温度225℃，四段温度225℃。
对比例2：
本发明是一种热塑性聚氨酯弹性体，它的制备方法包括如下步骤：
(1)将500g干燥PCL2000加入反应器中，在55℃下加入190g MDI，75℃下反应2.5h，得到聚氨酯预聚体A；
(2)将310.5g N,N-二甲基甲酰胺和4.6g BDO加入聚氨酯预聚体A中，85℃反应40min。再加入93.92g MDA，在115℃下搅拌混合均匀，倒入涂有脱模剂的浅托盘里，在100℃下真空干燥18h去除溶剂，室温冷却脱模后得到薄片，将所得薄片破碎成颗粒，即为封闭型的热塑性聚氨酯注塑粒料D；
(3)从进料斗开始，注塑温度依次设置为：一段温度245℃，二段温度255℃，三段温度260℃，四段温度260℃。将注塑粒料D加入注塑机中，注塑机螺杆推进失败，不能进行注塑成型。
聚氨酯弹性体的性能测试:
对实施例1-4和对比例1-2制备得到的聚氨酯弹性体进行性能测试按照以下方法进行，结果见表1。
硬度：硬度测试按照GB/T 531.1-2008进行；
拉伸强度：拉伸强度测试按照GB/T 528-2009进行；
撕裂强度：撕裂强度测试按照GB/T 529-2008进行；
耐磨性：耐磨性测试按照GB/T 9867-2008进行；
压缩永久变形：压缩永久变形测试按照GB/T 7759.1-2015进行，测试条件为100℃*24h，压缩率10％；
回弹性：回弹性测试按照GB/T 1681-2009进行。
表1聚氨酯弹性体的性能指标
上述检测结果表明本发明制备获得的热塑性聚氨酯弹性体具有优异的物理力学性能和低压缩永久变形性能。可以更好地适应高压密封件、汽车减震垫和其他要求具有高机械强度和低压缩永久变形部件的需要。
以上所述的仅是本发明的优选实施方式，应当指出，对于本领域的普通技术人员来说，在不脱离本发明创造构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。
Claims (6)
1.一种热塑性聚氨酯弹性体的制备方法，其特征在于，先合成封闭型聚氨酯树脂B；然后添加高反应活性扩链剂，真空干燥去除溶剂，冷却固化后造粒得到封闭型的热塑性聚氨酯粒料C；热塑性聚氨酯粒料C进行注塑加工，产品经后硫化制得；所述封闭型聚氨酯树脂B是先由低聚物多元醇和多异氰酸酯反应生成NCO基团封端的预聚体A，再加入催化剂及封闭剂和部分NCO基团反应，最后加入溶剂、小分子扩链剂反应至无残留NCO基团；
所述封闭剂是含有活性氢的小分子化合物，包括十八醇、二乙二醇单丁醚、壬基苯酚、对甲氧基苯酚、2,4,6-三氯苯酚、2-氯-4-硝基苯酚中的至少一种；
所述封闭剂中OH基团与预聚体A中NCO基团物质的量比为0.8-0.9；小分子扩链剂为二醇类扩链剂，包括乙二醇、二乙二醇、1，3-丙二醇，1，4-丁二醇、1，5-戊二醇、1，6-己二醇、1，4-环己醇、对苯二酚-双（β-羟乙基）醚和间苯二酚-双（β-羟乙基）醚中的至少一种；低聚物多元醇，采用己二酸系聚酯二元醇、芳香族聚酯二元醇、聚碳酸酯二元醇、聚己内酯二元醇或聚四氢呋喃二元醇中的一种或几种；高反应活性扩链剂是胺类扩链剂。
2.根据权利要求1所述的热塑性聚氨酯弹性体的制备方法，其特征在于，所述溶剂为四氢呋喃、N,N-二甲基甲酰胺和N,N-二甲基乙酰胺中的至少一种，用量为预聚体A总质量的40%-50%。
3.根据权利要求1所述的热塑性聚氨酯弹性体的制备方法，其特征在于，所述低聚物多元醇的分子量为500-4000；多异氰酸酯是脂肪族异氰酸酯和芳香族异氰酸酯中的至少一种；催化剂为辛酸亚锡、二月桂酸二丁基锡、辛酸锌、辛酸铅、环烷酸锌、异辛酸铋、三亚乙基二胺中的至少一种，用量为预聚体A总质量的0.05%-0.1%；小分子扩链剂中OH基团与预聚体A中NCO基团物质的量比为0.1-0.2；高反应活性扩链剂中NH基团与预聚体A中NCO基团的物质的量比为0.78-0.93。
4.根据权利要求1所述的热塑性聚氨酯弹性体的制备方法，其特征在于，它包括如下步骤：
a、将干燥的低聚物多元醇加入反应器中，加热至45-55℃，加入多异氰酸酯，在70-80℃下反应2.0-3.0h，得到预聚体A；
b、将计量好的催化剂及封闭剂加入上述预聚体A中，于80-90℃下反应2.0-3.0h，再加入相应的溶剂和小分子扩链剂，在80-90℃下反应40-60min，得到封闭型的聚氨酯树脂B；
c、将高反应活性扩链剂加入上述封闭型聚氨酯树脂B中，在110-120℃下搅拌混合均匀，倒入涂有脱模剂的浅托盘里，在90-110℃下真空干燥16-20h去除溶剂，室温冷却脱模后得到薄片，将所得薄片破碎成颗粒，即为封闭型热塑性聚氨酯粒料C；
d、将所述热塑性聚氨酯粒料C加入注塑机中注塑成型，制品放入100-120℃烘箱中后硫化20-24h，即得产品。
5.根据权利要求4所述的热塑性聚氨酯弹性体的制备方法，其特征在于，在步骤d中，从进注塑机的料斗开始，注塑温度依次设置为：一段温度80-90℃，二段温度100-110℃，三段温度120-150℃，四段温度160-190℃。
6.一种如权利要求1-5任意一项所述的热塑性聚氨酯弹性体的制备方法制备得到的热塑性聚氨酯弹性体的应用，其特征在于，它是用于加工薄壁制品，或是需要高机械强度和低压缩永久变形的部件。
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