CN110183843B - 一种耐黄变的热塑性聚氨酯发泡材料及其制备方法 - Google Patents

一种耐黄变的热塑性聚氨酯发泡材料及其制备方法 Download PDF

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CN110183843B
CN110183843B CN201910411191.3A CN201910411191A CN110183843B CN 110183843 B CN110183843 B CN 110183843B CN 201910411191 A CN201910411191 A CN 201910411191A CN 110183843 B CN110183843 B CN 110183843B
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thermoplastic polyurethane
yellowing
polyurethane elastomer
foam
resistant
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CN110183843A (zh
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宋红玮
王光阜
杨冲冲
任光雷
钮华荣
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Miracll Chemicals Co Ltd
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Miracll Chemicals Co Ltd
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Priority to CN201910411191.3A priority Critical patent/CN110183843B/zh
Publication of CN110183843A publication Critical patent/CN110183843A/zh
Priority to JP2021566987A priority patent/JP7361415B2/ja
Priority to BR112021022846A priority patent/BR112021022846A2/pt
Priority to US17/594,669 priority patent/US20220213253A1/en
Priority to EP20805765.3A priority patent/EP3950842A4/en
Priority to PCT/CN2020/087850 priority patent/WO2020228540A1/zh
Priority to KR1020217035828A priority patent/KR20210151127A/ko
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Abstract

本发明涉及一种耐黄变的热塑性聚氨酯发泡材料及其制备方法，属于高分子发泡材料领域，所述耐黄变的热塑性聚氨酯发泡材料包括由脂肪族二异氰酸酯、扩链剂、多元醇、抗氧剂、UV吸收剂和UV光稳定剂反应制得的热塑性聚氨酯弹性体，所述热塑性聚氨酯弹性体的软化点为90‑160℃，邵氏硬度为40A‑98A，熔融指数为5‑250g/10min。所制备的耐黄变的热塑性聚氨酯发泡材料具有优异的耐黄变性能，发泡密度可控，泡孔尺寸均匀。

Description

一种耐黄变的热塑性聚氨酯发泡材料及其制备方法
技术领域
本发明属于高分子发泡材料领域，具体涉及一种耐黄变的热塑性聚氨酯发泡材料及其制备方法。
背景技术
以塑料为基体，通过物理或化学方法在塑料内部填充大量气泡，得到聚合物发泡材料。泡沫材料具有密度低、隔热隔音、比强度高、缓冲等一列优点，因此在包装业、工业、农业、交通运输业、军事工业、航天工业以及日用品等领域得到广泛应用。常用的泡沫塑料品种有聚氨酯(PU)软质和硬质泡沫塑料、聚苯乙烯(PS)泡沫塑料、聚乙烯(PE)泡沫塑料、聚丙烯(PP)泡沫塑料等。但是聚氨酯泡沫塑料在发泡过程中容易残留异氰酸酯，对人体有害，并且发泡材料无法回收利用。聚苯乙烯泡沫塑料产品降解困难，易产生“白色污染”问题，联合国环境组织已决定停止使用PS泡沫塑料产品。聚乙烯泡沫塑料耐高温性能较差，不适合在高温领域内应用。
热塑性聚氨酯弹性体(TPU)具有较宽泛的硬度范围，优异的耐磨性、机械强度、耐水、耐油、耐化学腐蚀、耐霉菌，对环境友好，可回收利用等优点。通过将发泡热塑性聚氨酯粒子填充到模具中，利用水蒸气进行加热成型可得到模塑发泡制品。此种制品在保留原基体优异的性能之外，同时拥有优异的回弹性，形状多样性，低密度，可以在较宽的温度范围内使用。基于上述优点，TPU发泡材料在许多工业领域(汽车工业、包装材料)以及日常生活领域(鞋材、枕头、床垫)具有非常广泛的应用前景。
热塑性聚氨酯发泡材料(E-TPU)在专利文献WO2007/082838A、WO2010/136398A、CN102229709A、CN102276785A、CN103183805A中已经被公开，采用的TPU树脂原料普遍是由MDI等芳族异氰酸酯合成的。热塑性聚氨酯发泡材料制品在户外使用过程中，会受到长时间的阳光照射，由MDI等芳族异氰酸酯合成的TPU树脂发泡材料在紫外线的作用下芳香环的二氨基甲酸酯桥键结构会自动氧化成醌-亚胺键或偶氮化合物，同时伴随制品变黄和力学性能的下降。目前现有公开的专利技术是通过在热塑性聚氨酯树脂原料中添加大量的耐UV助剂提高材料的抗黄变性能，但现有技术仍存在以下缺陷：(1)抗UV助剂的加入无法从源头上解决TPU变黄的本质这一事实是个问题，并且随着制品使用时间的延长，抗UV助剂效果会逐渐降低，并最终导致制品的性能大大降低，使用寿命缩短。(2)抗UV助剂通常是在制备热塑性聚氨酯材料或后续改性热塑性聚氨酯材料的过程中加入，特别是针对耐黄变性能要求高的行业，如鞋材领域，需要加入大量的抗UV助剂实现制品使用寿命的延长。然而大量抗UV助剂的加入会极大的影响到热塑性聚氨酯弹性体合成过程的稳定性和后续热塑性聚氨酯发泡粒子的最终性能。因此，开发一种具有优异耐黄变性能的热塑性聚氨酯发泡材料是目前亟待解决的问题。
发明内容
本发明为了解决上述技术问题提供一种耐黄变的热塑性聚氨酯发泡材料及其制备方法，所制备的耐黄变的热塑性聚氨酯发泡材料具有优异的耐黄变性能，发泡密度可控，泡孔尺寸均匀。
本发明解决上述技术问题的技术方案如下：一种耐黄变的热塑性聚氨酯发泡材料，包括由脂肪族二异氰酸酯、扩链剂、多元醇、抗氧剂、UV吸收剂和UV光稳定剂反应制得的热塑性聚氨酯弹性体，所述热塑性聚氨酯弹性体的软化点为90-160℃，优选95-150℃，特别优选100-150℃，邵氏硬度为40A-98A，优选60-90A，特别优选75-88A，熔融指数为5-250g/10min。
本发明耐黄变的热塑性聚氨酯发泡材料的有益效果是：
本发明所制备的发泡材料在300h长时间加速测试下的耐黄变等级为5级，不黄变，耐黄变性能非常好，耐黄变性能明显优于目前传统的热塑性聚氨酯发泡材料，并且能得到密度0.05-0.5g/cm3的发泡材料，发泡密度可控，泡孔尺寸均匀，同时兼顾有良好的回弹性和机械强度性能，由于脂肪族型热塑性聚氨酯在长时间光照环境下不会发生氨基甲酸酯桥键结构自动氧化成醌-亚胺键或偶氮化合物变黄，更能够提高耐黄变性能。
在上述技术方案的基础上，本发明还可以做如下改进。
进一步，所述脂肪族二异氰酸酯包括六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、苯二亚甲基二异氰酸酯(XDI)或氢化苯基甲烷二异氰酸酯(H12MDI)、环已基二亚甲基二异氰酸酯(H6XDI)、环己基二异氰酸酯中的一种或多种的混合物。
采用上述进一步方案的有益效果是：选用上述原料，使得发泡材料耐黄变性能更好。
进一步，所述扩链剂包括1，2-乙二醇、1，3-丙二醇、1，4-丁二醇、1，6-己二醇和环己烷二甲醇中的一种或多种混合物。
采用上述进一步方案的有益效果是：选用上述原料作为扩链剂能够提高耐黄变的热塑性聚氨酯发泡材料的机械性能。
进一步，所述抗氧剂用量为占所述热塑性聚氨酯弹性体总量的0-0.3％，所述抗氧剂为受阻酚类抗氧化剂或亚磷酸酯类抗氧剂。
进一步，所述UV吸收剂用量为占所述热塑性聚氨酯弹性体总量的0.5-1.5％，所述UV吸收剂为苯并三唑类紫外线吸收剂、甲脒类紫外线吸收剂、三嗪类紫外线吸收剂或苯甲酮类紫外线吸收剂；
进一步，所述UV光稳定剂用量为占所述热塑性聚氨酯弹性体总量的0.5-4％，所述UV光稳定剂为受阻胺类光稳定剂。
采用上述进一步方案的有益效果是：进一步提高耐黄变效果。
进一步，所述多元醇为官能度为1.9-2.1的聚碳酸酯多元醇、聚己内酯多元醇或聚醚多元醇中的一种或多种混合物。
采用上述进一步方案的有益效果是：能够提高制成的热塑性聚氨酯发泡材料的回弹性。
本发明还提供一种耐黄变的热塑性聚氨酯发泡材料制备方法，包括热塑性聚氨酯弹性体，将所述热塑性聚氨酯弹性体，经过物理发泡工艺得到耐黄变的热塑性聚氨酯发泡材料，所述热塑性聚氨酯发泡材料密度为0.05-0.5g/cm3，泡孔尺寸为10-200um。
本发明耐黄变的热塑性聚氨酯发泡材料的制备方法的有益效果是：通过本制备方法能够保持由热塑性聚氨酯弹性体发泡制成的热塑性聚氨酯发泡材料具有良好的机械性能。
进一步，所述物理发泡工艺优选通过以下方式进行：包括取100重量份的热塑性聚氨酯弹性体，1-60重量份的物理发泡剂和100-500的重量份水，加入到耐压容器中搅拌形成悬浮液，然后升温至80-160℃，保持压力为10-250bar，恒温恒压0-180分钟，最后将压力容器内的悬浮液排放到大气环境中，得到耐黄变的热塑性聚氨酯发泡材料。
采用上述进一步方案的有益效果是：通过预混合物料进行升温并控制压力，实现快速发泡，发泡后的热塑性聚氨酯发泡材料具有良好的拉伸强度和回弹性。
进一步，所述物理发泡工艺还可以通过以下方式进行：包括取100重量份的热塑性聚氨酯弹性体投入挤出机中熔融，然后在挤出机的末端注入物理发泡剂，控制压力为10-250bar，控制挤出机模头温度为80-180℃，模头压力为10-150bar，最后通过模头挤出得到耐黄变的热塑性聚氨酯发泡材料。
采用上述进一步方案的有益效果是：通过挤出机来实现热塑性聚氨酯弹性体，能够直接制成发泡颗粒或发泡板材状，适用范围更广。
进一步，所述物理发泡工艺包括取100重量份的热塑性聚氨酯弹性体投入到耐压容器中，并注入1-100重量份的物理发泡剂到耐压容器中，使压力达到10-350bar，压力维持1-48h，使物理发泡剂在热塑性聚氨酯弹性体内部达到溶解平衡，然后将溶解平衡的物料置于100-140℃温度环境内加热发泡，得到耐黄变的热塑性聚氨酯发泡材料。
采用上述进一步方案的有益效果是：先增压在进行发泡，使得发泡剂能够完全进入到热塑性聚氨酯弹性体，发泡效果更好，回弹性更优良。
进一步，所述物理发泡剂包括氮气、二氧化碳、空气、甲烷、丙烷、丁烷或戊烷中的一种或几种混合物。
采用上述进一步方案的有益效果是：发泡效果更好。
另外本发明还提供上述热塑性聚氨酯发泡材料在弹性泡沫领域中的应用，特别适用于鞋材，地面覆盖物，交通工具部件，玩具等。
具体实施方式
以下对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
一种耐黄变的热塑性聚氨酯发泡材料，包括由脂肪族二异氰酸酯、扩链剂、多元醇、抗氧剂、UV吸收剂和UV光稳定剂反应制得的热塑性聚氨酯弹性体。
具体的，通过以下方法制备得到：采用脂肪族二异氰酸酯、摩尔质量为500-10000g/mol的多元醇以及摩尔质量为50-500g/mol的扩链剂混合，使用挤出反应型挤出机，采用一锅法或预聚物方法在150-200℃下进行反应，生产热塑性聚氨酯弹性体。
上述制备热塑性聚氨酯弹性体的反应中各组分的调节指数为80-110；具体的指数为：脂肪族二异氰酸酯中的异氰酸酯基团的摩尔数与扩链剂和多元醇中对异氰酸酯基团具有反应性基团的摩尔数的比率。
所述热塑性聚氨酯弹性体的软化点为90-160℃，通过岛津CFT-500系列流变仪测得软化点；邵氏硬度为40A-98A，通过邵氏A型硬度计测量硬度；熔融指数为5-250g/10min，根据ASTM D1238，在210℃，施加5kg负荷测试得到熔融指数；发泡材料的耐黄变等级为4.5-5级，其根据ASDM-D1148采用340nmUVA灯，灯照射强度为0.77W/m2/nm或HG/T3689-2001A法于300h照射测试得到的，根据IS0105-A02：1993，耐黄变等级是在标准光源D65下评定，5级代表材料未变黄，4.5级代表材料只有微弱的变黄，1级代表材料变黄非常严重。
具体的，所述脂肪族二异氰酸酯为六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、苯二亚甲基二异氰酸酯(XDI)或氢化苯基甲烷二异氰酸酯(H12MDI)、环已基二亚甲基二异氰酸酯(H6XDI)、环己基二异氰酸酯；
所述扩链剂包括摩尔质量为50-500g/mol的脂肪族、芳香族或脂环族二醇化合物；具体的所述扩链剂为C原子数为2-14的1，2-乙二醇、1，3-丙二醇、1，4-丁二醇、1，6-己二醇或环己烷二甲醇，或者扩链剂为2-羟乙基醚、间苯二醇双(羟乙基)醚或1，4-二羟甲基环己烷；
优选地，所述扩链剂为1，4-丁二醇。
优选地，所述抗氧剂用量为占其总量的0-0.3％，优选的抗氧剂用量为占其总量的0-0.1％，抗氧剂为受阻酚类抗氧化剂或亚磷酸酯类抗氧剂，具体的牌号为BASF(巴斯夫)公司的Irganox1010、Irganox1076、Irganox1098、Irganox3114、Irganox126、Irgafos168或Irgafos 618；所述UV吸收剂用量为占所述热塑性聚氨酯弹性体总量的0.5-1.5％，优选的UV吸收剂用量为占所述热塑性聚氨酯弹性体总量的0.8-1.5％，UV吸收剂为苯并三唑类紫外线吸收剂、甲脒类紫外线吸收剂、三嗪类紫外线吸收剂或苯甲酮类紫外线吸收剂，具体的牌号为BASF公司的TinuvinP、Tinuvin327、Tinuvin328、Tinuvin329、Tinuvin234、Tinuvin312、TinuvinUV-1或TinuvinUV-3；所述UV光稳定剂用量为占所述热塑性聚氨酯弹性体总量的0.5-4％，优选地UV光稳定剂用量为占其总量的1-3％，UV光稳定剂为受阻胺类光稳定剂，具体的牌号为Tinuvin571、Tinuvin770、Tinuvin622、Tinuvin944或Tinuvin144；
所述多元醇为官能度为1.9-2.1的聚碳酸酯多元醇、聚酯多元醇或聚醚多元醇中的一种或多种混合物，聚酯多元醇的摩尔质量为800-1200g/mol，聚醚多元醇的摩尔质量为500-2000g/mol；
优选地，所述多元醇为官能度为2的聚醚多元醇，具体的聚醚多元醇可为聚己二酸乙二醇酯二醇(PEA)，聚己二酸二甘醇酯二醇(PDA)，聚己二酸丁二醇酯二醇(PBA)，聚己二酸丙二醇酯二醇(PPA)，聚氧化丙烯二醇，聚四氢呋喃多元醇(PTMEG)；优选为聚己二酸丁二醇酯二醇(PBA)与聚四氢呋喃多元醇(PTMEG)的混合物。
实施例1
一种耐黄变的热塑性聚氨酯发泡材料制备方法，包括由30kg的六亚甲基二异氰酸酯、11kg的1，4-丁二醇、100kg的聚己二酸丁二醇酯二醇与聚四氢呋喃多元醇按质量比为1∶1的比例混合组成的混合物、阻酚类抗氧化剂、苯并三唑类紫外线吸收剂和受阻胺类光稳定剂投入双螺杆反应挤出机中在150-180℃下反应制得的热塑性聚氨酯弹性体，苯并三唑类紫外线吸收剂的具体牌号为TinuvinP，具体用量占其总量的0.5％，受阻胺类光稳定剂用量为占其总量的0.5％，具体的牌号为Tinuvin571，热塑性聚氨酯弹性体粒子的软化点为90℃，邵氏硬度为40A，熔融指数为250g/10min；
取100重量份的上述热塑性聚氨酯弹性体，30重量份的丁烷和300重量份的水，加入到500L的高压反应釜中搅拌形成悬浮液，然后升温至100℃，保持压力为10bar，然后将压力容器内的悬浮液排放到大气环境中，干燥处理，得到耐黄变的热塑性聚氨酯发泡材料的颗粒物，所述热塑性聚氨酯发泡材料密度为0.05g/cm3，泡孔尺寸为10-40um；
将上述得到的热塑性聚氨酯发泡材料填充到长300mm*宽250mm*厚50mm的模具中。采用2bar的水蒸气沿模具厚度方向压缩10％使热塑性聚氨酯发泡材料粘结成型，最终得到模塑泡沫制品。将所得到的泡沫制品在50℃*50％RH(湿度)下放置2小时之后，在80℃的恒温室内进行2小时干燥，最后在25℃*50％RH放置2小时后，评价其性能。
实施例2
一种耐黄变的热塑性聚氨酯发泡材料制备方法，包括由70kg的异佛尔酮二异氰酸酯、15kg的1，4-丁二醇、100kg的聚四氢呋喃多元醇、受阻酚类抗氧化剂、苯并三唑类紫外线吸收剂和受阻胺类光稳定剂投入双螺杆挤出机中在150-200℃下反应制得，受阻酚类抗氧化剂具体牌号为抗氧剂Irganox1010，具体用量占其总量的0.05％，苯并三唑类紫外线吸收剂的具体牌号为Tinuvin 327，具体用量占其总量的0.8％，受阻胺类光稳定剂用量为占其总量的1％，具体的牌号为Tinuvin 770，热塑性聚氨酯弹性体粒子的软化点为160℃，邵氏硬度为98A，熔融指数为5g/10min；
取100重量份的上述热塑性聚氨酯弹性体，60重量份的二氧化碳和500重量份的水，加入到1200L的高压反应釜中搅拌形成悬浮液，然后升温至130℃，保持压力为100bar，恒温恒压180分钟，最后将压力容器内的悬浮液排放到大气环境中，干燥处理，得到耐黄变的热塑性聚氨酯发泡材料的颗粒物，所述热塑性聚氨酯发泡材料密度为0.5g/cm3，泡孔尺寸为70-100um；
将上述得到的热塑性聚氨酯发泡材料填充到长300mm*宽250mm*厚50mm的模具中。采用2bar的水蒸气沿模具厚度方向压缩10％使热塑性聚氨酯发泡材料粘结成型，最终得到模塑泡沫制品。将所得到的泡沫制品在50℃*50％RH下放置2小时之后，在80℃的恒温室内进行2小时干燥，最后在25℃*50％RH放置2小时后，评价其性能。
实施例3
一种耐黄变的热塑性聚氨酯发泡材料制备方法，包括热塑性聚氨酯弹性体由51kg的氢化苯二亚甲基二异氰酸酯、12kg的1，4-丁二醇、100kg聚己二酸丁二醇酯二醇、受阻酚类抗氧化剂、苯并三唑类紫外线吸收剂和受阻胺类光稳定剂投入双螺杆挤出机中在150-200℃下反应制得，受阻酚类抗氧化剂具体牌号为抗氧剂Irganox1076，具体用量占其总量的0.1％，苯并三唑类紫外线吸收剂的具体牌号为Tinuvin312，具体用量占其总量的1％，受阻胺类光稳定剂用量为占其总量的2％，具体的牌号为Tinuvin622，热塑性聚氨酯弹性体粒子的软化点为125℃，邵氏硬度为85A，熔融指数为100g/10min；
取100重量份的上述热塑性聚氨酯弹性体，30重量份的氮气和500重量份的水，加入到1000L的高压反应釜中搅拌形成悬浮液，然后升温至130℃，保持压力为70bar，恒温恒压70分钟，最后将压力容器内的悬浮液排放到大气环境中，干燥处理，得到耐黄变的热塑性聚氨酯发泡材料的颗粒物，所述热塑性聚氨酯发泡材料密度为0.15g/cm3，泡孔尺寸为100-120um；
将上述得到的热塑性聚氨酯发泡材料填充到长300mm*宽250mm*厚50mm的模具中。采用2bar的水蒸气沿模具厚度方向压缩10％使热塑性聚氨酯发泡材料粘结成型，最终得到模塑泡沫制品。将所得到的泡沫制品在50℃*50％RH下放置2小时之后，在80℃的恒温室内进行2小时干燥，最后在25℃*50％RH放置2小时后，评价其性能。
实施例4
一种耐黄变的热塑性聚氨酯发泡材料制备方法，包括热塑性聚氨酯弹性体由45kg的氢化二苯基甲烷二异氰酸酯、10g的1，4-丁二醇、100kg的聚四氢呋喃多元醇、受阻酚类抗氧化剂、苯并三唑类紫外线吸收剂和受阻胺类光稳定剂投入双螺杆挤出机中在150-200℃下反应制得，受阻酚类抗氧化剂具体牌号为抗氧剂Irganox1098，具体用量占其总量的0.1％，苯并三唑类紫外线吸收剂的具体牌号为TinuvinUV-1，具体用量占其总量的1.5％，受阻胺类光稳定剂用量为占其总量的3％，具体的牌号为Tinuvin944，热塑性聚氨酯弹性体粒子的软化点为145℃，邵氏硬度为80A，熔融指数为50g/10min；
取100重量份的上述热塑性聚氨酯弹性体投入双螺杆挤出机中熔融，控制螺杆温度为100-180℃，然后在挤出机的末端通过增压泵注入50重量份的氮气，控制挤出机模头温度为100℃，模头压力为100bar，最后通过模头挤出发泡，再通过水下切断得到耐黄变的热塑性聚氨酯发泡材料的颗粒物，所述热塑性聚氨酯发泡材料密度为0.25g/cm3，泡孔尺寸为70-100um；
将上述得到的热塑性聚氨酯发泡材料填充到长300mm*宽250mm*厚50mm的模具中。采用2bar的水蒸气沿模具厚度方向压缩10％使热塑性聚氨酯发泡材料粘结成型，最终得到模塑泡沫制品。将所得到的泡沫制品在50℃*50％RH下放置2小时之后，在80℃的恒温室内进行2小时干燥，最后在25℃*50％RH放置2小时后，评价其性能。
实施例5
一种耐黄变的热塑性聚氨酯发泡材料制备方法，包括热塑性聚氨酯弹性体由65kg的氢化二苯基甲烷二异氰酸酯、12kg的1，4-丁二醇、100kg的聚四氢呋喃多元醇、受阻酚类抗氧化剂、苯并三唑类紫外线吸收剂和受阻胺类光稳定剂投入双螺杆挤出机中在150-200℃下反应制得，受阻酚类抗氧化剂具体牌号为抗氧剂Irgafos168，具体用量占其总量的0.3％，苯并三唑类紫外线吸收剂的具体牌号为TinuvinUV-3，具体用量占其总量的1.2％，受阻胺类光稳定剂用量为占其总量的4％，具体的牌号为Tinuvin144，热塑性聚氨酯弹性体粒子的软化点为110℃，邵氏硬度为90A，熔融指数为20g/10min；
取100重量份的上述热塑性聚氨酯弹性体投入双螺杆挤出机中熔融，控制螺杆温度为100-180℃，然后在挤出机的末端通过增压泵注入30重量份的二氧化碳，控制挤出机模头温度为100℃，模头压力为80bar，最后通过模头挤出发泡，再通过水下切断得到耐黄变的热塑性聚氨酯发泡板型材料的颗粒物，厚度为20mm，所述热塑性聚氨酯发泡材料密度为0.25g/cm3，泡孔尺寸为100-120um；
将所得到的发泡板材在50℃*50％RH下放置2小时之后，在80℃的恒温室内进行2小时干燥，最后在25℃*50％RH放置2小时后，评价其性能。
实施例6
一种耐黄变的热塑性聚氨酯发泡材料制备方法，包括热塑性聚氨酯弹性体由55kg异佛尔酮二异氰酸酯、15kg的1，4-丁二醇、100kg的聚四氢呋喃多元醇、受阻酚类抗氧化剂、苯并三唑类紫外线吸收剂和受阻胺类光稳定剂投入双螺杆挤出机中在150-200℃下反应制得，受阻酚类抗氧化剂具体牌号为抗氧剂Irgafos618，具体用量占其总量的0.15％，苯并三唑类紫外线吸收剂的具体牌号为Tinuvin234，具体用量占其总量的1.5％，受阻胺类光稳定剂用量为占其总量的2.5％，具体的牌号为Tinuvin571，热塑性聚氨酯弹性体粒子的软化点为155℃，邵氏硬度为88A，熔融指数为40g/10min；
取100重量份的上述热塑性聚氨酯弹性体投入到200L的耐压容器中，并注入100重量份的氮气到耐压容器中，使耐压容器压力达到150bar，压力维持48h，使氮气在热塑性聚氨酯弹性体内部达到溶解平衡，物理发泡剂渗透进入热塑性聚氨酯弹性体内部，溶解平衡是指将物理发泡剂在进入热塑性聚氨酯弹性体内部后，分散均匀，然后将溶解平衡的物料置于140℃水蒸气进行加热从而使热塑性聚氨酯弹性体进行发泡，得到耐黄变的热塑性聚氨酯发泡材料的颗粒物，所述热塑性聚氨酯发泡材料密度为0.22g/cm3，泡孔尺寸为30-60um；
将上述得到的热塑性聚氨酯发泡材料填充到长300mm*宽250mm*厚50mm的模具中。采用2bar的水蒸气沿模具厚度方向压缩10％使热塑性聚氨酯发泡材料粘结成型，最终得到模塑泡沫制品。将所得到的泡沫制品在50℃*50％RH下放置2小时之后，在80℃的恒温室内进行2小时干燥，最后在25℃*50％RH放置2小时后，评价其性能。
通过对实施例1-6制得的模塑泡沫制品进行测试，通过拉力机测试拉伸强度、断裂伸长率、撕裂强度和回弹性，根据ASDM-D1148采用340nmUVA灯，灯照射强度为0.77W/m2/nm得到耐黄变等级I，根据HG/T3689-2001A法于300h照射测试得到发泡材料的耐黄变等级II，的具体测试数据如下表：
表1
Figure BDA0002061655520000121
由表中的数据可以看出，相比于市场现有的热塑性聚氨酯发泡的泡沫制品，根据实施例1-6制得的热塑性聚氨酯发泡的泡沫制品，在300h加速测试下的耐黄变等级为4.5-5级，耐黄变性能非常好，明显优于目前市面上的热塑性聚氨酯发泡材料制成的泡沫制品，并且本热塑性聚氨酯发泡的泡沫制品同样具有良好的回弹性和机械强度性能。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (2)

1.一种耐黄变的热塑性聚氨酯发泡材料，其特征在于，热塑性聚氨酯弹性体由30kg的六亚甲基二异氰酸酯、11kg的1,4-丁二醇、100kg的以1:1质量比混合的聚己二酸丁二醇酯二醇与聚四氢呋喃多元醇的混合物、受阻酚类抗氧化剂、TinuvinP和Tinuvin571投入到双螺杆反应挤出机中在150-180℃下反应制得，TinuvinP的用量占原料总量的0.5％，Tinuvin571的用量占原料总量的0.5％，热塑性聚氨酯弹性体粒子的软化点为90℃，邵氏硬度为40A，熔融指数为250g/10min；
取100重量份的上述热塑性聚氨酯弹性体，30重量份的丁烷和300重量份的水，加入到500L的高压反应釜中搅拌形成悬浮液，然后升温至100℃，保持压力为10bar，然后将压力容器内的悬浮液排放到大气环境中，干燥处理，得到耐黄变的热塑性聚氨酯发泡材料。
2.一种如权利要求1所述的耐黄变的热塑性聚氨酯发泡材料在弹性泡沫领域中的应用，其中，所述弹性泡沫为鞋材、地面覆盖物、交通工具部件或玩具。
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