CN104341577A - 一种聚氨酯微孔弹性体及其制备方法 - Google Patents
一种聚氨酯微孔弹性体及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种聚氨酯微孔弹性体的制备方法,由A组分和B组分反应制得,A组分包括聚酯多元醇A100份、增硬防缩剂18~38份、水0.5~1.2份、三乙烯二胺0.15~0.25份、异辛酸锡0.02~0.15份、有机硅泡沫稳定剂0.5~1.2份、甲缩醛0.3~0.8份、一氟二氯乙烷0.2~0.8份,所述增硬防缩剂为乙二醇与纳米聚苯乙烯混合物或1,4-丁二醇与纳米聚苯乙烯混合物;所述B组分包括4,4-二苯基甲烷二异氰酸酯100份、液化MDI5~7份、聚酯多元醇B30~50份、聚醚15~25份。本发明方法制得的聚氨酯微孔弹性体密度较低、硬度提高明显、收缩率、压缩永久变形率下降明显。
Description
技术领域:
本发明属于高分子材料制造领域,特别涉及一种低密度高硬度低收缩聚氨酯微孔弹性体及其制备方法。
技术背景:
聚氨酯鞋底由于具有弹性好、耐磨、穿着舒适等特点,所以得到了广泛使用。生产过程中为了降低成本和穿着的舒适度,人们主要是通过聚氨酯发泡的方法生产低密度的聚氨酯鞋底。但是该方法制得的聚氨酯鞋底的收缩率、压缩永久变形率大。为了解决聚氨酯鞋底的收缩率大的问题,有关人员往在生产低密度聚氨酯鞋底的过程中添加开孔剂,降低聚氨酯泡沫壁的表面张力,使泡孔破裂,提高聚氨酯鞋底泡孔的开孔率,可以改善鞋底制品成型时的收缩问题。但是鞋底硬度明显下降,压缩永久变形率较大,穿一段时间鞋底的厚度就会变薄,鞋底的形状会严重改变,影响鞋子的穿着舒适性和美观。为了鞋底硬度低这一问题,CN200810191723.9公开了一种低密度高硬度聚氨酯微孔弹性体及其制备方法,但是该方法主要是通过调节原料组份中异氰酸酯、扩链剂的加入量即提高聚氨酯中硬段的比例来提高聚氨酯鞋底硬度的,所以该法提高聚氨酯的硬度值不够显著,并且不能解决鞋底压缩永久变形率大的问题,鞋底仍然存在尺寸不够稳定,长期穿着时容易变薄、变形的缺陷。并且该方法反应步骤过多,生产工艺复杂、周期长。
发明内容:
本发明的目的是提供一种高硬度低收缩低压缩永久变形聚氨酯微孔弹性体及制备方法,以解决在低密度情况下聚氨酯弹性体鞋底材料仍能保持高硬度低收缩、低压缩永久变形的技术难题。
本发明采用的技术方案是:
一种聚氨酯微孔弹性体的制备方法,所述聚氨酯微孔弹性体由A组分和B组分反应制得,其中
A组分包括以下质量份的组分:
所述三乙烯二胺以三乙烯二胺的乙二醇溶液的形式加入,所述三乙烯二胺的乙二醇溶液是将三乙烯二胺和乙二醇按体积比1:2配制得到;三乙烯二胺0.15~0.25份的质量份是指三乙烯二胺的乙二醇溶液中三乙烯二胺的质量。
B组分由以下质量份的组分组成:
所述A组分或B组分中,所述聚酯多元醇A或B由二元醇与己二酸缩聚制得,数均分子量为1000~2500,所述二元醇为乙二醇、二乙二醇、甘油中的一种或两种以上的混合。
所述聚酯多元醇A、B只是用于区分A组分和B组分中的聚酯多元醇,A或B并不具有任何实质上的化学意义。
所述A组分优选包括以下质量份的组分:
所述三乙烯二胺以三乙烯二胺的乙二醇溶液的形式加入,所述三乙烯二胺的乙二醇溶液是将三乙烯二胺和乙二醇按体积比1:2配制得到;三乙烯二胺0.22份的质量份是指三乙烯二胺的乙二醇溶液中三乙烯二胺的质量。
所述B组分优选由以下质量份的组分组成:
具体的,所述聚酯多元醇A或B可按以下方法制得:二元醇和己二酸在催化剂四异丙基钛酸酯的作用下,在氮气保护下于145℃~225℃进行聚酯化反应,检测酸值,当酸值降低到2mgKOH/g以下时停止反应,制得聚酯多元醇A或B;所述二元醇、己二酸的物质的量之比为1.2:1;
所述催化剂四异丙基钛酸酯的质量用量通常为二元醇和己二酸总质量的0.03%。
进一步,所述聚酯多元醇A或B更优选按以下方法制得:取二元醇、己二酸,按照醇酸摩尔比为1.2:1加入到装有温度计、油水分离器和搅拌器的四口烧瓶中,充氮气保护10min,缓慢加热,物料熔融后开动搅拌器,当温度达到145℃时开始出水,控制出水速率及顶温在(100±2)℃范围内,此时加入二元醇和己二酸总质量的0.03wt%的催化剂四异丙基钛酸酯,并逐渐升温,同时加大搅拌速率,控制内温在225℃反应4h,当顶温下降至70℃以下时,取样测酸值,当试样酸值低于15mgKOH/g时开始抽真空,于-0.08~-0.1MPa真空度下反应,当酸值小于2.0mgKOH/g时结束反应,制得聚酯多元醇A或B;其羟值在55~57mgKOH/g之间,相对分子质量为1000~2500,优选为1800~2000。
所述的有机硅泡沫稳定剂优选PF-802、DC-3043或DC-3042中的一种或两种以上的混合。
所述增硬防缩剂为乙二醇与纳米聚苯乙烯混合物或1,4-丁二醇与纳米聚苯乙烯混合物,所述的乙二醇与纳米聚苯乙烯混合物或1,4-丁二醇与纳米聚苯乙烯混合物中,纳米聚苯乙烯的粒径为80~300纳米,优选200~300纳米。
所述乙二醇与纳米聚苯乙烯混合物或1,4-丁二醇与纳米聚苯乙烯混合物可以按以下方法制得:乙二醇或1,4-丁二醇与纳米聚苯乙烯乳液按照体积比1:1~2的比例混合均匀,升温70~90℃,抽真空到-0.08~-0.1MPa,脱除水分,完成相转移,得到均匀分散的乙二醇与纳米聚苯乙烯混合物或1,4-丁二醇与纳米聚苯乙烯混合物。
所述纳米聚苯乙烯乳液是纳米聚苯乙烯分散在水中的乳液,固含量为30%~50%,粒径80~300纳米,优选粒径200~300纳米。具体所述纳米聚苯乙烯乳液按以下方法制得:
乳化剂十二烷基硫酸钠溶于水中,加入磷酸三钠,在氮气保护下加入苯乙烯,快速搅拌乳化2~5h,然后滴加引发剂过硫酸铵水溶液,所得反应液搅拌下升温到75~80℃,保温聚合反应8~10h小时,冷却,制得固含量30%~50%的纳米聚苯乙烯乳液,所述苯乙烯、十二烷基硫酸钠、磷酸三钠、过硫酸铵的质量比为1:0.03~0.05:0.005~0.01:0.01~0.02,优选1:0.04:0.007:0.014;
所述过硫酸铵先溶于水中配成过硫酸铵水溶液,再加入反应体系中,所述过硫酸铵水溶液的质量分数一般为3~7%。
所述反应液中溶剂为水,包括起始用于溶解乳化剂十二烷基硫酸钠的水以及用于溶解过硫酸铵的水,反应液中水的总用量以制得的聚苯乙烯乳液固含量30%~50%计算得到,一般使反应液中苯乙烯的质量分数为30%~50%即可,即水的总用量为苯乙烯的质量的1~2.3倍。
所述的三乙烯二胺使用时,首选按照三乙烯二胺:乙二醇体积比=1:2的比例稀释后使用。
所述的4,4-二苯基甲烷二异氰酸酯简称MDI,分子量为250,所述的液化MDI为碳化二亚胺改性MDI,优选MDI-100HL。
所述的聚醚又称聚醚多元醇,优选HSH聚醚多元醇,更优选HSH-215,羟值68~83mgKOH/g,酸值≤0.15mgKOH/g,水份≤0.10%。
进一步,所述A组分按以下方法获得:将聚酯多元醇A、增硬防缩剂、三乙烯二胺和乙二醇体积比1:2的混合溶液、异辛酸锡、有机硅泡沫稳定剂、水、甲缩醛和一氟二氯乙烷按组方比加入反应釜,升温到50~65℃混合均匀,再冷却至40℃出料,即获得A组分。
所述B组分按以下方法获得:氮气保护的反应釜中,按组方比例加入MDI、液化MDI,升温到60~65℃,再加入组方量的聚酯多元醇B、聚醚,于60℃~82℃反应3.5~4小时,真空脱除气泡,降温至44~50℃,出料,密封保存,即得B组分。B组分在长期保存时可以加入少量磷酸保证组分稳定,这是本领域技术人员公知的。
所述聚氨酯微孔弹性体按以下方法制备:控制A组分和B组分的温度在40~50℃范围内,调整A组分和B组分的用量,使A组分的活泼氢的当量数与B组分的异氰酸酯(-NCO)的当量数之比为1:1,将两组分快速充分混合,注入50~53℃的模具反应成型,2~4分钟脱模,制得所述聚氨酯微孔弹性体制品。
其中,A组分的活泼氢的当量数以及B组分的-NCO的当量数可按照本领域技术人员公知方法检测得到,具体的,按照GBT 22313-2008检测多元醇水含量,HGT 2708-1995检测聚酯多元醇中酸值,HGT 2709-1995检测聚酯多元醇中羟值,由此计算出A组份活泼氢的当量数。按照HGT 2409-1992测定异氰酸酯基含量,计算出B组份异氰酸酯当量数。
所制得的聚氨酯微孔弹性体的硬度为70~90邵氏A,密度为0.23~0.35g/cm3。
本发明的有益效果在于:
(1)聚氨酯中引入聚苯乙烯亚纳米粒子,因为聚苯乙烯粒子属于刚性材料,使制得的鞋底材料比以前其它的方法具有更高的硬度。
(2)聚氨酯中引入聚苯乙烯亚纳米粒子,利用聚苯乙烯与聚氨酯相容性不好的特点,致使聚氨酯泡孔界面形成亚纳米级孔隙,能够释放出少量发泡气体,带出热量,避免热量集中,形成细腻开孔。
(3)由于材料中有刚性聚苯乙烯亚纳米粒子,且形成开孔泡沫结构,泡沫冷却后泡孔收缩小,鞋底压缩永久变形率低,鞋底尺寸稳定性好,涂敷修饰层时敷着力强。
(4)加工工艺简单,成本降低。
本申请所述的低密度高硬度聚氨酯微孔弹性体收缩率、压缩永久变形率低,可以用于在鞋底材料的生产中。
具体实施方式
下面以具体实施例来对本发明的技术方案作进一步说明,但本发明的保护范围不限于此。
实施例1-6
按照表1中组分比例投料,其中聚酯多元醇是由乙二醇与己二酸缩聚制得,数均分子量为2000,羟值在56mgKOH/g。
制备方法为:称取乙二醇74.4g、己二酸146g,按照醇酸摩尔比为1.2:1加入到装有温度计、油水分离器和搅拌器的四口烧瓶中,充氮气保护10min,缓慢加热,物料熔融后开动搅拌器。当温度达到145℃左右时开始出水,控制出水速率及顶温在(100±2)℃范围内,加入0.066g催化剂四异丙基钛酸酯。并逐渐升温,同时加大搅拌速率,最终内温控制在225℃反应4h,当顶温下降至70℃以下时,取样测酸值,当试样酸值低于15mgKOH/g时开始抽真空,于-0.08~-0.1MPa真空度下反应,当酸值小于2.0mgKOH/g时结束反应。制得聚酯多元醇,其羟值在55~57mgKOH/g之间,相对分子质量约为2000。用于A组分和B组分的制备中。
所述的有机硅泡沫稳定剂为PF-802、DC-3043、DC-3042,具体投料参见表1。
纳米聚苯乙烯乳液合成:在三口烧瓶中加入90mL水和1.6g十二烷基硫酸钠乳化剂,搅拌溶解,再加入0.3g磷酸三钠搅拌溶解,通氮气保护,再加入43g苯乙烯,快速搅拌乳化2h时间后,在40min内滴加10mL含0.6g过硫酸铵的水溶液,继续搅拌,升温到75℃,恒温聚合8h,得到纳米聚苯乙烯乳液,粒径200~300纳米,固物含量30%。
乙二醇与纳米聚苯乙烯混合物或1,4-丁二醇与纳米聚苯乙烯混合物制备方法为:纳米聚苯乙烯乳液与乙二醇或1,4-丁二醇按体积比1:1混合均匀,升温85℃,抽真空到-0.1MPa,脱除水分,完成相转移,得到均匀的乙二醇与纳米聚苯乙烯混合物或者1,4-丁二醇与纳米聚苯乙烯混合物。
A组分制备:将聚酯多元醇、增硬防缩剂、三乙烯二胺和乙二醇体积比1:2的混合溶液、异辛酸锡、有机硅泡沫稳定剂、水、甲缩醛和一氟二氯乙烷按表1投料量加入反应釜。升温到55℃混合均匀,再冷却至40℃出料,即得A组分。
MDI分子量为250,液化MDI为MDI-100HL。
聚醚为HSH-215,羟值68~83mgKOH/g,酸值≤0.15mgKOH/g,水份≤0.10%。
B组份制备:氮气保护的反应釜中加入MDI、液化MDI升温到65℃,加入聚酯多元醇、聚醚于82℃反应3.5小时,真空脱除气泡,降温至45℃,出料,密封保存,即得B组份。
表1:
三乙烯二胺按照表1中的用量,预先和乙二醇按体积比1:2混合配成三乙烯二胺的乙二醇溶液,加入A组分中。
聚氨酯微孔弹性体的制备:控制A组份和B组份的温度在40~50℃范围内,调整A组份和B组份的用量,使A组份的活泼氢的当量数与B组份的-NCO的当量数之比为1:1,将两组份快速充分混合,注入52℃的模具反应成型,脱模,熟化,得到制品。
按照GBT 22313-2008多元醇水含量的测定,HGT 2708-1995聚酯多元醇中酸值的测定,HGT 2709-1995聚酯多元醇中羟值的测定,计算出A组份活泼氢的当量数。按照HGT 2409-1992测定异氰酸酯基含量,计算出B组份异氰酸酯当量数。
实施例结果:
按照GB/T 2411-2008测试邵氏硬度(A),按照GB7759-87,实验条件为70℃、22h、压缩率20%,测试压缩永久变形率。所得结果见表2:
表2
收缩率=(模具尺寸-制品尺寸)/模具尺寸
实例对比结果说明本方法制得的聚氨酯微孔弹性体密度较低、硬度提高明显、收缩率、压缩永久变形率下降明显。
Claims (10)
1.一种聚氨酯微孔弹性体的制备方法,所述聚氨酯微孔弹性体由A组分和B组分反应制得,其特征在于所述A组分包括以下质量份的组分:
所述三乙烯二胺以三乙烯二胺的乙二醇溶液的形式加入,所述三乙烯二胺的乙二醇溶液是将三乙烯二胺和乙二醇按体积比1:2配制得到;所述B组分由以下质量份的组分组成:
所述A组分或B组分中,所述聚酯多元醇A或B由二元醇与己二酸缩聚制得,数均分子量为1000~2500,所述二元醇为乙二醇、二乙二醇、甘油中的一种或两种以上的混合;
所述A组分中,所述增硬防缩剂为乙二醇与纳米聚苯乙烯混合物或1,4-丁二醇与纳米聚苯乙烯混合物,所述的乙二醇与纳米聚苯乙烯混合物或1,4-丁二醇与纳米聚苯乙烯混合物中,纳米聚苯乙烯的粒径为80~300纳米。
2.如权利要求1所述的方法,其特征在于所述乙二醇与纳米聚苯乙烯混合物或1,4-丁二醇与纳米聚苯乙烯混合物按以下方法制得:乙二醇或1,4-丁二醇与纳米聚苯乙烯乳液按照体积比1:1~2的比例混合均匀,升温70~90℃,抽真空到-0.08~-0.1MPa,脱除水分,完成相转移,分别制得均匀分散的乙二醇与纳米聚苯乙烯混合物或1,4-丁二醇与纳米聚苯乙烯混合物。
3.如权利要求2所述的方法,其特征在于所述纳米聚苯乙烯乳液是纳米聚苯乙烯分散在水中的乳液,固含量为30%~50%,纳米聚苯乙烯的粒径80~300纳米。
4.如权利要求3所述的方法,其特征在于所述纳米聚苯乙烯乳液按以下方法制得:
乳化剂十二烷基硫酸钠溶于水中,加入磷酸三钠,在氮气保护下加入苯乙烯,快速搅拌乳化2~5h,然后滴加引发剂过硫酸铵水溶液,所得反应液搅拌下升温到75~80℃,保温聚合反应8~10h小时,冷却,制得固含量30%~50%的纳米聚苯乙烯乳液,所述苯乙烯、十二烷基硫酸钠、磷酸三钠、过硫酸铵的质量比为1:0.03~0.05:0.005~0.01:0.01~0.02。
5.如权利要求4所述的方法,其特征在于所述反应液中苯乙烯的质量分数为30%~50%。
6.如权利要求1所述的方法,其特征在于所述的有机硅泡沫稳定剂为PF-802、DC-3043或DC-3042中的一种或两种以上的混合。
7.如权利要求1所述的方法,其特征在于所述液化MDI为MDI-100HL。
8.如权利要求1所述的方法,其特征在于所述聚醚为HSH-215。
9.如权利要求1所述的方法,其特征在于所述A组分按以下方法获得:将聚酯多元醇A、增硬防缩剂、三乙烯二胺和乙二醇体积比1:2的混合溶液、异辛酸锡、有机硅泡沫稳定剂、水、甲缩醛和一氟二氯乙烷按组方比加入反应釜,升温到50~65℃混合均匀,再冷却至40℃出料,即得A组分;
所述B组分按以下方法获得:氮气保护的反应釜中,按组方比例加入4,4-二苯基甲烷二异氰酸酯、液化MDI,升温到60~65℃,再加入组方量的聚酯多元醇B、聚醚,于60℃~82℃反应3.5~4小时,真空脱除气泡,降温至44~50℃,出料,密封保存,即得B组分。
10.如权利要求1所述的方法,其特征在于所述聚氨酯微孔弹性体按以下方法制备:控制A组分和B组分的温度在40~50℃范围内,调整A组分和B组分的用量,使A组分的活泼氢的当量数与B组分的异氰酸酯的当量数之比为1:1,将两组分快速充分混合,注入50~53℃的模具反应成型,2~4分钟脱模,制得所述聚氨酯微孔弹性体制品。
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