CN109180905B - 低压缩形变高弹性聚氨酯鞋垫组合料及其制备方法 - Google Patents

低压缩形变高弹性聚氨酯鞋垫组合料及其制备方法 Download PDF

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CN109180905B
CN109180905B CN201810732344.XA CN201810732344A CN109180905B CN 109180905 B CN109180905 B CN 109180905B CN 201810732344 A CN201810732344 A CN 201810732344A CN 109180905 B CN109180905 B CN 109180905B
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代金辉
孙清峰
辛兰霞
郭勇生
崔玉志
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Shandong Dongda Inov Polyurethane Co Ltd
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Abstract

本发明属于聚氨酯制品技术领域,具体的涉及一种低压缩形变高弹性聚氨酯鞋垫及其制备方法。由重量比为100:70~90的A组分和B组分制成;A组分由以下原料制成:聚醚多元醇、聚四氢呋喃类多元醇、聚合物聚醚多元醇、泡沫稳定剂、高活性硅烷稳定剂、交联剂、扩链剂、发泡剂和延迟性催化剂,交联剂由交联剂A和四官能度聚醚多元醇NT403组成;B组分由以下原料制成:聚醚多元醇、二苯基甲烷二异氰酸酯、碳化二亚胺改性的二苯基甲烷二异氰酸酯和小分子醇。低压缩形变高弹性聚氨酯鞋垫组合料选用低气味,低挥发性的环保原料,生产工艺简单,室温下浇筑即可完成,减少了加热模具所造成的能源浪费,降低了生产成本,提高了生产效率。

Description

低压缩形变高弹性聚氨酯鞋垫组合料及其制备方法
技术领域
本发明属于聚氨酯制品技术领域,具体的涉及一种低压缩形变高弹性聚氨酯鞋垫组合料及其制备方法。
背景技术
聚氨酯树脂包括弹性体、泡沫、涂料和纤维等,现已广泛应用于石油行业,汽车行业、航天行业等,且在人民生活的各个方面都随处可见,而鞋垫与人民的生活密切相关。但传统鞋垫,一般为布料鞋垫,舒适度低,弹性差。而聚氨酯鞋垫因其舒适,耐用,越来越受到广大人民的喜爱。
欧索莱是制备聚氨酯发泡鞋垫的一种生产工艺。一般采用大模具浇注聚氨酯发泡料模压成型,密度在90-180kg/m3之间,成型后切割成不同厚度的片材,与其他材料一起热压成型鞋垫。
相比于传统的布料鞋垫,欧索莱鞋垫作为聚醚型聚氨酯鞋垫,舒适度高,抗疲劳;相比聚酯型和常见的模塑鞋垫,还具有弹性佳,透气性好,生产操作简单,成本比较低等诸多优点,因此备受鞋店及其制备企业的青睐。
传统的聚醚型聚氨酯鞋垫生产工艺采用逐个鞋垫成型,操作复杂,效率低,且鞋垫的质量稳定性差。
发明内容
本发明的目的是克服现有技术的不足,提供一种低压缩形变高弹性聚氨酯鞋垫组合料。该组合料选用低气味,低挥发性的环保原料,生产工艺简单,室温下浇筑即可完成;所制备的聚氨酯制品具有弹性高、压缩形变低、透气性佳、手感好、环保无污染等优点;本发明同时提供了其制备方法。
本发明所述的低压缩形变高弹性聚氨酯鞋垫组合料,由重量比为100:70~90的A组分和B组分制成,其中:
以重量百分数计,A组分由以下原料制成:
Figure BDA0001721215750000011
Figure BDA0001721215750000021
交联剂由交联剂A和四官能度聚醚多元醇NT403组成;
B组分由以下原料制成:
Figure BDA0001721215750000022
其中:
A组分中聚醚多元醇为甘油封端,数均分子量为4500~7000g/mol,优选KE810(f=3,羟值28mg KOH/g),工业级,可利亚多元醇(南京)有限公司生产;聚四氢呋喃类多元醇为四氢呋喃通过阳离子开环聚合所得,工业级,巴斯夫公司。
聚合物聚醚多元醇为乙烯基聚醚多元醇为基础,用苯乙烯和丙烯腈接枝共聚,固含量>30%的高活性聚醚多元醇;优选KE880S(f=3,羟值20mg KOH/g),工业级,可利亚多元醇(南京)有限公司。
扩链剂是乙二醇(EG)、一缩二乙二醇(DEG)、1,4-丁二醇(1,4-BG)或一缩二丙二醇(DPG)中的一种或几种;交联剂A是二乙醇胺(DEOA)、三乙醇胺(TEA)或甘油中的一种或几种;发泡剂是水。
泡沫稳定剂采用聚硅氧烷-氧化烯烃嵌段共聚物,是DC6070或DC2525中的一种或两种;延迟性催化剂是BL-17或8154中的一种或两种,工业级,空气化工产品有限公司。
高活性硅烷稳定剂采用MIAX硅酮表面活性剂L-580,工业级,迈图高新材料集团。
B组分中聚醚多元醇为甘油封端,数均分子量为4500~7000g/mol,优选EP-330NG、ED-28或EP-3600中的一种或几种;小分子醇是乙二醇、甘油或1,4丁二醇中的一种或多种。
本发明所述的低压缩形变高弹性聚氨酯鞋垫组合料的制备方法,具体包括以下步骤:
(1)A组分料的制备
先将基于配方量的聚醚多元醇、聚四氢呋喃(PTMG)类多元醇、聚合物聚醚多元醇投入反应釜中搅拌,然后依次加入称量好的扩链剂、延迟性催化剂、泡沫稳定剂、高活性硅烷稳定剂和普通小分子的交联剂;投完所有料后,在室温条件下,转速为60-100转/分钟,搅拌1-2小时,取样进行检验,满足工艺参数,发出满意泡沫,即得A组分合格产品;
(2)B组分料的制备
B组分料严格控制工艺流程,首先抽入纯MDI,控制温度在50℃以下;然后将温度低于45℃的聚醚多元醇抽入反应釜中,搅拌15分钟,温度维持在50℃左右,分批次加入小分子醇,在30分钟内升温至60-65℃,保温30分钟;检测NCO%含量达到设定值时,加入碳化二亚胺改性的异氰酸酯,搅拌30min,检测NCO%含量达到设定值时,降温至10-40℃即可;
(3)使用时,将A、B组分料按A/B=100/70~90的质量比混合均匀后浇入模具即得低压缩形变高弹性聚氨酯鞋垫制品。
其中:
分批次加入小分子醇,具体是分四次加入小分子醇:首先加入B组分中所用小分子醇总质量的25%,不通蒸汽自然反应15分钟;观察温度,温度稳定在50-55℃;再加入25%的小分子醇,自然反应15分钟;温度稳定在50-55℃;继续加入25%的小分子醇,自然反应15分钟,温度应稳定在55-60℃范围;加入剩余25%的小分子醇,继续自然反应15分钟,温度稳定在55-60℃范围;在30分钟内升温至60-65℃,保温30分钟,检测NCO含量。
上述小分子醇的质量分数为占B组分所用小分子醇的总质量。
聚醚交联剂NT403粘度大,室温条件下不易分散,为更好的分散使用的NT403,将基于配方量的NT403均匀分散在发泡剂水中,然后加入反应釜中搅拌。
由该组合料生产的低压缩形变高弹性聚氨酯鞋垫送往德国莱茵技术(上海)有限公司检测,测试方法:酸消化后,用电感耦合等离字体发射光谱仪做分析。测试结果如表1所示,测试标准为QB/T 4340:2012。
表1低压缩形变高弹性聚氨酯鞋垫的重金属含量测试结果
Figure BDA0001721215750000031
注:1n.d.=not detected未检出。
由表1可知,由该配方试制的低压缩形变高弹性聚氨酯鞋垫产品,重金属铅镉砷的报告检出限低于要求值,完全满足了市场上对鞋垫的重金属要求的中华人民共和国轻工行业标准。
本发明与现有技术相比,具有以下有益效果:
(1)本发明所述的低压缩形变高弹性聚氨酯鞋垫组合料选用低气味,低挥发性的环保原料,生产工艺简单,室温下浇筑即可完成,减少了加热模具所造成的能源浪费,降低了生产成本,提高了生产效率。
(2)本发明的聚醚型聚氨酯鞋垫采用块状发泡,切割成型,一次可连续生产多个鞋垫,效率高,生产工艺简单且鞋垫的质量稳定性佳。
(3)本发明的产品引入了高性能的PTMG类聚醚,极大的提高了低压缩形变高弹性聚氨酯鞋垫的力学性能和回弹性;引入了新型的四官能度聚醚交联剂NT403,NT403和普通的交联剂协同使用,通过构建新型网络结构,提高了产品的手感和回弹性,同时高官能度NT403的引入,极大的降低了产品的压缩永久变形;用延迟性催化剂代替常规催化剂,引入高活性硅烷稳定剂,通过配方优化配制成A料,所得鞋垫泡孔均匀,尺寸稳定性好;B料采用自制的改性异氰酸酯,利用蒸汽压很低(1.5*104Pa,20℃)的二苯基甲烷二异氰酸酯和碳化二亚胺改性的二苯基甲烷二异氰酸酯和聚醚多元醇进行预聚所得,同时引入小分子醇作为交联剂,所得制品回弹性高,压缩永久变形小,且不含TDI等易挥发组分,环保无污染。
具体实施方式
以下结合实施例对本发明作进一步描述。
实施例1
本实施例1的低压缩形变高弹性聚氨酯鞋垫组合料具体如下:
以重量百分数计,A组分由以下原料制成:
Figure BDA0001721215750000041
B组分由以下原料制成:
Figure BDA0001721215750000042
本实施例1所述的低压缩形变高弹性聚氨酯鞋垫组合料的制备方法,具体包括以下步骤:
(1)A组分的制备
将称量好的KE810与聚四氢呋喃类多元醇PTMG、KE880S投入反应釜中搅拌,然后依次加入称量好的DC6070和L-580、DEOA、EG、BL-17和8154,NT403粘度比较大,为将NT403更好的分散,将事先称量好的NT403完全均匀溶入水中,然后加入反应釜。在室温的条件下搅拌混合1小时后,取样检测,满足生产工艺,得到需要的泡沫,即得A组分合格产品。
(2)B组分的制备
B组分首先将室温条件下的EP-330NG和ED-28加入反应釜中,搅拌升温至90-100℃,真空条件下(-0.09MPa)脱水脱气1-2小时,(保证含水量≤0.05%)然后将温度降温到50℃左右(若温度低于45℃,通蒸汽1-2min,使温度稳定维持在50℃左右),抽入温度低于55℃的纯MDI,然后加入25%的乙二醇,不通蒸汽自然反应15分钟。观察温度,温度稳定在50-55℃。再加入25%的乙二醇,自然反应15分钟。温度稳定在50-55℃;继续加入25%的乙二醇,自然反应15分钟,温度应稳定在55-60°范围;加入剩余25%的乙二醇,继续自然反应15分钟,温度稳定在55-60℃范围;在30分钟内升温至60-65℃,保温30分钟。检测NCO%含量达到设定值时,加入碳化二亚胺改性的MDI,搅拌30min,检测NCO%含量达到设定值时,即得到所需B组分。
(3)使用时,将A、B料组分按照100:90的重量配比混合均匀后筑入模具即得所需低压缩形变高弹性聚氨酯鞋垫制品。
实施例2
本实施例2的低压缩形变高弹性聚氨酯鞋垫组合料具体如下:
以重量百分数计,A组分由以下原料制成:
Figure BDA0001721215750000051
B组分由以下原料制成:
Figure BDA0001721215750000061
本实施例2所述的低压缩形变高弹性聚氨酯鞋垫组合料的制备方法,具体包括以下步骤:
(1)A组分的制备
将称量好的KE810与聚四氢呋喃类多元醇PTMG、KE880S投入反应釜中搅拌,然后依次加入称量好的DC6070和L-580、DEOA、EG、BL-17和8154,NT403粘度比较大,为将NT403更好的分散,将事先称量好的NT403完全均匀溶入水中,然后加入反应釜。在室温的条件下搅拌混合1小时后,取样检测,满足生产工艺,得到需要的泡沫,即得A组分合格产品。
(2)B组分的制备
首先将室温条件下的EP-330NG和ED-28加入反应釜中,搅拌升温至90-100℃,真空条件下(-0.09MPa)脱水脱气1-2小时,(保证含水量≤0.05%)然后将温度降温到50℃左右(若温度低于45℃,通蒸汽1-2min,使温度稳定维持在50℃左右),抽入温度低于55℃的纯MDI,然后加入25%的1,4丁二醇,不通蒸汽自然反应15分钟。观察温度,温度稳定在50-55℃。再加入25%的1,4丁二醇,自然反应15分钟。温度稳定在50-55℃;继续加入25%的1,4丁二醇,自然反应15分钟,温度应稳定在55-60℃范围;加入剩余25%的1,4丁二醇,继续自然反应15分钟,温度稳定在55-60℃范围;在30分钟内升温至60-65℃,保温30分钟。检测NCO%含量达到设定值时,加入碳化二亚胺改性的MDI,搅拌30min,检测NCO%含量达到设定值时,即得到所需B组分。
(3)使用时,将A、B料组分按照100:85的重量配比混合均匀后筑入模具即得所需低压缩形变高弹性聚氨酯鞋垫制品。
实施例3
本实施例3的低压缩形变高弹性聚氨酯鞋垫组合料具体如下:
以重量百分数计,A组分由以下原料制成:
Figure BDA0001721215750000062
Figure BDA0001721215750000071
B组分由以下原料制成:
Figure BDA0001721215750000072
本实施例3所述的低压缩形变高弹性聚氨酯鞋垫组合料的制备方法,具体包括以下步骤:
(1)A组分的制备
将称量好的KE810与聚四氢呋喃类多元醇PTMG、KE880S投入反应釜中搅拌,然后依次加入称量好的DC6070和L-580、DEOA、EG、BL-17和8154,NT403粘度比较大,为将NT403更好的分散,将事先称量好的NT403完全均匀溶入水中,然后加入反应釜。在室温的条件下搅拌混合1小时后,取样检测,满足生产工艺,得到需要的泡沫,即得A组分合格产品。
(2)B组分的制备
首先将室温条件下的EP-330NG和ED-28加入反应釜中,搅拌升温至90-100℃,真空条件下(-0.09MPa)脱水脱气1-2小时,(保证含水量≤0.05%)然后将温度降温到50℃左右(若温度低于45℃,通蒸汽1-2min,使温度稳定维持在50℃左右),抽入温度低于55℃的MDI,然后加入25%的乙二醇与甘油的混合物,不通蒸汽自然反应15分钟。观察温度,温度稳定在50-55℃。再加入25%的乙二醇与甘油的混合物,自然反应15分钟。温度稳定在50-55℃;继续加入25%的乙二醇与甘油的混合物,自然反应15分钟,温度应稳定在55-60°范围;加入剩余25%的乙二醇与甘油的混合物,继续自然反应15分钟,温度稳定在55-60℃范围;在30分钟内升温至60-65℃,保温30分钟。检测NCO%含量达到设定值时,加入碳化二亚胺改性的MDI,搅拌30min,检测NCO%含量达到设定值时,即得到所需B组分。
(3)使用时,将A、B料组分按照100:70的重量配比混合均匀后筑入模具即得所需低压缩形变高弹性聚氨酯鞋垫制品。
对实施例1-3制备得到的低压缩形变高弹性聚氨酯鞋垫制品进行性能测试,测试结果如下表2所示:
表2实施例1-3制备的低压缩形变高弹性聚氨酯鞋垫制品性能测试表
Figure BDA0001721215750000081

Claims (6)

1.一种低压缩形变高弹性聚氨酯鞋垫组合料,其特征在于:由重量比为100:70~90的A组分和B组分制成,其中:
以重量百分数计,A组分由以下原料制成:
Figure FDA0002833573410000011
交联剂由交联剂A和四官能度聚醚多元醇NT403组成,交联剂A与四官能度聚醚多元醇NT403的质量比为1.36:0.4或1.82:0.46;交联剂A是二乙醇胺、三乙醇胺或甘油中的一种或几种;
B组分由以下原料制成:
Figure FDA0002833573410000012
A组分中聚醚多元醇为甘油封端,数均分子量为4500~7000g/mol;聚四氢呋喃类多元醇为四氢呋喃通过阳离子开环聚合所得;
聚合物聚醚多元醇为乙烯基聚醚多元醇为基础,用苯乙烯和丙烯腈接枝共聚,固含量>30%的高活性聚醚多元醇;
B组分中聚醚多元醇为甘油封端,数均分子量为4500~7000g/mol;小分子醇是乙二醇、甘油或1,4丁二醇中的一种或多种。
2.根据权利要求1所述的低压缩形变高弹性聚氨酯鞋垫组合料,其特征在于:扩链剂是乙二醇、一缩二乙二醇、1,4-丁二醇或一缩二丙二醇中的一种或几种;发泡剂是水。
3.根据权利要求1所述的低压缩形变高弹性聚氨酯鞋垫组合料,其特征在于:泡沫稳定剂采用聚硅氧烷-氧化烯烃嵌段共聚物,是DC6070或DC2525中的一种或两种;延迟性催化剂是BL-17或8154中的一种或两种。
4.根据权利要求1所述的低压缩形变高弹性聚氨酯鞋垫组合料,其特征在于:高活性硅烷稳定剂采用MIAX硅酮表面活性剂L-580。
5.一种权利要求1所述的低压缩形变高弹性聚氨酯鞋垫组合料的制备方法,其特征在于:具体包括以下步骤:
(1)A组分料的制备
先将基于配方量的聚醚多元醇、聚四氢呋喃类多元醇、聚合物聚醚多元醇投入反应釜中搅拌,然后依次加入称量好的扩链剂、延迟性催化剂、泡沫稳定剂、高活性硅烷稳定剂和交联剂、发泡剂;投完所有料后,在室温条件下,转速为60-100转/分钟,搅拌1-2小时,取样进行检验,满足工艺参数,发出满意泡沫,即得A组分合格产品;
(2)B组分料的制备
B组分料严格控制工艺流程,首先抽入纯MDI,控制温度在50℃以下;然后将温度低于45℃的聚醚多元醇抽入反应釜中,搅拌15分钟,温度维持在50℃,分批次加入小分子醇,在30分钟内升温至60-65℃,保温30分钟;检测NCO%含量达到设定值时,加入碳化二亚胺改性的异氰酸酯,搅拌30min,检测NCO%含量达到设定值时,降温至10-40℃即可;
(3)使用时,将A、B组分料按A/B=100/70~90的质量比混合均匀后浇入模具即得低压缩形变高弹性聚氨酯鞋垫制品。
6.根据权利要求5所述的低压缩形变高弹性聚氨酯鞋垫组合料的制备方法,其特征在于:步骤(2)中所述的分批次加入小分子醇,具体是分四次加入小分子醇:首先加入25%的小分子醇,不通蒸汽自然反应15分钟;观察温度,温度稳定在50-55℃;再加入25%的小分子醇,自然反应15分钟;温度稳定在50-55℃;继续加入25%的小分子醇,自然反应15分钟,温度应稳定在55-60℃范围;加入剩余25%的小分子醇,继续自然反应15分钟,温度稳定在55-60℃范围;在30分钟内升温至60-65℃,保温30分钟,检测NCO含量。
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