CN105111405A - 一种耐寒软质中低密度聚氨酯树脂 - Google Patents

一种耐寒软质中低密度聚氨酯树脂 Download PDF

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CN105111405A
CN105111405A CN201510448362.1A CN201510448362A CN105111405A CN 105111405 A CN105111405 A CN 105111405A CN 201510448362 A CN201510448362 A CN 201510448362A CN 105111405 A CN105111405 A CN 105111405A
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魏欣
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Abstract

本发明公开了一种耐寒软质中低密度聚氨酯树脂，其中各组分比例按重量份计为A组分：所述聚氨酯树脂各组分比例按重量份计为A组分：75～88份聚酯多元醇、7～8份二元醇扩链剂、3～8份催化剂、0.3～1.2份有机硅匀泡剂和0.35～0.65份水；B组分：70～75份多异氰酸酯、30～32份聚酯多元醇、5～10份的聚醚多元醇。本发明的聚氨酯树脂在中低密度下还能保持软质耐寒的特性，产品制备原料易得，方法简单，可重复性好，成本低廉，可以实现大批量生产；生产原料无毒无害，绿色环保。

Description

一种耐寒软质中低密度聚氨酯树脂
技术领域
本发明涉及一种聚氨酯鞋用树脂，尤其涉及一种耐寒软质中低密度聚氨酯树脂，属于聚氨酯树脂制备技术领域。
背景技术
由于聚氨酯鞋底具有轻便耐磨、弹性好、不断底、防滑、防油、穿着舒适等特点，其越来越受到消费者欢迎。我国拥有世界上最大的制鞋产业，鞋的产量占到世界总产量的50％；但使用聚氨酯弹性体作为鞋底材料仅占总鞋底材料的6％左右，对比欧美国家25％以上的占有率，市场份额相对较小。因此可见，聚氨酯弹性体材料在国内市场有着巨大的潜力。
聚氨酯发泡一般为组合料，包括多元醇组合料、异氰酸酯组合料，组分依不同组合成份、不同比例于灌注机混合灌注于鞋底模内发泡成型，制造出不同发泡密度，不同物性要求的产品。
现有技术中，聚氨酯鞋用树脂的多元醇组合料主要是由聚酯多元酸或聚醚多元醇与整泡剂、交联剂、水混合而成，异氰酸酯组合料主要包括二苯基甲烷二异氰酸酯、聚酯多元醇或聚醚多元醇。按照普通配方制造的普通鞋底在密度低的情况下难以保持耐寒软质特性，所以，解决鞋底在密度低的情况下难以保持耐寒软质的技术难题是现在鞋业领域的重要课题。
发明内容
本发明的目的是提供一种耐寒软质中低密度聚氨酯树脂，以解决上述现有技术中尚未解决的难题。
本发明采用的技术方案为：一种耐寒软质中低密度聚氨酯树脂，其特征在于：所述聚氨酯树脂各组分比例按重量份计为A组分：75～88份聚酯多元醇、7～8份二元醇扩链剂、3～8份催化剂、0.3～1.2份有机硅匀泡剂和0.35～0.65份水；B组分：70～75份多异氰酸酯、30～32份聚酯多元醇、5～10份的聚醚多元醇。
进一步地，所述聚酯多元醇官能度为2.0～2.2，分子量1600～1800，酸值为0.6～0.7mgKOH/g。
进一步地，所述多异氰酸酯为4，4-二苯基甲烷二异氰酸酯或改性4，4-二苯基甲烷二异氰酸酯的一种或两者混合物。
进一步地，所述聚醚多元醇官能度2.0～2.2，分子量为3800～4200。
进一步地，所述催化剂中含有固体含钛化合物和碱金属，含钛化合物和碱金属的摩尔比为1～10∶0.1～1。
有益效果：本发明的聚氨酯鞋用树脂，在中低密度下还能保持软质耐寒的特性；本发明的产品制备原料易得，方法简单，可重复性好，成本低廉，可以实现大批量生产；本发明的产品生产原料无毒无害，绿色环保。
具体实施方式
下面的实施列可以使本专业技术人员更全面的理解本发明，但并不因此将本发明限制在所述的实施例范围之中。
实施例1
(1)A组分的制备：取75份聚酯多元醇、7份扩链剂乙二醇、3份催化剂、0.3份有机硅匀泡剂及0.35份水依次加入反应釜中，保持反应釜温度为50℃，搅拌3小时后出料，密封保存，即制得A组份；
其中，聚酯多元醇官能度为2，分子量1600，聚酯多元醇由乙二醇、二乙二醇与己二酸反应制得；
(2)B组份的制备：在50℃的反应釜中通入氮气，将70份4，4-二苯基甲烷二异氰酸酯投入反应釜中，而后取30份聚酯多元醇、5份的聚醚多元醇分3次加入反应釜中，保持反应釜温度为65℃，反应3小时，降温至40℃，出料，通入氮气密封保存，即制得B组份；
其中，聚醚多元醇官能度2，分子量为3800。
(3)A、B组分的混合：将步骤(1)制得的A组份和步骤(2)制得的B组份利用聚氨酯低压发泡机混合搅拌均匀，注入鞋模后成型，3分钟后脱模制得聚氨酯耐寒软质中低密度鞋用树脂成品；其中鞋模温度为45℃，A组份、B组份的温度均为40℃。
经检验，聚氨酯鞋用树脂成型密度为0.500g/cm3，硬度为邵氏C60，外观平整，未出现收缩变形，-20℃屈绕角度为90度，频率为100次/分钟，4万次无裂痕。
实施例2
改变A组分中成分比例为86份聚酯多元醇、7份二元醇扩链剂、5份催化剂、0.8份有机硅匀泡剂和0.55份水；
改变B组分中成分比例为72份改性4，4-二苯基甲烷二异氰酸酯、31份聚酯多元醇、8份的聚醚多元醇，按照实施例1所述的生产方法进行制造。
经检验，聚氨酯鞋用树脂成型密度为0.498g/cm3，硬度为邵氏C56，外观平整，未出现收缩变形，-25℃屈绕角度为90度，频率为100次/分钟，4万次无裂痕。
实施例3
改变A组分中成分比例为88份聚酯多元醇、8份二元醇扩链剂、8份催化剂、1.2份有机硅匀泡剂和0.65份水；
改变B组分中成分比例为75份改性4，4-二苯基甲烷二异氰酸酯、32份聚酯多元醇、10份的聚醚多元醇，按照实施例1所述的生产方法进行制造。
经检验，聚氨酯鞋用树脂成型密度为0.486g/cm3，硬度为邵氏C53，外观平整，未出现收缩变形，-20℃屈绕角度为90度，频率为100次/分钟，4万次无裂痕。

Claims (5)

1.一种耐寒软质中低密度聚氨酯树脂，其特征在于：所述聚氨酯树脂各组分比例按重量份计为A组分：75～88份聚酯多元醇、7～8份二元醇扩链剂、3～8份催化剂、0.3～1.2份有机硅匀泡剂和0.35～0.65份水；B组分：70～75份多异氰酸酯、30～32份聚酯多元醇、5～10份的聚醚多元醇。
2.根据权利要求1所述的一种耐寒软质中低密度聚氨酯树脂，其特征在于：所述聚酯多元醇官能度为2.0～2.2，分子量1600～1800，酸值为0.6～0.7mgKOH/g。
3.根据权利要求1所述的一种耐寒软质中低密度聚氨酯树脂，其特征在于：所述多异氰酸酯为4，4-二苯基甲烷二异氰酸酯或改性4，4-二苯基甲烷二异氰酸酯的一种或两者混合物。
4.根据权利要求1所述的一种耐寒软质中低密度聚氨酯树脂，其特征在于：所述聚醚多元醇官能度2.0～2.2，分子量为3800～4200。
5.根据权利要求1所述的一种耐寒软质中低密度聚氨酯树脂，其特征在于：所述催化剂中含有固体含钛化合物和碱金属，含钛化合物和碱金属的摩尔比为1～10∶0.1～1。
CN201510448362.1A 2015-07-27 2015-07-27 一种耐寒软质中低密度聚氨酯树脂 Pending CN105111405A (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106905508A (zh) * 2017-03-15 2017-06-30 盐城旭城塑料制品有限公司 一种醚酯泡绵及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101486788A (zh) * 2008-12-30 2009-07-22 浙江华峰新材料股份有限公司 一种低密度高硬度聚氨酯微孔弹性体及其制备方法
CN101735597A (zh) * 2009-12-07 2010-06-16 无锡双象化学工业有限公司 一种超低密度高硬度聚氨酯鞋用树脂及制备方法
CN101845218A (zh) * 2010-06-09 2010-09-29 黎明化工研究院 一种聚酯型聚氨酯微孔鞋底材料及其制备方法
CN102504181A (zh) * 2011-09-30 2012-06-20 无锡双象化学工业有限公司 聚氨酯耐寒软质中低密度鞋用树脂及其制备方法
CN103965433A (zh) * 2014-05-24 2014-08-06 浙江奥康鞋业股份有限公司 鞋底用软质低密度聚氨酯泡沫材料

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101486788A (zh) * 2008-12-30 2009-07-22 浙江华峰新材料股份有限公司 一种低密度高硬度聚氨酯微孔弹性体及其制备方法
CN101735597A (zh) * 2009-12-07 2010-06-16 无锡双象化学工业有限公司 一种超低密度高硬度聚氨酯鞋用树脂及制备方法
CN101845218A (zh) * 2010-06-09 2010-09-29 黎明化工研究院 一种聚酯型聚氨酯微孔鞋底材料及其制备方法
CN102504181A (zh) * 2011-09-30 2012-06-20 无锡双象化学工业有限公司 聚氨酯耐寒软质中低密度鞋用树脂及其制备方法
CN103965433A (zh) * 2014-05-24 2014-08-06 浙江奥康鞋业股份有限公司 鞋底用软质低密度聚氨酯泡沫材料

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106905508A (zh) * 2017-03-15 2017-06-30 盐城旭城塑料制品有限公司 一种醚酯泡绵及其制备方法

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