CN112831019A - 镜面型超高弹聚氨酯鞋底树脂及其制备方法 - Google Patents

镜面型超高弹聚氨酯鞋底树脂及其制备方法 Download PDF

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CN112831019A
CN112831019A CN202011630861.XA CN202011630861A CN112831019A CN 112831019 A CN112831019 A CN 112831019A CN 202011630861 A CN202011630861 A CN 202011630861A CN 112831019 A CN112831019 A CN 112831019A
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polyurethane sole
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甘经虎
李海朝
任明月
张伟
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Shandong Dongda Inov Polyurethane Co Ltd
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Abstract

本发明涉及聚氨酯弹性体技术领域，具体涉及一种镜面型超高弹聚氨酯鞋底树脂及其制备方法。所述的镜面型超高弹聚氨酯鞋底树脂，由A组分和B组分组成，A组分由聚四氢呋喃醇、聚酯聚合物多元醇、扩链剂、交联剂、发泡剂、硅油、催化剂、抗氧剂组成；B组分由聚乙二醇、聚醚多元醇、异氰酸酯和储存稳定剂组成。本发明的镜面型超高弹聚氨酯鞋底树脂，安全环保、流动性好，制作的鞋底密度250‑350kg/m3不收缩，鞋底具有超高弹特点，回弹达到60％以上，鞋底表面结皮光亮、呈镜面状，便于后期喷漆进行处理；本发明还提供其制备方法，生产工序简单，一次成型，无需后期高温硫化，节能降耗。

Description

镜面型超高弹聚氨酯鞋底树脂及其制备方法
技术领域
本发明涉及聚氨酯弹性体技术领域，具体涉及一种镜面型超高弹聚氨酯鞋底树脂及其制备方法。
背景技术
聚氨酯鞋底具有质轻、耐磨、强度可调等特点，可以制成不同功能用途的鞋底。随着人民对美好生活的向往和对自身健康的重视，越来越多的人加入到户外运动中。由此，人们对鞋类产品舒适性和弹性等提出了更高的要求。鞋底既要注重美观大方，在其表面根据喜好可以喷涂五颜六色的颜色，更要注重其安全性和舒适感。原始型、传统型的单密度，双密度聚氨酯浇注鞋底已不能满足人们对它的欣赏，逐渐会被淘汰，而研制开发一种富有轻质高弹性环保鞋底产品，将是历史创新，会成为未来鞋底市场发展的主流方向，受到更多关注。
专利CN 107200911B报道了一种超轻弹环保鞋底及其制备方法，其在传统EVA材质的基础上通过加入聚氨酯橡胶、沙林树脂和烯烃嵌段共聚物，虽然在一定程度上提高了发泡鞋底的弹性和韧性，但是其制备工艺非常复杂，二次定型，注塑机需要165-180℃高温，发泡釜需要8-60MPa的高压，这种高温高压生产环境存在极大安全隐患。
专利CN 110520457A公布了一种具有高球回弹率的低密度聚氨酯弹性体泡沫，通过对聚四氢呋喃二醇等的配方设计提高了制品的弹性，但是配方体系会使用金属催化剂，这对人体及环境并不十分友好，并且制品密度为330-400Kg/m3，若制作更低密度鞋底会收缩变形，表面更无法做到镜面状，后期对鞋材表面进行喷漆处理，因不光亮会直接影响鞋底的美观。
发明内容
本发明的目的是提供一种镜面型超高弹聚氨酯鞋底树脂，安全环保、流动性好，制作的鞋底密度250-350kg/m3不收缩，鞋底具有超高弹特点，回弹达到60％以上，鞋底表面结皮光亮、呈镜面状，便于后期喷漆进行处理；本发明还提供其制备方法，生产工序简单，一次成型，无需后期高温硫化，节能降耗。
本发明所述的镜面型超高弹聚氨酯鞋底树脂，由A组分和B组分按重量比100:80-120组成，A组分由以下重量百分比的原料组成，其中聚四氢呋喃醇和聚酯聚合物多元醇的总重量为100％，其余原料以占聚四氢呋喃醇和聚酯聚合物多元醇总重量的百分比计：
Figure BDA0002874701360000011
Figure BDA0002874701360000021
B组分由以下重量百分含量的原料和50ppm储存稳定剂组成：
聚乙二醇 30-50％
聚醚多元醇 5-10％
异氰酸酯 45-60％。
聚酯聚合物多元醇的固含量为15-35％，羟值为56-75mg KOH/g，由乙二醇、二乙二醇、1，4-丁二醇中的一种或多种与己二酸进行缩聚反应制得数均分子量为1000～3500为基础聚酯，再用苯乙烯或丙烯腈中的一种或两种进行接枝共聚制得；优选山东一诺威聚氨酯股份有限公司的PE-245T。
聚四氢呋喃醇为四氢呋喃开环聚合而成，官能度为2.0，数均分子量为1800-2000；优选PTMEG-1800、PTMEG-2000(巴斯夫)或PTMG2000(晓星集团)。
扩链剂为乙二醇。
交联剂为三羟甲基丙烷、丙三醇、二乙醇胺、三乙醇胺的一种或多种。
发泡剂为H2O。
硅油为聚硅氧烷-氧化烯烃嵌段共聚物；优选L-1500(迈图高新材料)，DC3042、DC-193、DC2525(美国空气化工)中的一种或多种。
催化剂为叔胺类催化剂；优选三乙烯二胺(赢创公司)与乙二醇以35：65比例混合。
抗氧剂为酚类抗氧剂，优选抗氧剂1010。
聚乙二醇的数均分子量为1500-3000；优选PEG-1500、PEG-2000或SD-2003，均为上海东大化学有限公司生产。
聚醚多元醇的官能度为2-3，数均分子量为4000-6000；优选ED-28、EP-3600或EP-330NG，均为山东蓝星东大化工有限责任公司生产。
异氰酸酯为碳化二亚胺改性MDI、MDI-50、4,4-二苯基甲烷二异氰酸酯中的一种或多种；优选MDI-100(万华化学)、44C(科思创)、103C(巴斯夫)中的一种或多种。
储存稳定剂为磷酸、苯甲酰氯的一种或两种；优选磷酸。
B组分的NCO含量为15-18％。
本发明所述的镜面型超高弹聚氨酯鞋底树脂的制备方法，包括以下步骤：
(1)制备A组分：将聚四氢呋喃多元醇、聚酯聚合物多元醇投入反应釜，开启搅拌，然后加入扩链剂、交联剂、发泡剂、硅油、催化剂和抗氧剂，55-65℃下充分搅拌2-4h，即得A组分；
(2)制备B组分：将聚乙二醇、聚醚多元醇加入反应釜，开启搅拌将其混合均匀，升温到90-100℃，真空脱气，降温至40-55℃，再加入异氰酸酯和储存稳定剂，在70-80℃反应2-4h，降温至30-45℃，即得B组分；
(3)使用时，将A组分和B组分分别加热到完全融化至无结晶体，再分别注入低压浇注机A组分、B组分的料罐中，按照A:B＝100:80-120的重量比，充分混合后注入模温55-60℃的鞋模，6-10min脱模，继续50-60℃熟化1-3h做喷漆处理，即得镜面型超高弹聚氨酯鞋底。
与现有技术相比，本发明有以下有益效果：
(1)本发明的聚氨酯树脂安全环保，对身体和环境不会产生毒害作用，属于环境友好型产品；
(2)本发明的聚氨酯树脂制得的鞋底密度更低，250-350kg/m3不收缩，鞋底具有超高弹特点，回弹达到60％以上，鞋底表面结皮光亮、呈镜面状，便于后期喷漆处理；
(3)本发明的制备方法易实施，工序简单，制品一次成型、无需后期高温硫化，利于工业化生产。
具体实施方式
以下结合实施例说明本发明，但不限定本发明。
实施例1
(1)制备A组分：分别称量PTMEG1800为75kg，PE-245T为25kg，乙二醇为6kg，丙三醇为1kg，DC193为0.5kg，H2O为0.85kg，催化剂1.6kg，抗氧剂1010为0.5kg。将称量好的PTMEG1800、PE-245T投入反应釜中，开启搅拌，然后加入扩链剂、交联剂、发泡剂、硅油、催化剂和抗氧剂，60℃下充分搅拌3h，检验合格后即得A组分。
(2)制备B组分：将SD-2003为45kg，EP-3600为5kg加入反应釜，开启搅拌将其混合均匀，升温到100℃，真空脱气3h，降温至45℃，再加入MDI-100为45kg和103C为5kg，在75±2℃反应3h，检测合格，降温至45℃，装桶即得B组分。
(3)使用时，将A组分和B组分分别加热到完全融化至无结晶体，再分别注入低压浇注机A组分、B组分的料罐中，按照A:B＝100:90的重量比，充分完全混合后注入模温60℃的鞋模，7min脱模，继续60℃熟化2h，做喷漆处理，即得镜面型超高弹聚氨酯鞋底。
实施例2
(1)制备A组分：分别称量PTMEG2000为90kg，PE-245T为10kg，乙二醇为4kg，二乙醇胺为1.5kg，L1500为0.4kg，H2O为0.75kg，催化剂1.5kg，抗氧剂1010为0.5kg。将称量好的PTMEG2000、PE-245T投入反应釜中，开启搅拌，然后加入扩链剂、交联剂、发泡剂、硅油、催化剂和抗氧剂，55℃下充分搅拌3h，检验合格后即得A组分。
(2)制备B组分：将PEG-2000为40kg，ED-28为8kg加入反应釜，开启搅拌将其混合均匀，升温到100℃，真空脱气3h，降温至45℃，再加入MDI-100为40kg和103C为12kg，在75±2℃反应3小时，检测合格，降温至30℃装桶即得B组分。
(3)使用时，将A组分和B组分分别加热到完全融化至无结晶体，再分别注入低压浇注机A组分、B组分的料罐中，按照A:B＝100:85的重量比，充分完全混合后注入模温55-60℃的鞋模，8min脱模，继续50-60℃熟化2h做喷漆处理，即得镜面型超高弹聚氨酯鞋底。
实施例3
(1)制备A组分：分别称量PTMEG1500为80kg，PE-245T为20kg，乙二醇为4.5kg，三乙醇胺为0.8kg，DC193为0.5kg，H2O为0.7kg，催化剂1.8kg，抗氧剂1010为0.5kg。将称量好的PTMEG1500、PE-245T投入反应釜中，开启搅拌，然后加入扩链剂、交联剂、发泡剂、硅油、催化剂和抗氧剂，55-65℃下充分搅拌3h，检验合格后即得A组分。
(2)制备B组分：将SD-2003为50kg，EP-330N为5kg加入反应釜，开启搅拌将其混合均匀，升温到100℃，真空脱气3h，降温至45℃，再加入MDI-100为40kg和103C为5kg，在75±2℃反应3小时，检测合格，降温至35℃装桶即得B组分。
(3)使用时，将A组分和B组分分别加热到完全融化至无结晶体，再分别注入低压浇注机A组分、B组分的料罐中，按照A:B＝100:105的重量比，充分完全混合后注入模温55℃的鞋模，8min脱模，继续55℃熟化2h做喷漆处理，即得镜面型超高弹聚氨酯鞋底。
实施例4
(1)制备A组分：分别称量PTMEG2000为70kg，PE-245T为30kg，乙二醇为3.5kg，丙三醇为1.6kg，DC193为0.4kg，H2O为0.9kg，催化剂1.5kg，抗氧剂1010为0.6kg。将称量好的PTMEG2000、PE-245T投入反应釜中，开启搅拌，然后加入扩链剂、交联剂、发泡剂、硅油、催化剂和抗氧剂，65℃下充分搅拌3h，检验合格后即得A组分。
(2)制备B组分：将PEG-2000为35kg，ED-28为10kg加入反应釜，开启搅拌将其混合均匀，升温到100℃，真空脱气3h，降温至45℃，再加入MDI-100为40kg和103C为15kg，在75±2℃反应3h，检测合格，降温至40℃装桶即得B组分。
(3)使用时，将A组分和B组分分别加热到完全融化至无结晶体，再分别注入低压浇注机A组分、B组分的料罐中，按照A:B＝100:112的重量比，充分完全混合后注入模温55℃的鞋模，10min脱模，继续50℃熟化2h做喷漆处理，即得镜面型超高弹聚氨酯鞋底。
对比例1
采用专利CN110520457A中实施例3的配方和制备方法制备超高弹聚氨酯鞋底。
对比例2
(1)制备A组分：分别称量聚醚多元醇EP-3600(官能度3，羟值28mg KOH/g，分子量6000，山东蓝星东大股份有限公司)为80kg，PE-245T为20kg，乙二醇为3.5kg，丙三醇为1.6kg，DC193为0.4kg，H2O为0.9kg，催化剂1.5kg，抗氧剂1010为0.6kg。将称量好的EP-3600、PE-245T投入反应釜中，开启搅拌，然后加入扩链剂、交联剂、发泡剂、硅油、催化剂和抗氧剂，65℃下充分搅拌3h，检验合格后即得A组分。
(2)制备B组分：将PEG-2000为35kg，ED-28为10kg加入反应釜，开启搅拌将其混合均匀，升温到100℃，真空脱气3h，降温至45℃，再加入MDI-100为40kg和103C为15kg，在75±2℃反应3h，检测合格，降温至40℃装桶即得B组分。
(3)使用时，将A组分和B组分分别加热到完全融化至无结晶体，再分别注入低压浇注机A组分、B组分的料罐中，按照A:B＝100:92的重量比，充分完全混合后注入模温55℃的鞋模，10min脱模，继续50℃熟化2h做喷漆处理，即得聚氨酯鞋底。
对比例3
(1)制备A组分：分别称量PTMEG2000为70kg，PE-245T为30kg，1,4-丁二醇为5.0kg，丙三醇为1.6kg，DC193为0.4kg，H2O为0.8kg，催化剂1.5kg，抗氧剂1010为0.6kg。将称量好的PTMEG2000、PE-245T投入反应釜中，开启搅拌，然后加入扩链剂、交联剂、发泡剂、硅油、催化剂和抗氧剂，65℃下充分搅拌3h，检验合格后即得A组分。
(2)制备B组分：将PEG-2000为35kg，ED-28为10kg加入反应釜，开启搅拌将其混合均匀，升温到100℃，真空脱气3h，降温至45℃，再加入MDI-100为40kg和103C为15kg，在75±2℃反应3h，检测合格，降温至40℃装桶即得B组分。
(3)使用时，将A组分和B组分分别加热到完全融化至无结晶体，再分别注入低压浇注机A组分、B组分的料罐中，按照A:B＝100:110的重量比，充分完全混合后注入模温55℃的鞋模，10min脱模，继续50℃熟化2h做喷漆处理，即得聚氨酯鞋底。
对比例4
(1)制备A组分：分别称量PTMEG2000为70kg，PE-245T为30kg，乙二醇为3.5kg，丙三醇为1.6kg，DC193为0.4kg，H2O为0.8kg，催化剂1.5kg，抗氧剂1010为0.6kg。将称量好的PTMEG2000、PE-245T投入反应釜中，开启搅拌，然后加入扩链剂、交联剂、发泡剂、硅油、催化剂和抗氧剂，65℃下充分搅拌3h，检验合格后即得A组分。
(2)制备B组分：将PTMEG2000为40kg，ED-28为5kg加入反应釜，开启搅拌将其混合均匀，升温到100℃，真空脱气3h，降温至45℃，再加入MDI-100为40kg和103C为15kg，在75±2℃反应3h，检测合格，降温至40℃装桶即得B组分。
(3)使用时，将A组分和B组分分别加热到完全融化至无结晶体，再分别注入低压浇注机A组分、B组分的料罐中，按照A:B＝100:96的重量比，充分完全混合后注入模温55℃的鞋模，10min脱模，继续50℃熟化2h做喷漆处理，即得聚氨酯鞋底。
将实施例1-4和对比例1-4所得的超高弹聚氨酯鞋底进行性能测试，其中镜面型超高弹聚氨酯鞋底的性能测试是对10mm厚的样片测试结果，制品密度参照GB/T 6343-2009进行测试，硬度参照GB/T 3903.4-2017进行测试，拉伸强度、伸长率、剥离强度参照GB/T 528-2009进行测试，回弹参照ASTMD7121-2005进行测试，屈挠次数参照GB/T 3903.1-2017进行测试。
测试结果如表1所示。
表1实施例1-4和对比例1-4制备的超高弹聚氨酯鞋底的性能测试结果
Figure BDA0002874701360000061
从表1可以看出，本发明制备的聚氨酯鞋底密度更低，250-350kg/m3不收缩，鞋底具有超高弹特点，回弹达到60％以上，且鞋底表面结皮光亮、呈镜面状，便于后期喷漆处理。

Claims (10)

1.一种镜面型超高弹聚氨酯鞋底树脂，其特征在于：由A组分和B组分按重量比100:80-120组成，A组分由以下重量百分比的原料组成，其中聚四氢呋喃醇和聚酯聚合物多元醇的总重量为100％，其余原料以占聚四氢呋喃醇和聚酯聚合物多元醇总重量的百分比计：
Figure FDA0002874701350000011
B组分由以下重量百分含量的原料和50ppm储存稳定剂组成：
聚乙二醇 30-50％
聚醚多元醇 5-10％
异氰酸酯 45-60％；
聚酯聚合物多元醇的固含量为15-35％，羟值为56-75mg KOH/g，由乙二醇、二乙二醇、1，4-丁二醇中的一种或多种与己二酸进行缩聚反应制得数均分子量为1000～3500为基础聚酯，再用苯乙烯或丙烯腈中的一种或两种进行接枝共聚制得。
2.根据权利要求1所述的镜面型超高弹聚氨酯鞋底树脂，其特征在于：聚四氢呋喃醇为四氢呋喃开环聚合而成，官能度为2.0，数均分子量为1800-2000。
3.根据权利要求1所述的镜面型超高弹聚氨酯鞋底树脂，其特征在于：扩链剂为乙二醇。
4.根据权利要求1所述的镜面型超高弹聚氨酯鞋底树脂，其特征在于：交联剂为三羟甲基丙烷、丙三醇、二乙醇胺、三乙醇胺的一种或多种。
5.根据权利要求1所述的镜面型超高弹聚氨酯鞋底树脂，其特征在于：发泡剂为H2O；硅油为聚硅氧烷-氧化烯烃嵌段共聚物；催化剂为叔胺类催化剂；抗氧剂为酚类抗氧剂。
6.根据权利要求1所述的镜面型超高弹聚氨酯鞋底树脂，其特征在于：聚乙二醇数均分子量为1500-3000。
7.根据权利要求1所述的镜面型超高弹聚氨酯鞋底树脂，其特征在于：聚醚多元醇的官能度为2-3，数均分子量为4000-6000。
8.根据权利要求1所述的镜面型超高弹聚氨酯鞋底树脂，其特征在于：异氰酸酯为碳化二亚胺改性MDI、MDI-50、4,4-二苯基甲烷二异氰酸酯中的一种或多种。
9.根据权利要求1所述的镜面型超高弹聚氨酯鞋底树脂，其特征在于：储存稳定剂为磷酸、苯甲酰氯的一种或两种。
10.一种权利要求1-9任一项所述的镜面型超高弹聚氨酯鞋底树脂的制备方法，其特征在于：包括以下步骤：
(1)制备A组分：将聚四氢呋喃多元醇、聚酯聚合物多元醇投入反应釜，开启搅拌，然后加入扩链剂、交联剂、发泡剂、硅油、催化剂和抗氧剂，55-65℃下充分搅拌2-4h，即得A组分；
(2)制备B组分：将聚乙二醇、聚醚多元醇加入反应釜，开启搅拌将其混合均匀，升温到90-100℃，真空脱气，降温至40-55℃，再加入异氰酸酯和储存稳定剂，在70-80℃反应2-4h，降温至30-45℃，即得B组分；
(3)使用时，将A组分和B组分分别加热到完全融化至无结晶体，再分别注入低压浇注机A组分、B组分的料罐中，按照A:B＝100:80-120的重量比，充分混合后注入模温55-60℃的鞋模，6-10min脱模，继续50-60℃熟化1-3h做喷漆处理，即得镜面型超高弹聚氨酯鞋底。
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