CN110144111A - 一种轻质加麻聚氨酯鞋底及其制备方法 - Google Patents

一种轻质加麻聚氨酯鞋底及其制备方法 Download PDF

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CN110144111A
CN110144111A CN201910299418.XA CN201910299418A CN110144111A CN 110144111 A CN110144111 A CN 110144111A CN 201910299418 A CN201910299418 A CN 201910299418A CN 110144111 A CN110144111 A CN 110144111A
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吕正军
王连波
秦壮利
李宁
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Quanzhou Bonnie Biotechnology Co Ltd
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Abstract

本发明公开了一种轻质加麻聚氨酯鞋底,包括下述重量份的各原料:偶氮二甲酰胺3‑4、聚山梨酯0.7‑1、亚磷酸1‑2、聚碳酸酯二醇80‑100、异佛尔酮二异氰酸酯60‑70、引发剂1‑2、二月桂酸二丁基锡0.5‑1、色膏0.1‑0.2、轻质填料分散液50‑63、对甲基苯磺酸0.01‑0.02,本发明的鞋底材料质轻、抗冲击性好,耐磨性高,综合性能优越。

Description

一种轻质加麻聚氨酯鞋底及其制备方法
技术领域
本发明属于鞋底材料领域,具体涉及一种轻质加麻聚氨酯鞋底及其制备方法。
背景技术
聚氨酯鞋底材料具有以下优点:
1、具有轻柔、保暖、耐油、耐曲挠、耐磨等特点,比橡胶耐磨6倍以上,可按使用要求在很宽范围调节密度与硬度,可制成双色(双密度)的双层鞋底,下底为微发泡的高耐磨工作表面,内底为穿着舒适的弹性泡沫;
2、极轻,比重仅0.3-0.8,比常用的鞋底材料轻很多,对要求耐冲击、防穿孔的厚底鞋更合适,全世界安全防护鞋(劳保鞋)中15%采用聚氨酯(PU)鞋底。
3、模具要求较低,制作方便投资节省(发泡时对模具压力较小。
4、成型方法简单可靠,既可生产鞋底亦可生产连帮鞋,(PU底和各种面料的粘接力特强)品种及产量变化灵活,适合于现代工业生产;
然而,目前生产的聚氨酯鞋底,存在耐磨性能差,不耐水解, 容易导致鞋底龟裂、断裂的发生,造成聚氨酯鞋底的应用范围存在一定的局限性。
发明内容
本发明的目的是提供一种轻质加麻聚氨酯鞋底及其制备方法。
为实现上述目的,本发明采用以下技术方案:
一种轻质加麻聚氨酯鞋底,包括下述重量份的各原料:
偶氮二甲酰胺3-4、聚山梨酯0.7-1、亚磷酸1-2、聚碳酸酯二醇80-100、异佛尔酮二异氰酸酯60-70、引发剂1-2、二月桂酸二丁基锡0.5-1、色膏0.1-0.2、轻质填料分散液50-63、对甲基苯磺酸0.01-0.02。
所述的引发剂为过氧化二异丙苯。
所述轻质填料分散液是由下述重量份的原料组成的:
小苏打2-3、木屑40-55、轻质碳酸钙10-15、双酚a0.3-0.7、三羟甲基丙烷3-5、甲基丙烯酸甲酯15-20、过硫酸铵0.5-0.8。
所述轻质填料分散液的制备方法,包括以下步骤:
(1)取过硫酸铵,加入到其重量40-60倍的去离子水中,搅拌均匀,得过硫酸铵水溶液;
(2)取木屑,磨成细粉,与小苏打混合,在75-80℃下保温搅拌1-2小时,冷却至常温,与甲基丙烯酸甲酯混合,加入到混合料重量10-14倍的去离子水中,搅拌均匀,送入到反应釜中,通入氮气,调节反应釜温度为65-70℃,保温搅拌3-5小时,出料,抽滤,将滤饼水洗,常温干燥,得改性木粉;
(3)取三羟甲基丙烷,加入到其重量10-14倍的碳酸二甲酯中,搅拌均匀,加入上述改性木粉、轻质碳酸钙,超声10-20分钟,加入双酚a,在50-55℃下保温搅拌1-2小时,冷却至常温,即得所述轻质填料分散液。
一种轻质加麻聚氨酯鞋底的制备方法,包括以下步骤:
(1)取异佛尔酮二异氰酸酯重量的10-12%,与亚磷酸混合,加入到轻质填料分散液中,搅拌均匀,加入对甲基苯磺酸,升高温度为90-95℃,保温搅拌1-2小时,蒸馏除去碳酸二甲酯,得改性酯原料;
(2)取引发剂,加入到其重量30-44倍的丙酮中,搅拌均匀,得引发剂溶液;
(3)取改性酯原料,与剩余的异佛尔酮二异氰酸酯混合,加入聚碳酸酯二醇、搅拌均匀,送入到反应釜中,通入氮气,加入二月桂酸二丁基锡、偶氮二甲酰胺,在50-60℃下保温搅拌30-40分钟,滴加上述引发剂溶液,滴加完毕后搅拌反应1-2小时,冷却出料,旋蒸脱去丙酮,得改性聚氨酯母料;
(4)取上述改性聚氨酯母料,与聚山梨酯、色膏混合,加入适量水,搅拌均匀,得预混料;
(5)取3mm×3mm的网格麻绳,挂在鞋模的上下模具钉上,喷湿麻绳,将上述预混料注入到模具内,模具的预热温度为55-60℃,经过10-15分钟高温成型,开模取出,修剪余边,即可。
本发明的优点:
本发明首先将木屑处理后与甲基丙烯酸甲酯单体共混,在引发剂作用下聚合,改善了木纤维的表面活性,然后与三羟甲基丙烷共混分散到碳酸二甲酯溶液中,通过聚甲基丙烯酸甲酯的改性,有效的提高了木纤维在有机溶剂中的分散性能,再通过三羟甲基丙烷与油酸的酯交换反应,将得到的酯化料与异佛尔酮二异氰酸酯单体共混聚合,从而进一步改善了碳酸钙填料、木纤维在聚氨酯基体间的分散性能,提高了成品材料的力学稳定性强度;
本发明的鞋底材料质轻、抗冲击性好,耐磨性高,综合性能优越。
具体实施方式
实施例1
一种轻质加麻聚氨酯鞋底,包括下述重量份的各原料:
偶氮二甲酰胺3、聚山梨酯0.7、亚磷酸1、聚碳酸酯二醇80、异佛尔酮二异氰酸酯60-、引发剂1、二月桂酸二丁基锡0.5、色膏0.1、轻质填料分散液50、对甲基苯磺酸0.01。
所述的引发剂为过氧化二异丙苯。
所述轻质填料分散液是由下述重量份的原料组成的:
小苏打2、木屑40、轻质碳酸钙10、双酚a0.3、三羟甲基丙烷3、甲基丙烯酸甲酯15、过硫酸铵0.5。
所述轻质填料分散液的制备方法,包括以下步骤:
(1)取过硫酸铵,加入到其重量40倍的去离子水中,搅拌均匀,得过硫酸铵水溶液;
(2)取木屑,磨成细粉,与小苏打混合,在75℃下保温搅拌1小时,冷却至常温,与甲基丙烯酸甲酯混合,加入到混合料重量10倍的去离子水中,搅拌均匀,送入到反应釜中,通入氮气,调节反应釜温度为65℃,保温搅拌3小时,出料,抽滤,将滤饼水洗,常温干燥,得改性木粉;
(3)取三羟甲基丙烷,加入到其重量10-14倍的碳酸二甲酯中,搅拌均匀,加入上述改性木粉、轻质碳酸钙,超声10分钟,加入双酚a,在50℃下保温搅拌1小时,冷却至常温,即得所述轻质填料分散液。
一种轻质加麻聚氨酯鞋底的制备方法,包括以下步骤:
(1)取异佛尔酮二异氰酸酯重量的10%,与亚磷酸混合,加入到轻质填料分散液中,搅拌均匀,加入对甲基苯磺酸,升高温度为90℃,保温搅拌1小时,蒸馏除去碳酸二甲酯,得改性酯原料;
(2)取引发剂,加入到其重量30-44倍的丙酮中,搅拌均匀,得引发剂溶液;
(3)取改性酯原料,与剩余的异佛尔酮二异氰酸酯混合,加入聚碳酸酯二醇、搅拌均匀,送入到反应釜中,通入氮气,加入二月桂酸二丁基锡、偶氮二甲酰胺,在50℃下保温搅拌30分钟,滴加上述引发剂溶液,滴加完毕后搅拌反应1-2小时,冷却出料,旋蒸脱去丙酮,得改性聚氨酯母料;
(4)取上述改性聚氨酯母料,与聚山梨酯、色膏混合,加入适量水,搅拌均匀,得预混料;
(5)取3mm×3mm的网格麻绳,挂在鞋模的上下模具钉上,喷湿麻绳,将上述预混料注入到模具内,模具的预热温度为55℃,经过10分钟高温成型,开模取出,修剪余边,即可。
实施例2
一种轻质加麻聚氨酯鞋底,包括下述重量份的各原料:
偶氮二甲酰胺4、聚山梨酯1、亚磷酸2、聚碳酸酯二醇100、异佛尔酮二异氰酸酯70、引发剂2、二月桂酸二丁基锡1、色膏0.2、轻质填料分散液63、对甲基苯磺酸0.02。
所述的引发剂为过氧化二异丙苯。
所述轻质填料分散液是由下述重量份的原料组成的:
小苏打3、木屑55、轻质碳酸钙15、双酚a0.7、三羟甲基丙烷5、甲基丙烯酸甲酯20、过硫酸铵0.8。
所述轻质填料分散液的制备方法,包括以下步骤:
(1)取过硫酸铵,加入到其重量60倍的去离子水中,搅拌均匀,得过硫酸铵水溶液;
(2)取木屑,磨成细粉,与小苏打混合,在80℃下保温搅拌2小时,冷却至常温,与甲基丙烯酸甲酯混合,加入到混合料重量14倍的去离子水中,搅拌均匀,送入到反应釜中,通入氮气,调节反应釜温度为70℃,保温搅拌5小时,出料,抽滤,将滤饼水洗,常温干燥,得改性木粉;
(3)取三羟甲基丙烷,加入到其重量14倍的碳酸二甲酯中,搅拌均匀,加入上述改性木粉、轻质碳酸钙,超声20分钟,加入双酚a,在55℃下保温搅拌2小时,冷却至常温,即得所述轻质填料分散液。
一种轻质加麻聚氨酯鞋底的制备方法,包括以下步骤:
(1)取异佛尔酮二异氰酸酯重量的12%,与亚磷酸混合,加入到轻质填料分散液中,搅拌均匀,加入对甲基苯磺酸,升高温度为95℃,保温搅拌2小时,蒸馏除去碳酸二甲酯,得改性酯原料;
(2)取引发剂,加入到其重量30-44倍的丙酮中,搅拌均匀,得引发剂溶液;
(3)取改性酯原料,与剩余的异佛尔酮二异氰酸酯混合,加入聚碳酸酯二醇、搅拌均匀,送入到反应釜中,通入氮气,加入二月桂酸二丁基锡、偶氮二甲酰胺,在60℃下保温搅拌40分钟,滴加上述引发剂溶液,滴加完毕后搅拌反应2小时,冷却出料,旋蒸脱去丙酮,得改性聚氨酯母料;
(4)取上述改性聚氨酯母料,与聚山梨酯、色膏混合,加入适量水,搅拌均匀,得预混料;
(5)取3mm×3mm的网格麻绳,挂在鞋模的上下模具钉上,喷湿麻绳,将上述预混料注入到模具内,模具的预热温度为60℃,经过15分钟高温成型,开模取出,修剪余边,即可。
性能测试:
拉伸强度和断裂伸长率按G B / T 5 2 8 - 2 0 0 9进行、回弹性按GB/T 1681-2009进行;DIN磨耗测试按DIN 53516标准进行测试;
本发明实施例1的轻质加麻聚氨酯鞋底:
制品密度:261kg/m3
拉伸强度:29Mpa;
断裂伸长率:663%;
冲击回弹性:52%;
DIN磨耗(体积):21mm3
本发明发明实施例2的轻质加麻聚氨酯鞋底:
制品密度:254kg/m3
拉伸强度:31.3Mpa;
断裂伸长率:650%;
冲击回弹性:51%;
DIN磨耗(体积):21mm3

Claims (5)

1.一种轻质加麻聚氨酯鞋底,其特征在于,包括下述重量份的各原料:
偶氮二甲酰胺3-4、聚山梨酯0.7-1、亚磷酸1-2、聚碳酸酯二醇80-100、异佛尔酮二异氰酸酯60-70、引发剂1-2、二月桂酸二丁基锡0.5-1、色膏0.1-0.2、轻质填料分散液50-63、对甲基苯磺酸0.01-0.02。
2.根据权利要求1所述的一种轻质加麻聚氨酯鞋底,其特征在于,所述的引发剂为过氧化二异丙苯。
3.根据权利要求1所述的一种轻质加麻聚氨酯鞋底,其特征在于,所述轻质填料分散液是由下述重量份的原料组成的:
小苏打2-3、木屑40-55、轻质碳酸钙10-15、双酚a0.3-0.7、三羟甲基丙烷3-5、甲基丙烯酸甲酯15-20、过硫酸铵0.5-0.8。
4.根据权利要求3所述的一种轻质加麻聚氨酯鞋底,其特征在于,所述轻质填料分散液的制备方法,包括以下步骤:
(1)取过硫酸铵,加入到其重量40-60倍的去离子水中,搅拌均匀,得过硫酸铵水溶液;
(2)取木屑,磨成细粉,与小苏打混合,在75-80℃下保温搅拌1-2小时,冷却至常温,与甲基丙烯酸甲酯混合,加入到混合料重量10-14倍的去离子水中,搅拌均匀,送入到反应釜中,通入氮气,调节反应釜温度为65-70℃,保温搅拌3-5小时,出料,抽滤,将滤饼水洗,常温干燥,得改性木粉;
(3)取三羟甲基丙烷,加入到其重量10-14倍的碳酸二甲酯中,搅拌均匀,加入上述改性木粉、轻质碳酸钙,超声10-20分钟,加入双酚a,在50-55℃下保温搅拌1-2小时,冷却至常温,即得所述轻质填料分散液。
5.一种如权利要求1所述轻质加麻聚氨酯鞋底的制备方法,其特征在于,包括以下步骤:
(1)取异佛尔酮二异氰酸酯重量的10-12%,与亚磷酸混合,加入到轻质填料分散液中,搅拌均匀,加入对甲基苯磺酸,升高温度为90-95℃,保温搅拌1-2小时,蒸馏除去碳酸二甲酯,得改性酯原料;
(2)取引发剂,加入到其重量30-44倍的丙酮中,搅拌均匀,得引发剂溶液;
(3)取改性酯原料,与剩余的异佛尔酮二异氰酸酯混合,加入聚碳酸酯二醇、搅拌均匀,送入到反应釜中,通入氮气,加入二月桂酸二丁基锡、偶氮二甲酰胺,在50-60℃下保温搅拌30-40分钟,滴加上述引发剂溶液,滴加完毕后搅拌反应1-2小时,冷却出料,旋蒸脱去丙酮,得改性聚氨酯母料;
(4)取上述改性聚氨酯母料,与聚山梨酯、色膏混合,加入适量水,搅拌均匀,得预混料;
(5)取3mm×3mm的网格麻绳,挂在鞋模的上下模具钉上,喷湿麻绳,将上述预混料注入到模具内,模具的预热温度为55-60℃,经过10-15分钟高温成型,开模取出,修剪余边,即可。
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