CN112143154B - 应用于手套的聚氨酯改性丁腈胶乳的制备方法 - Google Patents

应用于手套的聚氨酯改性丁腈胶乳的制备方法 Download PDF

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CN112143154B
CN112143154B CN202011039237.2A CN202011039237A CN112143154B CN 112143154 B CN112143154 B CN 112143154B CN 202011039237 A CN202011039237 A CN 202011039237A CN 112143154 B CN112143154 B CN 112143154B
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周欢欢
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Abstract

本发明提供了一种应用于手套的聚氨酯改性丁腈胶乳的制备方法,属于高分子材料技术领域。它包括以下步骤:1)聚氨酯种子乳液的制备;2)水相预乳化液及引发剂水溶液的配制;3)初产品的制备;无氧反应体系,加入聚氨酯种子乳液,去离子水,有机硅分散剂,催化剂,部分水相预乳化液搅拌分散30分钟;升温至20℃~30℃,开始滴加剩余的水相预乳化液,丁二烯,丙烯腈,引发剂水溶液;再升温至30~50℃,保温反应5~8小时;4)聚氨酯改性丁腈胶乳的制备。本发明生产出来的丁腈胶乳,粒径分布较窄,流动性良好。经高速机械稳定仪测试,胶乳的稳定性好,用该乳液制成的医用丁腈手套,具有更好的柔软舒适性,透明性,弹性。

Description

应用于手套的聚氨酯改性丁腈胶乳的制备方法
技术领域
本发明属于高分子材料领域,涉及一种应用于手套的聚氨酯改性丁腈胶乳的制备方法。
背景技术
鉴于国内存在巨大的医疗行业需求缺口,中国作为一个人口大国,近些年都在不断完善医疗服务体系和提高医疗保障的质量,在2020抗击新型冠状病毒的过程中,国家强有力的医疗保障和应急***显现出了巨大的作用。另一方面,也充分突显了一个强大的医疗保障体系对一个国家的和平发展与繁荣稳定的重要作用。因此,医用丁腈手套作为常见的医用必备防护用品,其需求量随着人们的防护意识的不断增强,需求量也与日俱增,医用丁腈手套因其具有优良的综合性能,被广泛的应用于个人防护和医用领域,显现出了巨大的需求和发展空间。
目前,市场上的医用丁腈手套,在柔软性和穿戴的舒适便利性存在着一些不足,一般都需要加入一些淀粉或其他粉末来改善穿戴时的舒适性,且一般偏厚和偏硬;成品医用丁腈手套的生产批次之间存在质量差异,在强度和耐老化等方面存在着一些缺陷,主要是丁腈胶乳在聚合过程中,分子量的分布不均,分子结构之间存在较大差异,手套在加工过程中硫化不均匀,导致最终生产出来的成品医用丁腈手套的品质受影响。
此外,国内的医用丁腈手套胶乳的产能不高,不足以满足现阶段的需求,大部分用于生产医用丁腈手套的丁腈胶乳依赖于进口,导致国内医用丁腈手套的发展在一定程度上受限,因此开发高品质的医用丁腈手套用丁腈胶乳对于促进国内医疗事业的发展具有重要作用。
发明内容
本发明的目的是针对上述问题,提供了一种应用于手套的聚氨酯改性丁腈胶乳的制备方法。
为达到上述目的,本发明采用了下列技术方案:
应用于手套的聚氨酯改性丁腈胶乳的制备方法,各组分按重量份数计,包括以下步骤,
1)聚氨酯种子乳液的制备:向除水后的反应釜中投入50~60份聚合物二醇,搅拌升温至40~60℃,加入30~40份二异氰酸酯类单体,反应1小时,再加入4~10份含羟甲基酸类单体,升温至60~80℃,加入0.1~0.3份催化剂,保温反应1~2小时,加入3~5份醇胺类中和剂或多烷基胺类中和剂,加入300~500份去离子水,高速乳化10~30分钟,降温至25℃~35℃,配制成聚氨酯种子乳液,过滤,备用;
2)水相预乳化液及引发剂水溶液的配制:在配料罐中投入40~50份去离子水,1~2份阴离子乳化剂,0.3~0.8份分子量调节剂,0.02~0.05份pH缓冲剂,0.1~0.2份电解质,搅拌1.5~2小时,配制成水相预乳化液,备用;
用10~20份去离子水与0.5~1.0份引发剂,配制成引发剂水溶液,溶剂分散均匀后,备用;
3)初产品的制备:向除氧后的反应釜中通惰性气体,加入10~15份聚氨酯种子乳液,40~50份去离子水,3~5份有机硅分散剂,0.1~0.2份催化剂,从步骤2中制得的水相预乳化液中取1/10~3/20加入,搅拌分散30分钟;
升温至20℃~30℃,开始滴加剩余的步骤2中制得的水相预乳化液,60~80份丁二烯,20~40份丙烯腈,步骤2中制得的引发剂水溶液,滴加4~8小时,同时滴加完成所有滴加相;再升温至30~50℃,保温反应5~8小时,保温期间,每隔1~2小时取一次样,计算转化率,当转化率达到95%以上时,停止反应;
4)聚氨酯改性丁腈胶乳的制备:降温至20℃~30℃,加入0.1~0.3份终止剂,用4~10份中和剂调节pH至6~8,均匀分散30~50分钟后,抽真空,脱除易挥发份,制得应用于手套的聚氨酯改性丁腈胶乳。
其中,在步骤1)中,反应釜通过抽真空达到除水的效果。在步骤1)中,配制的聚氨酯种子乳液为半透明的乳液,粒径大小在30nm~50nm。在步骤2)中,向除氧后的反应釜中通氮气。
在上述的应用于手套的聚氨酯改性丁腈胶乳的制备方法,在步骤1)中,聚合物二醇的分子量为500~1000g/mol。
在上述的应用于手套的聚氨酯改性丁腈胶乳的制备方法,在步骤1)中,聚合物二醇为聚碳酸酯二醇,聚己内酯二醇,不饱和聚酯二醇,聚氧乙烯醚二醇,聚氧丙烯醚二醇中的一种以上。
在上述的应用于手套的聚氨酯改性丁腈胶乳的制备方法,在步骤1)中,二异氰酸酯类单体为异佛尔酮二异氰酸酯,二苯基甲烷二异氰酸酯,聚六亚甲基二异氰酸酯,甲苯二异氰酸酯中的一种以上。
在上述的应用于手套的聚氨酯改性丁腈胶乳的制备方法,在步骤1)中,含羟甲基酸类单体为二羟甲基丙酸,三羟甲基甘氨酸,二羟甲基丁酸,对羟甲基苯甲酸中的一种以上。
在上述的应用于手套的聚氨酯改性丁腈胶乳的制备方法,在步骤1)中,醇胺类中和剂为三乙醇胺。
在上述的应用于手套的聚氨酯改性丁腈胶乳的制备方法,在步骤1)中,多烷基胺类中和剂为三乙基胺。
在上述的应用于手套的聚氨酯改性丁腈胶乳的制备方法,在步骤2)中,阴离子乳化剂为乙二醇醚磷酸钾,烷基聚醚磷酸钠,油酸甲基氨基乙基磺酸钠,椰油基葡糖苷羟丙基磺酸酯钠,酰胺基聚氧乙烯醚硫酸钠,月桂醇聚氧乙烯醚羧酸钠中一种以上。
在上述的应用于手套的聚氨酯改性丁腈胶乳的制备方法,在步骤3)中,有机硅分散剂为氨基硅油改性聚乙二醇,羟基硅油改性聚氧乙烯醚,含氢硅油改性聚乙二醇,乙烯基硅油改性聚氧乙烯醚中的一种以上。
在上述的应用于手套的聚氨酯改性丁腈胶乳的制备方法,催化剂为新癸酸铋,异辛酸铋,油酸铋中的一种以上。
在上述的应用于手套的聚氨酯改性丁腈胶乳的制备方法,在步骤4)中,降温至20℃~30℃,加入终止剂,用4~10份中和剂调节pH至6~8,均匀分散30~50分钟后,抽真空,脱除易挥发份,卸压,卸料,过滤,制得应用于手套的聚氨酯改性丁腈胶乳。
与现有的技术相比,本发明的优点在于:
1)本发明采用种子乳液聚合的工艺,在聚合过程中严格控制反应温度,以制备出分子量分布均匀,粒径分布窄的丁腈胶乳,间接的提高了手套的强度,弹性和透明性,可以制备出超薄的医用丁腈手套,提高原材料的利用效率。
2)本发明通过聚氨酯种子乳液中醇类与异氰酸酯类单体的配比,调整了胶乳的软硬度。本发明中加入具有反应活性的有机硅分散剂,调整胶乳聚合物的表面微观结构,可以大大的提高手套表面的滑爽性,在丁腈手套的使用过程中,降低皮肤与手套之间的表面能,提高穿戴手套时的舒适便捷性。
3)本发明在丁腈手套的制备过程中,无需加入硫磺分散体,即可自交联达到很高的强度,可以广泛用于医用超薄丁腈手套的生产制造。
因此,本发明解决解决和改善目前医用丁腈手套用丁腈胶乳存在的分子量分布不均,及穿戴舒适性的问题。本发明制备的丁腈胶乳应用于医用超薄丁腈手套的制备,具有广阔的应用和发展前景。
本发明的其它优点、目标和特征将部分通过下面的说明体现,部分还将通过对本发明的研究和实践而为本领域的技术人员所理解。
具体实施方式
下面对本发明结合实施例进行进一步说明。
实施例1
应用于手套的聚氨酯改性丁腈胶乳的制备方法,各组分按重量份数计,包括以下步骤,
1)聚氨酯种子乳液的制备:向除水后的反应釜中投入50份聚合物二醇,搅拌升温至40℃,加入30份二异氰酸酯类单体,反应1小时,再加入4份含羟甲基酸类单体,升温至60℃,加入0.1份催化剂,保温反应1小时,加入3份醇胺类氢氧化钠,加入300份去离子水,高速乳化10分钟,降温至25℃,配制成聚氨酯种子乳液,过滤,备用;
2)水相预乳化液及引发剂水溶液的配制:在配料罐中投入40份去离子水,1份阴离子乳化剂,0.3份十二碳硫醇,0.02份pH缓冲剂,0.1份电解质,搅拌1.5小时,配制成水相预乳化液,备用;
用10份去离子水与0.5份引发剂,配制成引发剂水溶液,溶剂分散均匀后,备用;
3)初产品的制备:向除氧后的反应釜中通惰性气体,加入10份聚氨酯种子乳液,40份去离子水,3份有机硅分散剂,0.1份催化剂,从步骤2中制得的水相预乳化液中取1/10加入,搅拌分散30分钟;
升温至20℃,开始滴加剩余的步骤2中制得的水相预乳化液,60份丁二烯,20份丙烯腈,步骤2中制得的引发剂水溶液,滴加4小时,同时滴加完成所有滴加相;再升温至30℃,保温反应5小时,保温期间,每隔1小时取一次样,计算转化率,当转化率达到95%以上时,停止反应;
4)聚氨酯改性丁腈胶乳的制备:降温至20℃,加入0.1份多硫化钠,用4份氢氧化钠调节pH至6,均匀分散30分钟后,抽真空,脱除易挥发份,制得应用于手套的聚氨酯改性丁腈胶乳。
在步骤1)中,聚合物二醇的分子量为500~1000g/mol。在步骤1)中,聚合物二醇为聚碳酸酯二醇。
在步骤1)中,二异氰酸酯类单体为异佛尔酮二异氰酸酯。
在步骤1)中,含羟甲基酸类单体为二羟甲基丙酸。
在步骤1)中,醇胺类中和剂为三乙醇胺。
在步骤2)中,阴离子乳化剂为乙二醇醚磷酸钾。
在步骤3)中,有机硅分散剂为氨基硅油改性聚乙二醇。
催化剂为新癸酸铋。
实施例2
应用于手套的聚氨酯改性丁腈胶乳的制备方法,各组分按重量份数计,包括以下步骤,
1)聚氨酯种子乳液的制备:向除水后的反应釜中投入60份聚合物二醇,搅拌升温至60℃,加入40份二异氰酸酯类单体,反应1小时,再加入10份含羟甲基酸类单体,升温至80℃,加入0.3份催化剂,保温反应2小时,加入5份多烷基胺类中和剂,加入500份去离子水,高速乳化30分钟,降温至35℃,配制成聚氨酯种子乳液,过滤,备用;
2)水相预乳化液及引发剂水溶液的配制:在配料罐中投入50份去离子水,2份阴离子乳化剂,0.8份NDM,0.05份pH缓冲剂,0.2份电解质,搅拌2小时,配制成水相预乳化液,备用;
用20份去离子水与1.0份引发剂,配制成引发剂水溶液,溶剂分散均匀后,备用;
3)初产品的制备:向除氧后的反应釜中通惰性气体,加入15份聚氨酯种子乳液,50份去离子水,5份有机硅分散剂,0.2份催化剂,从步骤2中制得的水相预乳化液中取3/20加入,搅拌分散30分钟;
升温至30℃,开始滴加剩余的步骤2中制得的水相预乳化液,80份丁二烯,40份丙烯腈,步骤2中制得的引发剂水溶液,滴加8小时,同时滴加完成所有滴加相;再升温至50℃,保温反应8小时,保温期间,每隔2小时取一次样,计算转化率,当转化率达到95%以上时,停止反应;
4)聚氨酯改性丁腈胶乳的制备:降温至30℃,加入0.3份二甲基二硫代氨基甲酸钠,用10份碳酸氢钠调节pH至8,均匀分散50分钟后,抽真空,脱除易挥发份,制得应用于手套的聚氨酯改性丁腈胶乳。
其中,在步骤1)中,反应釜通过抽真空达到除水的效果。在步骤1)中,配制的聚氨酯种子乳液为半透明的乳液,粒径大小在30nm~50nm。在步骤2)中,向除氧后的反应釜中通氮气。
在步骤1)中,聚合物二醇的分子量为500~1000g/mol。
在步骤1)中,聚合物二醇为聚己内酯二醇和不饱和聚酯二醇。
在步骤1)中,二异氰酸酯类单体为二苯基甲烷二异氰酸酯和聚六亚甲基二异氰酸酯。
在步骤1)中,含羟甲基酸类单体为三羟甲基甘氨酸和二羟甲基丁酸。
在步骤1)中,多烷基胺类中和剂为三乙基胺。
在步骤2)中,阴离子乳化剂为烷基聚醚磷酸钠和油酸甲基氨基乙基磺酸钠。
在步骤3)中,有机硅分散剂为羟基硅油改性聚氧乙烯醚和含氢硅油改性聚乙二醇。
催化剂为异辛酸铋。
实施例3
应用于手套的聚氨酯改性丁腈胶乳的制备方法,各组分按重量份数计,包括以下步骤,
1)聚氨酯种子乳液的制备:对反应釜抽真空进行除水,投入52份聚合物二醇,搅拌升温至45℃,加入31份二异氰酸酯类单体,反应1小时,再加入5份含羟甲基酸类单体,升温至61℃,加入0.15份催化剂,保温反应1.2小时,加入3.5份醇胺类中和剂,加入350份去离子水,高速乳化15分钟,降温至28℃,配制成半透明的聚氨酯种子乳液,粒径大小在35nm,过滤,备用;
2)水相预乳化液及引发剂水溶液的配制:在配料罐中投入42份去离子水,1.2份阴离子乳化剂,0.4份异丙醇,0.03份pH缓冲剂,0.15份电解质,搅拌1.6小时,配制成水相预乳化液,备用;
用12份去离子水与0.6份引发剂,配制成引发剂水溶液,溶剂分散均匀后,备用;
3)初产品的制备:向除氧后的反应釜中通氮气,加入12份聚氨酯种子乳液,42份去离子水,3.5份有机硅分散剂,0.15份催化剂,从步骤2中制得的水相预乳化液中取1/8加入,搅拌分散30分钟;
升温至21℃,开始滴加剩余的步骤2中制得的水相预乳化液,62份丁二烯,25份丙烯腈,步骤2中制得的引发剂水溶液,滴加4.5小时,同时滴加完成所有滴加相;再升温至35℃,保温反应6小时,保温期间,每隔1.2小时取一次样,计算转化率,当转化率达到95%以上时,停止反应;
4)聚氨酯改性丁腈胶乳的制备:降温至22℃,加入0.15份亚硝酸钠,用5份碳酸钠调节pH至7,均匀分散32分钟后,抽真空,脱除易挥发份,卸压,卸料,过滤,制得应用于手套的聚氨酯改性丁腈胶乳。
在步骤1)中,聚合物二醇为聚氧乙烯醚二醇。
在步骤1)中,二异氰酸酯类单体为甲苯二异氰酸酯。
在步骤1)中,含羟甲基酸类单体为对羟甲基苯甲酸。
在步骤1)中,醇胺类中和剂为三乙醇胺。
在步骤2)中,阴离子乳化剂为椰油基葡糖苷羟丙基磺酸酯钠。
在步骤3)中,有机硅分散剂为乙烯基硅油改性聚氧乙烯醚。
催化剂为油酸铋。
实施例4
应用于手套的聚氨酯改性丁腈胶乳的制备方法,各组分按重量份数计,包括以下步骤,
1)聚氨酯种子乳液的制备:向除水后的反应釜中投入58份聚合物二醇,搅拌升温至55℃,加入39份二异氰酸酯类单体,反应1小时,再加入9份含羟甲基酸类单体,升温至78℃,加入0.28份催化剂,保温反应1.8小时,加入4.5份醇胺类中和剂,加入490份去离子水,高速乳化28分钟,降温至32℃,配制成聚氨酯种子乳液,过滤,备用;
2)水相预乳化液及引发剂水溶液的配制:在配料罐中投入48去离子水,1.9份阴离子乳化剂,0.7份2,4-二苯基-4-甲基-1-戊烯,0.04份pH缓冲剂,0.18份氯化钠,搅拌1.8小时,配制成水相预乳化液,备用;
用19份去离子水与0.9份引发剂,配制成引发剂水溶液,溶剂分散均匀后,备用;
3)初产品的制备:向除氧后的反应釜中通惰性气体,加入14份聚氨酯种子乳液,49份去离子水,4.5份有机硅分散剂,0.19份催化剂,从步骤2中制得的水相预乳化液中取1/8加入,搅拌分散30分钟;
升温至28℃,开始滴加剩余的步骤2中制得的水相预乳化液,78份丁二烯,39份丙烯腈,步骤2中制得的引发剂水溶液,滴加7小时,同时滴加完成所有滴加相;再升温至45℃,保温反应7小时,保温期间,每隔1.9小时取一次样,计算转化率,当转化率达到95%以上时,停止反应;
4)聚氨酯改性丁腈胶乳的制备:降温至28℃,加入0.25份二乙基羟胺,用9份三乙基胺调节pH至7,均匀分散45分钟后,抽真空,脱除易挥发份,制得应用于手套的聚氨酯改性丁腈胶乳。
在步骤1)中,聚合物二醇的分子量为500~1000g/mol。在步骤1)中,聚合物二醇为聚碳酸酯二醇,聚己内酯二醇,不饱和聚酯二醇,聚氧乙烯醚二醇和聚氧丙烯醚二醇。
在步骤1)中,含羟甲基酸类单体为二羟甲基丙酸,三羟甲基甘氨酸,二羟甲基丁酸和对羟甲基苯甲酸。
在步骤1)中,醇胺类中和剂为三乙醇胺。
在步骤1)中,多烷基胺类中和剂为三乙基胺。
在步骤2)中,阴离子乳化剂为乙二醇醚磷酸钾,烷基聚醚磷酸钠,油酸甲基氨基乙基磺酸钠,椰油基葡糖苷羟丙基磺酸酯钠,酰胺基聚氧乙烯醚硫酸钠和月桂醇聚氧乙烯醚羧酸钠。
在步骤3)中,有机硅分散剂为氨基硅油改性聚乙二醇,羟基硅油改性聚氧乙烯醚,含氢硅油改性聚乙二醇和乙烯基硅油改性聚氧乙烯醚中。
催化剂为新癸酸铋,异辛酸铋和油酸铋。
实施例5
应用于手套的聚氨酯改性丁腈胶乳的制备方法,各组分按重量份数计,包括以下步骤,
1)聚氨酯种子乳液的制备:向除水后的反应釜中投入55份聚合物二醇,搅拌升温至50℃,加入35份二异氰酸酯类单体,反应1小时,再加入8份含羟甲基酸类单体,升温至70℃,加入0.2份催化剂,保温反应1.5小时,加入4份多烷基胺类中和剂,加入400份去离子水,高速乳化20分钟,降温至30℃,配制成聚氨酯种子乳液,过滤,备用;
2)水相预乳化液及引发剂水溶液的配制:在配料罐中投入45份去离子水,1.5份阴离子乳化剂,0.6份分子量调节剂,0.04份pH缓冲剂,0.15份电解质,搅拌1.8小时,配制成水相预乳化液,备用;
用15份去离子水与0.7份引发剂,配制成引发剂水溶液,溶剂分散均匀后,备用;
3)初产品的制备:向除氧后的反应釜中通惰性气体,加入12份聚氨酯种子乳液,45份去离子水,4份有机硅分散剂,0.15份催化剂,从步骤2中制得的水相预乳化液中取1/10加入,搅拌分散30分钟;
升温至25℃,开始滴加剩余的步骤2中制得的水相预乳化液,70份丁二烯,30份丙烯腈,步骤2中制得的引发剂水溶液,滴加6小时,同时滴加完成所有滴加相;再升温至40℃,保温反应6.5小时,保温期间,每隔1.5小时取一次样,计算转化率,当转化率达到95%以上时,停止反应;
4)聚氨酯改性丁腈胶乳的制备:降温至25℃,加入0.2份二乙基羟胺,用8份氨水调节pH至7,均匀分散40分钟后,抽真空,脱除易挥发份,制得应用于手套的聚氨酯改性丁腈胶乳。
在步骤1)中,聚合物二醇为聚氧丙烯醚二醇。
在步骤1)中,二异氰酸酯类单体为聚六亚甲基二异氰酸酯和甲苯二异氰酸酯。
在步骤1)中,含羟甲基酸类单体为三羟甲基甘氨酸。
在步骤1)中,多烷基胺类中和剂为三乙基胺。
在步骤2)中,阴离子乳化剂为酰胺基聚氧乙烯醚硫酸钠和月桂醇聚氧乙烯醚羧酸钠。
在步骤3)中,有机硅分散剂为含氢硅油改性聚乙二醇。
催化剂为新癸酸铋。
对比例
对比例与实施例5基本相同,不同之处在于:(1)步骤1)中,加入40份聚合物二醇和10份二异氰酸酯类单体。(2)步骤3)中,不加入有机硅分散剂。(3)步骤3)中,加入聚氨酯种子乳液、去离子水、有机硅分散剂、催化剂、部分水相预乳化液后,升温至20℃~30℃,此后操作不再改变反应温度。
将实施例1-5的方法制备的应用于手套的聚氨酯改性丁腈胶乳与对比例的丁腈胶乳进行物性测试结果见附表。
表1
Figure GDA0003987501680000121
通过上表可知,采用本发明配比及方法制备的应用于手套的聚氨酯改性丁腈胶乳粒径均匀,流动性良好,能够生产质量均匀医用丁腈手套。经高速机械稳定仪测试,胶乳的稳定性好,具有理想的粘度、机械稳定性、聚合凝聚物,能够满足医用丁腈手套穿戴使用过程中的防护需求,生产的手套具有更好的柔软舒适性,透明性,弹性。
应用例
将实施例1-5制得的聚氨酯改性丁腈胶乳及对比文件制得的胶乳加入手套摸具,进行浸渍处理,低温硫化烘干,水洗,高温硫化烘干,生产出医用手套。
对实施例1-5以及对比例作耐磨性、耐穿刺性、耐割性的性能测试,测试结果如表2所示。
表2
耐磨(等级) 耐刺穿(等级) 耐切割性(等级)
实施例1 6 4 5
实施例2 5 4 2
实施例3 6 5 3
实施例4 5 3 2
实施例5 7 5 5
对比例 2 1 1
观察表2可得知,利用实施例1-5得到的聚氨酯改性丁腈胶乳制备的乳胶手套的耐磨效果、耐刺穿性能、耐切割性更佳,能够满足医用丁腈手套穿戴使用过程中的防护需求,生产的手套具有更好的柔软舒适性,透明性,弹性。
本文中所描述的具体实施例仅仅是对本发明精神作举例说明。本发明所属技术领域的技术人员可以对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,但并不会偏离本发明的精神或者超越所附权利要求书所定义的范围。

Claims (9)

1.应用于手套的聚氨酯改性丁腈胶乳的制备方法,其特征在于:各组分按重量份数计,包括以下步骤,
1)聚氨酯种子乳液的制备:向除水后的反应釜中投入50~60份聚合物二醇,搅拌升温至40~60℃,加入30~40份二异氰酸酯类单体,反应1小时,再加入4~10份含羟甲基酸类单体,升温至60~80℃,加入0.1~0.3份催化剂,保温反应1~2小时,加入3~5份醇胺类中和剂或多烷基胺类中和剂,加入300~500份去离子水,高速乳化10~30分钟,降温至25℃~35℃,配制成聚氨酯种子乳液,过滤,备用;
2)水相预乳化液及引发剂水溶液的配制:在配料罐中投入40~50份去离子水,1~2份阴离子乳化剂,0.3~0.8份分子量调节剂,0.02~0.05份pH缓冲剂,0.1~0.2份电解质,搅拌1.5~2小时,配制成水相预乳化液,备用;
用10~20份去离子水与0.5~1.0份引发剂,配制成引发剂水溶液,溶剂分散均匀后,备用;
3)初产品的制备:向除氧后的反应釜中通惰性气体,加入10~15份聚氨酯种子乳液,40~50份去离子水,3~5份有机硅分散剂,0.1~0.2份催化剂,从步骤2中制得的水相预乳化液中取1/10~3/20加入,搅拌分散30分钟;
升温至20℃~30℃,开始滴加剩余的步骤2中制得的水相预乳化液,60~80份丁二烯,20~40份丙烯腈,步骤2中制得的引发剂水溶液,滴加4~8小时,同时滴加完成所有滴加相;再升温至30~50℃,保温反应5~8小时,保温期间,每隔1~2小时取一次样,计算转化率,当转化率达到95%以上时,停止反应;
4)聚氨酯改性丁腈胶乳的制备:降温至20℃~30℃,加入0.1~0.3份终止剂,用4~10份中和剂调节pH至6~8,均匀分散30~50分钟后,抽真空,脱除易挥发份,制得应用于手套的聚氨酯改性丁腈胶乳;
其中在步骤1)中,含羟甲基酸类单体为二羟甲基丙酸,三羟甲基甘氨酸,二羟甲基丁酸,对羟甲基苯甲酸中的一种以上。
2.根据权利要求1所述的应用于手套的聚氨酯改性丁腈胶乳的制备方法,其特征在于:在步骤1)中,聚合物二醇的分子量为500~1000g/mol。
3.根据权利要求1或2所述的应用于手套的聚氨酯改性丁腈胶乳的制备方法,其特征在于:在步骤1)中,聚合物二醇为聚碳酸酯二醇,聚己内酯二醇,不饱和聚酯二醇,聚氧乙烯醚二醇,聚氧丙烯醚二醇中的一种以上。
4.根据权利要求1所述的应用于手套的聚氨酯改性丁腈胶乳的制备方法,其特征在于:在步骤1)中,二异氰酸酯类单体为异佛尔酮二异氰酸酯,二苯基甲烷二异氰酸酯,聚六亚甲基二异氰酸酯,甲苯二异氰酸酯中的一种以上。
5.根据权利要求1所述的应用于手套的聚氨酯改性丁腈胶乳的制备方法,其特征在于:在步骤1)中,醇胺类中和剂为三乙醇胺;多烷基胺类中和剂为三乙基胺。
6.根据权利要求1所述的应用于手套的聚氨酯改性丁腈胶乳的制备方法,其特征在于:在步骤2)中,阴离子乳化剂为乙二醇醚磷酸钾,烷基聚醚磷酸钠,油酸甲基氨基乙基磺酸钠,椰油基葡糖苷羟丙基磺酸酯钠,酰胺基聚氧乙烯醚硫酸钠,月桂醇聚氧乙烯醚羧酸钠中一种以上。
7.根据权利要求1所述的应用于手套的聚氨酯改性丁腈胶乳的制备方法,其特征在于:在步骤3)中,有机硅分散剂为氨基硅油改性聚乙二醇,羟基硅油改性聚氧乙烯醚,含氢硅油改性聚乙二醇,乙烯基硅油改性聚氧乙烯醚中的一种以上。
8.根据权利要求1所述的应用于手套的聚氨酯改性丁腈胶乳的制备方法,其特征在于:催化剂为新癸酸铋,异辛酸铋,油酸铋中的一种以上。
9.根据权利要求1所述的应用于手套的聚氨酯改性丁腈胶乳的制备方法,其特征在于:在步骤4)中,降温至20℃~30℃,加入终止剂,用4~10份中和剂调节pH至6~8,均匀分散30~50分钟后,抽真空,脱除易挥发份,卸压,卸料,过滤,制得应用于手套的聚氨酯改性丁腈胶乳。
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