CN111138619A - 一种合成革用无溶剂紫外光固化聚氨酯的制备方法 - Google Patents

一种合成革用无溶剂紫外光固化聚氨酯的制备方法 Download PDF

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CN111138619A
CN111138619A CN201911309718.8A CN201911309718A CN111138619A CN 111138619 A CN111138619 A CN 111138619A CN 201911309718 A CN201911309718 A CN 201911309718A CN 111138619 A CN111138619 A CN 111138619A
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solvent
parts
synthetic leather
accounts
reaction kettle
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黄小平
戴启彬
黄明珠
张嘉栋
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Fujian Xiaowei Jinshi Technology Incubation Co ltd
Fujian Chengjie Polymer Material Co ltd
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Fujian Xiaowei Jinshi Technology Incubation Co ltd
Fujian Chengjie Polymer Material Co ltd
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Abstract

本发明公开了一种合成革用无溶剂紫外光固化聚氨酯的制备方法，将一定重量份的异氰酸酯加入反应釜内，并向反应釜中充满氮气，之后搅拌升温至65‑75℃，然后将真空脱水后的二元醇与催化剂加入反应釜中，持续搅拌升温至80℃，并恒温搅拌1‑2小时，之后先向反应釜中添加小分子扩链剂进行扩链反应，扩链反应0.5‑1.5小时后，再加入亲水性扩链剂进行亲水反应，反应1‑2小时后。该合成革用无溶剂紫外光固化聚氨酯的制备方法，对聚氨酯进行改性处理，还能够在解决目前溶剂型聚氨酯合成革工艺中溶剂的污染问题和聚氨酯合成革产中品DMF的残留引起的产品安全问题上，进一步的提高了聚氨酯的固化成膜稳固性，易老化性。

Description

一种合成革用无溶剂紫外光固化聚氨酯的制备方法
技术领域
本发明属于聚氨酯合成革技术领域，具体涉及一种合成革用无溶剂紫外光固化聚氨酯的制备方法。
背景技术
聚氨酯合成革是模拟天然皮革的组织结构和使用性能，并可作为天然皮革代用品的复合材料。通常以无纺布模拟网状层，以发泡聚氨酯涂层模拟粒面层，所得到的合成革正、反面都与皮革十分相似，并具有一定的透气性，比普通人造革更接近天然皮革，广泛用于制作鞋、靴、箱包和球类等。。
现阶段聚氨酯合成革的生产制备已开始采用无溶剂紫外光固化聚氨酯，以避免使用溶剂型聚氨酯时产生的污染问题，但是现阶段对于无溶剂紫外光固化聚氨酯，其在制备过程中，其稳定性和耐抗性较差，对于环境的适应差，导致，在其使用寿命大大的降低，进而会影响其进行销售。
发明内容
本发明的目的在于提供一种合成革用无溶剂紫外光固化聚氨酯的制备方法，以解决上述背景技术中提出的问题。
为实现上述目的，本发明提供如下技术方案：
一种合成革用无溶剂紫外光固化聚氨酯的制备方法，包括以下步骤：
S1、将一定重量份的异氰酸酯加入反应釜内，并向反应釜中充满氮气，之后搅拌升温至65-75℃，然后将真空脱水后的二元醇与催化剂加入反应釜中，持续搅拌升温至80℃，并恒温搅拌1-2小时；
S2、在S1中反应釜恒温搅拌完成后，先向反应釜中添加小分子扩链剂进行扩链反应，扩链反应0.5-1.5小时后，再加入亲水性扩链剂进行亲水反应，反应1-2小时后；
S3、继续向反应釜中加入丙烯酸反应液，并在70-80℃下继续反应2-3小时，反应完成后，之后将聚硅氧烷加入其中，并继续搅拌0.5小时后，加入阻燃剂和光热稳定剂继续搅拌0.5小时；
S4、将S3中加热搅拌完成后的反应物，迅速冷却，并在冷却完成后加入光引发剂，即得到无溶剂紫外光固化聚氨酯。
优选的，S1中，异氰酸酯包括甲苯二异氰酸酯、二苯基亚甲基二异氰酸酯、异佛尔酮二异氰酸酯中的一种或多种任意比例的混合物，且异氰酸酯在原料中占总份数的30-50份。
优选的，S1中，多元醇为为聚氧化丙烯二元醇、苯酐聚酯二元醇、聚己二酸新戊二醇酯二醇、聚碳酸酯二元醇、聚己内酯二元醇和聚四氢呋喃二元醇中的一种或几种，其中元醇占总份数的50-80份。
优选的，S1中，催化剂为辛酸亚锡、二月桂酸正丁基锡、有机Bi盐催化剂、有机Zn盐催化剂中的一种或几种，催化剂占总份数的1-3份。
优选的，S2中，小分子扩链剂为1,2-丙二醇、1,4-丁二醇、2-甲基-1,3-丙二醇、新戊二醇或三甲基戊二醇，占总份数的5-20份，亲水性扩链剂为二羟甲基丙酸，占总份数的15-30份。
优选的，S3中，丙烯酸反应液为丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、甲基丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基丙酯中的一种或多种的混合物，占总份数的20-40份。
优选的，S3中，阻燃剂为微胶囊化红磷，占总份数的0.5-2份，光热稳定剂为紫外线吸收剂、受阻胺类光稳定剂或抗氧剂，占总份数的0.4-0.8份。
优选的，S4中，光引发剂为苯基双甲基苯甲酰基氧代磷、苯基三甲基苯甲酰基氧代磷、羟基环乙基苯基甲酮中的一种或两种混合物，占总份数的0.2-0.4份。
本发明的技术效果和优点：该合成革用无溶剂紫外光固化聚氨酯的制备方法，首先通过不添加任何溶剂，没有任何溶剂的污染问题，同时对聚氨酯进行改性处理，还能够在解决目前溶剂型聚氨酯合成革工艺中溶剂的污染问题和聚氨酯合成革产中品DMF的残留引起的产品安全问题上，进一步的提高了聚氨酯的固化成膜稳固性，易老化性，另外在制备的过程中加入阻燃剂和聚硅氧烷，其聚硅氧烷提高固化时的防水性能，而阻燃剂的使用，提高固化成膜后的阻燃性能，提高其使用的寿命。
具体实施方式
下面将结合本发明的内容，对本发明中的技术方案进行清楚、完整地描述，显然，所描述的内容仅仅是本发明一部分内容，而不是全部的内容。基于本发明中的内容，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他内容，都属于本发明保护的范围。
实施例1
本发明提供了一种合成革用无溶剂紫外光固化聚氨酯的制备方法，包括以下步骤：
包括以下步骤：
S1、将一定重量份的异氰酸酯加入反应釜内，并向反应釜中充满氮气，之后搅拌升温至65℃，然后将真空脱水后的二元醇与催化剂加入反应釜中，持续搅拌升温至80℃，并恒温搅拌1小时；
S2、在S1中反应釜恒温搅拌完成后，先向反应釜中添加小分子扩链剂进行扩链反应，扩链反应0.5小时后，再加入亲水性扩链剂进行亲水反应，反应1小时后；
S3、继续向反应釜中加入丙烯酸反应液，并在70℃下继续反应2小时，反应完成后，之后将聚硅氧烷加入其中，并继续搅拌0.5小时后，加入阻燃剂和光热稳定剂继续搅拌0.5小时；
S4、将S3中加热搅拌完成后的反应物，迅速冷却，并在冷却完成后加入光引发剂，即得到无溶剂紫外光固化聚氨酯。
具体的，S1中，异氰酸酯包括甲苯二异氰酸酯、二苯基亚甲基二异氰酸酯、异佛尔酮二异氰酸酯中的一种或多种任意比例的混合物，且异氰酸酯在原料中占总份数的30份。
具体的，S1中，多元醇为为聚氧化丙烯二元醇、苯酐聚酯二元醇、聚己二酸新戊二醇酯二醇、聚碳酸酯二元醇、聚己内酯二元醇和聚四氢呋喃二元醇中的一种或几种，其中元醇占总份数的50份。
具体的，S1中，催化剂为辛酸亚锡、二月桂酸正丁基锡、有机Bi盐催化剂、有机Zn盐催化剂中的一种或几种，催化剂占总份数的1份。
具体的，S2中，小分子扩链剂为1,2-丙二醇、1,4-丁二醇、2-甲基-1,3-丙二醇、新戊二醇或三甲基戊二醇，占总份数的5份，亲水性扩链剂为二羟甲基丙酸，占总份数的15份。
具体的，S3中，丙烯酸反应液为丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、甲基丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基丙酯中的一种或多种的混合物，占总份数的20份。
具体的，S3中，阻燃剂为微胶囊化红磷，占总份数的0.5份，光热稳定剂为紫外线吸收剂、受阻胺类光稳定剂或抗氧剂，占总份数的0.4份。
具体的，S4中，光引发剂为苯基双甲基苯甲酰基氧代磷、苯基三甲基苯甲酰基氧代磷、羟基环乙基苯基甲酮中的一种或两种混合物，占总份数的0.2份。
实施例2
一种合成革用无溶剂紫外光固化聚氨酯的制备方法，包括以下步骤：
S1、将一定重量份的异氰酸酯加入反应釜内，并向反应釜中充满氮气，之后搅拌升温至70℃，然后将真空脱水后的二元醇与催化剂加入反应釜中，持续搅拌升温至80℃，并恒温搅拌1.5小时；
S2、在S1中反应釜恒温搅拌完成后，先向反应釜中添加小分子扩链剂进行扩链反应，扩链反应1小时后，再加入亲水性扩链剂进行亲水反应，反应1.5小时后；
S3、继续向反应釜中加入丙烯酸反应液，并在75℃下继续反应2.5小时，反应完成后，之后将聚硅氧烷加入其中，并继续搅拌0.5小时后，加入阻燃剂和光热稳定剂继续搅拌0.5小时；
S4、将S3中加热搅拌完成后的反应物，迅速冷却，并在冷却完成后加入光引发剂，即得到无溶剂紫外光固化聚氨酯。
具体的，S1中，异氰酸酯包括甲苯二异氰酸酯、二苯基亚甲基二异氰酸酯、异佛尔酮二异氰酸酯中的一种或多种任意比例的混合物，且异氰酸酯在原料中占总份数的40份。
具体的，S1中，多元醇为为聚氧化丙烯二元醇、苯酐聚酯二元醇、聚己二酸新戊二醇酯二醇、聚碳酸酯二元醇、聚己内酯二元醇和聚四氢呋喃二元醇中的一种或几种，其中元醇占总份数的65份。
具体的，S1中，催化剂为辛酸亚锡、二月桂酸正丁基锡、有机Bi盐催化剂、有机Zn盐催化剂中的一种或几种，催化剂占总份数的2份。
具体的，S2中，小分子扩链剂为1,2-丙二醇、1,4-丁二醇、2-甲基-1,3-丙二醇、新戊二醇或三甲基戊二醇，占总份数的15份，亲水性扩链剂为二羟甲基丙酸，占总份数的22份。
具体的，S3中，丙烯酸反应液为丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、甲基丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基丙酯中的一种或多种的混合物，占总份数的30份。
具体的，S3中，阻燃剂为微胶囊化红磷，占总份数的1.5份，光热稳定剂为紫外线吸收剂、受阻胺类光稳定剂或抗氧剂，占总份数的0.6份。
具体的，S4中，光引发剂为苯基双甲基苯甲酰基氧代磷、苯基三甲基苯甲酰基氧代磷、羟基环乙基苯基甲酮中的一种或两种混合物，占总份数的0.3份。
实施例3
一种合成革用无溶剂紫外光固化聚氨酯的制备方法，包括以下步骤：
S1、将一定重量份的异氰酸酯加入反应釜内，并向反应釜中充满氮气，之后搅拌升温至75℃，然后将真空脱水后的二元醇与催化剂加入反应釜中，持续搅拌升温至80℃，并恒温搅拌2小时；
S2、在S1中反应釜恒温搅拌完成后，先向反应釜中添加小分子扩链剂进行扩链反应，扩链反应1.5小时后，再加入亲水性扩链剂进行亲水反应，反应2小时后；
S3、继续向反应釜中加入丙烯酸反应液，并在80℃下继续反应3小时，反应完成后，之后将聚硅氧烷加入其中，并继续搅拌0.5小时后，加入阻燃剂和光热稳定剂继续搅拌0.5小时；
S4、将S3中加热搅拌完成后的反应物，迅速冷却，并在冷却完成后加入光引发剂，即得到无溶剂紫外光固化聚氨酯。
具体的，S1中，异氰酸酯包括甲苯二异氰酸酯、二苯基亚甲基二异氰酸酯、异佛尔酮二异氰酸酯中的一种或多种任意比例的混合物，且异氰酸酯在原料中占总份数的50份。
具体的，S1中，多元醇为为聚氧化丙烯二元醇、苯酐聚酯二元醇、聚己二酸新戊二醇酯二醇、聚碳酸酯二元醇、聚己内酯二元醇和聚四氢呋喃二元醇中的一种或几种，其中元醇占总份数的80份。
具体的，S1中，催化剂为辛酸亚锡、二月桂酸正丁基锡、有机Bi盐催化剂、有机Zn盐催化剂中的一种或几种，催化剂占总份数的3份。
具体的，S2中，小分子扩链剂为1,2-丙二醇、1,4-丁二醇、2-甲基-1,3-丙二醇、新戊二醇或三甲基戊二醇，占总份数的20份，亲水性扩链剂为二羟甲基丙酸，占总份数的30份。
具体的，S3中，丙烯酸反应液为丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、甲基丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基丙酯中的一种或多种的混合物，占总份数的40份。
具体的，S3中，阻燃剂为微胶囊化红磷，占总份数的2份，光热稳定剂为紫外线吸收剂、受阻胺类光稳定剂或抗氧剂，占总份数的0.8份。
具体的，S4中，光引发剂为苯基双甲基苯甲酰基氧代磷、苯基三甲基苯甲酰基氧代磷、羟基环乙基苯基甲酮中的一种或两种混合物，占总份数的0.4份。
最后应说明的是：以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换,凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (8)

1.一种合成革用无溶剂紫外光固化聚氨酯的制备方法，其特征在于：包括以下步骤：
S1、将一定重量份的异氰酸酯加入反应釜内，并向反应釜中充满氮气，之后搅拌升温至65-75℃，然后将真空脱水后的二元醇与催化剂加入反应釜中，持续搅拌升温至80℃，并恒温搅拌1-2小时；
S2、在S1中反应釜恒温搅拌完成后，先向反应釜中添加小分子扩链剂进行扩链反应，扩链反应0.5-1.5小时后，再加入亲水性扩链剂进行亲水反应，反应1-2小时后；
S3、继续向反应釜中加入丙烯酸反应液，并在70-80℃下继续反应2-3小时，反应完成后，之后将聚硅氧烷加入其中，并继续搅拌0.5小时后，加入阻燃剂和光热稳定剂继续搅拌0.5小时；
S4、将S3中加热搅拌完成后的反应物，迅速冷却，并在冷却完成后加入光引发剂，即得到无溶剂紫外光固化聚氨酯。
2.根据权利要求1所述的一种合成革用无溶剂紫外光固化聚氨酯的制备方法，其特征在于：S1中，异氰酸酯包括甲苯二异氰酸酯、二苯基亚甲基二异氰酸酯、异佛尔酮二异氰酸酯中的一种或多种任意比例的混合物，且异氰酸酯在原料中占总份数的30-50份。
3.根据权利要求1所述的一种合成革用无溶剂紫外光固化聚氨酯的制备方法，其特征在于：S1中，多元醇为为聚氧化丙烯二元醇、苯酐聚酯二元醇、聚己二酸新戊二醇酯二醇、聚碳酸酯二元醇、聚己内酯二元醇和聚四氢呋喃二元醇中的一种或几种，其中元醇占总份数的50-80份。
4.根据权利要求1所述的一种合成革用无溶剂紫外光固化聚氨酯的制备方法，其特征在于：S1中，催化剂为辛酸亚锡、二月桂酸正丁基锡、有机Bi盐催化剂、有机Zn盐催化剂中的一种或几种，催化剂占总份数的1-3份。
5.根据权利要求1所述的一种合成革用无溶剂紫外光固化聚氨酯的制备方法，其特征在于：S2中，小分子扩链剂为1,2-丙二醇、1,4-丁二醇、2-甲基-1,3-丙二醇、新戊二醇或三甲基戊二醇，占总份数的5-20份，亲水性扩链剂为二羟甲基丙酸，占总份数的15-30份。
6.根据权利要求1所述的一种合成革用无溶剂紫外光固化聚氨酯的制备方法，其特征在于：S3中，丙烯酸反应液为丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、甲基丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基丙酯中的一种或多种的混合物，占总份数的20-40份。
7.根据权利要求1所述的一种合成革用无溶剂紫外光固化聚氨酯的制备方法，其特征在于：S3中，阻燃剂为微胶囊化红磷，占总份数的0.5-2份，光热稳定剂为紫外线吸收剂、受阻胺类光稳定剂或抗氧剂，占总份数的0.4-0.8份。
8.根据权利要求1所述的一种合成革用无溶剂紫外光固化聚氨酯的制备方法，其特征在于：S4中，光引发剂为苯基双甲基苯甲酰基氧代磷、苯基三甲基苯甲酰基氧代磷、羟基环乙基苯基甲酮中的一种或两种混合物，占总份数的0.2-0.4份。
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CN115433537A (zh) * 2022-09-15 2022-12-06 江苏矽时代材料科技有限公司 一种高黏结性紫外光固化的胶黏剂及其制备方法和应用

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