CN105566607A - 一种改性聚氨酯丙烯酸酯及其制备方法 - Google Patents

一种改性聚氨酯丙烯酸酯及其制备方法 Download PDF

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CN105566607A
CN105566607A CN201610113137.7A CN201610113137A CN105566607A CN 105566607 A CN105566607 A CN 105566607A CN 201610113137 A CN201610113137 A CN 201610113137A CN 105566607 A CN105566607 A CN 105566607A
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何兴帮
胡志峰
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Shenzhen Zicai Technology Co Ltd
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Abstract

本发明公开了一种改性聚氨酯丙烯酸酯,按照重量份的原料包括:二元醇预聚物150-500份、聚天门冬氨酸酯50-100份、二异氰酸酯基团单体80-135份、羟基丙烯酸酯类单体30-50份、催化剂0.3-0.8份、阻聚剂0.3-0.8份、抗氧剂0.3-0.8份。所述改性聚氨酯丙烯酸酯的制备方法包括以下步骤:(1)预聚反应:将二元醇预聚物和二异氰酸酯单体加入到反应釜中,搅拌,升温,保温;(2)扩链反应:将聚天门冬氨酸酯加入反应釜中,保温;(3)封端反应:将羟基丙烯酸酯类单体、催化剂、阻聚剂加入反应釜中,保温,测NCO%,当NCO%≤0.5%时,降温出料。本发明将聚天门冬氨酸酯型聚脲结构引入到聚氨酯丙烯酸酯体系,获得聚脲弹性体的优点,可以制备各种新类型改性聚氨酯丙烯酸酯,提供了更多的选择。

Description

一种改性聚氨酯丙烯酸酯及其制备方法
技术领域
本发明涉及一种化工紫外光固化材料领域,具体是一种改性聚氨酯丙烯酸酯及其制备方法。
背景技术
紫外光固化材料由于具有环保、经济、高效等特点,已经广泛由于各种涂料、油墨、胶粘剂等领域。其中聚氨酯丙烯酸酯材料含有丙烯酸酯官能团和氨基甲酸酯键,固化后具有较好的柔韧性、优异的耐磨性、良好的耐化学性和耐高低温性能等,因而在紫外光固化材料领域具有广泛的应用。但是聚氨酯丙烯酸酯也有不少缺点,紫外光固化速率慢,尤其是大分子两官聚氨酯丙烯酸酯固化速度更慢,韧性和强度难以兼顾等缺陷。
聚天门冬氨酸酯是由脂肪族伯胺与马来酸酯通过Michael加成(伯胺与马来酸酯的双键加成)反应制备而成。其结构如式所示:
(其中R、R1为烷基链段)
聚天门冬氨酸酯与异氰酸酯类单体反应可以制备聚脲弹性体,聚脲弹性体由于其特殊的结构具有低温韧性好、防腐、耐磨、抗湿滑、耐老化、抗热冲击及良好的耐介质性能等许多优异的物理力学性能,广泛应用于防水、防腐、耐磨等领域。
发明内容
本发明的目的在于提供一种改性聚氨酯丙烯酸酯及其制备方法,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:一种改性聚氨酯丙烯酸酯,按照重量份的原料包括:按照重量份的原料包括:二元醇预聚物150-500份、聚天门冬氨酸酯50-100份、二异氰酸酯基团单体80-135份、羟基丙烯酸酯类单体30-50份、催化剂0.3-0.8份、阻聚剂0.3-0.8份、抗氧剂0.3-0.8份。
作为本发明进一步的方案:按照重量份的原料包括:二元醇预聚物325份、聚天门冬氨酸酯75份、二异氰酸酯基团单体108份、羟基丙烯酸酯类单体40份、催化剂0.5份、阻聚剂0.5份、抗氧剂0.5份。
作为本发明再进一步的方案:所述二元醇预聚物包括聚酯二元醇系列、聚醚二元醇系列、聚己内酯二醇系列、聚碳酸酯二醇系列中的一种或几种的混合体。
作为本发明再进一步的方案:所述聚天门冬氨酸酯的结构为:
其中,R和R1为烷基链结构。
作为本发明再进一步的方案:所述二异氰酸酯基团单体包括甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲苯二异氰酸酯、六亚甲基二异氰酸酯中的一种或几种的混合物。
作为本发明再进一步的方案:所述羟基丙烯酸酯类单体包括丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、4-羟丁基丙烯酸酯的一种或几种的混合物。
作为本发明再进一步的方案:所述催化剂用于催化羟基与异氰酸酯反应,包括二月桂酸二丁基锡、二丁基二氯化锡、辛酸亚锡、羧酸铋中的一种或几种的混合物。
作为本发明再进一步的方案:所述阻聚剂包括对苯醌、对苯二酚、2,5-二羟基对苯醌、对羟基苯甲醚、2,5-二叔丁基对苯二酚、甲基氢醌、氢醌单甲醚中的一种或几种的混合物。
作为本发明再进一步的方案:包括以下步骤:
(1)预聚反应:将所述二元醇预聚物和所述二异氰酸酯单体加入到反应釜中,搅拌,升温至40℃-90℃,保温时间为2-4小时;
(2)扩链反应:预聚反应结束后,将所述聚天门冬氨酸酯加入反应釜中,保持温度40℃-90℃,保温时间为30-60分钟;
(3)封端反应:将所述羟基丙烯酸酯类单体、所述催化剂、所述阻聚剂加入反应釜中,保持温度40℃-90℃,保温2小时后,测NCO%,当NCO%≤0.5%时,降温出料。
作为本发明再进一步的方案:所述扩链反应和封端反应合并到一起进行,其具体制备方法如下:预聚反应结束后,将所述聚天门冬氨酸酯、所述羟基丙烯酸酯类单体、所述催化剂、所述阻聚剂加入反应釜中,保持温度40℃-90℃,保温2小时后,测NCO%,当NCO%≤0.5%时,降温出料。
与现有技术相比,本发明的有益效果是:将聚天门冬氨酸酯型聚脲结构引入到聚氨酯丙烯酸酯体系,获得聚脲弹性体的优点,可以制备各种新类型改性聚氨酯丙烯酸酯,提供了更多的选择。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,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实施例,都属于本发明保护的范围。
实施例1:在装有搅拌、温度计的反应瓶中加入250克分子量为1000的聚己二酸己二醇酯二醇和87克甲苯二异氰酸酯,升温至60-70℃,保温3h后测试NCO%≤7%时,降温至50℃以下,加入聚天门冬氨酸酯F420(珠海飞扬新材料股份有限公司)约69克,升温至60-70℃保温1h后,降温至50℃以下,加入丙烯酸羟乙酯35克、二月桂酸二丁基锡约0.43克、对羟基苯甲醚约0.43克,升温至70-80℃,保温2h后,测试NCO%≤0.5%,降温出料。
实施例2:在装有搅拌、温度计的反应瓶中加入250克分子量为1000的聚己二酸己二醇酯二醇和111.2克异佛尔酮二异氰酸酯,升温至60-70℃,保温3h后测试NCO%≤6.5%时,降温至50℃以下,加入聚天门冬氨酸酯F520(珠海飞扬新材料股份有限公司)约73克,升温至60-70℃保温1h后,降温至50℃以下,加入丙烯酸羟乙酯35克、二月桂酸二丁基锡约0.43克、对羟基苯甲醚约0.43克,升温至70-80℃,保温2h后,测试NCO%≤0.5%,降温出料。
实施例3:在装有搅拌、温度计的反应瓶中加入250克分子量为1000的聚四氢呋喃二醇和111.2克异佛尔酮二异氰酸酯,升温至60-70℃,保温3h后测试NCO%≤6.5%时,降温至50℃以下,加入聚天门冬氨酸酯F220(珠海飞扬新材料股份有限公司)约57克,升温至60-70℃保温1h后,降温至50℃以下,加入丙烯酸羟乙酯35克、二月桂酸二丁基锡约0.43克、对羟基苯甲醚约0.43克,升温至70-80℃,保温2h后,测试NCO%≤0.5%,降温出料。
实施例4:在装有搅拌、温度计的反应瓶中加入250克分子量为1000的聚己内酯二醇和111.2克异佛尔酮二异氰酸酯,升温至60-70℃,保温3h后测试NCO%≤6.5%时,降温至50℃以下,加入聚天门冬氨酸酯F220(珠海飞扬新材料股份有限公司)约57克、己二醇二丙烯酸酯约100g、阻聚剂约0.43克,升温至60-70℃保温1h后,降温至50℃以下,加入丙烯酸羟乙酯35克、二月桂酸二丁基锡约0.43克、对羟基苯甲醚约0.3克,升温至70-80℃,保温2h后,测试NCO%≤0.5%,降温出料。
实施例5:在装有搅拌、温度计的反应瓶中加入250克分子量为1000的聚碳酸酯二醇和131.2克二环己基甲烷二异氰酸酯,升温至60-70℃,保温3h后测试NCO%≤6.5%时,降温至50℃以下,加入聚天门冬氨酸酯F220(珠海飞扬新材料股份有限公司)约57克、己二醇二丙烯酸酯约100g、丙烯酸羟乙酯35克、二月桂酸二丁基锡约0.43克、对羟基苯甲醚约0.45克,升温至70-80℃,保温2h后,测试NCO%≤0.5%,降温出料。
对于本领域技术人员而言,显然本发明不限于上述示范性实施例的细节,而且在不背离本发明的精神或基本特征的情况下,能够以其他的具体形式实现本发明。因此,无论从哪一点来看,均应将实施例看作是示范性的,而且是非限制性的,本发明的范围由所附权利要求而不是上述说明限定,因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。
此外,应当理解,虽然本说明书按照实施方式加以描述,但并非每个实施方式仅包含一个独立的技术方案,说明书的这种叙述方式仅仅是为清楚起见,本领域技术人员应当将说明书作为一个整体,各实施例中的技术方案也可以经适当组合,形成本领域技术人员可以理解的其他实施方式。

Claims (10)

1.一种改性聚氨酯丙烯酸酯,其特征在于,按照重量份的原料包括:按照重量份的原料包括:二元醇预聚物150-500份、聚天门冬氨酸酯50-100份、二异氰酸酯基团单体80-135份、羟基丙烯酸酯类单体30-50份、催化剂0.3-0.8份、阻聚剂0.3-0.8份、抗氧剂0.3-0.8份。
2.根据权利要求1所述的改性聚氨酯丙烯酸酯,其特征在于,按照重量份的原料包括:二元醇预聚物325份、聚天门冬氨酸酯75份、二异氰酸酯基团单体108份、羟基丙烯酸酯类单体40份、催化剂0.5份、阻聚剂0.5份、抗氧剂0.5份。
3.根据权利要求1所述的改性聚氨酯丙烯酸酯,其特征在于,所述二元醇预聚物包括聚酯二元醇系列、聚醚二元醇系列、聚己内酯二醇系列、聚碳酸酯二醇系列中的一种或几种的混合体。
4.根据权利要求1所述的改性聚氨酯丙烯酸酯,其特征在于,所述聚天门冬氨酸酯的结构为:
其中,R和R1为烷基链结构。
5.根据权利要求1所述的改性聚氨酯丙烯酸酯,其特征在于,所述二异氰酸酯基团单体包括甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲苯二异氰酸酯、六亚甲基二异氰酸酯中的一种或几种的混合物。
6.根据权利要求1所述的改性聚氨酯丙烯酸酯,其特征在于,所述羟基丙烯酸酯类单体包括丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、4-羟丁基丙烯酸酯的一种或几种的混合物。
7.根据权利要求1所述的改性聚氨酯丙烯酸酯,其特征在于,所述催化剂用于催化羟基与异氰酸酯反应,包括二月桂酸二丁基锡、二丁基二氯化锡、辛酸亚锡、羧酸铋中的一种或几种的混合物。
8.根据权利要求1所述的改性聚氨酯丙烯酸酯,其特征在于,所述阻聚剂包括对苯醌、对苯二酚、2,5-二羟基对苯醌、对羟基苯甲醚、2,5-二叔丁基对苯二酚、甲基氢醌、氢醌单甲醚中的一种或几种的混合物。
9.一种如权利要求1-8任一所述的改性聚氨酯丙烯酸酯的制备方法,其特征在于,包括以下步骤:
(1)预聚反应:将所述二元醇预聚物和所述二异氰酸酯单体加入到反应釜中,搅拌,升温至40℃-90℃,保温时间为2-4小时;
(2)扩链反应:预聚反应结束后,将所述聚天门冬氨酸酯加入反应釜中,保持温度40℃-90℃,保温时间为30-60分钟;
(3)封端反应:将所述羟基丙烯酸酯类单体、所述催化剂、所述阻聚剂加入反应釜中,保持温度40℃-90℃,保温2小时后,测NCO%,当NCO%≤0.5%时,降温出料。
10.根据权利要求9所述的改性聚氨酯丙烯酸酯的制备方法,其特征在于,所述扩链反应和封端反应合并到一起进行,其具体制备方法如下:预聚反应结束后,将所述聚天门冬氨酸酯、所述羟基丙烯酸酯类单体、所述催化剂、所述阻聚剂加入反应釜中,保持温度40℃-90℃,保温2小时后,测NCO%,当NCO%≤0.5%时,降温出料。
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