CN114213618A - 一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂及其制备方法 - Google Patents

一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂及其制备方法 Download PDF

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CN114213618A
CN114213618A CN202111592243.5A CN202111592243A CN114213618A CN 114213618 A CN114213618 A CN 114213618A CN 202111592243 A CN202111592243 A CN 202111592243A CN 114213618 A CN114213618 A CN 114213618A
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polybutadiene rubber
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张武
康伦国
姚东生
陈有权
徐景华
阳京辉
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Union Foshan Chemical Co Ltd
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Abstract

本发明提供一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂及其制备方法,按重量份计,其组成为:二异氰酸酯100.0~200.0份、1,4‑丁二醇10.0~18.0份、三羟甲基丙烷3.0~8.0份、低聚物多元醇75.0~180.0份、二羟甲基丙酸9.0~18.0份、二月桂酸二丁基锡0.02~0.1份、交联单体2.5~4.0份、端羟基液体聚丁二烯橡胶10.0~20.0份、乙醇2.0~6.0份、丙酮50.0~100.0份、中和剂7.0~20.0份、去离子水500.0~900.0份;本发明制得的一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂是将端羟基液体聚丁二烯橡胶与聚氨酯树脂通过化学键相连,结构稳定;其具有良好的抗流挂性、抗冲击性能好、交联密度高以及良好的柔韧性等性能,可制备成单组分或双组分水性涂料。

Description

一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂及其制备 方法
技术领域
本发明涉及一种改性水性聚氨酯树脂及其制备方法,尤其涉及到一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂,属于水性合成树脂技术领域。
背景技术
聚氨酯是由低聚物多元醇、小分子多元醇、多异氰酸酯和扩链剂反应而成,反应原料及工艺因素对聚氨酯材料形态有很大影响,聚氨酯的合成很灵活,因此为对它改性提供了良好的条件,聚氨酯树脂对金属、塑料、橡胶、木质等具有很高粘结性,聚氨酯树脂具有优异耐磨、耐擦伤、耐溶剂、耐辐射、低温弹性等性能,广泛应用于泡沫塑料、橡胶、纤维、涂料、油墨、粘合剂、皮革等领域。
聚氨酯树脂的硬度一般比其他常规的树脂的硬度要高,但是硬度高容易造成漆膜脆性大,因此如何提高聚氨酯树脂的柔韧性成为聚氨酯树脂的热点。
中国专利CN108329847A公开了一种铝基覆铜箔板用高性能导热绝缘胶膜及其制备方法。铝基覆铜箔板用高导热绝缘胶膜,包括:固体环氧树脂5%~30%;硼改性酚醛树脂固化剂1%~30%;热塑性树脂1%~20%;增韧剂1%~10%;偶联剂0.01%~3%;触变剂0.1%~5%;溶剂20%~40%;导热填料30%~70%。采用硼改性酚醛固化剂明显著提高了胶膜的耐热性和抗剥离强度,并大大改善胶膜的储存期和操作期;上述发明有加入端羟基液体聚丁二烯作为增韧剂,但其属于物理混合。
发明内容
为解决上述所述的技术问题,本发明加入端羟基液体聚丁二烯橡胶,端羟基液体聚丁二烯橡胶中含有羟基,端羟基液体聚丁二烯橡胶能与聚氨酯树脂通过化学键相连,性能稳定持久,柔韧性好。
本发明的首要目的提供一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂。
本发明的另一目的提供一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂的制备方法。
为了解决上面所述的技术问题,本发明采取以下技术方案:本发明涉及一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂,按重量份计,其组成为:二异氰酸酯100.0~200.0份、1,4-丁二醇10.0~18.0份、三羟甲基丙烷3.0~8.0份、低聚物多元醇75.0~180.0份、二羟甲基丙酸9.0~18.0份、二月桂酸二丁基锡0.02~0.1份、交联单体2.5~4.0份、端羟基液体聚丁二烯橡胶10.0~20.0份、乙醇2.0~6.0份、丙酮50.0~100.0份、中和剂7.0~20.0份、去离子水500.0~900.0份。
所述的低聚物二元醇为分子量在1000~4000之间的聚四氢呋喃醚二醇、聚碳酸酯二元醇、聚己内酯二元醇、聚乙二醇多元醇中的一种或几种的组合。
所述的中和剂为三乙胺、氨水、二甲基乙醇胺中的一种或几种的组合。
所述的交联单体为丙烯酸羟乙酯、丙烯酸羟丙酯中的一种或两种的组合。
所述的二异氰酸酯为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯中的一种或几种的组合。
所述的一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂的制备方法,包括以下步骤:
a、在多功能反应釜中,按配方的重量份依次加入1,4-丁二醇、三羟甲基丙烷、低聚物多元醇、二羟甲基丙酸搅拌,加热升温至110~115℃之间真空脱水2.0h,降温;
b、然后滴加二异氰酸酯,0.5h滴加完毕后,加入二月桂酸二丁基锡,控制温度在82℃~84℃搅拌反应2h,然后加入交联单体与端羟基液体聚丁二烯橡胶继续反应搅拌1.5h,视体系粘度补加丙酮,测定NCO值,达到与设计值接近时为止;
c、降温,加入乙醇,搅拌条件下缓慢滴加中和剂,加入计算量的去离子水,继续搅拌分散,脱丙酮,过滤,即制端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂。
1)、本发明制得的一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂是将端羟基液体聚丁二烯橡胶与聚氨酯树脂通过化学键相连,结构稳定,性能持久,柔韧性良好;
2)、本发明制得的端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂,具有良好的抗流挂性、抗冲击性能好、交联密度高、储存性能好以及良好的柔韧性等性能,可制备成单组分水性涂料,也可以制备成双组分水性涂料。
具体实施方式
下面结合实施例对本发明的端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂做进一步的描述。可以理解的是,此处所描述的具体实施例仅仅用于解释相关发明,而非对该发明的限定。
实施例1
一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂,其制备工艺如下:
本实施例一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂,按重量份计,其组成为:甲苯二异氰酸酯160.0份、1,4-丁二醇14.0份、三羟甲基丙烷5.0份、聚碳酸酯二元醇140.0份、二羟甲基丙酸14.0份、二月桂酸二丁基锡0.06份、丙烯酸羟乙酯2.5份、端羟基液体聚丁二烯橡胶15.0份、乙醇4.0份、丙酮80.0份、氨水11.0份、去离子水800.0份。
本实施例所述的一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂的制备方法,包括以下步骤:
a、在多功能反应釜中,按配方的重量份依次加入1,4-丁二醇、三羟甲基丙烷、聚碳酸酯二元醇、二羟甲基丙酸搅拌,加热升温至110~115℃之间真空脱水2.0h,降温;
b、然后滴加甲苯二异氰酸酯,0.5h滴加完毕后,加入二月桂酸二丁基锡,控制温度在82℃~84℃搅拌反应2h,然后加入丙烯酸羟乙酯与端羟基液体聚丁二烯橡胶继续反应搅拌1.5h,视体系粘度补加丙酮,测定NCO值,达到与设计值接近时为止;
c、降温,加入乙醇,搅拌条件下缓慢滴加氨水,加入计算量的去离子水,继续搅拌分散,脱丙酮,过滤,即制端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂,其固含为29.6%。
实施例2
一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂,其制备工艺如下:
本实施例一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂,按重量份计,其组成为:异佛尔酮二异氰酸酯180.0份、1,4-丁二醇14.0份、三羟甲基丙烷6.0份、聚四氢呋喃醚二醇150.0份、二羟甲基丙酸16.0份、二月桂酸二丁基锡0.08份、丙烯酸羟丙酯3.0份、端羟基液体聚丁二烯橡胶18.0份、乙醇5.0份、丙酮90.0份、三乙胺15.0份、去离子水880.0份。
本实施例所述的一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂的制备方法,包括以下步骤:
a、在多功能反应釜中,按配方的重量份依次加入1,4-丁二醇、三羟甲基丙烷、聚四氢呋喃醚二醇、二羟甲基丙酸搅拌,加热升温至110~115℃之间真空脱水2.0h,降温;
b、然后滴加异佛尔酮二异氰酸酯,0.5h滴加完毕后,加入二月桂酸二丁基锡,控制温度在82℃~84℃搅拌反应2h,然后加入交联单体与端羟基液体聚丁二烯橡胶继续反应搅拌1.5h,视体系粘度补加丙酮,测定NCO值,达到与设计值接近时为止;
c、降温,加入乙醇,搅拌条件下缓慢滴加三乙胺,加入计算量的去离子水,继续搅拌分散,脱丙酮,过滤,即制端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂,其固含为29.8%。
实施例3
一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂,其制备工艺如下:
本实施例一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂,按重量份计,其组成为:六亚甲基二异氰酸酯130.0份、1,4-丁二醇12.0份、三羟甲基丙烷5.0份、聚己内酯二元醇120.0份、二羟甲基丙酸12.0份、二月桂酸二丁基锡0.08份、丙烯酸羟乙酯3.5份、端羟基液体聚丁二烯橡胶14.0份、乙醇4.0份、丙酮70.0份、二甲基乙醇胺15.0份、去离子水650.0份。
本实施例所述的一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂的制备方法,包括以下步骤:
a、在多功能反应釜中,按配方的重量份依次加入1,4-丁二醇、三羟甲基丙烷、聚己内酯二元醇、二羟甲基丙酸搅拌,加热升温至110~115℃之间真空脱水2.0h,降温;
b、然后滴加六亚甲基二异氰酸酯,0.5h滴加完毕后,加入二月桂酸二丁基锡,控制温度在82℃~84℃搅拌反应2h,然后加入丙烯酸羟乙酯与端羟基液体聚丁二烯橡胶继续反应搅拌1.5h,视体系粘度补加丙酮,测定NCO值,达到与设计值接近时为止;
c、降温,加入乙醇,搅拌条件下缓慢滴加二甲基乙醇胺,加入计算量的去离子水,继续搅拌分散,脱丙酮,过滤,即制端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂,其固含为30.5%。
对比例1
本实施例一种常规改性水性聚氨酯树脂,按重量份计,其组成为:异佛尔酮二异氰酸酯176.0份、1,4-丁二醇15.4份、三羟甲基丙烷5.2份、聚乙二醇多元醇165.0份、二羟甲基丙酸16.0份、二月桂酸二丁基锡0.08份、丙烯酸羟丙酯3.4份、乙醇5.0份、丙酮90.0份、三乙胺15.0份、去离子水850.0份。
本实施例所述的一种常规改性水性聚氨酯树脂的制备方法,包括以下步骤:
a、在多功能反应釜中,按配方的重量份依次加入1,4-丁二醇、三羟甲基丙烷、聚乙二醇多元醇、二羟甲基丙酸搅拌,加热升温至110~115℃之间真空脱水2.0h,降温;
b、然后滴加异佛尔酮二异氰酸酯,0.5h滴加完毕后,加入二月桂酸二丁基锡,控制温度在82℃~84℃搅拌反应2h,然后加入丙烯酸羟丙酯继续反应搅拌1.5h,视体系粘度补加丙酮,测定NCO值,达到与设计值接近时为止;
c、降温,加入乙醇,搅拌条件下缓慢滴加三乙胺,加入计算量的去离子水,继续搅拌分散,脱丙酮,过滤,即制常规改性水性聚氨酯树脂,其固含为29.9%。
性能指标测试:分别取上述实施例1、实施例2、实施例3和对比例1等量的样品,然后分别加入6%的成膜助剂醇酯十二,按照国家相关标准,分别测试其性能。
将按照相关标准,对配置好的样品进行性能指标测试,测试结果如表1所示。
其中,附着力:按照GB/T1720-1988的规定进行测试;
硬度:按照GB/T6739-2006的规定进行检测;
耐水性:按照GB/T1733-93的规定进行检测;
柔韧性:按照GB/T1731-1993的规定进行检测;
耐冲击性:按照GB/T1732-2020的规定进行检测;
抗流挂性:按照GB/T9264-2012的规定进行检测。
表1:涂层的性能技术指标
Figure BDA0003429583110000071
Figure BDA0003429583110000081
由表1可以看出本发明的实施例1、实施例2、实施例3的附着力、柔韧性、耐冲击性以及抗流挂性要明显好于对比例1(常规改性水性聚氨酯树脂)的附着力、柔韧性、耐冲击性以及抗流挂性等性能,这表明在本发明的一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂具有良好的附着力、柔韧性、耐冲击性以及抗流挂性等性能。
以上描述仅为本申请的较佳实施例以及对所运用技术原理的说明;本领域技术人员应当理解,本申请中所涉及的发明范围,并不限于上述技术特征的特定组合而成的技术方案,同时也应涵盖在不脱离所述发明构思的情况下,由上述技术特征或其等同特征进行任意组合而形成的其它技术方案。例如上述特征与本申请中公开的(但不限于)具有类似功能的技术特征进行互相替换而形成的技术方案。

Claims (6)

1.一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂,其特征在于:所述的端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂,按重量份计,其组成为:二异氰酸酯100.0~200.0份、1,4-丁二醇10.0~18.0份、三羟甲基丙烷3.0~8.0份、低聚物多元醇75.0~180.0份、二羟甲基丙酸9.0~18.0份、二月桂酸二丁基锡0.02~0.1份、交联单体2.5~4.0份、端羟基液体聚丁二烯橡胶10.0~20.0份、乙醇2.0~6.0份、丙酮50.0~100.0份、中和剂7.0~20.0份、去离子水500.0~900.0份。
2.如权利要求1所述的一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂,其特征在于:所述的低聚物二元醇为分子量在1000~4000之间的聚四氢呋喃醚二醇、聚碳酸酯二元醇、聚己内酯二元醇、聚乙二醇多元醇中的一种或几种的组合。
3.如权利要求1所述的一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂,其特征在于:所述的中和剂为三乙胺、氨水、二甲基乙醇胺中的一种或几种的组合。
4.如权利要求1所述的一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂,其特征在于:所述的交联单体为丙烯酸羟乙酯、丙烯酸羟丙酯中的一种或两种的组合。
5.如权利要求1所述的一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂,其特征在于:所述的二异氰酸酯为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯中的一种或几种的组合。
6.如权利要求1所述的一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂,其特征在于:所述的一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂,其制备方法,包括如下步骤:
a、在多功能反应釜中,按配方的重量份依次加入1,4-丁二醇、三羟甲基丙烷、低聚物多元醇、二羟甲基丙酸搅拌,加热升温至110~115℃之间真空脱水2.0h,降温;
b、然后滴加二异氰酸酯,0.5h滴加完毕后,加入二月桂酸二丁基锡,控制温度在82℃~84℃搅拌反应2h,然后加入交联单体与端羟基液体聚丁二烯橡胶继续反应搅拌1.5h,视体系粘度补加丙酮,测定NCO值,达到与设计值接近时为止;
c、降温,加入乙醇,搅拌条件下缓慢滴加中和剂,加入计算量的去离子水,继续搅拌分散,脱丙酮,过滤,即制端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂。
CN202111592243.5A 2021-12-23 2021-12-23 一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂及其制备方法 Withdrawn CN114213618A (zh)

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