CN111909354B - 一种水性聚氨酯树脂及其制备方法与应用 - Google Patents
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Abstract
本发明公开了一种水性聚氨酯树脂及其制备方法与应用,所述水性聚氨酯树脂通过多元醇预聚体、亲水单体、异氰酸酯单体、功能单体、扩链剂、有机碱反应得到,所述亲水单体为二羟基类化合物、聚乙二醇、季胺盐中的至少一种,所述功能单体为三羟甲基丙烷、季戊四醇、单甘酯、不饱和脂肪酸中的至少一种。该水性聚氨酯树脂制备的汽车用水性中涂漆具有优异的抗石击性及漆膜硬度,同时其制备的汽车用水性色漆具有优异的附着力及柔韧性,综合性能强,能满足汽车领域更高涂装工艺的要求。
Description
技术领域
本发明属于水性涂料技术领域,特别涉及一种水性聚氨酯树脂及其制备方法与应用。
背景技术
随着经济的不断发展,人们对汽车的需求量逐年递增。与其配套的涂料产业也得到了长远的发展。然而,在汽车涂料高速发展的同时,也给环境带来了巨大的影响。为了保护生态环境,与汽车涂装相关的法律法规陆续出台。我国在《清洁生产标准汽车制造业(涂装)》中提出VOC排放量要求≤40g/m2,这使得水性涂料得到了快速发展。为了减少涂料使用量及涂装能源消耗,涂装工艺不断更新换代,从水性3C2B涂装工艺发展到3C1B涂装工艺,再到目前最先进的水性免中涂紧凑汽车涂装工艺B1B2。涂装工艺的进步使得涂装流程缩短、减少预烘烤的同时,大大降低VOC排放,节约成本,保护环境。涂装工艺不断发展的同时,与其配套的水性树脂也在不断的进步,尤其是水性聚氨酯树脂越来越受到人们的关注。水性聚氨酯树脂主要用在汽车用水性中涂漆和汽车用水性色漆中,现有水性聚氨酯树脂制得的汽车用水性中涂漆抗石击性较差。
发明内容
本发明旨在至少解决现有技术中存在的技术问题之一。为此,本发明提出一种水性聚氨酯树脂,其制备的汽车用水性中涂漆具有优异的抗石击性,能满足汽车领域更高涂装工艺的要求。
本发明的上述技术目的是通过以下技术方案得以实现的:
一种水性聚氨酯树脂,所述水性聚氨酯树脂通过多元醇预聚体、亲水单体、异氰酸酯单体、功能单体、扩链剂、有机碱反应得到,所述亲水单体为二羟基类化合物、聚乙二醇、季胺盐中的至少一种,所述功能单体为三羟甲基丙烷、季戊四醇、单甘酯、不饱和脂肪酸中的至少一种。
优选的,所述二羟基类化合物为二羟基酸类化合物及二羟基磺酸盐类化合物中的至少一种。
优选的,所述二羟基磺酸盐类化合物为1,4-二羟基-2-丁烷磺酸钠,1,2-二羟基-3-丙磺酸钠中的至少一种。
优选的,所述的二羟基酸类化合物为二羟甲基丁酸、二羟甲基丙酸中的至少一种。
优选的,所述不饱和脂肪酸为蓖麻油、大豆油、棕榈油中的至少一种。
优选的,所述1,4-二羟基-2-丁烷磺酸钠、三羟甲基丙烷和棕榈油的重量比为1:1:(2-3)。
优选的,所述水性聚氨酯树脂的酸值为10-50mg KOH/g,粘度为100-6000mPa·s,数均分子量为4500-100000,固含量为30-65%。
优选的,所述的多元醇预聚体为聚碳酸酯多元醇、聚醚多元醇、聚酯多元醇中的至少一种。
优选的,所述的催化剂为有机锡化合物、有机铋化合物中的至少一种。
进一步优选的,所述的催化剂为为氯化亚锡、单丁基氧化锡、二丁基醋酸锡、二月桂酸锡、马来酸二丁基锡、辛酸亚锡、月桂酸铋中的至少一种。
优选的,所述的亲水单体为二羟甲基丁酸、二羟甲基丙酸、1,4-二羟基-2-丁烷磺酸钠,1,2-二羟基-3-丙磺酸钠、聚乙二醇、季胺盐中的至少一种。
优选的,所述的异氰酸酯单体为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、苯二甲基二异氰酸酯、环己烷二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯中的至少一种。
优选的,所述的扩链剂为乙二醇、1,2-丙二醇、1,4-丁二醇、二甘醇、1,6-己二醇、乙二胺、己二胺、一缩二丙二醇中的至少一种。
优选的,所述有机碱包括三乙胺、三乙醇胺、N,N`-二甲基乙醇胺、N,N`-二异丙基乙胺、二异丙胺中的至少一种。
本发明的另一个目的在于提供一种上述水性聚氨酯树脂制备方法:
一种如上所述的水性聚氨酯树脂的制备方法,包括以下步骤:
(1)在惰性气体保护下,将多元醇预聚体、亲水单体、异氰酸酯单体、催化剂加入到反应器中,升温,反应;
(2)加入功能单体,反应,再加入扩链剂,搅拌反应,降温,加入有机碱进行中和反应;
(3)在剪切条件下加入水,搅拌,即得水性聚氨酯树脂。
本发明的第三个目的在于提供一种涂料,所述涂料包括如上所述的水性聚氨酯树脂。
如上所述的水性聚氨酯树脂在涂料及水性免中涂紧凑汽车涂装工艺中的应用。
本发明的有益效果是:
(1)本发明水性聚氨酯树脂不含任何有机溶剂,其以水作为稀释剂,极大降低了VOC,减少对环境影响。
(2)本发明水性聚氨酯树脂内部接入亲水单体及功能单体,使得用其制成的汽车用水性中涂漆具有优异的抗石击性及漆膜硬度,其抗石击性能达到1级,且其漆膜硬度能达到75以上,此外,当亲水单体为1,4-二羟基-2-丁烷磺酸钠,功能单体为三羟甲基丙烷和棕榈油,且1,4-二羟基-2-丁烷磺酸钠、三羟甲基丙烷和棕榈油的重量比为1:1:(2-3),用该水性聚氨酯树脂制备的汽车用水性中涂漆具有最优的性能,其抗石击性能达到1级的同时漆膜硬度能达到95以上。
(3)本发明水性聚氨酯树脂内部接入亲水单体及功能单体,使得用其制成的汽车用水性色漆具有优异的附着力、柔韧性、耐水性、耐酸性及耐碱性,其附着力能达到1级以上,且当亲水单体为1,4-二羟基-2-丁烷磺酸钠,功能单体为三羟甲基丙烷和棕榈油,且1,4-二羟基-2-丁烷磺酸钠、三羟甲基丙烷和棕榈油的重量比为1:1:(2-3),用该水性聚氨酯树脂制备的汽车用水性色漆具有最优的性能,其附着力能达到0级。
(4)本发明水性聚氨酯树脂的酸值为10-50mg KOH/g,树脂的粘度为100-6000mPa·s,树脂的数均分子量为4500-100000,树脂的固含量为30-65%,而这些特性保证了其在应用到汽车用水性中涂漆和汽车用水性色漆中时,使得汽车用水性中涂漆和汽车用水性色漆均具有优异的性能。
具体实施方式
下面结合具体实施例对本发明做进一步的说明。
实施例1:
一种水性聚氨酯树脂,包括以下重量份数的原料:
聚碳酸酯二醇:20份;
二羟甲基丁酸:5份;
异佛尔酮二异氰酸酯:20份;
季戊四醇:4份;
1.2-丙二醇:5份;
二月桂酸锡:1份;
三乙胺:4份。
其制备方法,包括以下步骤:
(1)在氮气保护下,将20份聚碳酸酯二醇、5份二羟甲基丁酸、20份异佛尔酮二异氰酸酯、1份二月桂酸锡加入到反应器中,升温到80℃,反应2h;
(2)加入4份季戊四醇,进一步反应2h,再加入5份1.2-丙二醇,搅拌反应1h,降温,加入4份三乙胺进行中和反应;
(3)在高剪切条件下加入112份去离子水,搅拌2h,即得水性聚氨酯树脂,水性聚氨酯树脂的酸值为12.5mg KOH/g,粘度为3300mPa·s,树脂的数均分子量为6000,固含量为35.6%。
实施例2:
一种水性聚氨酯树脂,包括以下重量份数的原料:
聚酯二醇:25份;
1,4-二羟基-2-丁烷磺酸钠:3份;
二苯基甲烷二异氰酸酯:15份;
六亚甲基二异氰酸酯:5份;
三羟甲基丙烷:3份;
棕榈油:6份;
1,4-丁二醇:6份;
月桂酸铋:1.5份;
N,N`-二甲基乙醇胺:6份。
其制备方法,包括以下步骤:
(1)在氮气保护下,将25份聚酯二醇、3份1,4-二羟基-2-丁烷磺酸钠、15份二苯基甲烷二异氰酸酯、5份六亚甲基二异氰酸酯、1.5份月桂酸铋加入到反应器中,升温到90℃,反应3h;
(2)加入3份三羟甲基丙烷、6份棕榈油,进一步反应3h,再加入6份1,4-丁二醇,搅拌反应2h,降温,加入6份N,N`-二甲基乙醇胺进行中和反应;
(3)在高剪切条件下加入145份去离子水,搅拌1h,即得水性聚氨酯树脂,水性聚氨酯树脂的酸值为15.8mg KOH/g,粘度为4800mPa·s,树脂的数均分子量为7000,固含量为35.9%。
实施例3:
一种水性聚氨酯树脂,包括以下重量份数的原料:
聚醚二醇:30份;
1,4-二羟基-2-丁烷磺酸钠:2份;
环己烷二亚甲基二异氰酸酯:25份;
三羟甲基丙烷:2份;
棕榈油:5份;
己二胺:3份;
氯化亚锡:1.2份;
N,N`-二异丙基乙胺:6份。
其制备方法,包括以下步骤:
(1)在氮气保护下,将30份聚醚二醇、2份1,4-二羟基-2-丁烷磺酸钠、25份环己烷二亚甲基二异氰酸酯、1.2份氯化亚锡加入到反应器中,升温到75℃,反应4h;
(2)加入2份三羟甲基丙烷、5份棕榈油,进一步反应2h,再加入3份己二胺,搅拌反应2h,降温,加入6份N,N`-二异丙基乙胺进行中和反应;
(3)在高剪切条件下加入135份去离子水,搅拌3h,即得水性聚氨酯树脂,水性聚氨酯树脂的酸值为21.6mg KOH/g,粘度为5500mPa·s,树脂的数均分子量为9200,固含量为35.3%。
实施例4:
一种水性聚氨酯树脂,包括以下重量份数的原料:
聚碳酸酯二醇:5份;
1,4-二羟基-2-丁烷磺酸钠:2份;
甲苯二异氰酸酯:5份;
三羟甲基丙烷:2份;
棕榈油:6份;
乙二醇:5份;
单丁基氧化锡:0.6份;
三乙醇胺:8份。
其制备方法,包括以下步骤:
(1)在氮气保护下,将5份聚碳酸酯二醇、2份1,4-二羟基-2-丁烷磺酸钠、5份甲苯二异氰酸酯、0.6份单丁基氧化锡加入到反应器中,升温到100℃,反应1h;
(2)加入2份三羟甲基丙烷、6份棕榈油,进一步反应4h,再加入5份乙二醇,搅拌反应4h,降温,加入8份三乙醇胺进行中和反应;
(3)在高剪切条件下加入120份去离子水,搅拌1h,即得水性聚氨酯树脂,水性聚氨酯树脂的酸值为22.5mg KOH/g,粘度为3200mPa·s,树脂的数均分子量为9500,固含量为35.7%。
实施例5:
一种水性聚氨酯树脂,包括以下重量份数的原料:
聚酯二醇:8份;
聚乙二醇:6份;
1,2-二羟基-3-丙磺酸钠:6份
苯二甲基二异氰酸酯:22份;
大豆油:5份;
蓖麻油:5份;
1,6-己二醇:8份;
二丁基醋酸锡:3份;
二异丙胺:5份。
其制备方法,包括以下步骤:
(1)在氮气保护下,将8份聚酯二醇、6份聚乙二醇、6份1,2-二羟基-3-丙磺酸钠、22份苯二甲基二异氰酸酯、3份二丁基醋酸锡加入到反应器中,升温到70℃,反应4h;
(2)加入5份大豆油、5份蓖麻油,进一步反应2h,再加入8份1,6-己二醇,搅拌反应1h,降温,加入5份二异丙胺进行中和反应;
(3)在高剪切条件下加入150份去离子水,搅拌3h,即得水性聚氨酯树脂,水性聚氨酯树脂的酸值为25.5mg KOH/g,粘度为3600mPa·s,树脂的数均分子量为9800,固含量为35.1%。
实施例6:
一种水性聚氨酯树脂,包括以下重量份数的原料:
聚醚二醇:23份;
二羟甲基丙酸:8份;
四甲基苯二亚甲基二异氰酸酯:15份;
单甘酯:12份;
一缩二丙二醇:10份;
马来酸二丁基锡:5份;
三乙胺:7份。
其制备方法,包括以下步骤:
(1)在氮气保护下,将23份聚醚二醇、8份二羟甲基丙酸、15份四甲基苯二亚甲基二异氰酸酯、5份马来酸二丁基锡加入到反应器中,升温到90℃,反应2.5h;
(2)加入12份单甘酯,进一步反应3h,再加入10份一缩二丙二醇,搅拌反应2.5h,降温,加入7份三乙胺进行中和反应;
(3)在高剪切条件下加入140份去离子水,搅拌2h,即得水性聚氨酯树脂,水性聚氨酯树脂的酸值为22.3mg KOH/g,粘度为3550mPa·s,树脂的数均分子量为9900,固含量为35.5%。
对比例1:
一种水性聚氨酯树脂,包括以下重量份数的原料:
聚醚二醇:30份;
环己烷二亚甲基二异氰酸酯:25份;
三羟甲基丙烷:2份;
棕榈油:5份;
己二胺:3份;
氯化亚锡:1.2份;
N,N`-二异丙基乙胺:6份。
其制备方法,包括以下步骤:
(1)在氮气保护下,将30份聚醚二醇、25份环己烷二亚甲基二异氰酸酯、1.2份氯化亚锡加入到反应器中,升温到75℃,反应4h;
(2)加入2份三羟甲基丙烷、5份棕榈油,进一步反应2h,再加入3份己二胺,搅拌反应2h,降温,加入6份N,N`-二异丙基乙胺进行中和反应;
(3)在高剪切条件下加入135份去离子水,搅拌3h,即得水性聚氨酯树脂,水性聚氨酯树脂的酸值为19.3mg KOH/g,粘度为4600mPa·s,树脂的数均分子量为8600,固含量为29.3%。
对比例2:
一种水性聚氨酯树脂,包括以下重量份数的原料:
聚醚二醇:30份;
1,4-二羟基-2-丁烷磺酸钠:2份;
环己烷二亚甲基二异氰酸酯:25份;
己二胺:3份;
氯化亚锡:1.2份;
N,N`-二异丙基乙胺:6份。
其制备方法,包括以下步骤:
(1)在氮气保护下,将30份聚醚二醇、2份1,4-二羟基-2-丁烷磺酸钠、25份环己烷二亚甲基二异氰酸酯、1.2份氯化亚锡加入到反应器中,升温到75℃,反应4h;
(2)加入3份己二胺,搅拌反应2h,降温,加入6份N,N`-二异丙基乙胺进行中和反应;
(3)在高剪切条件下加入135份去离子水,搅拌3h,即得水性聚氨酯树脂,水性聚氨酯树脂的酸值为19.5mg KOH/g,粘度为4500mPa·s,树脂的数均分子量为8500,固含量为28.5%。
试验例:
按照表1的配方制备10组汽车用水性中涂漆,其中第1至6组汽车用水性中涂漆中的水性聚氨酯树脂分别使用实施例1至实施例6制备的水性聚氨酯树脂,第7至8组汽车用水性中涂漆中的水性聚氨酯树脂分别使用对比例1及对比例2制备的水性聚氨酯树脂,第9组汽车用水性中涂漆中的水性聚氨酯树脂使用市售的同类水性聚氨酯树脂(东莞某化工有限公司生产,牌号为MR-712W),第10组汽车用水性中不添加水性聚氨酯树脂,分别测试最终制得的汽车用水性中涂漆的性能,测试结果如表2所示。
表1.汽车用水性中涂漆配方
表2.汽车用水性中涂漆性能测试结果
按照表3的配方制备9组汽车用水性色漆,其中第1至6组汽车用水性色漆中的水性聚氨酯树脂分别使用实施例1至实施例6制备的水性聚氨酯树脂,第7至8组汽车用水性色漆中的水性聚氨酯树脂分别使用对比例1及对比例2制备的水性聚氨酯树脂,第9组汽车用水性色漆中的水性聚氨酯树脂使用市售的同类水性聚氨酯树脂(东莞某化工有限公司生产,牌号为MR-712W),分别测试最终制得的汽车用水性色漆的性能,测试结果如表4所示。
表3.汽车用水性色漆配方
表4.汽车用水性色漆性能测试结果
由表2可知,利用本发明的水性聚氨酯树脂制备的汽车用水性中涂漆,具有优异的抗石击性,抗石击等级能达到1级,同时其具有优异的漆膜硬度,其漆膜硬度在75以上,最高能达到98,满足在汽车涂装领域对汽车用水性中涂漆的性能要求。将第2至4组与其它组对比可知,当水性聚氨酯树脂配方中亲水单体为1,4-二羟基-2-丁烷磺酸钠,功能单体为三羟甲基丙烷和棕榈油,且1,4-二羟基-2-丁烷磺酸钠、三羟甲基丙烷和棕榈油的重量比为1:1:(2-3)时,最终制得的汽车用水性中涂漆具有更优异的漆膜硬度,其漆膜硬度能达到95以上,对比第3组、第7组及第8组可知,当水性聚氨酯树脂配方中不含亲水单体和功能单体任意一种时,最终制得的汽车用水性中涂漆的抗石击性能及漆膜硬度性能均会较大幅度下降,对比第3组和第9组可知,本发明的水性聚氨酯树脂在对汽车用水性中涂漆的抗石击性能及漆膜硬度性能的正向贡献上远大于市售的同类型水性聚氨酯树脂,对比第3组和第10组可知,当汽车用水性中涂漆中不含水性聚氨酯树脂时,其抗石击及漆膜硬度会大幅下降。
由表4可知,利用本发明的水性聚氨酯树脂制备的汽车用水性色漆,具有优异的附着力,其附着力等级能达到1级以上,同时其形成的漆膜具有优异的柔韧性,在进行柔韧性测试时,在4倍放大镜下观察漆膜,无网纹、无裂纹、无剥落。此外利用本发明的水性聚氨酯树脂制备的汽车用水性色漆还具有优异的耐水性、耐酸性及耐碱性,满足在汽车涂装领域对汽车用水性色漆的性能要求。将第2至4组与其它组对比可知,当水性聚氨酯树脂配方中亲水单体为1,4-二羟基-2-丁烷磺酸钠,功能单体为三羟甲基丙烷和棕榈油,且1,4-二羟基-2-丁烷磺酸钠、三羟甲基丙烷和棕榈油的重量比为1:1:(2-3)时,最终制得的汽车用水性色漆具有更优异的附着力,其附着力能达到0级,对比第3组、第7组及第8组可知,当水性聚氨酯树脂配方中不含亲水单体和功能单体任意一种时,最终制得的汽车用水性色漆的附着力性能、柔韧性、耐水性、耐酸性及耐碱性均会下降,对比第3组和第9组可知,本发明的水性聚氨酯树脂在对汽车用水性色漆附着力性能、柔韧性、耐水性、耐酸性及耐碱性的正向贡献上远大于市售的同类型水性聚氨酯树脂。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (5)
1.一种水性聚氨酯树脂,其特征在于,所述水性聚氨酯树脂通过多元醇预聚体、亲水单体、异氰酸酯单体、功能单体、扩链剂、有机碱反应得到,所述亲水单体为1,4-二羟基-2-丁烷磺酸钠,所述功能单体为三羟甲基丙烷及棕榈油,且1,4-二羟基-2-丁烷磺酸钠、三羟甲基丙烷和棕榈油的重量比为1:1:(2-3),所述水性聚氨酯树脂的制备方法,包括以下步骤:
(1)在惰性气体保护下,将多元醇预聚体、亲水单体、异氰酸酯单体、催化剂加入到反应器中,升温到70-100℃,反应1-4h;
(2)加入功能单体,反应2-4h,再加入扩链剂,搅拌反应1-4h,降温,加入有机碱进行中和反应;
(3)在剪切条件下加入水,搅拌1-3h,即得水性聚氨酯树脂。
2.根据权利要求1所述的一种水性聚氨酯树脂,所述水性聚氨酯树脂的酸值为10-50mgKOH/g,粘度为100-6000mPa·s,数均分子量为4500-100000,固含量为30-65%。
3.根据权利要求1所述的一种水性聚氨酯树脂,其特征在于:所述的多元醇预聚体为聚碳酸酯多元醇、聚醚多元醇、聚酯多元醇中的至少一种。
4.一种涂料,其特征在于,所述涂料包括权利要求1至3任一项所述的水性聚氨酯树脂。
5.如权利要求1至3任一项所述水性聚氨酯树脂在汽车涂装工艺中的应用。
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