CN110746571A - Apao改性聚氨酯水性树脂及其制备方法 - Google Patents
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Abstract
本发明涉及一种APAO改性聚氨酯水性树脂,按重量份计,其组成为:二异氰酸酯25.0~60.0份、低聚物多元醇20.0~45.0份、丙烯酸羟乙酯接枝APAO 4.0~10.0份、扩链剂6.0~15.0份、二羟甲基丙酸2.5~5.0份、丙烯酸羟丙酯0.5~1.2份、二月桂酸二丁基锡0.03~0.1份、乙醇2.5~10.0份、乙二胺3.0~6.0份、中和剂2.5~10.0份、去离子水120.0~180.0份;本发明制得的APAO改性聚氨酯水性树脂,具有优良的附着力、耐水性、耐老化性、耐盐雾性、良好的抗流挂性等特点;可用于水性木器涂料、水性工业涂料、防水涂料等。
Description
技术领域
本发明涉及一种改性聚氨酯水性树脂,尤其涉及到一种APAO改性聚氨酯水性树脂及其制备方法,属于水性树脂合成技术领域。
背景技术
目前大量被使用的聚氨酯涂料以溶剂型为主,但随着人们环保意识的增强和环保法规的确立,传统的溶剂型化学品的挥发性有机化合物(VOC)和有害空气污染物(HAP)的排放愈来愈受到严格限制。
制备聚氨酯的水性化技术,以水代替有机溶剂,不仅提高了生产和施工的安全性,避免了有机溶剂的可燃性和毒性,而且能减少或消除聚氨酯固化过程中有机溶剂挥发带来的环境问题。同时,由于水性聚氨酯以水为介质,气味小、节能、操作加工方便等优点。但聚氨酯水性化后其耐水性、附着力、抗流挂性能等都会有一定程度的下降,制约了水性聚氨酯材料的应用。因此目前针对聚氨酯材料的改性研究逐渐增多。
中国专利CN105859977A公开了一种有机硅/丙烯酸酯/环氧树脂改性聚氨酯的制备方法,包括如下操作步骤:步骤一:将多元醇、二异氰酸酯、二羟基羧酸和扩链剂在氮气下放入反应釜;步骤二:将步骤一中得到的聚氨酯预聚体降温到45℃以下,加入有机胺、硅烷偶联剂、去离子水和二元胺;步骤三:将水相和油相依次加入到步骤二中的有机硅改性聚氨酯中;步骤四:将环氧树脂加入步骤三中的有机硅/丙烯酸酯改性聚氨酯中。
中国专利CN105601861A公开了一种有机硅改性水性聚氨酯树脂的合成方法,包括以下具体步骤:首先将聚酯多元醇Novomer真空脱水,滴加二异氰酸酯,反应得到聚氨酯预聚体I;然后把多羟基羧酸加入到聚氨酯预聚体I中,再滴加二元醇单体,反应得到聚氨酯预聚体;再把三羟甲基丙烷加入到聚氨酯预聚体中,反应得到聚氨酯预聚物;往聚氨酯预聚物中加入有机胺进行成盐反应,再加硅烷偶联剂,再加入去离子水,再加二元胺扩链、搅拌,乳化得到高硬度有机硅改性水性聚氨酯树脂。
上述发明针对水性聚氨酯树脂的改性,其性能均有一定的提升,但其抗流挂性能较差,且耐水性以及附着力不足。
发明内容
为了解决所述的技术问题,本发明在聚氨酯分子结构上引入APAO,APAO(非晶态α-烯烃共聚物)是一种低分子量的非晶态塑性体材料,由a-烯烃经聚合反应生成,微观结构上是一种非晶态的、无规则的排列状态,故该材料具有许多结晶性聚合物所不具备的特性,其具有良好的抗流挂性以及附着力,因此在其应用上也具有特殊性。
本发明在聚氨酯树脂分子结构通过化学键引入APAO,能有效提高水性聚氨酯树脂的附着力以及防流挂性能,且其以化学键相连,性能稳定可靠,制备成水性涂料后无需外加抗流挂剂与附着力促进剂。
本发明的目的在于提供一种APAO改性聚氨酯水性树脂。
本发明的另一目的提供一种APAO改性聚氨酯水性树脂的制备方法。
为满足本发明的一种APAO改性聚氨酯水性树脂,按重量份计,其组成为:二异氰酸酯25.0~60.0份、低聚物多元醇20.0~45.0份、丙烯酸羟乙酯接枝APAO 4.0~10.0份、扩链剂6.0~15.0份、二羟甲基丙酸2.5~5.0份、丙烯酸羟丙酯0.5~1.2份、二月桂酸二丁基锡0.03~0.1份、乙醇2.5~10.0份、乙二胺3.0~6.0份、中和剂2.5~10.0份、去离子水120.0~180.0份。
所述的丙烯酸羟乙酯接枝APAO采用溶剂法制得。
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、苯二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯中的一种或几种的组合。
所述的低聚物多元醇为聚四氢呋喃二元醇、聚碳酸酯二元醇、聚己内酯二元醇、聚环氧乙烷多元醇、聚醚二元醇、聚环氧丙烷多元醇中的一种或几种的组合;所述的低聚物多元醇分子量为1000~3000。
所述的扩链剂为丙二醇、丁二醇、己二醇、新戊二醇、二缩二乙二醇、一缩二丙二醇、2-丁基-2-乙基-1,3-丙二醇、2,4-二乙基-1,5-戊二醇、三羟甲基丙烷中的一种或几种的组合。
所述的中和剂为三乙胺、氨水、二甲基乙醇胺中的至少一种。
本发明提供一种APAO改性聚氨酯水性树脂的制备方法,其制备工艺如下:
a)、在多功能反应器中,按配方重量份,依次加入低聚物多元醇、扩链剂、二羟甲基丙酸,升温至105~110℃,真空下脱水1.5~2.0h;
b)、降温至60~70℃,加入二异氰酸酯后通入N2,滴加配方量的二月桂酸二丁基锡,然后升温到80~82℃反应2.0~2.5h,得到亲水性聚氨酯预聚物;加入适量溶剂调节粘度,升温至84~85℃,加入丙烯酸羟丙酯,继续搅拌反应1.0h,然后升温至88~90℃,加入丙烯酸羟乙酯接枝APAO,保温反应1.5~2.0h,检测,当NCO值与设计值一致为止;
c)、继续搅拌将温度降至45℃以下,缓慢滴加中和剂,继续搅拌反应,加入计算量去离子水,高速分散均匀,然后加入乙二胺搅拌反应,最后加入乙醇,脱溶剂,过滤,即得APAO改性聚氨酯水性树脂。
本发明所述的溶剂为丙酮等,本发明添加的溶剂仅起到调节预聚体粘度的作用,视粘度变化酌情添加。
本发明制得的APAO改性聚氨酯水性树脂,具有优良的附着力、耐水性、耐老化性、耐盐雾性、良好的抗流挂性等特点;可用于水性木器涂料、水性工业涂料、防水涂料等。
具体实施方式
本发明结合以下实施例对APAO改性聚氨酯水性树脂的制备做进一步描述。
实施例1
一种APAO改性聚氨酯水性树脂,按重量份计,由以下配方组成:异佛尔酮二异氰酸酯42.0份、聚四氢呋喃二元醇32.0份、丙烯酸羟乙酯接枝APAO 7.0份、丁二醇8.0份、三羟甲基丙烷2.5份、二羟甲基丙酸3.5份、丙烯酸羟丙酯0.8份、二月桂酸二丁基锡0.06份、乙醇5.0份、乙二胺4.5份、三乙胺6.8份、去离子水150.0份。
本实施例中一种APAO改性聚氨酯水性树脂的制备方法,包括以下步骤:
a)、在多功能反应器中,按配方重量份,依次加入聚四氢呋喃二元醇、丁二醇、三羟甲基丙烷、二羟甲基丙酸,升温至110℃,真空下脱水1.5h;
b)、降温至65℃,加入异佛尔酮二异氰酸酯后通入N2,滴加配方量的二月桂酸二丁基锡,然后升温到82℃反应2.0h,得到亲水性聚氨酯预聚物;加入适量溶剂调节粘度,升温至84~85℃,加入丙烯酸羟丙酯,继续搅拌反应1.0h,然后升温至88~90℃,加入丙烯酸羟乙酯接枝APAO,保温反应2.0h,检测,当NCO值与设计值一致为止;
c)、继续搅拌将温度降至42℃,缓慢滴加三乙胺,继续搅拌反应,加入计算量去离子水,高速分散均匀,然后加入乙二胺搅拌反应,最后加入乙醇,脱溶剂,过滤,即得APAO改性聚氨酯水性树脂,记为样品1。
实施例2
一种APAO改性聚氨酯水性树脂,按重量份计,由以下配方组成:甲苯二异氰酸酯35.0份、聚碳酸酯二元醇35.0份、丙烯酸羟乙酯接枝APAO 6.0份、新戊二醇7.0份、一缩二丙二醇4.0份、二羟甲基丙酸4.0份、丙烯酸羟丙酯0.7份、二月桂酸二丁基锡0.06份、乙醇6.8份、乙二胺4.5份、氨水5.0份、去离子水140.0份。
本实施例中一种APAO改性聚氨酯水性树脂的制备方法,包括以下步骤:
a)、在多功能反应器中,按配方重量份,依次加入聚碳酸酯二元醇、新戊二醇、一缩二丙二醇、二羟甲基丙酸,升温至105℃,真空下脱水2.0h;
b)、降温至70℃,加入甲苯二异氰酸酯后通入N2,滴加配方量的二月桂酸二丁基锡,然后升温到82℃反应2.0h,得到亲水性聚氨酯预聚物;加入适量溶剂调节粘度,升温至84~85℃,加入丙烯酸羟丙酯,继续搅拌反应1.0h,然后升温至88~90℃,加入丙烯酸羟乙酯接枝APAO,保温反应2.0h,检测,当NCO值与设计值一致为止;
c)、继续搅拌将温度降至42℃,缓慢滴加氨水,继续搅拌反应,加入计算量去离子水,高速分散均匀,然后加入乙二胺搅拌反应,最后加入乙醇,脱溶剂,过滤,即得APAO改性聚氨酯水性树脂,记为样品2。
实施例3
一种APAO改性聚氨酯水性树脂,按重量份计,由以下配方组成:六亚甲基二异氰酸酯28.0份、聚醚二元醇35.0份、丙烯酸羟乙酯接枝APAO 4份、丁二醇8.8份、二羟甲基丙酸4.0份、丙烯酸羟丙酯0.6份、二月桂酸二丁基锡0.05份、乙醇6.0份、乙二胺4.0份、三乙胺5.0份、去离子水130.0份。
本实施例中一种APAO改性聚氨酯水性树脂的制备方法,包括以下步骤:
a)、在多功能反应器中,按配方重量份,依次加入聚醚二元醇、丁二醇、二羟甲基丙酸,升温至110℃,真空下脱水1.5h;
b)、降温至60℃,加入六亚甲基二异氰酸酯后通入N2,滴加配方量的二月桂酸二丁基锡,然后升温到80~82℃反应2.5h,得到亲水性聚氨酯预聚物;加入适量溶剂调节粘度,升温至84~85℃,加入丙烯酸羟丙酯,继续搅拌反应1.0h,然后升温至88~90℃,加入丙烯酸羟乙酯接枝APAO,保温反应1.5h,检测,当NCO值与设计值一致为止;
c)、继续搅拌将温度降至40℃,缓慢滴加三乙胺,继续搅拌反应,加入计算量去离子水,高速分散均匀,然后加入乙二胺搅拌反应,最后加入乙醇,脱溶剂,过滤,即得APAO改性聚氨酯水性树脂,记为样品3。
性能指标测试:将上述实例中样品1、样品2、样品3与常规的水性聚氨酯树脂4,按照表1的原料配方制备成涂料,对应的涂料样品分别记为涂料1、涂料2、涂料3、涂料4,并分别测试其性能。
表1:涂料配方
原料名称 | 规格 | 用量/% |
水 | 去离子水 | 10 |
润湿剂 | 407 | 0.2 |
多功能助剂 | AMP-95 | 0.4 |
水性树脂 | 样品水性树脂 | 85 |
成膜助剂 | 丙二醇甲醚醋酸酯 | 4.0 |
消泡剂 | NXZ | 0.2 |
流平剂 | BYK-333 | 0.2 |
将配置好的涂料按照相关标准耐水性(GB/T1733-1993)、附着力(GB/T9286-1998)、耐盐雾性(GB/T1771-2007)、铅笔硬度(GB/T6739-1996)、抗流挂性(GB/T9264-2012)等进行性能指标测试,测试结果如表2所示。
表2:涂层的性能技术指标
检测项目 | 涂料1 | 涂料2 | 涂料3 | 涂料4 |
耐水性 | 20d | 18d | 16d | 6d |
附着力 | 0级 | 0级 | 0级 | 2级 |
铅笔硬度 | 2H | 2H | 2H | HB |
耐盐雾性 | 800h | 720h | 600h | 240h |
丰满度(目测) | 良好 | 良好 | 良好 | 一般 |
抗流挂性 | 良好 | 良好 | 良好 | 一般 |
由表2可以看出本发明的实施例1、实施例2、实施例3样品的附着力、防流挂性、耐水性等性能远远超过常规的水性聚氨酯树脂。
尽管本发明已作了详细说明并引证了实施例,但对于本领域的普通技术人员,显然可以按照上述说明而做出的各种方案、修改和改动,都应该包括在权利要求的范围之内。
Claims (8)
1.一种APAO改性聚氨酯水性树脂,其特征在于:所述的APAO改性聚氨酯水性树脂,按重量份计,其组成为:二异氰酸酯25.0~60.0份、低聚物多元醇20.0~45.0份、丙烯酸羟乙酯接枝APAO 4.0~10.0份、扩链剂6.0~15.0份、二羟甲基丙酸2.5~5.0份、丙烯酸羟丙酯0.5~1.2份、二月桂酸二丁基锡0.03~0.1份、乙醇2.5~10.0份、乙二胺3.0~6.0份、中和剂2.5~10.0份、去离子水120.0~180.0份。
2.根据权利要求1所述的APAO改性聚氨酯水性树脂,其特征在于:所述的丙烯酸羟乙酯接枝APAO采用溶剂法制得。
3.根据权利要求1所述的APAO改性聚氨酯水性树脂,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、苯二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯中的一种或几种的组合。
4.根据权利要求1所述的APAO改性聚氨酯水性树脂,其特征在于:所述的低聚物多元醇为聚四氢呋喃二元醇、聚碳酸酯二元醇、聚己内酯二元醇、聚环氧乙烷多元醇、聚醚二元醇、聚环氧丙烷多元醇中的一种或几种的组合;所述的低聚物多元醇分子量为1000~3000。
5.根据权利要求1所述的APAO改性聚氨酯水性树脂,其特征在于:所述的扩链剂为丙二醇、丁二醇、己二醇、新戊二醇、二缩二乙二醇、一缩二丙二醇、2-丁基-2-乙基-1,3-丙二醇、2,4-二乙基-1,5-戊二醇、三羟甲基丙烷中的一种或几种的组合。
6.根据权利要求1所述的APAO改性聚氨酯水性树脂,其特征在于:所述的中和剂为三乙胺、氨水、二甲基乙醇胺中的至少一种。
7.根据权利要求1所述的APAO改性聚氨酯水性树脂,其特征在于:所述的APAO改性聚氨酯水性树脂,制备工艺如下:
a)、在多功能反应器中,按配方重量份,依次加入低聚物多元醇、扩链剂、二羟甲基丙酸,升温至105~110℃,真空下脱水1.5~2.0h;
b)、降温至60~70℃,加入二异氰酸酯后通入N2,滴加配方量的二月桂酸二丁基锡,然后升温到80~82℃反应2.0~2.5h,得到亲水性聚氨酯预聚物;加入适量溶剂调节粘度,升温至84~85℃,加入丙烯酸羟丙酯,继续搅拌反应1.0h,然后升温至88~90℃,加入丙烯酸羟乙酯接枝APAO,保温反应1.5~2.0h,检测,当NCO值与设计值一致为止;
c)、继续搅拌将温度降至45℃以下,缓慢滴加中和剂,继续搅拌反应,加入计算量去离子水,高速分散均匀,然后加入乙二胺搅拌反应,最后加入乙醇,脱溶剂,过滤,即得APAO改性聚氨酯水性树脂。
8.根据权利要求1或7所述的APAO改性聚氨酯水性树脂,其特征在于:所述的溶剂为丙酮等,本发明添加的溶剂仅起到调节预聚体粘度的作用,视粘度变化酌情添加。
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