CN112794982A - 一种聚氨酯丙烯酸酯及其制备方法和应用 - Google Patents
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Abstract
本发明公开了一种聚氨酯丙烯酸酯及其制备方法和应用,所述聚氨酯丙烯酸酯包括如下按重量份计算的组分:二异氰酸酯20~35份;磺酸盐聚酯二元醇35~75份;二元醇扩链剂2~5份;阻聚剂0.05~0.1份;含羟基的丙烯酸酯单体封端剂3~10份;所述磺酸盐聚酯二元醇与所述二元醇扩链剂的质量比为(12~25):1。所述聚氨酯丙烯酸酯制备成漆膜后具有低气味、硬度和柔韧性好。
Description
技术领域
本发明涉及固化涂料技术领域,更具体地,涉及一种聚氨酯丙烯酸酯及其制备方法和应用。
背景技术
聚氨酯由于其独特的结构,良好的加工性,可调节软/硬段的灵活性而被广泛应用于胶粘剂、油墨、涂料、纺织品和生物材料等领域。随着人们环保意识的日益增强以及国家法规的日益严格,传统的溶剂型聚氨酯的使用受到越来越多的限制,水性聚氨酯受到人们更多的关注。
水性聚氨酯安全环保,无毒不燃,但存在耐水性、耐磨性、力学性能等方面的不足,聚丙烯酸酯耐水性、耐候性良好,原料成本低廉易获取,但聚丙烯酸酯制备成涂料成漆膜时,漆膜的柔韧性、硬度较差。聚氨酯丙烯酸酯可以将两者的优点得到最大的互补。
如中国专利(CN111253547A)公开了一种磺酸盐紫外光固化水性聚氨酯及其制备方法,首先利用丙烯酸、二缩水甘油醚为原料制备得到UV大单体,然后利用其与二异氰酸酯、聚酯二元醇、小分子多元醇、磺酸盐亲水单体、反应制备得到目标产物聚氨酯丙烯酸酯,但是反应过程繁琐,时间较长,聚氨酯丙烯酸酯光固化速率较慢。
中国专利(CN108503792A)公开了一种水性聚氨酯丙烯酸酯树脂以及制备方法。体系中含有巯基单体导致气味较大,且从数据上看漆膜的硬度和柔韧性都不好。
发明内容
本发明为克服上述水性聚氨酯丙烯酸酯树脂制备成漆膜时,其气味重、硬度不高、柔韧性不好的缺陷,提供一种聚氨酯丙烯酸酯。
本发明的另一目的在于提供所述聚氨酯丙烯酸酯的制备方法。
本发明的另一目的在于提供所述聚氨酯丙烯酸酯的应用。
为实现上述目的,本发明采用的技术方案是:
一种聚氨酯丙烯酸酯,包括如下按重量份计算的组分:
所述磺酸盐聚酯二元醇与所述二元醇扩链剂的质量比为(12~25):1。
常规地,在聚氨酯丙烯酸酯合成过程中,一般会加入羧酸类扩链剂,这类物质需要在后期需要加入胺类中和剂,但是胺类中和剂有较大的气味,本发明在体系中采用二元醇扩链剂来替代羧酸类扩链剂,有效避免了气味分子的使用,且二元醇扩链剂的加入,会增加了最后漆膜的柔韧性,本专利在保证低气味的同时,可保证漆膜具有优异的柔韧性和硬度。当所述磺酸盐聚酯二元醇与所述二元醇扩链剂的质量比为(12~25):1,由聚氨酯丙烯酸酯制备成漆膜时,漆膜的柔韧性和硬度进一步增加,这是因为硬段微相区融入到软段微相区当中,硬段部分在软段部分当中起到物理交联的作用,限制分子链的相对移动,从而提高了漆膜的力学性能。
优选地,所述磺酸盐聚酯二元醇与所述二元醇扩链剂的质量比为(15~20):1。当所述磺酸盐聚酯二元醇与所述二元醇扩链剂的质量比为(15~20):1时,漆膜硬度和柔韧性都得到提升。
优选地,所述二异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯中的一种。
优选地,所述磺酸盐聚酯二元醇的重均分子量为1000~1200。
优选地,所述二元醇扩链剂为1,4-丁二醇、新戊二醇中的一种。
优选地,所述阻聚剂为对羟基苯甲醚、对苯二酚中的一种
优选地,,所述含羟基的丙烯酸酯单体封端剂为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、季戊四醇三丙烯酸酯中的一种。
本发明还提供所述聚氨酯丙烯酸酯的制备方法,包括如下步骤:
S1.将二异氰酸酯、磺酸盐聚酯二元醇混合均匀,加入有机锡类催化剂,在70~80℃下反应得到聚氨酯预聚体I;
S2.在70~80℃下,将二元醇扩链剂加入到步骤S1中的聚氨酯预聚体I,混合反应得到聚氨酯预聚体II;
S3.在70~80℃,将阻聚剂、含羟基的丙烯酸酯单体封端剂加入到步骤S2的聚氨酯预聚体II中,混合反应得到聚氨酯丙烯酸酯。
S4.将步骤S3的聚氨酯丙烯酸酯加入去离子水乳化后出料,得到固含量为40%的聚氨酯丙烯酸酯乳液。
所述聚氨酯丙烯酸酯在制备光固化涂料中的应用。
与现有技术相比,本发明的有益效果是:
本发明提供了一种聚氨酯丙烯酸酯,本发明在体系中采用二元醇扩链剂来替代羧酸类扩链剂,有效避免了气味分子的使用,且二元醇扩链剂的加入,会增加了最后漆膜的柔韧性,本专利在保证低气味的同时,可保证漆膜具有优异的柔韧性和硬度。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,但本发明的实施方式不限于此。
本发明所采用的试剂、方法和设备,如无特殊说明,均为本技术领域常规试剂、方法和设备。
下面结合实施例和对比例来详细说明本发明。
实施例和对比例均通过以下方法制备聚氨酯丙烯酸酯,按照表1~3的重量比称取各组分;具体步骤如下:
S1.将二异氰酸酯、磺酸盐聚酯二元醇混合均匀,加入二月桂酸二丁基锡,在70~80℃下反应得到聚氨酯预聚体I;
S2.在70~80℃下,将二元醇扩链剂加入到步骤S1中的聚氨酯预聚体I,混合反应得到聚氨酯预聚体II;
S3.在70~80℃,将阻聚剂、含羟基的丙烯酸酯单体封端剂加入到步骤S2的聚氨酯预聚体II中,混合反应得到主链含磺酸盐亲水基团的聚氨酯丙烯酸酯。
S4.将步骤S3的聚氨酯丙烯酸酯加入去离子水乳化0.5h后出料,得到固含量为40%的聚氨酯丙烯酸酯乳液。
实施例1~7
表1实施例1~7的配方(份)
实施例8~11和对比例1~3
表2实施例8~11和对比例1~3的配方(份)
上述实施例和对比例均通过下述方法进行性能测试:
本发明的聚氨酯丙烯酸酯在UV涂料的应用。配方具体的组分按照质量份计算如下:
聚氨酯丙烯酸酯100份;
光引发剂3份
1.拉伸测试
采用美特斯工业***(中国)有限公司的CMT4204电子万能试验机按GB/T 1040.3-2006进行测试,试样为哑铃型,尺寸为50mm*4mm*0.5mm,拉伸速率为50mm/min,拉伸强度和断裂伸长率反应的是漆膜的柔韧性。
2.铅笔硬度根据GB/T 6739-2006测试漆膜的铅笔硬度。
表3实施例和对比例的数据
从实施例1~12看,用实施例制备的漆膜均表现出良好的力学性能。实施例1~3改变了二异氰酸酯的用量,这导致漆膜的拉伸强度增大,断裂伸长率减小。这是因为随着二异氰酸酯用量的增加,聚氨酯丙烯酸酯结构内的氨基甲酸酯、脲基结构增多,漆膜的刚性增大。实施例4~7改变了磺酸盐二元醇的用量,从而导致聚氨酯链中软段含量上升,聚氨酯链度的规整性遭到破坏,导致漆膜的力学强度下降,断裂伸长率上升,但磺酸盐聚酯二元醇与所述二元醇扩链剂的质量比为(12~25):1在这中间变化具有较好的力学强度和断裂伸长率,且当磺酸盐聚酯二元醇与所述二元醇扩链剂的质量比为(15~20):1时,效果更好。实施例10~11改变了封端剂的用量,这主要影响聚氨酯丙烯酸酯的双键含量。随着封端剂用量增加,双键含量上升,漆膜内交联联程度上升,漆膜的力学强度提高。
上述实施例1~11中不含气味分子,所以制成漆膜的气味非常低。
从对比例1~3看,对比例1没有加入二元醇扩链剂,这会导致胶膜的力学性能差,体现出软而脆;对比例2和对比例3中的磺酸盐聚酯二元醇与所述二元醇扩链剂的质量比为(15~20):1都不在这个范围内,胶膜的柔韧性和力学性能差,限制了其应用。
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明权利要求的保护范围之内。
Claims (9)
2.根据权利要求1所述聚氨酯丙烯酸酯,其特征在于,磺酸盐聚酯二元醇与二元醇扩链剂的质量比为(15~20):1。
3.根据权利要求1所述聚氨酯丙烯酸酯,其特征在于,所述二异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯中的一种。
4.根据权利要求1所述聚氨酯丙烯酸酯,其特征在于,所述磺酸盐聚酯二元醇的重均分子量为1000~1200。
5.根据权利要求1所述聚氨酯丙烯酸酯,其特征在于,所述二元醇扩链剂为1,4-丁二醇、新戊二醇中的一种。
6.根据权利要求1所述聚氨酯丙烯酸酯,其特征在于,所述阻聚剂为对羟基苯甲醚、对苯二酚中的一种。
7.根据权利要求1所述聚氨酯丙烯酸酯,其特征在于,所述含羟基的丙烯酸酯单体封端剂为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、季戊四醇三丙烯酸酯中的一种。
8.根据权利要求1~7任一项所述聚氨酯丙烯酸酯的制备方法,其特征在于,包括如下步骤:
S1.将二异氰酸酯、磺酸盐聚酯二元醇混合均匀,加入有机锡类催化剂,在70~80℃下反应得到聚氨酯预聚体I;
S2.在70~80℃下,将二元醇扩链剂加入到步骤S1中的聚氨酯预聚体I,混合反应得到聚氨酯预聚体II;
S3.在70~80℃,将阻聚剂、含羟基的丙烯酸酯单体封端剂加入到步骤S2的聚氨酯预聚体II中,混合反应得到聚氨酯丙烯酸酯。
9.根据权利要求1~7任一项所述聚氨酯丙烯酸酯在制备光固化涂料中的应用。
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CN114806489A (zh) * | 2022-05-20 | 2022-07-29 | 广东新辉化学有限公司 | 一种水性聚氨酯粘结剂及其制备方法和应用 |
CN115433341A (zh) * | 2022-09-08 | 2022-12-06 | 黎明化工研究设计院有限责任公司 | 一种亲水性聚氨酯丙烯酸酯、亲水性三官丙烯酸酯及其制备方法和应用 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114806489A (zh) * | 2022-05-20 | 2022-07-29 | 广东新辉化学有限公司 | 一种水性聚氨酯粘结剂及其制备方法和应用 |
CN115433341A (zh) * | 2022-09-08 | 2022-12-06 | 黎明化工研究设计院有限责任公司 | 一种亲水性聚氨酯丙烯酸酯、亲水性三官丙烯酸酯及其制备方法和应用 |
CN115433341B (zh) * | 2022-09-08 | 2024-01-05 | 黎明化工研究设计院有限责任公司 | 一种亲水性聚氨酯丙烯酸酯、亲水性三官丙烯酸酯及其制备方法和应用 |
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