CN108892767A - 一种室温多重固化水性聚氨酯乳液的制备方法 - Google Patents

一种室温多重固化水性聚氨酯乳液的制备方法 Download PDF

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CN108892767A
CN108892767A CN201810617084.1A CN201810617084A CN108892767A CN 108892767 A CN108892767 A CN 108892767A CN 201810617084 A CN201810617084 A CN 201810617084A CN 108892767 A CN108892767 A CN 108892767A
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张良均
阮红梅
陈刚
樊庆春
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Wuhan Institute of Technology
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Abstract

本发明公开了一种室温多重固化水性聚氨酯乳液的制备方法。包括以下步骤：二异氰酸酯、低聚物二元醇、亲水扩链剂、不饱和脂肪酸单甘油酯、二羟基二烷基甲酮及少量催化剂发生聚合反应，加中和剂中和，加水乳化，得到水性聚氨酯羟基组分，向其加入含酰肼基的肼单体，搅拌均匀，再加入水可分散异氰酸酯固化剂即得产物。本发明采用双键氧化固化、酮肼交联和多异氰酸酯基团交联固化的三重固化方式，加快了树脂的固化速度，提高了涂膜的交联密度和耐水性。

Description

一种室温多重固化水性聚氨酯乳液的制备方法
技术领域
本发明属于有机合成技术领域，具体涉及一种室温多重固化水性聚氨酯乳液的制备方法。
背景技术
随着人们环保意识的加强以及环保法规的日益严格，含有VOC的涂料正在逐渐被市场淘汰，转而被水性涂料所代替。水性聚氨酯具有韧性好、耐高温、耐低温、抗紫外线性能优异的特点，并且不具有易挥发、易燃、易爆、有毒等缺点，目前已成为涂料应用较多的成膜物质。但是目前的水性聚氨酯涂料的耐水性、固化时间和耐盐雾性等性能还无法满足社会的要求，需要进行改性。
由于水性聚氨酯结构中存在亲水基团，使得涂层耐水性、耐盐雾性和机械性能较差，严重限制了其使用范围。交联改性是提高水性聚氨酯的耐水性、耐盐雾性和机械性能最有效的改性方法。
中国专利CN107857845A公开了一种单组分高温自交联水性聚氨酯的制备方法，其制备的单组分自交联水性聚氨酯的储存稳定性、耐水、耐碱性、耐化学品性、弹性等都得到很大的提高，但是没有涉及到固化时间。。
中国专利CN103773210A公布了一种双组分水性聚氨酯涂料组合物的制备方法，其制备的双组分水性聚氨酯涂料组合物具有耐高温黄变性，由其制备的涂膜在150℃下烘烤1天后的色差值小于3.0。所得的产品没有疏水基团，耐水性很差，且不能常温固化。
发明内容
本发明的目的在于提供一种能够广泛应用于工业大型机械设备的水性防腐涂料制备方法，通过多重固化方式，加快树脂的固化速度，避免高温烘烤，同时还提高涂膜的交联密度和耐水性。
为达到上述目的，采用技术方案如下：
一种室温多重固化水性聚氨酯乳液的制备方法，包括以下步骤：
1)水性聚氨酯羟基组分的合成
在氮气保护下，将低聚物二元醇、亲水扩链剂、不饱和脂肪酸单甘油酯、二羟基二烷基甲酮、催化剂混合，升温到50～60℃，搅拌，滴加二异氰酸酯，约1～1.5h滴完，保温1～1.5h，升温至75～80℃，保温3～4h，然后降温到50～60℃，加中和剂中和30～40min，加入丙酮调节粘度，最后降到室温，加水乳化，减压脱除丙酮制得水性聚氨酯羟基组分；
2)室温交联固化体系的制备
将所得的水性聚氨酯羟基组分和含酰肼基的肼单体混合，搅拌均匀，得到室温可成膜的水性聚氨酯乳液，再加入水可分散异氰酸酯固化剂，搅拌均匀，即得到室温多重固化的水性聚氨酯防腐乳液。
按上述方案，步骤1中二异氰酸酯、低聚物二元醇、亲水扩链剂、不饱和脂肪酸单甘油酯、二羟基二烷基甲酮的加料摩尔比为(3～7.5)：(1～3)：(1～2)：(1～3)：(1～2)，催化剂为二丁基锡二月桂酸酯。
按上述方案，步骤2中水性聚氨酯羟基组分、含酰肼基的肼单体和水可分散异氰酸酯固化剂的质量比10：(0.2～1.2)：(0.3～0.7)。
按上述方案，步骤1中所述低聚物二元醇包括分子量为400～2000的聚醚二元醇和聚酯二元醇中一种或混合；所述的聚醚二元醇包括聚环氧乙烷二醇、聚环氧丙烷二醇、聚四氢呋喃二醇以及他们的共聚二醇中的任意一种或混合；所述的聚酯二元醇包括聚己内酯二醇、聚己二酸乙二醇酯二醇、聚己二酸-1,4-丁二醇酯二醇、聚己二酸己二醇酯二醇中的任意一种或混合。
按上述方案，所述的亲水扩链剂包括二羟甲基丙酸、二羟甲基丁酸、二羟甲基戊酸、二羟甲基己酸、二羟甲基庚酸、二羟甲基壬酸、二羟甲基葵酸中的任意一种或混合。
按上述方案，所述的不饱和脂肪酸单甘油酯包括梓油酸单甘油酯、油酸单甘油酯，亚油酸单甘油酯、桐油酸单甘油酯、苏子油酸单甘油酯、大麻油酸单甘油脂、豆油酸单甘油脂、葵花子油酸单甘油脂、棉子油酸单甘油脂中的任意一种或混合。
按上述方案，所述的二羟基二烷基甲酮为二羟甲基甲酮、4,4′-二羟基二苯甲酮、二羟基二环己基甲酮、(3,5-二羟基苯基)-苯基甲酮、2,4-二羟基二苯甲酮，3,4-二羟基二苯甲酮中的任意一种或者混合。
按上述方案，所述的二异氰酸酯为甲苯二异氰酸酯、二苯甲烷二异氰酸酯、己二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基二亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、三甲基己二异氰酸酯、六氢甲苯二异氰酸酯中的任意一种或者混合。
按上述方案，所述的中和剂为二乙醇胺、三乙醇胺、三乙胺、N,N-二甲基异丙醇胺中的任意一种或混合。
按上述方案，所述含酰肼基的肼单体为水合肼、碳酸二酰肼、草酸二酰肼、丁二酸二酰肼、己二酸二酰肼中的任意一种或混合。
本发明步骤1所涉及的反应方程式如下：
其中n1的范围为150≤n1≤450，n2的范围为1≤n1≤120；n3的范围为50≤n1≤180；n4的范围为6≤n4≤34；n5的范围为1≤n1≤180；n6的范围为50≤n6≤150。
R1表示碳原子数为2～18的脂肪族碳链或者是碳原子数为6的脂环族或芳香族基团；
R2表示含有1～8个碳原子数的烷基。
R3表示碳原子数为10～20的不饱和脂肪酸。
R4表示碳原子数为1～6的烷基。
对于现有技术，本发明具有如下优点：
采用不饱和脂肪酸单甘油酯和二羟基二烷基甲酮改性水性聚氨酯后，最终制备的树脂的硬度、附着力、力学性能和耐盐雾性都得到明显提高。
采用双键氧化固化、酮肼交联和多异氰酸酯基团交联固化的三重固化方式，加快了树脂的固化速度，避免了高温烘烤，同时还提高了涂膜的交联密度、耐水性和耐盐雾性。
具体实施方式
以下实施例进一步阐释本发明的技术方案，但不作为对本发明保护范围的限制。
实施例1：
称2.68g二羟甲基丙酸，24g聚环氧丙烷二醇800(PPG1000)，3.58g豆油单甘油酯，1.8g二羟甲基甲酮，0.04g二丁基锡二月桂酸酯于四口烧瓶中，升温至60℃，搅拌使二羟甲基丙酸和二羟甲基甲酮溶解，从恒压漏斗滴加12.19g甲苯二异氰酸酯，1h滴完，保温1h，然后升温到80℃，保温4h，降温到60℃，加入2.02g三乙胺中和，反应30min，加入丙酮调节粘度，降到室温，在快速搅拌下加入去离子水86g乳化5min，减压脱除丙酮，制得固含量为35％的水性聚氨酯羟基组分。
称取10g上述制备的水性聚氨酯羟基组分，加入0.2g碳酸二酰肼搅拌30min，得到室温可成膜的酮肼交联型水性聚氨酯乳液，在该体系中加入0.3g水可分散异氰酸酯固化剂，搅拌均匀，得到室温多重固化的水性聚氨酯乳液。
实施例2：
称2.96g二羟甲基丁酸，24g聚环氧乙烷二醇800(PPG800)，5.9g葵花油单甘油酯，2.26g二羟基二环己基甲酮，0.04g二丁基锡二月桂酸酯于四口烧瓶中，升温至60℃，搅拌使二羟甲基丁酸和二羟基二环己基甲酮溶解，从恒压漏斗滴加15.02g二苯甲烷二异氰酸酯，1h滴完，保温1h，然后升温到80℃，保温4h，降温到60℃，加入2.1g二乙醇胺中和，反应30min，加入丙酮调节粘度，降到室温，在快速搅拌下加入去离子水97.1g乳化5min，减压脱除丙酮，制得固含量为35％的水性聚氨酯羟基组分。
称取10g上述制备的水性聚氨酯羟基组分，加入0.3g己二酸二酰肼搅拌30min，得到室温可成膜的酮肼交联型水性聚氨酯乳液，在该体系中加入0.3g水可分散异氰酸酯固化剂，搅拌均匀，得到室温多重固化的水性聚氨酯乳液。
实施例3：
称3.24g二羟甲基戊酸，30g聚环氧丙烷二醇1000(PPG1000)，3.53g大麻油酸甘油酯，0.9g二羟甲基甲酮和1.13g二羟基二环己基甲酮，0.04g二丁基锡二月桂酸酯于四口烧瓶中，升温至60℃，搅拌使二羟甲基戊酸、二羟甲基甲酮和二羟基二环己基甲酮溶解，从恒压漏斗滴加13.17g苯二亚甲基二异氰酸酯，1h滴完，保温1h，然后升温到80℃，保温4h，降温到60℃，加入2.98g三乙醇胺中和，反应30min，加入丙酮调节粘度，降到室温，在快速搅拌下加入去离子水102.13g乳化5min，减压脱除丙酮，制得固含量为35％的水性聚氨酯羟基组分。
称取10g上述制备的水性聚氨酯羟基组分，加入0.4g水合肼搅拌30min，得到室温可成膜的酮肼交联型水性聚氨酯乳液，在该体系中加入0.4g水可分散异氰酸酯固化剂，搅拌均匀，得到室温多重固化的水性聚氨酯乳液。
实施例4：
称1.76g二羟甲基己酸，20g聚碳酸酯二元醇1000(PPG1000)，4.28g2,4-二羟基二苯甲酮，7.1g苏子油酸单甘油酯，0.05g二丁基锡二月桂酸酯于四口烧瓶中，升温至60℃，搅拌使二羟甲基己酸和2,4-二羟基二苯甲酮溶解，从恒压漏斗滴加14.66g四甲基二亚甲基二异氰酸酯，1h滴完，保温1h，然后升温到80℃，保温4h，降温到60℃，加入1.02g三乙胺中和，反应30min，加入丙酮调节粘度，降到室温，在快速搅拌下加入去离子水79.65g乳化5min，减压脱除丙酮，制得固含量为35％的水性聚氨酯羟基组分。
称取10g上述制备的水性聚氨酯羟基组分，加入0.9g碳酸二酰肼搅拌30min，得到室温可成膜的酮肼交联型水性聚氨酯乳液，在该体系中加入0.6g水可分散异氰酸酯固化剂，搅拌均匀，得到室温多重固化的水性聚氨酯乳液。
实施例5：
称1.9g二羟甲基庚酸，15g己二酸己二醇酯二醇1500(PPG1500)，4.28g4,4-二羟基二苯甲酮，10.58g桐油酸单甘油酯，0.05g二丁基锡二月桂酸酯于四口烧瓶中，升温至60℃，搅拌使二羟甲基庚酸和4,4-二羟基二苯甲酮溶解，从恒压漏斗滴加13.34g异佛尔酮二异氰酸酯，1h滴完，保温1h，然后升温到80℃，保温4h，降温到60℃，加入1.49g三乙醇胺中和，反应30min，加入丙酮调节粘度，降到室温，在快速搅拌下加入去离子水86.6g乳化5min，减压脱除丙酮，制得固含量为35％的水性聚氨酯羟基组分。
称取10g上述制备的水性聚氨酯羟基组分，加入1.2g己二酸二酰肼搅拌30min，得到室温可成膜的酮肼交联型水性聚氨酯乳液，在该体系中加入0.7g水可分散异氰酸酯固化剂，搅拌均匀，得到室温多重固化的水性聚氨酯乳液。
实施例6：
称2.04g二羟甲基壬酸，16g聚四氢呋喃二醇800(PPG800)，4.28g4,4-二羟基二苯甲酮和2,4-二羟基二苯甲酮，11.61g梓油单甘油酯，0.05g二丁基锡二月桂酸酯于四口烧瓶中，升温至60℃，搅拌使二羟甲基壬酸、4,4-二羟基二苯甲酮和2,4-二羟基二苯甲酮溶解，从恒压漏斗滴加18.34g二环己基甲烷二异氰酸酯，1h滴完，保温1h，然后升温到80℃，保温4h，降温到60℃，加入1.05g二乙醇胺中和，反应30min，加入丙酮调节粘度，降到室温，在快速搅拌下加入去离子水99.12g乳化5min，减压脱除丙酮，制得固含量为35％的水性聚氨酯羟基组分。
称取10g上述制备的水性聚氨酯羟基组分，加入1g丁二酸二酰肼搅拌30min，得到室温可成膜的酮肼交联型水性聚氨酯乳液，在该体系中加入0.7g水可分散异氰酸酯固化剂，搅拌均匀，得到室温多重固化的水性聚氨酯乳液。
实施例7：
称2.18g二羟甲基葵酸，16g聚己二酸乙二醇酯二醇800(PPG800)，2.14g3,4-二羟基二苯甲酮，10.59g亚麻酸甘油酯，0.05g二丁基锡二月桂酸酯于四口烧瓶中，升温至60℃，搅拌使二羟甲基葵酸和3,4-二羟基二苯甲酮溶解，从恒压漏斗滴加10.51g三甲基己二异氰酸酯，1h滴完，保温1h,然后升温到80℃，保温4h，降温到60℃，加入1.03gN,N-二甲基异丙醇胺中和，反应30min，加入丙酮调节粘度，降到室温，在快速搅拌下加入去离子水98.43g乳化5min，减压脱除丙酮，制得固含量为35％的水性聚氨酯羟基组分。
称取10g上述制备的水性聚氨酯羟基组分，加入0.8g己二酸二酰肼在该体系中搅拌30min，得到室温可成膜的酮肼交联型水性聚氨酯乳液，在该体系中加入0.6g水可分散异氰酸酯固化剂，搅拌均匀，得到室温多重固化的水性聚氨酯乳液。
实施例8：
称1.34g二羟甲基丙酸，24g聚四氢呋喃二醇800(PPG800)，2.16g(3,5-二羟基苯基)-苯基甲酮，3.52g亚油酸单甘油酯，0.04g二丁基锡二月桂酸酯于四口烧瓶中，升温至60℃，搅拌使二羟甲基丙酸和(3,5-二羟基苯基)-苯基甲酮溶解，从恒压漏斗滴加8.41g己二异氰酸酯，1h滴完，保温1h，然后升温到80℃，保温4h，降温到60℃，加入1.03gN,N-二甲基异丙醇胺中和，反应30min，加入丙酮调节粘度，降到室温，在快速搅拌下加入去离子水75.2g乳化5min,减压脱除丙酮，制得固含量为35％的水性聚氨酯羟基组分。
称取10g上述制备的水性聚氨酯羟基组分，加入0.7g草酸二酰肼搅拌30min，得到室温可成膜的酮肼交联型水性聚氨酯乳液，在该体系中加入0.5g水可分散异氰酸酯固化剂，搅拌均匀，得到室温多重固化的水性聚氨酯乳液。
实施例1-8中漆膜性能检测结果如表1所示。
其中，柔韧性：按标准GB/T1731-1993测定；硬度：按标准GB/T6739-2006测定；耐水性：按标准GB/T10834-1989测定；耐盐雾性按标准GB/T1771-91测定；储存稳定性：按标准GB/T6753.3-1986测定；表干时间以及实干时间的成膜温度为30℃。

Claims (10)

1.一种室温多重固化水性聚氨酯乳液的制备方法，其特征在于包括以下步骤：
1)水性聚氨酯羟基组分的合成
在氮气保护下，将低聚物二元醇、亲水扩链剂、不饱和脂肪酸单甘油酯、二羟基二烷基甲酮、催化剂混合，升温到50～60℃，搅拌，滴加二异氰酸酯，约1～1.5h滴完，保温1～1.5h，升温至75～80℃，保温3～4h，然后降温到50～60℃，加中和剂中和30～40min，加入丙酮调节粘度，最后降到室温，加水乳化，减压脱除丙酮制得水性聚氨酯羟基组分；
2)室温交联固化体系的制备
将所得的水性聚氨酯羟基组分和含酰肼基的肼单体混合，搅拌均匀，得到室温可成膜的水性聚氨酯乳液，再加入水可分散异氰酸酯固化剂，搅拌均匀，即得到室温多重固化的水性聚氨酯防腐乳液。
2.如权利要求1所述室温多重固化水性聚氨酯乳液的制备方法，其特征在于步骤1中二异氰酸酯、低聚物二元醇、亲水扩链剂、不饱和脂肪酸单甘油酯、二羟基二烷基甲酮的加料摩尔比为(3～7.5)：(1～3)：(1～2)：(1～3)：(1～2)，催化剂为二丁基锡二月桂酸酯。
3.如权利要求1所述室温多重固化水性聚氨酯乳液的制备方法，其特征在于步骤2中水性聚氨酯羟基组分、含酰肼基的肼单体和水可分散异氰酸酯固化剂的质量比10：(0.2～1.2)：(0.3～0.7)。
4.如权利要求1所述室温多重固化水性聚氨酯乳液的制备方法，其特征在于步骤1中所述低聚物二元醇包括分子量为400～2000的聚醚二元醇和聚酯二元醇中一种或混合；所述的聚醚二元醇包括聚环氧乙烷二醇、聚环氧丙烷二醇、聚四氢呋喃二醇以及他们的共聚二醇中的任意一种或混合；所述的聚酯二元醇包括聚己内酯二醇、聚己二酸乙二醇酯二醇、聚己二酸-1,4-丁二醇酯二醇、聚己二酸己二醇酯二醇中的任意一种或混合。
5.如权利要求1所述室温多重固化水性聚氨酯乳液的制备方法，其特征在于所述的亲水扩链剂包括二羟甲基丙酸、二羟甲基丁酸、二羟甲基戊酸、二羟甲基己酸、二羟甲基庚酸、二羟甲基壬酸、二羟甲基葵酸中的任意一种或混合。
6.如权利要求1所述室温多重固化水性聚氨酯乳液的制备方法，其特征在于所述的不饱和脂肪酸单甘油酯包括梓油酸单甘油酯、油酸单甘油酯，亚油酸单甘油酯、桐油酸单甘油酯、苏子油酸单甘油酯、大麻油酸单甘油脂、豆油酸单甘油脂、葵花子油酸单甘油脂、棉子油酸单甘油脂中的任意一种或混合。
7.如权利要求1所述室温多重固化水性聚氨酯乳液的制备方法，其特征在于所述的二羟基二烷基甲酮为二羟甲基甲酮、4,4′-二羟基二苯甲酮、二羟基二环己基甲酮、(3,5-二羟基苯基)-苯基甲酮、2,4-二羟基二苯甲酮，3,4-二羟基二苯甲酮中的任意一种或者混合。
8.如权利要求1所述室温多重固化水性聚氨酯乳液的制备方法，其特征在于所述的二异氰酸酯为甲苯二异氰酸酯、二苯甲烷二异氰酸酯、己二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基二亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、三甲基己二异氰酸酯、六氢甲苯二异氰酸酯中的任意一种或者混合。
9.如权利要求1所述室温多重固化水性聚氨酯乳液的制备方法，其特征在于所述的中和剂为二乙醇胺、三乙醇胺、三乙胺、N,N-二甲基异丙醇胺中的任意一种或混合。
10.如权利要求1所述室温多重固化水性聚氨酯乳液的制备方法，其特征在于所述含酰肼基的肼单体为水合肼、碳酸二酰肼、草酸二酰肼、丁二酸二酰肼、己二酸二酰肼中的任意一种或混合。
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CN111978502A (zh) * 2020-08-18 2020-11-24 北京化工大学常州先进材料研究院 一种氨酯油丙烯酸酯光固化树脂及其制备方法
CN113817133A (zh) * 2021-09-18 2021-12-21 湖南松井新材料股份有限公司 可室温自交联水性非离子型聚氨酯分散体及其制备方法和应用
CN113912810A (zh) * 2021-10-12 2022-01-11 福建华夏蓝新材料科技有限公司 一种单组分水性聚氨酯分散体及其制备方法
CN114015008A (zh) * 2021-11-25 2022-02-08 广东一三七化工科技有限公司 聚氨酯乳液、其制备方法及印花用涂料及其制备方法
CN115286762A (zh) * 2022-05-10 2022-11-04 华南理工大学 一种uv诱导自交联聚氨酯水分散体及其制备方法和应用
CN115286762B (zh) * 2022-05-10 2024-04-09 华南理工大学 一种uv诱导自交联聚氨酯水分散体及其制备方法和应用

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