CN105418870A - 一种蓖麻油/丙烯酸复合改性水性聚氨酯乳液及其制备方法 - Google Patents

一种蓖麻油/丙烯酸复合改性水性聚氨酯乳液及其制备方法 Download PDF

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CN105418870A
CN105418870A CN201510856799.9A CN201510856799A CN105418870A CN 105418870 A CN105418870 A CN 105418870A CN 201510856799 A CN201510856799 A CN 201510856799A CN 105418870 A CN105418870 A CN 105418870A
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weight
viscotrol
polyurethane emulsion
vinylformic acid
composite modified
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李洁
黄蒙
赵其中
刘卫峰
孙凌
廖群晖
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Shanghai Huayi Paint Co Ltd
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Shanghai Huayi Paint Co Ltd
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Abstract

本发明涉及一种蓖麻油/丙烯酸复合改性水性聚氨酯乳液及其制备方法，该复合改性水性聚氨酯乳液合成配方按重量百分比计，组成包括：8～15重量％的二异氰酸酯单体；5～16重量％的蓖麻油；4～8重量％的大分子多元醇；0.1～0.5重量％的多羟基丙烯酸树脂；1～6重量％的小分子扩链剂；1～5重量％的亲水性扩链剂；0.01～0.1重量％的催化剂；3～8重量％的助溶剂；0.4～4.5重量％的中和剂；0.4～3重量％的后扩链剂；57～67重量％的去离子水。该复合改性水性聚氨酯乳液具有交联结构，在力学性能、干性、耐水性和耐湿热性等方面相比于现有的水性聚氨酯乳液性能有很大提高。

Description

一种蓖麻油/丙烯酸复合改性水性聚氨酯乳液及其制备方法
技术领域
本发明属于涂料技术领域，特别涉及一种蓖麻油/丙烯酸复合改性水性聚氨酯乳液及其制备方法。
背景技术
涂料工业是现代社会中VOC排放的第二大污染源。随着各国环保法规的完善和环保意识的增强，传统溶剂型涂料的发展越来越受到限制。水性聚氨酯因其以水作为分散介质，不含或含有少量有机溶剂，具有无毒、不易燃烧、不污染环境、安全可靠等优点，符合涂料工业的发展要求。
随着水性聚氨酯市场的不断推广，对聚氨酯的性能要求也越来越高。传统的水性聚氨酯具有涂膜耐水性差、光泽度低、丰满度较差和力学性能差的缺陷，已难以满足要求。对水性聚氨酯的改性越来越受到人们的重视，改性方法出现多样化，其中交联改性是目前研究最为广泛的一种方法，即在聚合物中引入功能性的成分，使其分子链产生交联，形成交联网状结构，以提高聚合物在耐水、耐热、耐溶剂及力学等方面的性能。
中国专利CN102786637公开一种复合改性的水性聚氨酯树脂及其制备方法，采用蓖麻油、环氧树脂、丙烯酸酯等复合改性，涂料在成膜过程中交联密度高，漆膜硬度高、光泽高、耐水性好、耐溶剂性好。但其预聚物粘度过大，导致乳化时分散困难、乳液粒径大。
中国专利CN101967222公开一种环氧化蓖麻油改性的水性聚氨酯的制备方法，采用环氧化改性的蓖麻油作为原料，解决了环氧改性水性聚氨酯时，普通环氧树脂(如E44、E51等)与异氰酸酯反应效率低，改性产物稳定性差的缺点，使产品的稳定性及耐水性都有了一定程度的提高。但环氧化蓖麻油制备工艺较复杂，产率较低，不适宜工业生产。
中国专利CN101280053公开一种由可再生型多元醇制备丙烯酸改性水性聚氨酯的方法，将聚氨酯预聚物与丙烯酸类单体混合乳化后，采用乳液聚合的方法制备出具有网络互穿结构的聚氨酯乳液，这种乳液具有高耐候性、耐化学性、耐水性的优点，但乳液粒径较大，储存稳定性差。
水性聚氨酯的主要原料，聚醚/聚酯多元醇来自石油等不可再生资源，随着全球石油资源紧缺、价格上涨等问题的日益严峻，寻找合适的石油资源的替代品已成为关系着国计民生的大问题。蓖麻油是含长链脂肪基的多羟基化合物，羟值为163mgKOH/g，不仅含有30％二官能度的物质，还含有70％三官能度的物质，其中三官能度的蓖麻油可以作为交联剂用以提高体系的交联度，二官能度蓖麻油可以替代部分大分子多元醇。蓖麻油作为天然的原材料，不仅来源丰富、价格低廉，用于替代大分子多元醇，可缓解石油资源的短缺，降低聚氨酯的成本，且其组分中的非极性长链脂肪酸可以赋予涂膜良好的柔韧性、耐水性、耐曲挠性以及耐寒性。
丙烯酸树脂是水性聚氨酯改性材料中最重要的一种，它将聚氨酯的韧性及弹性与丙烯酸酯的良好保色性、光稳定性、硬度及低成本综合在一起，可以弥补单一聚氨酯水分散体的缺点和单一丙烯酸水分散体热粘冷脆，柔韧性差，不耐溶剂的缺点。目前的研究大多采用乳液聚合的方法合成有网络互穿结构的聚氨酯乳液，但通常在自由基引发聚合的丙烯酸酯乳液中，聚合单体并不能完全参加反应，具有单体转化率低，乳液不稳定，放置易分层的缺点。
本发明选用一种羟基丙烯酸树脂对水性聚氨酯进行改性，这种羟基丙烯酸树脂是由聚苯乙烯-烯丙醇共聚所得的一种多元醇，这种结构可以使丙烯酸树脂与聚氨酯单体充分反应，从而提高树脂的交联度，另外其分子中含有大量苯基，还可以改善树脂的硬度，同时增加干燥速度，改善流平性和对底材的附着力。
发明内容
本发明旨在克服目前水性聚氨酯乳液的干燥时间长、耐水性差、耐化学品性不佳等诸多缺点，通过内交联法，提高漆膜的干性、硬度和耐水性，改善流平性和对底材的附着力，从而得到性能优良的水性聚氨酯乳液。
本发明的技术方案如下：一种蓖麻油/丙烯酸复合改性水性聚氨酯乳液，该复合改性水性聚氨酯乳液合成配方按重量百分比计，组成包括：8重量％～15重量％的二异氰酸酯单体；5重量％～16重量％的蓖麻油；4重量％～8重量％的大分子多元醇；0.1重量％～0.5重量％的多羟基丙烯酸树脂；1重量％～6重量％的小分子扩链剂；1重量％～5重量％的亲水性扩链剂；0.01重量％～0.1重量％的催化剂；3重量％～8重量％的助溶剂；0.4重量％～4.5重量％的中和剂；0.4重量％～3重量％的后扩链剂；57重量％～67重量％的去离子水。
本发明中所述的二异氰酸酯单体选自：甲苯二异氰酸酯(TDI)、二苯甲烷二异氰酸酯(MDI)、己二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、三甲基己二异氰酸酯(TMDI)、二环己基甲烷二异氰酸酯(HMDI)、苯二亚甲基二异氰酸酯(XDI)、四甲基苯二亚甲基二异氰酸酯(TMXDI)、六氢甲苯二异氰酸酯(HTDI)中的一种或几种。
本发明中所述的大分子多元醇选自：分子量1000～2000的聚乙二醇、分子量1000～2000的聚丙二醇、分子量1500～2500的聚碳酸酯二醇、分子量1000～2000的聚四氢呋喃中的一种或几种。
本发明中所述的多羟基丙烯酸树脂的组成包括：40～70重量％的苯乙烯单体和30～60重量％的烯丙醇单体，通过自由基聚合反应而得到，羟值为100～230mgKOH/g。
本发明中所述的小分子扩链剂选自：乙二醇、丙二醇、1，3-丙二醇、1，3-丁二醇、1，4-丁二醇、新戊二醇、1,6-己二醇、一缩二乙二醇、甘油、季戊四醇、二季戊四醇、三羟甲基丙烷、三羟甲基乙烷中的一种或几种；所述的亲水性扩链剂选自：二羟甲基丙酸、二羟甲基丁酸中的一种或几种。
本发明中所述的助溶剂选自：二丙二醇二甲醚、丙酮、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、丁酮中的一种或几种。
本发明中所述的催化剂选自：辛酸亚锡、二月桂酸二丁基锡中的一种或几种。
本发明中所述的中和剂选自：三乙醇胺、三乙胺、正丙胺中的一种或几种。
本发明中所述的后扩链剂选自：乙二胺、二乙烯三胺、丙二胺、己二胺、二乙醇胺中的一种或几种。
本发明中所述的蓖麻油/丙烯酸复合改性水性聚氨酯乳液的制备方法，包括如下步骤：
(1)预聚体的制备：按配比将计量的大分子多元醇、蓖麻油、多羟基丙烯酸树脂和催化剂加入反应瓶中，搅拌转速为200～300r/min，升温至35～50℃，在此温度下滴加二异氰酸酯单体，20min内滴加完毕，缓慢升温至55～95℃，保温2～4h后降温至50℃以下得到预聚体；
(2)扩链：向预聚体中分别加入小分子扩链剂、亲水性扩链剂、催化剂、助溶剂，搅拌并升温至90～125℃，保温3h，当-NCO含量达到2％～6.5％后，降温至30℃以下；
(3)中和：向反应体系中加入中和剂和助溶剂，搅拌0.5～1.5h后出料，得预聚物，备用；
(4)乳化：在另一反应瓶中加入计量的去离子水，将搅拌器转速调整至300～750r/min，保持温度稳定在30℃以下，将步骤(3)中所得预聚物缓慢倒入反应瓶中乳化，充分搅拌10min后，加入后扩链剂，继续搅拌0.5～1.5h；
(5)脱除溶剂：在温度为20～50℃、真空度0.07～0.1MPa的条件下减压蒸馏1.5～3.5h脱除反应中低沸点溶剂，过滤并包装，即得蓖麻油/丙烯酸复合改性水性聚氨酯乳液，该蓖麻油/丙烯酸复合改性水性聚氨酯乳液的固体份含量为30重量％～35重量％。
本发明提供一种蓖麻油/丙烯酸复合改性水性聚氨酯乳液具有交联结构，在力学性能、干性、耐水性和耐湿热性等方面相比于现有的水性聚氨酯乳液性能有很大提高。
本发明一种蓖麻油/丙烯酸复合改性水性聚氨酯乳液有以下创新点和优点：
1.采用来源丰富、可再生的蓖麻油替代部分大分子多元醇，减少大量使用石油资源对环境的污染，不但降低了成本，且其分子中含有较长的疏水的脂肪酸链，使得涂膜的耐水性有明显的提高；
2.选用一种羟基丙烯酸树脂代替丙烯酸酯类单体，使丙烯酸酯与聚氨酯发生接枝反应，提高树脂的交联度，从而使树脂的干性、硬度与丰满度都有了较大的提高；
3.本发明的方法工艺简单，生产成本低，经济效益良好，所得的水性聚氨酯乳液可在10～15min内表干，24h内硬度可达H，漆膜光泽度和丰满度高，耐溶剂性好。
具体实施方式
下面通过实施例对本发明的内容作进一步具体说明，但本发明的范围决不局限于这些实施例。
实施例1
一种蓖麻油/丙烯酸复合改性水性聚氨酯乳液的具体制备方法步骤如下：
(1)依次在一个装有搅拌装置、温度计和通氮气保护的1000mL四口烧瓶中加入69.7g聚碳酸酯二醇(分子量2500)、80g蓖麻油、1.5g多羟基丙烯酸树脂(羟值为210mgKOH/g)，搅拌转速为200～300r/min，升温至40℃，在此温度下滴加118g甲苯二异氰酸酯，20min内滴加完毕，缓慢升温至90℃，保温2～4h后降温至40℃；
(2)加入18.5g1，4-丁二醇、3g三羟甲基丙烷、16.9g二羟甲基丙酸、80gN-甲基吡咯烷酮、0.3g二月桂酸二丁基锡，105℃保温3h；
(3)开始测NCO，当NCO值达到2.4％后，降温至30℃以下加入12.1g三乙胺和丙酮，搅拌30min，得预聚物，备用；
(4)在另一反应瓶中加入588g去离子水，将搅拌器转速调整500～750r/min，保持温度稳定在20℃，将步骤(3)中所得预聚物缓慢倒入反应瓶中乳化，充分搅拌10min后，加入7.4g乙二胺，继续搅拌0.5h；
(5)在温度为35～40℃、真空度0.07～0.09MPa的条件下减压蒸馏1.5～3.5h，脱除丙酮，过滤并包装，即得一种蓖麻油/丙烯酸复合改性水性聚氨酯乳液，固体份含量为30％(重量)。
实施例2
一种蓖麻油丙烯酸复合改性水性聚氨酯乳液的具体制备方法步骤如下：
(1)依次在一个装有搅拌装置、温度计和通氮气保护的1000mL四口烧瓶中加入65.9g聚四氢呋喃(分子量1000)、72.2g蓖麻油、2.7多羟基丙烯酸树脂(羟值为115mgKOH/g)，搅拌转速为200～300r/min，升温至50℃，在此温度下滴加105g己二异氰酸酯，20min内滴加完毕，缓慢升温至95℃，保温2～4h后降温至50℃；
(2)加入16.7g1，4-丁二醇、多羟基丙烯酸树脂、15.3g二羟甲基丙酸、50gN-甲基吡咯烷酮、0.1g二月桂酸二丁基锡，118℃保温3h；
(3)开始测NCO，当NCO值达到4.7％后，降温至30℃以下加入10.9g三乙胺和丙酮；搅拌30min，得预聚物，备用；
(4)在另一反应釜中加入645g去离子水，将搅拌器转速调整500～750r/min，保持温度稳定在20℃，将步骤(3)中所得预聚物缓慢倒入反应瓶中乳化，充分搅拌10min后，加入8.7g己二胺，继续搅拌0.5h；
(5)在温度为35～40℃、真空度0.07～0.09MPa的条件下减压蒸馏1.5～2.5h，脱除丙酮，过滤并包装，即得一种蓖麻油丙烯酸复合改性水性聚氨酯乳液，固体份含量为33％(重量)。
实施例3
一种蓖麻油丙烯酸复合改性水性聚氨酯乳液的具体制备方法步骤如下：
(1)依次在一个装有搅拌装置、温度计和通氮气保护的1000mL四口烧瓶中加入40.9g聚丙二醇(分子量2000)、77.7g蓖麻油、1.2g多羟基丙烯酸树脂(羟值为180mgKOH/g)搅拌转速为200～300r/min，升温至60℃，在此温度下滴加143g异佛尔酮二异氰酸酯，20min内滴加完毕，缓慢升温至95℃，保温2～4h后降温至50℃；
(2)加入17.9g1，4-丁二醇、16.4g二羟甲基丁酸、50gN-甲基吡咯烷酮、0.1g二月桂酸二丁基锡，118℃保温3h；
(3)开始测NCO，当NCO值达到6.2％后，降温至30℃以下加入11.8g三乙胺和丙酮，搅拌30min，得预聚物，备用；
(4)在另一反应釜中加入630g去离子水，将搅拌器转速调整500～750r/min，保持温度稳定在35℃，将步骤(3)中所得预聚物缓慢倒入反应釜中乳化，充分搅拌10min后，加入8.9g二乙烯三胺，继续搅拌0.5h；
(5)在温度为35～40℃、真空度0.07～0.09MPa的条件下减压蒸馏1.5～3.5h，脱除丙酮，过滤并包装，即得一种蓖麻油丙烯酸复合改性水性聚氨酯乳液，固体份含量为32％(重量)。
实施例4
采用上述配方和工艺制备的水性聚氨酯乳液，对其进行性能检测，并与样品作对比，如表1所示。
表1水性聚氨酯乳液的性能测试对比
由表1可以看出，蓖麻油/丙烯酸复合改性水性聚氨酯乳液在干性、硬度、光泽、耐水性、耐醇性、耐湿热性等方面均优于市售水性聚氨酯。在耐水性方面尤其突出。

Claims (10)

1.一种蓖麻油/丙烯酸复合改性水性聚氨酯乳液，其特征在于，所述的一种蓖麻油/丙烯酸复合改性水性聚氨酯乳液合成配方按重量百分比计，组成包括：8重量％～15重量％的二异氰酸酯单体；5重量％～16重量％的蓖麻油；4重量％～8重量％的大分子多元醇；0.1重量％～0.5重量％的多羟基丙烯酸树脂；1重量％～6重量％的小分子扩链剂；1重量％～5重量％的亲水性扩链剂；0.01重量％～0.1重量％的催化剂；3重量％～8重量％的助溶剂；0.4重量％～4.5重量％的中和剂；0.4重量％～3重量％的后扩链剂；57重量％～67重量％的去离子水。
2.根据权利要求1所述的一种蓖麻油/丙烯酸复合改性水性聚氨酯乳液，其特征在于，所述的二异氰酸酯单体选自：甲苯二异氰酸酯、二苯甲烷二异氰酸酯、己二异氰酸酯、异佛尔酮二异氰酸酯、三甲基己二异氰酸酯、二环己基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯、六氢甲苯二异氰酸酯中的一种或几种。
3.根据权利要求1所述的一种蓖麻油/丙烯酸复合改性水性聚氨酯乳液，其特征在于，所述的大分子多元醇选自：分子量1000～2000的聚乙二醇、分子量1000～2000的聚丙二醇、分子量1500～2500的聚碳酸酯二醇、分子量1000～2000的聚四氢呋喃中的一种或几种。
4.根据权利要求1所述的一种蓖麻油/丙烯酸复合改性水性聚氨酯乳液，其特征在于，所述的多羟基丙烯酸树脂的组成包括：40～70重量％的苯乙烯单体和30～60重量％的烯丙醇单体，通过自由基聚合反应而得到，羟值为100～230mgKOH/g。
5.根据权利要求1所述的一种蓖麻油/丙烯酸复合改性水性聚氨酯乳液，其特征在于，所述的小分子扩链剂选自：乙二醇、丙二醇、1，3-丙二醇、1，3-丁二醇、1，4-丁二醇、新戊二醇、1,6-己二醇、一缩二乙二醇、甘油、季戊四醇、二季戊四醇、三羟甲基丙烷、三羟甲基乙烷中的一种或几种；所述的亲水性扩链剂选自：二羟甲基丙酸、二羟甲基丁酸中的一种或几种。
6.根据权利要求1所述的一种蓖麻油/丙烯酸复合改性水性聚氨酯乳液，其特征在于，所述的助溶剂选自：二丙二醇二甲醚、丙酮、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、丁酮中的一种或几种。
7.根据权利要求1所述的一种蓖麻油/丙烯酸复合改性水性聚氨酯乳液，其特征在于，所述的催化剂选自：辛酸亚锡、二月桂酸二丁基锡中的一种或几种。
8.根据权利要求1所述的一种蓖麻油/丙烯酸复合改性水性聚氨酯乳液，其特征在于，所述的中和剂选自：三乙醇胺、三乙胺、正丙胺中的一种或几种。
9.根据权利要求1所述的一种蓖麻油/丙烯酸复合改性水性聚氨酯乳液，其特征在于，所述的后扩链剂选自：乙二胺、二乙烯三胺、丙二胺、己二胺、二乙醇胺中的一种或几种。
10.一种权利要求1所述的蓖麻油/丙烯酸复合改性水性聚氨酯乳液的制备方法，其特征在于，该方法包括如下步骤：
(1)预聚体的制备：按配比将计量的大分子多元醇、蓖麻油、多羟基丙烯酸树脂和催化剂加入反应瓶中，搅拌转速为200～300r/min，升温至35～50℃，在此温度下滴加二异氰酸酯单体，20min内滴加完毕，缓慢升温至55～95℃，保温2～4h后降温至50℃以下得到预聚体；
(2)扩链：向预聚体中分别加入小分子扩链剂、亲水性扩链剂、催化剂、助溶剂，搅拌并升温至90～125℃，保温3h，当-NCO含量达到2％～6.5％后，降温至30℃以下；
(3)中和：向反应体系中加入中和剂和助溶剂，搅拌0.5～1.5h后出料，得预聚物，备用；
(4)乳化：在另一反应瓶中加入计量的去离子水，将搅拌器转速调整至300～750r/min，保持温度稳定在30℃以下，将步骤(3)中所得预聚物缓慢倒入反应瓶中乳化，充分搅拌10min后，加入后扩链剂，继续搅拌0.5～1.5h；
(5)脱除溶剂：在温度为20～50℃、真空度0.07～0.1MPa的条件下减压蒸馏1.5～3.5h脱除反应中低沸点溶剂，过滤并包装，即得蓖麻油/丙烯酸复合改性水性聚氨酯乳液，该蓖麻油/丙烯酸复合改性水性聚氨酯乳液的固体份含量为30重量％～35重量％。
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