CN105949435A - 一种自阻燃型水性聚氨酯乳液及其制备方法 - Google Patents

一种自阻燃型水性聚氨酯乳液及其制备方法 Download PDF

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CN105949435A
CN105949435A CN201610506768.5A CN201610506768A CN105949435A CN 105949435 A CN105949435 A CN 105949435A CN 201610506768 A CN201610506768 A CN 201610506768A CN 105949435 A CN105949435 A CN 105949435A
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谢义鹏
许钧强
康伦国
姚东生
孙小光
周利军
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Shaoguan Union Chemical Co Ltd
Union Foshan Chemical Co Ltd
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Abstract

本发明涉及一种自阻燃型水性聚氨酯乳液，其特征在于：所述的自阻燃型水性聚氨酯乳液，是利用含有惰性卤素官能团的异氰酸酯单体，通过化学键方式把含卤素的阻燃基团固定在聚氨酯树脂结构上，不易解离，合成后的聚氨酯乳液具有自阻燃性能，制备涂料时不需要另外添加其它阻燃剂就可起到持久阻燃作用；本发明还提供一种自阻燃型水性聚氨酯乳液的制备方法。本发明制得的自阻燃型水性聚氨酯乳液具有极好的附着力、柔韧性，制成的涂膜具有耐污性、耐水性、耐碱性、耐久性、持久自阻燃性能，广泛用于木器、钢结构、建筑的阻燃涂料，既起到装饰作用，又起到保护作用。

Description

一种自阻燃型水性聚氨酯乳液及其制备方法
技术领域
本发明涉及一种水性聚氨酯乳液的制备方法，尤其涉及到一种自阻燃型水性聚氨酯乳液的制备方法，属于水性合成树指技术领域。
技术背景
国内外相继制定了严厉的环保法规来限制挥发性有机化合物(VOC)向大气排放，高性能、环保化已成为涂料发展的方向。聚氨酯树脂的合成由传统的溶剂型向水性聚氨酯转变，水性聚氨酯涂料以水为溶剂，具有无污染、安全可靠、机械性能优良、相容性好、易于改性等优点，以其耐久性和耐化学性而著名，在木器漆领域与汽车涂料领域由于其优异的性能，受到用户的青睐。
但聚氨酯乳液存在固含量较小、成膜时间长、涂层可燃点低等缺点，专利和文章中存在大量有关改性水性聚氨酯研究与应用的发表。例如，中国专利号CN201510973379.9本发明公开了一种丙烯酸酯改性水性聚氨酯乳液及其制备方法，利用丙烯酸酯对水性聚氨酯进行改性，得到综合性能优异的聚氨酯材料，利用丙烯酸酯参与反应将双键引入到聚氨酯主链，随后引发丙烯酸单体的聚合，能够形成复杂的网状结构，相比较传统水性聚氨酯来说，耐水性、耐热性、力学性能有了明显的提高。
另一方面，随着人们生活水平的提高，阻燃建筑涂料、阻燃饰面涂料受到消费者的欢迎。中国专利号CN201510667076.4公开了一种环氧树脂改性的水性聚氨酯阻燃涂料及其制备方法，通过加入阻燃剂达到涂料阻燃标准，其优点为水性聚氨酯阻燃涂料不仅涂膜硬度高、耐水性好，而且它耐火时间长、发烟量少、阻燃性好、无毒无害。但由于加入阻燃剂聚磷酸铵、三聚氰胺和季戊四醇等小分子、可溶性化合物或有害物，因此存在阻燃剂易游离于涂料表面、阻燃时效短、涂层对人体有害等缺点。
发明内容
为克服现有技术的缺点和不足，本发明的首要目的在于提供一种自阻燃型水性聚氨酯乳液。
本发明的另一目的在于提供上述一种自阻燃型水性聚氨酯乳液的制备方法，所述制备方法具有工艺简便、易于控制、聚合体系稳定、转化率高的特点。
本发明的一种自阻燃型水性聚氨酯乳液，是通过在异氰酸酯单体中引入惰性含溴官能团或含氯官能团，合成后的聚氨酯树脂中含有阻燃的卤素基团，因此不需要另加其它阻燃剂自身便可起阻燃作用，由于阻燃型卤素基团与丙烯酸树脂通过化学键结合，不易解离，因此具有持久阻燃性。
本发明制备的自阻燃型水性聚氨酯乳液应用到涂料中，不需要额外添加其它阻燃剂即可使涂料具有持久阻燃剂。
一种自阻燃型水性聚氨酯乳液制备方法如下，包括以下步骤：
a、将20.0～35.0份聚酯多元醇或聚醚多元醇、2.0～6.0份二羟甲基丙酸、15.0～40.0份含卤素官能团的异氰酸酯单体，在300～600r/min搅拌条件、氮气保护下、80～100℃反应1～2h，反应至所测得的-NCO含量达到用二正丁胺-甲苯溶液滴定所规定的理论值；
b、保持a中其他条件不变，将体系降温至60～80℃，加入30～50份的稀释剂调节体系粘度，接着加入2.0～10.0份的小分子扩链剂及0.02～0.1份的二月桂酸二丁基锡，然后用二正丁胺-甲苯溶液测定-NCO含量，当-NCO含量达到理论值时，即得到改性聚氨酯预聚物；
c、改性聚氨酯预聚物的中和、乳化、水相扩链：保持上述转速，将步骤b制得的反应体系降温到35～45℃，加入2.0～5.0份的中和剂三乙胺，中和3～10min；接着加入80.0～150.0份去离子水，之后提高转速到1000～1200r/min，稀释乳化10～30min；然后降低搅拌转速到200～500r/min，将1.0～3.0份的有机胺扩链剂溶解到20.0～40.0份的去离子水中，用10～30min将有机胺扩链剂溶液滴加到反应体系中，在水相扩链反应1～2h，然后减压蒸馏出溶剂，得到一种自阻燃型水性聚氨酯乳液。
所述的聚酯多元醇为聚己二酸丁二醇酯二元醇、聚碳酸酯二元醇或聚己内酯二元醇中的一种或几种的组合，分子量为1000～3000；所述的聚醚多元醇为聚四氢呋喃醚二醇、聚四亚甲基醚二醇，聚环氧丙烷醚二醇中的一种或几种的组合，分子量为1000～3000。
含卤素官能团的异氰酸酯单体为含有惰性溴官能团异氰酸酯单体或含有惰性氯官能团异氰酸酯单体；所述的含有惰性溴官能团的异氰酸酯单体，包括溴取代的甲苯二异氰酸酯、溴取代的二苯基甲烷二异氰酸酯；其中溴代甲苯二异氰酸酯包括单溴、二溴与三溴取代甲苯二异氰酸酯；溴代二苯基甲烷二异氰酸酯包括单溴、二溴、三溴与四溴取代的二苯基甲烷二异氰酸酯，其中多取代溴官能团的异氰酸酯单体中包括了溴取代基在苯环上所有可能位置。
所述的含有惰性氯官能团的异氰酸酯单体，包括氯取代的甲苯二异氰酸酯、氯取代的二苯基甲烷二异氰酸酯；其中氯代甲苯二异氰酸酯包括单氯、二氯与三溴氯取代甲苯二异氰酸酯；氯代二苯基甲烷二异氰酸酯包括单氯、二氯、三氯与四氯取代的二苯基甲烷二异氰酸酯，其中多取代氯官能团的异氰酸酯单体中包括了氯取代基在苯环上所有可能位置。
所述的稀释剂为丙酮、丁酮、N，N-二甲基甲酰胺、N-甲基吡咯烷酮中的一种或几种的组合。
所述的小分子扩链剂为小分子多元醇，为乙二醇、1,2-丙二醇、1,4-丁二醇、1,6-己二醇、1,5-戊二醇、三羟甲基丙烷、新戊二醇或二甘醇的一种或几种的组合。
所述的有机胺扩链剂为乙二胺，二乙烯三胺，己二胺，哌嗪的一种或几种的组合。
本发明的一种自阻燃型水性聚氨酯乳液优点，在于聚氨酯乳液合成中所用的异氰酸酯单体中含有溴官能团，一方面通过增加异氰酸酯单体的刚性改性聚氨酯树脂乳液成膜后的硬度，另一方面在聚氨酯高分子中引入阻燃型溴官能团，使聚氨酯乳液成膜后的涂层具有自阻燃型性能，且该阻燃性能由于溴原子不会游离，具有持久性。本发明制得的自阻燃型水性聚氨酯乳液具有良好的附着力、耐沾污性、耐水性、耐碱性、耐久性、持久自阻燃性能，广泛用于木器、钢结构、建筑的阻燃涂料，既起到装饰作用，又起到保护作用。
具体实施方式
实施例1
a、将20.0份聚四氢呋喃醚二醇-2000、2.0份二羟甲基丙酸、15.0份一溴甲苯二异氰酸酯、20.0份二溴甲苯二异氰酸酯，在600r/min搅拌条件、氮气保护下、80℃反应2h，反应至所测得的-NCO含量达到用二正丁胺-甲苯溶液滴定所规定的理论值；
b、保持a中其他条件不变，将体系降温至80℃，加入30.0份丁酮，接着加入2.0份的1,4-丁二醇及0.02份的二月桂酸二丁基锡，然后用二正丁胺-甲苯溶液测定-NCO含量，当-NCO含量达到理论值时，即得到溴改性聚氨酯预聚物；
c、保持上述转速，将步骤b制得的反应体系降温到35℃，加入2.0份的中和剂三乙胺，中和3min；接着加入80.0份水，之后提高转速到1200r/min，稀释乳化30min；然后降低搅拌转速到500r/min，将1.0份的乙二胺溶解到20.0份的水中，用30min将此乙二胺溶液滴加到反应体系中，在水相扩链反应2h，然后减压蒸馏出溶剂，得到一种自阻燃型水性聚氨酯乳液，记为样品1。
实施例2
a、将15.0份聚己二酸丁二醇酯二元醇-1500、10.0份聚环氧丙烷醚二醇-2100、6.0份二羟甲基丙酸、30.0份三氯二苯基甲烷二异氰酸酯，在300r/min搅拌条件、氮气保护下、80℃反应2h，反应至所测得的-NCO含量达到用二正丁胺-甲苯溶液滴定所规定的理论值；
b、保持a中其他条件不变，将体系降温至60℃，加入50.0份丙酮，接着加入10.0份的1,6-己二醇及0.1份的二月桂酸二丁基锡，然后用二正丁胺-甲苯溶液测定-NCO含量，当-NCO含量达到理论值时，即得到溴改性聚氨酯预聚物；
c、保持上述转速，将步骤b制得的反应体系降温到45℃，加入5.0份的中和剂三乙胺，中和10min；接着加入150.0份水，之后提高转速到1000r/min，稀释乳化20min；然后降低搅拌转速到200r/min，将3.0份的己二胺溶解到40.0份的水中，用10min将此己二胺溶液滴加到反应体系中，在水相扩链反应1.5h，然后减压蒸馏出溶剂，得到一种自阻燃型水性聚氨酯乳液，记为样品2。
实施例3
a、将20.0份聚己内酯二元醇、3.2份二羟甲基丙酸、20.0份三溴二苯基甲烷二异氰酸酯，在500r/min搅拌条件、氮气保护下、90℃反应2h，反应至所测得的-NCO含量达到用二正丁胺-甲苯溶液滴定所规定的理论值；
b、保持a中其他条件不变，将体系降温至70℃，加入30.0份的N-甲基吡咯烷酮，接着加入3.0份的三羟甲基丙烷及0.04份的二月桂酸二丁基锡，然后用二正丁胺-甲苯溶液测定-NCO含量，当-NCO含量达到理论值时，即得到溴改性聚氨酯预聚物；
c、保持上述转速，将步骤b制得的反应体系降温到40℃，加入3.0份的中和剂三乙胺，中和8min；接着加入120.0份水，之后提高转速到1200r/min，稀释乳化15min；然后降低搅拌转速到300r/min，将2.0份的乙二胺溶解到40.0份的水中，用20min将此乙二胺溶液滴加到反应体系中，在水相扩链反应2h，减压蒸馏出溶剂，得到一种自阻燃型水性聚氨酯乳液，记为样品3。
阻燃性能测试：将上述实施例中样品1、样品2、样品3与常规的聚氨酯乳液4，按照表1的原料配方制备成聚氨酯阻燃涂料，对应的阻燃涂料样品分别记为涂料1、涂料2、涂料3、涂料4。按照相关标准测试涂层的阻燃性能与涂料中游离未反应阻燃单体含量。
表1：涂料配方
将配置好的涂料按照GB12441-2005测试阻燃性能，测试结果如表2所示。
表2：涂层阻燃性能技术指标
由表2可以看出本发明的实施例1、实施例2、实施例3样品的阻燃性能合格，阻燃性能远远超过常规的聚氨酯乳液。
本发明的自阻燃型水性聚氨酯乳液制成的涂料，采用气相色谱法检测涂料样品中游离阻燃单体的含量，测试结果如表3所示。
表3：游离单体含量
由表3看出，用本发明的自阻燃型水性聚氨酯乳液制成的涂料，由于含卤的阻燃基团是通过化学键方式固定在树脂结构上，不易游离解析脱落，具有持久自阻燃性。
尽管本发明已作了详细说明并引用了实施例，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 (6)

1.一种自阻燃型水性聚氨酯乳液，其特征在于：所述的自阻燃型水性聚氨酯乳液，是利用含有惰性卤素官能团的异氰酸酯单体，通过化学键方式把含卤素的阻燃基团固定在聚氨酯树脂结构上，合成后的聚氨酯乳液具有自阻燃性能，制备涂料时不需要另外添加其它阻燃剂就可起到持久阻燃性能；
所述的自阻燃型水性聚氨酯乳液，其制备工艺如下：
a、将20.0～35.0份聚酯多元醇或聚醚多元醇、2.0～6.0份二羟甲基丙酸、15.0～40.0份含卤素官能团的异氰酸酯单体，在300～600r/min搅拌条件、氮气保护下、80～100℃反应1～2h，反应至所测得的-NCO含量达到用二正丁胺-甲苯溶液滴定所规定的理论值；
b、保持a中其他条件不变，将体系降温至60～80℃，加入30～50份的稀释剂调节体系粘度，接着加入2.0～10.0份的小分子扩链剂及0.02～0.1份的二月桂酸二丁基锡，然后用二正丁胺-甲苯溶液测定-NCO含量，当-NCO含量达到理论值时，即得到改性聚氨酯预聚物；
c、改性聚氨酯预聚物的中和、乳化、水相扩链：保持上述转速，将步骤b制得的反应体系降温到35～45℃，加入2.0～5.0份的中和剂三乙胺，中和3～10min；接着加入80.0～150.0份去离子水，之后提高转速到1000～1200r/min，稀释乳化10～30min；然后降低搅拌转速到200～500r/min，将1.0～3.0份的有机胺扩链剂溶解到20.0～40.0份的去离子水中，用10～30min将有机胺扩链剂溶液滴加到反应体系中，在水相扩链反应1～2h，然后减压蒸馏出溶剂，得到一种自阻燃型水性聚氨酯乳液。
2.如权利要求1所述的一种自阻燃型水性聚氨酯乳液，其特征在于：所述的聚酯多元醇为聚己二酸丁二醇酯二元醇、聚碳酸酯二元醇或聚己内酯二元醇中的一种或几种的组合，分子量为1000～3000；所述的聚醚多元醇为聚四氢呋喃醚二醇、聚四亚甲基醚二醇，聚环氧丙烷醚二醇中的一种或几种的组合，分子量为1000～3000。
3.如权利要求1所述的一种自阻燃型水性聚氨酯乳液，其特征在于：所述的含卤素官能团的异氰酸酯单体为含有惰性溴官能团异氰酸酯单体或含有惰性氯官能团异氰酸酯单体；所述的含有惰性溴官能团的异氰酸酯单体，包括溴取代的甲苯二异氰酸酯、溴取代的二苯基甲烷二异氰酸酯；所述的溴代甲苯二异氰酸酯包括单溴、二溴与三溴取代甲苯二异氰酸酯；所述的溴代二苯基甲烷二异氰酸酯包括单溴、二溴、三溴与四溴取代的二苯基甲烷二异氰酸酯；
所述的含有惰性氯官能团的异氰酸酯单体，包括氯取代的甲苯二异氰酸酯、氯取代的二苯基甲烷二异氰酸酯；所述的氯代甲苯二异氰酸酯包括单氯、二氯与三溴氯取代甲苯二异氰酸酯；所述的氯代二苯基甲烷二异氰酸酯包括单氯、二氯、三氯与四氯取代的二苯基甲烷二异氰酸酯。
4.如权利要求1所述的一种自阻燃型水性聚氨酯乳液，其特征在于：所述的稀释剂为丙酮、丁酮、N，N-二甲基甲酰胺、N-甲基吡咯烷酮中的一种或几种的组合。
5.如权利要求1所述的一种自阻燃型水性聚氨酯乳液，其特征在于：所述的小分子扩链剂为小分子多元醇为乙二醇、1,2-丙二醇、1,4-丁二醇、1,6-己二醇、1,5-戊二醇、三羟甲基丙烷、新戊二醇或二甘醇的一种或几种的组合。
6.如权利要求1所述的一种自阻燃型水性聚氨酯乳液，其特征在于：所述的有机胺扩链剂为乙二胺，二乙烯三胺，己二胺，哌嗪的一种或几种的组合。
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