CN106221551B - 阻燃、防水与低voc的聚氨酯涂料制备方法 - Google Patents
阻燃、防水与低voc的聚氨酯涂料制备方法 Download PDFInfo
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- CN106221551B CN106221551B CN201610761163.0A CN201610761163A CN106221551B CN 106221551 B CN106221551 B CN 106221551B CN 201610761163 A CN201610761163 A CN 201610761163A CN 106221551 B CN106221551 B CN 106221551B
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Abstract
本发明公开了阻燃、防水与低VOC的聚氨酯涂料制备方法，向预聚体A中加入三甲基硅醇3.5g和甲乙酮16.8g，于75℃条件下反应3.5h，加入步骤（1）制备的改性次磷酸锰7.2g、4‑羧基苯硼酸3.6g和氨三乙酸2.8g，反应温度85℃，反应时间1h，加入三乙胺14.5g进行中和反应60min，加入4,8‑二羟基喹啉‑2‑甲酸2.8g、水110g进行搅拌乳化1h，得到阻燃、防水与低VOC的聚氨酯涂料，所制备的阻燃、防水与低VOC的聚氨酯涂料环保、价格低廉，广泛应用于墙体、家具、金属器具表面，作为塑料、玻璃、造纸、纺织的粘合剂。
Description
技术领域
本发明涉及一种聚氨酯涂料的制备方法，特别涉及阻燃、防水与低VOC聚氨酯涂料制备方法。
背景技术
聚氨酯主要应用于皮革涂饰、纺织印染、造纸业、建筑涂料以及胶粘剂等领域。由于喷涂于内外墙体、家具或者金属器具表面的涂料和油漆，与人类直接或间接接触，因此有毒、有害涂料时刻威胁着人们的健康。另外，由于使用的领域常接触太阳光，而太阳光线中含有大量对有色物体有害的紫外光，其波长约290～460nm，这些有害的紫外光通过化学上的氧化还原作用，使涂料发生颜色的变化。
聚氨酯进行聚合常采用二月桂酸二丁基锡做催化剂，但由于重金属锡随着聚氨酯的降解而对环境造成危害，如何对二月桂酸二丁基锡催化残余的锡进行固定，降低聚氨酯涂料残余物对环境的危害程度，已经成为一个技术难题。
水性聚氨酯（又称水基聚氨酯）是一种在聚氨酯的分子链中含有亲水性基团的聚氨酯树脂，与水具有很强的亲和性，采用特定的工艺能使之在水中分散并形成稳定的体系。水性聚氨酯主要应用于皮革涂饰、纺织印染、造纸业、建筑涂料、胶粘剂和铸钢涂料等方面，所涉及的几乎都是易燃材料，这些材料在使用时如未经阻燃处理，必然成为引发火灾的安全隐患。水性聚氨酯的阻燃化，是水性聚氨酯功能化的重要方向之一。
聚氨酯涂料，即氨基甲酸酯涂料，其涂膜分子中含有相当数量的聚氨基甲酸酯键。聚氨酯涂料除含氨酯键以外，还含有脲键、醚键、酯键、脲基甲酸酯键，是一种性能优良、应用广泛的涂料
VOC(Volatile Organic Compounds)是指溶剂型涂料中可挥发的与人体接触或吸入后可导致疾病的溶剂。聚氨酯涂料中常含有 VOC。VOC 对人体的健康危害很大，它不但对皮肤具有侵蚀作用，而且对人体中枢神经系统、造血器官、呼吸系统有刺激和破坏作用，可引起头疼、恶心、胸闷、乏力、呕吐等症状，严重时会抽搐、昏迷甚至死亡。全球每年因使用有毒化学溶剂型涂料而造成的环境破坏和人体伤害带来的经济损失高达数百亿美元。因此，世界上主要的涂料生产国纷纷出台了限制 VOC 的排放污染法规。例如在国际上，按照欧共体生态标志产品——有关 VOC 限量的规定，人们家庭装修使用最多的一类涂料是30 g/L，我国的涂料国家强制性标准《室内装饰装修材料内墙涂料中有害物质限量》规定 VOC 不得超过 200 g/L。因此，发展低 VOC 聚氨酯涂料是聚氨酯涂料发展的方向。
发明内容
本发明所要解决的技术问题是，提供阻燃、防水与低VOC的聚氨酯涂料制备方法，并通过选择催化剂进行有效固定减轻其毒性并提高聚合产率，降低VOC含量。
本发明的技术方案如下：
1.阻燃、防水与低VOC的聚氨酯涂料制备方法，其特征在于：
（1）、改性次磷酸锰的制备：在带有搅拌器、温度计的250ml三口瓶中加入次磷酸锰11.2g、硼酸25.6g、二乙醇胺28g、六苯氧基环三磷腈7.2g和根皮甙2.8g以及水65g，调节pH到4，加热到80℃，搅拌反应2h，加入乙二胺四乙酸二钾1.6g，70℃搅拌反应1h，得到改性次磷酸锰；
（2）、在带有搅拌器、冷凝管、温度计的250ml三口瓶中加入偶氮二甲酸二苄酯0.25g、聚四氢呋喃醚二醇72g与六亚甲基二异氰酸酯18g，于70℃下反应1h，得到聚氨酯预聚体A，所述聚四氢呋喃醚二醇的分子量为500；
（3）、向预聚体A中加入0.68g六氢均三氮硼烷和8.8g甲乙酮，于70℃条件下反应3.0h，加入1g步骤（1）制备的改性次磷酸锰、3.2g4-羧基苯硼酸和N-羟基硫代琥珀酰亚胺3.5g，反应温度70℃，反应时间1h，加入7.8g三乙胺进行中和反应70min，水70g进行搅拌乳化1h，得到阻燃、防水与低VOC的聚氨酯涂料。
2. 阻燃、防水与低VOC的聚氨酯涂料制备方法，其特征在于：
（1）、改性次磷酸锰的制备：在带有搅拌器、温度计的250ml三口瓶中加入次磷酸锰5.2g、硼酸8g、二乙醇胺18g、二苯基乙醇酸14g和4-羟基苯乙胺2.9g以及水70g，调节pH到4，加热到60℃，搅拌反应2h，加入乙二胺四乙酸二钾1.6g，70℃搅拌反应2h，得到改性次磷酸锰；
（2）、在带有搅拌器、冷凝管、温度计的500ml三口瓶中加入；四甲基氯化铵0.74g、聚四氢呋喃醚二醇70g和六亚甲基二异氰酸酯30g，于80℃下反应4h，得到聚氨酯预聚体A，所述聚四氢呋喃醚二醇的分子量为1000；
（3）、向预聚体A中加入三甲基硅醇3.5g和甲乙酮16.8g，于75℃条件下反应3.5h，加入步骤（1）制备的改性次磷酸锰7.2g、4-羧基苯硼酸3.6g和氨三乙酸2.8g，反应温度85℃，反应时间1h，加入三乙胺14.5g进行中和反应60min，加入4,8-二羟基喹啉-2-甲酸2.8g、水110g进行搅拌乳化1h，得到阻燃、防水与低VOC的聚氨酯涂料。
3.阻燃、耐光性与低VOC的聚氨酯涂料制备方法，其特征在于：
（1）、改性次磷酸锰的制备：在带有搅拌器、温度计的250ml三口瓶中加入次磷酸锰8.2g、硼酸26.4g、二乙醇胺22.6g、六羟甲基三聚氰胺13g和二苯基乙醇酸2.8g以及水55g，调节pH到4，加热到80℃，搅拌反应1h，乙二胺四乙酸二钾0.9g，60℃搅拌反应2h，得到改性次磷酸锰；
（2）、在带有搅拌器、冷凝管、温度计的500ml三口瓶中，加入硬脂基三甲基氯化铵0.52g、聚四氢呋喃醚二醇80g和六亚甲基二异氰酸酯36g，于70℃下反应2h，得到聚氨酯预聚体A，所述聚四氢呋喃醚二醇的分子量为1000；
（3）、向预聚体A中加入氨三乙酸2.6g和甲乙酮21.4g，于80℃条件下反应2.5h，加入步骤（1）制备的改性次磷酸锰7.9g、4-羧基苯硼酸4.8g和二苯甲烷双马来酰亚胺3.6g，反应温度85℃，反应时间3.5h，加入三乙胺16.2g进行中和反应40min，加入水杨酸钠3.2g、水160g搅拌进行乳化1h，得到阻燃、防水与低VOC的聚氨酯涂料。
4.阻燃、防水与低VOC的聚氨酯涂料制备方法，其特征在于：
（1）、改性次磷酸锰的制备：在带有搅拌器、温度计的250ml三口瓶中加入次磷酸锰6.4g、硼酸14g、二乙醇胺23.2g、六苯氧基环三磷腈9.5g和根皮甙5.5g以及水80g，调节pH到4，加热到80℃，搅拌反应2h，加入乙二胺四乙酸二钾1.5g，50℃搅拌反应3h，得到改性次磷酸锰；
（2）、在带有搅拌器、冷凝管、温度计的250ml三口瓶中加入三乙基铝0.35g、聚四氢呋喃醚二醇60g与六亚甲基二异氰酸酯20g，于80℃下反应2h，得到聚氨酯预聚体A，所述聚四氢呋喃醚二醇的分子量为1000；
（3）、向预聚体A中加入氨三乙酸0.52g和甲乙酮9.2g，于70℃条件下反应3.5h，加入4g步骤（1）制备的改性次磷酸锰、3.6g4-羧基苯硼酸和氨基脲2.6g，反应温度80℃，反应时间1h，加入7.5g三乙胺进行中和反应30min，加入水70g进行搅拌乳化1h，得到阻燃、防水与低VOC的聚氨酯涂料。
5.阻燃、防水与低VOC的聚氨酯涂料制备方法，其特征在于：
（1）、改性次磷酸锰的制备：在带有搅拌器、温度计的250ml三口瓶中加入次磷酸锰3.2g、硼酸9g、二乙醇胺36g、三聚氰胺氰尿酸盐15g和二苯基乙醇酸3.2g以及水80g，调节pH到4，加热到70℃，搅拌反应2h，加入乙二胺四乙酸二钾1.8g，70℃搅拌反应2h，得到改性次磷酸锰；
（2）、在带有搅拌器、冷凝管、温度计的500ml三口瓶中加入异丙基氯化镁0.94g、聚四氢呋喃醚二醇100g和六亚甲基二异氰酸酯50g，于90℃下反应1h，得到聚氨酯预聚体A，所述聚四氢呋喃醚二醇的分子量为2000；
（3）、向预聚体A中加入三甲基硅醇4.2g和甲乙酮25.5g，于75℃条件下反应3.5h，加入步骤（1）制备的改性次磷酸锰9.9g、4-羧基苯硼酸7.4g和四乙烯五胺2.8g，反应温度95℃，反应时间1h，加入三乙胺15.5g进行中和反应60min，加入4,8-二羟基喹啉-2-甲酸3.7g、水75g进行搅拌乳化1h，得到阻燃、防水与低VOC的聚氨酯涂料。
本发明的优势在于：
（1）偶氮二甲酸二苄酯、四甲基氯化铵、硬脂基三甲基氯化铵、三乙基铝和异丙基氯化镁替代传统的优势在于锡化合物催化剂；
（2）N-羟基硫代琥珀酰亚胺、氨三乙酸、二苯甲烷双马来酰亚胺、氨基脲、四乙烯五胺对聚合物进行交联，改善了传统HDI聚氨酯强度不高的缺陷，同时对反应物进行螯合，增加了吸收小分子，降低了释放的VOC；
（3）六氢均三氮硼烷、三甲基硅醇、氨三乙酸不仅具有扩链剂、而且具有耐光性；
（4）六苯氧基环三磷腈、三聚氰胺氰尿酸盐、六羟甲基三聚氰胺具有阻燃作用， 根皮甙、二苯基乙醇酸对阻燃进行增效，提高其阻燃性。
具体实施方式
下面结合实例进一步说明本发明。
实例一
（1）、改性次磷酸锰的制备：在带有搅拌器、温度计的250ml三口瓶中加入次磷酸锰11.2g、硼酸25.6g、二乙醇胺28g、六苯氧基环三磷腈7.2g和根皮甙2.8g以及水65g，调节pH到4，加热到80℃，搅拌反应2h，加入乙二胺四乙酸二钾1.6g，70℃搅拌反应1h，得到改性次磷酸锰；
（2）、在带有搅拌器、冷凝管、温度计的250ml三口瓶中加入偶氮二甲酸二苄酯0.25g、聚四氢呋喃醚二醇72g与六亚甲基二异氰酸酯18g，于70℃下反应1h，得到聚氨酯预聚体A，所述聚四氢呋喃醚二醇的分子量为500；
(3）、向预聚体A中加入0.68g六氢均三氮硼烷和8.8g甲乙酮，于70℃条件下反应3.0h，加入1g步骤（1）制备的改性次磷酸锰、3.2g4-羧基苯硼酸和N-羟基硫代琥珀酰亚胺3.5g，反应温度70℃，反应时间1h，加入7.8g三乙胺进行中和反应70min，水70g进行搅拌乳化1h，得到阻燃、防水与低VOC的聚氨酯涂料。
实例二
（1）、改性次磷酸锰的制备：在带有搅拌器、温度计的250ml三口瓶中加入次磷酸锰5.2g、硼酸8g、二乙醇胺18g、二苯基乙醇酸14g和4-羟基苯乙胺2.9g以及水70g，调节pH到4，加热到60℃，搅拌反应2h，加入乙二胺四乙酸二钾1.6g，70℃搅拌反应2h，得到改性次磷酸锰；
（2）、在带有搅拌器、冷凝管、温度计的500ml三口瓶中加入；四甲基氯化铵0.74g、聚四氢呋喃醚二醇70g和六亚甲基二异氰酸酯30g，于80℃下反应4h，得到聚氨酯预聚体A，所述聚四氢呋喃醚二醇的分子量为1000；
（3）、向预聚体A中加入三甲基硅醇3.5g和甲乙酮16.8g，于75℃条件下反应3.5h，加入步骤（1）制备的改性次磷酸锰7.2g、4-羧基苯硼酸3.6g和氨三乙酸2.8g，反应温度85℃，反应时间1h，加入三乙胺14.5g进行中和反应60min，加入4,8-二羟基喹啉-2-甲酸2.8g、水110g进行搅拌乳化1h，得到阻燃、防水与低VOC的聚氨酯涂料。
实例三
（1）、改性次磷酸锰的制备：在带有搅拌器、温度计的250ml三口瓶中加入次磷酸锰8.2g、硼酸26.4g、二乙醇胺22.6g、六羟甲基三聚氰胺13g和二苯基乙醇酸2.8g以及水55g，调节pH到4，加热到80℃，搅拌反应1h，乙二胺四乙酸二钾0.9g，60℃搅拌反应2h，得到改性次磷酸锰；
（2）、在带有搅拌器、冷凝管、温度计的500ml三口瓶中，加入硬脂基三甲基氯化铵0.52g、聚四氢呋喃醚二醇80g和六亚甲基二异氰酸酯36g，于70℃下反应2h，得到聚氨酯预聚体A，所述聚四氢呋喃醚二醇的分子量为1000；
（3）、向预聚体A中加入氨三乙酸2.6g和甲乙酮21.4g，于80℃条件下反应2.5h，加入步骤（1）制备的改性次磷酸锰7.9g、4-羧基苯硼酸4.8g和二苯甲烷双马来酰亚胺3.6g，反应温度85℃，反应时间3.5h，加入三乙胺16.2g进行中和反应40min，加入水杨酸钠3.2g、水160g搅拌进行乳化1h，得到阻燃、防水与低VOC的聚氨酯涂料。
实例四
（1）、改性次磷酸锰的制备：在带有搅拌器、温度计的250ml三口瓶中加入次磷酸锰6.4g、硼酸14g、二乙醇胺23.2g、六苯氧基环三磷腈9.5g和根皮甙5.5g以及水80g，调节pH到4，加热到80℃，搅拌反应2h，加入乙二胺四乙酸二钾1.5g，50℃搅拌反应3h，得到改性次磷酸锰；
（2）、在带有搅拌器、冷凝管、温度计的250ml三口瓶中加入三乙基铝0.35g、聚四氢呋喃醚二醇60g与六亚甲基二异氰酸酯20g，于80℃下反应2h，得到聚氨酯预聚体A，所述聚四氢呋喃醚二醇的分子量为1000；
（3）、向预聚体A中加入氨三乙酸0.52g和甲乙酮9.2g，于70℃条件下反应3.5h，加入4g步骤（1）制备的改性次磷酸锰、3.6g4-羧基苯硼酸和氨基脲2.6g，反应温度80℃，反应时间1h，加入7.5g三乙胺进行中和反应30min，加入水70g进行搅拌乳化1h，得到阻燃、防水与低VOC的聚氨酯涂料。
实例五
（1）、改性次磷酸锰的制备：在带有搅拌器、温度计的250ml三口瓶中加入次磷酸锰3.2g、硼酸9g、二乙醇胺36g、三聚氰胺氰尿酸盐15g和二苯基乙醇酸3.2g以及水80g，调节pH到4，加热到70℃，搅拌反应2h，加入乙二胺四乙酸二钾1.8g，70℃搅拌反应2h，得到改性次磷酸锰；
（2）、在带有搅拌器、冷凝管、温度计的500ml三口瓶中加入异丙基氯化镁0.94g、聚四氢呋喃醚二醇100g和六亚甲基二异氰酸酯50g，于90℃下反应1h，得到聚氨酯预聚体A，所述聚四氢呋喃醚二醇的分子量为2000；
（3）、向预聚体A中加入三甲基硅醇4.2g和甲乙酮25.5g，于75℃条件下反应3.5h，加入步骤（1）制备的改性次磷酸锰9.9g、4-羧基苯硼酸7.4g和四乙烯五胺2.8g，反应温度95℃，反应时间1h，加入三乙胺15.5g进行中和反应60min，加入4,8-二羟基喹啉-2-甲酸3.7g、水75g进行搅拌乳化1h，得到阻燃、防水与低VOC的聚氨酯涂料。
下面通过相关实验数据进一步说明本发明的有益效果：PU-1是选自于无锡市波涛化工有限公司的聚氨酯防腐面漆。
表一阻燃、防水与低VOC的聚氨酯涂料所成膜性能
| 实验组 | 实例一 | 实例二 | 实例三 | 实例四 | 实例五 | PU-1 |
| 硬度 | B | B | B | B | B | B |
| 附着力/ 级 | 3 | 3 | 2 | 2 | 2 | 2 |
| 柔韧性/mm | 2 | 3 | 3 | 3 | 3 | 2 |
从表二可以发现，从膜外观、硬度、附着力、柔韧性方面性能较好。
表二阻燃、防水性与低VOC的聚氨酯涂料所得膜的力学性能
| 实验组 | 实例一 | 实例二 | 实例三 | 实例四 | 实例五 |
| 断裂伸长率/% | 158 | 169 | 145 | 132 | 198 |
| 抗张强度/MPa | 6.3 | 5.9 | 5.6 | 7.8 | 6.5 |
| 抗磨耗/级 | 4.0 | 3.5 | 4.5 | 4.5 | 4.0 |
表二中指标的检测方法参考（蒋维祺.皮革成品理化检验[M].中国轻工业出版社，1999），本发明涂料所得膜断裂伸长率、抗张强度、抗磨均表现较好。
阻燃性是通过烟密度法（最大烟密度、达到最大烟密度时间）、氧指数、垂直燃烧指标（有焰燃烧时间、无焰燃烧时间）来衡量，断裂伸长率表征其力学性能。
表三阻燃、耐光性与低VOC的聚氨酯涂料所得膜的阻燃性
| 实例一 | 实例二 | 实例三 | 实例四 | 实例五 | |
| 最大烟密度 | 13 | 27 | 26 | 17 | 8 |
| 达到最大烟密度时间/s | 180 | 195 | 195 | 240 | 180 |
| 氧指数 | 28.6 | 26.9 | 25.9 | 27.8 | 27.6 |
| 有焰燃烧时间/s | 8.5 | 8.8 | 12.6 | 10.9 | 9.2 |
| 无焰燃烧时间/s | 0.1 | 0.2 | 0.3 | 0.4 | 0 |
表三各项指标的检测分别依据如下标准：烟密度依据GB8323-2008来测定，氧指数采用GB/T5454-1997《纺织品燃烧性能试验-氧指数法》测定；有焰燃烧时间和无焰燃烧时间是由GB/T 5455-1997《纺织品燃烧能试验-垂直法》来测定。
由表三可知，本发明与耐光性聚氨酯涂料与胶粘剂所得膜燃烧时，最大烟密度显著降低，达到最大烟密度时间显著延长，氧指数明显提高，燃烧时间明显缩短。
依据 GB24408-2009外墙涂料中有害物质限量标准进行测试:
表四阻燃、防水与低VOC的聚氨酯涂料VOC
| 实例一 | 实例二 | 实例三 | 实例四 | 实例五 | |
| 挥发性有机化合物(VOC)含量 | 116 | 122 | 145 | 156 | 117 |
表五阻燃、防水与低VOC的聚氨酯涂料的其中重要性能
| 实例一 | 实例二 | 实例三 | 实例四 | 实例五 | |
| 不透水性(0.3Mpa,30min) | 不渗漏 | 不渗漏 | 不渗漏 | 不渗漏 | 不渗漏 |
| 涂膜表干时间/h | 1.5（不粘手） | 2（不粘手） | 3（不粘手） | 1.5（不粘手） | 2（不粘手） |
| 涂膜实干时间/h | 5（不粘着） | 8（不粘着） | 7（不粘着） | 6（不粘着） | 5（不粘着） |
Claims (5)
1.阻燃、防水与低VOC的聚氨酯涂料制备方法，其特征在于：
（1）、改性次磷酸锰的制备：在带有搅拌器、温度计的250ml三口瓶中加入次磷酸锰11.2g、硼酸25.6g、二乙醇胺28g、六苯氧基环三磷腈7.2g和根皮甙2.8g以及水65g，调节pH到4，加热到80℃，搅拌反应2h，加入乙二胺四乙酸二钾1.6g，70℃搅拌反应1h，得到改性次磷酸锰；
（2）、在带有搅拌器、冷凝管、温度计的250ml三口瓶中加入偶氮二甲酸二苄酯0.25g、聚四氢呋喃醚二醇72g与六亚甲基二异氰酸酯18g，于70℃下反应1h，得到聚氨酯预聚体A，所述聚四氢呋喃醚二醇的分子量为500；
(3）、向预聚体A中加入0.68g六氢均三氮硼烷和8.8g甲乙酮，于70℃条件下反应3.0h，加入1g步骤（1）制备的改性次磷酸锰、3.2g4-羧基苯硼酸和N-羟基硫代琥珀酰亚胺3.5g，反应温度70℃，反应时间1h，加入7.8g三乙胺进行中和反应70min，水70g进行搅拌乳化1h，得到阻燃、防水与低VOC的聚氨酯涂料。
2.阻燃、防水与低VOC的聚氨酯涂料制备方法，其特征在于：
（1）、改性次磷酸锰的制备：在带有搅拌器、温度计的250ml三口瓶中加入次磷酸锰5.2g、硼酸8g、二乙醇胺18g、二苯基乙醇酸14g和4-羟基苯乙胺2.9g以及水70g，调节pH到4，加热到60℃，搅拌反应2h，加入乙二胺四乙酸二钾1.6g，70℃搅拌反应2h，得到改性次磷酸锰；
（2）、在带有搅拌器、冷凝管、温度计的500ml三口瓶中加入四甲基氯化铵0.74g、聚四氢呋喃醚二醇70g和六亚甲基二异氰酸酯30g，于80℃下反应4h，得到聚氨酯预聚体A，所述聚四氢呋喃醚二醇的分子量为1000；
（3）、向预聚体A中加入三甲基硅醇3.5g和甲乙酮16.8g，于75℃条件下反应3.5h，加入步骤（1）制备的改性次磷酸锰7.2g、4-羧基苯硼酸3.6g和氨三乙酸2.8g，反应温度85℃，反应时间1h，加入三乙胺14.5g进行中和反应60min，加入4,8-二羟基喹啉-2-甲酸2.8g、水110g进行搅拌乳化1h，得到阻燃、防水与低VOC的聚氨酯涂料。
3.阻燃、耐光性与低VOC的聚氨酯涂料制备方法，其特征在于：
（1）、改性次磷酸锰的制备：在带有搅拌器、温度计的250ml三口瓶中加入次磷酸锰8.2g、硼酸26.4g、二乙醇胺22.6g、六羟甲基三聚氰胺13g和二苯基乙醇酸2.8g以及水55g，调节pH到4，加热到80℃，搅拌反应1h，乙二胺四乙酸二钾0.9g，60℃搅拌反应2h，得到改性次磷酸锰；
（2）、在带有搅拌器、冷凝管、温度计的500ml三口瓶中，加入硬脂基三甲基氯化铵0.52g、聚四氢呋喃醚二醇80g和六亚甲基二异氰酸酯36g，于70℃下反应2h，得到聚氨酯预聚体A，所述聚四氢呋喃醚二醇的分子量为1000；
（3）、向预聚体A中加入氨三乙酸2.6g和甲乙酮21.4g，于80℃条件下反应2.5h，加入步骤（1）制备的改性次磷酸锰7.9g、4-羧基苯硼酸4.8g和二苯甲烷双马来酰亚胺3.6g，反应温度85℃，反应时间3.5h，加入三乙胺16.2g进行中和反应40min，加入水杨酸钠3.2g、水160g搅拌进行乳化1h，得到阻燃、防水与低VOC的聚氨酯涂料。
4.阻燃、防水与低VOC的聚氨酯涂料制备方法，其特征在于：
（1）、改性次磷酸锰的制备：在带有搅拌器、温度计的250ml三口瓶中加入次磷酸锰6.4g、硼酸14g、二乙醇胺23.2g、六苯氧基环三磷腈9.5g和根皮甙5.5g以及水80g，调节pH到4，加热到80℃，搅拌反应2h，加入乙二胺四乙酸二钾1.5g，50℃搅拌反应3h，得到改性次磷酸锰；
（2）、在带有搅拌器、冷凝管、温度计的250ml三口瓶中加入三乙基铝0.35g、聚四氢呋喃醚二醇60g与六亚甲基二异氰酸酯20g，于80℃下反应2h，得到聚氨酯预聚体A，所述聚四氢呋喃醚二醇的分子量为1000；
（3）、向预聚体A中加入氨三乙酸0.52g和甲乙酮9.2g，于70℃条件下反应3.5h，加入4g步骤（1）制备的改性次磷酸锰、3.6g4-羧基苯硼酸和氨基脲2.6g，反应温度80℃，反应时间1h，加入7.5g三乙胺进行中和反应30min，加入水70g进行搅拌乳化1h，得到阻燃、防水与低VOC的聚氨酯涂料。
5.阻燃、防水与低VOC的聚氨酯涂料制备方法，其特征在于：
（1）、改性次磷酸锰的制备：在带有搅拌器、温度计的250ml三口瓶中加入次磷酸锰3.2g、硼酸9g、二乙醇胺36g、三聚氰胺氰尿酸盐15g和二苯基乙醇酸3.2g以及水80g，调节pH到4，加热到70℃，搅拌反应2h，加入乙二胺四乙酸二钾1.8g，70℃搅拌反应2h，得到改性次磷酸锰；
（2）、在带有搅拌器、冷凝管、温度计的500ml三口瓶中加入异丙基氯化镁0.94g、聚四氢呋喃醚二醇100g和六亚甲基二异氰酸酯50g，于90℃下反应1h，得到聚氨酯预聚体A，所述聚四氢呋喃醚二醇的分子量为2000；
（3）、向预聚体A中加入三甲基硅醇4.2g和甲乙酮25.5g，于75℃条件下反应3.5h，加入步骤（1）制备的改性次磷酸锰9.9g、4-羧基苯硼酸7.4g和四乙烯五胺2.8g，反应温度95℃，反应时间1h，加入三乙胺15.5g进行中和反应60min，加入4,8-二羟基喹啉-2-甲酸3.7g、水75g进行搅拌乳化1h，得到阻燃、防水与低VOC的聚氨酯涂料。
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Inventor after: Dong Lizhi Inventor after: Mei Shaofeng Inventor after: Zhou Zeqian Inventor after: Zheng Qi Inventor after: Li Muying Inventor before: Duan Baorong Inventor before: Di Zhiyu |
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Denomination of invention: Preparation of flame retardant, waterproof and low VOC polyurethane coatings Effective date of registration: 20200904 Granted publication date: 20180313 Pledgee: Jiaozuo chuangji high end intelligent Industrial Park Co., Ltd Pledgor: HEBEI CHENYANG INDUSTRY & TRADE Group Ltd. Registration number: Y2020980005723 |
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