CN104530371B - 一种无卤持久型阻燃水基聚氨酯及其制备方法 - Google Patents

一种无卤持久型阻燃水基聚氨酯及其制备方法 Download PDF

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CN104530371B
CN104530371B CN201410849087.XA CN201410849087A CN104530371B CN 104530371 B CN104530371 B CN 104530371B CN 201410849087 A CN201410849087 A CN 201410849087A CN 104530371 B CN104530371 B CN 104530371B
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范浩军
章培昆
田赛琦
陈意
颜俊
石碧
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Abstract

本发明属于高分子材料合成技术领域，具体涉及一种无卤持久型阻燃水基聚氨酯及其制备方法，其由下述原料重量份制成：在催化剂存在的条件下，将聚醚或聚酯二元醇60‑100份、芳香族或脂肪族二异氰酸酯30‑50份、小分子二元醇扩链剂2‑6份混合，反应2‑3h；加入含羧基的短链脂肪族二元醇4‑8份以及溶剂5‑20份，反应2‑3小时；加入含氨基的反应性膨胀型阻燃剂20‑30份和溶剂10‑30份，继续反应2‑3小时，得到以‑NCO封端的预聚体；采用4‑8份三乙胺来中和预聚体，并高速分散于去离子水中。本发明公开的无卤持久型阻燃水基聚氨酯将膨胀型阻燃剂通过化学键嵌段到水基聚氨酯结构单元中，制备工艺易于控制，性能易于调节，阻燃效果优异，适用于皮革涂饰、合成革制造、建筑材料和粘胶剂等行业。

Description

一种无卤持久型阻燃水基聚氨酯及其制备方法
技术领域
本发明属于高分子材料合成技术领域，具体涉及一种无卤持久型阻燃水基聚氨酯及其制备方法。
背景技术
水基聚氨酯以水为分散介质，具有无毒、环保、易改性、综合性能优良等优点，广泛用于皮革涂饰、合成革制造、建筑保温材料、织物涂层、墙纸和胶粘剂等行业。但水基聚氨酯含大量可燃的碳氢链段，未经阻燃处理的水基聚氨酯胶膜的极限氧指数（LOI）仅为17%左右，属于易燃材料，且燃烧后释放大量的HCN、CO等有毒气体，因而水基聚氨酯的阻燃化是水性材料发展过程亟待解决的问题之一。
中国专利CN102212181A公开了一种含溴阻燃聚醚的水性聚氨酯树脂及制备方法，并作为织物等的阻燃涂层胶，具有很好的阻燃性能和水洗牢度。但该阻燃水性聚氨酯树脂含有卤素，其在受热分解过程中会产生刺激性、腐蚀性的卤化氢有毒气体及烟雾，造成二次污染和伤害。
中国专利CN102418276A描述了一种阻燃型水性聚氨酯的制备方法，该方法将水溶性阻燃剂二乙基-N-双羟乙基-氨甲基磷酸酯高速分散于聚氨酯水溶液，所得水性聚氨酯具有较强的复合功能，抗燃性能好，产品复配协同性好。但磷酸酯类阻燃剂易水解，导致胶膜阻燃效果与力学性能下降，且外加小分子阻燃剂的方法存在添加量比较大、使用过程中易迁移析出等缺陷。
中国专利CN101781517A提供了一种阻燃型水性聚氨酯的制备方法，所得聚氨酯在阻燃性、力学性能均大幅度提高。但是，该阻燃水基聚氨酯选用四羟基磷化合物（与六亚甲基二异氰酸酯反应）为阻燃成分，分子中的四个羟基与聚氨酯反应形成交联网状结构，高官能度使聚合过程不易控制（易凝胶），过渡交联对聚氨酯涂层材料的热力学性能的调控产生不利影响。
发明内容
本发明的目的是针对上述现有技术的不足，提供一种无卤持久型阻燃水基聚氨酯及其制备方法。
本发明提供的无卤持久型阻燃水基聚氨酯，其特征在于：
（1）该阻燃水基聚氨酯将阻燃剂通过化学键嵌段到聚氨酯结构单元中，使用过程中阻燃剂不迁移析出，具有持久阻燃性；
（2）该水基聚氨酯以磷、氮为主要阻燃元素，其在受热分解时发生分子内磷-氮协效阻燃效应，在基材表面形成均匀、致密的炭质泡沫层，具有隔热、隔氧、抑烟、防滴落等作用，具有良好的阻燃性和热稳定性；
（3）该阻燃水基聚氨酯所用阻燃剂以芳杂环形式存在，其分子中的磷酸酯键形成内环结构，耐水解，制备的持久性阻燃水基聚氨酯储存稳定性优良。
本发明提供的上述无卤持久型阻燃水基聚氨酯及其制备方法，其特征在于包括以下步骤，其中所用原料均以重量份数计：
（1）将聚醚或聚酯二元醇60-100份、芳香族或脂肪族二异氰酸酯30-50份、小分子二元醇扩链剂2-6份和催化剂0.01-0.2份加入反应容器，在持续搅拌和氮气气氛保护下，升温至75-85℃反应2-3小时制得预聚体；
（2）在所得的预聚体中加入含羧基的短链脂肪族二元醇4-8份以及溶剂5-20份，并维持在75-85℃反应2-3小时，获得具有嵌段结构的预聚体；
（3）将含氨基的反应性膨胀型阻燃剂20-30份和溶剂10-30份加入（2）中所得的预聚体中，于75-85℃继续反应2-3小时，即得含有阻燃成分的以-NCO封端的预聚体；
（4）用4-8份三乙胺来中和该预聚体，在高剪切力作用下，将预聚体分散于去离子水中。
上述方法中所述的无卤持久型阻燃水基聚氨酯及其制备方法，其中以固体含量为基准计，固含量为20%-40%，羧基的质量分数为1.0%-1.5%，异氰酸根指数（R值）为1.1-1.5。
上述方法中所述的无卤持久型阻燃水基聚氨酯及其制备方法，其特征在于该方法中所用的聚醚或聚酯二元醇为数均分子量为1000-4000的聚己二酸乙二醇酯二醇、聚己二酸丙二醇酯二醇、聚丙二醇，数均分子量为1000-6000的聚己二酸丁二醇酯二醇，数均分子量为2000-6000的聚己内酯二醇、聚碳酸酯二醇或数均分子量为2000-4000的聚乙二醇、聚四氢呋喃中的一种或其组合。
上述方法中所述的无卤持久型阻燃水基聚氨酯及其制备方法，其特征在于该方法中所用的芳香族或脂肪族二异氰酸酯为异佛二酮二异氰酸酯、2,4-甲苯二异氰酸酯、4,4’-二苯甲烷二异氰酸酯、六亚甲基二异氰酸酯、对苯二异氰酸酯或碳化二亚胺和脲酮亚胺改性的4,4’-二苯甲烷二异氰酸酯中的任一种。
上述方法中所述的无卤持久型阻燃水基聚氨酯及其制备方法，其特征在于该方法中所用的小分子二元醇扩链剂为1,4-丁二醇、1,6-己二醇、1,3-丙二醇、乙二醇、二乙烯基乙二醇或一缩二乙二醇中的任一种。
上述方法中所述的无卤持久型阻燃水基聚氨酯及其制备方法，其特征在于该方法中所用的催化剂为月桂酸二丁基锡、辛酸亚锡、二甲基环己胺或二甲基环己胺中的任一种。
上述方法中所述的无卤持久型阻燃水基聚氨酯及其制备方法，其特征在于该方法中所用的含羧基的短链脂肪族二元醇为二羟甲基丙酸、二羟甲基丁酸或酒石酸中的任一种。
上述方法中所用的溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、甲乙酮和二甲基亚砜中的至少一种。
上述方法中所用的含氨基的反应性膨胀型阻燃剂具有如下结构通式，其中 为二氨基-1,3,5-三嗪衍生物。
上述方法中所用的含氨基的反应性膨胀型阻燃剂中的二氨基-1,3,5-三嗪衍生物选用2,4-二氨基-6-苯基-1,3,5-三嗪、2,4-二氨基-6-甲氧基-1,3,5-三嗪、2,4-二氨基-6-甲基-1,3,5-三嗪、2-乙烯基-4,6-二氨基-1,3,5-三嗪、2,4-二氨基-6-羟基-1,3,5-三嗪或2,4-二氨基-6-[2-(2-甲基-1-咪唑)乙基]-1,3,5-三嗪中的任一种。
上述方法中所用的含氨基的反应性膨胀型阻燃剂的具体合成路线为：
。
本发明与现有技术相比，具有以下积极效果：
（1）本发明提供的无卤持久型阻燃水基聚氨酯将阻燃剂通过化学键嵌段到聚氨酯结构单元中，解决了市面上大多数外添加型阻燃剂与水基聚氨酯配伍性差、易迁移析出和渗透等问题，使用过程中阻燃剂不迁移析出，具有持久阻燃性；
（2）本发明提供的无卤持久型阻燃水基聚氨酯选用的阻燃剂集酸源、炭源和气源“三位一体”，具有较高的磷、氮阻燃成分，无卤、低烟、低毒、环保，高温时热稳定性好，成炭率高，受热时发生分子内磷-氮协效阻燃效应，膨胀性能显著，具有良好的阻燃效果；
（3）本发明提供的无卤持久型阻燃水基聚氨酯所用的膨胀型阻燃剂以芳杂环形式存在，分子中的磷酸酯键形成内环结构，制备的阻燃水基聚氨酯具有良好的耐水解性，且胶膜的力学性能优良；
（4）本发明提供的无卤持久型阻燃水基聚氨酯制备过程中阻燃剂中的2个活性伯氨基与异氰酸酯反应形成线性大分子，工艺易于控制，性能易于调节，该阻燃水基聚氨酯可广泛应用于皮革涂饰、合成革涂层、建筑防火材料、涂料、墙纸和胶粘剂等行业。
附图说明
图1为实施例1所制备的无卤持久型阻燃水基聚氨酯与不含阻燃剂的水基聚氨酯的红外光谱对比图。
图1为无卤持久型阻燃水基聚氨酯与普通水基聚氨酯的红外光谱对比图，阻燃水基聚氨酯的红外谱图出现了几个特征吸收峰：3223cm-1和1669cm-1处为N-H的吸收峰，1578cm-1、1525cm-1和1382cm-1处是三嗪环的特征吸收峰，1260cm-1为P=O的伸缩振动吸收峰，1021cm-1处是P-O-C的伸缩振动峰，1087cm-1和778cm-1分别为P-N的伸缩振动峰和弯曲振动峰。这些特征吸收峰的出现表明本发明提供的无卤持久型阻燃水基聚氨酯的成功制备，含氨基的反应性膨胀型阻燃剂已嵌段到水基聚氨酯结构单元中。
图2为实施例1所制备的无卤持久型阻燃水基聚氨酯的热重（TG）曲线图。
图2所示TG图采用德国耐驰公司TG209F1热重分析仪测试，将约5mg真空干燥后的无卤持久型阻燃水基聚氨酯和普通水基聚氨酯样品分别放入坩埚，密封，在N2气氛下以10℃/min的升温速率从40℃加热至600℃。从图中可知，无卤持久型阻燃水基聚氨酯具有优良的高温稳定性和成炭能力，且最大热分解速率下降，说明本发明所制备的无卤持久型阻燃水基聚氨酯具有良好的阻燃效果。
具体实施方式
下面通过实施例对本发明进行具体描述，有必要在此指出的是以下实施例只是用于对本发明进行进一步的说明，不能理解为对本发明保护范围的限制，该领域的技术熟练人员可以根据上述本发明的内容做出一些非本质的改进和调整，仍属于本发明的保护范围。
值得说明的是：1）以下各实施例所得无卤持久型阻燃水基聚氨酯乳液先置于聚四氟乙烯模板中，室温下缓慢风干，再放入80℃真空干燥箱中干燥至胶膜质量不再变化，得到厚度为3.0mm的透明、无气泡、表面平整的聚氨酯乳胶膜，再进行相关测试；2）以下各实施例所得无卤持久型阻燃水基聚氨酯胶膜的极限氧指数（LOI）依据ASTM D2863-10标准进行测试，UL-94垂直燃烧性能依据ASTM D3801-10标准进行测试。
实施例1
（1）将数均分子量为2000的聚丙二醇60份、异佛二酮二异氰酸酯30份、1,4-丁二醇2份和月桂酸二丁基锡0.01份加入反应容器，在持续搅拌和氮气气氛保护下，升温至85℃反应3小时制得预聚体；
（2）在所得的预聚体中加入二羟甲基丙酸4份以及N,N-二甲基甲酰胺10份，并维持在85℃反应2小时，获得具有嵌段结构的预聚体；
（3）将季戊四醇双磷酸酯二磷酰氯缩2,4-二氨基-6-甲氧基-1,3,5-三嗪20份和N, N-二甲基甲酰胺10份加入（2）中所得的预聚体中，于85℃继续反应2小时，即得含有阻燃成分的以-NCO封端的预聚体；
（4）用4份三乙胺来中和该预聚体，在高剪切力作用下，将预聚体分散于250份去离子水中。
实施例2
（1）将数均分子量为2000的聚四氢呋喃50份、数均分子量为2000的聚碳酸酯二醇50份、六亚甲基二异氰酸酯30份、一缩二乙二醇2.5份和二甲基环己胺0.05份加入反应容器，在持续搅拌和氮气气氛保护下，升温至75℃反应2小时制得预聚体；
（2）在所得的预聚体中加入二羟甲基丁酸5份以及N,N-二甲基乙酰胺15份，并维持在75℃反应2小时，获得具有嵌段结构的预聚体；
（3）将季戊四醇双磷酸酯二磷酰氯缩2,4-二氨基-6-羟基-1,3,5-三嗪25份和二甲基亚砜20份加入（2）中所得的预聚体中，于80℃继续反应3小时，即得含有阻燃成分的以-NCO封端的预聚体；
（4）用6份三乙胺来中和该预聚体，在高剪切力作用下，将预聚体分散于360份去离子水中。
实施例3
（1）将数均分子量为4000的聚己内酯二醇100份、2,4-甲苯二异氰酸酯40份、1,6-己二醇6份和辛酸亚锡0. 2份加入反应容器，在持续搅拌和氮气气氛保护下，升温至80℃反应1.5小时制得预聚体；
（2）在所得的预聚体中加入二羟甲基丁酸6份以及N,N-二甲基乙酰胺15份，并维持在75℃反应2小时，获得具有嵌段结构的预聚体；
（3）将季戊四醇双磷酸酯二磷酰氯缩2,4-二氨基-6-苯基-1,3,5-三嗪30份和甲乙酮30份加入（2）中所得的预聚体中，于75℃继续反应2小时，即得含有阻燃成分的以-NCO封端的预聚体；
（4）用4份三乙胺来中和该预聚体，在高剪切力作用下，将预聚体分散于400份去离子水中。
实施例4
（1）将数均分子量为6000的聚己二酸丁二醇酯二醇20份、数均分子量为2000的聚己二酸丙二醇酯二醇80份、4,4’-二苯甲烷二异氰酸酯50份、二乙烯基乙二醇3份和月桂酸二丁基锡0.1份加入反应容器，在持续搅拌和氮气气氛保护下，升温至75℃反应3小时制得预聚体；
（2）在所得的预聚体中加入二羟甲基丙酸8份以及二甲基亚砜5份，并维持在75℃反应1小时，获得具有嵌段结构的预聚体；
（3）将季戊四醇双磷酸酯二磷酰氯缩2,4-二氨基-6-甲基-1,3,5-三嗪30份和N,N-二甲基甲酰胺15份加入（2）中所得的预聚体中，于75℃继续反应3小时，即得含有阻燃成分的以-NCO封端的预聚体；
（4）用8份三乙胺来中和该预聚体，在高剪切力作用下，将预聚体分散于500份去离子水中。
以下是本发明实施例1-4制得的无卤持久型阻燃水基聚氨酯的极限氧指数和垂直燃烧性能，结果见表1。
表1 无卤持久型阻燃水基聚氨酯的阻燃性能测试结果
。

Claims (7)

1.一种无卤持久型阻燃水基聚氨酯的制备方法，其特征在于包括以下步骤，其中所用原料均以重量份数计：
(1)将聚醚或聚酯二元醇60-100份、芳香族或脂肪族二异氰酸酯30-50份、小分子二元醇扩链剂2-6份和催化剂0.01-0.2份加入反应容器，在持续搅拌和氮气气氛保护下，升温至75-85℃反应2-3小时制得预聚体；
(2)在所得的预聚体中加入含羧基的短链脂肪族二元醇4-8份以及溶剂5-20份，并维持在75-85℃反应2-3小时，获得具有嵌段结构的预聚体；
(3)将含氨基的反应性膨胀型阻燃剂20-30份和溶剂10-30份加入(2)中所得的预聚体中，于75-85℃继续反应2-3小时，即得含有阻燃成分的以-NCO封端的预聚体；
(4)用4-8份三乙胺来中和该预聚体，在高剪切力作用下，将预聚体分散于去离子水中，得到无卤持久型阻燃水基聚氨酯；其中以固体含量为基准计，固含量为20％-40％，羧基的质量分数为1.0％-1.5％，异氰酸根指数(R值)为1.1-1.5；
所述步骤(3)中含氨基的反应性膨胀型阻燃剂具有如下结构通式其中为二氨基-1,3,5-三嗪衍生物；
所述二氨基-1,3,5-三嗪衍生物为2,4-二氨基-6-苯基-1,3,5-三嗪、2,4-二氨基-6-甲氧基-1,3,5-三嗪、2,4-二氨基-6-甲基-1,3,5-三嗪、2-乙烯基-4,6-二氨基-1,3,5-三嗪、2,4-二氨基-6-羟基-1,3,5-三嗪或2,4-二氨基-6-[2-(2-甲基-1-咪唑)乙基]-1,3,5-三嗪。
2.根据权利要求1所述的无卤持久型阻燃水基聚氨酯的制备方法，其特征在于该方法中所用的聚醚或聚酯二元醇为数均分子量为1000-4000的聚己二酸乙二醇酯二醇、聚己二酸丙二醇酯二醇、聚丙二醇，数均分子量为1000-6000的聚己二酸丁二醇酯二醇，数均分子量为2000-6000的聚己内酯二醇、聚碳酸酯二醇或数均分子量为2000-4000的聚乙二醇、聚四氢呋喃中的一种或其组合。
3.根据权利要求1所述的无卤持久型阻燃水基聚氨酯的制备方法，其特征在于该方法中所用的芳香族或脂肪族二异氰酸酯为异佛二酮二异氰酸酯、2,4-甲苯二异氰酸酯、4,4’-二苯甲烷二异氰酸酯、六亚甲基二异氰酸酯、对苯二异氰酸酯或碳化二亚胺和脲酮亚胺改性的4,4’-二苯甲烷二异氰酸酯中的任一种。
4.根据权利要求1所述的无卤持久型阻燃水基聚氨酯的制备方法，其特征在于该方法中所用的小分子二元醇扩链剂为1,4-丁二醇、1,6-己二醇、1,3-丙二醇、乙二醇、二乙烯基乙二醇或一缩二乙二醇中的任一种。
5.根据权利要求1所述的无卤持久型阻燃水基聚氨酯的制备方法，其特征在于该方法中所用的催化剂为月桂酸二丁基锡、辛酸亚锡、二甲基环己胺或二甲基环己胺中的任一种。
6.根据权利要求1所述的无卤持久型阻燃水基聚氨酯的制备方法，其特征在于该方法中所用的含羧基的短链脂肪族二元醇为二羟甲基丙酸、二羟甲基丁酸或酒石酸中的任一种。
7.根据权利要求1所述的无卤持久型阻燃水基聚氨酯的制备方法，其特征在于该方法中所用的溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、甲乙酮和二甲基亚砜中的至少一种。
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