CN104262575B - 一种磷酸酯基环氧改性水性聚氨酯及其制备方法 - Google Patents
一种磷酸酯基环氧改性水性聚氨酯及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种具有阻燃作用的磷酸酯基环氧树脂改性水性聚氨酯及其制备方法，其特征在于合成原料中加入磷酸酯基聚酯多元醇。利用磷酸酯基聚酯多元醇将聚氨酯水性化，提高水性聚氨酯的阻燃性。本发明所制备的磷酸酯基环氧改性水性聚氨酯强度和硬度高、耐磨性、附着力，柔韧性能优异，尤其是阻燃性能好，是具有综合性能的环保型高分子材料。
Description
技术领域：
本发明属于聚氨酯生产技术领域，具体涉及一种基于磷酸酯基的环氧改性水性聚氨酯及其制备方法。
背景技术：
水性聚氨酯是一类能溶于水或能均匀分散在水中的高分子材料，因其以水为分散介质，零VOC排放，得到环境的认可，因其优良的性能已被广泛应用于涂料、黏合剂、涂层等行业。
然而水性聚氨酯在硬度和拉伸强度等力学性能方面仍然存在着一些缺陷，使其应用范围受到限制。环氧改性水性聚氨酯弥补了这些缺陷，环氧树脂的-OH基团与聚氨酯的-NCO基团反应时可以将支化点引入聚氨酯主链，产生环氧与聚氨酯共聚，实现化学改性。目前，环氧改性水性聚氨酯的研究已经日趋成熟，如中国发明CN201210437562，报道了一种封闭型环氧改性水性聚氨酯的制备方法，发明是以MDI、N210、DEG、DMBA为原料制备预聚体，以 E44和己内酰胺封端改性预聚体，三乙胺进行中和反应生成盐，利用乙二胺的水溶液进行乳化扩链，制得环氧改性水性聚氨酯乳液，得到的乳液涂膜具有较好的稳定性、耐水性和力学性能。
但是，现有公开涉及的论文和专利仅限于环氧改性水性聚氨酯的研制，没有具有阻燃作用的磷酸酯基环氧树脂改性水性聚氨酯制备的报道。
发明内容：
本发明提供了一种具有阻燃作用的磷酸酯基环氧树脂改性水性聚氨酯及其制备方法。
具体技术方案：
一种磷酸酯基环氧改性水性聚氨酯，主要由环氧树脂、大分子多元醇、异氰酸酯、扩链剂、交联剂、催化剂、成盐剂、水原料合成得到，其特征在于，原料还包括磷酸酯基聚酯多元醇。
其中，所述磷酸酯基聚酯多元醇的数均分子量为1000～5000，含有两个或两个以上羟基官能团，一个磷酸酯基，磷元素含量为1.0%-2.0%。其典型结构式如下：
Mn=1000-5000。
其中，所述环氧树脂为为双酚A型环氧树脂如E-44、E-51，其环氧值分别为0.44和0.51。
其中，所述大分子多元醇为聚氧化丙烯二醇、聚四氢呋喃醚二醇；聚己内酯二元醇、聚碳酸酯二醇、聚己二酸丁二醇酯二醇、聚己二酸1,6-己二醇酯二醇、聚己二酸三羟甲基丙烷酯二醇、聚己二酸乙二醇酯二醇、聚己二酸二甘醇酯二醇、聚己二酸1,2-丙二醇酯二醇、聚己二酸2-甲基丙二醇酯二醇、聚己二酸戊二醇酯二醇、聚烯烃多元醇、端羟基环氧化聚丁二烯树脂；其数均分子量优选1000～4000。
其中，所述异氰酸酯可以包括甲苯二异氰酸酯(TDI)，分子式：C9H6N2O2，分子量：174.15；二苯基甲烷二异氰酸酯(MDI)，分子式：C15H10N2O2，分子量：250.25萘二异氰酸酯(NDI)，分子式：C12H6N2O2，分子量：210.19；对苯二异氰酸酯(PPDI)，分子式：C8H4N2O2，分子量：160.13；苯二亚甲基二异氰酸酯(XDI)，分子式：C10H8N2O2，分子量：188.19；四甲基间苯二亚甲基二异氰酸酯(TMXDI)，分子式：C14H16N2O2，分子量：244.3。
其中，所述扩链剂为小分子扩链剂，具体为一缩二乙二醇、乙二醇、丙二醇、一缩二丙二醇、新戊二醇、丁二醇、己二醇、三甲基戊二醇、二羟甲基环己烷、环己二醇、丁基乙基丙二醇、二乙基戊二醇、辛二醇、庚二醇、壬二醇等。
其中，所述交联剂为三羟甲基丙烷或甘油、三羟甲基乙烷、己三醇、季戊四醇、三乙醇胺、聚氧化丙烯三醇。
其中，所述催化剂为辛酸亚锡和二月桂酸二丁锡，或有机锌盐，或有机铋盐。
其中，所述成盐剂为三乙胺、氨水、甲基乙醇胺。
一种磷酸酯基环氧改性水性聚氨酯制备方法，其特征在于包括以下步骤：
a.将10～75克大分子多元醇、1～60克环氧树脂混合，再加入40～75克异氰酸酯，在干燥氮气保护下，90～100℃反应160～180分钟，得到端异氰酸酯基环氧改性聚氨酯预聚体；
b.将环氧改性聚氨酯预聚体降温至40℃，分别加入5～20克扩链剂、0.5～3.0克交联剂、0.15～0.50克催化剂、4.0～8.0克磷酸酯基聚酯多元醇、20～50毫升丙酮，在70℃下反应100～150分钟时，再加入20～30毫升丙酮，继续反应，当总反应时间达到250～350分钟时，即得到符合设计分子量的磷酸酯基环氧改性聚氨酯；
c.将所得磷酸酯基环氧改性树脂降温到40℃，转入乳化装置中，在高速剪切下加入4.0～8.5毫升成盐剂，中和1分钟后，加入200～400克水乳化，即得到本发明的磷酸酯基环氧改性水性聚氨酯。
所述磷酸酯基环氧改性水性聚氨酯为一种半透明，泛蓝光水分散体，固含量为20%～40%、黏度为100～1000mPa·s、粒径分布在0.1～10μm。
本发明的优点在于，在环氧树脂引入聚氨酯结构中以结合二者的优点而提高聚合物的性能的基础上，利用磷酸酯聚酯多元醇将聚氨酯水性化，提高水性聚氨酯的阻燃性，并拓展其使用领域。本发明所制备的酸酯基环氧改性水性聚氨酯强度和硬度高、耐磨性、附着力，柔韧性能优异，尤其是阻燃性能好，是具有优异综合性能的环保型高分子材料，在木材涂饰、橡塑、金属涂饰等装饰领域具有广阔的应用前景。
具体实施方式：
实施例1：
将经过110℃真空脱水1小时的14.5克环氧树脂E-44和42.5克聚氧化丙烯二醇（Mn=1000）的混合溶液中加入70.3克甲苯二异氰酸酯，在80℃下反应3小时；用冰水将反应体系降温至40℃，得到端异氰酸酯基环氧改性芳香族聚氨酯预聚体。分别加入含磷聚酯二元醇7.2克，扩链剂一缩二乙二醇16.5克，交联剂三羟甲基丙烷1.3克，以及0.05克辛酸亚锡和0.1克二月桂酸二丁锡，加入40毫升丙酮以降低反应体系粘度，在70℃下反应3小时，过程中需要适当的加入配方总量2~5%丙酮来降低反应体系粘度；用冰水降低体系温度至40℃，最终得到符合设计分子量的异氰酸酯基环氧改性芳香族聚氨酯；将物料倒入乳化桶中，在高速搅拌下，加入7.4毫升三乙胺中和1分钟后，加入340克水乳化得到固含量为33%的磷酸酯基环氧改性水性聚氨酯。
所述磷酸酯基环氧改性水性聚氨酯为一种半透明，泛蓝光高分子水分散体，抗张强度(MPa)：16.8，断裂伸长率(%)：421，硬度（邵D）：42，耐盐性（5%NaCl，96h，重量增加，%）：2.7，耐水性（96h重量增加，%）：1.2，阻燃性（650℃残炭量），%：18.4。
实施例2：
将经过110℃真空脱水1小时的32.0克环氧树脂E-44和20.1克聚四氢呋喃醚二醇（Mn=1000）的混合溶液中加入67.4克苯二亚甲基二异氰酸酯，在80℃下反应3小时；用冰水将反应体系降温至40℃，分别加入含磷聚酯二元醇6.1克，扩链剂乙二醇6.6克，交联剂三羟甲基乙烷1.3克，以及0.05克辛酸亚锡和0.1克二月桂酸二丁锡，加入45毫升丙酮以降低反应体系粘度，在70℃下反应4小时，过程中需要适当的加入丙酮来降低反应体系粘度；用冰水降低体系温度至40℃，并将物料倾倒入乳化桶中，在高速搅拌下，加入6.1毫升三乙胺中和1分钟后，加入285克水乳化得到磷酸酯基环氧改性水性聚氨酯。
所述磷酸酯基环氧改性水性聚氨酯为一种半透明，泛蓝光非电解质高分子水分散体，抗张强度(MPa)：19.8，断裂伸长率(%)：306，硬度（邵D）：52，耐盐性（5%NaCl，96h，重量增加，%）：2.3，耐水性（96h重量增加，%）：1.0，阻燃性（650℃残炭量），%：14.7。
实施例3：
将经过110℃真空脱水1小时的24.8克环氧树脂E-51，32.1克聚己二酸乙二醇酯二醇（Mn=2000）和31.2克聚己二酸1,6-己二醇酯二醇（Mn=2000）的混合溶液中加入48.8克萘二异氰酸酯，在80℃下反应3小时；用冰水将反应体系降温至40℃，分别加入含磷聚酯二元醇7.8克，新戊二醇7.2克，己二醇4.4克，交联剂聚氧化丙烯三醇（Mn=300）3.2克，以及0.05克辛酸亚锡和0.1克有机铋，加入40毫升丙酮以降低反应体系粘度，在70℃下反应4小时，过程中需要适当的加入丙酮来降低反应体系粘度；用冰水降低体系温度至40℃，并将物料倾倒入乳化桶中，在高速搅拌下，加入8.1毫升三乙胺中和1分钟后，加入360克水乳化得到磷酸酯基环氧改性水性聚氨酯。
所述磷酸酯基环氧改性水性聚氨酯为一种半透明，泛蓝光非电解质高分子水分散体，抗张强度(MPa)：23，断裂伸长率(%)：220，硬度（邵D）：48，耐盐性（5%NaCl，96h，重量增加，%）：1.8，耐水性（96h重量增加，%）：1.1，阻燃性（650℃残炭量），%：19.8。
实施例4：
将经过110℃真空脱水1小时的31.1克环氧树脂E-44，57.0克聚碳酸酯二醇（Mn=2000）的混合溶液中加入22.2克四甲基间苯二亚甲基二异氰酸酯和21.2克二甲基联苯二异氰酸酯混合物，在80℃下反应3小时；用冰水将反应体系降温至40℃，分别加入含磷聚酯二元醇7.2克，1,4-丁二醇4.8克，三甲基戊二醇3.3克，季戊四醇1.7克，以及0.12克辛酸亚锡和0.28克有机锌，加入40毫升丙酮以降低反应体系粘度，在70℃下反应4小时，过程中需要适当的加入丙酮来降低反应体系粘度；用冰水降低体系温度至40℃，并将物料倾倒入乳化桶中，在高速搅拌下，加入9.1毫升三乙胺中和1分钟后，加入380克水乳化得到磷酸酯基环氧改性水性聚氨酯。
所述磷酸酯基环氧改性水性聚氨酯为一种半透明，泛蓝光高分子水分散体，抗张强度(MPa)：21.5，断裂伸长率(%)：243，硬度（邵D）：54，耐盐性（5%NaCl，96h，重量增加，%）：1.2，耐水性（96h重量增加，%）：0.6，阻燃性（650℃残炭量），%：16.1。
实施例5：
将经过100℃真空脱水1小时的34.2克环氧树脂E-44，2.1克聚氧化丙烯二醇（Mn=1000）和22.3克聚己内酯（Mn=2000）的混合溶液中加入46.8克四甲基间苯二亚甲基二异氰酸酯，在80℃下反应3小时；用冰水将反应体系降温至40℃，分别加入含磷聚酯二元醇5.3克，一缩二丙二醇10.5克，三羟甲基丙烷0.8克，以及0.05克辛酸亚锡和0.10克二月桂酸二丁锡，加入25毫升丙酮以降低反应体系粘度，在70℃下反应4小时，过程中需要适当的加入丙酮来降低反应体系粘度；用冰水降低体系温度至40℃，并将物料倾倒入乳化桶中，在高速搅拌下，加入5.3毫升三乙胺中和1分钟后，加入320克水乳化得到磷酸酯基环氧改性水性聚氨酯。
所述磷酸酯基环氧改性水性聚氨酯为一种半透明，泛蓝光高分子水分散体，抗张强度(MPa)：19.2，断裂伸长率(%)：386，硬度（邵D）：43，耐盐性（5%NaCl，96h，重量增加，%）：2.6，耐水性（96h重量增加，%）：2.1，阻燃性（650℃残炭量），%：12.7。
其主要性能指标：
| 测试项目 | 测试数据 |
| pH | 6～8 |
| 抗张强度(MPa) | 18～32 |
| 断裂伸长率(%) | 100～420 |
| 100%模量(MPa) | 12～24 |
| 硬度（邵D） | 40～60 |
| 耐盐性（5%NaCl，96h）重量增加，% | 1.8～3.1 |
| 耐水性（96h）重量增加，% | 0.2～1.6 |
| 阻燃性（650℃残炭量），% | 8.0～22.2 |
由表中数据可以看出，本发明所制备的磷酸酯基环氧改性水性聚氨酯树脂是阴离子体系，与碱性和中性树脂能混配使用，强度大，耐磨性、附着力及硬度性能优异，阻燃性好，耐高低温、耐化学品，尤其是阻燃性好，是综合性能好的环保型高分子材料，可以广泛应用于木材涂饰、橡塑、金属涂饰等装饰领域。
Claims (1)
1.一种磷酸酯基环氧改性水性聚氨酯制备方法，主要由环氧树脂、大分子多元醇、异氰酸酯、扩链剂、交联剂、催化剂、成盐剂、水原料合成得到，上述原料中还包括磷酸酯基聚酯多元醇，所述磷酸酯基聚酯多元醇的数均分子量为1000 ～ 5000，含有两个或两个以上羟基官能团，一个磷酸酯基，磷元素含量1.0%-2.0%；
其特征在于包括以下步骤：
a. 将10 ～ 75 克大分子多元醇、1 ～ 60 克环氧树脂混合，再加入40 ～ 75 克异氰酸酯，在干燥氮气保护下，90 ～ 100℃反应160 ～ 180 分钟，得到端异氰酸酯基环氧改性聚氨酯预聚体；
b. 将环氧改性聚氨酯预聚体降温至40℃，分别加入5 ～ 20 克扩链剂、0.5 ～ 3.0 克交联剂、0.15 ～ 0.50 克催化剂、4.0 ～ 8.0 克磷酸酯基聚酯多元醇、20 ～ 50 毫升丙酮，在70℃下反应100 ～ 150 分钟时，再加入20 ～ 30 毫升丙酮，继续反应，当总反应时间达到250 ～350 分钟时，即得到符合设计分子量的磷酸酯基环氧改性聚氨酯；
c. 将所得磷酸酯基环氧改性树脂降温到40℃，转入乳化装置中，在高速剪切下加入4.0 ～ 8.5 毫升成盐剂，中和1 分钟后，加入200 ～ 400 克水乳化，即得到磷酸酯基环氧改性水性聚氨酯。
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| CN108264624A (zh) * | 2018-01-18 | 2018-07-10 | 成都利亨聚氨酯新材料有限公司 | 聚氨酯组合聚醚、聚氨酯硬质泡沫及其制备方法 |
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