CN113354790A - 一种含氟含磷水性聚氨酯材料及其制备方法 - Google Patents
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Abstract
本发明涉及一种含氟含磷水性聚氨酯材料及其制备方法,其特征在于,其主要原料组份的摩尔比为:异佛尔酮二异氰酸酯IPDI﹕聚醚多元醇PPG‑2000﹕多元醇A﹕亲水扩链剂二羟甲基丙烷DMPA=(2~5):(0~1):(0~1):(1~1.5)。本发明的含氟含磷水性聚氨酯在保持水性聚氨酯优异性能的前提下,具有超高的疏水性能,吸水率显著降低,同时交联结构增强其机械加工性能,为性能优异水性聚氨酯涂层材料提供新的选择。
Description
技术领域
本发明涉及新型含氟含磷水性聚氨酯技术领域,具体的来说,是一种含氟含磷水性聚氨酯材料及其制备方法。
背景技术
水性聚氨酯(WPU)是一类用水取代有机溶剂作为分散介质,其分散体系中没有或者只有极微量的有机溶剂的聚氨酯体系。与传统的PU相比水性聚氨酯符合发展绿色工业资源、能源、无污染的三个前提和经济(economy)、效率(effieiency)、生态(ecology)、能源(energy)的四E原则,在各个行业中有很好的发展前景。水性聚氨酯除了具有一般PU所特有的柔韧度好、强度高、抗老化和耐摩擦等的优异性能外,还具有以下的优点:1)无溶剂、无污染、成本低;2)水性聚氨酯乳液粒子直径小(10~200nm),成膜性能好在低温条件下也不用加入成膜剂助剂;3)水性聚氨酯分子软硬段的比例调控范围宽,可以根据需要制备不同性能的材料。水性聚氨酯虽然具有以上诸多优点,但是其本身仍然存在一些不可避免的缺陷:1)采用水作为分散的溶剂,导致挥发速度慢,成膜时间长;2)力学性能和热稳定性能差;3)耐候性、耐水性、耐溶剂性能差;4)对水性聚氨酯进行改性时,配套的其它型树脂的选择范围窄,不能满足需要。
WPU材料性能主要影响因素为软硬段结构、比例以及软硬断之间的相互作用,其中异氰酸酯单体和扩链剂的种类和用量决定刚性链段缔合所需的内聚能,影响硬段微区的结晶程度和软硬段相分离程度;软段低聚物多元醇(聚酯、聚醚、端羟基橡胶等)的结构和种类则赋予了聚氨酯更多的功能可设计性。然而针对上述对水性聚氨酯的缺陷,目前的科学研究大部分集中在通过对其改性而使其具有更高性能或新的功能。水性聚氨酯的改性方法包括物理改性和化学改性两种,主要有水性聚氨酯与其他聚合物材料的共混,水性聚氨酯与其它聚合物的接枝或嵌段,水性聚氨酯体系的交联,或者聚合形成互穿网络等。
合成的新型含氟含磷水性聚氨酯材料具有较好的耐水性,优异的阻燃性,热分解温度高,又具有优异的综合性能,因而可更广泛的应用于纺织、家居、汽车、航空航天等领域。
发明内容
本发明的目的之一在于提供一种新型含氟含磷水性聚氨酯材料。该材料具有耐水性好、热分解温度高、阻燃性能好和其它综合性能优异等特点;本发明的目的之二在于提供该新型含氟含磷水性聚氨酯材料的制备方法。
为实现上述目的,本发明采取如下技术方案:
一种含氟含磷水性聚氨酯材料,其特征在于,其主要原料组份的摩尔比为:
异佛尔酮二异氰酸酯IPDI﹕聚醚多元醇PPG-2000﹕多元醇A﹕亲水扩链剂二羟甲基丙烷DMPA=(2~5):(0~1):(0~1):(1~1.5)。
一种多元醇A的化学结构为:
一种含氟含磷水性聚氨酯材料的制备方法,其包含技术步骤为:
一、多元醇A的制备:
(1)将提纯后的聚二氯膦腈HDCP溶于四氢呋喃(THF)溶剂中配置成B溶液;
聚二氯膦腈HDCP在四氢呋喃(THF)溶剂中的质量分数为1~50wt.%。
(2)将八氟-1,6-己二醇溶于四氢呋喃(THF)溶剂,称取等物质的量金属钠与八氟-1,6-己二醇反应,制备八氟-1,6-己二醇钠的四氢呋喃溶液配置成C溶液;
八氟-1,6-己二醇在四氢呋喃(THF)溶剂中的质量分数为1~50wt.%。
(3)将C溶液滴加到B溶液中,氮气保护,40℃反应12~24小时;旋蒸除去有机溶剂,用去离子水和乙醇反复提纯,40~100℃真空干燥12~24小时,得到具有双侧端基为羟基的多元醇A;
C溶液与B溶液的摩尔浓度比为2:1~3:1,二者体积比为1:1。
二、含氟含磷水性聚氨酯材料的制备
经过步骤一制备所得的多元醇A与聚醚多元醇PPG-2000混合,氮气保护下,加入异佛尔酮二异氰酸酯IPDI和二月桂酸二丁基锡T12催化剂,制备预聚体,逐步添加亲水扩链剂二羟甲基丙烷DMPA、中和剂三乙胺EDA、乳化扩链剂1,4-丁二醇BDO和水,得到含氟含磷水性聚氨酯材料。
二月桂酸二丁基锡T12催化剂与异佛尔酮二异氰酸酯IPDI的摩尔比为0.001:1~0.005:1。
中和剂三乙胺EDA与亲水扩链剂二羟甲基丙烷DMPA的摩尔比为0.6:1~1:1。
乳化扩链剂1,4-丁二醇BDO与异佛尔酮二异氰酸酯IPDI的摩尔比为0.03:1~0.1:1。
水性聚氨酯固含量为20~40wt.%。
与现有技术相比:本申请的技术特点在于:
本发明制备的含氟含磷水性聚氨酯具有优异的耐水性、疏水性、阻燃性能,较好的热稳定性能以及与WPU相似的其他优异性能。
附图说明
图1为实施例1制备的多元醇A的FTIR谱图;
图2为实施例1制备的含氟含磷水性聚氨酯水接触角。
具体实施方式
为了更好地理解本发明,下面结合实施例进一步阐明本发明的内容,但本发明的内容不仅仅局限于下面的实施例。
步骤一:将提纯后的定量聚二氯膦腈(HDCP)溶于四氢呋喃(THF)溶剂中配置成B溶液。将定量八氟-1,6-己二醇溶于四氢呋喃(THF)溶剂,称取等物质的量金属钠与八氟-1,6-己二醇反应,制备八氟-1,6-己二醇钠的四氢呋喃溶液配置成C溶液。将C溶液滴加到B溶液中,氮气保护,40℃反应12~24小时。旋蒸除去有机溶剂,用去离子水和乙醇反复提纯,40~100℃真空干燥12~24小时,得到具有双侧端基为羟基的多元醇A。
实施例1
步骤二:将经过步骤a所得的多元醇A(8.9g,0.005mol)与聚醚多元醇(PPG-2000)(20g,0.015mol)在三角烧瓶内均匀混合,氮气保护下,加入异佛尔酮二异氰酸酯(IPDI)(11.67g,0.0525mol)和2-3滴二月桂酸二丁基锡(T12)催化剂,在95℃下反应2h制备预聚体。将事先真空干燥的二羟甲基丙烷(DMPA)(2.01g,0.015mol)加入三颈烧瓶内,继续反应3h。将体系温度降到30℃,加入三乙胺(TEA)(1.52g,0.015mol)中和,再加入1,4-丁二醇(BDO)(2.025g,0.0225mol)和50ml水扩链乳化0.5h,获得新型含氟含磷水性聚氨酯材料。
实施例2
步骤二:将经过步骤a所得的多元醇A(8.9g,0.008mol)与聚醚多元醇(PPG-2000)(20g,0.012mol)在三角烧瓶内均匀混合,氮气保护下,加入异佛尔酮二异氰酸酯(IPDI)(11.67g,0.0525mol)和2-3滴二月桂酸二丁基锡(T12)催化剂,在95℃下反应2h制备预聚体。将事先真空干燥的二羟甲基丙烷(DMPA)(2.01g,0.015mol)加入三颈烧瓶内,继续反应3h。将体系温度降到30℃,加入三乙胺(TEA)(1.52g,0.015mol)中和,再加入1,4-丁二醇(BDO)(2.025g,0.0225mol)和50ml水扩链乳化0.5h,获得新型含氟含磷水性聚氨酯材料。
实施例3
步骤二:将经过步骤a所得的多元醇A(8.9g,0.01mol)与聚醚多元醇(PPG-2000)(20g,0.01mol)在三角烧瓶内均匀混合,氮气保护下,加入异佛尔酮二异氰酸酯(IPDI)(11.67g,0.0525mol)和2-3滴二月桂酸二丁基锡(T12)催化剂,在95℃下反应2h制备预聚体。将事先真空干燥的二羟甲基丙烷(DMPA)(2.01g,0.015mol)加入三颈烧瓶内,继续反应3h。将体系温度降到30℃,加入三乙胺(TEA)(1.52g,0.015mol)中和,再加入1,4-丁二醇(BDO)(2.025g,0.0225mol)和50ml水扩链乳化0.5h,获得新型含氟含磷水性聚氨酯材料。
实施例4
步骤二:将经过步骤a所得的多元醇A(8.9g,0.012mol)与聚醚多元醇(PPG-2000)(20g,0.008mol)在三角烧瓶内均匀混合,氮气保护下,加入异佛尔酮二异氰酸酯(IPDI)(11.67g,0.0525mol)和2-3滴二月桂酸二丁基锡(T12)催化剂,在95℃下反应2h制备预聚体。将事先真空干燥的二羟甲基丙烷(DMPA)(2.01g,0.015mol)加入三颈烧瓶内,继续反应3h。将体系温度降到30℃,加入三乙胺(TEA)(1.52g,0.015mol)中和,再加入1,4-丁二醇(BDO)(2.025g,0.0225mol)和50ml水扩链乳化0.5h,获得新型含氟含磷水性聚氨酯材料。
实施例5
步骤二:将经过步骤a所得的多元醇A(8.9g,0.015mol)与聚醚多元醇(PPG-2000)(20g,0.005mol)在三角烧瓶内均匀混合,氮气保护下,加入异佛尔酮二异氰酸酯(IPDI)(11.67g,0.0525mol)和2-3滴二月桂酸二丁基锡(T12)催化剂,在95℃下反应2h制备预聚体。将事先真空干燥的二羟甲基丙烷(DMPA)(2.01g,0.015mol)加入三颈烧瓶内,继续反应3h。将体系温度降到30℃,加入三乙胺(TEA)(1.52g,0.015mol)中和,再加入1,4-丁二醇(BDO)(2.025g,0.0225mol)和50ml水扩链乳化0.5h,获得新型含氟含磷水性聚氨酯材料。
实施例的试验效果:
通过傅里叶变换红外光谱测试、元素分析、扫描电子显微镜测试、热重测试、拉伸测试和摩擦磨损测试对本申请的含氟含磷水性聚氨酯材料进行了表征,测试结果请参见图1和图2。
通过傅里叶红外变换红外光谱仪对多元醇A的结构进行了表征,测试结果曲线如图1所示。由图可知,波数为3000-3500cm-1是羟基特征峰;波数在1612cm-1、1520cm-1和1410cm-1处吸收峰是八氟-1,6-己二醇特征峰;波数在1250cm-1处吸收峰是N=P伸缩振动特征峰和1173cm-1处吸收峰是-CF2-特征峰,波数为927cm-1处吸收峰是P-O-(Ar)特征峰波数在881cm-1处吸收峰是P-N特征峰,据此可以判断多元醇A含有八氟和线性聚膦腈结构。
图2为实施例1含氟含磷水性聚氨酯水接触角,其中a为空白玻璃片接触角,b为涂有水性聚氨酯膜的玻璃片。接触角由原来的107°增至为约141°这说明水性聚氨酯呈现出疏水性。造成疏水的原因为F元素在疏水性中有决定性的作用。
实施例1-5所得的含氟含磷水性聚氨酯材料的耐水性测试结果如下表1所示。水性聚氨酯耐水性及耐化学性测试方法,将试样涂布于聚四氟乙烯的试板上,在室温下放置7天自然干燥成膜。将涂膜(厚度约0.4mm)裁成30mm*30mm大小,在25℃下浸入自来水或者其它介质(如甲苯)中,24小时后观察或称量其在浸入前后的质量变化。吸水率的计算方法如下:
其中,m1和m2分别为浸入前后试样的质量。
表1水性聚氨酯材料吸水率
试样 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | GB/T19250-2013 |
吸水率 | 0.77% | 0.69% | 0.58% | 0.45% | 0.38% | ≤5% |
制备的水性聚氨酯材料吸水率的结果如表1所示。可以看出随着多元醇A含量增加,水性聚氨酯吸水率越低,耐水性提高。这是由于氟元素具有高疏水性,随着多元醇A含量增加,样条疏水性越高。多元醇A含量越多,水性聚氨酯交联结构增强,减少水分子深入分子链段,同样起到增强耐水性的效果。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员,在不脱离本发明构思的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围内。
Claims (9)
1.一种含氟含磷水性聚氨酯材料,其特征在于,其主要原料组份的摩尔比为:
异佛尔酮二异氰酸酯IPDI﹕聚醚多元醇PPG-2000﹕多元醇A﹕亲水扩链剂二羟甲基丙烷DMPA=(2~5):(0~1):(0~1):(1~1.5)。
3.一种含氟含磷水性聚氨酯材料的制备方法,其特征在于,其包含技术步骤为:
一、多元醇A的制备:
(1)将提纯后的聚二氯膦腈HDCP溶于四氢呋喃(THF)溶剂中配置成B溶液;
(2)将八氟-1,6-己二醇溶于四氢呋喃(THF)溶剂,称取等物质的量金属钠与八氟-1,6-己二醇反应,制备八氟-1,6-己二醇钠的四氢呋喃溶液配置成C溶液;
(3)将C溶液滴加到B溶液中,氮气保护,40℃反应12~24小时;旋蒸除去有机溶剂,用去离子水和乙醇反复提纯,40~100℃真空干燥12~24小时,得到具有双侧端基为羟基的多元醇A;
二、含氟含磷水性聚氨酯材料的制备
经过步骤一制备所得的多元醇A与聚醚多元醇PPG-2000混合,氮气保护下,加入异佛尔酮二异氰酸酯IPDI和二月桂酸二丁基锡T12催化剂,制备预聚体,逐步添加亲水扩链剂二羟甲基丙烷DMPA、中和剂三乙胺EDA、乳化扩链剂1,4-丁二醇BDO和水,得到含氟含磷水性聚氨酯材料。
4.如权利要求3所述的一种含氟含磷水性聚氨酯材料的制备方法,其特征在于,聚二氯膦腈HDCP在四氢呋喃(THF)溶剂中的质量分数为1~50%。
5.如权利要求3所述的一种含氟含磷水性聚氨酯材料的制备方法,其特征在于,八氟-1,6-己二醇在四氢呋喃(THF)溶剂中的质量分数为1~50%。
6.如权利要求3所述的一种含氟含磷水性聚氨酯材料的制备方法,其特征在于,C溶液与B溶液的摩尔浓度比为2:1~3:1,二者体积比为1:1。
7.如权利要求3所述的一种含氟含磷水性聚氨酯材料的制备方法,其特征在于,二月桂酸二丁基锡T12催化剂与异佛尔酮二异氰酸酯IPDI的摩尔比为0.001:1~0.005:1。
8.如权利要求3所述的一种含氟含磷水性聚氨酯材料的制备方法,其特征在于,中和剂三乙胺EDA与亲水扩链剂二羟甲基丙烷DMPA的摩尔比为0.6:1~1:1。
9.如权利要求3所述的一种含氟含磷水性聚氨酯材料的制备方法,其特征在于,乳化扩链剂1,4-丁二醇BDO与异佛尔酮二异氰酸酯IPDI的摩尔比为0.03:1~0.1:1。
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