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CN111662423A - 一种羟基功能化水性聚氨酯的制备方法 - Google Patents

一种羟基功能化水性聚氨酯的制备方法 Download PDF

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Publication number
CN111662423A
CN111662423A CN202010548808.9A CN202010548808A CN111662423A CN 111662423 A CN111662423 A CN 111662423A CN 202010548808 A CN202010548808 A CN 202010548808A CN 111662423 A CN111662423 A CN 111662423A
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China
Prior art keywords
waterborne polyurethane
hydroxyl
reaction
glycol
carboxyl
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CN202010548808.9A
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English (en)
Inventor
王军威
李晓云
亢茂青
李其峰
赵雨花
梁辰
冯月兰
殷宁
张清运
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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Priority to CN202010548808.9A priority Critical patent/CN111662423A/zh
Publication of CN111662423A publication Critical patent/CN111662423A/zh
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Abstract

本发明属于水性聚氨酯的制备方法及应用技术领域，具体涉及一种羟基功能化水性聚氨酯的制备方法。将多元醇聚合物及含羧基亲水剂脱水，加入反应器中，搅拌均匀后加入异氰酸酯化合物，反应得到水性聚氨酯预聚体；之后向水性聚氨酯预聚体中加入小分子二元醇及溶剂继续反应后降至室温；最后向上述反应产物中加入成盐剂，室温下搅拌反应后滴加去离子水乳化，之后加入扩链剂及羟基功能化单体，强烈搅拌并加热反应。反应结束后，通过减压蒸馏脱除溶剂即得羟基功能化水性聚氨酯。本发明环保无毒，经济性强，将羟基功能化单体引入水性聚氨酯中可利用羟基提高聚氨酯体系内的氢键作用；羟基作为活性基团可与其他化合物发生交联、接枝等反应改性水性聚氨酯。

Description

一种羟基功能化水性聚氨酯的制备方法
技术领域
本发明属于水性聚氨酯的制备方法及应用技术领域，具体涉及一种羟基功能化水性聚氨酯的制备方法。
背景技术
聚氨酯是一类分子结构中含有重复的氨基甲酸酯基团(-NHCOO-)的聚合物，一般由多元醇、异氰酸酯化合物和小分子扩链剂经加聚反应生成，因其具有优异的综合性能，可用作涂料、胶黏剂、泡沫、纤维等而得到广泛应用。目前应用较多的聚氨酯涂料和胶黏剂多为溶剂型，但由于有机溶剂毒性较大，在生产及产品应用过程中都会对人员健康及环境安全带来不利影响；另一方面，有机溶剂的使用会造成产品成本升高，不利于其应用推广。近年来，随着环境法规的日趋严格，以水为分散介质的水性聚氨酯以其低VOC排放、无毒且不燃而为人们所重视。
水性聚氨酯按其结构可分为离子型和非离子型，其中离子型水性聚氨酯应用更为普遍。随着水性聚氨酯应用领域的不断拓展，对其性能的要求也越来越高。为了更好地提高水性聚氨酯的综合性能，满足应用需求，功能化水性聚氨酯成为近年来的研究热点，国内外对功能化水性聚氨酯的探索主要包括分子结构功能化、共聚功能化及共混功能化等几种。
GE等利用二端羟丁基聚二甲基硅氧烷与改性后的亲水性二异氰酸酯反应制备出有机硅功能化双组份水性聚氨酯，由于引入Si-O-Si的交联网状结构，所得聚氨酯具有良好的热稳定性，耐热性显著提高。(Ge Zhen,Luo Yunjun.Progress in Organic Coatings,2013,76(11):1522-1526.)
MA等先以聚丙烯碳酸酯作为软段合成水性聚氨酯前驱体，再将聚丙烯酸酯单体与水性聚氨酯前驱体结合制备了丙烯酸酯功能化水性聚氨酯，聚氨酯薄膜的附着力、铅笔硬度、耐水性及热性能均有显著提高。(Ma Le,Song Lina,Li Fang,et al.Colloid&PolymerScience,2017,295(12):2299-2307.)
纳米材料功能化水性聚氨酯是一种新的共混功能化方法，所用纳米材料主要包括(1)纳米矿类黏土，包括蒙脱土、纳米SiO2、凹凸棒土等；(2)纳米碳材料，主要为石墨烯、碳纳米管、炭黑等；(3)纳米金属氧化物材料，包括纳米ZnO、纳米Fe3O4、纳米TiO2、纳米银等。DU等制备了聚4-苯乙烯磺酸钠改性处理的炭黑，并在pH值为5条件下与水性聚氨酯乳液聚合制备纳米炭黑功能化水性聚氨酯。探讨了炭黑用量对纳米炭黑功能化水性聚氨酯的结构和性能影响，通过SEM等研究杂化膜的物理化学性能，实验结果表明炭黑在水性聚氨酯乳液中呈现很好的分散性，纳米炭黑功能化水性聚氨酯的热稳定性和力学性能较纯水性聚氨酯有显著提高。(Di Yifan,Shi Pengwei,Li Qiuying,et al.Colloids and SurfacesA:Physicochemical and EngineeringAspects,2014,454:1-7.)
目前，对于功能化水性聚氨酯的研究主要集中在增强增韧、提高耐热性、耐水性，以及赋予材料电、光、磁等性能，其方式方法已有许多报道，但在聚氨酯制备时为了提高交联度和力学性能，多采用异氰酸酯过量的方法，整个体系中羟基含量很低甚至不含羟基，关于羟基功能化水性聚氨酯的报道很少。本发明旨在通过羟基功能化单体和不同的原料体系反应提供一种羟基功能化水性聚氨酯的制备方法，一方面可以利用羟基来提高聚氨酯体系内的氢键作用，进而提高水性聚氨酯的内聚力、抗渗透性、耐水性及粘接性能等；另一方面，羟基作为活性基团可进一步参与反应便于水性聚氨酯的改性。
发明内容
本发明的目的是提供一种羟基功能化水性聚氨酯，羟基能够赋予水性聚氨酯新的性能，此外，活性基团羟基与其他化合物如：脲甲醛树脂、密胺甲醛树脂、二醛类(乙二醛、戊二醛)以及无机盐如：硼化物(硼酸、硼酸钠)、含有钛、锆、钒、铬等无机物交联反应进一步改性聚氨酯。
为了达到上述目的，本发明采用了下列技术方案：通过羟基功能化单体的引入制备羟基功能化水性聚氨酯，借助功能化羟基赋予水性聚氨酯新的性能和反应活性：
一种羟基功能化水性聚氨酯的制备方法，包括以下步骤：
步骤1，将聚合物多元醇、含羧基亲水剂脱水，加入反应器中，搅拌均匀后加入异氰酸酯化合物，反应得到水性聚氨酯预聚体；
步骤2，向水性聚氨酯预聚体中加入小分子二元醇及溶剂，继续反应后降至室温；
步骤3，向步骤2的反应体系中加入成盐剂，室温下搅拌反应后，加去离子水乳化，之后加入扩链剂和羟基功能化单体，强烈搅拌后加热反应，反应结束后，通过减压蒸馏脱除溶剂，即制得羟基功能化水性聚氨酯。
由于聚氨酯是一种软硬段交互连接的嵌段聚合物，羟基功能化水性聚氨酯分子结构中的硬段主要由异氰酸酯化合物和扩链剂、羟基功能化单体组成，软段由聚合物多元醇组成，硬段、软段分子结构及交联度等对水性聚氨酯的性能有显著影响。因此，通过调整聚合物多元醇、异氰酸酯、扩链剂及羟基功能化单体的结构、分子量及比例，可以调节水性聚氨酯结构，赋予水性聚氨酯材料不同的性能以满足各种应用需求。
进一步，所述步骤1中聚合物多元醇为聚酯二醇、聚醚二醇或聚碳酸酯二醇中的一种或几种按任意比混合。其中，聚酯二醇结晶性好，所得水性聚氨酯粘接强度及拉伸强度高；聚醚二醇醚键内聚能较低、易于旋转，所得水性聚氨酯柔顺性及耐水解性能高；聚碳酸酯二醇含有碳酸酯基团，内聚能高，所得水性聚氨酯机械强度及耐油性好；不同结构聚合物多元醇混合对水性聚氨酯结构及性能有不同的影响。
所述聚酯二醇为聚己二酸乙二醇酯、聚己二酸丁二醇酯、聚己二酸乙二醇-丙二醇酯、聚己二酸乙二醇-丁二醇酯、聚己二酸己二醇酯、聚己二酸戊二醇酯、聚己二酸乙二醇-新戊二醇、聚ε-己内酯二醇中的一种或几种按任意比混合，不同结构聚酯二醇对水性聚氨酯结构及性能有不同的影响；
所述聚醚二醇为聚氧化丙烯二醇、聚乙二醇醚、聚丙二醇醚、聚四亚甲基醚二醇、聚氧化乙烯二醇、聚丁二烯多元醇等中的一种或几种按任意比混合，不同结构聚醚二醇对水性聚氨酯结构及性能有不同的影响；
所述聚碳酸酯二醇为聚碳酸己二醇酯、聚碳酸戊二醇酯、聚碳酸丁二醇酯中的一种或几种按任意比混合，不同结构聚碳酸酯二醇对水性聚氨酯结构及性能有不同的影响。
进一步，所述聚酯二醇、聚醚二醇或聚碳酸酯二醇的分子量优化为1000～2000。聚合物多元醇分子量过高，所得水性聚氨酯软段含量较多，拉伸强度较差；分子量低，所得水性聚氨酯较脆、伸长率较差。
进一步，所述步骤1中所述含羧基的亲水剂为2,2-二羟甲基丙酸、二羟基半酯和二氨基苯甲酸中的一种或几种按任意比混合，羧基作为亲水性基团可以提高水性聚氨酯在水中分散性。
进一步，所述步骤1中所述异氰酸酯化合物为甲苯二异氰酸酯、二苯基甲烷二异氰酸、对苯二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、4,4’-亚甲基双(环己基异氰酸酯)、间四亚甲基二甲苯二异氰酸酯中的一种或几种按任意比混合，不同结构异氰酸酯化合物对水性聚氨酯结构及性能有不同的影响。
进一步，所述步骤2中小分子二元醇为乙二醇、1,2-丙二醇、1,4-丁二醇、1,5-戊二醇、新戊二醇、1,6-己二醇、1,8-辛二醇、二甘醇中的一种或几种按任意比混合，小分子二元醇能够增加水性聚氨酯硬段含量，改变水性聚氨酯结构及性能。
进一步，所述步骤2中溶剂为丙酮、丁酮、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、甲基乙基酮、乙二醇单丁醚中的一种或几种按任意比混合，溶剂有助于水性聚氨酯黏度降低从而增加其分散性能。
进一步，所述步骤3中成盐剂为三乙胺、三丙胺、三丁胺、氢氧化钠和氨水中的一种或几种按任意比混合，成盐剂用于中和亲水剂从而进一步增加水性聚氨酯乳液稳定性。
进一步，所述步骤3中扩链剂为乙二胺、二乙烯三胺、三乙烯四胺、乙二醇、丙二醇、1,4-丁二醇、二甘醇、新戊二醇、1,6-己二醇、N,N-双(2-羟乙基)乙二胺中的一种或几种按任意比混合，不同结构扩链剂对水性聚氨酯结构及性能有不同的影响。
进一步，所述步骤3中羟基功能化单体为结构中含有羟基、伯胺基的多羟基多胺基醇胺化合物或多羟基化合物中的一种或几种按任意比混合，其结构通式如下：
Figure BDA0002541700720000051
羟基功能化单体一方面可以参与水性聚氨酯预聚体扩链反应，接入到水性聚氨酯分子主链中，另一方面可以提供功能性基团羟基从而改变水性聚氨酯性能及反应活性。
进一步，所述结构中含有羟基、伯胺基的多羟基多胺基醇胺化合物或多羟基化合物为2-羟基-1,3-丙二胺、3,3’-二羟基联苯胺、四乙羟基己二酰二胺、1,6-二氢-1-羟基-吡咯并[2,3-b]吡咯-2,3-二胺、丙三醇，或环碳酸酯与过量胺开环反应生成含β-羟基、氨酯基及胺基的多羟基多胺基醇胺化合物中的一种或几种按任意比混合。
所述开环反应为：
Figure BDA0002541700720000061
不同结构羟基功能化单体对水性聚氨酯结构及性能有不同的影响。
进一步，所述步骤1中聚合物多元醇与含羧基亲水剂摩尔比0.5～2:1，异氰酸酯化合物与聚合物多元醇和含羧基亲水剂总摩尔数之比1.8～3.5:1。由此所得水性聚氨酯软硬段比例合适，硬段间存在一定程度微相分离，所得水性聚氨酯胶膜拉伸强度、断裂伸长率、耐水性、粘接强度等性能较好。
进一步，所述步骤2中小分子二元醇用量为步骤1过量异氰酸酯化合物摩尔量的0.6～0.8倍；所述溶剂占上述聚合物多元醇、含羧基亲水剂物、异氰酸酯化合物质和小分子二元醇总质量的15％～30％。由此所得水性聚氨酯硬段增加，性能提高；黏度适中，利于在水中进行分散。
进一步，所述步骤3中成盐剂用量与含羧基亲水剂的摩尔比为1:1；所述去离子水用量按固含量计算，固含量控制在20％～45％；所述扩链剂和羟基功能化单体总用量与上述步骤反应后剩余异氰酸酯基团摩尔数相同，其中扩链剂和羟基功能化单体的摩尔比为0～99:100～1。成盐剂用量过多，会催化水性聚氨酯成膜过程中副反应，影响其活化期及胶膜外观，成盐剂用量过少，所得水性聚氨酯乳液稳定性较差。
进一步，所述步骤1中聚合物多元醇脱水的条件为减压100～140℃下脱水2～4h，含羧基亲水剂脱水的条件为在100～140℃下干燥箱中烘干10～14h脱水；所述反应的温度为70～95℃，时间为2～5h。
进一步，所述步骤2中继续反应的温度为50～65℃，时间为2～5h。
进一步，所述步骤3中室温下搅拌反应的时间为0.5～1h，所述强烈搅拌的时间为0.1～0.5h，加热反应的温度为40～55℃，时间为0.5～1h。
本发明对所得水性聚氨酯材料依据下述标准进行测试。
性能测试标准：
(1)耐水、耐溶剂性测试
将制备出的聚氨酯材料浸泡于去离子水中于25℃下放置并称量样品质量变化情况，至恒重时按下式计算样品的溶胀度：
Figure BDA0002541700720000071
S表示溶胀度，m0表示初始质量，m1是溶胀后达到恒重的重量。
(2)机械性能
按照标准GB1039-92中的规定制备哑铃型的样品进行测试，拉伸强度执行GB/T528-1998标准，断裂伸长率执行GB528-82标准，测试条件为：室温25℃,湿度55％。
(3)粘接性能
粘接强度按国标GB/T2791-1995测试其T-剥离强度，测试条件为：室温25℃,湿度55％。
(4)储存稳定性
将水性聚氨酯乳液放入密封的容器内在室温下放置，观察分散液的变化，不分层、不凝固即为储存稳定性好。
与现有技术相比本发明具有以下优点：
1、得到新型功能水性聚氨酯——羟基功能化水性聚氨酯，提高水性聚氨酯的内聚力、抗渗透性、耐水性及粘接性能等；
2、所得羟基功能化水性聚氨酯含有活性基团羟基，可进一步与其他化合物发生交联反应改性水性聚氨酯；
3、制备工艺简单、易操作，产品储存稳定性好。
具体实施方式
实施例1
一种羟基功能化水性聚氨酯的制备方法，包括以下步骤：
步骤1，将10g聚己二酸丁二醇酯(Mn＝1000)140℃下减压脱水2h，0.67g二羟甲基丙酸140℃下干燥箱中烘干10h脱水后加入反应器中，搅拌均匀后加入4.70g甲苯二异氰酸酯，在70℃反应4h得水性聚氨酯预聚体，其中过量甲苯二异氰酸酯2.09g；
步骤2，向水性聚氨酯预聚体中加入0.65g1,4-丁二醇及15％溶剂丙酮(占上述聚合物多元醇、含羧基亲水剂物、异氰酸酯化合物质和小分子二元醇总质量分数)在50℃继续反应3.5h后降至室温；
步骤3，向上述反应产物中加入0.51g三乙胺中和二羟甲基丙酸，室温下搅拌0.5h后按固含量为20％滴加去离子水乳化，之后加入0.43g羟基功能化单体2-羟基-1,3-丙二胺，强烈搅拌6min后加热至40℃反应1h。反应结束后，通过减压蒸馏脱除所加溶剂即得羟基功能化水性聚氨酯乳液。
乳液在室温下储存一年不分层，将所得水性聚氨酯乳液干燥制片后进行性能测试，胶膜拉伸强度为29.5MPa，断裂伸长率为565％，在水中浸泡达到溶胀平衡后溶胀度为12.03％，对基材PVC的24h终粘强度为2.75N/mm。
实施例2
一种羟基功能化水性聚氨酯的制备方法，包括以下步骤：
步骤1，将20g聚四亚甲基醚二醇(Mn＝2000)100℃下减压脱水4h，1.52g二氨基苯甲酸100℃下干燥箱中烘干14h脱水后加入反应器中，搅拌均匀后加入15.54g异佛尔酮二异氰酸酯，在75℃反应3.5h得水性聚氨酯预聚体，其中过量异佛尔酮二异氰酸酯11.10g；
步骤2，向水性聚氨酯预聚体中加入2.48g乙二醇及30％溶剂丁酮(占上述聚合物多元醇、含羧基亲水剂物、异氰酸酯化合物质和小分子二元醇总质量分数)在55℃继续反应2.5h后降至室温；
步骤3，向上述反应产物中加入1.43g三丙胺中和二氨基苯甲酸，室温下搅拌0.6h后按固含量为45％滴加去离子水乳化，之后加入0.30g扩链剂丙二醇及1.30g羟基功能化单体3,3’-二羟基联苯胺，强烈搅拌30min后加热至50℃反应0.7h。反应结束后，通过减压蒸馏脱除所加溶剂即得羟基功能化水性聚氨酯乳液。
乳液在室温下储存一年不分层，将所得水性聚氨酯乳液干燥制片后进行性能测试，胶膜拉伸强度为25.0MPa，断裂伸长率为756％，在水中浸泡达到溶胀平衡后溶胀度为11.25％，对基材PVC的24h终粘强度为2.68N/mm。
实施例3
一种羟基功能化水性聚氨酯的制备方法，包括以下步骤：
步骤1，将15g聚碳酸己二醇酯(Mn＝1500)120℃下减压脱水3h，0.94g二羟甲基丙酸120℃下干燥箱中烘干12h脱水后加入反应器中，搅拌均匀后加入10.63g二苯基甲烷二异氰酸酯，在80℃反应2.5h得水性聚氨酯预聚体，其中过量二苯基甲烷二异氰酸酯6.38g；
步骤2，向水性聚氨酯预聚体中加入1.36g1,2-丙二醇及21％溶剂乙二醇单丁醚(占上述聚合物多元醇、含羧基亲水剂物、异氰酸酯化合物质和小分子二元醇总质量分数)在65℃继续反应2h后降至室温；
步骤3，向上述反应产物中加入1.30g三丁胺中和二羟甲基丙酸，室温下搅拌1h后按固含量为35％滴加去离子水乳化，之后加入0.32g扩链剂乙二醇及0.55g羟基功能化单体3,3’-二羟基联苯胺和1.08g2-羟基-1,3-丙二胺，强烈搅拌10min后加热至55℃反应0.5h。反应结束后，通过减压蒸馏脱除所加溶剂即得羟基功能化水性聚氨酯乳液。
乳液在室温下储存一年不分层，将所得水性聚氨酯乳液干燥制片后进行性能测试，胶膜拉伸强度为30.2MPa，断裂伸长率为555％，在水中浸泡达到溶胀平衡后溶胀度为13.79％，对基材PVC的24h终粘强度为3.05N/mm。
实施例4
一种羟基功能化水性聚氨酯的制备方法，包括以下步骤：
将10g聚ε-己内酯二醇(Mn＝1000)115℃下减压脱水3.1h，0.91g个二氨基苯甲酸125℃下干燥箱中烘干11.6h脱水后加入反应器中，搅拌均匀后加入4.2g六亚甲基二异氰酸酯和5.11g异佛尔酮二异氰酸酯，在95℃反应2h得水性聚氨酯预聚体，其中过量六亚甲基二异氰酸酯和异佛尔酮二异氰酸酯总物质的量为0.032mol；
步骤2，向水性聚氨酯预聚体中加入2.16g新戊二醇及25％溶剂N,N-二甲基甲酰胺(占上述聚合物多元醇、含羧基亲水剂物、异氰酸酯化合物质和小分子二元醇总质量分数)在55℃继续反应4h后降至室温；
步骤3，向上述反应产物中加入0.41mL氨水中和二氨基苯甲酸，室温下搅拌0.7h后按固含量为26％滴加去离子水乳化，之后加入0.30g扩链剂二甘醇、0.17g乙二胺及2.30g羟基功能化单体乙二醇二缩水甘油醚环碳酸酯与过量丙二胺胺解产物，强烈搅拌15min后加热至45℃反应0.61h。反应结束后，通过减压蒸馏脱除所加溶剂即得羟基功能化水性聚氨酯乳液。
乳液在室温下储存一年不分层，将所得水性聚氨酯乳液干燥制片后进行性能测试，胶膜拉伸强度为28.9MPa，断裂伸长率为658％，在水中浸泡达到溶胀平衡后溶胀度为13.25％，对基材PVC的24h终粘强度为2.86N/mm。
实施例5
一种羟基功能化水性聚氨酯的制备方法，包括以下步骤：
步骤1，将5g聚己二酸丁二醇酯(Mn＝1000)和5g聚碳酸己二醇酯(Mn＝1000)107℃下减压脱水3.9h，0.61g二氨基苯甲酸和0.54g二羟甲基丙酸118℃下干燥箱中烘干10.9h脱水后加入反应器中，搅拌均匀后加入6.26g甲苯二异氰酸酯，在90℃反应2.1h得水性聚氨酯预聚体，其中过量甲苯二异氰酸酯3.13g；
步骤2，向水性聚氨酯预聚体中加入1.16g二甘醇及12％溶剂丙酮和10％丁酮(占上述聚合物多元醇、含羧基亲水剂物、异氰酸酯化合物质和小分子二元醇总质量分数)在65℃继续反应2h后降至室温；
步骤3，向上述反应产物中加入0.81g三乙胺中和二氨基苯甲酸和二羟甲基丙酸，室温下搅拌1h后按固含量为32％滴加去离子水乳化，之后加入0.41g扩链剂1,6-己二醇及1.44g羟基功能化单体1,4-丁二醇二缩水甘油醚环碳酸酯与过量乙二胺胺解产物，强烈搅拌27min后加热至55℃反应0.7h。反应结束后，通过减压蒸馏脱除所加溶剂即得羟基功能化水性聚氨酯乳液。
乳液在室温下储存一年不分层，将所得水性聚氨酯乳液干燥制片后进行性能测试，胶膜拉伸强度为29.5MPa，断裂伸长率为602％，在水中浸泡达到溶胀平衡后溶胀度为12.98％，对基材PVC的24h终粘强度为2.92N/mm。
实施例6
一种羟基功能化水性聚氨酯的制备方法，包括以下步骤：
步骤1，将10g聚己二酸丁二醇酯(Mn＝1000)135℃下减压脱水2h，1g二羟基半酯100℃下干燥箱中烘干12h脱水后加入反应器中，搅拌均匀后加入25.15g4,4’-亚甲基双(环己基异氰酸酯)，在85℃反应2.7h得水性聚氨酯预聚体，其中过量4,4’-亚甲基双(环己基异氰酸酯)17.29g；
步骤2，向水性聚氨酯预聚体中加入1.8g1,4-丁二醇和1.22g乙二醇及18％溶剂丙酮(占上述聚合物多元醇、含羧基亲水剂物、异氰酸酯化合物质和小分子二元醇总质量分数)在56℃继续反应2.8h后降至室温；
步骤3，向上述反应产物中加入1.52g三乙胺和0.34mL氨水中和二羟基半酯，室温下搅拌0.8h后按固含量为35％滴加去离子水乳化，之后加入1.34g扩链剂二乙烯三胺及4.29g羟基功能化单体四乙羟基己二酰二胺，强烈搅拌9min后加热至55℃反应0.8h。反应结束后，通过减压蒸馏脱除所加溶剂即得羟基功能化水性聚氨酯乳液。
乳液在室温下储存一年不分层，将所得水性聚氨酯乳液干燥制片后进行性能测试，胶膜拉伸强度为29.6MPa，断裂伸长率为587％，在水中浸泡达到溶胀平衡后溶胀度为13.56％，对基材PVC的24h终粘强度为2.99N/mm。
实施例7
一种羟基功能化水性聚氨酯的制备方法，包括以下步骤：
步骤1，将4g聚四亚甲基醚二醇(Mn＝2000)、3g聚丙二醇醚(Mn＝1000)和5g聚氧化丙烯二醇(Mn＝1000)126℃下减压脱水3h，1.11g二羟甲基丙酸131℃下干燥箱中烘干10.8h脱水后加入反应器中，搅拌均匀后加入10.16g异佛尔酮二异氰酸酯，在70℃反应5h得水性聚氨酯预聚体，其中过量异佛尔酮二异氰酸酯6.09g；
步骤2，向水性聚氨酯预聚体中加入1.71g新戊二醇及28.2％溶剂甲基乙基酮(占上述聚合物多元醇、含羧基亲水剂物、异氰酸酯化合物质和小分子二元醇总质量分数)在50℃继续反应5h后降至室温；
步骤3，向上述反应产物中加入0.33g氢氧化钠中和二羟甲基丙酸，室温下搅拌0.65h后按固含量为31.8％滴加去离子水乳化，之后加入0.12g扩链剂乙二胺和0.10g二乙烯三胺及0.72g羟基功能化单体2-羟基-1,3-丙二胺，强烈搅拌12min后加热至42℃反应0.99h。反应结束后，通过减压蒸馏脱除所加溶剂即得羟基功能化水性聚氨酯乳液。
乳液在室温下储存一年不分层，将所得水性聚氨酯乳液干燥制片后进行性能测试，胶膜拉伸强度为26.1MPa，断裂伸长率为721％，在水中浸泡达到溶胀平衡后溶胀度为12.51％，对基材PVC的24h终粘强度为2.72N/mm。
实施例8
一种羟基功能化水性聚氨酯的制备方法，包括以下步骤：
步骤1，将10.5g聚碳酸己二醇酯(Mn＝1500)和3g聚四亚甲基醚二醇(Mn＝1000)103℃下减压脱水3.6h，1.14g二氨基苯甲酸128℃下干燥箱中烘干12.3h脱水后加入反应器中，搅拌均匀后加入7.84g对苯二异氰酸酯，在79℃反应4.5h得水性聚氨酯预聚体，其中过量对苯二异氰酸酯5.04g；
步骤2，向水性聚氨酯预聚体中加入2.60g1,6-己二醇及19.3％溶剂丙酮(占上述聚合物多元醇、含羧基亲水剂物、异氰酸酯化合物质和小分子二元醇总质量分数)在53℃继续反应4.6h后降至室温；
步骤3，向上述反应产物中加入0.76g三乙胺中和二氨基苯甲酸，室温下搅拌0.75h后按固含量为31.8％滴加去离子水乳化，之后加入0.20g扩链剂乙二醇和0.32g二甘醇及0.30g羟基功能化单体2-羟基-1,3-丙二胺，强烈搅拌13.6min后加热至53℃反应0.75h。反应结束后，通过减压蒸馏脱除所加溶剂即得羟基功能化水性聚氨酯乳液。
乳液在室温下储存一年不分层，将所得水性聚氨酯乳液干燥制片后进行性能测试，胶膜拉伸强度为27.6MPa，断裂伸长率为626％，在水中浸泡达到溶胀平衡后溶胀度为12.96％，对基材PVC的24h终粘强度为2.89N/mm。
实施例9
一种羟基功能化水性聚氨酯的制备方法，包括以下步骤：
步骤1，将10g聚碳酸丁二醇酯(Mn＝1000)113℃下减压脱水3.2h，0.85g二羟基半酯108℃下干燥箱中烘干11.3h脱水后加入反应器中，搅拌均匀后加入8.70g甲苯二异氰酸酯和5.73g二苯基甲烷二异氰酸酯，在80℃反应3h得水性聚氨酯预聚体，其中过量甲苯二异氰酸酯和二苯基甲烷二异氰酸酯总物质的量为0.0459mol；
步骤2，向水性聚氨酯预聚体中加入4.25g1,6-己二醇和0.04g乙二醇及22.5％溶剂丁酮(占上述聚合物多元醇、含羧基亲水剂物、异氰酸酯化合物质和小分子二元醇总质量分数)在60℃继续反应3h后降至室温；
步骤3，向上述反应产物中加入1.01mL氨水和0.08g氢氧化钠中和二羟基半酯，室温下搅拌0.86h后按固含量为40.2％滴加去离子水乳化，之后加入1.98g羟基功能化单体3,3’-二羟基联苯胺，强烈搅拌18min后加热至48℃反应0.6h。反应结束后，通过减压蒸馏脱除所加溶剂即得羟基功能化水性聚氨酯乳液。
乳液在室温下储存一年不分层，将所得水性聚氨酯乳液干燥制片后进行性能测试，胶膜拉伸强度为29.4MPa，断裂伸长率为557％，在水中浸泡达到溶胀平衡后溶胀度为13.42％，对基材PVC的24h终粘强度为2.95N/mm。
实施例10
一种羟基功能化水性聚氨酯的制备方法，包括以下步骤：
步骤1，将10g聚丁二烯多元醇(Mn＝1000)132℃下减压脱水2h，0.40g二羟甲基丙酸和0.59g二氨基苯甲酸135℃下干燥箱中烘干11h脱水后加入反应器中，搅拌均匀后加入12.37g间四亚甲基二甲苯二异氰酸酯，在82℃反应2.6h得水性聚氨酯预聚体，其中过量间四亚甲基二甲苯二异氰酸酯8.25g；
步骤2，向水性聚氨酯预聚体中加入1.18g1,6-己二醇和1.06g乙二醇及17.9％溶剂乙二醇单丁醚(占上述聚合物多元醇、含羧基亲水剂物、异氰酸酯化合物质和小分子二元醇总质量分数)在58℃继续反应3.1h后降至室温；
步骤3，向上述反应产物中加入0.20g三乙胺和0.70g三丙胺中和二羟甲基丙酸和二氨基苯甲酸，室温下搅拌0.78h后按固含量为36.7％滴加去离子水乳化，之后加入2.77g羟基功能化单体1,4-丁二醇二缩水甘油醚环碳酸酯与过量乙二胺胺解产物，强烈搅拌21min后加热至55℃反应0.51h。反应结束后，通过减压蒸馏脱除所加溶剂即得羟基功能化水性聚氨酯乳液。
乳液在室温下储存一年不分层，将所得水性聚氨酯乳液干燥制片后进行性能测试，胶膜拉伸强度为30.1MPa，断裂伸长率为521％，在水中浸泡达到溶胀平衡后溶胀度为11.98％，对基材PVC的24h终粘强度为2.72N/mm。
实施例11
一种羟基功能化水性聚氨酯的制备方法，包括以下步骤：
步骤1，将8.2gmoL聚己二酸己二醇酯(Mn＝1000)和1.8g聚己二酸乙二醇-丙二醇酯(Mn＝1000)138℃下减压脱水2.1h，0.84g二氨基苯甲酸128℃下干燥箱中烘干12.1h脱水后加入反应器中，搅拌均匀后加入8.33g六亚甲基二异氰酸酯，在92℃反应2.1h得水性聚氨酯预聚体，其中过量六亚甲基二异氰酸酯5.73g；
步骤2，向水性聚氨酯预聚体中加入1.13g1,4-丁二醇和1.33g1,6-己二醇及18.9％溶剂丙酮(占上述聚合物多元醇、含羧基亲水剂物、异氰酸酯化合物质和小分子二元醇总质量分数)在63℃继续反应3.5h后降至室温；
步骤3，向上述反应产物中加入0.33g三丙胺和0.59g三丁胺中和二氨基苯甲酸，室温下搅拌0.51h后按固含量为29.9％滴加去离子水乳化，之后加入1.50g扩链剂N,N-双(2-羟乙基)乙二胺及0.009g羟基功能化单体丙三醇，强烈搅拌25min后加热至51℃反应0.6h。反应结束后，通过减压蒸馏脱除所加溶剂即得羟基功能化水性聚氨酯乳液。
乳液在室温下储存一年不分层，将所得水性聚氨酯乳液干燥制片后进行性能测试，胶膜拉伸强度为28.7MPa，断裂伸长率为603％，在水中浸泡达到溶胀平衡后溶胀度为13.87％，对基材PVC的24h终粘强度为3.02N/mm。
实施例12
一种羟基功能化水性聚氨酯的制备方法，包括以下步骤：
步骤1，将9g聚乙二醇醚(Mn＝1000)和1g聚丙二醇醚(Mn＝1000)128℃下减压脱水2.5h，1.03g二氨基苯甲酸135℃下干燥箱中烘干10.5h脱水后加入反应器中，搅拌均匀后加入1.88g六亚甲基二异氰酸酯和5.47g间四亚甲基二甲苯二异氰酸酯，在90℃反应2.5h得水性聚氨酯预聚体，其中过量六亚甲基二异氰酸酯和间四亚甲基二甲苯二异氰酸酯总物质的量为0.0168mol；
步骤2，向水性聚氨酯预聚体中加入0.77g1,2-丙二醇及23.4％溶剂丁酮(占上述聚合物多元醇、含羧基亲水剂物、异氰酸酯化合物质和小分子二元醇总质量分数)在60℃继续反应3h后降至室温；
步骤3，向上述反应产物中加入1.26g三丁胺中和二氨基苯甲酸，室温下搅拌0.99h后按固含量为30.7％滴加去离子水乳化，之后加入1.02g羟基功能化单体1,6-二氢-1-羟基-吡咯并[2,3-b]吡咯-2,3-二胺，强烈搅拌10min后加热至50℃反应0.76h。反应结束后，通过减压蒸馏脱除所加溶剂即得羟基功能化水性聚氨酯乳液。
乳液在室温下储存一年不分层，将所得水性聚氨酯乳液干燥制片后进行性能测试，胶膜拉伸强度为26.3MPa，断裂伸长率为679％，在水中浸泡达到溶胀平衡后溶胀度为12.05％，对基材PVC的24h终粘强度为2.56N/mm。

Claims (18)

1.一种羟基功能化水性聚氨酯的制备方法，其特征在于，包括以下步骤：
步骤1，将聚合物多元醇、含羧基亲水剂脱水，加入反应器中，搅拌均匀后加入异氰酸酯化合物，反应得到水性聚氨酯预聚体；
步骤2，向水性聚氨酯预聚体中加入小分子二元醇及溶剂，继续反应后降至室温；
步骤3，向步骤2的反应体系中加入成盐剂，室温下搅拌反应后，加去离子水乳化，之后加入扩链剂和羟基功能化单体，强烈搅拌后加热反应，反应结束后，通过减压蒸馏脱除溶剂，即制得羟基功能化水性聚氨酯。
2.根据权利要求1所述的一种羟基功能化水性聚氨酯的制备方法，其特征在于，所述步骤1中聚合物多元醇为聚酯二醇、聚醚二醇或聚碳酸酯二醇中的一种或几种按任意比混合。
3.根据权利要求2所述的一种羟基功能化水性聚氨酯的制备方法，其特征在于，所述聚酯二醇为聚己二酸乙二醇酯、聚己二酸丁二醇酯、聚己二酸乙二醇-丙二醇酯、聚己二酸乙二醇-丁二醇酯、聚己二酸己二醇酯、聚己二酸戊二醇酯、聚己二酸乙二醇-新戊二醇、聚ε-己内酯二醇中的一种或几种按任意比混合；
所述聚醚二醇为聚氧化丙烯二醇、聚乙二醇醚、聚丙二醇醚、聚四亚甲基醚二醇、聚氧化乙烯二醇、聚丁二烯多元醇等中的一种或几种按任意比混合；
所述聚碳酸酯二醇为聚碳酸己二醇酯、聚碳酸戊二醇酯、聚碳酸丁二醇酯中的一种或几种按任意比混合。
4.根据权利要求3所述的一种羟基功能化水性聚氨酯的制备方法，其特征在于，所述聚酯二醇、聚醚二醇或聚碳酸酯二醇的分子量为1000～2000。
5.根据权利要求1所述的一种羟基功能化水性聚氨酯的制备方法，其特征在于，所述步骤1中所述含羧基的亲水剂为2,2-二羟甲基丙酸、二羟基半酯和二氨基苯甲酸中的一种或几种按任意比混合。
6.根据权利要求1所述的一种羟基功能化水性聚氨酯的制备方法，其特征在于，所述步骤1中所述异氰酸酯化合物为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、对苯二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、4,4’-亚甲基双(环己基异氰酸酯)、间四亚甲基二甲苯二异氰酸酯中的一种或几种按任意比混合。
7.根据权利要求1所述的一种羟基功能化水性聚氨酯的制备方法，其特征在于，所述步骤2中小分子二元醇为乙二醇、1,2-丙二醇、1,4-丁二醇、1,5-戊二醇、新戊二醇、1,6-己二醇、1,8-辛二醇、二甘醇中的一种或几种按任意比混合。
8.根据权利要求1所述的一种羟基功能化水性聚氨酯的制备方法，其特征在于，所述步骤2中所述溶剂为丙酮、丁酮、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、甲基乙基酮、乙二醇单丁醚中的一种。
9.根据权利要求1所述的一种羟基功能化水性聚氨酯的制备方法，其特征在于，所述步骤3中成盐剂为三乙胺、三丙胺、三丁胺、氢氧化钠和氨水中的一种或几种按任意比混合。
10.根据权利要求1所述的一种羟基功能化水性聚氨酯的制备方法，其特征在于，所述步骤3中扩链剂为乙二胺、二乙烯三胺、三乙烯四胺、乙二醇、丙二醇、1,4-丁二醇、二甘醇、新戊二醇、1,6-己二醇、N,N-双(2-羟乙基)乙二胺中的一种或几种按任意比混合。
11.根据权利要求1所述的一种羟基功能化水性聚氨酯的制备方法，其特征在于，所述步骤3中羟基功能化单体为结构中含有羟基、伯胺基的多羟基多胺基醇胺化合物或多羟基化合物中的一种或几种按任意比混合，其结构通式如下：
Figure FDA0002541700710000031
12.根据权利要求11所述的一种羟基功能化水性聚氨酯的制备方法，其特征在于，所述结构中含有羟基、伯胺基的多羟基多胺基醇胺化合物或多羟基化合物为2-羟基-1,3-丙二胺、3,3’-二羟基联苯胺、四乙羟基己二酰二胺、1,6-二氢-1-羟基-吡咯并[2,3-b]吡咯-2,3-二胺、丙三醇，或环碳酸酯与过量胺开环反应生成含β-羟基、氨酯基及胺基的多羟基多胺基醇胺化合物中的一种或几种按任意比混合。
13.根据权利要求1所述的一种羟基功能化水性聚氨酯的制备方法，其特征在于，所述步骤1中聚合物多元醇与含羧基亲水剂摩尔比0.5～2:1，异氰酸酯化合物与聚合物多元醇和含羧基亲水剂总摩尔数之比1.8～3.5:1。
14.根据权利要求1所述的一种羟基功能化水性聚氨酯的制备方法，其特征在于，所述步骤2中小分子二元醇用量为步骤1过量异氰酸酯化合物摩尔量的0.6～0.8倍；所述溶剂占上述聚合物多元醇、含羧基亲水剂物、异氰酸酯化合物质和小分子二元醇总质量的15％～30％。
15.根据权利要求1所述的一种羟基功能化水性聚氨酯的制备方法，其特征在于，所述步骤3中成盐剂用量与含羧基亲水剂的摩尔比为1:1；所述去离子水用量按固含量计算，固含量控制在20％～45％；所述扩链剂和羟基功能化单体总用量与上述步骤反应后剩余异氰酸酯基团摩尔数相同，其中扩链剂和羟基功能化单体的摩尔比为0～99:100～1。
16.根据权利要求1所述的一种羟基功能化水性聚氨酯的制备方法，其特征在于，所述步骤1中聚合物多元醇脱水的条件为减压100～140℃下脱水2～4h，含羧基亲水剂脱水的条件为在100～140℃下干燥箱中烘干10～14h脱水；所述反应的温度为70～95℃，时间为2～5h。
17.根据权利要求1所述的一种羟基功能化水性聚氨酯的制备方法，其特征在于，所述步骤2中继续反应的温度为50～65℃，时间为2～5h。
18.根据权利要求1所述的一种羟基功能化水性聚氨酯的制备方法，其特征在于，所述步骤3中室温下搅拌反应的时间为0.5～1h，所述强烈搅拌的时间为0.1～0.5h，加热反应的温度为40～55℃，时间为0.5～1h。
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