CN111825828A - 一种封闭剂、封闭型水性树脂及其制备方法、互穿网络结构聚合物 - Google Patents

一种封闭剂、封闭型水性树脂及其制备方法、互穿网络结构聚合物 Download PDF

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CN111825828A
CN111825828A CN202010673036.1A CN202010673036A CN111825828A CN 111825828 A CN111825828 A CN 111825828A CN 202010673036 A CN202010673036 A CN 202010673036A CN 111825828 A CN111825828 A CN 111825828A
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polyurethane
chain extender
based resin
temperature
closed water
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祝方明
车俊峥
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Foshan Tongjun Environmental Protection Technology Co ltd
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Abstract

本发明公开了一种封闭剂以及采用该封闭剂封端处理的封闭型水性树脂，同时还公开了封闭型水性树脂的制备方法以及封闭型水性树脂方法和解封后获得的聚氨酯/聚丙烯酸酯互穿网络结构聚合物。本发明的封闭剂在30～50℃下就能与异氰酸酯发生封闭反应，且反应速率快，封闭效率高，并且在较低的温度(约120℃左右)下能解封闭；制备过程绿色环保，无明显异味，制备条件较为温和的特点；制得的封闭型水性树脂综合性能优良，解封闭后封闭剂FEMA经自由基聚合生成聚丙烯酸酯，并能与水性树脂形成性能互补的互穿网络结构聚合物，而基于聚氨酯和聚丙烯酸酯在性质上的互补性，所获得的互穿网络结构聚合物兼具了二者的优点。

Description

一种封闭剂、封闭型水性树脂及其制备方法、互穿网络结构聚 合物
技术领域
本发明涉及聚氨酯领域，特别涉及一种水性树脂封闭剂，以及使用该封闭剂进行封端的封闭型水性树脂(也叫封闭型水性聚氨酯)及其制备方法，同时还涉及封闭型水性聚氨酯树脂解封后所形成的聚氨酯/聚丙烯酸酯互穿网络结构聚合物。
背景技术
封闭型水性聚氨酯是指聚氨酯分子中的异氰酸酯基被封闭后与水形成的分散体系，在室温下稳定，能长期储存，同时也具有普通水性聚氨酯价廉、安全、不燃烧、无毒，不污染环境等优点。加热到一定温度时，封闭型水性聚氨酯中的水分挥发并发生解封闭反应，又生成活性的异氰酸酯基，并发生交联反应，形成固化聚氨酯，从而提高了水性聚氨酯的耐水性和耐溶剂性能。但是，封闭型水性聚氨酯还存在一些不足，如耐水、耐磨、耐腐蚀和光亮性差，柔软性、弹性、机械力学性能也不好，特别是解封闭温度高，解封闭时间长，封闭剂解封后产物的处理困难，如有些高沸点的封闭剂解封后就留在产品里，将会对产品的性能产生不良影响，限制了它的应用范围。
发明内容
本发明要解决的技术问题是提供一种封闭剂，该封闭剂在30～50℃下就能与异氰酸酯发生封闭反应，且反应速率快，封闭效率高；同时还提供了一种由该封闭剂进行封端的水性树脂，即水性聚氨酯，其在120℃左右的条件下解封闭，解封闭产生的FEMA经自由基聚合生成聚丙烯酸酯，而聚丙烯酸酯能与聚氨酯形成互穿网络结构聚合物，该互穿网络结构聚合物力学性能优异，可应用于轻纺、皮革加工、涂料、木材加工、建材、造纸和胶粘剂等行业。
为了解决上述技术问题，本发明的技术方案为一种封闭剂(FEMA)，其化学式如下所示：
Figure BDA0002582370250000011
进一步优选，其制备方法为：以对苯二酚为阻聚剂，环己烷为反应介质，甲基丙烯酸-2-羟基乙酯与甲酸酯化反应制得，酯化反应于Dean-Stark装置中进行，回流20～30h后，减压旋转蒸发除去环己烷与甲酸，得到液体状粗产物，再以1∶1的乙醚和石油醚混合液为淋洗液，采用柱色谱法分离提纯粗产物，得纯的FEMA。
本发明的另一技术方案：一种封闭型水性树脂，由以下以质量份数计的原料制备而成：聚酯二元醇0～25％，聚醚二元醇0～25％，异佛尔酮二异氰酸酯5～15％，催化剂0.06～0.08％，2，2-二羟甲基丙酸1～3％，三羟甲基丙烷1～2％，封闭剂8～10％，三乙胺1～5％，纯水50～60％，聚酯二元醇与聚醚二元醇的百分比不同时为0。该树脂也为水性聚氨酯，后续的内容直接以水性聚氨酯表达。
封闭型水性聚氨酯的制备原料主要由聚酯和聚醚二元醇，二异氰酸酯，水性扩链剂，催化剂，中和剂，封闭剂和纯水七部分组成；本发明中聚酯和聚醚二元醇的分子量为1000～3000，聚酯单元赋予聚氨酯分子链刚性，聚醚单元赋予聚氨酯分子链柔顺性，两者皆属软段部分；在微观结构上，软段构成了该聚氨酯的连续相，起到分散应力的作用，使材料具有一定的缓冲功能，在宏观上体现为弹性。
进一步优选，聚酯二元醇、聚醚二元醇总的羟基与异佛尔酮二异氰酸酯中的异氰酸酯基的摩尔比为1∶1.1～2.0。
进一步优选，聚酯二元醇为聚己内酯(PCL)二元醇，分子量1000～3000。
进一步优选，聚醚二元醇为聚乙二醇醚(PEG)二元醇或聚四氢呋喃醚(PTMG)二元醇，分子量1000～3000。
进一步优选，催化剂为二月桂酸二丁基锡。
进一步优选，二异氰酸酯为异佛尔酮二异氰酸酯。
本发明所述异氰酸酯为异佛尔酮二异氰酸酯，此类异氰酸酯两个异氰酸基的活性不同，容易形成聚合物。异氰酸酯和羟基反应生成氨基甲酸酯基团单元，该单元在聚氨酯分子中作为硬段，聚集时可形成微晶结构，起到承受应力的作用；在材料受到外力的时候，软段形成的连续相传递外界压力，使应力分散，保证材料良好的弹性。
进一步优选，扩链剂选自2，2-二羟甲基丙酸、三羟甲基丙烷中至少一种；再进一步优选，扩链剂由扩链剂A和扩链剂B组成，其中扩链剂A为2，2-二羟甲基丙酸，扩链剂B为三羟甲基丙烷，在体系反应时，扩链剂A先添加，扩链剂B后添加。
本发明所述水性扩链剂A为2，2-二羟甲基丙酸，扩链剂的主要功能是增加分子量，使其具有预定的力学性能；2，2-二羟甲基丙酸扩链剂上的羧酸基与中和剂反应生成具有较强亲水性的阴离子，使得水性聚氨酯材料能均匀地分散在水里。
本发明所述水性扩链剂B为三羟甲基丙烷，可以改善水性聚氨酯与非极性材料的附着力，降低聚氨酯的弹性模量，提高其断裂伸长率和粘弹性。
本发明的另一技术方案，制备封闭型水性聚氨酯的方法，步骤如下：
S1.在氮气气氛中将减压干燥好的聚酯二元醇或/和聚醚二元醇加热到60～90℃，同时加入少量的催化剂反应20～40min；
S2.将温度调至40～60℃，加入水性扩链剂A丙酮溶液反应180～300min，再加入扩链剂B丙酮溶液反应30～60min；
S3.将温度调至30～50℃，加入封闭剂反应30～60min至异氰酸酯基含量为零；
S4.恒温下加入丙酮稀释，再加入三乙胺反应30～60min；
S5.将温度调至室温，加入纯水分散；
S6.室温下减压旋转蒸发除去丙酮。
进一步优选，S1步骤的反应温度为80℃，聚合时间为30min。
进一步优选，S2步骤中的水性扩链剂A的反应温度为50℃，反应时间为240min；水性扩链剂B的反应温度为50℃，反应时间为45min。
进一步优选，S3步骤中封闭剂反应温度为40℃，反应时间为45min。
进一步优选，S4步骤中的反应温度为40℃，反应时间为30min。
进一步优选，S5步骤中的纯水分散温度为室温。
进一步优选，S5步骤中的旋转蒸发温度为室温。
本发明的再一技术方案，一种聚氨酯/聚丙烯酸酯互穿网络结构聚合物，其由本发明所制备的封闭型水性聚氨酯解封闭后获得，其解封闭温度为100～130℃、解封闭时间为10～30min。
进一步优选，封闭型水性聚氨酯中加入少量过硫酸铵搅拌均匀，涂膜，110℃下解封闭15min，得到聚氨酯/聚丙烯酸酯互穿网络聚合物。
采用上述技术方案，通过制备获得的封闭剂，其在30～50℃下就能与异氰酸酯发生封闭反应，且反应速率快，封闭效率高，并且在较低的温度(约120℃左右)下能解封闭；本发明的封闭型水性聚氨酯，制备过程绿色环保，无明显异味，制备条件较为温和的特点；制得的封闭型水性聚氨酯综合性能优良，解封闭后封闭剂FEMA经自由基聚合生成聚丙烯酸酯，并能与聚氨酯形成性能互补的互穿网络结构聚合物，而基于聚氨酯和聚丙烯酸酯在性质上的互补性，所获得的互穿网络结构聚合物兼具了二者的优点，拓宽了封闭型水性聚氨酯的应用领域，其可应用于轻纺、皮革加工、涂料、木材加工、建材、造纸和胶粘剂等行业。
具体实施方式
下面对本发明的具体实施方式作进一步说明。在此需要说明的是，对于这些实施方式的说明用于帮助理解本发明，但并不构成对本发明的限定。此外，下面所描述的本发明各个实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互组合。
除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备，以下实施例所用试剂和材料均为市购。
实施例1
封闭剂FEMA的制备：
将10.0ml甲基丙烯酸-2-羟基乙酯(约80mmol)，35ml甲酸(约950mmol)，0.1mg对苯二酚和50ml环己烷加入到Dean-Stark装置中，回流24h后，旋蒸除去环己烷与甲酸。得到液状的粗产物；再以体积比50∶50(V∶V)的乙醚与石油醚混合液为淋洗液，采用柱色谱法分离提纯粗产物，得到11.4g FEMA，产率约为90％。
基于傅里叶变换红外光谱(FTIR)、核磁共振氢谱(1H NMR)和碳谱(13C NMR)表征，合成的FEMA结构明确、纯度较高。
将实施例1中获得的封闭剂应用于封闭型水性聚氨酯的制备，具体实施如下：
实施例2
将40.0g(20.0mmol)分子量为2000的PCL二元醇加入装有电动搅拌器、温度计、冷凝管和氮气进出口的四口烧瓶中，85℃下减压低速(250rad/min)搅拌干燥30min；氮气保护下，加入17.8g(80.0mmol)异佛尔酮二异氰酸酯和12.6mg(0.02mmol)二月桂酸二丁基锡恒温聚合30min，生成端异氰酸酯基聚氨酯预聚物；降温至60℃，加入10mL2，2-二羟甲基丙酸(3.78g，28.0mmol)丙酮溶液扩链反应4h，再加入2mL三羟甲基丙烷(0.94g，3.5mmol)丙酮溶液扩链反应60min；降温至45℃并加人适量的丙酮以降低聚氨酯溶液粘度，加入18.5g(117.1mmol)FEMA封闭反应30min；最后室温下加入40mL纯水和2.83g(28.0mmol)三乙胺快速(1200rad/min)搅拌30min，室温下减压蒸发除去丙酮，得到封闭型水性聚氨酯。固含量52％，聚氨酯颗粒的流体力学半径(Rh)为102nm，异氰酸酯基的封闭率为98％。
实施例3
将40.0g(20.0mmol)分子量为2000的PTMG醚二元醇加入装有电动搅拌器、温度计、冷凝管和氮气进出口的四口烧瓶中，85℃下减压低速(250rad/min)搅拌干燥30min；氮气保护下，加入17.8g(80.0mmol)异佛尔酮二异氰酸酯和12.6mg(0.02mmol)二月桂酸二丁基锡恒温聚合30min，生成端异氰酸酯基聚氨酯预聚物；降温至60℃，加入10mL2，2-二羟甲基丙酸(3.78g，28.0mmol)丙酮溶液扩链反应4h，再加入2mL三羟甲基丙烷(0.94g，3.5mmol)丙酮溶液扩链反应60min；降温至45℃并加人适量的丙酮以降低聚氨酯溶液粘度，加入18.5g(117.1mmol)FEMA封闭反应30min；最后室温下加入40mL纯水和2.83g(28.0mmol)三乙胺快速(1200rad/min)搅拌30min，室温下减压蒸发除去丙酮，得到封闭型水性聚氨酯。固含量61％，聚氨酯颗粒的流体力学半径(Rh)为48nm，异氰酸酯基的封闭率为98％。
实施例4
将40.0g(20.0mmol)分子量为2000的PEG二元醇加入装有电动搅拌器、温度计、冷凝管和氮气进出口的四口烧瓶中，85℃下减压低速(250rad/min)搅拌干燥30min；氮气保护下，加入17.8g(80.0mmol)异佛尔酮二异氰酸酯和12.6mg(0.02mmol)二月桂酸二丁基锡恒温聚合30min，生成端异氰酸酯基聚氨酯预聚物；降温至60℃，加入10mL2，2-二羟甲基丙酸(3.78g，28.0mmol)丙酮溶液扩链反应4h，再加入2mL三羟甲基丙烷(0.94g，3.5mmol)丙酮溶液扩链反应60min；降温至45℃并加人适量的丙酮以降低聚氨酯溶液粘度，加入18.5g(117.1mmol)FEMA封闭反应30min；最后室温下加入40mL纯水和2.83g(28.0mmol)三乙胺快速(1200rad/min)搅拌30min，室温下减压蒸发除去丙酮，得到封闭型水性聚氨酯。固含量62％，聚氨酯颗粒的流体力学半径(Rh)为45nm，异氰酸酯基的封闭率为98％。
实施例5
将30.0g(15.0mmol)分子量为2000的PCL二元醇和10.0g(5.0mmol)分子量为2000的PTMG醚二元醇加入装有电动搅拌器、温度计、冷凝管和氮气进出口的四口烧瓶中，85℃下减压低速(250rad/min)搅拌干燥30min；氮气保护下，加入17.8g(80.0mmol)异佛尔酮二异氰酸酯和12.6mg(0.02mmol)二月桂酸二丁基锡恒温聚合30min，生成端异氰酸酯基聚氨酯预聚物；降温至60℃，加入10mL2，2-二羟甲基丙酸(3.78g，28.0mmol)丙酮溶液扩链反应4h，再加入2mL三羟甲基丙烷(0.94g，3.5mmol)丙酮溶液扩链反应60min；降温至45℃并加人适量的丙酮以降低聚氨酯溶液粘度，加入18.5g(117.1mmol)FEMA封闭反应30min；最后室温下加入40mL纯水和2.83g(28.0mmol)三乙胺快速(1200rad/min)搅拌30min，室温下减压蒸发除去丙酮，得到封闭型水性聚氨酯。固含量54％，聚氨酯颗粒的流体力学半径(Rh)为91nm，异氰酸酯基的封闭率为98％。
实施例6
将10.0g(5.0mmol)分子量为2000的PCL二元醇和30.0g(15.0mmol)分子量为2000的PTMG醚二元醇加入装有电动搅拌器、温度计、冷凝管和氮气进出口的四口烧瓶中，85℃下减压低速(250rad/min)搅拌干燥30min；氮气保护下，加入17.8g(80.0mmol)异佛尔酮二异氰酸酯和12.6mg(0.02mmol)二月桂酸二丁基锡恒温聚合30min，生成端异氰酸酯基聚氨酯预聚物；降温至60℃，加入10mL2，2-二羟甲基丙酸(3.78g，28.0mmol)丙酮溶液扩链反应4h，再加入2mL三羟甲基丙烷(0.94g，3.5mmol)丙酮溶液扩链反应60min；降温至45℃并加人适量的丙酮以降低聚氨酯溶液粘度，加入18.5g(117.1mmol)FEMA封闭反应30min；最后室温下加入40mL纯水和2.83g(28.0mmol)三乙胺快速(1200rad/min)搅拌30min，室温下减压蒸发除去丙酮，得到封闭型水性聚氨酯。固含量58％，聚氨酯颗粒的流体力学半径(Rh)为63nm，异氰酸酯基的封闭率为98％。
实施例7
将20.0g(10.0mmol)分子量为2000的PCL二元醇和20.0g(10.0mmol)分子量为2000的PTMG醚二元醇加入装有电动搅拌器、温度计、冷凝管和氮气进出口的四口烧瓶中，85℃下减压低速(250rad/min)搅拌干燥30min；氮气保护下，加入17.8g(80.0mmol)异佛尔酮二异氰酸酯和12.6mg(0.02mmol)二月桂酸二丁基锡恒温聚合30min，生成端异氰酸酯基聚氨酯预聚物；降温至60℃，加入10mL2，2-二羟甲基丙酸(3.78g，28.0mmol)丙酮溶液扩链反应4h，再加入2mL三羟甲基丙烷(0.94g，3.5mmol)丙酮溶液扩链反应60min；降温至45℃并加人适量的丙酮以降低聚氨酯溶液粘度，加入18.5g(117.1mmol)FEMA封闭反应30min；最后室温下加入40mL纯水和2.83g(28.0mmol)三乙胺快速(1200rad/min)搅拌30min，室温下减压蒸发除去丙酮，得到封闭型水性聚氨酯。固含量56％，聚氨酯颗粒的流体力学半径(Rh)为79nm，异氰酸酯基的封闭率为98％。
实施例8
将20.0g(10.0mmol)分子量为2000的PCL二元醇和20.0g(10.0mmol)分子量为2000的PTMG醚二元醇加入装有电动搅拌器、温度计、冷凝管和氮气进出口的四口烧瓶中，85℃下减压低速(250rad/min)搅拌干燥30min；氮气保护下，加入20.36g(91.5mmol)异佛尔酮二异氰酸酯和12.6mg(0.02mmol)二月桂酸二丁基锡恒温聚合30min，生成端异氰酸酯基聚氨酯预聚物；降温至60℃，加入10mL2，2-二羟甲基丙酸(3.78g，28.0mmol)丙酮溶液扩链反应4h；降温至45℃并加人适量的丙酮以降低聚氨酯溶液粘度，加入18.5g(117.1mmol)FEMA封闭反应30min；最后室温下加入40mL纯水和2.83g(28.0mmol)三乙胺快速(1200rad/min)搅拌30min，室温下减压蒸发除去丙酮，得到封闭型水性聚氨酯。固含量61％，聚氨酯颗粒的流体力学半径(Rh)为41nm，异氰酸酯基的封闭率为98％。
实施例9
将20.0g(10.0mmol)分子量为2000的PCL二元醇和20.0g(10.0mmol)分子量为2000的PTMG醚二元醇加入装有电动搅拌器、温度计、冷凝管和氮气进出口的四口烧瓶中，85℃下减压低速(250rad/min)搅拌干燥30min；氮气保护下，加入17.8g(80.0mmol)异佛尔酮二异氰酸酯和12.6mg(0.02mmol)二月桂酸二丁基锡恒温聚合30min，生成端异氰酸酯基聚氨酯预聚物；降温至60℃，加入10mL2，2-二羟甲基丙酸(3.78g，28.0mmol)丙酮溶液扩链反应4h，再加入2mL三羟甲基丙烷(2.82g，10.5mmol)丙酮溶液扩链反应60min；降温至45℃并加人适量的丙酮以降低聚氨酯溶液粘度，加入18.5g(117.1mmol)FEMA封闭反应30min；最后室温下加入40mL纯水和2.83g(28.0mmol)三乙胺快速(1200rad/min)搅拌30min，室温下减压蒸发除去丙酮，得到封闭型水性聚氨酯。固含量47％，聚氨酯颗粒的流体力学半径(Rh)为214nm，异氰酸酯基的封闭率为98％。
实施例10
将20.0g(10.0mmol)分子量为2000的PCL二元醇和20.0g(10.0mmol)分子量为2000的PTMG醚二元醇加入装有电动搅拌器、温度计、冷凝管和氮气进出口的四口烧瓶中，85℃下减压低速(250rad/min)搅拌干燥30min；氮气保护下，加入17.8g(80.0mmol)异佛尔酮二异氰酸酯和12.6mg(0.02mmol)二月桂酸二丁基锡恒温聚合30min，生成端异氰酸酯基聚氨酯预聚物；降温至60℃，加入10mL2，2-二羟甲基丙酸(3.78g，28.0mmol)丙酮溶液扩链反应4h，再加入2mL三羟甲基丙烷(3.75g，14.0mmol)丙酮溶液扩链反应60min；降温至45℃并加人适量的丙酮以降低聚氨酯溶液粘度，加入18.5g(117.1mmol)FEMA封闭反应30min；最后室温下加入40mL纯水和2.83g(28.0mmol)三乙胺快速(1200rad/min)搅拌30min，室温下减压蒸发除去丙酮，得到封闭型水性聚氨酯。固含量42％，聚氨酯颗粒的流体力学半径(Rh)为559nm，异氰酸酯基的封闭率为98％。
实施例11
将20.0g(10.0mmol)分子量为2000的PCL二元醇和20.0g(10.0mmol)分子量为2000的PTMG醚二元醇加入装有电动搅拌器、温度计、冷凝管和氮气进出口的四口烧瓶中，85℃下减压低速(250rad/min)搅拌干燥30min；氮气保护下，加入26.36g(91.5mmol)异佛尔酮二异氰酸酯和12.6mg(0.02mmol)二月桂酸二丁基锡恒温聚合30min，生成端异氰酸酯基聚氨酯预聚物；降温至60℃，加入12mL 2，2-二羟甲基丙酸(4.46g，33.0mmol)丙酮溶液扩链反应4h；降温至45℃并加人适量的丙酮以降低聚氨酯溶液粘度，加入18.5g(117.1mmol)FEMA封闭反应30min；最后室温下加入40mL纯水和3.34g(33.0mmol)三乙胺快速(1200rad/min)搅拌30min，室温下减压蒸发除去丙酮，得到封闭型水性聚氨酯。固含量58％，聚氨酯颗粒的流体力学半径(Rh)为60nm，异氰酸酯基的封闭率为98％。
实施例12
将20.0g(10.0mmol)分子量为2000的PCL二元醇和20.0g(10.0mmol)分子量为2000的PTMG醚二元醇加入装有电动搅拌器、温度计、冷凝管和氮气进出口的四口烧瓶中，85℃下减压低速(250rad/min)搅拌干燥30min；氮气保护下，加入17.8g(80.0mmol)异佛尔酮二异氰酸酯和12.6mg(0.02mmol)二月桂酸二丁基锡恒温聚合30min，生成端异氰酸酯基聚氨酯预聚物；降温至60℃，加入10mL2，2-二羟甲基丙酸(3.78g，28.0mmol)丙酮溶液扩链反应4h，再加入2mL三羟甲基丙烷(0.94g，3.5mmol)丙酮溶液扩链反应60min；降温至45℃并加人适量的丙酮以降低聚氨酯溶液粘度，加入18.5g(117.1mmol)FEMA封闭反应30min；最后室温下加入40mL纯水和2.83g(28.0mmol)三乙胺快速(1200rad/min)搅拌30min，室温下减压蒸发除去丙酮，得到封闭型水性聚氨酯。固含量52％，聚氨酯颗粒的流体力学半径(Rh)为113nm，异氰酸酯基的封闭率为98％。
针对上述实施例7、11、12中得到的封闭型水性聚氨酯进行解封闭，并测试解封后所形成聚合物的力学性能，依次如下实施例所示：
实施例13
往实施例7的封闭型水性聚氨酯中加入少量过硫酸铵搅拌均匀，涂膜，110℃下解封闭15min，得到聚氨酯与聚丙烯酸酯互穿网络聚合物。按照国家标准GB/T528-92对固化聚氨酯膜力学性能测定，杨氏模量为1.74MPa，抗拉强度0.77MPa，断裂伸长率为2161.8％进行测试，拉伸的速率为25mm/min。
实施例14
往实施例11的封闭型水性聚氨酯中加入少量过硫酸铵搅拌均匀，涂膜，110℃下解封闭15min，得到聚氨酯与聚丙烯酸酯互穿网络聚合物。按照国家标准GB/T528-92对固化聚氨酯膜力学性能测定，杨氏模量为5.04MPa，抗拉强度2.48MPa，断裂伸长率为1338.4％进行测试，拉伸的速率为25mm/min。
实施例15
往实施例12的封闭型水性聚氨酯中加入少量过硫酸铵搅拌均匀，涂膜，110℃下解封闭15min，得到聚氨酯与聚丙烯酸酯互穿网络聚合物。按照国家标准GB/T528-92对固化聚氨酯膜力学性能测定，杨氏模量为5.54MPa，抗拉强度0.83MPa，断裂伸长率为973.6％进行测试，拉伸的速率为25mm/min。
以上对本发明的实施方式作了详细说明，但本发明不限于所描述的实施方式。对于本领域的技术人员而言，在不脱离本发明原理和精神的情况下，对这些实施方式进行多种变化、修改、替换和变型，仍落入本发明的保护范围内。

Claims (10)

1.一种封闭剂，其特征在于：其化学式如下所示，
Figure FDA0002582370240000011
2.根据权利要求1所述的封闭剂，其特征在于：以对苯二酚为阻聚剂，环己烷为反应介质，甲基丙烯酸-2-羟基乙酯与甲酸酯化反应制得。
3.根据权利要求2所述的封闭剂，其特征在于：所述酯化反应于Dean-Stark装置中进行，回流20～30h后，减压旋转蒸发除去环己烷与甲酸，得到液体状粗产物，再以体积比为1∶1的乙醚和石油醚混合液为淋洗液，采用柱色谱法分离提纯所述粗产物。
4.一种应用权利要求1至3中任一项中所述封闭剂的封闭型水性树脂，其特征在于：由以下以质量百分比的原料制备而成：聚酯二元醇0～25％，聚醚二元醇0～25％，异佛尔酮二异氰酸酯5～15％，催化剂0.06～0.08％，2，2-二羟甲基丙酸1～3％，三羟甲基丙烷1～2％，封闭剂8～10％，三乙胺1～5％，纯水50～60％，聚酯二元醇与聚醚二元醇的百分比不同时为0。
5.根据权利要求4所述的封闭型水性树脂，其特征在于：所述聚酯二元醇为聚己内酯二元醇，分子量1000～3000；所述聚醚二元醇为聚乙二醇醚二元醇或聚四氢呋喃醚二元醇，分子量1000～3000，所述催化剂为二月桂酸二丁基锡，所述二异氰酸酯为异佛尔酮二异氰酸酯。
6.根据权利要求4所述的封闭型水性树脂，其特征在于：所述扩链剂选自2，2-二羟甲基丙酸、三羟甲基丙烷中至少一种。
7.根据权利要求4所述的封闭型水性树脂，其特征在于：所述扩链剂由扩链剂A和扩链剂B组成，其中扩链剂A为2，2-二羟甲基丙酸，扩链剂B为三羟甲基丙烷，在体系反应时，扩链剂A先添加，扩链剂B后添加。
8.一种制备权利要求7所述的封闭型水性树脂的方法，其特征在于，步骤如下：
S1.在氮气气氛中将减压干燥好的聚酯二元醇或/和聚醚二元醇加热到60～90℃，同时加入少量的催化剂反应20～40min；
S2.将温度调至40～60℃，加入水性扩链剂A丙酮溶液反应180～300min，再加入扩链剂B丙酮溶液反应30～60min；
S3.将温度调至30～50℃，加入封闭剂反应30～60min至异氰酸酯基含量为零；
S4.恒温下加入丙酮稀释，再加入三乙胺反应30～60min；
S5.将温度调至室温，加入纯水分散；
S6.室温下减压旋转蒸发除去丙酮。
9.一种由权利要求4至7中任一项所述的封闭型水性树脂解封闭后与聚丙烯酸酯形成的互穿网络结构聚合物，其特征在于：所述封闭型水性树脂解封闭温度为100～130℃、解封闭时间为10～30min。
10.根据权利要求9所述的聚氨酯/聚丙烯酸酯互穿网络结构聚合物，其特征在于，所述封闭型水性树脂中加入少量过硫酸铵搅拌均匀，涂膜，110℃下解封闭15min。
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