CN114561145A - 一种含有亚胺键的自修复水性聚氨酯涂料 - Google Patents
一种含有亚胺键的自修复水性聚氨酯涂料 Download PDFInfo
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- CN114561145A CN114561145A CN202210201176.8A CN202210201176A CN114561145A CN 114561145 A CN114561145 A CN 114561145A CN 202210201176 A CN202210201176 A CN 202210201176A CN 114561145 A CN114561145 A CN 114561145A
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Abstract
本发明公开了一种含有亚胺键的自修复水性聚氨酯涂料,涉及涂料技术领域,通过合成含有亚胺键的不同类型聚氨酯扩链剂,与不同的聚氨酯软链段、异氰酸酯和亲水扩链剂反应,制备出一系列含有亚胺键的自修复水性聚氨酯涂料;室温下有良好的自修复效果,80℃下修复2h后,修复率达到99.2%。本发明制备的自修复水性聚氨酯涂料,制备工艺简单,原料便宜易得,涂层具有较高的自修复率,便于工业涂层的维护保养。
Description
技术领域
本发明涉及涂料合成领域,具体涉及一种具有自修复性能的绿色环保水性聚氨酯涂料。
背景技术
水性聚氨酯涂料以水替代有机溶剂,相比传统的溶剂型聚氨酯涂料,使用更加绿色环保。水性聚氨酯涂料因其优异的耐磨性、耐化学腐蚀性、高强度、易于改性设计等优点,被广泛用于服装、建筑、交通运输、航空航天、医疗用品等各个领域,但是水性聚氨酯涂层在使用过程中,会因为碰撞、腐蚀、光降解等外界环境的影响,涂层产生微裂纹,造成材料力学性能的下降,影响涂层的功能化作用。因此,开发具有自修复功能的水性聚氨酯涂料有重要的应用价值。
根据愈合方法可分为添加愈合剂的外源型自愈合和本征型自愈合,外源型自修复,通过将修复剂封装在聚氨酯材料的内部,当材料遭受外界损伤,装有修复剂的载体破裂,释放修复剂,达到修复效果,但是外源型自修复因为修复剂的消耗,不能重复使用。而通过设计、修改聚氨酯分子结构的本征型自愈合则更加受到关注。通常在聚氨酯中引入动态共价键来达到自愈合的效果,比如亚胺键、酰腙键、二硫键、硼酸酯键、D-A反应等。此外像氢键、离子键、主客体相互作用,金属配体等非共价键也常被引入聚氨酯中,在光、热、微波等条件刺激下,聚氨酯链段流动,裂纹和损伤被修复。中国发明专利CN112210060A公开了一种可自主修复、绿色的高韧性聚氨酯弹性体及制备方法,具体将充当软段部分的聚己内酯-聚四氢呋喃-聚己内酯(PCL-PTHF-PCL)溶于N,N-二甲基甲酰胺(DMF)中后,加入羟基或氨基封端二硫化物扩链剂得到可自主修复、绿色的高韧性聚氨酯弹性体,材料的拉伸强度为9MPa,截断后室温下放置7小时,修复率仅为93%。中国发明专利CN111410731A公开了一种基于羧酸根-三价铁离子自修复聚氨酯弹性体的制备方法,拉伸强度最高只有5.2MPa,修复率则为92%。
因此提供一种拉伸强度高修复率高的产品是急需解决的。
发明内容
本发明的目的是提供一种含有亚胺键的自修复水性聚氨酯涂料,以解决现有技术中自修复材料修复率底的技术缺陷。
为达到上述目的,本发明采用的技术方案是:
本发明提供一种含有亚胺键的自修复水性聚氨酯涂料,其特征在于,所述涂料的制备方法包括以下步骤:
步骤1、含有亚胺键的聚氨酯扩链剂的制备
按1:4~1:8的质量比将化合物A溶于溶剂A中得到混合物A,按1:15~1:20的质量比将化合物B溶解于溶剂A中得到混合物B,向混合物A中加入催化剂A得到混合物C,将混合物C缓慢滴入混合物B中,并磁力搅拌,采用油浴加热至100℃回流5h,所得溶液进行室温冷却后减压抽滤并用无水乙醇润洗3至4次,取出滤饼真空干燥后,得到含有亚胺键的目标产物A;其中,所述化合物A含有一个-OH和一个-CHO,所述化合物B含有2个-NH2,且化合物A和B的摩尔比为2:1~2.2:1;
步骤2、含有亚胺键的水性聚氨酯涂料的制备
将聚合物二元醇预先在120℃下真空脱水2h,得到原料A备用;在氮气保护下取质量比为20:8:1.25:1.25:1:0.5:31的原料A、二异氰酸酯、亲水扩链剂、目标产物A、小分子扩链剂、催化剂和溶剂B混合后于85℃反应8h;
步骤3、将步骤2所得反应体系降温至35℃后将入与亲水扩链剂等摩尔量的中和剂反应5min后加入去离子水乳化,旋转脱除溶剂B,获得含有亚胺键的自修复水性聚氨酯涂料。
进一步,所述化合物A具体为对羟基苯甲醛、间羟基苯甲醛、水杨醛、香草醛中的一种。
进一步,化合物B为对苯二胺,间苯二胺、领苯二胺中的一种。
进一步,所述聚合物二元醇为聚己二酸1,4丁二醇酯二醇(PBA)、聚己内酯二醇(PCL)、聚碳酸酯二醇(PCDL)、聚四氢呋喃二醇(PTMG)中的一种。
进一步,所述二异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯甲烷二异氰酸酯、六亚甲基二异氰酸酯或二环己基甲烷4,4'二异氰酸酯中的一种。
进一步,所述催化剂为二丁基二月桂酸锡,所述溶剂A为无水乙醇,所述溶剂B为丙酮或丁酮中的一种。
进一步,所述亲水扩链剂为2,2-二羟甲基丙酸或2,2-二羟甲基丁酸中的一种,所述小分子扩链剂为1,4-丁二醇,所述中和剂为三乙胺。
本发明有益的技术效果在于:
(1)本发明首先用含有-CHO、-OH和含有-NH2的化合物反应生成含有亚胺键的扩链剂,与聚合物多元醇和二元异氰酸酯反应,再用阴离子单体对其进行扩链,最后与乙酸中和成盐、乳化,制得自修复水性聚氨酯涂料;合成的聚氨酯涂料不需要外添加修复剂,也无需改变聚氨酯基质单元,具有良好的力学性能,可长久维持聚氨酯涂层的自修复性能,并利于自修复聚氨酯涂料的进一步推广。
(2)合成亚胺键的原料经济便宜,反应简单迅速,工艺绿色环保。
(3)制备的自修复水性聚氨酯涂料自修复率高达99.2%,自修复效果优异且力学性能强,最高达到52MPa,使得其在交通运输、工业涂料和柔性电子器件等方面具有潜在的应用前景。
附图说明
图1为实施例1所得涂料的红外谱图;
图2为实施例1所得涂膜在0、5、10、30min下划痕自修复测试结果图;
图3为实施例2所得涂膜在0、5、10、30min下划痕自修复测试结果图;
图4为实施实例1所得的自修复聚氨酯涂膜经过破碎处理后的结果图。
图5为实施实例1所得的自修复聚氨酯涂膜经过破碎修复后的聚氨酯涂膜结果图。
具体实施方式
下面将结合本发明实施例,对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
一种含有亚胺键的自修复水性聚氨酯涂料,其制备方法包括如下步骤:
(1)含有亚胺键的聚氨酯扩链剂的制备
将10g对苯二胺和150ml无水乙醇加入500ml三颈烧瓶中加热至完全溶解获得混合物B,将12g对羟基苯甲醛溶于150ml无水乙醇中得到混合物A,向混合物A中加入1.2ml乙酸作催化剂获得混合物C,将混合物C缓慢滴入混合物B中,磁力搅拌,采用油浴加热至100℃回流5h。所得反应体系室温下冷却,析出大量淡黄色晶体,减压抽滤,用无水乙醇润洗3~4次,取出滤饼,真空干燥,得到化合物C—对苯二胺缩对羟基苯甲醛双席夫碱。
(2)含有亚胺键的水性聚氨酯涂料的制备
将聚四氢呋喃二醇(PTMG)预先在120℃下真空脱水2h后备用,在N2保护下将40gPTMG、16g异佛尔酮二异氰酸酯(IPDI)、2.5g 2,2-二羟甲基丁酸(DMBA)、2.2g对苯二胺缩对羟基苯甲醛双席夫碱、1.8g 1,4-丁二醇(BDO)和2滴二月桂酸二丁基锡(DBTDL)加入三颈烧瓶中,并加入55g丁酮作为溶剂于85℃反应8h。
降低温度至35℃,加入与DMBA等摩尔量的中和剂三乙胺(TEA),反应5min,加入去离子水乳化30min,旋蒸脱除丁酮,获得含有亚胺键的自修复水性聚氨酯涂料。
取10g上述合成的涂料,铺入聚四氟乙烯板中,室温自然放置48h去除水分,40℃烘箱放置48h至完全干燥,获得涂膜。
采用傅里叶变换红外光谱仪(FTIR)对制得的聚氨酯涂膜进行全反射测试,分辨率2cm–1,测试范围为400~4000cm–1,所得结果如图1,其主要特征吸收峰为3325cm-1、1701cm-1、1602cm-1、1515cm-1等,表明已经成功制得含有亚胺键的自修复聚氨酯。
聚氨酯涂膜自修复测试:
力学性能测试:将完全干燥的涂膜裁剪成4mm×25mm的哑铃状,以100mm/min拉伸速度,采用电子拉力试验机进行力学性能测试,当涂膜被拉断时记录数据。
划痕修复测试:在涂膜表面用刀片划出宽度为20~50μm,深度为涂膜厚度的80%的划痕,放置在恒温加热板上加热以修复划痕。
自修复测试:将涂膜裁剪成4mm×25mm的哑铃状后,用刀片将涂膜一分为二后紧密贴合,放入烘箱中定时定温进行修复。
实施实例1所得的涂膜拉伸强度为31.94MPa,断裂伸长率为1154.2,在60℃下修复5min后划痕完全消失,见附图2,完全截断后,80℃下修复2h后,涂膜拉伸强度为31.70MPa,断裂伸长率为1039.0,自修复率为99.2%。
将所得涂膜经过破碎处理后所得结果如图4,在热压机中经过100℃,10min,5MPa的热压处理后,重新变为一块光滑完整的涂膜如图5。
实施例2
一种含有亚胺键的自修复水性聚氨酯涂料,其制备方法包括如下步骤:
(1)含有亚胺键的聚氨酯扩链剂的制备
将10g邻苯二胺和150ml无水乙醇加入500ml三颈烧瓶中加热至完全溶解获得混合物B,将12g水杨醛溶于150ml无水乙醇中获得混合物A,向混合物A中加入1.2ml乙酸作催化剂获得混合物C,将混合物C缓慢滴入混合物B中,磁力搅拌,采用油浴加热至100℃回流5h。所得反应体系室温下冷却,析出大量淡黄色晶体,减压抽滤,用无水乙醇润洗3~4次,取出滤饼,真空干燥,得到化合物C—邻苯二胺缩水杨醛双席夫碱。
(2)含有亚胺键的水性聚氨酯涂料的制备
将聚己内酯二醇(PCL)预先在120℃下真空脱水2h后备用,在N2保护下将40g PCL、16g异佛尔酮二异氰酸酯(IPDI)、2.3g 2,2-二羟甲基丙酸(DMPA)、2.2g邻苯二胺缩水杨醛双席夫碱、1.8g 1,4-丁二醇(BDO)和2滴DBTDL加入三颈烧瓶中,并加入55g丁酮作为溶剂85℃反应8h。
降低温度至35℃,加入与DMPA等摩尔量的中和剂三乙胺(TEA),反应5min,加入去离子水乳化30min。旋蒸脱除丁酮,获得含有亚胺键的自修复水性聚氨酯涂料。
取10g上述合成的涂料,铺入聚四氟乙烯模板中,室温自然放置48h去除水分,40℃烘箱放置48h至完全干燥,获得涂膜。
进行实施例1中涉及的性能测试,可得:
本实施例制得拉伸强度为28.98MPa、断裂伸长率为1436%的自修复聚氨酯涂膜,完全截断后,在60℃下修复30min后划痕完全消失,见附图3。80℃下修复2h后,涂膜拉伸强度为28.40MPa,断裂伸长率为1364%,自修复率为98.0%。
实施例3
一种含有亚胺键的自修复水性聚氨酯涂料,其制备方法包括如下步骤:
(1)含有亚胺键的聚氨酯扩链剂的制备
将10g对苯二胺和150ml无水乙醇加入500ml三颈烧瓶中加热至完全溶解获得混合物B,将15g香草醛溶于150ml无水乙醇中获得混合物A,向混合物A中加入1.5ml乙酸作催化剂获得混合物C,将混合物C缓慢滴入混合物B中,磁力搅拌,采用油浴加热至100℃回流6h。所得反应体系室温下冷却,析出大量淡黄色晶体,减压抽滤,用无水乙醇润洗3~4次,取出滤饼,真空干燥,得到化合物C—对苯二胺缩香草醛双席夫碱。
(2)含有亚胺键的水性聚氨酯涂料的制备
将聚己二酸1,4丁二醇酯二醇(PBA)预先在120℃下真空脱水2h后备用,在N2保护下将40g PBA、20g二环己基甲烷4,4'二异氰酸酯(HMDI)、2.5g 2,2-二羟甲基丁酸(DMBA)、2.7g对苯二胺缩香草醛双席夫碱、1.8g 1,4-丁二醇(BDO)和2滴DBTDL加入三颈烧瓶中,并加入60g丁酮作为溶剂85℃反应8h。
降低温度至35℃,加入与DMBA等摩尔量的中和剂三乙胺(TEA),反应5min,加入去离子水乳化30min。旋蒸脱除丁酮,获得含有亚胺键的自修复水性聚氨酯涂料。
取10g上述合成的涂料,铺入聚四氟乙烯模板中,室温自然放置48h去除水分,40℃烘箱放置48h至完全干燥,获得涂膜。
进行实施例1中涉及的性能测试,可得:
本实施例制得拉伸强度为52.06MPa、断裂伸长率为1305%的自修复聚氨酯涂膜,完全截断后,80℃下修复2h后,涂膜拉伸强度为39.41MPa,断裂伸长率为998%,自修复率为75.8%。
实施例4
一种含有亚胺键的自修复水性聚氨酯涂料,其制备方法包括如下步骤:
(1)含有亚胺键的聚氨酯扩链剂的制备
将10g间苯二胺和150ml无水乙醇加入500ml三颈烧瓶中加热至完全溶解获得混合物B,将12g间羟基苯甲醛溶于150ml无水乙醇中获得混合物A,向混合物A中加入1.2ml乙酸作催化剂获得混合物C,将混合物C缓慢滴入混合物B中,磁力搅拌,采用油浴加热至100℃回流5h。所得反应体系室温下冷却,析出大量淡黄色晶体,减压抽滤,用无水乙醇润洗3~4次,取出滤饼,真空干燥,得到化合物C—间苯二胺缩间羟基苯甲醛双席夫碱。
(2)含有亚胺键的水性聚氨酯涂料的制备
将聚四氢呋喃二醇(PTMG)预先在120℃下真空脱水2h后备用,在N2保护下将40gPTMG、12g异佛尔酮二异氰酸酯(IPDI)、2g 2,2-二羟甲基丁酸(DMBA)、1.7g间苯二胺缩间羟基苯甲醛双席夫碱、1g 1,4-丁二醇(BDO)和2滴DBTDL加入三颈烧瓶中,并加入50g丙酮作为溶剂60℃反应12h。
降低温度至35℃,加入与DMBA等摩尔量的中和剂三乙胺(TEA),反应5min,加入去离子水乳化30min。旋蒸脱除丙酮,获得含有亚胺键的自修复水性聚氨酯涂料。
取10g上述合成的涂料,铺入聚四氟乙烯模板中,室温自然放置48h去除水分,40℃烘箱放置48h至完全干燥,获得涂膜。
进行实施例1中涉及的性能测试,可得:
本实施例制得拉伸强度为21.32MPa、断裂伸长率为1407%的自修复聚氨酯涂膜,完全截断后,60℃下修复2h后,涂膜拉伸强度为19.88MPa,断裂伸长率为1236%,自修复率为93.2%,80℃下修复2h后,涂膜拉伸强度为21.02MPa,断裂伸长率为1396%,自修复率为98.6%。
实施例5
一种含有亚胺键的自修复水性聚氨酯涂料,其制备方法包括如下步骤:
(1)含有亚胺键的聚氨酯扩链剂的制备
将10g对苯二胺和150ml无水乙醇加入500ml三颈烧瓶中加热至完全溶解获得混合物B,将12g对羟基苯甲醛溶于150ml无水乙醇中获得混合物A,向混合物A中加入1.2ml乙酸作催化剂获得混合物C,将混合物C缓慢滴入混合物B中,磁力搅拌,采用油浴加热至100℃回流5h。所得反应体系室温下冷却,析出大量淡黄色晶体,减压抽滤,用无水乙醇润洗3~4次,取出滤饼,真空干燥,得到化合物C—对苯二胺缩对羟基苯甲醛双席夫碱。
(2)含有亚胺键的水性聚氨酯涂料的制备
将聚四氢呋喃二醇(PTMG)预先在120℃下真空脱水2h后备用,在N2保护下将40gPTMG、13.5g二环己基甲烷4,4二异氰酸酯(HMDI)、2g 2,2-二羟甲基丁酸(DMBA)、1.7g对苯二胺缩对羟基苯甲醛双席夫碱、1g 1,4-丁二醇(BDO)和2滴DBTDL加入三颈烧瓶中,并加入50g丙酮作为溶剂60℃反应12h。
降低温度至35℃,加入与DMBA等摩尔量的中和剂三乙胺(TEA),反应5min,加入去离子水乳化30min。旋蒸脱除丙酮,获得含有亚胺键的自修复水性聚氨酯涂料。
取10g上述合成的涂料,铺入聚四氟乙烯模板中,室温自然放置48h去除水分,40℃烘箱放置48h至完全干燥,获得涂膜。
进行实施例1中涉及的性能测试,可得:
本实施例制得拉伸强度为25.06MPa、断裂伸长率为1364%的自修复聚氨酯涂膜,完全截断后,室温下自修复24h后,涂膜拉伸强度为18.72MPa,断裂伸长率为1023%,自修复率为74.7%。80℃下修复2h后,涂膜拉伸强度为23.96MPa,断裂伸长率为1210%,自修复率为95.6%。
中国发明专利CN113651938A所制得的聚氨酯最高拉伸强度仅8.46MPa,修复率为95%;中国发明专利CN113512173A所制得的自修复聚氨酯经过80℃,4h的处理修复率最高为96.8%;中国发明专利CN111875821A采用四氢呋喃做溶剂合成了有自修复效果的聚氨酯,最高修复率为98%。与上述发明专利相比,本发明专利制得的水性聚氨酯自修复涂膜最高拉伸强度为52MPa,经过较短的时间和较低的温度(80℃,2h)修复后,最高修复率可达99.2%,并且工艺简单,易于控制,合成过程绿色经济,得到的自修复聚氨酯不会因溶剂挥发而对人体和自然环境产生危害。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种含有亚胺键的自修复水性聚氨酯涂料,其特征在于,所述涂料的制备方法包括以下步骤:
步骤1、含有亚胺键的聚氨酯扩链剂的制备
按1:4~1:8的质量比将化合物A溶于溶剂A中得到混合物A,按1:15~1:20的质量比将化合物B溶解于溶剂A中得到混合物B,向混合物A中加入催化剂A得到混合物C,将混合物C缓慢滴入混合物B中,并磁力搅拌,采用油浴加热至100℃回流5h,所得溶液进行室温冷却后减压抽滤并用无水乙醇润洗3至4次,取出滤饼真空干燥后,得到含有亚胺键的目标产物A;其中,所述化合物A含有一个-OH和一个-CHO,所述化合物B含有2个-NH2,且化合物A和B的摩尔比为2:1~2.2:1;
步骤2、含有亚胺键的水性聚氨酯涂料的制备
将聚合物二元醇预先在120℃下真空脱水2h,得到原料A备用;在氮气保护下取质量比为20:8:1.25:1.25:1:0.5:31的原料A、二异氰酸酯、亲水扩链剂、目标产物A、小分子扩链剂、催化剂和溶剂B混合后于85℃反应8h;
步骤3、将步骤2所得反应体系降温至35℃后将入与亲水扩链剂等摩尔量的中和剂反应5min后加入去离子水乳化,旋转脱除溶剂B,获得含有亚胺键的自修复水性聚氨酯涂料。
2.根据权利要求1所述的一种含有亚胺键的自修复水性聚氨酯涂料,其特征在于,所述化合物A具体为对羟基苯甲醛、间羟基苯甲醛、水杨醛、香草醛中的一种。
3.根据权利要求2所述的一种含有亚胺键的自修复水性聚氨酯涂料,其特征在于,化合物B为对苯二胺,间苯二胺、领苯二胺中的一种。
4.根据权利要求3所述的一种含有亚胺键的自修复水性聚氨酯涂料,其特征在于,所述聚合物二元醇为聚己二酸1,4丁二醇酯二醇、聚己内酯二醇、聚碳酸酯二醇、聚四氢呋喃二醇中的一种。
5.根据权利要求4所述的一种含有亚胺键的自修复水性聚氨酯涂料,其特征在于,所述二异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯甲烷二异氰酸酯、六亚甲基二异氰酸酯或二环己基甲烷4,4'二异氰酸酯中的一种。
6.根据权利要求5所述的一种含有亚胺键的自修复水性聚氨酯涂料,其特征在于,所述催化剂为二丁基二月桂酸锡,所述溶剂A为无水乙醇,所述溶剂B为丙酮或丁酮中的一种。
7.根据权利要求5所述的一种含有亚胺键的自修复水性聚氨酯涂料,其特征在于,所述亲水扩链剂为2,2-二羟甲基丙酸或2,2-二羟甲基丁酸中的一种,所述小分子扩链剂为1,4-丁二醇,所述中和剂为三乙胺。
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