CN115340658A - 一种低表面能弹性异氰酸酯固化剂及其制备方法和应用 - Google Patents

一种低表面能弹性异氰酸酯固化剂及其制备方法和应用 Download PDF

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CN115340658A
CN115340658A CN202110526155.9A CN202110526155A CN115340658A CN 115340658 A CN115340658 A CN 115340658A CN 202110526155 A CN202110526155 A CN 202110526155A CN 115340658 A CN115340658 A CN 115340658A
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宁亮
王贤明
吴连锋
李镇
卢敏
王飞
易敏华
王志勇
万众
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Marine Chemical Research Institute Co Ltd
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Abstract

本发明公开了一种低表面能弹性异氰酸酯固化剂及其制备方法和应用。低表面能弹性异氰酸酯固化剂由包括聚ε‑己内酯多元醇、聚醚多元醇、聚碳酸酯多元醇、扩链剂、异佛尔酮二异氰酸酯、有机溶剂、催化剂、低表面能改性氟碳树脂和纳米补强剂的原料制备而成,制得固化剂的NCO含量为2.0~3.0mol/kg,固含量为65%~77%。使用本发明中的低表面能弹性异氰酸酯固化剂制备聚氨酯涂料,可降低聚氨酯涂层的表面能,降低吸潮率,增加强度和弹性,有更好的抗侵蚀能力,提高耐老化性,有更好的环境适应性,可应用于电磁窗表面的聚氨酯涂料。

Description

一种低表面能弹性异氰酸酯固化剂及其制备方法和应用
技术领域
本发明涂料技术领域,进一步地说,是涉及一种低表面能弹性异氰酸酯固化剂及其制备方法和应用。
背景技术
制造电磁窗的主要材料为树脂基复合材料,其长期曝露在温度骤变、砂石冲蚀、光化学和热老化、潮湿等复杂环境下,常发生吸潮、老化甚至破坏等问题,导致寿命减少、性能下降,影响装备性能。
目前的主要防护方法是采用聚氨酯涂料在电磁窗表面进行均匀涂敷。在使用条件并不苛刻的常规环境下,电磁窗的聚氨酯涂料使用情况良好,但随着装备服役环境越来越复杂、条件越来越苛刻,常规的聚氨酯涂料体系在这样的使用环境下易出现吸潮、水解、应力开裂等问题,引起分子主链断裂、分子量降低、拉伸强度和断裂伸长率急剧下降,从而严重影响防护效果和透波性能,尤其是盐雾、湿热、酸性等复杂海洋环境大气对其破坏性更大。
综上所述,现有技术的电磁窗用聚氨酯涂料在海洋环境大气等苛刻条件下,易发生潮解导致涂层破坏,需要对电磁窗用聚氨酯涂料进行改进,提高涂层的防潮性、有效缓解因环境因素导致涂层破坏,在各种苛刻的使用条件下,仍能保证电磁窗的防护效果和透波性能。
发明内容
为解决现有技术中存在的问题,本发明提供了一种低表面能弹性异氰酸酯固化剂及其制备方法和应用。
使用本发明中的低表面能弹性异氰酸酯固化剂制备聚氨酯涂料,可降低聚氨酯涂层的表面能(降低吸潮率)、同时增加强度和弹性(抵抗冲刷侵蚀)、提高耐老化性(环境影响),全面提升聚氨酯涂层的环境适应性。
低表面能可以避免表面形成水膜导致电磁窗透波性能下降;高强高弹可应对砂石、雨滴高速冲蚀;耐老化性能主要针对光化学老化和热老化;全面提升聚氨酯涂料的耐苛刻环境性能。
本发明的目的之一是提供一种低表面能弹性异氰酸酯固化剂。
所述低表面能弹性异氰酸酯固化剂由包括聚ε-己内酯多元醇、聚醚多元醇、聚碳酸酯多元醇、扩链剂、异佛尔酮二异氰酸酯、有机溶剂、催化剂、低表面能改性氟碳树脂和纳米补强剂的原料制备而成;
以异佛尔酮二异氰酸酯为100重量份,各组分按重量份计:
Figure BDA0003065853080000021
所述低表面能弹性异氰酸酯固化剂的-NCO含量为2.0~3.0mol/kg,固含量为65%~77%;
本发明的一种优选的实施方式中,
所述聚ε-己内酯多元醇的平均分子量为1700~2300。
本发明的一种优选的实施方式中,
所述聚醚多元醇的平均分子量为1800~2200;更优选为聚四氢呋喃;和/或,
所述聚碳酸酯多元醇的平均分子量为1600~2400;更优选为聚碳酸酯二醇。
本发明的一种优选的实施方式中,
所述扩链剂为C3~C6的二元醇中的一种,优选为1,4-丁二醇、二乙二醇、1,4-环己醇、丙二醇中的一种;和/或,
所述有机溶剂可采用现有技术中本领域通常采用的有机溶剂,为芳香类溶剂、酯类溶剂、醚酯类溶剂中的至少一种,优选为二甲苯、芳香烃碳氢化合物(S100、S150)、醋酸丁酯、醋酸乙酯、乙二醇乙醚醋酸酯、丙二醇甲醚醋酸酯中的至少一种;和/或,
所述催化剂可采用现有技术中本领域通常采用的催化剂,为有机锡类催化剂、有机铋类催化剂中的至少一种,有机锡类催化剂优选为二月桂酸二丁基锡、辛酸亚锡中的至少一种,有机铋催化剂可优选美国领先的BICat8118、BICat8108中的至少一种。
本发明的一种优选的实施方式中,
所述低表面能改性氟碳树脂是用全氟烷基异氰酸酯化合物对氟碳树脂进行改性的聚合物,优选海洋化工研究院生产的WN-FNCO-0302;和/或,
所述纳米补强剂为气相二氧化硅,优选德固赛的R972或R974。
本发明的目的之二是提供一种低表面能弹性异氰酸酯固化剂的制备方法,包括:
将聚ε-己内酯多元醇、聚醚多元醇、聚碳酸酯多元醇混合物A熔化后,在57℃~63℃、氮气保护下滴入异佛尔酮二异氰酸酯与有机溶剂的混合物B中,反应1~2h后,滴加扩链剂,再滴加完催化剂后升温至82~88℃,反应3~4h后,降温至57℃~63℃,加入低表面能改性氟碳树脂和纳米补强剂,反应1~2h后,得到所述低表面能弹性异氰酸酯固化剂。
本发明的一种优选的实施方式中,
混合物A滴入混合物B的滴加速度、扩链剂的滴加速度、催化剂的滴加速度均为3~5滴/秒。
本发明的目的之三是提供一种低表面能弹性异氰酸酯固化剂的应用。
所述低表面能弹性异氰酸酯固化剂应用于电磁窗表面的聚氨酯涂料。
本发明具体可以采取以下技术方案:
所述低表面能弹性异氰酸酯固化剂包括:
聚ε-己内酯多元醇、聚醚多元醇、聚碳酸酯多元醇、扩链剂、异佛尔酮二异氰酸酯、有机溶剂、催化剂、低表面能改性氟碳树脂,纳米补强剂;
以异佛尔酮二异氰酸酯为100重量份,各组分按重量份计:
Figure BDA0003065853080000041
基本性能见下表1:
表1固化剂基本参数
序号 性能 参考值
1 外观 无色透明
2 -NCO含量,mol/kg 2.0~3.0
3 固含量,% 65~77
所述聚ε-己内酯多元醇的平均分子量为1700~2300,本发明优选湖南聚仁PCL-耐水解系列2200A或2202B;
所述聚醚多元醇是平均分子量为1800~2200的聚四氢呋喃,本发明优选杜邦的PTMG-2000、巴斯夫的POLY THF 2000或山西三维的PTMG-2000;
所述聚碳酸酯多元醇是平均分子量为1600~2400的聚碳酸酯二醇,本发明优选大赛璐的CD-220或CD220HL;
所述的扩链剂是一种小分子二元醇扩链剂,本发明优选1,4-丁二醇、二乙二醇、1,4-环己醇、丙二醇;
所述的异佛尔酮二异氰酸酯是一种脂环族二异氰酸酯,耐光性好、不黄变,本发明优选德国Huels AG、Bayer公司相关产品;
所述有机溶剂为芳香类溶剂、酯类溶剂或醚酯类溶剂。可采用现有技术中本领域通常采用的有机溶剂,本发明中:所述芳香类溶剂可优选为二甲苯、芳香烃碳氢化合物(S100、S150),所述酯类溶剂可优选为醋酸丁酯、醋酸乙酯,所述醚酯类溶剂可优选为乙二醇乙醚醋酸酯、丙二醇甲醚醋酸酯。
所述的催化剂为有机锡类或更环保的有机铋类。可采用现有技术中本领域通常采用的催化剂,本发明中:所述的有机锡类催化剂可优选二月桂酸二丁基锡、辛酸亚锡,所述环保有机铋催化剂可优选美国领先的BICat8118、BICat8108;
所述的低表面能改性氟碳树脂是利用全氟烷基异氰酸酯化合物对氟碳树脂进行改性的聚合物,可优选海洋化工研究院生产的WN-FNCO-0302,由包括以下步骤的方法制备的:
(1)将氟碳树脂和有机溶剂混合后升温至57℃~63℃,充氮保温40~45min;
(2)加入含全氟烷基异氰酸酯化合物,质量为F-0302氟碳树脂质量的10~15重量份,同时滴加1~2‰的催化剂;
所述催化剂为二月桂酸二丁基锡、辛酸亚锡、有机铋的一种或组合;
本发明的全氟烷基的异氰酸酯化合物为专利申请(专利号为CN101143840A,发明名称为“含全氟烷基链段的多异氰酸酯的制备及应用”)中的全氟烷基异氰酸酯化合物。
(3)57℃~63℃保温1~2h后,升温至67℃~73℃,继续充氮保温3~4h;
(4)温度降至50℃以下出料,制得所述低表面改性氟碳树脂。
所述的纳米补强剂是气相二氧化硅,本发明优选德固赛的R972或R974;
本发明提供一种电磁窗用低表面能弹性异氰酸酯固化剂的制备方法,包括:
(1)将异佛尔酮二异氰酸酯与有机溶剂的混合物升温至57℃~63℃,充氮保温40~45min;
(2)滴加熔化后的聚已内酯多元醇、聚醚多元醇、聚碳酸酯多元醇混合物,滴加速度控制3~5滴/秒;
(3)57℃~63℃保温反应1~2h;
(4)滴加扩链剂,滴加速度控制3~5滴/秒;
(5)滴加催化剂,滴加速度控制3~5滴/秒,滴加结束后,体系升温至85℃保温反应3~4h;
(6)降温至57℃~63℃,加入低表面能改性氟碳树脂和纳米补强剂,保温反应1~2h;
(7)温度降到室温后出料包装。
与现有技术相比,本发明的有益效果:
本发明的涂料是一种电磁窗用低表面能弹性异氰酸酯固化剂,使用本发明中的低表面能弹性异氰酸酯固化剂制备聚氨酯涂料,可降低聚氨酯涂层的表面能,降低吸潮率,避免表面形成水膜导致电磁窗透波性能下降;同时增加聚氨酯涂层强度和弹性,可应对砂石、雨滴高速冲蚀,抵抗侵蚀;提高耐老化性,包括光化学老化和热老化,降低环境影响,全面提升聚氨酯涂料的耐环境能力。
本发明作为双组份聚氨酯体系中的B组分,与体系中的A组分(羟基组分)混合后发生交联反应,固化后形成涂层,常温干燥固化,与常规弹性聚氨酯涂层体系相比较,本发明通过弹性聚氨酯微区软硬段控制、低表面能预聚物改性、纳米补强剂补强、聚合物设计与合成等技术,综合提升电磁窗涂层在复杂气象条件下的的防潮性、抗水解性、力学性能和耐候性,一定程度上缓解透波率下降、水解降解、力学性能下降、粉化破坏等问题。
具体实施方式
下面结合具体实施例对本发明进行具体的描述,有必要在此指出的是以下实施例只用于对本发明的进一步说明,不能理解为对本发明保护范围的限制,本领域技术人员根据本发明内容对本发明做出的一些非本质的改进和调整仍属本发明的保护范围。
实施例中低表面能氟碳树脂为海洋化工研究院生产的WN-FNCO-0302;
实施例所用其它原料均为常规市购原料。
低表面能氟碳树脂的制备:
实施例中所用低表面能氟碳树脂是利用全氟烷基异氰酸酯化合物对氟碳树脂进行改性的聚合物,产品牌号为海洋化工研究院生产的WN-FNCO-0302。
制备过程如下:
(1)将F-0302氟碳树脂升温至60℃,充氮保温45min;
(2)加入含全氟烷基的异氰酸酯化合物,质量为F-0302氟碳树脂质量的12%,同时滴加1‰的二月桂酸二丁基锡催化剂;
(3)60℃保温2h后,升温至70℃,继续充氮保温4h;
(4)温度降至50℃以下出料,制得所述低表面改性氟碳树脂。
表2实施例中的原材料明细表
Figure BDA0003065853080000071
Figure BDA0003065853080000081
实施例1
异佛尔酮二异氰酸酯为100重量份,聚ε-己内酯多元醇2200A 50重量份;聚醚多元醇20重量份;聚碳酸酯多元醇25重量份;1,4-丁二醇7重量份;二甲苯30重量份;醋酸丁酯30重量份;BICat8118催化剂0.3重量份;低表面能改性氟碳树脂6重量份;德固赛R972纳米补强剂3重量份。
制备方法包括:
(1)将异佛尔酮二异氰酸酯与有机溶剂的混合物升温至60℃,充氮保温40min;
(2)滴加熔化后的聚已内酯多元醇、聚醚多元醇、聚碳酸酯多元醇混合物,滴加速度控制3~5滴/秒;
(3)60℃保温反应2h;
(4)滴加扩链剂,滴加速度控制3~5滴/秒;
(5)滴加催化剂,滴加速度控制3~5滴/秒,滴加结束后,体系升温至85℃保温反应4h;
(6)降温至60℃,加入低表面能改性氟碳树脂和纳米补强剂的混合物,保温反应2h;
(7)温度降到室温后出料包装。
实施例2
异佛尔酮二异氰酸酯为100重量份,聚ε-己内酯多元醇2202B 70重量份;聚醚多元醇POLY THF 2000 6重量份;聚碳酸酯多元醇CD220HL 6重量份;1,4-环己醇1.5重量份;醋酸丁酯50重量份;丙二醇甲醚醋酸酯50重量份;BICat8118催化剂0.8重量份;低表面能改性氟碳树脂25重量份;德固赛R972纳米补强剂6重量份。
制备方法同实施例1。
实施例3
异佛尔酮二异氰酸酯为100重量份,聚ε-己内酯多元醇2202B 60重量份;聚醚多元醇POLY THF 2000 8重量份;聚碳酸酯多元醇CD220HL 8重量份;1,4-环己醇5重量份;醋酸丁酯40重量份;丙二醇甲醚醋酸酯40重量份;BICat8118催化剂1.6重量份;低表面能改性氟碳树脂8重量份;德固赛R972纳米补强剂10重量份。
制备方法同实施例1。
实施例4
异佛尔酮二异氰酸酯为100重量份,聚ε-己内酯多元醇2202B 60重量份;聚醚多元醇POLY THF 2000 15重量份;聚碳酸酯多元醇CD220HL 20重量份;1,4-环己醇3重量份;醋酸丁酯40重量份;丙二醇甲醚醋酸酯40重量份;BICat8118催化剂1.2重量份;低表面能改性氟碳树脂15重量份;德固赛R974纳米补强剂3重量份。
制备方法同实施例1。
实施例5
异佛尔酮二异氰酸酯为100重量份,聚ε-己内酯多元醇2200A 70重量份;聚醚多元醇POLY THF 2000 20重量份;聚碳酸酯多元醇CD220HL 25重量份;1,4-环己醇1.5重量份;醋酸丁酯50重量份;丙二醇甲醚醋酸酯60重量份;BICat8118催化剂0.7重量份;低表面能改性氟碳树脂25重量份;德固赛R972纳米补强剂7重量份。
制备方法同实施例1。
实施例6
异佛尔酮二异氰酸酯为100重量份,聚ε-己内酯多元醇2200A 50重量份;聚醚多元醇POLY THF 2000 6重量份;聚碳酸酯多元醇CD220HL 6重量份;1,4-环己醇2重量份;醋酸丁酯40重量份;丙二醇甲醚醋酸酯40重量份;BICat8118催化剂1.2重量份;低表面能改性氟碳树脂6重量份;德固赛R974纳米补强剂5重量份。
制备方法:
(1)将异佛尔酮二异氰酸酯与有机溶剂的混合物升温至63℃,充氮保温40min;
(2)滴加熔化后的聚已内酯多元醇、聚醚多元醇、聚碳酸酯多元醇混合物,滴加速度控制3~5滴/秒;
(3)63℃保温反应1h;
(4)滴加扩链剂,滴加速度控制3~5滴/秒;
(5)滴加催化剂,滴加速度控制3~5滴/秒,滴加结束后,体系升温至88℃保温反应3h;
(6)降温至63℃,加入低表面能改性氟碳树脂和纳米补强剂的混合物,保温反应1h;
(7)温度降到室温后出料包装。
表3实施例1~6的性能测试结果
Figure BDA0003065853080000101
Figure BDA0003065853080000111
常规羟基丙烯酸树脂为Hypomer FS-4365A,与常规异氰酸酯固化剂拜耳N75按照-OH:-NCO=1:1反应后,漆膜抗张强度为9MPa,断裂伸长率为40%,憎水角为83°。
由此可见,与常规异氰酸酯固化剂制得漆膜相比,本发明的固化剂制得漆膜在抗张强度、断裂伸长率和憎水角方面均明显提升,使用本发明中的低表面能弹性异氰酸酯固化剂制备的聚氨酯涂料,涂层的表面能更低,可有效降低吸潮率,强度和弹性更高,可抵抗冲刷侵蚀,有更好的环境适应性,可应用于电磁窗表面,在各种苛刻的使用条件下,仍能保证电磁窗的防护效果和透波性能。

Claims (10)

1.一种低表面能弹性异氰酸酯固化剂,其特征在于:
所述低表面能弹性异氰酸酯固化剂由包括聚ε-己内酯多元醇、聚醚多元醇、聚碳酸酯多元醇、扩链剂、异佛尔酮二异氰酸酯、有机溶剂、催化剂、低表面能改性氟碳树脂和纳米补强剂的原料制备而成;
以异佛尔酮二异氰酸酯为100重量份,各组分按重量份计:
Figure FDA0003065853070000011
所述低表面能弹性异氰酸酯固化剂的-NCO含量为2.0~3.0mol/kg,固含量为65%~77%。
2.如权利要求1所述的低表面能弹性异氰酸酯固化剂,其特征在于:
Figure FDA0003065853070000012
Figure FDA0003065853070000021
3.如权利要求1所述的低表面能弹性异氰酸酯固化剂,其特征在于:
所述聚ε-己内酯多元醇的平均分子量为1700~2300。
4.如权利要求1所述的低表面能弹性异氰酸酯固化剂,其特征在于:
所述聚醚多元醇的平均分子量为1800~2200;和/或,
所述聚碳酸酯多元醇的平均分子量为1600~2400。
5.如权利要求1所述的低表面能弹性异氰酸酯固化剂,其特征在于:
所述扩链剂为C3~C6的二元醇中的一种;和/或,
所述有机溶剂为芳香类溶剂、酯类溶剂、醚酯类溶剂中的至少一种;和/或,
所述催化剂为有机锡类催化剂、有机铋类催化剂中的至少一种。
6.如权利要求5所述的低表面能弹性异氰酸酯固化剂,其特征在于:
所述扩链剂为1,4-丁二醇、二乙二醇、1,4-环己醇、丙二醇中的一种;和/或,
所述有机溶剂为二甲苯、醋酸丁酯、醋酸乙酯、乙二醇乙醚醋酸酯、丙二醇甲醚醋酸酯中的至少一种;和/或,
所述有机锡类催化剂为二月桂酸二丁基锡、辛酸亚锡中的至少一种。
7.如权利要求1所述的低表面能弹性异氰酸酯固化剂,其特征在于:
所述低表面能改性氟碳树脂是用含全氟烷基异氰酸酯化合物对氟碳树脂进行改性的聚合物;和/或,
所述纳米补强剂为气相二氧化硅。
8.一种如权利要求1~7之一所述的低表面能弹性异氰酸酯固化剂的制备方法,其特征在于所述方法包括:
将聚ε-己内酯多元醇、聚醚多元醇、聚碳酸酯多元醇混合熔化后得到混合物A;异佛尔酮二异氰酸酯与有机溶剂混合,得到混合物B;在57℃~63℃、氮气保护下将混合物A滴入混合物B中,反应1~2h后,滴加扩链剂、催化剂后升温至82~88℃,反应3~4h后,降温至57℃~63℃,加入低表面能改性氟碳树脂和纳米补强剂,反应1~2h后,得到所述低表面能弹性异氰酸酯固化剂。
9.如权利要求8所述的低表面能弹性异氰酸酯固化剂的制备方法,其特征在于:
混合物A滴入混合物B的滴加速度、扩链剂的滴加速度、催化剂的滴加速度均为3~5滴/秒。
10.如权利要求1~7之一所述的低表面能弹性异氰酸酯固化剂应用于电磁窗表面的聚氨酯涂料。
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