CN106753151B - 一种防爆破冲击聚脲涂层及其制备方法 - Google Patents
一种防爆破冲击聚脲涂层及其制备方法 Download PDFInfo
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- CN106753151B CN106753151B CN201611082325.4A CN201611082325A CN106753151B CN 106753151 B CN106753151 B CN 106753151B CN 201611082325 A CN201611082325 A CN 201611082325A CN 106753151 B CN106753151 B CN 106753151B
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- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种防爆破冲击聚脲涂层及其制备方法，属于涂料组合物领域。一种防爆破冲击聚脲涂层，其包括A、B两种组分，所述A组分为由40～60份异氰酸酯、40～60份聚酯多元醇、1～10份石墨烯浆料反应得到的半预聚物组分；所述B组分由10～30份扩链剂、15～30份聚醚多元醇、40～60份端氨基聚醚、1～10份石墨烯浆料、颜料及微量助剂组成。所述聚脲涂层具备高物理强度、高抗剪切、高速冲击及高速大形变下强度保持率高、低温柔韧性好等性能，适应防爆场合的应用。
Description
技术领域
本发明涉及一种防爆破冲击聚脲涂层及其制备方法，属于涂料组合物领域。
背景技术
喷涂聚脲材料具有不含任何溶剂、成膜强度好、涂层耐老化、施工快捷等优点，是一种具有极大发展潜力的防护涂层。在海底管道、埋地管道防腐、储罐防腐、混凝土保护、防水、矿山耐磨、军用蒙皮、装甲内衬、底盘防护等领域应用前景是非常广阔的。我国目前聚脲涂层的应用，主要在工业重防腐、建筑物防渗透、防水、耐磨等领域。聚脲材料应用于军用蒙皮、装甲内衬、复合装甲、防弹盾牌、防弹头盔时，需要材料本身具有良好的抗高速撞击性能，其不但要求具有超高的物理强度，更要求其在高速冲击下表现出良好的抗撕裂性能，现有聚脲产品难以满足此项需求。
目前的解决方法是采用增加填料和提高硬段含量来改善这个问题。但是，填料的过量加入将导致材料在高速冲击下产生无机填料和树脂的分离，表现为高速冲击下强度下降极大，硬段含量的提高虽然增加了强度，但其硬度也大大提高，导致其低温柔韧性不好，在低温下易碎裂，难以满足要求。
喷涂聚脲技术是继水性涂料、高固含量涂料、粉末涂料之后发展起来的环保绿色功能材料。喷涂聚脲材料不含任何溶剂、成膜强度好、涂层耐老化、施工快捷等优点，是一种具有极大发展潜力的防护涂层。在海底管道、埋地管道防腐、储罐防腐、混凝土保护、防水、矿山耐磨、军用蒙皮、装甲内衬、底盘防护等领域应用前景是非常广阔的。我国目前聚脲涂层的应用，主要在工业重防腐、建筑物防渗透、防水、耐磨等领域。聚脲材料应用于军用蒙皮、装甲内衬、复合装甲、防弹盾牌、防弹头盔时，需要材料本身具有良好的抗高速撞击性能，其不但要求具有超高的物理强度，更要求其在高速冲击下表现出良好的抗撕裂性能，现有聚脲产品难以满足此项需求。
中国专利201410557843.1涉及一种防爆吸能聚脲弹性涂料及制备方法。该涂料由A、B组分构成，其中A组分由40～80重量份异氰酸酯、15～35重量份聚醚多元醇、0～10重量份扩链剂以及5～15重量份稀释剂组成；B组分由40～80重量份端氨基聚醚、20～40重量份胺扩链剂、0～10重量份填料以及0～10重量份助剂组成。该发明的防爆吸能聚脲弹性涂料，经喷涂得到的涂层在具有超高强度性能的同时，仍具有良好柔韧性，可有效抵御爆炸物的冲击波和碎片，特别适合于用作武器装备的复合装甲以及军事设施的防护层。
上述发明提及了防爆吸能聚脲材料，其A组份采用聚醚型多元醇与异氰酸酯合成，B组分中采用添加填料及助剂提高性能。添加型填料及助剂在材料使用过程中与高分子链段将产生相分离及添加型助剂的逸出，导致材料的物理性能呈下降趋势，同时采取聚醚合成预聚物组份其链段内聚能较弱，表现为其物理强度较小。
综上所述，现有技术主要存在以下问题：
1.添加填料，添加量大，不易分散，高速冲击下与树脂微观分离，导致强度急剧下降。
2.普通聚脲涂层撕裂强度差，难以满足防爆需求。
3.依靠填料及硬段含量提高强度，导致材料硬度过高，低温下脆性大。
发明内容
为解决现有技术存在的难以同时满足高强度、高速冲击下强度保持、高撕裂、低温柔韧性等需求这一问题，本发明提供一种防爆破冲击聚脲涂层及其制备方法。
本发明的采用的技术方案如下：
一种防爆破冲击聚脲涂层，其包括A、B两种组分，所述A组分为由40～60份异氰酸酯、40～60份聚酯多元醇、1～10份石墨烯浆料反应得到的半预聚物组分；所述B组分由10～30份扩链剂、15～30份聚醚多元醇、40～60份端氨基聚醚、1～10份石墨烯浆料、颜料及微量助剂组成。
所述异氰酸酯选自二苯基甲烷二异氰酸酯及其聚合体、碳化二亚胺改性二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、氢化二苯基甲烷二异氰酸酯、三苯基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、三甲基1,6-六亚甲基二异氰酸酯的一种或几种。
所述聚酯多元醇选自聚碳酸酯多元醇和聚己内酯多元醇，其中至少包含一种支化型聚酯多元醇。
所述扩链剂选自甲基二乙醇胺、异佛尔酮二胺(IPDA)、二乙基甲苯二胺、二甲硫基甲苯二胺、二乙基甲苯二胺、N,N’-二烷基二胺、N,N’-二烷基甲基二胺、1,4-双仲丁氨基苯、4,4’-双仲基氨基二苯基甲烷、4,4'-亚甲基双(3-氯-2,6-二乙基苯胺)(M-CDEA)、4,4-亚甲基双(2,6-二乙基苯胺)(M-DEA)、N,N’-双仲戊基环己烷二胺中的一种或几种。
所述聚醚多元醇选自聚氧化丙烯二醇、聚氧化丙烯三醇、四羟丙基乙二胺、聚四氢呋喃二醇中的一种或几种。
所述A组分(半预聚物组分)在70-120℃下反应制得，异氰酸酯与聚酯多元醇聚合后，其NCO含量为15-25％，加入所述石墨烯浆料进一步反应后NCO含量为10-20％，粘度为1000-3000cps。
所述石墨烯浆料为改性石墨烯浆料，其制备方法包括以下步骤：首先对石墨进行表面氧化改性，使其表面含有大量的含氧基团，然后采用氨基硅烷对其进行二次改性并利用超声波纳米分散手段进行分散，其表面羟基基团进一步丰富，含氧基团中的羟基可获得具有良好储存稳定性的石墨烯浆料，可与异氰酸酯基团发生化学交联反应。
一种制备所述的防爆破冲击聚脲涂层的方法，将所述A、B组分利用高压喷涂设备按体积比1:1的比例进行喷涂，即可制得所述防爆破冲击聚脲涂层。
本发明与现有技术相比具有如下优异技术效果：
1、本发明通过化学改性与物理共混相结合的方法，制备在爆炸冲击波载荷作用下具有优异防爆性能的喷涂聚脲涂层。其中，A组分采用的异氰酸酯与改性石墨烯反应结合，形成化学交联结构，与B组份再次反应后形成稳定的化学结构成为软硬段分布更为均衡的聚脲树脂结构，不分离，不逸出，石墨烯作为化学交联点，形成网络结构，提高了其物理性能。
2、本发明A、B组份中不含有非反应型填料，即摒弃了物理添加型增强填料，使得原料在不采用任何稀释剂或降粘剂的情况下流动性极好，适合喷涂成型；避免了采用提高聚脲硬段含量的方式提高强度导致的低温脆性问题。采用此方式制备的聚脲材料高速冲击下性能稳定，撕裂强度极高，低温柔韧性好，可满足防爆破需求。
3、本发明采用石墨烯改变预聚物主链结构，同时在B组份中添加粘度低、流动性好的石墨烯浆料，其增强性能较普通物理添加方式具有更好地效果，实现具备高物理强度、高抗剪切、高速冲击及高速大形变下强度保持率高的聚脲涂层，适应防爆场合的应用。
具体实施方式
以下结合实施例对本发明做进一步解释：
实施例1：
本实施案例的抗爆炸冲击聚脲涂层配方如下：
A组分
MDI-50 50
MS-202(聚碳酸酯多元醇) 45
改性石墨烯浆料 5
B组分
改性石墨烯浆料制备：将天然鳞片石墨(青岛和兴，800目)与硝酸钠混合后加入反应容器内，加入浓硫酸，常温反应2h后加入高锰酸钾，升温至40℃反应3h后加入去离子水升温至90℃加入双氧水，洗涤干燥，然后将其与MDI-50、DMF、氨基硅烷KH550混合后超声分散，90℃下进行真空干燥抽出溶剂，制得无溶剂液体石墨烯浆料。
将45份MS-202加入反应釜中，然后加入5份改性石墨烯浆料，加热至110℃抽真空3小时后加入50份MDI-50，85-105℃反应3小时，获得半预聚物A组分。
将B组分依次加入搅拌罐搅拌均匀，进入砂磨机研磨2.5小时后，制得B组分。
将A、B组分采用高压喷涂机喷涂，A、B两种组分料经抽料泵输送到主机，经加温加压并精确计量后在动态混合室内混合均匀，喷涂到表面并快速固化成型。按照GB9278规定条件下放置7天后进行性能测定。
表1性能测定结果
| 拉伸强度 | 33MPa |
| 伸长率 | 520％ |
| 表干时间 | 30S |
| 撕裂强度 | 108kN/m |
| 耐低温性能 | -50℃不开裂 |
实施例2：
A组分
B组分
将50份MS-650B、5份改性石墨烯浆料加入反应釜中，加热至110度抽真空3小时后加入30份MDI-100、15份H12MDI(氢化MDI)，105℃反应3小时，获得半预聚物A组分。
将B组分依次加入搅拌罐搅拌均匀，进入砂磨机研磨2.5小时后，制得B组分。
将A、B组分采用高压喷涂机喷涂，A、B两种组分料经抽料泵输送到主机，经加温加压并精确计量后在动态混合室内混合均匀，喷涂到表面并快速固化成型。按照GB9278规定条件下放置7天后进行性能测定。
表2性能测定结果
| 拉伸强度 | 32MPa |
| 伸长率 | 390％ |
| 表干时间 | 18S |
| 撕裂强度 | 102kN/m |
| 耐低温性能 | -50℃不开裂 |
实施例3：
配方同实施例2
将实施例2的A、B组份采用低压浇注机浇注，两组分经由储料罐进入比例泵精确计量后，在浇注头进行高速螺旋混合，挤出或注射到塑料模板上固化成型。
按照GB9278规定条件下放置7天后进行性能测定。
表3性能测定结果
| 拉伸强度 | 42MPa |
| 伸长率 | 350％ |
| 表干时间 | 18S |
| 撕裂强度 | 123kN/m |
| 耐低温性能 | -50℃不开裂 |
Claims (7)
1.一种防爆破冲击聚脲涂层，其特征在于，包括A、B两种组分，所述A组分为由40～60份异氰酸酯、40～60份聚酯多元醇、l～10份石墨烯浆料反应得到的半预聚物组分：所述B组分由10～30份扩链剂、15～30份聚醚多元醇、40～60份端氨基聚醚、1～10份石墨烯浆料、颜料及微量助剂组成；
所述石墨烯浆料为改性石墨烯浆料；
所述改性石墨烯浆料的制备方法包括以下步骤：首先对石墨进行表面氧化改性，然后采用氨基硅烷对其进行二次改性并利用超声波纳米分散手段进行分散，制得表面含有大量羟基基团的石墨烯浆料；
所述A、B组分按体积比1：1的比例进行混合喷涂，即可制得所述防爆破冲击聚脲涂层。
2.根据权利要求1所述的防爆破冲击聚脲涂层，其特征在于，所述异氰酸酯选自二苯基甲烷二异氰酸酯及其聚合体、碳化二亚胺改性二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、氢化二苯基甲烷二异氰酸酯、三苯基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、三甲基1,6-六亚甲基二异氰酸酯的一种或几种。
3.根据权利要求1所述的防爆破冲击聚脲涂层，其特征在于，所述聚酯多元醇选自聚碳酸酯多元醇和聚己内酯多元醇，其中至少包含一种支化型聚酯多元醇。
4.根据权利要求1所述的防爆破冲击聚脲涂层，其特征在于，所述扩链剂选自甲基二乙醇胺、异佛尔酮二胺、二乙基甲苯二胺、二甲硫基甲苯二胺、N,N'-二烷基二胺、N,N'-二烷基甲基二胺、1,4-双仲丁氨基苯、4,4'-亚甲基双(3-氯-2,6-二乙基苯胺)、4,4'-亚甲基双(2,6-二乙基苯胺)、N,N'-双仲戊基环己烷二胺中的一种或几种。
5.根据权利要求1所述的防爆破冲击聚脲涂层，其特征在于，所述聚醚多元醇选自聚氧化丙烯二醇、聚氧化丙烯三醇、聚四氢呋喃二醇中的一种或几种。
6.根据权利要求1所述的防爆破冲击聚脲涂层，其特征在于，所述半预聚物组分在70-120℃下反应制得，异氰酸酯与聚酯多元醇聚合后，其NCO含量为15-25％，加入所述石墨烯浆料进一步反应后NCO含量为10-20％，粘度为1000-3000cps。
7.一种制备权利要求1-6任意一项所述的防爆破冲击聚脲涂层的方法，其特征在于，将所述A、B组分利用高压喷涂设备按体积比1:1的比例进行喷涂，即可制得所述防爆破冲击聚脲涂层。
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