CN107353803B - 一种高效防火聚氨酯涂饰材料及其制备方法 - Google Patents

一种高效防火聚氨酯涂饰材料及其制备方法 Download PDF

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CN107353803B
CN107353803B CN201710701080.7A CN201710701080A CN107353803B CN 107353803 B CN107353803 B CN 107353803B CN 201710701080 A CN201710701080 A CN 201710701080A CN 107353803 B CN107353803 B CN 107353803B
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桑阳
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Abstract

本发明涉及一种高效防火聚氨酯涂饰材料及其制备方法。由聚醚、扩链剂、重质碳酸钙、石英粉、氢氧化铝、聚磷酸铵、三聚氰胺、季戊四醇、钛白粉、铁红、催化剂、防沉剂、除水剂、阻燃剂构成的主料和由异氰酸酯预聚物构成的辅料，经混合搅拌均匀制得。使用时涂刷在基材表面即可。本发明的材料具有高效防火性，强附着力，耐候性好和耐水性强，在传统防火涂料的基础上，融合聚氨酯作为新材料的成膜物质，极大的提高了产品本身的物理机械性能以及防火性能。

Description

一种高效防火聚氨酯涂饰材料及其制备方法
技术领域
本发明属于防火涂饰材料领域，具体地涉及一种用于建筑、电力、轨道交通等领域，具有多功能性高效防火的聚氨酯涂饰材料及其制备方法。
背景技术
在国际国内的很多领域都在使用着防火涂饰产品，这是一种新材料，主要用于附着于可燃基材表面，平时起装饰作用，一旦遇火会形成致密的保护层，从而保护基材。在建筑领域，随着近年来多起火灾均是由于劣质易燃外墙保温板引起的，国家及各地方均出台了各种对外墙保温板防火性能的要求，以及施工的要求，但是保温效果好的材料防火性能差，而防火性能达标的产品保温效果不如人意，再加上价格高，运输不便利等因素，因此在实际应用过程中防火与保温难以兼顾。在电力领域，电缆沟槽、控制柜、防火隔断处1.5米都须刷涂线缆防火涂料。目前广泛使用的线缆防火涂料主要是水性线缆防火涂料，主要被喜利得等公司的产品所占据。在金属表面防火涂饰领域主要涉及铝镁合金，如动车高铁的车厢以及内部的部分涂饰，由于铝镁合金具有质量轻、强度高、耐腐蚀性好、散热性好、抗压强度高等优点而广泛使用，但是其熔点较低，一旦发生火灾，在起火10-15分钟即可达到铝镁合金的熔点，达到其熔点后由于强度下降就会发生垮塌，目前在动车车厢内使用的防火涂饰材料是SVT公司的一款水性防火涂料。在这些领域使用的防火饰面材料目前均以水性基材为主，但是水性基材饰面材料(涂料)有着施工效率低(多次施工才能达到预期要求)，耐候耐水性差、附着力较低(尤其是电缆防火涂料与电缆直接涂刷，过厚或内层未干即刷外层会导致整块涂料剥离)、弹性韧性较低。
发明内容
本发明的目的在于探究一种高效防火聚氨酯涂饰材料，并以此生产一种适用于多领域、高性能防火涂饰材料，满足各行业的特殊需求。
本发明是通过以下技术方案实现的：一种高效防火聚氨酯涂饰材料，由主料和辅料按重量比2-12:1，经搅拌混合制得。
所述的主料由聚醚、扩链剂、重质碳酸钙、石英粉、氢氧化铝、聚磷酸铵、三聚氰胺、季戊四醇、钛白粉、铁红、催化剂、防沉剂、除水剂和阻燃剂组成。
所述的辅料为异氰酸酯预聚体。
上述的一种高效防火聚氨酯涂饰材料，所述的主料按重量份配比组成为：聚醚70-120份、扩链剂0-30份、重质碳酸钙0-40份、石英粉0-40份、氢氧化铝20-100份、聚磷酸铵10-60份、三聚氰胺5-20份、季戊四醇0-20份、钛白粉5-25份、铁红2-5份、催化剂0.01-2份、防沉剂0.01-4份、除水剂0.01-4份和阻燃剂10-25份。
上述的一种高效防火聚氨酯涂饰材料，所述的聚醚为二元聚醚和/或三元聚醚和/或聚醚多元醇330N。所述的二元聚醚为分子量为1000-4000的二元聚醚；所述的三元聚醚为分子量为500-6000的三元聚醚。
上述的一种高效防火聚氨酯涂饰材料，所述的扩链剂为丁二醇、MOCA(4,4'-二氨基-3,3'-二氯二苯甲烷)、HQEE(氢醌-双(β-羟乙基)醚)、乙醇胺或二乙醇胺。
上述的一种高效防火聚氨酯涂饰材料，所述的催化剂为季铵盐与有机铋的组合。优选的，按重量比，季铵盐:有机铋＝1:(1-3)。更优选的，季铵盐为DY-2958(上海德音化学有限公司)、DY-50(上海德音化学有限公司)或DY-235(上海德音化学有限公司)；有机铋为异辛酸铋或辛癸酸铋或Umicore 8118(比利时Umicore)或Umicore 8008(比利时Umicore)。
上述的一种高效防火聚氨酯涂饰材料，所述的防沉剂为BYK410或BYK420。
上述的一种高效防火聚氨酯涂饰材料，所述的除水剂为恶唑烷或氧化钙。优选的，恶唑烷为3-丁基-2-(1-乙基戊基)噁唑烷(Incozol 2)。
上述的一种高效防火聚氨酯涂饰材料，所述的阻燃剂为WSFR-HF-4(浙江万盛股份有限公司)、磷酸三苯酯或磷酸苯酯。
本发明中，异氰酸酯预聚体，可以为市售产品(市售产品如Desmodur E21(科思创聚合物有限公司)，Desmodur E14(科思创聚合物有限公司)。也可以通过液化MDI(如Bayer44V20L)与聚醚(如330N)进行预聚反应，得到异氰酸酯预聚体。
一种高效防火聚氨酯涂饰材料的制备方法，包括如下步骤：
1)制备主料：将聚醚、扩链剂和阻燃剂加入反应釜中，真空脱水2h，分2-3次加入重质碳酸钙、石英粉、氢氧化铝、聚磷酸铵、三聚氰胺、季戊四醇、钛白粉、铁红，每次投料完毕，搅拌并真空脱水1h，全部投料完毕后真空脱水3h，最后加入催化剂、防沉剂、除水剂，继续真空脱水50min，出料灌装；
2)按重量比2-12:1，将主料和辅料搅拌混合，装罐。
本发明的有益效果是：
1.本发明，将二元聚醚和三元聚醚的混合聚醚与扩链剂复配，通过调控不同软段与硬段的比例，丰富最终产品的性能，满足多方面的需求。
2.本发明，取重质碳酸钙、石英粉和氢氧化铝，这三种材料在高温情况下会产生莫来石等耐高温结构，有助于产品在火焰中的耐火时间。
3.本发明，将聚磷酸铵、三聚氰胺和季戊四醇复配，这三种材料为化学膨胀的主要成分，在遇火燃烧的过程中，能将材料中的有机物催化成碳，形成碳泡沫层，起到隔热阻火的功效。
4.本发明，钛白粉和铁红，在常态下起到颜料的作用，在遇火的情况下，可与重质碳酸钙、石英粉和氢氧化铝的莫来石结构和聚磷酸铵、三聚氰胺和季戊四醇的化学膨胀组分共同形成耐火结构，阻止火焰快速蔓延，防止饰面层被火焰烧穿。
5.本发明，催化剂在实际应用过程中选用了季铵盐与有机铋催化剂的共同搭配使用，提高了产品对水气湿度的敏感性，保证产品表面光滑无气泡。
6.本发明，采用防沉剂，保证产品在存储的过程中不易发生固液分离的沉降现象，同时有一定的增稠触变作用，降低产品使用施工过程中的流淌性，避免发生流挂现象。
7.本发明，采用除水剂，除去产品体系内剩余的微量水分，提高产品在一定湿度环境下不发生发泡现象。
8.本发明，采用阻燃剂，提高产品阻燃性能，同时改变产品流变性能。
9.本发明，以聚氨酯为基材，具有一次施工即可达到目标要求，施工效率高，耐水耐候性好，附着力强，韧性好，抗弯折等优点。
10.本发明的高效防火聚氨酯涂饰材料的氧指数≥32，高于同类产品，同时在遇火的过程中会形成一层致密的“壳”结构分散火焰、隔绝空气、保护基材。具有高效防火性、强附着力，耐候性好，耐水性强，是一种双组分反应型涂饰材料。
11.本发明，采用无溶剂技术，绿色环保，无论在生产或使用过程中都不会逸出产生对人体有毒有害的组分。
12.本发明，采用聚氨酯作为防火涂饰材料的基材，具有灵活的性能，满足用户不同的需求，如在电力领域，将本产品涂饰在电缆表面用作电缆防火涂料时，不仅可提供卓越防火性能，同时抗弯折性能远超其他电缆防火涂料，还兼顾施工效率高，一次即可达到所需防火厚度要求；在建筑领域，将本产品涂饰在保温板表面，可极大提供保温板阻燃性能，同时增大其耐水耐候性；在其他领域，如将本产品涂饰在铝镁合金表面，可极大延长合金在火焰中淬火时间，为火灾施救提供充足的时间。本产品除具有卓越的耐火阻燃性能，还具有耐水、耐候、表面光洁、附着力强、施工简易的一款高效防火聚氨酯涂饰材料。
具体实施方式
高效防火聚氨酯涂饰材料的制备方法，包括如下步骤：
1)主料的制备：将聚醚、扩链剂和阻燃剂加入反应釜中，真空脱水2h，分2-3次加入重质碳酸钙、石英粉、氢氧化铝、聚磷酸铵、三聚氰胺、季戊四醇、钛白粉、铁红，每次投料完毕，搅拌并真空脱水1h，上述物料全部投料完毕后，再真空脱水3h，最后加入催化剂、防沉剂、除水剂，继续真空脱水50min，出料灌装。
2)将辅料异氰酸酯预聚体按比例与主料混合搅拌均匀，灌装。
实施例1
主料和辅料的配比如表1，制备的产品的防火性能满足GB/T 28374-2012的要求。
表1
实施例2
主料和辅料的配比如表2，制备的产品的防火性能满足GB/T 28374-2012的要求。
表2
实施例3
主料和辅料的配比如表3，制备的产品的防火性能满足GB/T 28374-2012的要求。
表3
实施例4
主料和辅料的配比如表4，制备的产品的防火性能满足GB/T 28374-2012的要求。
表4
实施例5
主料和辅料的配比如表5，制备的产品的防火性能满足GB/T 28374-2012的要求。
表5
实施例6
主料和辅料的配比如表6，制得的高效防火聚氨酯涂饰材料的性能见表7。
表6
表7
序号 项目 检测结果
1 状态 均一、无结块
2 细度/μm ≤90
3 粘度/s ≥70
4 干燥时间/h ≤5
5 耐油性/d 浸泡7天，涂层无起皱，无脱落，无起泡
6 耐盐水性/d 浸泡7天，涂层无起皱，无脱落，无起泡
7 耐湿热性/d 经过7天实验，涂层无起皱，无脱落，无起泡
8 耐冻融循环/次 经过15次循环，涂层无起皱，无脱落，无起泡
9 抗弯性 涂层无起皱，无脱落，无起泡
10 阻燃性 碳化高度＜1m
。

Claims (6)

1.一种高效防火聚氨酯涂饰材料，其特征在于，采用无溶剂技术，由主料和辅料，按重量比2-12 : 1，经搅拌混合制得：
所述主料按重量份配比组成为：聚醚70-120份、扩链剂10-30份、重质碳酸钙30-40份、石英粉30-40份、氢氧化铝20-100份、聚磷酸铵10-60份、三聚氰胺5-20份、季戊四醇10-20份、钛白粉5-25份、铁红2-5份、催化剂0.01-2份、防沉剂0.01-4份、除水剂0.01-4份和阻燃剂10-25份；
所述催化剂为季铵盐与有机铋的组合；按重量比，季铵盐 :有机铋=1 :（1-3）；
所述的阻燃剂为WSFR-HF-4、磷酸三苯酯或磷酸苯酯；
所述的辅料为异氰酸酯预聚体。
2.根据权利要求1所述的一种高效防火聚氨酯涂饰材料，其特征在于，所述的聚醚为二元聚醚和/或三元聚醚和/或聚醚多元醇330N。
3.根据权利要求1所述的一种高效防火聚氨酯涂饰材料，其特征在于，所述的扩链剂为丁二醇、MOCA、HQEE 、乙醇胺或二乙醇胺。
4.根据权利要求1所述的一种高效防火聚氨酯涂饰材料，其特征在于，所述的防沉剂为BYK410或BYK420。
5.根据权利要求1所述的一种高效防火聚氨酯涂饰材料，其特征在于，所述的除水剂为恶唑烷或氧化钙。
6.一种如权利要求1所述的高效防火聚氨酯涂饰材料的制备方法，其特征在于：包括如下步骤：
1）制备主料：将聚醚、扩链剂和阻燃剂加入反应釜中，真空脱水2h，分2-3次加入重质碳酸钙、石英粉、氢氧化铝、聚磷酸铵、三聚氰胺、季戊四醇、钛白粉、铁红，每次投料完毕，搅拌并真空脱水1h，全部投料完毕后真空脱水3h，最后加入催化剂、防沉剂、除水剂，继续真空脱水50min，出料灌装；
2）按重量比2-12 : 1，将主料和辅料搅拌混合，装罐。
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