CN111793459B - 新型阻燃低收缩聚氨酯泡沫填缝剂 - Google Patents

新型阻燃低收缩聚氨酯泡沫填缝剂 Download PDF

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CN111793459B
CN111793459B CN202010574698.3A CN202010574698A CN111793459B CN 111793459 B CN111793459 B CN 111793459B CN 202010574698 A CN202010574698 A CN 202010574698A CN 111793459 B CN111793459 B CN 111793459B
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CN111793459A (zh
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王伟
丁文昌
冯树良
杨开
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Anhui Nandaxing New Material Technology Co ltd
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Abstract

本发明公开了新型阻燃低收缩聚氨酯泡沫填缝剂，包括：聚酯多元醇、聚醚多元醇、催化剂、阻燃剂、泡沫稳定剂、发泡剂和异氰酸酯，所述的阻燃剂包括反应型阻燃剂和添加型阻燃剂，本发明克服了现有技术的不足，本发明使用碱性的有机蒙脱土对填缝剂进行改性有效的对含氯阻燃剂产生的毒性物质进行中和和吸收，降低了填缝剂使用时产生的泡沫的收缩率。

Description

新型阻燃低收缩聚氨酯泡沫填缝剂
技术领域
本发明涉及聚氨酯泡沫填缝剂技术领域，具体属于新型阻燃低收缩聚氨酯泡沫填缝剂。
背景技术
单组分聚氨酯泡沫填缝剂(简称OCF)系一种特殊湿固化硬质聚氨酯泡沫体系。由聚氨酯预聚物、催化剂、发泡剂等装填于耐压气雾罐中，当料从罐中喷射至孔洞或缝隙中时，迅速发泡膨胀并与空气中或基体上的水分反应而固化。固化的泡沫具有填缝、粘接、密封、隔热等多种效果。OCF因其优异的填缝效果而成为一种理想的填缝材料，应用范围及发展前途极其广阔。
目前OCF的生产几乎都采用“罐内聚合”生产工艺，即首先将多元醇，催化剂，助剂和异氰酸酯灌入气雾罐中，封好阀门后，再将发泡剂(抛射剂)充入，然后充分摇动，使罐内物料混合均匀并发生反应，形成聚氨酯预聚物、助剂和抛射剂的混合物，即得到罐装OCF产品。
由于单组分聚氨酯泡沫经过了两次发泡，即首先由抛射剂将聚氨酯预聚物吹成沫状体，然后沫状体继续与空气中的水分反应生成CO2，进一步使泡沫体膨胀，因此，最后形成密度较低且具有一定闭孔率的固化泡沫(15-30kg/m3)。随着泡沫体内气体的逸出，如此低密度的聚氨酯泡沫具有较大的收缩倾向。收缩率的大小对其填充密封效果有较大的影响。例如将OCF用于塑钢门窗和水泥墙体之间的密封时，如果收缩率过大，就会造成泡沫和墙体之间脱离，形成缝隙，造成墙体冷桥或漏水现象。
对于材料的阻燃性来说，聚氨酯材料和其它有机聚合物一样是一种可燃性聚合物。聚氨酯泡沫的密度小，比表面大，与非泡沫材料相比更容易燃烧，燃烧和分解产生大量有毒烟雾，对人的生命威胁极大。因此聚氨酯阻燃问题显得很突出。聚氨酯泡沫的许多应用领域如建筑材料、床垫、家具、保温材料、汽车坐垫及内饰材料等，都有阻燃要求。在研究阻燃时，一般通过在生产配方中添加含氯、溴、磷、锑、氮、硼等元素的有机阻燃剂或无机阻燃剂，也可以采用含阻燃元素的反应性阻燃剂为泡沫原料。阻燃剂的添加，提高了泡沫的阻燃性，以延缓燃烧、阻烟甚至使着火部位自熄。
目前应用最多的阻燃剂大都含有卤素，由于含卤阻燃剂的材料在燃烧时产生的有毒气体多，烟雾大，卤素阻燃剂在世界范围内正逐步被淘汰。人们发现，蒙脱土加入聚合物机体中，不但可以制得性能优越的纳米复合材料，而且可以提高材料的尺寸稳定性和阻燃性，是一种性价比很好的填料。当前对于蒙脱土纳米复合材料的研究也是很热门的。
蒙脱土是一类天然黏土矿物，基本结构单元是由一片铝氧八面体夹在两片硅氧四面体之间靠共用氧原子而形成的层状结构，此类矿物的结构是一种2∶1型层状硅酸盐，即是来源于这类夹心结构。每一个片层的厚度约为1nm；长和宽各约为100nm。蒙脱土的这种结构赋予了其特种性能，可以制备不同形式的纳米复合材料。
制备聚合物/蒙脱土纳米复合材料的各种方法统称为插层复合法(Intercalationcompounding)。它是将单体或聚合物以液体、熔体或溶液的方式插入经插层剂处理后的层状硅酸盐片层之间，进而破坏硅酸盐的片层结构，使其剥离成厚度为1nm的基本单元，并均匀分散在聚合物基体中，以实现高分子与粘土在纳米尺度上的复合。
将有机蒙脱土作为填料加入OCF中，通过剧烈剪切搅拌将其分散于聚酯多元醇或聚醚多元醇中，与异氰酸酯灌装于气雾罐中，再灌入推进剂得到聚氨酯预聚体，在使用中可得到纳米级上的复合，由于材料纳米复合后，在阻燃和收缩性上有很好的改善。
发明内容
本发明的目的是提供新型阻燃低收缩聚氨酯泡沫填缝剂，克服了现有技术的不足。
为解决上述问题，本发明所采取的技术方案如下：
新型阻燃低收缩聚氨酯泡沫填缝剂，包括：聚酯多元醇、聚醚多元醇、催化剂、阻燃剂、泡沫稳定剂、发泡剂和异氰酸酯，所述的阻燃剂包括反应型阻燃剂和添加型阻燃剂。
其中，所述的反应型阻燃剂为磷酸三氯异丙酯、氯化石蜡、三(一缩二丙二醇)亚磷酸酯，三(聚氧化烯烃)磷酸酯，三(聚氧化烯烃)亚磷酸酯，三(氰化多元醇)磷酸酯二溴戊二醇的聚醚多元醇溶液、溴化季戊四醇及四溴苯酐系列阻燃多元醇、聚醚Ixol B251或聚醚Ixol M125中的一种或多种。
其中，所述的添加型阻燃剂为有机蒙脱土、三(2-氯丙基)磷酸酯、三(2-氯乙基)磷酸酯、三(二氯丙基)磷酸酯、四(2-氯乙基)亚乙基二磷酸酯、甲基膦酸二甲酯或多溴二苯醚中的一种。
其中，所述的有机蒙脱土PH＝8-9。
其中，所述的聚酯多元醇的官能度为2-4，分子量为400-10000，羟值为100-300mgKOH/g，所述的聚醚多元醇的官能度为2-4，分子量为400-10000，羟值为100-300mg KOH/g。
其中，所述的聚酯多元醇为含芳香环结构的聚酯，其官能度为2-3。
其中，异氰酸酯为官能度为2.2-2.9的多苯基甲烷多异氰酸酯或甲苯二异氰酸酯。
其中，所述的催化剂为双吗啉二乙基醚。
其中，所述的泡沫稳定剂为聚环氧乙烷和环氧丙烷接枝改性硅烷。
其中，所述的发泡剂为二甲醚、丙丁烷、1,1,1,2-四氟乙烷中的一种或多种。
本发明与现有技术相比较，本发明的实施效果如下：本发明使用碱性的有机蒙脱土对填缝剂进行改性，蒙脱土不仅起到了阻燃作用，而且蒙脱土经烷基氨处理后出现碱性，使蒙脱土能够有效的对含氯阻燃剂产生的毒性物质进行中和和吸收，显著降低了该填缝剂使用时含氯阻燃剂产生的毒性；此外，有机蒙脱土的加入，对填缝剂基体起到了支撑作用，使该填缝剂使用时产生的泡沫的收缩率得到了降低。
具体实施方式
下面将对本发明实施例中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。
本发明的聚酯多元醇采用市售产品的STEPANOL COMPANY公司生产的牌号为聚酯3152、聚酯2412、聚酯2352的产品；聚醚多元醇采用上海高桥石化三厂生产的牌号为聚醚-210、聚醚-310产品；异氰酸酯官能度为2.2-2.9的多苯基甲烷多异氰酸酯(p-MDI)、甲苯二异氰酸酯(TDI)或其改性体，可采用市售产品，例如HUNTSMAN CORP.公司生产的牌号为SUP50OS,SUP2085的产品，BASF CORP.公司生产的牌号为M20S的产品，BAYER CORP.公司生产的牌号为44V20L的产品，烟台万华聚氨酯公司生产的牌号为PM-200等的产品；蒙脱土采用市售产品，有机蒙脱土的制备方法为：将蒙脱土加入含有烷基氨(十六烷基三甲基氯化铵或十二烷基三甲基氯化铵或十八烷基三甲基氯化铵)的溶液中，然后搅拌加热至70℃，反应6小时，抽滤，同时用去离子水洗涤沉淀直至PH＝7或8或9，得到有机蒙脱土；泡沫稳定剂选自用于聚氨酯硬泡或聚异氰酸酯泡沫的表面活性剂，泡沫稳定剂为聚环氧乙烷和环氧丙烷接枝改性硅烷，可采用市售产品，例如德国高斯米特公司生产的牌号为B8404、B8460或B8462的产品，如美国迈图公司生产的牌号为L-6900、L-5440、L-5420、L-5421的产品，如美国气体产品公司生产的牌号为DC5604、DC193、DC5589的产品；Ixol B251和Ixol M125为Solvay公司的两种型号的阻燃聚醚。
实施例1
新型阻燃低收缩聚氨酯泡沫填缝剂的原料包括：氢化蓖麻油3kg、聚酯多元醇2kg、聚醚多元醇5kg、催化剂1kg、阻燃剂7kg、泡沫稳定剂2kg、发泡剂20kg和异氰酸酯60kg。聚醚多元醇使用质量比为1:1的聚醚-210和聚醚-310的混合物；聚酯多元醇为含芳香环结构的聚酯，其包括质量比为2:0的聚酯3152和聚酯2352；异氰酸酯为多苯基甲烷多异氰酸酯。
阻燃剂使用反应型阻燃剂和添加型阻燃剂组成的混合型阻燃剂，反应型阻燃剂和添加型阻燃剂的质量比为6:1。反应型阻燃剂为磷酸三氯异丙酯，添加型阻燃剂为有机蒙脱土，有机蒙脱土PH＝8，有机蒙脱土为十八烷基三甲基氯化铵有机化制得。催化剂为双吗啉二乙基醚。泡沫稳定剂为聚环氧乙烷。发泡剂为质量比为5:5:10的二甲醚、丙丁烷、1,1,1,2-四氟乙烷的混合物。
本发明的新型阻燃低收缩聚氨酯泡沫填缝剂的制备方法包括如下步骤：将催化剂、阻燃剂、泡沫稳定剂、发泡剂和异氰酸酯按质量比加入聚酯多元醇、聚醚多元醇中，剧烈搅拌一定时间，制成聚氨酯组合液，然后将异氰酸酯、聚氨酯组合液依次灌入气雾罐中，制得填缝剂。
实施例2
新型阻燃低收缩聚氨酯泡沫填缝剂的原料包括：氢化蓖麻油5kg、聚酯多元醇2kg、聚醚多元醇5kg、催化剂0.8kg、阻燃剂12.2kg、泡沫稳定剂2kg、发泡剂20kg和异氰酸酯53kg。聚醚多元醇使用质量比为0:5的聚醚-210和聚醚-310的混合物；聚酯多元醇为含芳香环结构的聚酯，其包括质量比为0:2的聚酯3152和聚酯2352；异氰酸酯为甲苯二异氰酸酯。
阻燃剂使用反应型阻燃剂和添加型阻燃剂组成的混合型阻燃剂，反应型阻燃剂和添加型阻燃剂的质量比为10.2:2。反应型阻燃剂为氯化石蜡，添加型阻燃剂为有机蒙脱土，有机蒙脱土PH＝9，有机蒙脱土为十六烷基三甲基氯化铵有机化制得。催化剂为双吗啉二乙基醚。泡沫稳定剂为环氧丙烷接枝改性硅烷。发泡剂为质量比为5:7:8的二甲醚、丙丁烷、1,1,1,2-四氟乙烷的混合物。
本发明的新型阻燃低收缩聚氨酯泡沫填缝剂的制备方法包括如下步骤：将催化剂、阻燃剂、泡沫稳定剂、发泡剂和异氰酸酯按质量比加入聚酯多元醇、聚醚多元醇中，剧烈搅拌一定时间，制成聚氨酯组合液，然后将异氰酸酯、聚氨酯组合液依次灌入气雾罐中，制得填缝剂。
实施例3
新型阻燃低收缩聚氨酯泡沫填缝剂的原料包括：聚酯多元醇3kg、聚醚多元醇11kg、催化剂0.7kg、阻燃剂12.3kg、泡沫稳定剂2kg、发泡剂20kg和异氰酸酯48kg。聚醚多元醇使用质量比为5:6的聚醚-210和聚醚-310的混合物；聚酯多元醇为含芳香环结构的聚酯，其包括质量比为1:2的聚酯3152和聚酯2352；异氰酸酯为多苯基甲烷多异氰酸酯。
阻燃剂使用反应型阻燃剂和添加型阻燃剂组成的混合型阻燃剂，反应型阻燃剂和添加型阻燃剂的质量比为12.3:3。反应型阻燃剂为磷酸三氯异丙酯，添加型阻燃剂为有机蒙脱土，有机蒙脱土PH＝8，有机蒙脱土为十二烷基三甲基氯化铵有机化制得。催化剂为双吗啉二乙基醚。泡沫稳定剂为聚环氧乙烷。发泡剂为质量比为6:6:8的二甲醚、丙丁烷、1,1,1,2-四氟乙烷的混合物。
本发明的新型阻燃低收缩聚氨酯泡沫填缝剂的制备方法包括如下步骤：将催化剂、阻燃剂、泡沫稳定剂、发泡剂和异氰酸酯按质量比加入聚酯多元醇、聚醚多元醇中，剧烈搅拌一定时间，制成聚氨酯组合液，然后将异氰酸酯、聚氨酯组合液依次灌入气雾罐中，制得填缝剂。
实施例4
新型阻燃低收缩聚氨酯泡沫填缝剂的原料包括：氢化蓖麻油3kg、聚酯多元醇2kg、聚醚多元醇10kg、催化剂0.6kg、阻燃剂22.4kg、泡沫稳定剂2kg、发泡剂20kg和异氰酸酯40kg。聚醚多元醇使用质量比为7:3的聚醚-210和聚醚-310的混合物；聚酯多元醇为含芳香环结构的聚酯，其包括质量比为0:2的聚酯3152和聚酯2352；异氰酸酯为多苯基甲烷多异氰酸酯。
阻燃剂使用反应型阻燃剂和添加型阻燃剂组成的混合型阻燃剂，反应型阻燃剂和添加型阻燃剂的质量比为18.4:4。反应型阻燃剂为氯化石蜡，添加型阻燃剂为有机蒙脱土，有机蒙脱土PH＝9，有机蒙脱土为十六烷基三甲基氯化铵有机化制得。催化剂为双吗啉二乙基醚。泡沫稳定剂为聚环氧乙烷。发泡剂为质量比为10:0:10的二甲醚、丙丁烷、1,1,1,2-四氟乙烷的混合物。
本发明的新型阻燃低收缩聚氨酯泡沫填缝剂的制备方法包括如下步骤：将催化剂、阻燃剂、泡沫稳定剂、发泡剂和异氰酸酯按质量比加入聚酯多元醇、聚醚多元醇中，剧烈搅拌一定时间，制成聚氨酯组合液，然后将异氰酸酯、聚氨酯组合液依次灌入气雾罐中，制得填缝剂。
实施例5
新型阻燃低收缩聚氨酯泡沫填缝剂的原料包括：氢化蓖麻油3kg、聚酯多元醇2kg、聚醚多元醇10kg、催化剂0.6kg、阻燃剂20kg、泡沫稳定剂2kg、发泡剂20kg和异氰酸酯50kg。聚醚多元醇使用质量比为5:3的聚醚-210和聚醚-310的混合物；聚酯多元醇为含芳香环结构的聚酯，其包括质量比为1:2的聚酯3152和聚酯2352；异氰酸酯为多苯基甲烷多异氰酸酯。
阻燃剂使用反应型阻燃剂和添加型阻燃剂组成的混合型阻燃剂，反应型阻燃剂和添加型阻燃剂的质量比为13:7。反应型阻燃剂为氯化石蜡，添加型阻燃剂为改性有机蒙脱土，改性有机蒙脱土PH＝9，改性有机蒙脱土的制备方法为：将5kg蒙脱土加入50kg含有1kg的十六烷基三甲基氯化铵的溶液中，然后搅拌加热至70℃，反应6小时，抽滤，同时用去离子水洗涤沉淀直至无Cl-离子检出为止(用硝酸银溶液检验)，得到有机蒙脱土；然后，将有机蒙脱土分散于30kg80℃的去离子水中，加入乙酰胆碱2kg，剧烈搅拌反应12小时，静置后，抽滤，烘干，得到改性有机蒙脱土。
催化剂为双吗啉二乙基醚。泡沫稳定剂为聚环氧乙烷。发泡剂为质量比为8:5:7的二甲醚、丙丁烷、1,1,1,2-四氟乙烷的混合物。
本发明的新型阻燃低收缩聚氨酯泡沫填缝剂的制备方法包括如下步骤：将催化剂、阻燃剂、泡沫稳定剂、发泡剂和异氰酸酯按质量比加入聚酯多元醇、聚醚多元醇中，剧烈搅拌一定时间，制成聚氨酯组合液，然后将异氰酸酯、聚氨酯组合液依次灌入气雾罐中，制得填缝剂。
对照例1
与实施例4的不同在于，有机蒙脱土PH＝7。
对照例2
与实施例4的不同在于，将有机蒙脱土替换为等质量的蒙脱土。
对照例3
与实施例4的不同在于，有机蒙脱土替换为等质量的氯化石蜡。
将实施例1-5互溶对照例1-3制得填缝剂喷涂，制成泡沫样品，按GB/T2406.2-2009标准测试产品氧指数、采用GB/T 8811-2008标准检测收缩率、按GB/T8323.2-2008标准测试产品的烟密度、按GB/T20285-2006标准中的方法测试产品烟毒性，结果如下表所示：
氧指数/％ 收缩率/％ 烟浓度(mg/L) 烟毒性等级
实施例1 28.6 2.6 43 ZA1
实施例2 28.2 2.5 45 ZA1
实施例3 28.9 2.4 38 ZA1
实施例4 29.1 2.0 42 ZA1
实施例5 29.4 2.1 73 AQ2
对照例1 28.1 3.0 11.4 ZA3
对照例2 28.3 2.7 10.8 ZA3
对照例3 24.6 3.7 5.6 WX
由上表数据可以明显看出，泡沫样品都具有阻燃性能，添加蒙脱土后，泡沫样品的阻燃性能得到了显著提升；本发明的有机蒙脱土对含氯阻燃剂产生的有毒物质具有明显的去除作用，特别是碱性有机蒙脱土，大幅降低了烟气的毒性，此外，本发明的发明人还发现，使用乙酰胆碱对有机蒙脱土进行改性，乙酰胆碱本身可燃，但含有氨基，可有效的对含氯阻燃剂产生的毒性起抑制作用，且效果明显。
此外，本发明的添加型阻燃剂也可以使用三(2-氯丙基)磷酸酯、三(2-氯乙基)磷酸酯、三(二氯丙基)磷酸酯、四(2-氯乙基)亚乙基二磷酸酯、甲基膦酸二甲酯或多溴二苯醚中的一种或多种进行代替，而反应型阻燃剂可以使用三(一缩二丙二醇)亚磷酸酯，三(聚氧化烯烃)磷酸酯，三(聚氧化烯烃)亚磷酸酯，三(氰化多元醇)磷酸酯二溴戊二醇的聚醚多元醇溶液、溴化季戊四醇及四溴苯酐系列阻燃多元醇、聚醚Ixol B251或聚醚Ixol M125中的一种或多种进行代替，同样可以使填缝剂具有阻燃能力。
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。

Claims (2)

1.阻燃低收缩聚氨酯泡沫填缝剂，其特征在于，包括：聚酯多元醇、聚醚多元醇、催化剂、阻燃剂、泡沫稳定剂、发泡剂和异氰酸酯，所述的阻燃剂包括磷酸三氯异丙酯和氯化石蜡中的一种与有机蒙脱土组成的混合物；
有机蒙脱土的制备方法为：将蒙脱土加入含有烷基氨的溶液中，然后搅拌加热至70℃，反应6小时，抽滤，同时用去离子水洗涤沉淀直至pH＝8或9，得到有机蒙脱土；
所述的聚酯多元醇的官能度为2-4，分子量为400-10000，羟值为100-300mg KOH/g，所述的聚醚多元醇的官能度为2-4，分子量为400-10000，羟值为100-300mgKOH/g；
异氰酸酯为官能度为2.2-2.9的多苯基甲烷多异氰酸酯或甲苯二异氰酸酯；
所述的催化剂为双吗啉二乙基醚；
所述的泡沫稳定剂为聚环氧乙烷或环氧丙烷接枝改性硅烷；
所述的发泡剂为二甲醚、丙丁烷、1,1,1,2-四氟乙烷中的一种或多种。
2.根据权利要求1所述的阻燃低收缩聚氨酯泡沫填缝剂，其特征在于，所述的聚酯多元醇为含芳香环结构的聚酯，其官能度为2-3。
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CN102352138A (zh) * 2011-08-17 2012-02-15 太原理工大学 蒙脱土阻燃剂有机改性方法
CN103923294A (zh) * 2013-01-10 2014-07-16 上海联合气雾制品灌装有限公司 单组份阻燃聚氨酯泡沫填缝剂的制备

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102352138A (zh) * 2011-08-17 2012-02-15 太原理工大学 蒙脱土阻燃剂有机改性方法
CN103923294A (zh) * 2013-01-10 2014-07-16 上海联合气雾制品灌装有限公司 单组份阻燃聚氨酯泡沫填缝剂的制备

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