CN110105528B - 一种无卤阻燃胶及其制备方法 - Google Patents
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Abstract
本发明公开了一种无卤阻燃胶及其制备方法。所述无卤阻燃胶包括A组分和B组分,以本质阻燃水性聚氨酯乳液作为A组分,以无机阻燃剂作为B组分,通过对B组分进行表面改性处理,使之与A组分具有良好的相容性;通过调节A组分与B组分不同配比,达到最佳的使用效果。本发明利用本质阻燃水性聚氨酯绿色环保,且阻燃性能稳定、粘结力强、成膜性能好、力学性能可调的优势,与无机阻燃剂复合制备出粘结性好、相容性好、阻燃性能优异的新型阻燃材料,其极限氧指数可达32%以上,燃烧等级为A级,拉伸强度可达到5.7Mpa以上,具有广阔的应用前景。
Description
技术领域
本发明涉及阻燃材料技术领域,尤其涉及一种无卤阻燃胶及其制备方法。
背景技术
聚氨酯是一类由软、硬段构成的-(NHCOO)n-型嵌段共聚物,其同时具有橡胶和塑料的基本特性,还具有其它高分子聚合材料所不具有的特殊物理性能,如较强的粘结能力、较高的机械强度、耐高温及耐候性等,因此,聚氨酯粘结剂材料是发展最快、用途最广的一种新材料,主要用于船舶、石油、化工、航空及建筑行业中的金属与金属、金属与非金属材料的粘结。一般的聚酯型聚氨酯胶粘剂阻燃性能和耐水解性能较差,因此,当粘结的物体处于潮湿的环境时,会大大降低两者的粘结强度,而且当物体处于火灾状态下,聚氨酯粘结剂还会起到助燃作用,加快火灾的蔓延。聚氨酯的阻燃化,是聚氨酯功能化的重要方向之一。
目前,现阶段国内外对于聚氨酯胶黏剂材料的阻燃改性,主要分为添加型阻燃改性与反应型阻燃改性。添加型阻燃改性应用较多的是添加无机阻燃剂,无机阻燃剂绿色环保,燃烧无烟雾,但是其阻燃效率低下,添加量大,且与有机聚合物相容性差,不易分散,分散后亲和力也不好,影响材料的抗冲击性能,使材料丧失柔韧性。反应型阻燃的阻燃性能好、稳定性好、对高聚物其它性能的影响较小,是一类理想的阻燃剂材料。但是,目前国内外制备的反应型阻燃剂,阻燃性提高的同时其它性能大幅下降,且制备工艺复杂,阻燃效果也有待进一步提高,同时,含卤阻燃剂燃烧后产生有毒气体和浓烟等,环保性较差。
发明内容
针对现有技术添加型阻燃剂改性中无机阻燃剂与有机聚合物相容性差以及阻燃性提高的同时其它性能大幅下降的问题,本发明提供一种无卤阻燃胶及其制备方法。
为解决上述技术问题,本发明提供的技术方案是:
一种无卤阻燃胶,包括A组分和B组分,所述A组分和所述B组分的质量比为10:0.5-2;
其中,所述A包括如下重量份数的原料组分:聚醚二元醇11-24份,二异氰酸酯12-21份,亲水扩链剂1.6-2.1份,中和剂0.8-1.2份,氮磷协效阻燃剂5-15份,含磷多元醇5-15份和水150-200份;
所述B组分为阴离子表面活性剂改性的无机阻燃剂。
相对于现有技术,本发明提供的无卤阻燃胶,通过氮磷协效阻燃剂对聚氨酯的硬段进行阻燃改性,通过含磷多元醇对聚氨酯的软段进行阻燃改性,得到软硬段共阻燃的本质阻燃水性聚氨酯乳液,使水性聚氨酯具有优异的本质阻燃属性;通过阴离子表面活性剂对无机阻燃剂进行改性,得到与本质阻燃水性聚氨酯乳液相容性良好的改性无机阻燃剂,有效解决了外添加阻燃剂在水性聚氨酯乳液中分散不均匀、易析出团聚等问题,通过将本质阻燃水性聚氨酯乳液与改性无机阻燃剂复配,得到有机无机协同阻燃改性的复合阻燃胶,显著提高了阻燃胶的阻燃效率和粘结力,阻燃胶的极限氧指数可达32%以上,燃烧等级为A级,拉伸强度可达到5.7Mpa以上。且本发明提供的阻燃胶中不含有卤素,在聚氨酯阻燃胶燃烧时不会产生有毒和腐蚀性气体,减少了对环境、人体、建筑物等的危害,绿色环保。
优选的,所述B组分的制备方法包括如下步骤:将无机阻燃剂、阴离子表面活性剂和水搅拌混合20-40min,超声处理0.5-3h,过滤,干燥,研磨,得阴离子表面活性剂改性的无机阻燃剂。
优选的,所述无机阻燃剂、所述阴离子表面活性剂和水的质量比为4.5-5.5:1-2:100。
通过采用阴离子表面活性剂对无机阻燃剂进行表面包覆改性,改变无机阻燃剂颗粒的表面状态,提高其表面活性,使其表面产生新的物理、化学功能,改性后无机阻燃剂与水性聚氨酯乳液之间的相容性增强,粘附力增强,扩大了无卤阻燃胶的应用领域。
优选的,所述无机阻燃剂为氢氧化镁、硫酸镁、氢氧化铝或膨胀型石墨中的一种或几种。
优选的,所述阴离子表面活性剂为十二烷基苯磺酸钠、硬脂酸钠或油酸钠中的一种或几种。
优选的阴离子表面活性剂可显著增强氢氧化镁、硫酸镁、氢氧化铝或膨胀型石墨与聚氨酯的相容性,改善上述阻燃剂在水性聚氨酯乳液中的分散性。
优选的,所述聚醚二元醇为聚丙二醇。
本发明中所述聚醚二元醇可以为聚四氢呋喃二醇、聚丙二醇、聚乙二醇等本领域中常规的聚醚二元醇,优选为聚丙二醇。
优选的,所述二异氰酸酯为甲苯二异氰酸酯。
本发明中所述二异氰酸酯可以为三甲基六亚甲基二异氰酸酯、甲苯二异氰酸酯、1,4-环己烷二异氰酸酯、四亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯等常见的二异氰酸酯。优选为甲苯二异氰酸酯。
优选的,所述亲水扩链剂为二羟甲基丙酸。
本发明中所述亲水扩链剂可以为本领域中常规的二羟甲基丙酸、二羟甲基丁酸、盐酸硫胺、1,4-丁二醇等,优选为二羟甲基丙酸。
优选的,所述中和剂为三乙胺。
优选的,所述氮磷协效阻燃剂为[[双(2-羟乙基)氨基]甲基]磷酸二乙酯。
在水性聚氨酯大分子中通过嵌段共聚的方法将甲基磷酸二乙酯引入到聚氨酯的软链上,使其作为最终产物的结构组成部分,赋予水性聚氨酯聚氨酯良好的耐久性和阻燃性,且在使用过程中性能稳定。
优选的,所述含磷多元醇为磷氮协效阻燃聚酯二元醇。
磷氮协效阻燃聚酯二元醇的制备方法已在相关专利CN 107417898A报道过,将磷氮结构的聚酯二元醇通过共聚反应引入聚氨酯的硬链上,可赋予水性聚氨酯优异的本质阻燃属性。
优选的,所述A组分的制备方法至少包括以下步骤:
步骤a,按照所述A组分的设计配比称取各组分,将称取的二异氰酸酯、亲水扩链剂、聚醚二元醇,混合均匀,在惰性气体保护下,于70-85℃反应2-4h,得聚氨酯预聚体;
步骤b,向所述聚氨酯预聚体中加入称取的氮磷协效阻燃剂,混合均匀,于75-85℃反应2-4h,然后加入称取的含磷多元醇,继续反应2-4h,降温至30-50℃,加入中和剂,反应25-35min,得到本质阻燃改性聚氨酯预聚体;
步骤c,将所述本质阻燃改性聚氨酯预聚体于搅拌条件下加入0-10℃的水中,乳化5-15min,得本质阻燃水性聚氨酯乳液,用增稠剂调节乳液的粘度至20-24s,即得A组分。
优选的,步骤b中加入中和剂前后还包括加入溶剂调节体系的粘度,所述溶剂为丙酮或丁酮中的一种或两种。
优选的,步骤c中,搅拌速度为3500-6500r/min。
本发明中所述惰性气体可以为本领域常规的任何一种惰性气体,比如,氮气、氦气或氩气等,优选为氮气。
可选的,所述增稠剂为水性聚氨酯用增稠剂NY-210、NY-201、NY-202、NY-206和NY-305中的一种,优先选择NY-305。
上述制备方法简单易行,便于实现大规模工业化生产。
本发明还提供了一种无卤阻燃胶的制备方法,所述制备方法至少包括以下步骤:
按照设计配比称取A组分和B组分,于20-30℃超声搅拌0.5-1h,得所述无卤阻燃胶。
本发明提供的无卤阻燃胶可以应用于颗粒类塑料材料阻燃改性中。
将含有阻燃功能基团的单体引入水性聚氨酯的分子结构中,使水性聚氨酯在具有较好机械性能、成膜性能等的基础上,同时具有较优的阻燃效果,将改性后的无机阻燃剂分散包裹于聚氨酯乳液中,使聚氨酯充当颗粒类塑料材料(如聚苯乙烯颗粒)和无机阻燃剂的粘结桥梁,利用聚氨酯粘结力强、成膜性能好的优势,提高颗粒类塑料材料与无机阻燃剂之间的粘结性和相容性,将其用于聚苯乙烯泡沫等颗粒类塑料材料的阻燃包覆改性,可大幅提高被改性材料的阻燃性、力学性能和耐水性能。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
实施例1
本发明实施例提供一种无卤阻燃胶,包括A组分和B组分,所述A组分和所述B组分的质量比为10:1,
其中,所述A组分包括如下重量份数的原料组分:聚丙二醇(N-210)24份,甲苯二异氰酸酯14份,二羟甲基丙酸(DMPA)1.8份,三乙胺1.0份,氮磷协效阻燃剂5份,含磷多元醇7.5份和水150份;
所述B组分为十二烷基苯磺酸钠改性的氢氧化镁。
所述氮磷协效阻燃剂为[[双(2-羟乙基)氨基]甲基]磷酸二乙酯(FCR-6),所述含磷多元醇为磷氮协效阻燃聚酯二元醇(PNJZ)。
上述A组分的制备步骤如下:
步骤一、将二羟甲基丙酸、聚丙二醇于110℃真空干燥箱中干燥12h;
步骤二、取四口瓶,加入称取的聚丙二醇N-210、甲苯二异氰酸酯(TDI)和二羟甲基丙酸(DMPA),通入氮气,安装冷凝回流管,油浴加热至85℃,反应2h;
步骤三、加入称取的磷氮协效阻燃聚酯二元醇(PNJZ),继续反应3h;
步骤四、加入称取的FRC-6,继续反应2h,反应过程中根据反应情况加入适量丁酮稀释体系粘度;
步骤五、降温至40℃,加入丁酮调节体系粘度,加入称取的三乙胺中和25min,得本质阻燃改性聚氨酯预聚体;
步骤六、在高速分散机3500r/min的转速搅拌下,将上述本质阻燃改性聚氨酯预聚体缓慢倒入称取的温度为10℃的去离子水中,高速乳化15min后,得到淡黄色乳液,放置12h;使用旋转蒸发仪除去乳液中的丁酮,加增稠剂调节粘度为21s,得到A组分。
上述B组分的制备步骤如下:
将4.7g氢氧化镁、1.1g十二烷基苯磺酸钠加入到100g蒸馏水中,磁力搅拌30min,然后超声处理1.5h,抽滤,将抽滤得到的固体在80℃烘箱中干燥24h,再于100℃下真空干燥2h,之后研磨成粉末,得到B组分。
上述无卤阻燃胶的制备步骤如下:
按A组分:B组分(质量比)=10:1的配比称取各组分,于25℃下进行超声处理,同时进行搅拌,30分钟后出料,即得有机/无机复合无卤阻燃胶,记为样品1#。经测试1#样品极限氧指数为31.1%,燃烧等级为A级,拉伸强度6.7MPa。
实施例2
本发明实施例提供一种无卤阻燃胶,包括A组分和B组分,所述A组分和所述B组分的质量比为10:0.5,
其中,所述A组分包括如下重量份数的原料组分:聚丙二醇11份,甲苯二异氰酸酯12份,二羟甲基丙酸2.1份,三乙胺1.2份,氮磷协效阻燃剂15份,含磷多元醇5份和水180份;
所述B组分为硬脂酸钠改性的硫酸镁。
所述氮磷协效阻燃剂为[[双(2-羟乙基)氨基]甲基]磷酸二乙酯(FCR-6),所述含磷多元醇为磷氮协效阻燃聚酯二元醇(PNJZ)。
上述A组分的制备步骤如下:
步骤一、将二羟甲基丙酸、聚丙二醇等于110℃真空干燥箱中干燥12h;
步骤二、取四口瓶,加入称取的聚丙二醇N-210、甲苯二异氰酸酯(TDI)和二羟甲基丙酸(DMPA),通入氮气,安装冷凝回流管,油浴加热至70℃,反应4h;
步骤三、加入称取的磷氮协效阻燃聚酯二元醇(JZP),继续反应4h;
步骤四、加入称取的FRC-6,继续反应4h,反应过程中根据反应情况加入适量丁酮稀释体系粘度;
步骤五、降温至30℃,加入丁酮稀释体系粘度,加入称取的三乙胺(TEA)中和35min;
步骤六、在高速分散机5000r/min的转速搅拌下,将上述步骤五得到的预聚体缓慢倒入称取的温度为0℃的去离子水中,高速乳化8min后,得到淡黄色乳液,放置12h;使用旋转蒸发仪除去乳液中的丁酮,加增稠剂调节粘度为22s,得到A组分。
上述B组分的制备步骤如下:
将5g硫酸镁、1.5g硬脂酸钠加入到100g蒸馏水中,磁力搅拌30min,然后超声处理1.5h,抽滤,将抽滤得到的固体在80℃烘箱中干燥24h,再于100℃下真空干燥2h,之后研磨成粉末,得到B组分。
上述无卤阻燃胶的制备步骤如下:
按A组分:B组分(质量比)=10:0.5的配比称取各组分,于20℃下进行超声处理,同时进行搅拌,45分钟后出料,即得有机/无机复合无卤阻燃胶,记为样品2#。经测试2#样品极限氧指数为33.9%,燃烧等级为A级,拉伸强度5.7MPa。
实施例3
本发明实施例提供一种无卤阻燃胶,包括A组分和B组分,所述A组分和所述B组分的质量比为10:2,
其中,所述A组分包括如下重量份数的原料组分:聚丙二醇18份,甲苯二异氰酸酯21份,二羟甲基丙酸1.6份,三乙胺0.8份,氮磷协效阻燃剂10份,含磷多元醇15份和水200份;
所述B组分为油酸钠改性的氢氧化铝。
所述氮磷协效阻燃剂为[[双(2-羟乙基)氨基]甲基]磷酸二乙酯(FCR-6),所述含磷多元醇为磷氮协效阻燃聚酯二元醇(PNJZ)。
上述A组分的制备步骤如下:
步骤一、将二羟甲基丙酸、聚丙二醇等于110℃真空干燥箱中干燥12h;
步骤二、取四口瓶,加入称取的聚丙二醇N-210、甲苯二异氰酸酯(TDI)和二羟甲基丙酸(DMPA),通入氮气,安装冷凝回流管,油浴加热至80℃,反应3h;
步骤三、加入称取的磷氮协效阻燃聚酯二元醇(PNJZ),反应2h;
步骤四、加入称取的FRC-6,继续反应3h,反应过程中根据反应情况加入适量丁酮稀释体系粘度;
步骤五、降温至50℃,加入丁酮稀释体系粘度,加入称取的三乙胺(TEA)中和30min;
步骤六、在高速分散机6500r/min的转速搅拌下,将上述步骤五得到的预聚体缓慢倒入称取的温度为5℃的去离子水中,高速乳化5min后,得到淡黄色乳液,放置12h;使用旋转蒸发仪除去乳液中的丁酮,加增稠剂调节粘度为24s,得到A组分。
上述B组分的制备步骤如下:
将5.5g氢氧化铝、2.0g十二烷基苯磺酸钠加入到100g蒸馏水中,磁力搅拌30min,然后超声处理1.5h,抽滤,将抽滤得到的固体在80℃烘箱中干燥24h,再于100℃下真空干燥2h,之后研磨成粉末,得到B组分。
上述无卤阻燃胶的制备步骤如下:
按A组分:B组分(质量比)=10:2的配比称取各组分,于30℃下进行超声处理,同时进行搅拌,60分钟后出料,即得有机/无机复合无卤阻燃胶,记为样品3#。经测试3#样品极限氧指数为32.8%,燃烧等级为A级,拉伸强度6.9MPa。
对比例1
本对比例提供一种无卤阻燃胶,包括A组分和B组分,A组分和B组分的质量比以及A组分和B组分的原料与实施例1相同,不同的是将A组分中的磷氮协效阻燃聚酯二元醇(PNJZ)替换为德国科莱恩的聚醚多元醇OP550。
上述无卤阻燃胶的制备方法也与实施例1相同,不同的是制备A组分时将磷氮协效阻燃聚酯二元醇(PNJZ)替换为德国科莱恩的聚醚多元醇OP550,其他反应条件均相同。
制备得到的无卤阻燃胶记为样品4#。经测试4#样品极限氧指数为27.5%,燃烧等级为B1级,拉伸强度3.9MPa。
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、等同替换或改进等,均应包含在本发明的保护范围之内。
Claims (6)
1.一种无卤阻燃胶,其特征在于,包括A组分和B组分,所述A组分和所述B组分的质量比为10:0.5-2;
其中,所述A组分包括如下重量份数的原料组分:聚醚二元醇11-24份,二异氰酸酯12-21份,亲水扩链剂1.6-2.1份,中和剂0.8-1.2份,氮磷协效阻燃剂5-15份,含磷多元醇5-15份和水150-200份;
所述B组分为阴离子表面活性剂改性的无机阻燃剂;
其中,所述氮磷协效阻燃剂为[[双(2-羟乙基)氨基]甲基]磷酸二乙酯,所述含磷多元醇为磷氮协效阻燃聚酯二元醇;
所述A组分的制备方法至少包括以下步骤:
步骤a,按照所述A组分的设计配比称取各组分,将称取的二异氰酸酯、亲水扩链剂、聚醚二元醇,混合均匀,在惰性气体保护下,于70-85℃反应2-4h,得聚氨酯预聚体;
步骤b,向所述聚氨酯预聚体中加入称取的氮磷协效阻燃剂,混合均匀,于75-85℃反应2-4h,然后加入称取的含磷多元醇,继续反应2-4h,降温至30-50℃,加入中和剂,反应25-35min,得到本质阻燃改性聚氨酯预聚体;
步骤c,将所述本质阻燃改性聚氨酯预聚体于搅拌条件下加入0-10℃的水中,乳化5-15min,加入增稠剂调节粘度至20-24s,得所述A组分;
所述B组分的制备方法包括如下步骤:将无机阻燃剂、阴离子表面活性剂和水搅拌混合20-40min,超声处理0.5-3h,过滤,干燥,研磨,得阴离子表面活性剂改性的无机阻燃剂。
2.如权利要求1所述的无卤阻燃胶,其特征在于,所述无机阻燃剂、所述阴离子表面活性剂和水的质量比为4.5-5.5:1-2:100。
3.如权利要求1-2任一项所述的无卤阻燃胶,其特征在于,所述无机阻燃剂为氢氧化镁、硫酸镁、氢氧化铝或膨胀型石墨中的一种或几种;和/或
所述阴离子表面活性剂为十二烷基苯磺酸钠、硬脂酸钠或油酸钠中的一种或几种。
4.如权利要求1所述的无卤阻燃胶,其特征在于,所述聚醚二元醇为聚丙二醇;和/或
所述二异氰酸酯为甲苯二异氰酸酯;和/或
所述亲水扩链剂为二羟甲基丙酸;和/或
所述中和剂为三乙胺。
5.如权要求1所述的无卤阻燃胶,其特征在于,步骤c中,搅拌速度为3500-6500r/min。
6.一种权利要求1所述的无卤阻燃胶的制备方法,其特征在于,至少包括如下步骤:按照设计配比称取A组分和B组分,于20-30℃超声搅拌0.5-1h,得所述无卤阻燃胶。
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