CN106832410B - 一种无机含硅阻燃协效剂 - Google Patents
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Abstract
一种无机含硅阻燃协效剂,属于阻燃领域。采用三硅酸镁并经过200℃‑800℃以上高温活化处理2‑36h时间、粒径低于100μm的颗粒作为阻燃协效剂。与膨胀型阻燃剂配合使用,起到很好的效果。
Description
技术领域
本发明属于阻燃领域,尤其涉及一种无机含硅阻燃协效剂。
背景技术
高分子材料与传统的金属材料,无机非金属材料相比,由于其在产品性能,耐候性,使用成本等方面所展现的优势,使得其应用范围与发展速度均大大超过了传统材料,在生产生活中已经不可或缺。但是,高分子材料的易燃性也越来越制约着它的应用该范围。根据公安部发布的《2015年全国火灾事故统计》,2015年全年共发生火灾33.8万起(全国),共造成2854人伤亡,其中1742人死亡,1112人受伤,直接造成经济损失39.5亿元,给人们的生命财产安全带来巨大危害。在这些火灾事故中,由于高分子材料的易燃性而导致的火灾不可胜数。因此高分子材料的阻燃改性意义重大,必不可少。
高分子材料的阻燃方法主要有添加型和反应型两种。添加型阻燃方法即通过物理共混的方式将阻燃剂均匀分散在材料中,从而获得阻燃性能。这种方法优势在于成本低,操作简单方便,缺点在于阻燃性能难以持久;反应型阻燃方法即阻燃剂能够同被阻燃物发生化学反应,使得阻燃元素或者结构引入但被阻燃物的结构当中,这种方法优势在于阻燃性能持久有效,效率高。
阻燃剂的引入能够提高材料的阻燃性能,但是另一方面,阻燃剂的大量引入对被阻燃物的自身性能也会带来影响,此外阻燃剂的价格一般较高,会提高材料的生产成本,因此提高阻燃剂的阻燃效率意义十分重大。比较成熟的阻燃协效体系是卤-锑体系,尤其是溴-锑协效体系的阻燃效率最高。由于卤系阻燃剂潜在的环境和人体危害性,目前阻燃的研究方向主要集中在无卤阻燃方向,其中含磷阻燃剂被视为最有可能取代卤系阻燃剂,但是目前成熟的含磷阻燃剂的阻燃效率一般低于卤系阻燃剂,提高其阻燃效率的方法主要有阻燃剂复配与添加阻燃协效剂的方法。锑系协效剂由于锑金属的价格飙升,与含磷阻燃剂协效效果差等原因,难以满足日益增长的需求,这就需要我们寻找新型的低廉、环保且高效的阻燃协效剂。
当前阻燃协效剂的研究热点主要集中在多酸,固体酸,金属盐或者金属氧化物,高岭土等无机粒子上。李娟等(专利公开号:105504350A)合成一种多酸基阻燃协效剂,特征在于该多酸基阻燃协效剂的结构通式为(A)nB,其中Bn-为通多或杂多酸阴离子,A+可以为有机、无机阳离子的一种或多种。研究表明,制得的哌嗪磷钼酸盐阻燃协效剂在阻燃聚丙烯树脂上的,添加0.5%该协效剂,阻燃效果达到V0等级需要阻燃剂添加量为15.5%,对比未加入该协效剂的阻燃PP需要25%的添加量才能达到V0等级。Lei等(J Therm Anal Calorim,2014(115):1065-1071)研究了ZnO和ZnCl在PP体系中的协效阻燃作用,研究表明通过与膨胀型阻燃剂复配,ZnO或ZnCl均能够有效提高PP的氧指数和垂直燃烧等级,阻燃效率明显提高。汪炉林等(专利公开号:102558868A)通过将锑化合物与滑石粉,无机硅酸盐,有机硅物质进行复配,制备出一种新型的阻燃协效剂,能够完全等量替代溴-锑阻燃体系中的三氧化二锑,可以用于制备低成本的阻燃ABS。
阻燃协效剂目前存在的问题主要是与含磷阻燃剂匹配,阻燃效率低,制备过程复杂以及价格成本高等。
发明内容
本发明的目的是克服现有技术的不足,提供一种新型的无机含硅阻燃协效剂。本发明选择三硅酸镁,通过对其进行高温活化与控制粒径范围,获得一种绿色高效的阻燃协效剂。
一种无机含硅阻燃协效剂,其特征在于,采用三硅酸镁并经过150℃-600℃(优选200℃-500℃)高温活化处理,活化处理时间为2-36小时(优选2.5-24h)、粒径范围为0.1-100μm(优选为20-60μm)的颗粒作为阻燃协效剂。
三硅酸镁是一种不定的含水硅酸镁,结构式为Mg2Si3O8·nH2O,其中MgO的质量百分含量不得少于20.0%,SiO2的质量百分含量不得少于45.0%;SiO2与MgO的质量含量的比值应为2.1~2.3。
进一步优选:
该无机含硅阻燃协效剂与膨胀型阻燃剂配合使用。
优选该无机含硅阻燃协效剂与膨胀型阻燃剂的质量比为1:1~50。
优选膨胀型阻燃剂包括酸源、碳源和气源,酸源、碳源和气源按照质量比2:(0~2):(0~2)混合而成,进一步优选2:(0.5~2):(0.5~2)。其中酸源为聚磷酸铵(APP)、密胺包覆聚磷酸铵(MAPP)、聚磷酸三聚氰胺(MPP)中的一种或几种,碳源为季戊四醇(PER)、双季戊四醇(DPER)、三季戊四醇(TPER)、酚醛树脂(PF)、淀粉(AM)、环糊精(DT)中的一种或几种,气源为三聚氰胺(MEL)、双氰胺(DCD/DICY)中的一种或几种。
本发明的优点以及积极效果:
1本发明选用的主要成分为三硅酸镁,生产工艺简单,价格低廉,对人与环境无危害,是一种低成本的环保高效阻燃协效剂。
2可以广泛的应用在塑料,树脂胶黏剂,涂料以及建筑材料等领域。
3由图1中XRD曲线的变化可看出本发明专利中三硅酸镁(MTS)阻燃协效剂在室温与高温下均为无定型结构硅酸盐,在高温下能够同膨胀型阻燃剂(IFR)中酸源发生化学反应,一部分转变为磷酸硅类物质与无定型的二氧化硅,能够有效提高被阻燃物的阻燃性能。
附图说明
图1三硅酸镁(MTS)不同条件下XRD曲线(酸源如为聚磷酸铵(APP))。
具体实施方式
下面结合实施例对本发明作进一步说明,但本发明并不限于以下实施例。
实施例1:
(1)将三硅酸镁进行300℃高温活化处理2h,降至室温后,研磨过600目筛,获得所需的阻燃协效剂。
(2)按照表1配料量制备硅烷封端聚醚密封胶,然后将制得的密封胶在模具中固化成型。其中膨胀型阻燃剂为聚磷酸铵(APP)、三聚氰胺(MEL)、季戊四醇(PER),质量比为3:1:1。其他助剂为增塑剂、硅烷偶联剂、催化剂等。
表1.硅烷封端聚醚密封胶配方
(3)待制得的密封胶万千固化成型后,进行阻燃性能测试,阻燃测试见表2.
表2阻燃性能测试结果
实施例2:
(1)将三硅酸镁进行450℃高温活化处理6h,降至室温后,研磨过600目筛,获得所需的阻燃协效剂。
(2)按照表3配料量,采用双辊挤出机进行挤出造粒,其中挤出温度为175~195℃,螺杆转速30~40r/min。然后将制得的粒料采用压片机压片成型。其中膨胀型阻燃剂为聚磷酸铵(APP)、三聚氰胺(MEL),质量比为2:1。
表3.阻燃聚丙烯配方
(3)对制得的阻燃聚丙烯材料进行阻燃性能测试,阻燃测试见表4。表4.阻燃性能测试结果
实施例3.
(1)将三硅酸镁进行350℃高温活化处理5h,降至室温后,研磨过600目筛,获得所需的阻燃协效剂。
(2)按照表5配料量制备水性聚氨酯涂料,其中膨胀型阻燃剂为聚磷酸铵(APP)、三聚氰胺(MEL)、季戊四醇(PER),质量比为3:1.5:2。表5中其他助剂为增稠剂,消泡剂,成膜剂,分散剂。
表5.阻燃聚氨酯涂料配方
(2)阻燃涂料制得后,参考GB/T1544.2—1995标准进行模拟大板燃烧实验,耐燃实验数据见表6。
表6.耐燃时间结果
Claims (10)
1.一种无机含硅阻燃协效剂,其特征在于,采用三硅酸镁并经过150-600℃高温活化处理,活化处理时间为2-36h,粒径范围为0.1-100μm的颗粒作为阻燃协效剂。
2.按照权利要求1所述的一种无机含硅阻燃协效剂,其特征在于,高温活化温度优选为200℃-500℃。
3.按照权利要求1所述的一种无机含硅阻燃协效剂,其特征在于,活化处理时间优选为2.5-24h。
4.按照权利要求1所述的一种无机含硅阻燃协效剂,其特征在于,粒径范围优选为20-60μm。
5.权利要求1所述的一种无机含硅阻燃协效剂的应用,其特征在于,无机含硅阻燃协效剂与膨胀型阻燃剂配合使用。
6.按照权利要求5所述的应用,其特征在于,无机含硅阻燃协效剂与膨胀型阻燃剂的质量比为1:1~50。
7.按照权利要求5所述的应用,其特征在于,膨胀型阻燃剂包括酸源、碳源和气源。
8.按照权利要求7所述的应用,其特征在于,酸源、碳源和气源的质量比:2:(0~2):(0~2)。
9.按照权利要求7所述的应用,其特征在于,酸源、碳源和气源的质量比:2:(0.5~2):(0.5~2)。
10.按照权利要求7所述的应用,其特征在于,酸源为聚磷酸铵(APP)、密胺包覆聚磷酸铵(MAPP)、聚磷酸三聚氰胺(MPP)中的一种或几种,碳源为季戊四醇(PER)、双季戊四醇(DPER)、三季戊四醇(TPER)、酚醛树脂(PF)、淀粉(AM)、环糊精(DT)中的一种或几种,气源为三聚氰胺(MEL)、双氰胺(DCD/DICY)中的一种或几种。
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