CN105482315A - 一种阻燃防腐地板及其制备方法 - Google Patents
一种阻燃防腐地板及其制备方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims abstract description 26
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- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims abstract description 16
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- 239000000178 monomer Substances 0.000 claims abstract description 8
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- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 28
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- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
本发明公开了一种阻燃防腐地板。本发明首先用甲胺使α-磷酸锆胶体化,然后将甲基丙烯酸三氟乙酯作为防腐单体,在聚合过程中嵌入并稳定存在于改性α-磷酸锆层间,在保证改性α-磷酸锆的耐热、抗水、抗冲击、阻燃的同时提高了防腐性能。
Description
技术领域
本发明涉及地板技术领域,尤其涉及一种阻燃防腐地板及其制备方法。
背景技术
PVC作为全球第二大通用塑料,拥有良好的综合性能,以及价格低廉、原料来源广泛等优势在各行各业发挥出重要作用。PVC发泡材料不仅继承了以上所有的优点,而且也存在一些性能的缺陷或不足,如强度,刚性以及热力学性能等等并没有达到人们的期望,尤其PVC发泡材料在燃烧的时候会释放出有毒浓烟,这些都严重地阻碍了PVC泡沫材料的发展和应用。随着近几年纳米在材料中所显示出的巨大潜力,使得通过层状无机物等改性形成纳米复合材料改善材料的综合性能成为近年来研究的热点。层状无机物经过有机改性后使得聚合物复合材料的热稳定性能,机械性能显著提高,特别是α-磷酸锆作为一种具有独特结构和性质的新型纳米粒子,具有纯度高,离子交换容量大容易实现插层或剥离结构,与聚合物复合容易形成纳米结构,这不仅赋予聚合物材料优良的机械性能、阻隔性能而且将层状纳米粒子应用到发泡材料中还能够起到发泡成核剂的作用以至于达到优化发泡质量的目的。另一方面,PVC发泡材料在阻燃和抑烟方面的劣势,也阻碍了其进一步的应用。而添加阻燃抑烟剂恰好可以很好的解决这一问题,前人的研究已经为我们奠定了良好的基础,有机锡类阻燃抑烟剂和钼类阻燃抑烟剂都展现出了优秀的阻燃抑烟效果,特别有机类的阻燃抑烟剂是同聚合物具有良好的相容性,这是其他阻燃剂难以达到的,因此相对于其他阻燃剂而言具有相当的开发前景,目前这两者联合使用于PVC的阻燃抑烟研究未见报道。所以,本论文旨在引入有机改性α-磷酸锆纳米填料,提高PVC发泡材料的发泡质量以及力学性能、热稳定性能等。
发明内容
本发明目的就是为了弥补已有技术的缺陷,提供一种阻燃防腐地板及其制备方法。
本发明是通过以下技术方案实现的:
一种阻燃防腐地板,它是由下述重量份的原料组成的:
水合硼酸锌2-3、八水氧氯化锆17-20、40-47%的盐酸10-15、80-85%的磷酸90-100、四羟甲基硫酸磷3-4、25-30%甲胺水溶液4-7、甲基丙烯酸三氟乙酯5-7、辛基异噻唑啉酮0.2-0.4、过硫酸铵0.06-0.1、二乙烯基苯0.01-0.02、偶氮二甲酰胺1-2、聚氯乙烯160-200、六甲基环三硅氧烷1-2、丙烯酸异辛酯6-10、聚四氟乙烯蜡3-5、氟硼酸钠1-2、松香醇2-3、聚醚醚酮1-2。
一种所述的阻燃防腐地板的制备方法,包括以下步骤:
(1)将八水氧氯化锆加入到15-18倍蒸馏水中,搅拌均匀,依次加入上述40-47%的盐酸、80-85%的磷酸,室温下电磁搅拌3-4天,过滤,用去离子水洗涤至PH为5,在60-65℃下真空干燥,研磨,得α-磷酸锆;
(2)将上述α-磷酸锆、水合硼酸锌混合,搅拌均匀,加入混合料重量2-3倍、10-15%的醋酸溶液,搅拌均匀,加入六甲基环三硅氧烷,300-400转/分搅拌20-30分钟,抽滤,在80-90℃下干燥10-16分钟,得阻燃α-磷酸锆;
(3)将上述氟硼酸钠加入到6-10倍去离子水中,搅拌均匀,加入聚四氟乙烯蜡,升高温度为80-87℃,滴加93-95%的硫酸,调节PH为2-3,保温反应1-2小时,加入松香醇、加入聚醚醚酮,搅拌至常温,得阻燃助剂;
(4)将辛基异噻唑啉酮加入到30-40倍20-30%的乙醇溶液中,搅拌均匀,加入甲基丙烯酸三氟乙酯,升高温度为70-75℃,加入二乙烯基苯,保温反应3-4小时,得防腐单体;
(5)将上述阻燃α-磷酸锆加入到90-100倍去离子水中,搅拌均匀,加入甲胺水溶液,超声30-35分钟,加入四羟甲基硫酸磷,搅拌分散10-16分钟,加入上述防腐单体,超声3-5分钟,加入过硫酸铵,在75-80℃下保温反应6-10小时,加入上述阻燃助剂,搅拌均匀,离心分离,将沉淀物洗涤、烘干,得有机改性磷酸锆;
(6)将上述有机改性磷酸锆与聚氯乙烯混合,送入高速搅拌机中,1000-1200r/min搅拌20-30分钟,缓慢升高温度为120-130℃,降低转速为300-400r/min,搅拌至46-50℃,再升高温度为130-140℃,加入剩余各原料,保温预热50-60分钟,通过挤出机熔融挤出,经过牵引切割、拉毛,即得。
本发明的优点是:
(1)本发明的地板具有很好的耐热稳定性:
采用四羟甲基硫酸磷作为改性剂,层间没有可以催化聚氯乙烯分解的因子,得到有机改性磷酸锆的层状结构,能够有效的起到能量和物质的阻隔作用;另一方面,有机改性α-磷酸锆的加入改善了聚氯乙烯发泡材料的发泡质量,使得泡孔均匀化,泡孔之间出现了明显的界限,即闭孔数量在增多,开孔结构减少,这种闭孔结构在热量传递的过程中吸收了大量的热,阻止热量的传播;另外,添加有机改性的α-磷酸锆会使得聚氯乙烯复合发泡材料在受到冲击的时候能够很好的保持泡孔的形状,使得泡孔保持原有的刚性和韧性,因此提高了聚氯乙烯气泡壁的厚度,增强了其抵抗外立场对其产生破坏的能力;
(2)本发明的地板具有很好的抗水性:
经过有机改性的α-磷酸锆,由于有机阳离子取代层间的H+或者有机阴离子的在α-磷酸锆层间的吸附作用而使得改性后的疏水性较为显著的提高;
(3)本发明的地板具有很好的抗冲击性能:
本发明采用四羟甲基硫酸磷作为改性剂明显提高了聚氯乙烯发泡材料的发泡质量,泡孔较为均匀,泡孔壁呈现球形,完整的泡孔壁通过发生形变吸收能量,则韧性增加;
(4)本发明的地板具有很好的阻燃性能:
α-磷酸锆自身是层状结构,并且经过改性后形成一定的剥离结构,不管是层状结构还是剥离结构,这些结构的存在,能够在聚合物燃烧时候可以起到物质和能量阻隔作用,且聚氯乙烯燃烧时能够释放出HCl,HCL气体自身具有明显的阻燃性;
(5)本发明首先用甲胺使α-磷酸锆胶体化,然后将甲基丙烯酸三氟乙酯作为防腐单体,在聚合过程中嵌入并稳定存在于改性α-磷酸锆层间,在保证改性α-磷酸锆的耐热、抗水、抗冲击、阻燃的同时提高了防腐性能。
具体实施方式
一种阻燃防腐地板,它是由下述重量份的原料组成的:
水合硼酸锌2、八水氧氯化锆17、40%的盐酸10、80%的磷酸90、四羟甲基硫酸磷3、25%甲胺水溶液4、甲基丙烯酸三氟乙酯5、辛基异噻唑啉酮0.2、过硫酸铵0.06、二乙烯基苯0.01、偶氮二甲酰胺1、聚氯乙烯160、六甲基环三硅氧烷1、丙烯酸异辛酯6、聚四氟乙烯蜡3、氟硼酸钠1、松香醇2、聚醚醚酮1。
一种所述的阻燃防腐地板的制备方法,包括以下步骤:
(1)将八水氧氯化锆加入到15倍蒸馏水中,搅拌均匀,依次加入上述40%的盐酸、80%的磷酸,室温下电磁搅拌3天,过滤,用去离子水洗涤至PH为5,在60℃下真空干燥,研磨,得α磷酸锆;
(2)将上述α磷酸锆、水合硼酸锌混合,搅拌均匀,加入混合料重量2倍、10%的醋酸溶液,搅拌均匀,加入六甲基环三硅氧烷,300转/分搅拌20分钟,抽滤,在80℃下干燥10分钟,得阻燃α磷酸锆;
(3)将上述氟硼酸钠加入到6倍去离子水中,搅拌均匀,加入聚四氟乙烯蜡,升高温度为80℃,滴加93%的硫酸,调节PH为2,保温反应1小时,加入松香醇、加入聚醚醚酮,搅拌至常温,得阻燃助剂;
(4)将辛基异噻唑啉酮加入到30倍20%的乙醇溶液中,搅拌均匀,加入甲基丙烯酸三氟乙酯,升高温度为70℃,加入二乙烯基苯,保温反应3小时,得防腐单体;
(5)将上述阻燃α磷酸锆加入到90倍去离子水中,搅拌均匀,加入甲胺水溶液,超声30分钟,加入四羟甲基硫酸磷,搅拌分散10分钟,加入上述防腐单体,超声3分钟,加入过硫酸铵,在75℃下保温反应6小时,加入上述阻燃助剂,搅拌均匀,离心分离,将沉淀物洗涤、烘干,得有机改性磷酸锆;
(6)将上述有机改性磷酸锆与聚氯乙烯混合,送入高速搅拌机中,1000r/min搅拌20分钟,缓慢升高温度为120℃,降低转速为300r/min,搅拌至46℃,再升高温度为130℃,加入剩余各原料,保温预热50分钟,通过挤出机熔融挤出,经过牵引切割、拉毛,即得。
性能测试:
密度:0.9g/cm3;
邵氏D硬度:79度;
弯度强度:24.4MPa;
无缺口冲击强度:77kJ/m2;
吸水率:0.484%;
抗冲击性能:无裂纹;
氧指数:37.1%;
45度角燃烧:难燃;
握钉力:2.2kN;
环保性能(甲醇释放量,干燥器法9-11L):0.2mg/L。
Claims (2)
1.一种阻燃防腐地板,其特征在于,它是由下述重量份的原料组成的:
水合硼酸锌2-3、八水氧氯化锆17-20、40-47%的盐酸10-15、80-85%的磷酸90-100、四羟甲基硫酸磷3-4、25-30%甲胺水溶液4-7、甲基丙烯酸三氟乙酯5-7、辛基异噻唑啉酮0.2-0.4、过硫酸铵0.06-0.1、二乙烯基苯0.01-0.02、偶氮二甲酰胺1-2、聚氯乙烯160-200、六甲基环三硅氧烷1-2、丙烯酸异辛酯6-10、聚四氟乙烯蜡3-5、氟硼酸钠1-2、松香醇2-3、聚醚醚酮1-2。
2.一种如权利要求1所述的阻燃防腐地板的制备方法,其特征在于,包括以下步骤:
(1)将八水氧氯化锆加入到15-18倍蒸馏水中,搅拌均匀,依次加入上述40-47%的盐酸、80-85%的磷酸,室温下电磁搅拌3-4天,过滤,用去离子水洗涤至PH为5,在60-65℃下真空干燥,研磨,得α-磷酸锆;
(2)将上述α-磷酸锆、水合硼酸锌混合,搅拌均匀,加入混合料重量2-3倍、10-15%的醋酸溶液,搅拌均匀,加入六甲基环三硅氧烷,300-400转/分搅拌20-30分钟,抽滤,在80-90℃下干燥10-16分钟,得阻燃α-磷酸锆;
(3)将上述氟硼酸钠加入到6-10倍去离子水中,搅拌均匀,加入聚四氟乙烯蜡,升高温度为80-87℃,滴加93-95%的硫酸,调节PH为2-3,保温反应1-2小时,加入松香醇、加入聚醚醚酮,搅拌至常温,得阻燃助剂;
(4)将辛基异噻唑啉酮加入到30-40倍20-30%的乙醇溶液中,搅拌均匀,加入甲基丙烯酸三氟乙酯,升高温度为70-75℃,加入二乙烯基苯,保温反应3-4小时,得防腐单体;
(5)将上述阻燃α-磷酸锆加入到90-100倍去离子水中,搅拌均匀,加入甲胺水溶液,超声30-35分钟,加入四羟甲基硫酸磷,搅拌分散10-16分钟,加入上述防腐单体,超声3-5分钟,加入过硫酸铵,在75-80℃下保温反应6-10小时,加入上述阻燃助剂,搅拌均匀,离心分离,将沉淀物洗涤、烘干,得有机改性磷酸锆;
(6)将上述有机改性磷酸锆与聚氯乙烯混合,送入高速搅拌机中,1000-1200r/min搅拌20-30分钟,缓慢升高温度为120-130℃,降低转速为300-400r/min,搅拌至46-50℃,再升高温度为130-140℃,加入剩余各原料,保温预热50-60分钟,通过挤出机熔融挤出,经过牵引切割、拉毛,即得。
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