CN114181433B - 一种聚氨酯基离子液体聚合物包覆红磷阻燃材料的制备方法 - Google Patents
一种聚氨酯基离子液体聚合物包覆红磷阻燃材料的制备方法 Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000003063 flame retardant Substances 0.000 title claims abstract description 64
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
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- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
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- KMBMQZQZBOLJHN-UHFFFAOYSA-N 2-methyloxirane;oxolane Chemical compound CC1CO1.C1CCOC1 KMBMQZQZBOLJHN-UHFFFAOYSA-N 0.000 claims 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种聚氨酯基离子液体聚合物包覆红磷阻燃材料的制备方法,所述的制备方法以红磷、多羟基化合物、离子液体及异氰酸酯为原料,步骤如下:将红磷和多羟基化合物、离子液体均匀分散在溶液中,然后在室温下搅拌加入异氰酸酯,再加入催化剂后进行聚合反应,反应时间为0.1~4小时,反应温度为室温~90℃,然后过滤产生的沉淀物,加热减压干燥去除溶剂,得到干燥的包覆红磷阻燃剂。本发明是将多羟基化合物、可反应型离子液体与异氰酸酯反应,直接原位聚合在红磷表面,制备出聚氨酯基离子液体包覆红磷阻燃剂。这种阻燃剂具有抗静电、阻燃效率高、与聚氨酯相容性好等特点,适用于各种有抗静电阻燃需求的聚氨酯制品的阻燃。
Description
技术领域
本发明涉及到一种阻燃抗静电聚氨酯离子液体聚合物包覆红磷阻燃剂的制备方法,提供一种能够同时具有抗静电和阻燃功能的包覆红磷阻燃材料的制备方法。
背景技术
阻燃剂是一种能够赋予聚合物材料难燃性的功能性助剂,可以起到延缓、避免材料引燃、燃烧的目的。目前阻燃材料主要分为卤素和非卤系阻燃体系。其中卤素体系以氯系、溴系阻燃剂为主,非卤素体系以含磷含氮阻燃剂为主,其中磷系阻燃剂中的红磷由于具有非卤素环保、优异的阻燃性而被广泛应用于高分子体系中。但是,红磷阻燃剂的主要缺点在于容易氧化,着火,析出,与高分子材料相容性不好等缺点限制了它的应用,需要对其进行包覆处理。
常见的包覆材料主要为高分子材料:如环氧树脂、密胺树脂、环氧树脂、不饱和聚酯等,这些方式所使用的包覆材料大多是绝缘材料,不能够提供抗静电功能,同时比较细的红磷粉末容易在摩擦下产生静电团聚乃至起火自燃现象,为了避免减少摩擦,行业内通常用加油的方式避免,但是这种办法又会导致包覆红磷阻燃效果降低;还有些包覆是不阻燃树脂,导致了大幅度降低了红磷的阻燃性能。
中国专利CN200610155489.5,提供了一种聚氨酯树脂用微胶囊化红磷及其制备方法,即将红磷用25%~35%的甘油去离子水溶液浸泡10~14H,在胶体磨研磨均匀后,过滤,滤饼用无水乙醇洗涤后置于60~90℃烘箱烘至恒重。再将上述处理过的红磷和水、多元醇混合,在胶体磨研磨均匀,在1000~5000RPM强烈搅拌下,加入质量为红磷质量的1~2倍的有机溶剂,继续搅拌30~60MIN,再降低搅拌速度为100~600RPM,将温度调为2~10℃后加入异氰酸酯溶液,反应完全,过滤,洗涤,干燥,制成聚氨酯树脂用微胶囊化红磷的成品。红磷进行微胶囊化后可直接加入聚氨酯树脂中,作为聚氨酯树脂的阻燃剂。
上述专利存在如下技术问题:此专利提供的包覆红磷技术所使用的树脂不具有阻燃、抗静电功能,不能同时实现抗静电、阻燃的功能;并且容易引起红磷粉的静电团聚,还会降低红磷本身的阻燃性能,因而需要优化改进。
现有技术目前尚未公开有同时具有抗静电和阻燃功能的包覆红磷阻燃材料。
发明内容
本发明的目的是克服现有技术的不足,提供一种聚氨酯基离子液体聚合物包覆红磷阻燃材料的制备方法,这是一种能够同时具有抗静电和阻燃功能的包覆红磷阻燃材料的制备方法。
本发明的技术方案如下:
一种聚氨酯基离子液体聚合物包覆红磷阻燃材料的制备方法,所述的制备方法以红磷、多羟基化合物、离子液体及异氰酸酯为原料,步骤如下:将红磷和多羟基化合物、离子液体均匀分散在溶液中,然后在室温下搅拌加入异氰酸酯,再加入催化剂后进行聚合反应,反应时间为0.1~4小时,反应温度为室温~90℃,然后过滤产生的沉淀物,加热减压干燥去除溶剂,得到干燥的包覆红磷阻燃剂。
为了提供一种同时具有抗静电、阻燃功能的包覆红磷阻燃剂,本发明的发明人进行了大量研究,意外地发现通过在传统的包覆路线中直接在分子链段中引入阻燃且导电效率高的离子液体,再进行原位聚合,得到的包覆红磷阻燃剂,其同时具有抗静电和阻燃功能。
前面提及的离子液体是指由阴阳离子构成的室温下呈现液体的盐,具有较好的导电性;带有磷、氮、氟元素的离子液体还具有较好的阻燃性能,与聚氨酯聚合形成的离子液体聚合物是一种具有阻燃、抗静电功能的材料,与聚氨酯相容性优异。用这种材料作为红磷包覆材料能够赋予红磷阻燃剂同时阻燃和抗静电的功能。同时还能起到避免红磷静电团聚和阻燃降低的功能。
进一步地,所述的多羟基化合物和离子液体的羟基总摩尔数与异氰酸酯的官能团摩尔比为0.9-1:0.9-1。
进一步地,所述的离子液体的添加量为多羟基化合物质量的0.2-20%;即当多羟基化合物质量为100g时,离子液体的添加量0.2-20g。更优选地,所述的离子液体的添加量为多羟基化合物质量的5-20%。
进一步地,所述的催化剂的添加量为除红磷外的原料总质量的0.05-2%;即当多羟基化合物、离子液体及异氰酸酯的总质量为100g时,催化剂的添加量0.05-2g。更优选地,所述的催化剂的添加量为除红磷外的原料总质量的0.5-1%。
进一步地,所述的红磷在整个原料总质量中的质量占比为50-90%;即当红磷、多羟基化合物、离子液体及异氰酸酯的总质量为100g时,红磷占50-90g。更优选地,所述的红磷在整个原料总质量中的质量占比为50-85%。
进一步地,所述红磷平均粒径为0.5-30微米。更优选地,所述红磷平均粒径为1-15微米。
进一步地,所述多羟基化合物为乙二醇、丙二醇、丙三醇、季戊四醇、丁二醇、新戊二醇、己二醇、聚乙二醇、聚丁二醇、聚己二醇、聚氧化丙烯二醇、聚四氢呋喃二醇、氧化丙烯-四氢呋喃二醇、N,N-二羟乙基胺甲基磷酸酯中的一种或者多种的混合物。
进一步地,所述的异氰酸酯为甲苯二异氰酸酯TDI、二苯基甲烷4,4’-二异氰酸酯MDI、1,6-己二异氰酸酯HDI中的任意一种与多苯基多亚甲基多异氰酸酯的混合物,或者是多苯基多亚甲基多异氰酸酯单体本身,当为异氰酸酯混合物时,TDI、MDI、HDI中的任意一种与多苯基多亚甲基多异氰酸酯两种异氰酸酯的摩尔比为1:0.6-1.2。
进一步地,所述的离子液体为1-羟乙基-3-甲基咪唑四氟硼酸盐或1-羟乙基-3-甲基咪唑六氟磷酸盐。
进一步地,所述的催化剂为月桂酸丁基锡或氯化亚锡。
本发明具有如下技术效果:
1)本发明的聚氨酯基离子液体聚合物包覆红磷阻燃材料的制备方法,是将多羟基化合物、可反应型离子液体与异氰酸酯反应,直接原位聚合在红磷表面,制备出聚氨酯基离子液体包覆红磷阻燃剂。这种阻燃剂具有与聚氨酯相容性好,阻燃效率高、抗静电的特点,适用于各种有抗静电阻燃需求的聚氨酯制品的阻燃。
2)从本申请的效果实施例可以看出:本发明实施例1~3的阻燃性能均能达到VTM-0的测试标准,材料的氧指数可以达到30以上,并且可以满足抗静电需求。对比例1的包覆红磷阻燃剂,由于制备过程中没有加入离子液体,其阻燃性能不如实施例1~3添加了离子液体的包覆红磷阻燃性能,另外,对比例1的包覆红磷阻燃体系,制备过程中没有加入离子液体,无抗静电性能。对比例2中直接加入了未包覆的红磷和离子液体单体,对比效果中可以看出,由于红磷没有包覆,与聚氨酯本身的相容性比较差导致了分散不均匀而阻燃性能降低,同时由于离子液体是以液体游离状态存在体系中的,很容易析出,与材料不相容,因而不能均匀分散在体系中,不能很好的发挥其抗静电性能和阻燃性能,同时由于从体系中析出来而导致聚氨酯的粘接剥离强度大大降低。
具体实施方式
以下结合具体实施例对本发明作进一步详细描述。
实施例1
本实施例的阻燃导电聚氨酯材料,所需的原料包括如下重量百分比的物质:
制备方法:将计量的红磷和多羟基化合物、离子液体均匀分散在溶液中,然后在室温下搅拌加入异氰酸酯,加入催化剂后进行聚合反应,反应时间为4小时,反应温度为70℃,然后过滤产生的沉淀物,加热减压干燥去除溶剂,得到干燥的包覆红磷阻燃剂。
实施例2
本实施例的阻燃导电聚氨酯材料,所需的原料包括如下重量百分比的物质:
制备方法:将计量的红磷和多羟基化合物、离子液体均匀分散在溶液中,然后在室温下搅拌加入异氰酸酯,加入催化剂后进行聚合反应,反应时间为1小时,反应温度为60℃,然后过滤产生的沉淀物,加热减压干燥去除溶剂,得到干燥的包覆红磷阻燃剂;
实施例3
本实施例的阻燃导电聚氨酯材料,所需的原料包括如下重量百分比的物质:
制备方法:将计量的红磷和多羟基化合物、离子液体均匀分散在溶液中,然后在室温下搅拌加入异氰酸酯,加入催化剂后进行聚合反应,反应时间为1小时,反应温度为室温至70℃,然后过滤产生的沉淀物,加热减压干燥去除溶剂,得到干燥的包覆红磷阻燃剂。
对比例1
本实施例的阻燃导电聚氨酯材料,所需的原料包括如下重量百分比的物质:
制备方法:将计量的红磷和多羟基化合物均匀分散在溶液中,然后在室温下搅拌加入异氰酸酯,加入催化剂后进行聚合反应,反应时间为1小时,反应温度为70℃,然后过滤产生的沉淀物,加热减压干燥去除溶剂,得到干燥的包覆红磷阻燃剂。
实施例1-3和对比例1的效果验证试验
做应用配方如下:在溶有100克聚乙二醇(分子量=1000)的1000克丁酮溶液中,加入HDI 16克和催化剂月桂酸丁基锡0.2克,在60~70℃下反应三个小时后冷却,得到无色透明的聚氨酯胶,冷却至室温后,再将实施例1-3和对比例1中制备得到的包覆红磷10克分别均匀分散在所得到的胶中,然后将该胶液涂布于PET基膜上,然后在烘箱中缓慢烘干溶剂,胶膜厚约150微米,将获得的带有阻燃胶的PET膜进行各种测试。
对比例2的效果验证试验
做应用配方如下:在溶有102.8克聚乙二醇(分子量=1000)的1000克丁酮溶液中,加入HDI 16.5克和催化剂月桂酸丁基锡0.2克,在60~70℃下反应三个小时后冷却,得到无色透明的聚氨酯胶,冷却至室温后,再将6克平均粒径3微米的红磷、0.65克离子液体1-羟乙基-3-甲基咪唑四氟硼酸盐加入上述聚氨酯胶中,搅拌均匀后将该胶液涂布于PET基膜上,然后在烘箱中缓慢烘干溶剂,胶膜厚约150微米,将获得的带有阻燃胶的PET膜进行各种测试。
测试方法:
1)阻燃性能UL-94和燃烧现象的测试方法按照UL94测试标准进行
2)抗静电性能测试方法按照GB/T 1410-2006进行
3)氧指数测试方法参考GB/T 2406-93
4)力学剥离强度测试方法参考GB/T2791-1995
测试结果见表1。
表1:实施例1-3与对比例1-2的性能对比
从测试结果可见:
1、实施例1~3的阻燃性能均能达到VTM-0的测试标准,材料的氧指数可以达到30以上,并且可以满足抗静电需求。
2、对比例1的包覆红磷阻燃剂,由于制备过程中没有加入离子液体,其阻燃性能不如实施例1~3添加了离子液体的包覆红磷阻燃性能,另外,对比例1的包覆红磷阻燃体系,制备过程中没有加入离子液体,无抗静电性能。
3、对比例2中直接加入了未包覆的红磷和离子液体单体,对比效果中可以看出,由于红磷没有包覆,与聚氨酯本身的相容性比较差导致了分散不均匀而阻燃性能降低,同时由于离子液体是以液体游离状态存在体系中的,很容易析出,与材料不相容,因而不能均匀分散在体系中,不能很好的发挥其抗静电性能和阻燃性能,同时由于从体系中析出来而导致聚氨酯的粘接剥离强度大大降低。
以上仅为本发明的实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书内容所作的等效变换,或直接或间接运用在其它相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (3)
1.一种聚氨酯基离子液体聚合物包覆红磷阻燃材料的制备方法,其特征在于,所述的制备方法以红磷、多羟基化合物、离子液体及异氰酸酯为原料,步骤如下:将红磷和多羟基化合物、离子液体均匀分散在溶液中,然后在室温下搅拌加入异氰酸酯,再加入催化剂后进行聚合反应,反应时间为0.1~4小时,反应温度为室温~90℃,然后过滤产生的沉淀物,加热减压干燥去除溶剂,得到干燥的包覆红磷阻燃剂;
所述的离子液体为1-羟乙基-3-甲基咪唑四氟硼酸盐或1-羟乙基-3-甲基咪唑六氟磷酸盐;
所述的异氰酸酯为甲苯二异氰酸酯TDI、二苯基甲烷4,4’-二异氰酸酯MDI、1,6-己二异氰酸酯HDI中的任意一种与多苯基多亚甲基多异氰酸酯的混合物,或者是多苯基多亚甲基多异氰酸酯单体本身,当为异氰酸酯混合物时,TDI、MDI、HDI中的任意一种与多苯基多亚甲基多异氰酸酯两种异氰酸酯的摩尔比为1:0.6-1.2;
所述的催化剂为月桂酸丁基锡或氯化亚锡;
所述的多羟基化合物和离子液体的羟基总摩尔数与异氰酸酯的官能团摩尔比为0.9-1:0.9-1;
所述的离子液体的添加量为多羟基化合物质量的0.2-20%;
所述的催化剂的添加量为除红磷外的原料总质量的0.05-2%;
所述的红磷在整个原料总质量中的质量占比为50-90%。
2.根据权利要求1所述的方法,其特征在于,所述红磷的平均粒径为0.5~30微米。
3.根据权利要求1所述的方法,其特征在于,所述多羟基化合物为乙二醇、丙二醇、丙三醇、季戊四醇、丁二醇、新戊二醇、己二醇、聚乙二醇、聚丁二醇、聚己二醇、聚氧化丙烯二醇、聚四氢呋喃二醇、氧化丙烯-四氢呋喃二醇、N,N-二羟乙基胺甲基磷酸酯中的一种或者多种的混合物。
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Denomination of invention: Preparation method of polyurethane based ionic liquid polymer coated red phosphorus flame retardant material Granted publication date: 20230905 Pledgee: Industrial and Commercial Bank of China Limited Huaibei Mudan Branch Pledgor: ANHUI CHANGHUAI NEW MATERIAL Co.,Ltd. Registration number: Y2024980010015 |