CN106928491A - 一种微胶囊化可膨胀石墨及其制法和在制备复合聚氨酯硬质泡沫中的应用 - Google Patents
一种微胶囊化可膨胀石墨及其制法和在制备复合聚氨酯硬质泡沫中的应用 Download PDFInfo
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- CN106928491A CN106928491A CN201710145269.2A CN201710145269A CN106928491A CN 106928491 A CN106928491 A CN 106928491A CN 201710145269 A CN201710145269 A CN 201710145269A CN 106928491 A CN106928491 A CN 106928491A
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- expansible graphite
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- epoxy resin
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Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及一种微胶囊化可膨胀石墨,它是一种三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨,即在可膨胀石墨外首先包裹三聚氰胺微胶囊,然后再包裹有环氧树脂微胶囊的三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨的微胶囊化可膨胀石墨。它可以作为阻燃剂用于制备聚氨酯硬质泡沫,所制得的聚氨酯硬质泡沫密度为60kg·m‑3左右;导热系数为0.03W·(m·k)‑1左右;压缩强度为0.60MPa左右;极限氧指数接近30%。本发明公开了其制法。
Description
技术领域
本发明涉及阻燃剂,涉及可膨胀石墨阻燃剂,具体涉及一种微胶囊化可膨胀石墨复合聚氨酯硬质泡沫。
背景技术
聚氨酯硬质泡沫塑料是一种性能优良的绝热材料,具有低密度,高比强度,优异的耐磨减震性能和低导热系数等,已经应用在工业和生活中的各个领域。聚氨酯硬质泡沫的缺点是易燃和耐高温性能差,接触火源会立即产生火焰,引起火灾造成的损失触目惊心,给人类的生命和财产带来了巨大的威胁,对其应用也产生了极大的限制。随着国家对公共场所及建筑材料的阻燃性能要求越来越高,聚氨酯硬质泡沫在防火性能方面的挑战也越来越大。目前,用于提高聚氨酯硬质泡沫材料阻燃性能的方法主要是向材料中加入阻燃剂,环保型的添加型阻燃剂由于无卤、低毒、成本低、效率高等优势备受人们的青睐,添加型阻燃剂主要分为有机和无机两大类,无机阻燃剂最大优势为低毒、抑烟、低腐蚀、价格低廉,但是要达到较高的阻燃效果,需在高分子材料中的添加量较高,最终必将影响基材的加工性能和力学性能,材料的相容性也会大大降低。单一阻燃剂的阻燃效率低,添加量大,为了更好的改善高分子材料的阻燃性能,可将两种或两种以上的阻燃剂同时加入材料中,通过阻燃剂间的协同作用来提高材料的阻燃性能。
一般情况下,阻燃效果的好坏直接取决于燃烧生成的炭层结构、炭层的膨胀倍率等。可膨胀石墨是一种典型的环境友好型膨胀型阻燃剂,材料燃烧时受热可使石墨片层迅速膨胀,从而形成膨胀型多孔炭层,阻止聚合物与热源间的热传导和氧气的扩散,减少挥发性可燃组分和热量的生成。当可膨胀石墨与其他助剂共同作用时,如果协同助剂能促进炭层的膨胀,生成致密的膨胀型炭层,二者就能起到很好的协同作用,显著提高材料的阻燃性能。磷系阻燃剂对可膨胀石墨能起很好的协同阻燃作用,如聚磷酸铵、红磷、磷酸酯和其他含磷化合物等。磷系阻燃剂能同时在凝聚相和气相起阻燃作用,受热时会分解生成磷的含氧酸,能催化含羟基化合物脱水成炭,在材料表面生成致密炭层,降低材料的质量损失速率和可燃物的生成量,而且磷的含氧酸多为粘稠状的半固态物质,也可在材料表面形成一层覆盖于致密炭层的液膜,降低炭层的透气性和保护炭层不被继续氧化,提高材料的阻燃性能。有机磷系阻燃剂热解所形成的气态产物中含有PO自由基,它可以捕获H自由基及OH自由基,致使火焰中的H自由基及OH自由基浓度大大下降,从而在气相起到抑制燃烧链式反应的作用。
中国发明专利CN1724577A公开了一种可膨胀石墨填充高密度硬质聚氨酯泡沫塑料的制备方法及装置,该方法是将聚醚多远醇、三乙醇胺、有机锡、硅油、水和可膨胀石墨按照一定配比用机械搅拌装置搅拌混合均匀,然后与一定量的异氰酸酯充分混合,浇注到模具中进行熟化处理得到制品。发明专利CN1756794A公开了一种无卤素的两组分泡沫材料体系及其在用于防火目的防火建筑材料中的用途,该发明描述了一种用于制备无卤素膨胀的防火泡沫的两组分泡沫体系,其具有多元醇成分、多异氰酸酯成分和防火剂成分,所述多元醇成分包括至少一种聚醚多元醇、一种用于多元醇与多异氰酸酯反应的催化剂、作为发泡剂的水,多异氰酸酯成分包括至少一种多异氰酸酯和根据需要的其它的助剂或添加材料。作为防火剂,使用膨胀石墨和ABC灭火粉末的组合物。发明专利CN1343226A公开了一种通过有机多异氰酸酯与多元醇在发泡剂、开孔剂和片状脱落石墨存在下制备开孔硬质聚氨酯泡沫塑料的方法,其中泡沫塑料的热导率为28—35mw/mk,这些泡沫塑料可用于其中需要具有阻燃性和低热导率的泡沫塑料的建筑工业中。以上发明专利虽然在材料防火性能方面有一定的提高,但却导致泡沫的力学性能下降和导热系数的增加;而且单纯的可膨胀石墨的加入,不可避免的造成了聚氨酯硬泡泡孔结构的破坏,使得所制得的制品普遍存在导热系数增高等问题。
微胶囊包覆技术能很好的解决无机阻燃剂与基体材料相容性和分散性差等缺点,本发明利用微胶囊包覆技术,设计并合成出有机化的微胶囊壁材,实现对可膨胀石墨的双层包覆,提升其在基体中的相容性和燃烧时的膨胀倍率。微胶囊化的双层包覆保护了可膨胀石墨芯材在聚氨酯材料的正常使用时不影响其力学性能,同时在特定条件下又能将可膨胀石墨芯材释放出来发挥其膨胀阻燃的作用。而且到目前为止,利用阻燃性的有机树脂双层包覆可膨胀石墨并应用于聚氨酯硬泡的研究报道还未发现。
发明内容
为了改善聚氨酯硬质泡沫塑料的防火性能差、无机阻燃剂与聚氨酯基体材料相容性差等状况,本发明主要目的是提供了一种微胶囊化可膨胀石墨。本发明一方面利用化学结构分子设计的方法,制备出三聚氰胺基树脂和环氧树脂双层包覆的可膨胀石墨,三聚氰胺基团和环氧基团的存在增强了与材料基体的相容性和材料的耐热性能,另一方面,加入磷酸酯类阻燃剂起到协效阻燃作用,磷酸酯类阻燃剂本身作为酸源,燃烧过程中加速促进膨胀炭层的形成,提高了聚氨酯材料的阻燃性能。
为了实现以上发明目的,本发明采用的技术方案如下:
一种微胶囊化可膨胀石墨,它是一种三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨,即在可膨胀石墨外首先包裹三聚氰胺微胶囊,然后再包裹有环氧树脂微胶囊的三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨的微胶囊化可膨胀石墨。
一种上述的微胶囊化可膨胀石墨的制法,它包括如下步骤:
(1)制备三聚氰胺树脂预聚物:取三聚氰胺与甲醛溶液以混合搅拌,再加入三乙醇胺水溶液调节pH为7.0-8.0,缓慢升温至60-85℃反应2-5h,得到粘稠状透明水溶性的三聚氰胺树脂预聚物;其中甲醛溶液的质量分数为37%,三乙醇胺水溶液的质量分数为10%,三聚氰胺与甲醛溶液的质量比为1:2-5;
(2)三聚氰胺树脂预聚物包覆可膨胀石墨:将可膨胀石墨加入到无水乙醇中,超声搅拌0.5-1h,加入阳离子表面活性剂十六烷基三甲基氯化铵,搅拌1-2h,最后缓慢加入三聚氰胺树脂预聚物,用稀盐酸调节pH为3.5-5.5,缓慢升温至65-85℃,反应2-5h后过滤,真空干燥得到三聚氰胺树脂微胶囊化的可膨胀石墨;其中稀盐酸溶液的质量分数为10%,可膨胀石墨与无水乙醇的质量比为1:10-25,可膨胀石墨与十六烷基三甲基氯化铵的质量比1:0.05-0.2,可膨胀石墨与三聚氰胺树脂预聚物的质量比为1:5-8;
(3)三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨:将三聚氰胺树脂微胶囊化的可膨胀石墨加入到聚乙烯醇水溶液中,再缓慢加入乙酸乙酯和低粘度的环氧树脂E-51,搅拌0.5-1h,用稀硫酸溶液调节pH为2.5-4.5,同时加热到60-75℃,保持3-6h后,冷却至室温,过滤,用去离子水洗涤,真空干燥,得到三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨;其中聚乙烯醇水溶液的浓度为10%,三聚氰胺树脂微胶囊化的可膨胀石墨与聚乙烯醇水溶液的质量比为1:10-25,乙酸乙酯与低粘度的环氧树脂E-51的质量比为1:1.5-3,三聚氰胺树脂微胶囊化的可膨胀石墨与乙酸乙酯的质量比为1:5-10。
所得到三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨用傅里叶红外光谱仪Nicolet 6700表征可膨胀石墨微胶囊包裹后的表面活性官能团,证明三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨具有三聚氰胺和环氧树脂的特征峰;激光散射粒度仪S3500表征可膨胀石墨微胶囊包裹前后的体积平均粒径变化,三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨的体积平均粒径为68.7-77μm,粒径分布指数为0.87-0.92。
上述的微胶囊化可膨胀石墨在制备阻燃聚氨酯硬质泡沫中的应用。
一种使用上述的微胶囊化可膨胀石墨作为阻燃剂的微胶囊化可膨胀石墨复合聚氨酯硬质泡沫,它包含A、B两种组分,A组分由以下质量份数的原料组成:聚醚多元醇:25-55份,聚酯多元醇:5-20份,稳定剂:2-4份,催化剂:0.5-3份,交联剂:0.5-1.5份,发泡剂:25-40份,阻燃剂:2-10份,微胶囊化可膨胀石墨:5-15份;B组分的质量份数为:多亚甲基多苯基多异氰酸酯:100-180份。
上述的微胶囊化可膨胀石墨复合聚氨酯硬质泡沫,所述的A组分中的阻燃剂为磷酯系液体阻燃剂;催化剂为三乙烯二胺、N,N-二甲基环己胺、N,N-二甲基苄胺、乙二胺、环己胺、1,3,5-三(二甲氨基丙基)六氢三嗪、五甲基二乙烯三胺的一种或几种的组合;稳定剂为聚醚改性硅油、有机硅稳泡剂AK-8805、有机硅稳泡剂AK-8811、有机硅稳泡剂AK-8803、有机硅稳泡剂AK-8832的一种或几种的组合;交联剂为三羟甲基丙烷、三乙醇胺、二乙醇胺、甘油的一种或几种的组合;聚醚多元醇为聚四氢呋喃多元醇或聚氧化丙烯多元醇的一种或几种,它们的羟值为420-480mgKOH/g,粘度为2000-3500mPa.s(25℃);所述聚酯多元醇为脂肪族聚酯多元醇或芳香族聚酯多元醇的一种或几种,它们的羟值为400-440mgKOH/g,粘度为4000-6000mPa.s(25℃);发泡剂为一氟二氯乙烷或环戊烷的一种或两种的组合物。
上述的微胶囊化可膨胀石墨复合聚氨酯硬质泡沫,所述的磷酯系液体阻燃剂优选的为磷酸三甲酯、磷酸三乙酯、磷酸三丁酯、磷酸三苯酯、磷酸三甲苯酯、磷酸三异丙基苯酯、四苯基间苯二酚二磷酸酯、四苯基双酚A二磷酸酯、甲基磷酸二甲酯的一种或几种的组合。
一种制备上述的微胶囊化可膨胀石墨复合聚氨酯硬质泡沫的方法,它是按上述微胶囊化可膨胀石墨复合聚氨酯硬质泡沫的配方量将多元醇、催化剂、稳定剂、交联剂、阻燃剂混合,以1500r/min搅拌速度搅拌5min,加入微胶囊化可膨胀石墨和发泡剂,再次以1500r/min搅拌速度搅拌3min得到A组份;与B组分通过高压发泡机设备进行充分混合,充分混合后的A、B组份经发泡机枪头注入恒温密闭模具中,经发泡、熟化和脱模得到微胶囊化可膨胀石墨复合聚氨酯硬质泡沫。
本发明与现有技术相比,本发明的优点在于:
1、设计并合成出有机化的微胶囊壁材,实现对可膨胀石墨的双层包覆,提升其在基体中的相容性和燃烧时的膨胀倍率。
2、同时利用微胶囊化技术和协效阻燃原理,制备出一种微胶囊化可膨胀石墨复合聚氨酯硬质泡沫。
3、微胶囊化的双层包覆保护可膨胀石墨在聚氨酯材料的正常使用时不影响其力学性能,同时在遇火时将可膨胀石墨芯材释放出来发挥其膨胀阻燃的作用。
4、选择出特定的具有协效阻燃效应的复配阻燃剂,添加量少,阻燃效率高。所得复合聚氨酯硬质泡沫具有较高的力学性能和阻燃性能。
附图说明
图1为微胶囊化可膨胀石墨制备过程示意图。
具体实施方式
以下提供本发明的一些具体实施例,以助于进一步理解本发明,但本发明的保护范围并不仅限于这些实施例。
本发明中微胶囊化可膨胀石墨复合聚氨酯硬质泡沫的制备方法为:
按配方量将多元醇、催化剂、稳定剂、交联剂、阻燃剂混合,以1500r/min搅拌速度搅拌5min,加入微胶囊化可膨胀石墨和发泡剂,再次以1500r/min搅拌速度搅拌3min得到A组份;与B组分通过高压发泡机设备进行充分混合,充分混合后的A、B组份经发泡机枪头注入恒温密闭模具中,经发泡、熟化、脱模得到微胶囊化可膨胀石墨复合聚氨酯硬质泡沫。
实施例中所用原料的来源:
聚四氢呋喃多元醇(羟值:420-480mgKOH/g,粘度:2000-3500mPa.s)、聚氧化丙烯多元醇(羟值:420-480mgKOH/g,粘度:2000-3500mPa.s)和脂肪族聚酯多元醇(羟值:400-440mgKOH/g,粘度:4000-6000mPa.s)、芳香族聚酯多元醇(羟值:400-440mgKOH/g,粘度:4000-6000mPa.s)均由山东联创节能新材料股份有限公司提供;乙二胺、三乙烯二胺、N,N-二甲基苄胺和五甲基二乙烯三胺由深圳点石坊科技有限公司提供;环己胺、N,N-二甲基环己胺和1,3,5-三(二甲氨基丙基)六氢三嗪由鱼台县海纳环保科技有限公司提供;聚醚改性硅油、有机硅稳泡剂AK-8805、AK-8811、AK-8803和AK-8832由江苏美思德化学股份有限公司提供;磷酸三甲酯、磷酸三乙酯、磷酸三苯酯、磷酸三异丙基苯酯、四苯基间苯二酚二磷酸酯、四苯基双酚A二磷酸酯和甲基磷酸二甲酯由天津利海石化有限公司提供;
环氧树脂E-51由岳阳巴陵石化公司提供;
三聚氰胺由济南泰星精细化工有限公司提供;
可膨胀石墨由南京先丰纳米材料科技有限公司提供;
十六烷基三甲基氯化铵由南京南试化学试剂有限公司;
多亚甲基多苯基多异氰酸酯由郑州科豫隆化工产品有限公司提供;
三羟甲基丙烷、甘油、一氟二氯乙烷由山东济宁华凯树脂有限公司提供;
二乙醇胺、环戊烷、三乙醇胺、乙酸乙酯、聚乙烯醇由国药集团化学试剂有限公司提供。
傅里叶红外光谱仪Nicolet 6700表征可膨胀石墨微胶囊包裹后的表面活性官能团;激光散射粒度仪S3500表征可膨胀石墨微胶囊包裹前后的体积平均粒径变化。
实施例1
微胶囊化可膨胀石墨的制备:
(1)制备三聚氰胺树脂预聚物:取三聚氰胺与甲醛溶液以一定的质量比混合搅拌,再加入三乙醇胺水溶液调节pH为7.0,缓慢升温至60℃反应2h,得到粘稠状透明水溶性的三聚氰胺树脂预聚物;其中甲醛溶液的质量分数为37%,三乙醇胺水溶液的质量分数为10%,三聚氰胺与甲醛溶液的质量比为1:2;
(2)三聚氰胺树脂预聚物包覆可膨胀石墨:将可膨胀石墨加入到无水乙醇中,超声搅拌0.5h,加入阳离子表面活性剂十六烷基三甲基氯化铵,搅拌1h,最后缓慢加入三聚氰胺树脂预聚物,用稀盐酸调节pH为3.5,缓慢升温至65℃,反应2h后过滤,真空干燥得到三聚氰胺树脂微胶囊化的可膨胀石墨;其中稀盐酸溶液的质量分数为10%,可膨胀石墨与无水乙醇的质量比为1:10,可膨胀石墨与十六烷基三甲基氯化铵的质量比1:0.05,可膨胀石墨与三聚氰胺树脂预聚物的质量比为1:5;
(3)三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨:将三聚氰胺树脂微胶囊化的可膨胀石墨加入到聚乙烯醇水溶液中,再缓慢加入乙酸乙酯和低粘度的环氧树脂E-51,搅拌0.5h,用稀硫酸溶液调节pH为2.5,同时加热到60℃,保持3h后,冷却至室温,过滤,用去离子水洗涤,真空干燥,得到三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨;其中聚乙烯醇水溶液的浓度为10%,三聚氰胺树脂微胶囊化的可膨胀石墨与聚乙烯醇水溶液的质量比为1:10,乙酸乙酯与低粘度的环氧树脂E-51的质量比为1:1.5,三聚氰胺树脂微胶囊化的可膨胀石墨与乙酸乙酯的质量比为1:5。
所得三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨的傅里叶红外光谱(KBr):三聚氰胺树脂单层包覆可膨胀石墨(814cm-1:1022、1651cm-1:N-H;1565cm-1:C=N;3340cm-1:-OH);
三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨(905cm-1:1180、1133cm-1:C-O-C;1520cm-1:3210cm-1:-OH)。
微胶囊化可膨胀石墨复合聚氨酯硬质泡沫的配方如下:
聚四氢呋喃多元醇PTMG2000(羟值420mgKOH/g):25份
芳香族聚酯多元醇LCS-400A(羟值400mgKOH/g):5份
AK-8805:2份
三乙烯二胺:0.25份
N,N-二甲基环己胺:0.25份
三羟甲基丙烷:0.5份
一氟二氯乙烷:25份
四苯基间苯二酚二磷酸酯:2份
微胶囊化可膨胀石墨:5份
多亚甲基多苯基多异氰酸酯:100份
实施例2
微胶囊化可膨胀石墨的制备:
(1)制备三聚氰胺树脂预聚物:取三聚氰胺与甲醛溶液以一定的质量比混合搅拌,再加入三乙醇胺水溶液调节pH为8.0,缓慢升温至85℃反应5h,得到粘稠状透明水溶性的三聚氰胺树脂预聚物;其中甲醛溶液的质量分数为37%,三乙醇胺水溶液的质量分数为10%,三聚氰胺与甲醛溶液的质量比为1:5;
(2)三聚氰胺树脂预聚物包覆可膨胀石墨:将可膨胀石墨加入到无水乙醇中,超声搅拌1h,加入阳离子表面活性剂十六烷基三甲基氯化铵,搅拌2h,最后缓慢加入三聚氰胺树脂预聚物,用稀盐酸调节pH为5.5,缓慢升温至85℃,反应5h后过滤,真空干燥得到三聚氰胺树脂微胶囊化的可膨胀石墨;其中稀盐酸溶液的质量分数为10%,可膨胀石墨与无水乙醇的质量比为1:25,可膨胀石墨与十六烷基三甲基氯化铵的质量比1:0.2,可膨胀石墨与三聚氰胺树脂预聚物的质量比为1:8;
(3)三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨:将三聚氰胺树脂微胶囊化的可膨胀石墨加入到聚乙烯醇水溶液中,再缓慢加入乙酸乙酯和低粘度的环氧树脂E-51,搅拌1h,用稀硫酸溶液调节pH为4.5,同时加热到75℃,保持6h后,冷却至室温,过滤,用去离子水洗涤,真空干燥得到三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨;其中聚乙烯醇水溶液的浓度为10%,三聚氰胺树脂微胶囊化的可膨胀石墨与聚乙烯醇水溶液的质量比为1:25,乙酸乙酯与低粘度的环氧树脂E-51的质量比为1:3,三聚氰胺树脂微胶囊化的可膨胀石墨与乙酸乙酯的质量比为1:10。
所得三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨的傅里叶红外光谱(KBr):三聚氰胺树脂单层包覆可膨胀石墨(810cm-1:1020、1643cm-1:N-H;1561cm-1:C=N;3330cm-1:-OH);
三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨(902cm-1:1180、1143cm-1:C-O-C;1520cm-1:3210cm-1:-OH)。
微胶囊化可膨胀石墨复合聚氨酯硬质泡沫的配方如下:
聚氧化丙烯多元醇2000(羟值480mgKOH/g):55份
芳香族聚酯多元醇LCS-440A(羟值440mgKOH/g):20份
AK-8811:2份
AK-8803:2份
五甲基二乙烯三胺:1份
N,N-二甲基环己胺:1份
乙二胺:1份
二乙醇胺::1份
甘油:0.5份
环戊烷:40份
磷酸三甲酯:5份
磷酸三乙酯:3份
甲基磷酸二甲酯:2份
微胶囊化可膨胀石墨:15份
多亚甲基多苯基多异氰酸酯:180份
实施例3
微胶囊化可膨胀石墨的制备:
(1)制备三聚氰胺树脂预聚物:取三聚氰胺与甲醛溶液以一定的质量比混合搅拌,再加入三乙醇胺水溶液调节pH为7.5,缓慢升温至80℃反应4h,得到粘稠状透明水溶性的三聚氰胺树脂预聚物;其中甲醛溶液的质量分数为37%,三乙醇胺水溶液的质量分数为10%,三聚氰胺与甲醛溶液的质量比为1:3;
(2)三聚氰胺树脂预聚物包覆可膨胀石墨:将可膨胀石墨加入到无水乙醇中,超声搅拌40min,加入阳离子表面活性剂十六烷基三甲基氯化铵,搅拌1.5h,最后缓慢加入三聚氰胺树脂预聚物,用稀盐酸调节pH为4.0,缓慢升温至70℃,反应4h后过滤,真空干燥得到三聚氰胺树脂微胶囊化的可膨胀石墨;其中稀盐酸溶液的质量分数为10%,可膨胀石墨与无水乙醇的质量比为1:15,可膨胀石墨与十六烷基三甲基氯化铵的质量比1:0.1,可膨胀石墨与三聚氰胺树脂预聚物的质量比为1:6;
(3)三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨:将三聚氰胺树脂微胶囊化的可膨胀石墨加入到聚乙烯醇水溶液中,再缓慢加入乙酸乙酯和低粘度的环氧树脂E-51,搅拌40min,用稀硫酸溶液调节pH为3.0,同时加热到70℃,保持5h后,冷却至室温,过滤,用去离子水洗涤,真空干燥得到三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨;其中聚乙烯醇水溶液的浓度为10%,三聚氰胺树脂微胶囊化的可膨胀石墨与聚乙烯醇水溶液的质量比为1:20,乙酸乙酯与低粘度的环氧树脂E-51的质量比为1:2,三聚氰胺树脂微胶囊化的可膨胀石墨与乙酸乙酯的质量比为1:8。
所得三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨的傅里叶红外光谱(KBr):三聚氰胺树脂单层包覆可膨胀石墨(821cm-1:1025、1651cm-1:N-H;1559cm-1:C=N;3335cm-1:-OH);
三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨(905cm-1:1180、1139cm-1:C-O-C;1520cm-1:3210cm-1:-OH)。
微胶囊化可膨胀石墨复合聚氨酯硬质泡沫的配方如下:
聚四氢呋喃多元醇PTMG2000(羟值450mgKOH/g)::20份
聚氧化丙烯多元醇2000(羟值480mgKOH/g):10份
脂肪族聚酯多元醇LCS-420A(羟值420mgKOH/g):10份
AK-8832:1.5份
AK-8805:1.5份
N,N-二甲基苄胺:1份
1,3,5-三(二甲氨基丙基)六氢三嗪:1份
甘油:1份
一氟二氯乙烷:30份
磷酸三甲酯:4份
四苯基双酚A二磷酸酯:4份
微胶囊化可膨胀石墨:10份
多亚甲基多苯基多异氰酸酯:150份
实施例4
微胶囊化可膨胀石墨的制备:
(1)制备三聚氰胺树脂预聚物:取三聚氰胺与甲醛溶液以一定的质量比混合搅拌,再加入三乙醇胺水溶液调节pH为7.0,缓慢升温至85℃反应5h,得到粘稠状透明水溶性的三聚氰胺树脂预聚物;其中甲醛溶液的质量分数为37%,三乙醇胺水溶液的质量分数为10%,三聚氰胺与甲醛溶液的质量比为1:3;
(2)三聚氰胺树脂预聚物包覆可膨胀石墨:将可膨胀石墨加入到无水乙醇中,超声搅拌40min,加入阳离子表面活性剂十六烷基三甲基氯化铵,搅拌2h,最后缓慢加入三聚氰胺树脂预聚物,用稀盐酸调节pH为3.5,缓慢升温至65℃,反应5h后过滤,真空干燥得到三聚氰胺树脂微胶囊化的可膨胀石墨;其中稀盐酸溶液的质量分数为10%,可膨胀石墨与无水乙醇的质量比为1:15,可膨胀石墨与十六烷基三甲基氯化铵的质量比1:0.05,可膨胀石墨与三聚氰胺树脂预聚物的质量比为1:8;
(3)三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨:将三聚氰胺树脂微胶囊化的可膨胀石墨加入到聚乙烯醇水溶液中,再缓慢加入乙酸乙酯和低粘度的环氧树脂E-51,搅拌1h,用稀硫酸溶液调节pH为2.5,同时加热到75℃,保持5h后,冷却至室温,过滤,用去离子水洗涤,真空干燥得到三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨;其中聚乙烯醇水溶液的浓度为10%,三聚氰胺树脂微胶囊化的可膨胀石墨与聚乙烯醇水溶液的质量比为1:10,乙酸乙酯与低粘度的环氧树脂E-51的质量比为1:2,三聚氰胺树脂微胶囊化的可膨胀石墨与乙酸乙酯的质量比为1:10。
所得三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨的傅里叶红外光谱(KBr):三聚氰胺树脂单层包覆可膨胀石墨(825cm-1:1032、1661cm-1:N-H;1563cm-1:C=N;3340cm-1:-OH);
三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨(915cm-1:1180、1139cm-1:C-O-C;1520cm-1:3280cm-1:-OH)。
微胶囊化可膨胀石墨复合聚氨酯硬质泡沫的配方如下:
聚四氢呋喃多元醇PTMG3000(羟值480mgKOH/g):25份
芳香族聚酯多元醇LCS-400A(羟值400mgKOH/g):5份
脂肪族聚酯多元醇LCS-420A(羟值420mgKOH/g):15份
AK-8805:2份
N,N-二甲基环己胺:1份
二乙醇胺:1.5份
一氟二氯乙烷:25份
四苯基间苯二酚二磷酸酯:1份
甲基磷酸二甲酯:7份
微胶囊化可膨胀石墨:8份
多亚甲基多苯基多异氰酸酯:180份
实施例1-4所测可膨胀石墨微胶囊包裹前后的体积平均粒径变化的结果:见表1.
EG:可膨胀石墨
MF(EG):三聚氰胺树脂单层包覆可膨胀石墨
EP-MF(EG):三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨
表1
通过激光粒度仪(美国Microtrac公司S3500型)测量双层树脂微胶囊包裹可膨胀石墨的粒度,得到其平均粒径值和粒径分布指数,实施例1-4中制备出的微胶囊化可膨胀石墨,表现出将可膨胀石墨很好地包裹在有机树脂层内部,树脂的不同增加了可膨胀石墨粒径的厚度,且颗粒大小较均一。
上述实施例1-4中微胶囊化可膨胀石墨复合聚氨酯硬质泡沫的性能测试结果:见表2.
表2
项目 | 测试标准 | 实施例1 | 实施例2 | 实施例3 | 实施例4 |
密度/kg·m-3 | GB/T 6343-2009 | 62.8 | 60.1 | 59.6 | 63.0 |
导热系数/W·(m·k)-1 | GB/T 10294-2008 | 0.028 | 0.031 | 0.030 | 0.026 |
压缩强度/MPa | GB/T 8813-2008 | 0.54 | 0.62 | 0.60 | 0.59 |
极限氧指数/% | GB/T 2406.2-2009 | 29 | 29 | 28 | 30 |
Claims (7)
1.一种微胶囊化可膨胀石墨,其特征是:它是一种三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨,即在可膨胀石墨外首先包裹三聚氰胺微胶囊,然后再包裹有环氧树脂微胶囊的三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨的微胶囊化可膨胀石墨。
2.一种权利要求1所述的微胶囊化可膨胀石墨的制法,其特征是:它包括如下步骤:
(1)制备三聚氰胺树脂预聚物:取三聚氰胺与甲醛溶液以混合搅拌,再加入三乙醇胺水溶液调节pH为7.0-8.0,缓慢升温至60-85℃反应2-5h,得到粘稠状透明水溶性的三聚氰胺树脂预聚物;其中甲醛溶液的质量分数为37%,三乙醇胺水溶液的质量分数为10%,三聚氰胺与甲醛溶液的质量比为1:2-5;
(2)三聚氰胺树脂预聚物包覆可膨胀石墨:将可膨胀石墨加入到无水乙醇中,超声搅拌0.5-1h,加入阳离子表面活性剂十六烷基三甲基氯化铵,搅拌1-2h,最后缓慢加入三聚氰胺树脂预聚物,用稀盐酸调节pH为3.5-5.5,缓慢升温至65-85℃,反应2-5h后过滤,真空干燥得到三聚氰胺树脂微胶囊化的可膨胀石墨;其中稀盐酸溶液的质量分数为10%,可膨胀石墨与无水乙醇的质量比为1:10-25,可膨胀石墨与十六烷基三甲基氯化铵的质量比1:0.05-0.2,可膨胀石墨与三聚氰胺树脂预聚物的质量比为1:5-8;
(3)三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨:将三聚氰胺树脂微胶囊化的可膨胀石墨加入到聚乙烯醇水溶液中,再缓慢加入乙酸乙酯和低粘度的环氧树脂E-51,搅拌0.5-1h,用稀硫酸溶液调节pH为2.5-4.5,同时加热到60-75℃,保持3-6h后,冷却至室温,过滤,用去离子水洗涤,真空干燥得到三聚氰胺树脂—环氧树脂双层包覆可膨胀石墨;其中聚乙烯醇水溶液的浓度为10%,三聚氰胺树脂微胶囊化的可膨胀石墨与聚乙烯醇水溶液的质量比为1:10-25,乙酸乙酯与低粘度的环氧树脂E-51的质量比为1:1.5-3,三聚氰胺树脂微胶囊化的可膨胀石墨与乙酸乙酯的质量比为1:5-10。
3.权利要求1所述的微胶囊化可膨胀石墨在制备阻燃聚氨酯硬质泡沫中的应用。
4.一种使用权利要求1所述的微胶囊化可膨胀石墨作为阻燃剂的微胶囊化可膨胀石墨复合聚氨酯硬质泡沫,其特征是:它包含A、B两种组分,A组分由以下质量份数的原料组成:聚醚多元醇:25-55份,聚酯多元醇:5-20份,稳定剂:2-4份,催化剂:0.5-3份,交联剂:0.5-1.5份,发泡剂:25-40份,阻燃剂:2-10份,微胶囊化可膨胀石墨:5-15份;B组分的质量份数为:多亚甲基多苯基多异氰酸酯:100-180份。
5.根据权利要求4所述的微胶囊化可膨胀石墨复合聚氨酯硬质泡沫,其特征是:所述的A组分中的阻燃剂为磷酯系液体阻燃剂;催化剂为三乙烯二胺、N,N-二甲基环己胺、N,N-二甲基苄胺、乙二胺、环己胺、1,3,5-三(二甲氨基丙基)六氢三嗪、五甲基二乙烯三胺的一种或几种的组合;稳定剂为聚醚改性硅油、有机硅稳泡剂AK-8805、有机硅稳泡剂AK-8811、有机硅稳泡剂AK-8803、有机硅稳泡剂AK-8832的一种或几种的组合;交联剂为三羟甲基丙烷、三乙醇胺、二乙醇胺、甘油的一种或几种的组合;聚醚多元醇为聚四氢呋喃多元醇或聚氧化丙烯多元醇的一种或几种,它们的羟值为420-480mgKOH/g,粘度为2000-3500mPa.s(25℃);所述聚酯多元醇为脂肪族聚酯多元醇或芳香族聚酯多元醇的一种或几种,它们的羟值为400-440mgKOH/g,粘度为4000-6000mPa.s(25℃);发泡剂为一氟二氯乙烷或环戊烷的一种或两种的组合物。
6.根据权利要求5所述的微胶囊化可膨胀石墨复合聚氨酯硬质泡沫,其特征是:所述的磷酯系液体阻燃剂为磷酸三甲酯、磷酸三乙酯、磷酸三丁酯、磷酸三苯酯、磷酸三甲苯酯、磷酸三异丙基苯酯、四苯基间苯二酚二磷酸酯、四苯基双酚A二磷酸酯、甲基磷酸二甲酯的一种或几种的组合。
7.一种制备权利要求5所述的微胶囊化可膨胀石墨复合聚氨酯硬质泡沫的方法,其特征是:它是按权利要求5所述微胶囊化可膨胀石墨复合聚氨酯硬质泡沫的配方量将多元醇、催化剂、稳定剂、交联剂、阻燃剂混合,以1500r/min搅拌速度搅拌5min,加入微胶囊化可膨胀石墨和发泡剂,再次以1500r/min搅拌速度搅拌3min得到A组份;与B组分通过高压发泡机设备进行充分混合,充分混合后的A、B组份经发泡机枪头注入恒温密闭模具中,经发泡、熟化和脱模得到微胶囊化可膨胀石墨复合聚氨酯硬质泡沫。
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