CN105462162B - 一种a级防火增韧热固性甲阶酚醛树脂及其制备方法 - Google Patents
一种a级防火增韧热固性甲阶酚醛树脂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种A级防火增韧热固性甲阶酚醛树脂及其制备方法，其特征在于：原料包括苯酚、甲醛、氢氧化钠、氢氧化钡、复合交联剂、纳米复合阻燃剂和氨水；其制备方法是首先在碱性催化剂作用下，苯酚和甲醛加热发生缩聚反应，得到初级甲阶酚醛树脂；再加入复合交联剂和纳米复合阻燃剂，经交联反应和阻燃处理，提高了甲阶酚醛树脂的阻燃性和交联度，最后经中和、脱水后，制得产品。本发明所得产品的燃烧氧指数达到72％以上，发泡保温板的粉化率在16％以下，3～10毫米板材垂直燃烧性能达到欧洲UL‑94标准V0级，综合防火性能达到国家标准GB8624‑2012《建筑材料及制品燃烧性能》的A2级。
Description
技术领域
本发明涉及新型外墙外保温阻燃复合材料技术领域，特别是涉及一种酚醛树脂阻燃复合材料。
背景技术
目前，我国使用的建筑外墙外保温材料，没有任何一种材料能够达到公安部要求的A级防火标准，最高防火等级只能达到B1级。而根据我国公安部消防局对外墙外保温材料防火等级的要求规定：所有外墙外保温材料的防火等级必须达到A2或以上级别标准。近年来，很多建筑结构的外墙外保温材料以一种新型的酚醛树脂保温板来替代硬质聚氨酯保温板。这些保温板虽然通过了多方改性，但其防火等级仍然只能达到B1级，且粉化严重，这些问题亟待解决。
发明内容
为了解决上述现有技术的不足，本发明提供了满足公安部消防局A级防火标准的一种高阻燃型增韧热固性甲阶酚醛树脂。所要解决的问题是通过缩聚、交联和聚合反应及共混的方法，对甲阶酚醛树脂原料进行阻燃和交联改性，以提高热固性甲阶酚醛树脂原料的阻燃性和韧性；同时通过对可发热固性甲阶酚醛树脂原料的阻燃和交联改性，使发泡保温板的粉化性能得到明显改善，抗火性能达到了A2级标准。
本发明解决技术问题，采用如下技术方案：
本发明A级防火增韧热固性甲阶酚醛树脂，其特点在于：所述的A级防火增韧热固性甲阶酚醛树脂由以下摩尔份数的原料组成：苯酚100份，甲醛150份～200份，氢氧化钠1份～1.5份，氢氧化钡1份～3份，复合交联剂3份～10份，纳米复合阻燃剂15份～30份，氨水0.6～1.5份。
优选的，所述的复合交联剂是由三聚氰胺和乙二胺按摩尔比2:1混合构成。
所述的纳米复合阻燃剂中各原料按重量百分比的组成为：八溴联苯醚40％～50％、纳米氧化铝10％～15％、纳米氢氧化镁10％～15％、纳米膨胀石墨10％～20％，三聚氰胺氨基磺酸盐10％～15％。
所述A级防火增韧热固性甲阶酚醛树脂的制备方法是：将各原料依次经加热催化缩聚、交联、聚合及中和反应、冷却并脱水后，制得A级防火增韧热固性甲阶酚醛树脂。具体包括以下步骤：
(1)将苯酚加热熔融后加入甲醛并搅拌均匀，然后加入催化剂氢氧化钠并加热，经催化缩聚反应，生成热固性初级甲阶酚醛树脂；
(2)在所述热固性初级甲阶酚醛树脂中加入复合交联剂，再加入催化剂氢氧化钡，经交联反应，生成增韧热固性初级甲阶酚醛树脂；
(3)在所述增韧热固性初级甲阶酚醛树脂中加入纳米复合阻燃剂，在加热下经聚合和共混，生成增韧阻燃热固性初级甲阶酚醛树脂；
(4)用氨水对所述增韧阻燃热固性初级甲阶酚醛树脂进行中和，调节PH值至7.0～7.5，然后脱水至粘度为11000～16000厘泊，制得A级防火增韧热固性甲阶酚醛树脂。
与现有技术相比，本发明的有益效果体现在：
本发明以苯酚和甲醛为原料，通过添加纳米复合阻燃剂和交联剂，对生成的初级甲阶酚醛树脂进行改性，改性后的热固性甲阶酚醛树脂较以相同的工艺生产的酚醛树脂保温板材料的粉化性能得到明显改善，抗火性能达到了相关标准的A2级。
具体实施方式
下面结合实施例对本发明作进一步的详细描述。
实施例1：
本实施例A级防火增韧热固性甲阶酚醛树脂由以下摩尔份数的原料组成：苯酚100份，甲醛150份，氢氧化钠1份，氢氧化钡1份，复合交联剂3份，纳米复合阻燃剂15份，氨水0.6份。
其中：复合交联剂是由三聚氰胺和乙二胺按摩尔比2:1混合构成。纳米复合阻燃剂中各原料按重量百分比的组成为：八溴联苯醚40％、纳米氧化铝10％、纳米氢氧化镁15％、纳米膨胀石墨20％，三聚氰胺氨基磺酸盐15％。
本实施例A级防火增韧热固性甲阶酚醛树脂的制备方法，包括以下步骤：
(1)将苯酚加热至50℃熔融，加入甲醛并搅拌均匀，然后加入催化剂氢氧化钠并加热至70℃，催化缩聚反应1.5h左右，在反应过程中控制反应温度在95～98℃，固含量达到83％，获得热固性初级甲阶酚醛树脂；
(2)在热固性初级甲阶酚醛树脂中加入复合交联剂，再加入催化剂氢氧化钡，在85℃～90℃下交联反应1h，生成增韧热固性初级甲阶酚醛树脂；
(3)在增韧热固性初级甲阶酚醛树脂中加入纳米复合阻燃剂，在70℃下聚合和共混1h，生成增韧阻燃热固性初级甲阶酚醛树脂；
(4)降温至50℃时，用氨水对增韧阻燃热固性初级甲阶酚醛树脂进行中和，调节pH值至7.0～7.5，然后脱水至粘度为11000厘泊，即制得A级防火增韧热固性甲阶酚醛树脂。
经测试，以本实施例所得树脂生产的发泡保温板的粉化率为15.6％，燃烧氧指数达到72.3％，3～10毫米成品板材垂直燃烧性能达到UL-94标准V0级，综合防火性能达到国家标准GB8624-2012《建筑材料及制品燃烧性能》的A2级。
实施例2
本实施例A级防火增韧热固性甲阶酚醛树脂由以下摩尔份数的原料组成：苯酚100份，甲醛200份，氢氧化钠1.5份，氢氧化钡3份，复合交联剂10份，纳米复合阻燃剂30份，氨水1.5份。
其中复合交联剂是由三聚氰胺和乙二胺按摩尔比2:1混合构成。纳米复合阻燃剂中各原料按重量百分比的组成为：八溴联苯醚50％、纳米氧化铝15％、纳米氢氧化镁10％、纳米膨胀石墨10％，三聚氰胺氨基磺酸盐15％。
本实施例A级防火增韧热固性甲阶酚醛树脂的制备方法，包括以下步骤：
(1)将苯酚加热至50℃熔融，加入甲醛并搅拌均匀，然后加入催化剂氢氧化钠并加热至70℃，催化缩聚反应1.5h，在反应过程中控制反应温度在95～98℃，固含量达到85％，获得热固性初级甲阶酚醛树脂；
(2)在热固性初级甲阶酚醛树脂中加入复合交联剂，再加入催化剂氢氧化钡，在85℃～90℃下交联反应1.2h，生成增韧热固性初级甲阶酚醛树脂；
(3)在增韧热固性初级甲阶酚醛树脂中加入纳米复合阻燃剂，在70℃下聚合和共混1h，生成增韧阻燃热固性初级甲阶酚醛树脂；
(4)降温至50℃时，用氨水对增韧阻燃热固性初级甲阶酚醛树脂进行中和，调节pH值至7.0～7.5，然后脱水至粘度为16000厘泊，即制得A级防火增韧热固性甲阶酚醛树脂。
经测试，以本实施例所得树脂生产的发泡保温板的的粉化率为15.1％，燃烧氧指数达到73.6％，3～10毫米成品板材垂直燃烧性能达到UL-94标准V0级，综合防火性能达到国家标准GB8624-2012《建筑材料及制品燃烧性能》的A2级。
实施例3
本实施例A级防火增韧热固性甲阶酚醛树脂由以下摩尔份数的原料组成：苯酚100份，甲醛170份，氢氧化钠1份，氢氧化钡2份，复合交联剂6份，纳米复合阻燃剂21份，氨水1.1份。
其中：复合交联剂是由三聚氰胺和乙二胺按摩尔比2:1混合构成。纳米复合阻燃剂中各原料按重量百分比组成为：八溴联苯醚50％、纳米氧化铝15％、纳米氢氧化镁15％、纳米膨胀石墨10％，三聚氰胺氨基磺酸盐10％。
本实施例A级防火增韧热固性甲阶酚醛树脂的制备方法，包括以下步骤：
(1)将苯酚加热至50℃熔融，加入甲醛并搅拌均匀，然后加入催化剂氢氧化钠并加热至70℃，催化缩聚反应1.5h左右，在反应过程中控制反应温度在95～98℃，固含量达到85％，获得热固性初级甲阶酚醛树脂；
(2)在热固性初级甲阶酚醛树脂中加入复合交联剂，再加入催化剂氢氧化钡，在85℃～90℃下交联反应1.5h，生成增韧热固性初级甲阶酚醛树脂；
(3)在增韧热固性初级甲阶酚醛树脂中加入纳米复合阻燃剂，在70℃下聚合和共混1h，生成增韧阻燃热固性初级甲阶酚醛树脂；
(4)降温至50℃时，用氨水对增韧阻燃热固性初级甲阶酚醛树脂进行中和，调节pH值至7.0～7.5，然后脱水至粘度为13600厘泊，即制得A级防火增韧热固性甲阶酚醛树脂。
经测试，以本实施例所得树脂生产的发泡保温板的的粉化率为15.3％，垂直燃烧氧指数达到75.1％，3～10毫米成品板材垂直燃烧性能达到UL-94标准V0级，综合防火性能达到国家标准GB8624-2012《建筑材料及制品燃烧性能》的A2级。
Claims (3)
1.一种A级防火增韧热固性甲阶酚醛树脂，其特征在于：所述的A级防火增韧热固性甲阶酚醛树脂由以下摩尔份数的原料组成：苯酚100份，甲醛150份～200份，氢氧化钠1份～1.5份，氢氧化钡1份～3份，复合交联剂3份～10份，纳米复合阻燃剂15份～30份，氨水0.6～1.5份；
所述的复合交联剂是由三聚氰胺和乙二胺按摩尔比2:1混合构成；
所述的纳米复合阻燃剂中各原料按重量百分比的组成为：八溴联苯醚40％～50％、纳米氧化铝10％～15％、纳米氢氧化镁10％～15％、纳米膨胀石墨10％～20％，三聚氰胺氨基磺酸盐10％～15％。
2.一种权利要求1所述A级防火增韧热固性甲阶酚醛树脂的制备方法，其特征在于：将各原料依次经加热催化缩聚、交联、聚合及中和反应、冷却并脱水后，制得A级防火增韧热固性甲阶酚醛树脂。
3.根据权利要求2所述的A级防火增韧热固性甲阶酚醛树脂的制备方法，其特征在于包括以下步骤：
(1)将苯酚加热熔融后加入甲醛并搅拌均匀，然后加入催化剂氢氧化钠并加热，经催化缩聚反应，生成热固性初级甲阶酚醛树脂；
(2)在所述热固性初级甲阶酚醛树脂中加入复合交联剂，再加入催化剂氢氧化钡，经交联反应，生成增韧热固性初级甲阶酚醛树脂；
(3)在所述增韧热固性初级甲阶酚醛树脂中加入纳米复合阻燃剂，在加热下经聚合和共混，生成增韧阻燃热固性初级甲阶酚醛树脂；
(4)用氨水对所述增韧阻燃热固性初级甲阶酚醛树脂进行中和，调节pH值至7.0～7.5，然后脱水至粘度为11000～16000厘泊，制得A级防火增韧热固性甲阶酚醛树脂。
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