CN106867140B - 一种阻燃隔热的聚氯乙烯泡沫材料及其制备方法 - Google Patents
一种阻燃隔热的聚氯乙烯泡沫材料及其制备方法 Download PDFInfo
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Abstract
一种阻燃隔热的聚氯乙烯泡沫材料及其制备方法,属于泡沫材料技术领域。解决了现有技术中,泡沫材料添加的阻燃剂多为有机小分子物质,添加量较多,不利于降低泡沫材料的导热系数,导致泡沫材料的隔热性能和耐热性能较差的问题。本发明的聚氯乙烯泡沫材料包括100重量份的聚氯乙烯树脂、0~80重量份酸酐、0~20重量份环氧化合物、30~150重量份异氰酸酯、1~15重量份发泡剂、0~4重量份催化剂、0~3重量份表面活性剂、0.5~10重量份三氧化二锑、0.1~5重量份100~15000目的石墨粉。该泡沫材料阻燃性能好,导热系数低,具备优异的隔热性能和耐热性能。
Description
技术领域
本发明属于泡沫材料技术领域,具体涉及一种阻燃隔热的聚氯乙烯泡沫材料及其制备方法。
背景技术
聚氯乙烯(PVC)泡沫材料由于具有较宽的使用温度和良好的耐腐蚀性能,被广泛应用于建筑、建材、装饰、家具、广告、汽车等行业。现有技术中,硬质聚氯乙烯交联泡沫材料的组分主要包括聚氯乙烯树脂、发泡剂(如偶氮二异丁腈和偶氮二甲酰胺)、异氰酸酯(如甲苯二异氰酸酯、碳化二亚胺——脲酮亚胺改性4,4‘-二苯基甲烷二异氰酸酯)和酸酐(如马来酸酐、邻苯二甲酸酐)。其制备方法是:先将固体物料和液体物料混合得到糊状物料,然后将糊状物料倒入模具中,在压力下升高温度,使模具内部糊状物料温度达到150-200℃,此时PVC树脂发生凝胶,发泡剂分解,模压时间控制为50-60s/mm,降温后开模,得到含有许多微小气泡的预发泡体,最后将预发泡体置于热水或者蒸汽中,加热完成二次膨胀,同时扩散进预发泡体内的水分会和异氰酸酯与酸酐发生一系列反应,产生二氧化碳气体并在泡沫体中形成交联结构,固化得到硬质泡沫。
当聚氯乙烯泡沫材料应用到阻燃领域时,需要进行阻燃改性,现有技术中,阻燃改性聚氯乙烯泡沫材料的方法主要是在聚氯乙烯泡沫材料中添加阻燃剂,如中国专利一种改性硬质交联聚氯乙烯阻燃泡沫及其制备方法(公开号104031326A),采用添加磷酸酯或含溴阻燃剂的方案将聚氯乙烯泡沫材料阻燃提高到B1级。
但是,现有技术中,聚氯乙烯泡沫材料添加的阻燃剂多为有机小分子物质,添加量较多,不利于降低泡沫材料的导热系数,导致泡沫材料的隔热性能和耐热性能较差的问题。
发明内容
本发明为解决上述技术问题,提供一种阻燃隔热的聚氯乙烯泡沫材料及其制备方法。
本发明的阻燃隔热的聚氯乙烯泡沫材料,包括:
优选的,所述酸酐为邻苯二甲酸酐、马来酸酐、琥珀酸酐、四氢苯酐、六氢苯酐、甲基四氢苯酐、甲基六氢苯酐、偏苯三甲酸酐、均苯四酐、环己烷-1,2羧酸酐、甲基内亚甲基四氢邻苯二甲酸酐中的一种或多种。
优选的,所述环氧化合物为双酚A缩水甘油醚、三羟甲基丙烷缩水甘油醚、丙三醇缩水甘油醚、乙二醇缩水甘油醚、环氧大豆油中的一种或多种。
优选的,所述异氰酸酯为甲苯二异氰酸酯(TDI)、碳化二亚胺-脲酮亚胺改性4,4‘-二苯基甲烷二异氰酸酯(液化MDI)和多亚甲基多苯基多异氰酸酯(PAPI)中的一种或多种。
优选的,所述发泡剂为偶氮二异丁腈(AIBN)、偶氮二甲酰胺(AC)、N,N-二亚硝基五亚甲基四胺(发泡剂H)中的一种或多种。
优选的,所述催化剂为N’,N”,N”’-三(二甲基氨基丙基)对称六氢三嗪、N-(α-羟乙基)亚乙基亚胺、吲哚、辛酸钠、异辛酸钾、油酸钾、硬脂酸钾中的一种或多种。
优选的,所述表面活性剂为吐温80、聚硅氧烷接枝聚醚化合物(DC-193)中的一种或两种。
优选的,所述石墨粉为400-2000目,更优选的为800-1500目。
优选的,还包括10-20重量份的填料,更优选,所述填料为碳酸钙和/或滑石粉。
优选的,所述聚氯乙烯树脂为悬浮树脂和/或糊树脂。
上述阻燃隔热的聚氯乙烯泡沫材料的制备方法,步骤如下:
步骤一、按组成及重量份称取各组分,混合均匀后,加入模具中,先在50~110℃预热5~30min,然后升压至11MPa~30MPa,升温至150℃~200℃,模压时间30-50s/mm,最后冷却至20℃~110℃后开模,得到发泡模压物;
步骤二、在水或水蒸气中,将得到的发泡模压物进行二次发泡和固化,得到阻燃隔热的聚氯乙烯泡沫材料。
优选的,步骤一中,升压至15MPa~25MPa,升温至180℃~200℃。
优选的,步骤一中,冷却至40℃~90℃。
优选的,步骤二中,二次发泡的温度为80℃~100℃,固化温度为40℃~70℃;更优选的,步骤二中,二次发泡的温度为85℃~95℃,固化温度为50℃~60℃。
与现有技术相比,本发明的有益效果:
本发明的阻燃隔热的聚氯乙烯泡沫材料采用三氧化二锑无机粉体作为阻燃剂,不仅其与体系中自身含有的氯协同阻燃,具有添加量少,不影响材料的耐热性的优点,而且可以起到成核剂作用,减小泡孔直径;
本发明的阻燃隔热的聚氯乙烯泡沫材料添加石墨粉,降低聚氯乙烯泡沫材料的导热系数,使泡沫材料具备优异的隔热性能和耐热性能,在做保温材料应用时可以减少材料的厚度,降低成本;
本发明的阻燃隔热的聚氯乙烯泡沫材料工艺简单、易操作。
具体实施方式
以下结合实施例进一步说明本发明,实施例中所用原料均可商购获得。
对比例
聚氯乙烯泡沫材料,由100重量份的聚氯乙烯树脂、80重量份的邻苯二甲酸酐、20重量份的双酚A缩水甘油醚、30重量份的TDI、15重量份的AIBN、4重量份的N’,N”,N”’-三(二甲基氨基丙基)对称六氢三嗪、3重量份的吐温80组成。
上述阻燃隔热的聚氯乙烯泡沫材料的制备:将上述各组分按重量份混合均匀后,加入模具中,先在50℃预热30min,然后升压至30MPa,升温至150℃,模压时间50s/mm,最后冷却至40℃后开模,得到发泡模压物;然后在水中,将得到的发泡模压物进行二次发泡和固化,二次发泡的温度为80℃,固化温度为40℃,得到聚氯乙烯泡沫材料。
实施例1
阻燃隔热的聚氯乙烯泡沫材料,由100重量份的聚氯乙烯树脂、80重量份的邻苯二甲酸酐、20重量份的双酚A缩水甘油醚、30重量份的TDI、15重量份的AIBN、4重量份的N’,N”,N”’-三(二甲基氨基丙基)对称六氢三嗪、3重量份的吐温80、10重量份的三氧化二锑和5重量份的石墨粉(100目)组成。
上述阻燃隔热的聚氯乙烯泡沫材料的制备:将上述各组分按重量份混合均匀后,加入模具中,先在50℃预热30min,然后升压至30MPa,升温至150℃,模压时间50s/mm,最后冷却至40℃后开模,得到发泡模压物;然后在水中,将得到的发泡模压物进行二次发泡和固化,二次发泡的温度为80℃,固化温度为40℃,得到阻燃隔热的聚氯乙烯泡沫材料。
实施例2
阻燃隔热的聚氯乙烯泡沫材料,由100重量份的聚氯乙烯树脂、150重量份的液化MDI、1重量份的AC、2重量份的吲哚、2重量份的DC-193、5重量份的三氧化二锑和2重量份的石墨粉(15000目)组成。
上述阻燃隔热的聚氯乙烯泡沫材料的制备:将上述各组分按重量份混合均匀后,加入模具中,先在110℃预热5min,然后升压至11MPa,升温至200℃,模压时间30s/mm,最后冷却至90℃后开模,得到发泡模压物;然后在水蒸气中,将得到的发泡模压物进行二次发泡和固化,二次发泡的温度为100℃,固化温度为70℃,得到阻燃隔热的聚氯乙烯泡沫材料。
实施例3
阻燃隔热的聚氯乙烯泡沫材料,由100重量份的聚氯乙烯树脂、50重量份的琥珀酸酐、10重量份的四氢苯酐、10重量份的丙三醇缩水甘油醚、60重量份的PAPI、10重量份的发泡剂H、3重量份的吐温80、5重量份的三氧化二锑和0.1重量份的石墨粉(400目)组成。
上述阻燃隔热的聚氯乙烯泡沫材料的制备:将上述各组分按重量份混合均匀后,加入模具中,先在90℃预热20min,然后升压至15MPa,升温至180℃,模压时间40s/mm,最后冷却至110℃后开模,得到发泡模压物;然后在水中,将得到的发泡模压物进行二次发泡和固化,二次发泡的温度为100℃,固化温度为70℃,得到阻燃隔热的聚氯乙烯泡沫材料。
实施例4
阻燃隔热的聚氯乙烯泡沫材料,由100重量份的聚氯乙烯树脂、20重量份的四氢苯酐、5重量份的环氧化合物环氧大豆油、100重量份的TDI、5重量份的发泡剂H、3重量份的硬脂酸钾、1重量份的表面活性剂DC-193、6重量份的三氧化二锑和0.5重量份的石墨粉(1500目)组成。
上述阻燃隔热的聚氯乙烯泡沫材料的制备:将上述各组分按重量份混合均匀后,加入模具中,先在90℃预热20min,然后升压至25MPa,升温至200℃,模压时间50s/mm,最后冷却至80℃后开模,得到发泡模压物;然后在水中,将得到的发泡模压物进行二次发泡和固化,二次发泡的温度为100℃,固化温度为40℃,得到阻燃隔热的聚氯乙烯泡沫材料。
实施例5
阻燃隔热的聚氯乙烯泡沫材料,由100重量份的聚氯乙烯树脂、40重量份的甲基六氢苯酐、10重量份的乙二醇缩水甘油醚、15重量份环氧大豆油、120重量份液化MDI、8重量份AC、0.5重量份的三氧化二锑、3重量份的石墨粉(800目)和10重量份的碳酸钙组成。
上述阻燃隔热的聚氯乙烯泡沫材料的制备:将上述各组分按重量份混合均匀后,加入模具中,先在60℃预热20min,然后升压至30MPa,升温至180℃,模压时间35s/mm,最后冷却至80℃后开模,得到发泡模压物;然后在水蒸气中,将得到的发泡模压物进行二次发泡和固化,二次发泡的温度为85℃,固化温度为60℃,得到阻燃隔热的聚氯乙烯泡沫材料。
对实施例1~5的阻燃隔热的聚氯乙烯泡沫材料的泡孔直径、阻燃性能和隔热性能进行检测,检测结果如表1所示。
表1实施例1~5的聚氯乙烯泡沫材料的泡孔直径、阻燃性能和隔热性能
导热系数(W/m·K) | 氧指数 | 泡孔直径(微米) | |
对比例 | 0.045 | 26 | 1000 |
实施例1 | 0.033 | 34 | 300 |
实施例2 | 0.035 | 35 | 200 |
实施例3 | 0.028 | 34 | 300 |
实施例4 | 0.036 | 36 | 250 |
实施例5 | 0.030 | 34 | 200 |
检测方法 | GB/T10801.1-2002 | GB/T2406-2009 | 扫描电镜 |
Claims (10)
1.阻燃隔热的聚氯乙烯泡沫材料,其特征在于,包括:
2.根据权利要求1所述的阻燃隔热的聚氯乙烯泡沫材料,其特征在于,所述酸酐为邻苯二甲酸酐、马来酸酐、琥珀酸酐、四氢苯酐、六氢苯酐、甲基四氢苯酐、甲基六氢苯酐、偏苯三甲酸酐、均苯四酐、环己烷-1,2羧酸酐、甲基内亚甲基四氢邻苯二甲酸酐中的一种或多种。
3.根据权利要求1所述的阻燃隔热的聚氯乙烯泡沫材料,其特征在于,所述环氧化合物为双酚A缩水甘油醚、三羟甲基丙烷缩水甘油醚、丙三醇缩水甘油醚、乙二醇缩水甘油醚、环氧大豆油中的一种或多种。
4.根据权利要求1所述的阻燃隔热的聚氯乙烯泡沫材料,其特征在于,所述异氰酸酯为甲苯二异氰酸酯、碳化二亚胺-脲酮亚胺改性4,4‘-二苯基甲烷二异氰酸酯和多亚甲基多苯基多异氰酸酯中的一种或多种。
5.根据权利要求1所述的阻燃隔热的聚氯乙烯泡沫材料,其特征在于,所述发泡剂为偶氮二异丁腈、偶氮二甲酰胺、N,N-二亚硝基五亚甲基四胺中的一种或多种。
6.根据权利要求1所述的阻燃隔热的聚氯乙烯泡沫材料,其特征在于,所述催化剂为N’,N”,N”’-三(二甲基氨基丙基)对称六氢三嗪、N-(α-羟乙基)亚乙基亚胺、吲哚、辛酸钠、异辛酸钾、油酸钾、硬脂酸钾中的一种或多种。
7.根据权利要求1所述的阻燃隔热的聚氯乙烯泡沫材料,其特征在于,所述表面活性剂为吐温80、聚硅氧烷接枝聚醚化合物中的一种或两种。
8.根据权利要求1所述的阻燃隔热的聚氯乙烯泡沫材料,其特征在于,还包括10-20重量份的填料,所述填料为碳酸钙和/ 或 滑石粉。
9.权利要求1-8任何一项所述的阻燃隔热的聚氯乙烯泡沫材料的制备方法,其特征在于,步骤如下:
步骤一、按组成及重量份称取各组分,混合均匀后,加入模具中,先在50~110℃预热5~30min,然后升压至11MPa~30MPa,升温至150℃~200℃,模压时间30-50s/mm,最后冷却至20℃~110℃后开模,得到发泡模压物;
步骤二、在水或水蒸气中,将得到的发泡模压物进行二次发泡和固化,得到阻燃隔热的聚氯乙烯泡沫材料。
10.根据权利要求9所述的阻燃隔热的聚氯乙烯泡沫材料的制备方法,其特征在于,所述步骤二中,二次发泡的温度为80℃~100℃,固化温度为40℃~70℃。
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