CN113651947A - 一种本征导热环氧树脂固化物及其制备方法 - Google Patents
一种本征导热环氧树脂固化物及其制备方法 Download PDFInfo
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Abstract
本发明属于热固性高分子材料领域,公开了一种本征导热环氧树脂固化物及其制备方法,该环氧树脂固化物由环氧预聚物、固化剂和催化剂固化而成,其中至少一种环氧预聚物和至少一种固化剂中均含有芳香酰胺结构;所述具有芳香酰胺结构的环氧预聚物为如结构式(1)或(2)或其混合结构;本发明同时通过环氧预聚物和固化剂向固化物中引入芳香酰胺结构,利用分子链间酰胺键产生的氢键强相互作用向环氧树脂固化网络中引入局域微观有序结构增大声子传播自由程,提高树脂本征导热性能。本发明环氧树脂固化物同时具有优良的机械、耐热性能,且制备工艺简单、结构可调,具有广阔的应用前景。
Description
技术领域
本发明涉及热固性高分子材料领域,具体是一种本征导热环氧树脂固化物及其制备方法。
背景技术
热固性树脂及其复合材料已经在航空航天、交通运输、电子封装等高新科技领域中得到了广泛应用。随着技术不断发展,科技产品轻量化、小型化的需求日益增长,高分子原件替代金属元件已成趋势,从而需要更有效的解决散热、易燃、热稳定性等问题,特别是普通热固性树脂的热导率普遍较低,严重制约其在众多领域的发展。通过填充高热导率粒子制备导热聚合物,已获得工业化应用,具有成本低、加工简便、适合工业化生产等优点,但因粒子填充量较高导致其机械性能严重劣化,且热导率提高有限。研究和理论计算表明,通过改善基体树脂来提高复合材料热导率远比提高导热粒子热导率更为有效。现有的热固性树脂尚难以同时满足热导率高、耐热温度高、易于加工等要求。
发明内容
本发明的目的是提出一种高热导率的热固性高分子材料,同时通过环氧预聚物和固化剂向固化物中引入芳香酰胺结构,利用分子链间酰胺键产生的氢键强相互作用向环氧树脂固化网络中引入局域微观有序结构增大声子传播自由程,制得的树脂具有更高的热导率,同时保持高耐热温度、良好的机械强度等性能。
本发明的另一目的是提出一种含有芳香酰胺结构本征导热环氧树脂的制备方法。
本发明的目的通过以下技术方案实现:
一种本征导热环氧树脂固化物,由环氧预聚物、固化剂和催化剂固化而成,其中至少一种环氧预聚物和至少一种固化剂中均含有芳香酰胺结构;
与含芳香酰胺结构环氧预聚物搭配使用的其他类型环氧预聚物结构不限,可以举例如下:邻苯二甲酸二缩水甘油酯、间苯二甲酸二缩水甘油酯、对苯二甲酸二缩水甘油酯、四氢邻苯二甲酸二缩水甘油酯、六氢邻苯二甲酸二缩水甘油酯、1,2-环氧环己烷-4,5-二甲酸二缩水甘油酯、内次甲基四氢邻苯二甲酸二缩水甘油酯、均苯三酸三缩水甘油酯、4,4’-二氨基二苯甲烷缩水甘油醚、二甲基海因缩水甘油醚、双酚A缩水甘油醚、多酚型缩水甘油醚等。
所述具有芳香酰胺结构的环氧预聚物为如下结构式(1)或(2)或其混合结构:
所述R1、R2可以为如下结构的任意一种:
优选地,所述具有芳香酰胺结构的固化剂为如下结构中的任意一种或多种:
与含芳香酰胺结构的固化剂搭配使用的其他类型固化剂结构不限,可以举例如下:对氨基苯甲酸对氨基苯酯、对苯二甲酸二对氨基苯酯、双(对氨基苯甲酸)-1,5-萘二酯、双(4-氨基苯基)-5-(4-氨基苯甲酰)间苯二甲酸酯、对苯二胺、间苯二胺、4,4'-二氨基二苯基醚、3,4'-二氨基二苯基醚、4,4'-二氨基二苯甲酮、4,4'-二氨基二苯基砜、3,4'-二氨基二苯基砜、4,4'-二氨基二苯甲烷、4,4'-(9-亚茀基)二苯胺、联苯胺、2,2-双[4-(4-氨基苯氧基)苯基]丙烷、2,2-双[4-(4-氨基苯氧基苯)]六氟丙烷、双[4-(4-氨基苯氧基)苯基]砜、4,4'-双(4-氨基苯氧基)联、1,4-双(4-氨基苯氧基)苯、1,3-双(4-氨基苯氧基)苯、双氰胺、脂肪胺、脂环胺、三氟化硼-胺络合物等。
优选地,所述催化剂为2,4,6-三(二甲氨基甲基)苯酚、2,4,6-三(二甲氨基甲基)苯酚三(2-乙基己酸)盐、2,4,6-三(二甲氨基甲基)苯酚三油酸盐、三乙胺、三乙醇胺、苄基二甲胺、邻羟基苄基二甲胺、乙酰丙酮盐、三苯基膦及其鏻盐、N-(2-羟基苯基)-N’,N’-二甲基脲、N-(2-羟基-4-硝基苯)-N’,N’-二甲基脲、N-(2-羟基-5-硝基苯)-N’,N’-二甲基脲、N-(4-氯-2-羟基苯)-N’,N’-二甲基脲、N-(5-氯-2-羟基苯)-N’,N’-二甲基脲、N-(3,5-二甲基-2-羟基苯)-N’,N’-二甲基脲、N-(4-氯基)-N’,N’-二甲基脲、咪唑、2-甲基咪唑、2-乙基-4-甲基咪唑、1-苄基-2-乙基咪唑、1-氨基乙基-2-甲基咪唑、咪唑啉、过氧化苯甲酰中的一种或两种以上。
优选地,所述环氧预聚物与固化剂的比例为反应基团的化学计量比,催化剂用量为总质量的0.1~5wt%。
所述环氧树脂固化物的制备方法,包括如下步骤:
(1)将各种组分加热熔融混合均匀后倒入模具中脱气,或将各种组分全部或部分溶解于溶剂中混合均匀、倒入模具脱气后烘干溶剂,或将各组分研磨成粉末状通过喷枪喷涂;
(2)在60℃~150℃预固化5min~12h,进一步在150℃~250℃后固化10min~6h,得到环氧树脂固化物。
优选地,所述预固化的条件为:100~150℃预固化0.5~2h;所述后固化的条件为:160~210℃后固化0.5~2h。
优选地,所述预固化的条件为:120~130℃预固化1~2h;所述后固化的条件为:180~200℃后固化1~2h。
优选地,所述溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甲基亚砜、四氢呋喃、苯、甲苯、二甲苯、乙醇、丁醇、异丁醇、环己酮、甲基环己酮、丙酮、丁酮、醋酸乙酯、醋酸丁酯、溶纤剂。
与现有技术相比,本发明具有如下优点和有益效果:
(1)本发明同时通过环氧预聚物和固化剂向固化物中引入芳香酰胺结构所制备的本征导热环氧树脂固化物具有优良导热、机械和耐热性能:环氧树脂固化物热导率可达到0.36~0.51W/(m·K);拉伸强度、模量、断裂伸长率分别可达86.5~97.8MPa、3.6~4.5GPa、4.3%~6.7%;弯曲强度可达147.5~163.7MPa;玻璃化转变温度为205~226℃,5%分解温度325~359℃。可作为先进复合材料热固性树脂基体使用。
(2)本发明制备的本征导热环氧树脂固化物结构任意可调,制备方法简单,易于规模化生产。
附图说明
图1为本发明实施例1制得的本征导热环氧树脂红外光谱图。
具体实施方式
下面结合具体实施例对本发明的作进一步说明,但本发明的内容不限于下述的实施例。
实施例1
将45.1g 4,4-二氨基苯酰替苯胺缩水甘油醚22.7g 4,4-二氨基苯酰替苯胺和0.2g 2-乙基-4-甲基咪唑溶于100mL N,N-二甲基甲酰胺中,倒入模具脱气后烘干溶剂。在120℃预固化1h,180℃后固化1h,固化结束后自然冷却至室温,得目标产物。图1为本征导热环氧树脂红外光谱图。根据ISO 22007标准进行测试热导率为0.43W/(m·K)。根据ASTM D638-14标准测定拉伸性能,拉伸强度、模量和断裂伸长率分别为95.3MPa、4.1GPa、5.1%;根据ASTM D790-10标准测定弯曲性能,弯曲强度为151.6MPa;树脂玻璃化转变温度为205℃,起始分解温度为325℃。
对照例1
将50g双酚A缩水甘油醚NPEL-128在80℃预热后添加12.5g 4,4'-二氨基二苯甲烷和0.1g 2-乙基-4-甲基咪唑,搅拌约15min成均相溶液,脱气,然后浇铸于100℃预热的模具中。固化程序为:100℃、1h,150℃、2h,固化结束后自然冷却至室温的目标产物。热导率为0.19W/(m·K),拉伸强度、模量和断裂伸长率分别为85.7MPa、2.9GPa、6.5%,弯曲强度为114.2MPa,树脂玻璃化转变温度为211℃,起始分解温度为374℃。
实施例2
将22.6g 3,3-二氨基苯酰替苯胺缩水甘油醚22.6g 3,4-二氨基苯酰替苯胺缩水甘油醚11.4g 4,4-二氨基苯酰替苯胺17.3g N,N'-双(4-氨基苯基)对苯二甲酰胺和0.3g 2,4,6-三(二甲氨基甲基)苯酚溶于150mL N-甲基吡咯烷酮中,倒入模具脱气后烘干溶剂。在120℃预固化1h,200℃后固化1h,固化结束后自然冷却至室温,得目标产物。热导率为0.51W/(m·K),拉伸强度、模量和断裂伸长率分别为90.5MPa、4.5GPa、4.3%,弯曲强度为163.7MPa,树脂玻璃化转变温度为223℃,起始分解温度为356℃。
对照例2
将22.6g 3,3-二氨基苯酰替苯胺缩水甘油醚22.6g 3,4-二氨基苯酰替苯胺缩水甘油醚19.8g 4,4'-二氨基二苯甲烷和0.3g 2,4,6-三(二甲氨基甲基)苯酚溶于150mL N-甲基吡咯烷酮中,倒入模具脱气后烘干溶剂。在120℃预固化1h,200℃后固化1h,固化结束后自然冷却至室温,得目标产物。热导率为0.22W/(m·K),拉伸强度、模量和断裂伸长率分别为84.7MPa、4.3GPa、4.6%,弯曲强度为160.3MPa,树脂玻璃化转变温度为207℃,起始分解温度为364℃。
实施例3
将17.1g 4-羟基-N-(4-羟苯基)苯甲酰胺缩水甘油醚和16.3g 1,2-环氧环己烷-4,5-二甲酸二缩水甘油酯加热至80℃,加入11.4g 4,4-二氨基苯酰替苯胺4.2g双氰胺和0.2g N-(2-羟基苯基)-N’,N’-二甲基脲快速混合均匀后,倒入模具脱气。在130℃预固化1h,180℃后固化1h,固化结束后自然冷却至室温,得目标产物。热导率为0.40W/(m·K),拉伸强度、模量和断裂伸长率分别为97.8MPa、3.8GPa、6.7%,弯曲强度为153.4MPa,树脂玻璃化转变温度为214℃,起始分解温度为344℃。
对照例3
将32.6g 1,2-环氧环己烷-4,5-二甲酸二缩水甘油酯加热至80℃,加入11.4g 4,4-二氨基苯酰替苯胺4.2g双氰胺和0.2g N-(2-羟基苯基)-N’,N’-二甲基脲快速混合均匀后,倒入模具脱气。在130℃预固化1h,180℃后固化1h,固化结束后自然冷却至室温,得目标产物。热导率为0.20W/(m·K),拉伸强度、模量和断裂伸长率分别为98.6MPa、4.1GPa、6.2%,弯曲强度为158.9MPa,树脂玻璃化转变温度为223℃,起始分解温度为351℃。
实施例4
将57.0g N,N'-双(4-氨基苯基)对苯二甲酰胺缩水甘油醚17.3g N,N'-双(4-氨基苯基)对苯二甲酰胺2.7g对苯二胺5.7g对氨基苯甲酸对氨基苯酯和0.1g苄基二甲胺溶于150mL N,N-二甲基甲酰胺中,倒入模具脱气后烘干溶剂。在120℃预固化1h,180℃后固化1h,固化结束后自然冷却至室温,得目标产物。热导率为0.39W/(m·K),拉伸强度、模量和断裂伸长率分别为86.5MPa、4.3GPa、4.9%,弯曲强度为161.3MPa,树脂玻璃化转变温度为207℃,起始分解温度为355℃。
对照例4
将57.0g N,N'-双(4-氨基苯基)对苯二甲酰胺缩水甘油醚8.1g对苯二胺5.7g对氨基苯甲酸对氨基苯酯和0.1g苄基二甲胺溶于150mL N,N-二甲基甲酰胺中,倒入模具脱气后烘干溶剂。在120℃预固化1h,180℃后固化1h,固化结束后自然冷却至室温,得目标产物。热导率为0.23W/(m·K),拉伸强度、模量和断裂伸长率分别为78.4MPa、4.7GPa、3.6%,弯曲强度为168.5MPa,树脂玻璃化转变温度为224℃,起始分解温度为363℃。
实施例5
将22.6g 4,4-二氨基苯酰替苯胺缩水甘油醚和34g双酚A缩水甘油醚NPEL-128加热至100℃,加入11.4g4,4-二氨基苯酰替苯胺8.5g 4,4'-二氨基二苯甲烷和0.1g 2-乙基-4-甲基咪唑快速混合均匀后,倒入模具脱气。在120℃预固化1h,180℃后固化1h,固化结束后自然冷却至室温,得目标产物。热导率为0.36W/(m·K),拉伸强度、模量和断裂伸长率分别为88.5MPa、3.6GPa、6.1%,弯曲强度为147.5MPa,树脂玻璃化转变温度为226℃,起始分解温度为359℃。
对照例5
将73.5g双酚A缩水甘油醚NPEL-128加热至100℃,加入11.4g 4,4-二氨基苯酰替苯胺8.5g 4,4'-二氨基二苯甲烷和0.1g 2-乙基-4-甲基咪唑快速混合均匀后,倒入模具脱气。在120℃预固化1h,180℃后固化1h,固化结束后自然冷却至室温,得目标产物。热导率为0.20W/(m·K),拉伸强度、模量和断裂伸长率分别为86.2MPa、3.0GPa、6.3%,弯曲强度为125.3MPa,树脂玻璃化转变温度为209℃,起始分解温度为366℃。
对照例6
将22.5g 4,4-二氨基苯酰替苯胺缩水甘油醚在100℃预热后添加12.4g 4,4'-二氨基二苯砜和0.1g 2-乙基-4-甲基咪唑,搅拌约10min成均相溶液,脱气,然后浇铸于100℃预热的模具中。固化程序为:150℃、1h,200℃、2h,固化结束后自然冷却至室温的目标产物。热导率为0.22W/(m·K),拉伸强度、模量和断裂伸长率分别为62.8MPa、6.6GPa、4.3%,弯曲强度为107.4MPa,树脂玻璃化转变温度为245℃,起始分解温度为357℃。
对照例7
将50g双酚A缩水甘油醚NPEL-128在150℃预热后添加14.5g 4,4-二氨基苯酰替苯胺和0.1g 2-乙基-4-甲基咪唑,搅拌约20min成均相溶液,脱气,然后浇铸于100℃预热的模具中。固化程序为:150℃、1h,200℃、2h,固化结束后自然冷却至室温的目标产物。热导率为0.21W/(m·K),拉伸强度、模量和断裂伸长率分别为78.7MPa、3.4GPa、5.1%,弯曲强度为126.7MPa,树脂玻璃化转变温度为223℃,起始分解温度为366℃。
表1.含有芳香酰胺结构的本征导热环氧树脂热导率结果
实施例/对照例 | 热导率(W/(m·K)) | 提高比例(%) |
对照例1 | 0.19 | - |
实施例1 | 0.43 | 126 |
对照例2 | 0.22 | 16 |
实施例2 | 0.51 | 168 |
对照例3 | 0.20 | 5 |
实施例3 | 0.40 | 111 |
对照例4 | 0.23 | 21 |
实施例4 | 0.39 | 105 |
对照例5 | 0.20 | 5 |
实施例5 | 0.36 | 89 |
对照例6 | 0.22 | 16 |
对照例7 | 0.21 | 11 |
备注:均以对照例1结果为比较对象。
表1结果表明,同时通过环氧预聚物和固化剂向固化物中引入芳香酰胺结构能够明显提高本征导热环氧树脂的热导率。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (8)
3.根据权利要求2所述的环氧树脂固化物,其特征在于,所述催化剂为2,4,6-三(二甲氨基甲基)苯酚、2,4,6-三(二甲氨基甲基)苯酚三(2-乙基己酸)盐、2,4,6-三(二甲氨基甲基)苯酚三油酸盐、三乙胺、三乙醇胺、苄基二甲胺、邻羟基苄基二甲胺、乙酰丙酮盐、三苯基膦及其鏻盐、N-(2-羟基苯基)-N’,N’-二甲基脲、N-(2-羟基-4-硝基苯)-N’,N’-二甲基脲、N-(2-羟基-5-硝基苯)-N’,N’-二甲基脲、N-(4-氯-2-羟基苯)-N’,N’-二甲基脲、N-(5-氯-2-羟基苯)-N’,N’-二甲基脲、N-(3,5-二甲基-2-羟基苯)-N’,N’-二甲基脲、N-(4-氯基)-N’,N’-二甲基脲、咪唑、2-甲基咪唑、2-乙基-4-甲基咪唑、1-苄基-2-乙基咪唑、1-氨基乙基-2-甲基咪唑、咪唑啉、过氧化苯甲酰中的一种或两种以上。
4.根据权利要求1或2或3所述的环氧树脂固化物,其特征在于,所述环氧预聚物与固化剂的比例为反应基团的化学计量比,催化剂用量为总质量的0.1~5wt%。
5.权利要求1或2或3或4所述环氧树脂固化物的制备方法,其特征在于,包括如下步骤:
(1)将各种组分加热熔融混合均匀后倒入模具中脱气,或将各种组分全部或部分溶解于溶剂中混合均匀、倒入模具脱气后烘干溶剂,或将各组分研磨成粉末状通过喷枪喷涂;
(2)在60℃~150℃预固化5min~12h,进一步在150℃~250℃后固化10min~6h,得到环氧树脂固化物。
6.根据权利要求5所述的制备方法,其特征在于,所述预固化的条件为:100~150℃预固化0.5~2h;所述后固化的条件为:160~210℃后固化0.5~2h。
7.根据权利要求6所述的制备方法,其特征在于,所述预固化的条件为:120~130℃预固化1~2h;所述后固化的条件为:180~200℃后固化1~2h。
8.根据权利要求5或6或7所述的制备方法,其特征在于,所述溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甲基亚砜、四氢呋喃、苯、甲苯、二甲苯、乙醇、丁醇、异丁醇、环己酮、甲基环己酮、丙酮、丁酮、醋酸乙酯、醋酸丁酯、溶纤剂。
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