CN104710617B - 聚酰胺酰亚胺高分子、石墨膜及其制备方法 - Google Patents
聚酰胺酰亚胺高分子、石墨膜及其制备方法 Download PDFInfo
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Abstract
本发明提供一种聚酰胺酰亚胺高分子,具有下列化学式(I):化学式(I)中,X1包括 X2包括
Description
【技术领域】
本发明关于一种聚酰胺酰亚胺高分子,特别关于一种导入二酸酐的聚酰胺酰亚胺高分子及由该聚酰胺酰亚胺高分子所构成的石墨膜及其制备方法。
【背景技术】
在电子产品不断走向轻、薄、短、小的趋势下,除了3C产品的散热需求,在电池、储能等产业,功率提高,散热需求也随之提升,由于人造石墨膜在平面方向具有很高的热传导值,可作为一种散热零件用于各种发热元件。
人造石墨膜的生产制作方式为使用特定的高分子膜材,分别经过1,000℃碳化(氮气环境)与2,400℃石墨化(氩气环境)处理,再进行后续辗压制程,即可获得石墨膜。
分析现有技术可发现,一般的聚酰胺酰亚胺膜(PAI film),在经高温2,400℃热处理后,由于石墨化度低,无法形成人造石墨膜。
【发明内容】
根据本发明一实施例,该聚酰胺酰亚胺高分子,具有如化学式(I)所示的化学结构:
化学式(I)中,X1包括 X2包括 以及m:n=8:2~6:4。所述高分子的重均分子量为20,000~60,000。
根据本发明的另一实施例,本发明提供一种石墨膜,其通过对聚酰胺酰亚胺高分子进行热处理制程所制备,其中该热处理制程的温度介于25~2,900℃,该聚酰胺酰亚胺高分子具有上述化学式(I)。
根据本发明的另一实施例,本发明提供一种石墨膜的制备方法,包括:对聚酰胺酰亚胺高分子进行热处理制程,以制备石墨膜,其中该热处理制程的温度介于25~2,900℃,该聚酰胺酰亚胺高分子具有上述化学式(I)。
本发明导入适当种类、比例(例如,若二酸酐比例过高,则无法涂布成聚酰胺酰亚胺膜,若二酸酐比例过低,则此聚酰胺酰亚胺膜经高温2,400℃以上温度热处理后,石墨化度低,无法形成石墨膜)的二酸酐于聚酰胺酰亚胺中,可提高分子量,增加聚酰胺酰亚胺的成膜性及韧性,并可降低分子运动性而提高分子排列性,此外,可通过增加聚酰胺酰亚胺膜的顺向性而提升其双折射率(例如0.04以上),并经由高温2,400℃以上温度的热处理后,可获得石墨化度为80%以上的人造石墨膜。
为让本发明的上述目的、特征及优点能更明显易懂,下文特举优选实施例,并配合所附的图式,作详细说明如下。
【具体实施方式】
根据本发明一实施例,本发明提供一种聚酰胺酰亚胺(PAI)高分子,具有下列化学式(I):
化学式(I)中,X1可包括
X2可包括
m与n的比例可介于8:2~6:4,或7.5:2.5~6.5:3.5。所述高分子的重均分子量为20,000~60,000,或者为30,000~50,000。
根据本发明的另一实施例,本发明提供一种石墨膜,其通过对聚酰胺酰亚胺(PAI)高分子进行热处理制程所制备。上述热处理制程的温度大体介于25~2,900℃。上述聚酰胺酰亚胺高分子具有下列化学式(I):
化学式(I)中,X1可包括
X2可包括
m与n的比例可介于8:2~6:4,或7.5:2.5~6.5:3.5。所述高分子的重均分子量为20,000~60,000,或者为30,000~50,000。
上述构成石墨膜的聚酰胺酰亚胺高分子中,其X2可包括 中的至少两种,例如,同时包括PMDA及BPDA,同时包括PMDA、BPDA及ODPA,或同时包括PMDA、BTDA及BPDA。
根据本发明的另一实施例,本发明提供一种石墨膜的制备方法,包括:对聚酰胺酰亚胺(PAI)高分子进行热处理制程,以制备石墨膜。
上述热处理制程的温度大体介于25~2,900℃。
上述聚酰胺酰亚胺高分子具有下列化学式(I):
化学式(I)中,X1可包括
X2可包括
m与n的比例可介于8:2~6:4,或7.5:2.5~6.5:3.5。所述高分子的重均分子量为20,000~60,000,或者为30,000~50,000。
上述热处理制程可包括碳化制程和石墨化制程。
上述碳化制程的温度大体介于25~1,300℃,上述石墨化制程的温度大体介于1,800~2,900℃。
本发明石墨膜的制备方法还包括导入氮气、氢气、氦气或氩气于碳化制程中,以及导入氩气、氢气或氦气于石墨化制程中。
相比于传统PAI,本发明导入适当种类、比例(例如,若二酸酐比例过高,则无法涂布成聚酰胺酰亚胺膜,若二酸酐比例过低,则此聚酰胺酰亚胺膜经高温2,400℃以上温度热处理后,石墨化度低,无法形成石墨膜)的二酸酐于聚酰胺酰亚胺中,可提高分子量,增加聚酰胺酰亚胺的成膜性及韧性,并可降低分子运动性而提高分子排列性,此外,可通过增加聚酰胺酰亚胺膜的顺向性而提升其双折射率(例如0.04以上),并经由高温2,400℃以上温度的热处理后,可获得石墨化度为80%以上的人造石墨膜。
实施例1
本发明石墨膜PAI-1的制备(聚酰胺酰亚胺高分子(X1=MDI,X2=PMDA+BPDA))
在室温下,于2升的四口反应器上架上搅拌器与加热套,将153.60克的偏苯三甲酸酐(trimellitic anhydride,TMA)、24.96克的均苯四甲酸酐(pyromellitic dianhydride,PMDA)、67.20克的3,3',4,4'-联苯四羧酸二酐(3,3',4,4'-biphenyl tetracarboxylicdianhydride,BPDA)以及300.00克的二苯基甲烷二异氰酸酯(methylene diphenylenediisocyanate,MDI)溶入1637.00克的NMP溶剂中均匀搅拌。将温度升至80℃反应1小时,然后将温度升至120℃反应2小时,最后将温度升至170℃反应2小时。反应完成后,等其降至室温,将溶液装入PE瓶中密封保存。此高分子的组成摩尔比例m为7,n为3,重均分子量为50,000。将此溶液(固含量为25.00wt%)涂布于玻璃上,并以热风烘箱进行干燥,于80℃干燥1小时,于150℃干燥1小时,于200℃干燥1小时,以及于240℃干燥12小时。待干燥程序结束后降回室温,再将其泡入水中进行脱膜。脱膜后,再进入热风烘箱干燥,于120℃干燥3小时。之后,进行碳化制程。碳化制程:以混合保护气氛予以保护(5~20%氢气与80~95%氮气,或是5~20%氢气与80~95%氩气及氦气),处理温度为25~1,300℃,升温速率<10℃/min,升温至1,300℃,碳化时间15小时以上,施加压力10~15Kgf/cm2。之后,进行石墨化制程。石墨化制程:以保护气氛氦气或氩气(纯度6N以上)予以保护,处理温度为1,800~2,800℃,升温速率<10℃/min,升温至2,800,石墨化时间8小时以上,施加压力15~25Kgf/cm2。至此,即可获得石墨膜PAI-1。之后,对石墨膜PAI-1进行有关双折射率与石墨化度的测量,结果记载于下表1。
实施例2
本发明石墨膜PAI-2的制备(聚酰胺酰亚胺高分子(X1=MDI,X2=PMDA+BPDA+ODPA))
在室温下,于1升的四口反应器上架上搅拌器与加热套,将67.74克的偏苯三甲酸酐(trimellitic anhydride,TMA)、12.81克的均苯四甲酸酐(pyromellitic dianhydride,PMDA)、17.28克的3,3',4,4'-联苯四羧酸二酐(3,3',4,4'-biphenyl tetracarboxylicdianhydride,BPDA)、36.45克的4,4'-氧联双邻苯二甲酸酐(4,4'-oxydiphthalicanhydride,ODPA)以及150.00克的二苯基甲烷二异氰酸酯(methylene diphenylenediisocyanate,MDI)溶入852.00克的NMP溶剂中,均匀搅拌。将温度升至80℃反应1小时,然后将温度升至120℃反应2小时,最后将温度升至170℃反应2小时。反应完成后,等其降至室温,将溶液装入PE瓶中密封保存。此高分子的组成摩尔比例m为6,n为4,重均分子量为40,000。将此溶液(固含量为25.00wt%)涂布于玻璃上,并以热风烘箱进行干燥,于80℃干燥1小时,于150℃干燥1小时,于200℃干燥1小时,以及于240℃干燥12小时。待干燥程序结束后降回室温,再将其泡入水中进行脱膜。脱膜后,再进入热风烘箱干燥,于120℃干燥3小时。之后,进行碳化制程。碳化制程:以混合保护气氛予以保护(5~20%氢气与80~95%氮气,或是5~20%氢气与80~95%氩气及氦气),处理温度为25~1,300℃,升温速率<10℃/min,升温至1,300℃,碳化时间15小时以上,施加压力10~15Kgf/cm2。之后,进行石墨化制程。石墨化制程:以保护气氛氦气或氩气(纯度6N以上)予以保护,处理温度为1,800~2,800℃,升温速率<10℃/min,升温至2,800,石墨化时间8小时以上,施加压力15~25Kgf/cm2。至此,即可获得石墨膜PAI-2。之后,对石墨膜PAI-2进行有关双折射率与石墨化度的测量,结果记载于下表1。
实施例3
本发明石墨膜PAI-3的制备(聚酰胺酰亚胺高分子(X1=MDI,X2=PMDA+BTDA+BPDA))
在室温下,于500毫升的四口反应器上架上搅拌器与加热套,将22.58克的偏苯三甲酸酐(trimellitic anhydride,TMA)、4.28克的均苯四甲酸酐(pyromelliticdianhydride,PMDA)、11.53克的3,3',4,4'-联苯四羧酸二酐(3,3',4,4'-biphenyltetracarboxylic dianhydride,BPDA)、6.31克的3,3',4,4'-二苯甲酮四羧酸二酐(3,3',4,4'-benzophenone tetracarboxylic dianhydride,BTDA)以及50.00克的二苯基甲烷二异氰酸酯(methylene diphenylene diisocyanate,MDI)溶入284.00克的NMP溶剂中均匀搅拌。将温度升至80℃反应1小时,然后将温度升至120℃反应2小时,最后将温度升至170℃反应2小时。反应完成后,等其降至室温,将溶液装入PE瓶中密封保存。此高分子的组成摩尔比例m为6,n为4,重均分子量为40,000。将此溶液(固含量为25.00wt%)涂布于玻璃上,并以热风烘箱进行干燥,于80℃干燥1小时,于150℃干燥1小时,于200℃干燥1小时,以及于240℃干燥12小时。待干燥程序结束后降回室温,再将其泡入水中进行脱膜。脱膜后,再进入热风烘箱干燥,于120℃干燥3小时。之后,进行碳化制程。碳化制程:以混合保护气氛予以保护(5~20%氢气与80~95%氮气,或是5~20%氢气与80~95%氩气及氦气),处理温度为25~1,300℃,升温速率<10℃/min,升温至1,300℃,碳化时间15小时以上,施加压力10~15Kgf/cm2。之后,进行石墨化制程。石墨化制程:以保护气氛氦气或氩气(纯度6N以上)予以保护,处理温度为1,800~2,900℃,升温速率<10℃/min,升温至2,800,石墨化时间8小时以上,施加压力15~25Kgf/cm2。至此,即可获得石墨膜PAI-3。之后,对石墨膜PAI-3进行有关双折射率与石墨化度的测量,结果记载于下表1。
实施例4
本发明石墨膜PAI-4的制备(聚酰胺酰亚胺高分子(X1=TODI,X2=PMDA+BPDA))
在室温下,于2升的四口反应器上架上搅拌器与加热套,将153.60克的偏苯三甲酸酐(trimellitic anhydride,TMA)、24.96克的均苯四甲酸酐(pyromellitic dianhydride,PMDA)、67.20克的3,3',4,4'-联苯四羧酸二酐(3,3',4,4'-biphenyl tetracarboxylicdianhydride,BPDA)以及316.82克的3,3'-二甲基-4,4'-联苯基二异氰酸酯(3,3'-dimethyl-4,4'-biphenylene diisocyanate,TODI)溶入1687.74克的NMP溶剂中均匀搅拌。将温度升至80℃反应1小时,然后将温度升至120℃反应2小时,最后将温度升至170℃反应2小时。反应完成后,等其降至室温,将溶液装入PE瓶中密封保存。此高分子的组成摩尔比例m为8,n为2,重均分子量为60,000。将此溶液(固含量为25.00wt%)涂布于玻璃上,并以热风烘箱进行干燥,于80℃干燥1小时,于150℃干燥1小时,于200℃干燥1小时,以及于240℃干燥12小时。待干燥程序结束后降回室温,再将其泡入水中进行脱膜。脱膜后,再进入热风烘箱干燥,于120℃干燥3小时。之后,进行碳化制程。碳化制程:以混合保护气氛予以保护(5~20%氢气与80~95%氮气,或是5~20%氢气与80~95%氩气及氦气),处理温度为25~1,300℃,升温速率<10℃/min,升温至1,300℃,碳化时间15小时以上,施加压力10~15Kgf/cm2。之后,进行石墨化制程。石墨化制程处理:以保护气氛氦气或氩气(纯度6N以上)予以保护,施加压力15~25Kgf/cm2,处理温度为1,800~2,800℃,升温速率<10℃/min,升温至2,800,石墨化时间8小时以上,施加压力15~25Kgf/cm2。至此,即可获得石墨膜PAI-4。之后,对石墨膜PAI-4进行有关双折射率与石墨化度的测量,结果记载于下表1。
实施例5
本发明石墨膜PAI-5的制备(聚酰胺酰亚胺高分子(X1=NDI,X2=PMDA+BPDA))
在室温下,于2升的四口反应器上架上搅拌器与加热套,将153.60克的偏苯三甲酸酐(trimellitic anhydride,TMA)、24.96克的均苯四甲酸酐(pyromellitic dianhydride,PMDA)、67.20克的3,3',4,4'-联苯四羧酸二酐(3,3',4,4'-biphenyl tetracarboxylicdianhydride,BPDA)以及251.96克的1,5-萘二异氰酸酯(1,5-naphthalene diisocyanate,NDI)溶入1493.16克的NMP溶剂中均匀搅拌。将温度升至80℃反应1小时,然后将温度升至120℃反应2小时,最后将温度升至170℃反应2小时。反应完成后,等其降至室温,将溶液装入PE瓶中密封保存。此高分子的组成摩尔比例m为8,n为2,重均分子量为50,000。此高分子的组成摩尔比例m为8,n为2,重均分子量为50,000。将此溶液(固含量为25.00wt%)涂布于玻璃上,并以热风烘箱进行干燥,于80℃干燥1小时,于150℃干燥1小时,于200℃干燥1小时,以及于240℃干燥12小时。待干燥程序结束后降回室温,再将其泡入水中进行脱膜。脱膜后,再进入热风烘箱干燥,于120℃干燥3小时。之后,进行碳化制程。碳化制程:以混合保护气氛予以保护(5~20%氢气与80~95%氮气,或是5~20%氢气与80~95%氩气及氦气),处理温度为25~1,300℃,升温速率<10℃/min,升温至1,300℃,碳化时间15小时以上,施加压力10~15Kgf/cm2。之后,进行石墨化制程。石墨化制程:以保护气氛氦气或氩气(纯度6N以上)予以保护,施加压力15~25Kgf/cm2,处理温度为1,800~2,800℃,升温速率<10℃/min,升温至2,800,石墨化时间8小时以上,施加压力15~25Kgf/cm2。至此,即可获得石墨膜PAI-5。之后,对石墨膜PAI-5进行有关双折射率与石墨化度的测量,结果记载于下表1。
比较实施例1
传统石墨膜PAI-6的制备(聚酰胺酰亚胺高分子)
在室温下,于500毫升的四口反应器上架上搅拌器与加热套,将37.68克的偏苯三甲酸酐(trimellitic anhydride,TMA)以及50.00克的二苯基甲烷二异氰酸酯(methylenediphenylene diisocyanate,MDI)溶入263.04克的NMP溶剂中均匀搅拌。将温度升至80℃反应1小时,然后将温度升至120℃反应2小时,再将温度升至170℃反应2小时。反应完成后,等其降至室温,将溶液装入PE瓶中密封保存。此高分子的重均分子量为30,000。将此溶液(固含量为25.00wt%)涂布于玻璃上,并以热风烘箱进行干燥,于80℃干燥1小时,于150℃干燥1小时,于200℃干燥1小时,以及于240℃干燥12小时。待干燥程序结束后降回室温,再将其泡入水中进行脱膜。脱膜后,再进入热风烘箱干燥,于120℃干燥3小时。之后,进行碳化制程。碳化制程:以混合保护气氛予以保护(5~20%氢气与80~95%氮气,或是5~20%氢气与80~95%氩气及氦气),处理温度为25~1,300℃,升温速率<10℃/min,升温至1,300℃,碳化时间15小时以上,施加压力10~15Kgf/cm2。之后,进行石墨化制程。石墨化制程:以保护气氛氦气或氩气(纯度6N以上)予以保护,处理温度为1,800~2,800℃,升温速率<10℃/min,升温至2,800,石墨化时间8小时以上,施加压力15~25Kgf/cm2。至此,即可获得石墨膜PAI-6。之后,对石墨膜PAI-6进行有关双折射率与石墨化度的测量,结果记载于下表1。
表1
虽然本发明已以多个优选实施例披露如上,然其并非用以限定本发明,任何本发明所属技术领域中的技术人员,在不脱离本发明的精神和范围内,应可作任意更改与润饰。因此,本发明的保护范围应以所附权利要求书限定的范围为准。
Claims (9)
1.一种聚酰胺酰亚胺高分子,具有下列化学式(I):
其中,
当X1为X2为(1)与的组合、(2) 与的组合、或(3)与的组合;当X1为X2为与的组合;当X1为X2为与的组合;以及
m:n=8:2~6:4,所述高分子的重均分子量为20,000~60,000。
2.如权利要求1所述的聚酰胺酰亚胺高分子,其中m:n=7.5:2.5~6.5:3.5,所述高分子的重均分子量为30,000~50,000。
3.一种石墨膜,其通过对聚酰胺酰亚胺高分子进行热处理制程所制备,其中该热处理制程的温度为25~2,900℃,且该聚酰胺酰亚胺高分子具有下列化学式(I):
其中,
当X1为X2为(1)与的组合、(2) 与的组合、或(3)与的组合;当X1为X2为与的组合;当X1为X2为与的组合;以及
m:n=8:2~6:4,所述高分子的重均分子量为20,000~60,000。
4.一种石墨膜的制备方法,包括:对聚酰胺酰亚胺高分子进行热处理制程,以制备石墨膜,其中该热处理制程的温度为25~2,900℃,且该聚酰胺酰亚胺高分子具有下列化学式(I):
其中,
当X1为X2为(1)与的组合、(2) 与的组合、或(3)与的组合;当X1为X2为与的组合;当X1为X2为与的组合;以及
m:n=8:2~6:4,所述高分子的重均分子量为20,000~60,000。
5.如权利要求4所述的石墨膜的制备方法,其中该热处理制程包括碳化制程与石墨化制程。
6.如权利要求5所述的石墨膜的制备方法,其中该碳化制程的温度为25~1,300℃。
7.如权利要求5所述的石墨膜的制备方法,其中该石墨化制程的温度为1,800~2,900℃。
8.如权利要求5所述的石墨膜的制备方法,还包括导入氮气、氢气、氩气或氦气于该碳化制程中。
9.如权利要求5所述的石墨膜的制备方法,还包括导入氩气、氢气或氦气于该石墨化制程中。
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JP6030620B2 (ja) | 2016-11-24 |
CN104710617A (zh) | 2015-06-17 |
TWI598294B (zh) | 2017-09-11 |
JP2015117372A (ja) | 2015-06-25 |
TW201524901A (zh) | 2015-07-01 |
US9371233B2 (en) | 2016-06-21 |
US20150166347A1 (en) | 2015-06-18 |
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