CN116376077A - 一种烧结聚酰亚胺薄膜及制作方法 - Google Patents
一种烧结聚酰亚胺薄膜及制作方法 Download PDFInfo
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Abstract
本发明提出了一种烧结聚酰亚胺薄膜的制作方法，包括如下步骤：S1、树脂合成：以等摩尔的芳香族二胺和芳香族二酐在极性溶剂中进行树脂合成，所用极性溶剂质量为芳香族二胺与芳香族二酐总质量的4‑7倍；S2、制膜：将合成好的树脂经脱泡过滤后，涂敷于钢带或其他承载模具上进行干燥成膜；S2、亚胺化：将干燥后的薄膜牵引如双向拉伸机进行拉伸并热亚胺化成型。本发明通过将芳香族二胺溶于极性溶剂中，再与芳香族二酐聚合制得聚酰亚胺酸树脂，并在树脂中引入导热材料，引导树酯固化化亚胺化时分子链沿二维排布均匀趋向排列，利于高温烧结时六角二维碳平面生长，避免因为聚酰亚胺薄膜热缩和结构问题带来的石墨膜褶皱不平和导热率低等问题。
Description
技术领域
本发明涉及聚酰亚胺薄膜生产领域，尤其涉及一种烧结聚酰亚胺薄膜及制作方法。
背景技术
聚酰亚胺作为人工石墨的原材料，产品结构直接影响石墨化难易程度、人工石墨的分子间力、产品的平整性和收缩性。其高强高模和耐候特性，在电子器件、航天飞行器等先进行业领域被广泛关注和热捧，聚酰亚胺在一定温度下发生高温分解，分子链重排形成六角炭结构，并规整生长形成石墨材料。科研人员研究聚酰亚胺薄膜石墨化过程，发现国产聚酰亚胺薄膜热缩不均、褶皱严重、导热率低，与国外产品热缩均匀、表面平整、结构致密、导热性等存在较大差异。国产聚酰亚胺薄膜多用予绝缘行业，烧结用聚酰亚胺薄膜主要依赖进口。
发明内容
本发明要解决的技术问题是克服现有技术存在的缺陷，本发明提出了一种烧结聚酰亚胺薄膜及制作方法，解决烧结石墨热缩大、褶皱多、导热率低等问题，实现石墨烧结原膜国产化供应。
为解决上述技术问题，本发明采用的技术方案是：一种烧结聚酰亚胺薄膜的制作方法，包括如下步骤：
S1、树脂合成：以等摩尔的芳香族二胺和芳香族二酐在极性溶剂中进行树脂合成，所用极性溶剂质量为芳香族二胺与芳香族二酐总质量的4-7倍；
S2、制膜：将合成好的树脂经脱泡过滤后，涂敷于钢带或其他承载模具上进行干燥成膜，模具温度控制120-250℃，成膜后残留溶剂含量为10％-60％；
S2、亚胺化：将干燥后的薄膜牵引如双向拉伸机进行拉伸并热亚胺化成型，控制亚胺化过程最高温度360-550℃，拉伸机出口温度80-350℃，拉伸比为0.8-1.3倍；
于树脂合成过程之中还包括石墨诱导材料以及表面维护剂，所述石墨诱导材料用量为树脂固体量的0.05％-8％，表面维护剂用量为树脂固体量的0.001％-5％。
进一步地，所述石墨诱导材料为碳化硅、氮化硼、氮化铝、钙磷化合物、碳酸钙、硫酸钙、硫酸钡，金属或非金属导热性石墨诱导材料的一种或几种组合。
进一步地，所述表面维护剂包括亚磷酸三苯酯、磷酸三苯酯、硅酸酯、硅氧烷、硅油、聚氨酯、植物油、动物油、石蜡、聚乙二醇、石油醚、不饱和聚酯、环氧树脂、酚醛塑料、苯乙烯中至少一种。
进一步地，所述芳香族二胺为ODA、PDA、TFDB、6FABP、OTFDB、MDA、SDA、和BZ中的一种或几种组合。
进一步地，所述芳香族二酐为BPDA、PMDA、ODPA、BTDA、TDPA、SDPA、HQDPA、RSDPA、CAPDA、BPADA中的一种或几种组合。
进一步地，所述极性溶剂为DMAC、DMF或NMP中任意一种。
进一步地，所述石墨诱导材料以及表面维护剂于105℃-110℃下干燥3-5h后研磨或破碎至10nm-10μm后预先分散至溶剂之中。
进一步地，一种烧结聚酰亚胺薄膜，依照烧结聚酰亚胺薄膜的制作方法制得，其导热率不低于1300W/MK。
与现有技术相比，本发明的有益效果包括：通过将芳香族二胺溶于极性溶剂中，再与芳香族二酐聚合制得聚酰亚胺酸树脂，并在树脂中引入导热材料，引导树酯固化化亚胺化时分子链沿二维排布均匀趋向排列，利于高温烧结时六角二维碳平面生长，从而实现聚酰亚胺薄膜石墨烧结原料国产化，避免因为聚酰亚胺薄膜热缩和结构问题带来的石墨膜褶皱不平和导热率低等问题。
具体实施方式
容易理解，根据本发明的技术方案，在不变更本发明实质精神下，本领域的一般技术人员可以提出可相互替换的多种结构方式以及实现方式。因此，以下具体实施方式仅是对本发明的技术方案的示例性说明，而不应当视为本发明的全部或者视为对本发明技术方案的限定或限制。
本发明通过设计分子链结构，引入石墨诱导材料和表层保护材料，引导分子链扁平化分不去想，缓解聚酰亚胺薄膜本身导热性差、层间疏松给石墨化带来的难题，促使分子链排布按二维化均匀生长的同时进行分子外表面维护，从而达到面内力学和热学指标均一的目的，解决聚酰亚胺薄膜高温烧结过程中出现的卷边、缩边、表面不均等人工石墨制品问题。
于本发明之中提供如下技术方案：包括树脂合成、添加剂预处理、制膜和亚胺化。
本发明采用芳香族二胺为ODA、PDA、TFDB、6FABP、OTFDB、MDA、SDA、和BZ中的一种或几种组合。采用芳香族二酐是BPDA、PMDA、ODPA、BTDA、TDPA、SDPA、HQDPA、RSDPA、CAPDA、BPADA中的一种或几种组合。采用溶剂为DMAC、DMF或NMP中的一种。添加石墨诱导材料为碳化硅、氮化硼、氮化铝、钙磷化合物、碳酸钙、硫酸钙、硫酸钡、金属或非金属等导热性石墨诱导材料的一种或几种组合。表面维护剂有：亚磷酸三苯酯、磷酸三苯酯、硅酸酯、硅氧烷、硅油、聚氨酯、植物油、动物油、石蜡、聚乙二醇、石油醚、不饱和聚酯、环氧树脂、酚醛塑料、苯乙烯等。
1)树脂合成：取等摩尔的芳香族二胺和芳香族二酐在极性溶剂中进行树脂合成。取用溶剂的质量是二胺与二酐总质量的4～7倍。诱导剂的用量是树脂固体量的0.05％～8％，添加直径为10纳米～10微米。诱导剂可以直接加入也可先用溶剂分散，添加时机可以在树脂合成的任何阶段。维护剂用量是树脂固体量的十万分之一至百分之五，维护剂可直接加入也可先分散到溶剂里面再加入。添加时机可以在树脂合成的任何阶段。
2)添加剂预处理：
a、干燥处理：将添加剂在105℃至110℃条件下，干燥3～5小时。
b、分散处理：干燥后的添加剂进行研磨或破碎至10纳米～10微米。也可将添加剂预先分散至同质溶剂中。
3)制膜：将合成好的树脂经脱泡过滤后，涂敷于钢带或其他承载模具上进行干燥成膜，模具温度控制120～250℃，成膜后残留溶剂含量约10％-60％。
4)亚胺化：将干燥后的薄膜牵引入双向拉伸机进行拉伸并热亚胺化成型，控制亚胺化过程最高温度360～550℃，控制拉伸机(或亚胺炉)出口温度80～350℃。控制拉伸比为0.80-1.3倍.
通过上述过程得到聚酰亚胺薄膜经高温烧结后得到，表面平整、细腻，导热率达到1300W/MK以上。
以下对本发明的优选实施例进行说明，应当理解，此处所描述的优选实施例仅用于说明和解释本专利，并不用于限制本发明专利。
实施例1、取ODA(二胺)100.12kg溶于900kgDMAC中、取用PMDA(二酐)109.6kg进行树脂合成，待树脂起粘后加入300克粒径为500纳米的氮化硼片状颗粒和500克亚磷酸三苯酯，充分分散至分布均匀。控制聚合温度不超过65℃，聚合时间为6小时，添加剂加入后分散时间不低于2小时，确保分散均匀。最终粘度控制为120pa.s，最终酐与胺的摩尔比为0.985:1，调粘时间约4小时，整个过程树脂温度控制在常温至60℃范围内。树脂脱泡后，通过刮板刀均匀涂覆在运转的钢带表面，在180℃条件下干燥成膜，成膜固含量为55％。干燥后的薄膜牵引入双向拉伸机，在1:1的牵伸条件下进行热法亚胺化，控制亚胺化过程最高温度480℃，控制拉伸机进口温度150℃，出口温度180℃。制得平整均匀的聚酰亚胺薄膜，拉伸强度248MPA,经逐步升温至2860℃烧结，得到表面平整导热率1590W/MK的人工石墨膜。
实施例2、分别取二胺ODA 100.12kg和PDA54.07kg溶于1500kgDMAC中、取用PMDA(二酐)218.12kg进行树脂合成，待树脂起粘后加入1.0公斤粒径为100纳米的碳化硅颗粒和100克聚乙二醇，充分分散至分布均匀。控制聚合温度不超过65℃，聚合时间为6小时，添加剂加入后分散时间不低于2小时，确保分散均匀。最终粘度控制为120pa.s，最终酐与胺的摩尔比为0.995:1，调粘时间约4小时，整个过程树脂温度控制在常温至60℃范围内。树脂脱泡后，通过刮板刀均匀涂覆在运转的钢带表面，在180℃条件下干燥成膜，成膜固含量为82％。干燥后的薄膜牵引入双向拉伸机，在1:1的牵伸条件下进行热法亚胺化，控制亚胺化过程最高温度390℃，控制拉伸机进口温度130℃，出口温度200℃。制得平整均匀的聚酰亚胺薄膜，拉伸强度236MPA,经逐步升温至2828℃烧结，得到表面平整导热率1700W/MK的人工石墨膜。
本发明的技术范围不仅仅局限于上述说明中的内容，本领域技术人员可以在不脱离本发明技术思想的前提下，对上述实施例进行多种变形和修改，而这些变形和修改均应当属于本发明的保护范围内。
Claims (8)
1.一种烧结聚酰亚胺薄膜的制作方法，其特征在于，包括如下步骤：
S1、树脂合成：以等摩尔的芳香族二胺和芳香族二酐在极性溶剂中进行树脂合成，所用极性溶剂质量为芳香族二胺与芳香族二酐总质量的4-7倍；
S2、制膜：将合成好的树脂经脱泡过滤后，涂敷于钢带或其他承载模具上进行干燥成膜，模具温度控制120-250℃，成膜后残留溶剂含量为10％-60％；
S2、亚胺化：将干燥后的薄膜牵引如双向拉伸机进行拉伸并热亚胺化成型，控制亚胺化过程最高温度360-550℃，拉伸机出口温度80-350℃，拉伸比为0.8-1.3倍；
于树脂合成过程之中还包括石墨诱导材料以及表面维护剂，所述石墨诱导材料用量为树脂固体量的0.05％-8％，表面维护剂用量为树脂固体量的0.001％-5％。
2.根据权利要求1所述的烧结聚酰亚胺薄膜的制作方法，其特征在于，所述石墨诱导材料为碳化硅、氮化硼、氮化铝、钙磷化合物、碳酸钙、硫酸钙、硫酸钡，金属或非金属导热性石墨诱导材料的一种或几种组合。
3.根据权利要求1所述的烧结聚酰亚胺薄膜的制作方法，其特征在于，所述表面维护剂包括亚磷酸三苯酯、磷酸三苯酯、硅酸酯、硅氧烷、硅油、聚氨酯、植物油、动物油、石蜡、聚乙二醇、石油醚、不饱和聚酯、环氧树脂、酚醛塑料、苯乙烯中至少一种。
4.根据权利要求1所述的烧结聚酰亚胺薄膜的制作方法，其特征在于，所述芳香族二胺为ODA、PDA、TFDB、6FABP、OTFDB、MDA、SDA、和BZ中的一种或几种组合。
5.根据权利要求1所述的烧结聚酰亚胺薄膜的制作方法，其特征在于，所述芳香族二酐为BPDA、PMDA、ODPA、BTDA、TDPA、SDPA、HQDPA、RSDPA、CAPDA、BPADA中的一种或几种组合。
6.根据权利要求1所述的烧结聚酰亚胺薄膜的制作方法，其特征在于，所述极性溶剂为DMAC、DMF或NMP中任意一种。
7.根据权利要求1所述的烧结聚酰亚胺薄膜的制作方法，其特征在于，所述石墨诱导材料以及表面维护剂于105℃-110℃下干燥3-5h后研磨或破碎至10nm-10μm后预先分散至溶剂之中。
8.一种烧结聚酰亚胺薄膜，其特征在于，依照权利要求1-7任一所述的烧结聚酰亚胺薄膜的制作方法制得，其导热率不低于1300W/MK。
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