技术领域technical field
本发明涉及聚酰亚胺薄膜技术领域，具体是一种填料取向增强的高导热聚酰亚胺复合薄膜及其制备方法。The invention relates to the technical field of polyimide films, in particular to a high thermal conductivity polyimide composite film with enhanced filler orientation and a preparation method thereof.
背景技术Background technique
随着智能手机、笔记本电脑等电子产品的升级换代，以及迷你、轻量化、高集成化逐渐成为亮点。这些电子产品的寿命和稳定性也日益受到关注，而影响寿命和稳定性的因素主要是系统的散热能力。目前，高导热的散热材料是电子行业的重要需求，具有导热功能的材料成为解决电子产品散热问题的关键技术。聚酰亚胺薄膜是目前已知的耐温等级最高的聚合物薄膜之一，其分子链中拥有稳定的芳杂环结构，使其具有优异的耐氧化稳定性、耐高温、优良的机械性能以及碳密度高等特性，这是其它聚合物难以实现的。然而，纯聚酰亚胺薄膜的导热性能比较差，导热系数只有0.19 W·m−1·K−1，这很大程度上的限制了它的应用，因此，具有高导热的聚酰亚胺薄膜的研发与制备是目前解决电子产业散热问题的迫切需求。With the upgrading of electronic products such as smart phones and notebook computers, as well as miniaturization, light weight and high integration, they have gradually become bright spots. The lifespan and stability of these electronic products are also increasingly concerned, and the main factor affecting the lifespan and stability is the heat dissipation capability of the system. At present, heat dissipation materials with high thermal conductivity are an important demand of the electronics industry, and materials with thermal conductivity have become the key technology to solve the heat dissipation problem of electronic products. Polyimide film is one of the known polymer films with the highest temperature resistance level. It has a stable aromatic heterocyclic structure in its molecular chain, which makes it have excellent oxidation resistance stability, high temperature resistance and excellent mechanical properties. As well as high carbon density properties, which are difficult to achieve with other polymers. However, the thermal conductivity of pure polyimide film is relatively poor, and the thermal conductivity is only 0.19 W·m−1 ·K−1 , which greatly limits its application. Therefore, polyimide with high thermal conductivity The research and development and preparation of thin films is an urgent need to solve the problem of heat dissipation in the electronic industry.
提高低导热系数聚酰亚胺薄膜的导热性能主要有两种途径：一种是在材料合成及成型加工过程中通过改变材料分子和链节的结构从而获得特殊物理结构，在聚合物内部建立利于声子传递的通道和网络，提高导热性能，如使用一些特殊单体或者对薄膜进行高度拉伸取向，但是制备工艺繁琐、难度大、成本高，距离工业化应用尚有一定的距离且导热系数提高幅度有限。而另一种是通过加入高导热无机填料，制备导热复合薄膜，将高导热无机填料引入聚酰亚胺基体中达到增加导热的目的，专利CN 108384235 A中采用氮化硼和氧化铝中的其中一种作为填料制备聚酰亚胺薄膜，并且加入量高达30%-60%，往往加入同一种导热填料对聚酰亚胺薄膜导热性能的提高有很大的局限性，而且在薄膜面内方向和面外方向上不能同时显著提高。专利CN 105111739 A公开了一种高导热聚酰亚胺薄膜的制备，该专利使用纳米级氧化铝、炭黑粉和氧化铁等作为填料达到提高导热率的目的，但填料之间相互独立，没有协同作用，薄膜的导热系数没有得到显著的提高。There are two main ways to improve the thermal conductivity of low thermal conductivity polyimide films: one is to obtain a special physical structure by changing the structure of the material molecules and chain links during the material synthesis and molding process, and to establish a favorable physical structure inside the polymer. Channels and networks for phonon transfer to improve thermal conductivity, such as the use of some special monomers or high-stretch orientation of the film, but the preparation process is cumbersome, difficult, and costly, and there is still a certain distance from industrial application and the thermal conductivity is improved. The range is limited. The other is to prepare a thermally conductive composite film by adding high thermal conductivity inorganic fillers, and introduce high thermal conductivity inorganic fillers into the polyimide matrix to achieve the purpose of increasing thermal conductivity. Patent CN 108384235 A uses boron nitride and aluminum oxide among them. A polyimide film is prepared as a filler, and the addition amount is as high as 30%-60%. Often adding the same thermal conductive filler has great limitations on the improvement of the thermal conductivity of the polyimide film, and the in-plane direction of the film is greatly limited. and the out-of-plane direction cannot be significantly improved at the same time. Patent CN 105111739 A discloses the preparation of a high thermal conductivity polyimide film. The patent uses nano-scale alumina, carbon black powder and iron oxide as fillers to achieve the purpose of improving thermal conductivity, but the fillers are independent of each other, and there is no Synergistically, the thermal conductivity of the films was not significantly improved.
本发明是通过在极性溶剂中添加两种以上不同形貌的填料混合而且至少一种为片状结构的导热填料，芳香族二酐与芳香族二胺在极性溶剂中缩聚反应生成聚酰胺酸，经过流道后再进一步热亚胺化得到高导热聚酰亚胺复合薄膜。当片状填料在经过狭长流道时，受剪切作用在薄膜面内发生取向，从而获得面内高导热性，同时其他非片状填料在片状填料之间形成导热连接，经过压延作用，进一步增强该导热连接，从而在厚度方向上完善导热网络，获得高的面外导热性。In the present invention, polyamide is formed by polycondensation reaction of aromatic dianhydride and aromatic diamine in polar solvent by adding two or more fillers with different shapes and mixing and at least one of which is a sheet-like structure. acid, and then further thermal imidization after passing through the flow channel to obtain a high thermal conductivity polyimide composite film. When the flaky filler passes through the narrow and long flow channel, it is oriented in the film surface by shearing action, so as to obtain high thermal conductivity in the plane. At the same time, other non-flaky fillers form a thermal connection between the flaky fillers. This thermally conductive connection is further enhanced to complete the thermally conductive network in the thickness direction, resulting in high out-of-plane thermal conductivity.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于克服现有技术的不足，而提供一种填料取向增强的高导热聚酰亚胺复合薄膜及其制备方法，该制备方法简单有效，便于工业化生产，制备得到的薄膜具有高导热性能和低热膨胀系数。The purpose of the present invention is to overcome the deficiencies of the prior art, and provide a high thermal conductivity polyimide composite film with enhanced filler orientation and a preparation method thereof. The preparation method is simple and effective, convenient for industrial production, and the prepared film has high thermal conductivity. performance and low coefficient of thermal expansion.
实现本发明目的的技术方案是：The technical scheme that realizes the object of the present invention is:
一种填料取向增强的高导热聚酰亚胺复合薄膜，该薄膜由含有导热填料的聚酰胺酸溶液经狭长、横截面积渐变的模头通道挤出、铺膜、压延、热亚胺化制成；其中导热填料由至少包含一种为片状导热填料的两种以上不同形貌的填料混合而成，片状导热填料与非片状导热填料的质量比为1：0.5-2。A high thermal conductivity polyimide composite film with enhanced filler orientation, the film is prepared by extrusion, film laying, calendering and thermal imidization of a polyamic acid solution containing a thermal conductivity filler through a narrow and long die channel with a gradual cross-sectional area. The thermally conductive filler is formed by mixing at least one type of filler with different shapes, which is a sheet-shaped thermally conductive filler, and the mass ratio of the sheet-shaped thermally conductive filler to the non-sheet-shaped thermally conductive filler is 1:0.5-2.
所述的导热填料，为氧化铝、氧化镁、氧化锌、氮化铝、氮化硼、氧化铁、碳化硅、铜粒子、银粒子、碳纳米管、石墨烯、鳞片状的碳粉、石墨中的至少两种，且至少包含一种片状导热填料。The thermally conductive fillers are aluminum oxide, magnesium oxide, zinc oxide, aluminum nitride, boron nitride, iron oxide, silicon carbide, copper particles, silver particles, carbon nanotubes, graphene, scaly carbon powder, graphite At least two of them, and at least one kind of sheet-like thermally conductive filler.
所述的薄膜厚度为25-150um，固含量为15%-30%。The thickness of the film is 25-150um, and the solid content is 15%-30%.
一种填料取向增强的高导热聚酰亚胺复合薄膜的制备方法，包括如下步骤：A preparation method of a high thermal conductivity polyimide composite film with enhanced filler orientation, comprising the following steps:
（1）将至少包含一种为片状导热填料的两种以上不同形貌的导热填料的混合，加入含有分散剂的极性溶剂中分散均匀后，加入芳香族二胺，使芳香族二胺完全溶解在溶剂中，得到均匀混合体系；(1) Mix at least one type of thermally conductive filler with different shapes, which is a sheet-like thermally conductive filler, add it to a polar solvent containing a dispersant and disperse it uniformly, and then add an aromatic diamine to make the aromatic diamine. Completely dissolved in the solvent to obtain a uniform mixing system;
（2）将芳香族二酐分批加入到步骤（1）得到的混合体系中，芳香族二酐全部加入后，搅拌充分反应，消泡处理后制得聚酰胺酸溶液；(2) adding the aromatic dianhydride to the mixed system obtained in step (1) in batches, after all the aromatic dianhydrides are added, stirring and fully reacting, and defoaming treatment to obtain a polyamic acid solution;
（3）将消泡后的聚酰胺酸溶液加入进料斗中，通过狭长、横截面积渐变的模头通道挤出、铺膜，脱除薄膜中部分溶剂，得到具有一定自撑性的聚酰胺酸凝胶膜，通过压延机得到预定厚度的胶膜，再进行热亚胺化处理，片状填料通过模头通道时，受剪切作用发生在薄膜面内取向，非片状填料在片状填料之间形成导热连接，冷却后制得高导热聚酰亚胺薄膜。(3) Add the defoamed polyamic acid solution into the feeding hopper, extrude and lay the film through the narrow and long die channel with gradual cross-sectional area, remove part of the solvent in the film, and obtain a self-supporting polyamide. For amic acid gel film, a film with a predetermined thickness is obtained by a calender, and then thermal imidization is performed. When the sheet filler passes through the die channel, the shearing effect occurs in the film surface orientation, and the non-sheet filler is in the sheet. A thermally conductive connection is formed between the fillers, and a high thermal conductivity polyimide film is obtained after cooling.
所述的芳香族二酐，为苯四甲酸二酐、二苯酮四酸二酐、4,4'-氧双邻苯二甲酸酐、3,3’,4,4’-联苯四甲酸二酐、双酚A二酐中的一种或多种。The aromatic dianhydrides are pyromellitic dianhydride, benzophenone tetraacid dianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic acid One or more of dianhydride and bisphenol A dianhydride.
所述的芳香族二胺，为二氨基二苯醚（ODA）、对苯二胺（p-PDA）、TAB中的一种或多种。The aromatic diamine is one or more of diaminodiphenyl ether (ODA), p-phenylenediamine (p-PDA) and TAB.
所述的极性溶剂，为N，N-二甲基乙酰胺(DMAC)和N-甲基吡咯烷酮(NMP)中的一种。The polar solvent is one of N,N-dimethylacetamide (DMAC) and N-methylpyrrolidone (NMP).
一种制备填料取向增强的高导热聚酰亚胺复合薄膜的模头，所述的模头，设有狭长、横截面积渐变的模头通道。The invention relates to a die head for preparing a high thermal conductivity polyimide composite film with enhanced filler orientation.
所述的模头通道，横截面为矩形，横截面积沿挤出方向逐渐减小。The die channel has a rectangular cross-section, and the cross-sectional area gradually decreases along the extrusion direction.
本发明提供了一种填料取向增强的高导热聚酰亚胺复合薄膜及其制备方法，薄膜的制备原理为：将导热填料有效的分散在极性溶剂中，通过芳香族二酐与芳香族二胺的缩聚反应生成聚酰胺酸，聚酰胺酸溶液通过一段狭长的挤出通道并经过矩形截面模头挤出，片状导热填料在经过狭长流道时，受剪切作用发生薄膜面内取向，从而获得面内高导热性；其他非片状填料在片状填料之间形成导热连接，经过压延作用，进一步增强该导热连接，从而在薄膜厚度方向上形成更加致密的导热网络，获得高的面外导热性，也即薄膜面内的导热通过片状填料的取向增强，薄膜厚度方向上通过非片状导热填料的协同增强，从而制得高导热聚酰亚胺复合薄膜。The invention provides a high thermal conductivity polyimide composite film with enhanced filler orientation and a preparation method thereof. The preparation principle of the film is as follows: the thermal conductivity filler is effectively dispersed in a polar solvent, and the The polycondensation reaction of amine generates polyamic acid, and the polyamic acid solution is extruded through a narrow and long extrusion channel and through a rectangular cross-section die. Thereby, high in-plane thermal conductivity is obtained; other non-flaky fillers form thermally conductive connections between flaky fillers, and through calendering, the thermally conductive connection is further enhanced, thereby forming a denser thermal conductive network in the direction of film thickness, and obtaining high surface The external thermal conductivity, that is, the thermal conductivity in the film surface, is enhanced by the orientation of the sheet fillers, and the film thickness direction is enhanced by the synergistic enhancement of the non-sheet thermal conductivity fillers, thereby obtaining a high thermal conductivity polyimide composite film.
本发明的有益效果是：The beneficial effects of the present invention are:
（1）采用不同形貌的导热填料，且限定其中一种为片状填料，通过片状导热填料与非片状导热填料的相互接触，形成一个不间断的导热网络，有效的提高薄膜的导热性能；(1) Use thermally conductive fillers with different morphologies, and one of them is limited to sheet-like fillers. Through the mutual contact of sheet-like thermally conductive fillers and non-sheet-like thermally conductive fillers, an uninterrupted thermal conduction network is formed, which effectively improves the thermal conductivity of the film. performance;
（2）采用一条细长且变径的模头，当PAA流经模头通道时，片状填料在经过狭长流道时，受剪切作用在薄膜面内发生取向，从而获得面内高导热性，同时其他非片状填料在片状填料之间形成导热连接，经过压延作用，进一步增加该导热连接，从而在厚度方向上形成良好的导热网络，获得高的面外导热性，使薄膜整体的导热率提高同时又降低了薄膜的热膨胀系数。(2) A slender and variable diameter die is used. When the PAA flows through the die channel, the flake filler will be oriented in the film surface by shearing action, so as to obtain high thermal conductivity in the surface. At the same time, other non-flaky fillers form a thermally conductive connection between the flaky fillers. After calendering, the thermally conductive connection is further increased, thereby forming a good thermal conductivity network in the thickness direction, obtaining high out-of-plane thermal conductivity, and making the film as a whole. The thermal conductivity increases while reducing the thermal expansion coefficient of the film.
附图说明Description of drawings
图1为生产聚酰亚胺薄膜的工艺流程示意图；Fig. 1 is the process flow schematic diagram of producing polyimide film;
图2为填料在薄膜横截面的结构示意图；Fig. 2 is the structural representation of filler in the cross section of film;
图3为模头通道的示意图；Fig. 3 is the schematic diagram of the die channel;
图1和图3展示了制备薄膜的工艺装备流程以及模头通道的示意图。Figures 1 and 3 show a schematic diagram of the process equipment flow and die channel for preparing thin films.
具体实施方式Detailed ways
以下通过实施案例对本发明进行进一步的描述，但不是对本发明的限制。The present invention is further described below through examples, but it is not intended to limit the present invention.
如图3所示，一种制备填料取向增强的高导热聚酰亚胺复合薄膜的模头，所述的模头，设有狭长、横截面积渐变的模头通道。As shown in FIG. 3 , a die head for preparing a high thermal conductivity polyimide composite film with enhanced filler orientation, the die head is provided with a narrow and long die channel with a gradual cross-sectional area.
所述的模头通道，横截面为矩形，横截面积沿挤出方向逐渐减小。The die channel has a rectangular cross-section, and the cross-sectional area gradually decreases along the extrusion direction.
下述实施例的复合薄膜采用如图1所示的工艺流程制备，制备出的复合薄膜横截面的结构如图2所示。The composite films of the following examples are prepared by the process flow shown in FIG. 1 , and the structure of the cross-section of the prepared composite films is shown in FIG. 2 .
实施例1Example 1
本实施例提供一种填料取向增强的高导热聚酰亚胺复合薄膜，该薄膜由下述质量份配比的原料制备而成：导热填料10份、分散剂2份、芳香族二酐50份、芳香族二胺45份、DMAC400份；其中导热填料为球状的氧化铝和片状的氮化硼的混合物，氧化铝和氮化硼质量比为1：1；芳香族二酐为苯四甲酸二酐（PMDA），芳香族二胺为二氨基二苯醚（ODA）；该薄膜的制备方法包括如下步骤：This embodiment provides a high thermal conductivity polyimide composite film with enhanced filler orientation. The film is prepared from the following raw materials in parts by mass: 10 parts of thermally conductive filler, 2 parts of dispersant, and 50 parts of aromatic dianhydride , 45 parts of aromatic diamine, 400 parts of DMAC; wherein the thermal conductive filler is a mixture of spherical alumina and flake boron nitride, the mass ratio of alumina and boron nitride is 1:1; the aromatic dianhydride is pyromellitic acid Dianhydride (PMDA), aromatic diamine is diaminodiphenyl ether (ODA); the preparation method of the film includes the following steps:
（1）将10质量份的球状的氧化铝和片状的氮化硼混合填料分散在含有2质量份聚乙烯吡咯烷酮（PVP）的400质量份的DMAC中超声2小时，再加入45质量份的ODA，机械搅拌至ODA完全溶解在溶剂中，得到均匀混合体系；(1) Disperse 10 parts by mass of spherical alumina and flaky boron nitride mixed filler in 400 parts by mass of DMAC containing 2 parts by mass of polyvinylpyrrolidone (PVP) for 2 hours, and then add 45 parts by mass of ODA, mechanically stir until ODA is completely dissolved in the solvent to obtain a uniform mixing system;
（2）将50质量份的PMDA分3次依次加入到步骤（1）制得的混合体系中，待全部加入后，机械搅拌反应4h小时，静置1h进行自行消泡后，得到聚酰胺酸溶液；(2) Add 50 parts by mass of PMDA to the mixed system prepared in step (1) in three successive steps. After all the additions, mechanically stir the reaction for 4 hours, and stand for 1 hour for self-defoaming to obtain polyamic acid. solution;
（3）将消泡后的聚酰胺酸溶液加入进料斗中，通过狭长、横截面积逐渐变小的挤出机模头通道挤出后，用刮刀控制薄膜的厚度，使聚酰胺酸溶液在钢带上成膜，加热脱除薄膜中部分溶剂，得到具有一定自撑性的PAA凝胶膜，通过压延机得到预定厚度的胶膜，再按80℃/1h＋100℃/1h＋150℃/40min＋230℃/1h＋300℃/1h＋350℃/0.5h的梯度进行升温工艺热亚胺化，亚胺化完成自然冷却，得到高导热聚酰亚胺薄膜。(3) Add the defoamed polyamic acid solution into the feeding hopper, and extrude it through the narrow and narrow extruder die channel with gradually smaller cross-sectional area, and use a scraper to control the thickness of the film to make the polyamic acid solution. Form a film on a steel belt, heat to remove part of the solvent in the film to obtain a PAA gel film with a certain self-supporting property, obtain a film with a predetermined thickness through a calender, and then press 80°C/1h+100°C/1h+150°C/40min+230°C The gradient of /1h+300°C/1h+350°C/0.5h is carried out for thermal imidization in a heating process, and the imidization is completed by natural cooling to obtain a high thermal conductivity polyimide film.
经试验检测，本实施例所制备的聚酰亚胺薄膜，其面内导热系数为3.06W·m−1·K−1，面外导热系数为0.65 W·m−1·K−1。Tests show that the polyimide film prepared in this example has an in-plane thermal conductivity of 3.06 W·m−1 ·K−1 and an out-of-plane thermal conductivity of 0.65 W·m−1 ·K−1 .
实施例2Example 2
本实施例提供一种填料取向增强的高导热聚酰亚胺复合薄膜，该薄膜由下述质量份配比的原料制备而成：导热填料12份、分散剂3份、芳香族二酐75份、芳香族二胺45份、极性溶剂400份；其中填料为球状的氧化铝和片状的氮化硼的混合物，氧化铝和氮化硼质量比为1：1；芳香族二酐为二苯酮四酸二酐（BTDA），芳香族二胺为二氨基二苯醚（ODA）；该薄膜的制备方法包括如下步骤：This embodiment provides a high thermal conductivity polyimide composite film with enhanced filler orientation. The film is prepared from the following raw materials in parts by mass: 12 parts of thermally conductive filler, 3 parts of dispersant, and 75 parts of aromatic dianhydride , 45 parts of aromatic diamine, 400 parts of polar solvent; wherein the filler is a mixture of spherical alumina and flake boron nitride, the mass ratio of alumina and boron nitride is 1:1; aromatic dianhydride is two The benzophenone tetraacid dianhydride (BTDA), the aromatic diamine is diaminodiphenyl ether (ODA); the preparation method of the film includes the following steps:
（1）将12质量份的球状的氧化铝和片状的氮化硼混合填料分散在含有3质量份斯洛柯silok 7117w的400质量份的DMAC中超声2小时，再加入45质量份的ODA，机械搅拌至ODA完全溶解在溶剂中，得到均匀混合体系；(1) Disperse 12 parts by mass of spherical alumina and flaky boron nitride mixed fillers in 400 parts by mass of DMAC containing 3 parts by mass of Silok 7117w and ultrasonically for 2 hours, and then add 45 parts by mass of ODA , and mechanically stir until ODA is completely dissolved in the solvent to obtain a uniform mixing system;
（2）将75质量份的BTDA分3次依次加入到步骤（1）制得的混合体系中，待全部加入后，机械搅拌反应4h小时，静置1h进行自行消泡后，得到聚酰胺酸溶液；(2) Add 75 parts by mass of BTDA to the mixed system prepared in step (1) in three successive steps. After all the additions, mechanically stir and react for 4 hours. After standing for 1 hour for self-defoaming, polyamic acid is obtained. solution;
（3）将消泡后的聚酰胺酸溶液加入进料斗中，通过狭长、横截面积逐渐变小的挤出机模头通道挤出后，用刮刀控制薄膜的厚度，使聚酰胺酸溶液在钢带上成膜，加热脱除薄膜中部分溶剂，得到具有一定自撑性的PAA凝胶膜，通过压延机得到预定厚度的胶膜，再按80℃/1h＋100℃/1h＋150℃/1h＋230℃/1h＋300℃/1h＋350℃/0.5h的梯度进行升温工艺热亚胺化，亚胺化完成自然冷却，得到高导热聚酰亚胺薄膜。(3) Add the defoamed polyamic acid solution into the feed hopper, and after extruding through the narrow and narrow extruder die channel with gradually smaller cross-sectional area, use a scraper to control the thickness of the film to make the polyamic acid solution. Form a film on a steel strip, heat to remove part of the solvent in the film, and obtain a PAA gel film with a certain self-supporting property, obtain a film with a predetermined thickness through a calender, and then press 80°C/1h+100°C/1h+150°C/1h+230°C The gradient of /1h+300°C/1h+350°C/0.5h is carried out for thermal imidization in a heating process, and the imidization is completed by natural cooling to obtain a high thermal conductivity polyimide film.
经试验检测，本实施例所制备的聚酰亚胺薄膜，其面内导热系数为2.85W·m−1·K−1，面外导热系数为0.73 W·m−1·K−1。Tests show that the polyimide film prepared in this example has an in-plane thermal conductivity of 2.85 W·m−1 ·K−1 and an out-of-plane thermal conductivity of 0.73 W·m−1 ·K−1 .
实施例3Example 3
本实施例提供一种填料取向增强的高导热聚酰亚胺复合薄膜，该薄膜由下述质量份配比的原料制备而成：导热填料12份、分散剂3份、芳香族二酐60份、芳香族二胺46份、极性溶剂430份；其中填料为片状的氮化铝和球状氧化铝的混合物，氮化铝和氧化铝质量比为1：1；芳香族二酐为苯四甲酸二酐（PMDA），芳香族二胺为二氨基二苯醚（ODA）和对苯二胺（p-PDA），ODA和PDA的摩尔比为7：3；该薄膜的制备方法包括如下步骤：This embodiment provides a high thermal conductivity polyimide composite film with enhanced filler orientation. The film is prepared from the following raw materials in parts by mass: 12 parts of thermally conductive filler, 3 parts of dispersant, and 60 parts of aromatic dianhydride , 46 parts of aromatic diamine, 430 parts of polar solvent; the filler is a mixture of flake aluminum nitride and spherical alumina, and the mass ratio of aluminum nitride and alumina is 1:1; the aromatic dianhydride is benzene tetrakis Formic acid dianhydride (PMDA), the aromatic diamine is diaminodiphenyl ether (ODA) and p-phenylenediamine (p-PDA), the molar ratio of ODA and PDA is 7:3; the preparation method of the film includes the following steps :
（1）将12质量份片状的氮化铝和球状氧化铝混合填料分散在含有3质量份PVP分散剂的430质量份的DMAC中超声2小时，再加入46质量份的ODA和PDA混合物，机械搅拌至ODA和PDA完全溶解在溶剂中，得到均匀混合体系；(1) Disperse 12 parts by mass of flaky aluminum nitride and spherical alumina mixed fillers in 430 parts by mass of DMAC containing 3 parts by mass of PVP dispersant and ultrasonically for 2 hours, then add 46 parts by mass of ODA and PDA mixture, Mechanical stirring until ODA and PDA are completely dissolved in the solvent to obtain a uniform mixing system;
（2）将60质量份的PMDA分3次依次加入到步骤（1）制得的混合体系中，待全部加入后，机械搅拌反应4h小时，静置1h进行自行消泡后，得到聚酰胺酸溶液；(2) Add 60 parts by mass of PMDA into the mixed system prepared in step (1) in three successive steps. After all the additions, mechanically stir the reaction for 4 hours, and stand for 1 hour for self-defoaming to obtain polyamic acid. solution;
（3）将消泡后的聚酰胺酸溶液加入进料斗中，通过狭长、横截面积逐渐变小的挤出机模头通道挤出后，用刮刀控制薄膜的厚度，使聚酰胺酸溶液在钢带上成膜，加热脱除薄膜中部分溶剂，得到具有一定自撑性的PAA凝胶膜，通过压延机得到预定厚度的胶膜，再按80℃/1h＋100℃/1h＋150℃/40min＋230℃/1h＋300℃/1h＋350℃/0.5h的梯度进行升温工艺热亚胺化，亚胺化完成自然冷却，得到高导热聚酰亚胺薄膜。(3) Add the defoamed polyamic acid solution into the feed hopper, and after extruding through the narrow and narrow extruder die channel with gradually smaller cross-sectional area, use a scraper to control the thickness of the film to make the polyamic acid solution. Form a film on a steel belt, heat to remove part of the solvent in the film to obtain a PAA gel film with a certain self-supporting property, obtain a film with a predetermined thickness through a calender, and then press 80°C/1h+100°C/1h+150°C/40min+230°C The gradient of /1h+300°C/1h+350°C/0.5h is carried out for thermal imidization in a heating process, and the imidization is completed by natural cooling to obtain a high thermal conductivity polyimide film.
经试验检测，本实施例所制备的聚酰亚胺薄膜，其面内导热系数为3.19W·m−1·K−1，面外导热系数为0.84 W·m−1·K−1。Tests show that the polyimide film prepared in this example has an in-plane thermal conductivity of 3.19 W·m−1 ·K−1 , and an out-of-plane thermal conductivity of 0.84 W·m−1 ·K−1 .
实施例4Example 4
本实施例提供一种填料取向增强的高导热聚酰亚胺复合薄膜，该薄膜由下述质量份配比的原料制备而成：导热填料22份、分散剂5份、芳香族二酐80份、芳香族二胺45份、极性溶剂550份；其中填料为四针状的氧化锌和片状的氮化硼的混合物，氧化锌和氮化硼质量比为1：1；芳香族二酐为二苯酮四酸二酐（BTDA），芳香族二胺为二氨基二苯醚（ODA）和对苯二胺（p-PDA），ODA和PDA的摩尔比为3：7；该薄膜的制备方法包括如下步骤：This embodiment provides a high thermal conductivity polyimide composite film with enhanced filler orientation. The film is prepared from the following raw materials in parts by mass: 22 parts of thermally conductive filler, 5 parts of dispersant, and 80 parts of aromatic dianhydride , 45 parts of aromatic diamine, 550 parts of polar solvent; wherein the filler is a mixture of four needle-shaped zinc oxide and flake-shaped boron nitride, the mass ratio of zinc oxide and boron nitride is 1:1; aromatic dianhydride It is benzophenone tetraacid dianhydride (BTDA), the aromatic diamine is diaminodiphenyl ether (ODA) and p-phenylenediamine (p-PDA), and the molar ratio of ODA and PDA is 3:7; The preparation method includes the following steps:
（1）将22质量份的四针状的氧化锌和片状的氮化硼混合填料分散在含有5质量份斯洛柯silok 7117w的550质量份的NMP中超声2小时，再加入45质量份的ODA和PDA混合物，机械搅拌至ODA和PDA完全溶解在溶剂中；(1) Disperse 22 parts by mass of four-needle-shaped zinc oxide and flake-shaped boron nitride mixed filler in 550 parts by mass of NMP containing 5 parts by mass of Silok 7117w, and sonicate for 2 hours, and then add 45 parts by mass The mixture of ODA and PDA is mechanically stirred until ODA and PDA are completely dissolved in the solvent;
（2）将80质量份的PMDA分3次依次加入到步骤（1）制得的混合体系中，待全部加入后，机械搅拌反应4h小时，静置1h进行自行消泡后，得到聚酰胺酸溶液；(2) Add 80 parts by mass of PMDA into the mixed system prepared in step (1) in three successive steps. After all the additions, mechanically stir the reaction for 4 hours, and then stand for 1 hour for self-defoaming to obtain polyamic acid. solution;
（3）将消泡后的聚酰胺酸溶液加入进料斗中，通过狭长、横截面积逐渐变小的挤出机模头通道挤出后，用刮刀控制薄膜的厚度，使聚酰胺酸溶液在钢带上成膜，加热脱除薄膜中部分溶剂，得到具有一定自撑性的PAA凝胶膜，通过压延机得到预定厚度的胶膜，再按80℃/1h＋100℃/1h＋150℃/40min＋230℃/1h＋300℃/1h＋350℃/0.5h的梯度进行升温工艺热亚胺化，亚胺化完成自然冷却，得到高导热聚酰亚胺薄膜。(3) Add the defoamed polyamic acid solution into the feed hopper, and after extruding through the narrow and narrow extruder die channel with gradually smaller cross-sectional area, use a scraper to control the thickness of the film to make the polyamic acid solution. Form a film on a steel belt, heat to remove part of the solvent in the film to obtain a PAA gel film with a certain self-supporting property, obtain a film with a predetermined thickness through a calender, and then press 80°C/1h+100°C/1h+150°C/40min+230°C The gradient of /1h+300°C/1h+350°C/0.5h is carried out for thermal imidization in a heating process, and the imidization is completed by natural cooling to obtain a high thermal conductivity polyimide film.
经试验检测，本实施例所制备的聚酰亚胺薄膜，其面内导热系数为3.45W·m−1·K−1，面外导热系数为0.64W·m−1·K−1。Tests show that the polyimide film prepared in this example has an in-plane thermal conductivity of 3.45W·m−1 ·K−1 and an out-of-plane thermal conductivity of 0.64W·m−1 ·K−1 .
实施例5Example 5
本实施例提供一种填料取向增强的高导热聚酰亚胺复合薄膜，该薄膜由下述质量份配比的原料制备而成：导热填料22份、分散剂5份、芳香族二酐60份、芳香族二胺46份、极性溶剂430份；其中填料为片状氮化铝、球状氧化铝和片状氮化硼的混合物，氮化铝、氧化铝和氮化硼的质量比为0.5：2：0.5；芳香族二酐为苯四甲酸二酐（PMDA），芳香族二胺为二氨基二苯醚（ODA）和对苯二胺（p-PDA），ODA和p-PDA的摩尔比为7：3；该薄膜的制备方法包括如下步骤：This embodiment provides a high thermal conductivity polyimide composite film with enhanced filler orientation. The film is prepared from the following raw materials in parts by mass: 22 parts of thermally conductive filler, 5 parts of dispersant, and 60 parts of aromatic dianhydride , 46 parts of aromatic diamine, 430 parts of polar solvent; the filler is a mixture of flake aluminum nitride, spherical aluminum oxide and flake boron nitride, and the mass ratio of aluminum nitride, aluminum oxide and boron nitride is 0.5 : 2: 0.5; the aromatic dianhydride is pyromellitic dianhydride (PMDA), the aromatic diamine is diaminodiphenyl ether (ODA) and p-phenylenediamine (p-PDA), the moles of ODA and p-PDA The ratio is 7:3; the preparation method of the film comprises the following steps:
（1）将22质量份的片状氮化铝、球状氧化铝和片状氮化硼的混合填料分散在含有5质量份PVP的430质量份的NMP中超声2小时，再加入46质量份的ODA和p-PDA混合物，机械搅拌至ODA和PDA完全溶解在溶剂中，得到均匀混合体系；(1) Disperse 22 parts by mass of the mixed filler of flaky aluminum nitride, spherical alumina and flaky boron nitride in 430 parts by mass of NMP containing 5 parts by mass of PVP and ultrasonically for 2 hours, and then add 46 parts by mass of The mixture of ODA and p-PDA is mechanically stirred until ODA and PDA are completely dissolved in the solvent to obtain a uniform mixing system;
（2）将60质量份的PMDA分3次依次加入到体系，待全部加入后，机械搅拌反应4h小时，静置1h进行自行消泡后，得到聚酰胺酸溶液；(2) Add 60 parts by mass of PMDA to the system in 3 times in turn, after all the additions, mechanically stir for 4 hours, and stand for 1 hour for self-defoaming to obtain a polyamic acid solution;
（3）将消泡后的聚酰胺酸溶液加入进料斗中，通过狭长、横截面积逐渐变小的挤出机模头通道挤出后，用刮刀控制薄膜的厚度，使聚酰胺酸溶液在钢带上成膜，加热脱除薄膜中部分溶剂，得到具有一定自撑性的PAA凝胶膜，通过压延机得到预定厚度的胶膜，再按80℃/1h＋100℃/1h＋150℃/40min＋230℃/1h＋300℃/1h＋350℃/0.5h的梯度进行升温工艺热亚胺化，亚胺化完成自然冷却，得到高导热聚酰亚胺薄膜。(3) Add the defoamed polyamic acid solution into the feeding hopper, and extrude it through the narrow and narrow extruder die channel with gradually smaller cross-sectional area, and use a scraper to control the thickness of the film to make the polyamic acid solution. Form a film on a steel belt, heat to remove part of the solvent in the film to obtain a PAA gel film with a certain self-supporting property, obtain a film with a predetermined thickness through a calender, and then press 80°C/1h+100°C/1h+150°C/40min+230°C The gradient of /1h+300°C/1h+350°C/0.5h is carried out for thermal imidization in a heating process, and the imidization is completed by natural cooling to obtain a high thermal conductivity polyimide film.
经试验检测，本实施例所制备的聚酰亚胺薄膜，其面内导热系数为4.05W·m−1·K−1，面外导热系数为0.97 W·m−1·K−1。Tests show that the polyimide film prepared in this example has an in-plane thermal conductivity of 4.05 W·m−1 ·K−1 and an out-of-plane thermal conductivity of 0.97 W·m−1 ·K−1 .
| Application Number | Priority Date | Filing Date | Title |
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| CN201910911469.3ACN110540752A (en) | 2019-09-25 | 2019-09-25 | A kind of filler orientation-enhanced high thermal conductivity polyimide composite film and preparation method thereof |
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| CN201910911469.3ACN110540752A (en) | 2019-09-25 | 2019-09-25 | A kind of filler orientation-enhanced high thermal conductivity polyimide composite film and preparation method thereof |
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| CN201910911469.3APendingCN110540752A (en) | 2019-09-25 | 2019-09-25 | A kind of filler orientation-enhanced high thermal conductivity polyimide composite film and preparation method thereof |
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| Date | Code | Title | Description |
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| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
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| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication | Application publication date:20191206 |