WO2020151079A1 - 聚酰亚胺厚膜和量子碳基膜、及其制备方法 - Google Patents

聚酰亚胺厚膜和量子碳基膜、及其制备方法 Download PDF

Info

Publication number
WO2020151079A1
WO2020151079A1 PCT/CN2019/079993 CN2019079993W WO2020151079A1 WO 2020151079 A1 WO2020151079 A1 WO 2020151079A1 CN 2019079993 W CN2019079993 W CN 2019079993W WO 2020151079 A1 WO2020151079 A1 WO 2020151079A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyimide
film
preparation
thick
intermediate composition
Prior art date
Application number
PCT/CN2019/079993
Other languages
English (en)
French (fr)
Inventor
刘萍
Original Assignee
深圳丹邦科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 深圳丹邦科技股份有限公司 filed Critical 深圳丹邦科技股份有限公司
Publication of WO2020151079A1 publication Critical patent/WO2020151079A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the invention relates to the preparation field of polyimide films, in particular to a polyimide thick film and quantum carbon-based film, and a preparation method thereof.
  • the chemical method of polyimide film is widely used in various applications, such as the field of electronic component insulation, semiconductor packaging, because of its outstanding heat resistance, chemical resistance, high mechanical bending strength, excellent electrical and physical properties, Dimensional stability and other advantages, such as polyimide film and copper foil composite to produce flexible substrates and flexible protective films, which are used in flexible circuit boards (FPC), flexible displays, and flexible solar power generation.
  • chemical polyimide films are sintered at high temperatures to form carbon-based films for mobile phone heat dissipation, notebook heat dissipation, communication router heat dissipation and chip heat dissipation.
  • the existing method of preparing polyimide film is usually prepared by the casting method.
  • the moisture permeability of the reverse side is relatively small, resulting in the interface between the metal and the polyimide film. It is easy to produce bubbles, which will cause the tendency of peeling.
  • the present invention provides a polyimide thick film and a quantum carbon-based film, and a preparation method thereof, which have good flatness and no tilt and warpage.
  • the present invention adopts the following technical solutions:
  • An embodiment of the present invention discloses a method for preparing a polyimide thick film, including the following steps:
  • A1 Hybridize an anhydride containing a phenyl group with a diamine to obtain a thermoplastic polyimide resin precursor
  • thermoplastic polyimide resin precursor obtained in step A1 with the monomer reactant, and form a monomer structure at both ends of the polyimide resin precursor through a bridging reaction to obtain an imide intermediate composition ;
  • step A3 Imidize the imide intermediate composition obtained in step A2 to obtain a resin solution mixture
  • step A4 The resin solution mixture obtained in step A3 is continuously and uniformly sprayed on the conveyor belt by a blow-out spray method, and cured and dried to obtain a polyimide thick film.
  • step A1 specifically includes: 20-30 parts by volume of 2,2-bis[4-(4-aminophenoxy)phenyl]propane and 20 parts by volume of 4,4'-diaminodiphenyl ether. ⁇ 30 parts and 3 ⁇ 7 parts by volume of diaminodianthracene ether are dissolved in N,N-dimethylformamide, and then 3,3',4,4'-benzophenone tetraacid dianhydride is added by volume 25-35 parts, then add 10-20 parts by volume of pyromellitic dianhydride, after a period of reaction, add 3,3',4,4'-benzophenonetetracarboxylic dianhydride and/or Pyromellitic dianhydride, so that the total number of moles of 3,3',4,4'-benzophenone tetracarboxylic dianhydride and pyromellitic dianhydride added is approximately equal to 2,2- Volume parts of bis[4-(4-aminophenoxy
  • the monomer reactant in step A2 is endomethine tetrahydrophthalic anhydride, and further, the mass ratio of the thermoplastic polyimide resin precursor to the monomer reactant is 10:1; further, step A2
  • the environment of the mixing reaction is a vacuum environment of -100 to -60°C.
  • step A3 specifically includes: first chemical imidization of the imide intermediate composition obtained in step A2, and then thermal imidization, to obtain a resin solution mixture.
  • the chemical imidization of the imide intermediate composition specifically includes: adding 3 to 10 moles of dehydrating agent and 1 to 2 moles per 100 moles of the imide intermediate composition
  • the dehydrating agent uses picoline
  • the cyclization catalyst uses benzoic anhydride.
  • the thermal imidization of the imide intermediate composition specifically includes: adding 1 to 3 moles of a thermal imidization catalyst per 100 moles of the imide intermediate composition, and further
  • the thermal imidization catalyst uses at least one of organic phosphorus compounds, inorganic nanoparticles or silicide nanoparticles.
  • the preparation method further includes the following steps:
  • step A5 The polyimide thick film of step A4 is peeled off from the conveyor belt and stretched in both directions. In the stretching process, infrared heating and inert gas protection are used, and then cured and heated to evaporate the solvent and deep cyclization , A thick polyimide film containing a multi-layer structure inclined monomer is obtained.
  • An embodiment of the present invention discloses a polyimide thick film prepared by the above-mentioned preparation method.
  • An embodiment of the present invention discloses a method for preparing a quantum carbon-based film, including:
  • Heat treatment is performed while pressing and pressing the laminated thick polyimide film.
  • the temperature of the heat treatment is lower than the temperature at which the thick polyimide film starts to thermally decompose, so that the thick polyimide film layer and the layer Combine to obtain a composite membrane;
  • An embodiment of the present invention discloses a quantum carbon-based film, which is prepared by the above-mentioned preparation method.
  • the beneficial effect of the present invention is that the present invention provides a method for preparing a thick polyimide film with improved warpage, and a blowout spraying method is used to prepare the thick polyimide film, which avoids the need for the preparation process. Bubbles are formed, and there are no volatile components to avoid warping; thus, a thick polyimide film with good flatness and no tilt and warpage can be produced. Furthermore, the polyimide thick film prepared by this preparation method can also meet the high-frequency and high-pressure base film technology of preparing quantum carbonized film by carbonization at high temperature, so that it can produce quantum carbon with high frequency 10GHz and high voltage above 100,000 volts. Basement membrane.
  • Fig. 1 is a schematic flow chart of a method for preparing a polyimide thick film according to a preferred embodiment of the present invention
  • Fig. 2 is a schematic flow chart of a method for preparing a quantum carbon-based film according to a preferred embodiment of the present invention.
  • a preferred embodiment of the present invention discloses a method for preparing a polyimide thick film, wherein the thickness of the polyimide thick film is 150-300 ⁇ m, and includes the following steps:
  • A1 Hybridize an anhydride containing a phenyl group with a diamine to obtain a thermoplastic polyimide resin precursor
  • step A1 specifically includes: adding 20-30 parts by volume of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 4,4'-diaminodiphenyl ether (4,4'-ODA) 20-30 parts by volume and diaminodianthracene ether (also called heterodiamine, the structural formula is ) Dissolve 3-7 parts by volume in N,N-dimethylformamide (DMF), and add 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) by volume 25 ⁇ 35 parts, then add 10-20 parts by volume of pyromellitic dianhydride (PMDA), and add 3,3',4,4'-benzophenone dianhydride (BTDA) after a period of reaction ) And/or pyromellitic dianhydride (PMDA) to make the added 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA)
  • the heterodiamine (diaminodianthracene ether) has a molecular weight of more than 1 million, gel synthesis is performed at -100°C, and a uniform film can be formed by a blowout spray method.
  • thermoplastic polyimide resin precursor obtained in step A1 with the monomer reactant, and form a monomer structure at both ends of the low molecular weight polyimide resin precursor through a bridging reaction to obtain an imide intermediate combination;
  • the monomer reactant is internal methine tetrahydrophthalic anhydride (that is, NA acid anhydride, the structural formula is ), the monomer reactant added therein is 10% by mass of the thermoplastic polyimide resin precursor; and the environment of the mixing reaction is a vacuum environment of -100°C to -60°C; the obtained imide intermediate
  • the structural formula of the composition is as follows:
  • the side chain is formed at the place where the diamine and the phenyl group of the anhydride are connected, and the intercalation is formed at the side chain, so that the two benzene rings form a double inclined structure; in this embodiment, the thermoplastic polyimide precursor
  • the monomer reactant is added to expand its molecular weight density, so that the monomer reactant polymerizes gradually to achieve thermal hardening characteristics, and the coating film has a better modulus at a temperature below -60°C.
  • step A3 Imidize the imide intermediate composition obtained in step A2 to obtain a resin solution mixture
  • the imide intermediate composition is first chemically imidized and then thermally imidized to obtain a resin solution mixture.
  • chemical imidization refers to adding a polyamic acid cyclization catalyst and a dehydrating agent to the imide intermediate composition to chemically dehydrate and cyclize the imide intermediate composition, heating and adding a drying combination if necessary The solvent is further removed to imidize the imide intermediate composition; specifically: 3-10 moles of dehydrating agent (such as picoline) is added to every 100 moles of imide intermediate composition ) And 1 to 2 moles of cyclization catalyst (for example, benzoic anhydride).
  • dehydrating agent such as picoline
  • cyclization catalyst for example, benzoic anhydride
  • Thermal imidization is by spraying and then heating. During the thermal imidization process, 1 to 3 moles of thermal imidization catalyst (for every 100 moles of imide intermediate composition) At least one of organophosphorus compounds, inorganic nanoparticles, or silicide nanoparticles).
  • step A4 The resin solution mixture obtained in step A3 is continuously and uniformly sprayed on the conveyor belt by a blow-out spray method, and cured and dried to obtain a polyimide thick film.
  • the resin solution mixture obtained in A3 is continuously and uniformly sprayed on the conveying steel belt with a blowout spraying device, and dried by a high-temperature curing device to obtain a self-supporting gel polyimide thick film;
  • the glue solution (resin solution mixture) is controlled under the freezing vacuum condition of -100°C ⁇ -60°C, the power is 0.8kw, and the viscosity flow rate reaches 10L/min.
  • step A5 The thick polyimide film of step A4 is peeled off the conveyor belt and stretched in both directions. In the stretching process, infrared heating is used and protected by inert gas (nitrogen or argon), and then cured and heated to evaporate the solvent And deep cyclization, to obtain a polyimide thick film containing a multilayer structure inclined monomer.
  • the hot melt viscosity of the prepared polyimide thick film is 10000 Pa.s, and the T g temperature is 260-360°C.
  • the blowout method is used to prepare the polyimide thick film, which avoids the formation of bubbles during the preparation process, does not contain volatile components, and avoids warping; therefore, through the above preparation method, A thick polyimide film with good flatness and no tilt and warpage is obtained.
  • Another preferred embodiment of the present invention discloses a polyimide thick film prepared by the above-mentioned preparation method.
  • a preferred embodiment of the present invention further discloses a method for preparing a quantum carbon-based film, which includes the following steps:
  • Heat treatment is performed while pressing and pressing the laminated thick polyimide film.
  • the temperature of the heat treatment is lower than the temperature at which the thick polyimide film starts to thermally decompose, so that the thick polyimide film layer and the layer Combine to form a composite membrane;
  • a quantum carbon-based film with a high frequency of 10 GHz and a high voltage of more than 100,000 volts is prepared by a roll-to-roll sintering method.
  • thermoplastic polyimide prepolymer obtained in step S1 with the monomer reactant NA anhydride under a vacuum environment of -100°C to -60°C, and obtain two low molecular weight polyimides through a bridge reaction. A monomer structure is formed at the end to obtain an imide intermediate composition. Specifically, the molar ratio of the thermoplastic polyimide precursor to NA acid anhydride is 100:10.
  • step S3 Add a cyclization catalyst, a dehydrating agent and a thermal imidization catalyst to the imide intermediate composition solution in step S2, and mix and stir to obtain a resin solution mixture.
  • dehydrating agent benzoic anhydride 3 moles are added to every 100 moles of polyamic acid solution.
  • step S4 Using a blowout spraying equipment to spray the resin solution mixture obtained in step S3 on the conveyor steel belt continuously and uniformly, and dry it through a high-temperature curing device to obtain a self-supporting gel polyimide thick film.
  • the glue to be sprayed is controlled under the freezing vacuum condition of -100°C to -60°C, the power is 0.8kw, and the viscosity flow rate reaches 10L/min.
  • S5 The thick film of gel polyamideimide in S4 is peeled off from the supporting steel belt and stretched in two directions. The stretching is heated by infrared and protected by nitrogen or argon, and then heated by a post-curing setting device, and further Evaporation of solvent and deep cyclization to obtain polyimide thick film containing multi-layer structure tilt monomer. 111 1
  • Example 1 the basic properties of the polyimide thick film prepared in Example 1 are as follows:
  • This preparation method shows that the polyimide thick film prepared by the aforementioned preparation method can meet the high-frequency and high-voltage base film technology for preparing quantum carbonized films by carbonization at high temperatures, so that high-frequency 10GHz and high-voltage above 100,000 volts can be produced. Quantum carbon-based film.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Nanotechnology (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

提供了聚酰亚胺厚膜和量子碳基膜、及其制备方法，其中聚酰亚胺厚膜的制备方法，包括：将含有苯基的酐与二胺杂化，得到热塑性聚酰亚胺树脂前驱体；将热塑性聚酰亚胺树脂前驱体与单体反应物混合，通过架桥反应使聚酰亚胺树脂前驱体的两末端形成单体结构，得到酰亚胺中间体组合物；将酰亚胺中间体组合物进行酰亚胺化，得到树脂溶液混合物；采用井喷式喷涂方法将树脂溶液混合物连续均匀喷涂在传送带上，经固化、干燥，得到聚酰亚胺厚膜。聚酰亚胺厚膜和量子碳基膜，平整性好且无倾斜翘曲。

Description

一种聚酰亚胺厚膜和量子碳基膜、及其制备方法 技术领域
本发明涉及聚酰亚胺膜的制备领域，尤其涉及一种聚酰亚胺厚膜和量子碳基膜、及其制备方法。
背景技术
采用化学法聚酰亚胺薄膜广泛用于各种用途，如电子元器件绝缘领域、半导体封装领域，因其具有突出的耐热性、耐化学品性、高机械弯曲强度、电学物理性质优良、尺寸稳定等优点，例如聚酰亚胺薄膜与铜箔复合制作柔性基材、柔性保护膜，用于挠性线路板(FPC)、柔性显示、柔性太阳能发电领域。最近，特别是将化学法聚酰亚胺薄膜通过高温烧结，制成碳基膜用于手机散热、笔记本散热、通信路由器散热以及芯片散热。
现有的制备聚酰亚胺膜的方法通常是采用流延法来制备，其中采用流延法制备厚膜合体膜时，由于反面透湿速度比较小，导致在金属与聚酰亚胺膜界面容易产生气泡，从而造成剥离的倾向。
以上背景技术内容的公开仅用于辅助理解本发明的构思及技术方案，其并不必然属于本专利申请的现有技术，在没有明确的证据表明上述内容在本专利申请的申请日已经公开的情况下，上述背景技术不应当用于评价本申请的新颖性和创造性。
发明内容
为解决上述技术问题，本发明提出一种聚酰亚胺厚膜和量子碳基膜、及其制备方法，平整性好且无倾斜翘曲。
为达到上述目的，本发明采用以下技术方案：
本发明的一个实施例公开了一种聚酰亚胺厚膜的制备方法，包括以下步骤：
A1：将含有苯基的酐与二胺杂化，得到热塑性聚酰亚胺树脂前驱体；
A2：将步骤A1得到的热塑性聚酰亚胺树脂前驱体与单体反应物混合，通过 架桥反应使聚酰亚胺树脂前驱体的两末端形成单体结构，得到酰亚胺中间体组合物；
A3：将步骤A2得到的酰亚胺中间体组合物进行酰亚胺化，得到树脂溶液混合物；
A4：采用井喷式喷涂方法将步骤A3得到的树脂溶液混合物连续均匀喷涂在传送带上，经固化、干燥，得到聚酰亚胺厚膜。
优选地，步骤A1具体包括：将2,2-双[4-(4-氨基苯氧基)苯基]丙烷体积份20～30份、4,4’-二氨基二苯基醚体积份20～30份和二氨基二蒽醚体积份3～7份溶解于N,N-二甲基甲酰胺中，再添加3,3’,4,4’-二苯甲酮四酸二酐体积份25～35份，然后添加均苯四甲酸二酸二酐体积份10～20份，反应一段时间后再补充加入3,3’,4,4’-二苯甲酮四酸二酐和/或均苯四甲酸二酸二酐，以使得加入的3,3’,4,4’-二苯甲酮四酸二酐和均苯四甲酸二酸二酐的总摩尔数大致等于2,2-双[4-(4-氨基苯氧基)苯基]丙烷体积份、4,4’-二氨基二苯基醚体积份和二氨基二蒽醚的总摩尔数，得到热塑性聚酰亚胺树脂前驱体。
优选地，步骤A2中的单体反应物为内次甲基四氢苯酐，进一步地，热塑性聚酰亚胺树脂前驱体与单体反应物的质量比例为10:1；更进一步地，步骤A2中的混合反应的环境为-100～-60℃的真空环境。
优选地，步骤A3中具体包括：将步骤A2得到的酰亚胺中间体组合物先进行化学酰亚胺化，然后进行热酰亚胺化，得到树脂溶液混合物。
优选地，其中将酰亚胺中间体组合物进行化学酰亚胺化具体包括：在每100摩尔量的酰亚胺中间体组合物中添加3～10摩尔量的脱水剂和1～2摩尔量的环化催化剂，进一步地，所述脱水剂采用甲基吡啶，所述环化催化剂采用苯甲酸酐。
优选地，将酰亚胺中间体组合物进行热酰亚胺化具体包括：在每100摩尔量的酰亚胺中间体组合物中加入1～3摩尔量的热酰亚胺化催化剂，进一步地，所述热酰亚胺化催化剂采用有机磷化合物、无机纳米粒子或硅化物纳米粒子中的至少一种。
优选地，所述制备方法还包括以下步骤：
A5：将步骤A4的聚酰亚胺厚膜从所述传送带上剥离下来，进行双向拉伸，拉伸过程中采用红外加温并进行惰性气体保护，然后经过固化加热以蒸发溶剂和 深度环化，得到含有多层结构倾斜单体的聚酰亚胺厚膜。
本发明的一个实施例公开了一种聚酰亚胺厚膜，采用上述的制备方法制得。
本发明的一个实施例公开了一种量子碳基膜的制备方法，包括：
B1：将多层采用上所述的制备方法制得的聚酰亚胺厚膜进行层叠；
B2：在对层叠的聚酰亚胺厚膜施压按合的同时进行热处理，热处理的温度低于聚酰亚胺厚膜开始热分解的温度，使得聚酰亚胺厚膜层与层之间产生结合，得到复合膜；
B3：在对得到的复合膜进行按压的同时继续升温到聚酰亚胺厚膜开始热分解温度以上进行热处理，得到碳化复合膜；
B4：在对碳化复合膜继续升温到2800～3000℃的同时向碳化复合膜中掺杂或注入纳米金属粒子，以在所述碳化复合膜的表面形成均匀的纳米量子点，形成具有多层石墨烯结构的量子碳基膜。
本发明的一个实施例公开了一种量子碳基膜，采用上述的制备方法制得。
与现有技术相比，本发明的有益效果在于：本发明提供具有改善翘曲的聚酰亚胺厚膜的制备方法，采用井喷式喷涂方法制备聚酰亚胺厚膜，避免了在制备过程中形成气泡，且不会有挥发性的组分，避免造成翘曲的现象；从而能够制得平整性好、无倾斜翘曲的聚酰亚胺厚膜。进一步通过该制备方法制得的聚酰亚胺厚膜还可满足在高温碳化制备量子碳化膜的高频、高压基膜技术，从而能够制得高频10GHz，高压在10万伏以上的量子碳基膜。
附图说明
图1是本发明优选实施例的聚酰亚胺厚膜的制备方法的流程示意图；
图2是本发明优选实施例的量子碳基膜的制备方法的流程示意图。
具体实施方式
下面对照附图并结合优选的实施方式对本发明作进一步说明。
如图1所示，本发明优选实施例公开了一种聚酰亚胺厚膜的制备方法，其中聚酰亚胺厚膜的厚度为150～300μm，包括以下步骤：
A1：将含有苯基的酐与二胺杂化，得到热塑性聚酰亚胺树脂前驱体；
具体地，步骤A1具体包括：将2,2-双[4-(4-氨基苯氧基)苯基]丙烷(BAPP)体积份20～30份、4,4’-二氨基二苯基醚(4,4’-ODA)体积份20～30份和二氨基二蒽醚(也称为异性二元胺，结构式为
Figure PCTCN2019079993-appb-000001
)体积份3～7份溶解于N,N-二甲基甲酰胺(DMF)中，再添加3,3’,4,4’-二苯甲酮四酸二酐(BTDA)体积份25～35份，然后添加均苯四甲酸二酸二酐(PMDA)体积份10～20份，反应一段时间后再补充加入3,3’,4,4’-二苯甲酮四酸二酐(BTDA)和/或均苯四甲酸二酸二酐(PMDA)，以使得加入的3,3’,4,4’-二苯甲酮四酸二酐(BTDA)和均苯四甲酸二酸二酐(PMDA)的总摩尔数大致等于2,2-双[4-(4-氨基苯氧基)苯基]丙烷(BAPP)、4,4’-二氨基二苯基醚(4,4’-ODA)和二氨基二蒽醚的总摩尔数，得到热塑性聚酰亚胺树脂前驱体。
其中，异性二元胺(二氨基二蒽醚)的分子量超过100万以上，在-100℃进行凝胶合成，通过井喷式喷涂法能够均匀成膜。
A2：将步骤A1得到的热塑性聚酰亚胺树脂前驱体与单体反应物混合，通过架桥反应使低分子量聚酰亚胺树脂前驱体的两末端形成单体结构，得到酰亚胺中间体组合物；
具体地，单体反应物为内次甲基四氢苯酐(也即NA酸酐，结构式为
Figure PCTCN2019079993-appb-000002
)，其中加入的单体反应物为热塑性聚酰亚胺树脂前驱体的10％质量份；并且，该混合反应的环境为-100℃～-60℃的真空环境；得到的酰亚胺中间体组合物的结构式如下：
Figure PCTCN2019079993-appb-000003
其中，在通过二胺和酐的苯基相连的地方形成侧链，在侧链处形成相嵌，使两个苯环形成双重倾斜结构；在本实施例中，在热塑性聚酰亚胺前驱体中加入单体反应物，使它分子量密度扩大，使单体反应物聚合逐步达到热硬化特性，在-60℃以下温度下喷涂中胶膜量有较好模量。
A3：将步骤A2得到的酰亚胺中间体组合物进行酰亚胺化，得到树脂溶液混合物；
具体地，将酰亚胺中间体组合物先进行化学酰亚胺化，然后进行热酰亚胺化，得到树脂溶液混合物。
其中，化学法酰亚胺化是指在酰亚胺中间体组合物中添加聚酰胺酸环化催化剂和脱水剂，使酰亚胺中间体组合物化学脱水环化，必要时加热和加入干燥组合物，进一步除去溶剂，使酰亚胺中间体组合物酰亚胺化；具体地：在每100摩尔量的酰亚胺中间体组合物中添加3～10摩尔量的脱水剂(例如甲基吡啶)和1～2摩尔量的环化催化剂(例如苯甲酸酐)。
热酰亚胺化是通过喷涂后再进行加热，在热酰亚胺化过程中，每100摩尔量的酰亚胺中间体组合物中加入1～3摩尔量的热酰亚胺化催化剂(为有机磷化合物、无机纳米粒子或硅化物纳米粒子中的至少一种)。
A4：采用井喷式喷涂方法将步骤A3得到的树脂溶液混合物连续均匀喷涂在传送带上，经固化、干燥，得到聚酰亚胺厚膜。
具体地，采用井喷式喷涂设备将A3中得到的树脂溶液混合物连续均匀喷涂在传送钢带上，经过高温固化装置进行干燥，得到自支撑性的凝胶聚酰亚胺厚膜；其中待喷涂的胶液(树脂溶液混合物)控制在-100℃～-60℃冷冻真空条件，功率0.8kw，粘度流量达到10L/min。
A5：将步骤A4的聚酰亚胺厚膜从传送带上剥离下来，进行双向拉伸，拉伸过程中采用红外加温并进行惰性气体(氮气或氩气)保护，然后经过固化加热以蒸发溶剂和深度环化，得到含有多层结构倾斜单体的聚酰亚胺厚膜。其中，制备得到的聚酰亚胺厚膜的热熔体粘度为10000Pa.s，T g温度为260～360℃。
在上述制备方法中，采用井喷法制备聚酰亚胺厚膜，避免了在制备过程中形成气泡，且不会有挥发性的组分，避免造成翘曲的现象；因此，通过上述制备方法，制得平整性好、无倾斜翘曲的聚酰亚胺厚膜。
本发明的另一优选实施例公开一种聚酰亚胺厚膜，采用上述制备方法制得。
如图2所示，本发明的优选实施例进一步公开了一种量子碳基膜的制备方法，包括以下步骤：
B1：将多层采用前述的制备方法制得的聚酰亚胺厚膜进行层叠；
B2：在对层叠的聚酰亚胺厚膜施压按合的同时进行热处理，热处理的温度低于聚酰亚胺厚膜开始热分解的温度，使得聚酰亚胺厚膜层与层之间产生结合，形成复合膜；
B3：在对得到的复合膜进行按压的同时继续升温到聚酰亚胺厚膜开始热分解温度以上进行热处理，得到碳化复合膜；
B4：在对碳化复合膜继续升温到2800～3000℃的同时向碳化复合膜中掺杂或注入纳米金属粒子，以在碳化复合膜的表面形成均匀的纳米量子点，形成具有多层石墨烯结构的量子碳基膜。
在上述制备方法中，通过卷到卷烧结法制备高频10GHz，高压在10万伏以上的量子碳基膜。
下述以具体实例对本发明的优选实施例作进一步的说明。
实施例一：
S1：在冷却10℃以下的N,N-二甲基甲酰胺(DMF)中溶解2,2-双[4-(4-氨基苯氧基)苯基]丙烷(BAPP)25mol和4,4’-二氨基二苯基醚(4,4’-ODA)25mol及二氨基二蒽醚5mol，添加3,3’,4,4’-二苯甲酮四酸二酐(BTDA)30mol，并溶解后添加均苯四甲酸二酸二酐(PMDA)15mol并搅拌2小时形成热塑性聚酰亚胺前聚体预聚物；反应一段时间后再补充加入3,3’,4,4’-二苯甲酮四酸二酐和/或均苯四甲酸二酐，从而最终实际上相当于合成摩尔比为大致等摩尔，得到热塑性聚酰亚胺预聚物；
S2：在-100℃～-60℃真空环境下，将步骤S1中得到的热塑性聚酰亚胺预聚物与单体反应物NA酸酐混合，通过架桥反应使低分子量聚酰亚胺得到两末端形成单体构造，获得酰亚胺中间体组合物。具体地，热塑性聚酰亚胺前聚体与NA酸酐的摩尔比为100:10。
S3：在步骤S2中的酰亚胺中间体组合物溶液中加入环化催化剂、脱水剂和热酰亚胺化催化剂进行混合搅拌得到树脂溶液混合物。具体地，每100摩尔量的 聚酰胺酸溶液中加入3摩尔量的脱水剂苯甲酸酐、1摩尔量的催化剂甲基吡啶和1摩尔量的有机含磷化合物、无机或硅化物纳米粒子中的一种或多种。
S4：采用井喷式喷涂设备将步骤S3中得到的树脂溶液混合物连续均匀喷涂在传送钢带上，经过高温固化装置进行干燥，得到自支撑性的凝胶聚酰亚胺厚膜。具体地，待喷涂的胶液控制在-100℃～-60℃冷冻真空条件，功率0.8kw，粘度流量达到10L/min。
S5：将S4中的凝胶聚酰胺亚胺厚膜从支撑钢带上剥离下来，进行双向拉伸，拉伸采用红外加温并进行氮气或氩气保护，然后经过后固化定型装置加热，进一步蒸发溶剂和深度环化得到含有多层结构倾斜单体的聚酰亚胺厚膜。111 1
其中，实施例一制得的聚酰亚胺厚膜的基本性能如下：
指标 单位 结果
外观 / 表面平整光滑
厚度 μm 150-300
拉伸强度 MPa 250
弹性模量 GPa 3
断裂伸长率 ％ 40
体积电阻 Ω·cm ≥3×10 14
表面电阻 Ω ≥1.3×10 14
吸湿性 ％ ≤1.2％
热膨胀系数 ppm/℃ ≤20ppm/℃
实施例二：
将上述制备的聚酰亚胺厚膜(厚度)一边切成15cm*15cm的正方形，叠层、热压，从常温以30℃/min速度升到300℃，保持30分钟，通过热媒油循环冷却，得到无断裂、无剥离、柔软性好、无翘曲、无起泡的PI复合膜，按着将温度升到1000℃保持30分钟，冷却后得到无褶、碳化完整、颜色一致、厚度均匀的碳化复合膜。进一步将碳化膜复合膜加热到2800℃-3000℃，保温1小时，并在此过程中掺杂或注入纳米金属粒子，在纯净的碳基膜表面形成分布均匀的纳米量子点，最终形成具有多层石墨烯结构的量子碳基膜。
通过该制备方法，说明前述制备方法制得的聚酰亚胺厚膜可满足在高温碳化制备量子碳化膜的高频、高压基膜技术，从而能够制得高频10GHz，高压在10万伏以上的量子碳基膜。
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的技术人员来说，在不脱离本发明构思的前提下，还可以做出若干等同替代或明显变型，而且性能或用途相同，都应当视为属于本发明的保护范围。

Claims (10)

  1. 一种聚酰亚胺厚膜的制备方法，其特征在于，包括以下步骤：
    A1：将含有苯基的酐与二胺杂化，得到热塑性聚酰亚胺树脂前驱体；
    A2：将步骤A1得到的热塑性聚酰亚胺树脂前驱体与单体反应物混合，通过架桥反应使聚酰亚胺树脂前驱体的两末端形成单体结构，得到酰亚胺中间体组合物；
    A3：将步骤A2得到的酰亚胺中间体组合物进行酰亚胺化，得到树脂溶液混合物；
    A4：采用井喷式喷涂方法将步骤A3得到的树脂溶液混合物连续均匀喷涂在传送带上，经固化、干燥，得到聚酰亚胺厚膜。
  2. 根据权利要求1所述的制备方法，其特征在于，步骤A1具体包括：将2,2-双[4-(4-氨基苯氧基)苯基]丙烷体积份20～30份、4,4’-二氨基二苯基醚体积份20～30份和二氨基二蒽醚体积份3～7份溶解于N,N-二甲基甲酰胺中，再添加3,3’,4,4’-二苯甲酮四酸二酐体积份25～35份，然后添加均苯四甲酸二酸二酐体积份10～20份，反应一段时间后再补充加入3,3’,4,4’-二苯甲酮四酸二酐和/或均苯四甲酸二酸二酐，以使得加入的3,3’,4,4’-二苯甲酮四酸二酐和均苯四甲酸二酸二酐的总摩尔数大致等于2,2-双[4-(4-氨基苯氧基)苯基]丙烷体积份、4,4’-二氨基二苯基醚体积份和二氨基二蒽醚的总摩尔数，得到热塑性聚酰亚胺树脂前驱体。
  3. 根据权利要求1所述的制备方法，其特征在于，步骤A2中的单体反应物为内次甲基四氢苯酐，进一步地，热塑性聚酰亚胺树脂前驱体与单体反应物的质量比例为10:1；更进一步地，步骤A2中的混合反应的环境为-100～-60℃的真空环境。
  4. 根据权利要求1所述的制备方法，其特征在于，步骤A3中具体包括：将步骤A2得到的酰亚胺中间体组合物先进行化学酰亚胺化，然后进行热酰亚胺化，得到树脂溶液混合物。
  5. 根据权利要求4所述的制备方法，其特征在于，其中将酰亚胺中间体组合物进行化学酰亚胺化具体包括：在每100摩尔量的酰亚胺中间体组合物中添加3～10摩尔量的脱水剂和1～2摩尔量的环化催化剂，进一步地，所述脱水剂采用甲基吡啶，所述环化催化剂采用苯甲酸酐。
  6. 根据权利要求4所述的制备方法，其特征在于，将酰亚胺中间体组合物进行热酰亚胺化具体包括：在每100摩尔量的酰亚胺中间体组合物中加入1～3摩尔量的热酰亚胺化催化剂，进一步地，所述热酰亚胺化催化剂采用有机磷化合物、无机纳米粒子或硅化物纳米粒子中的至少一种。
  7. 根据权利要求1至6任一项所述的制备方法，其特征在于，还包括以下步骤：
    A5：将步骤A4的聚酰亚胺厚膜从所述传送带上剥离下来，进行双向拉伸，拉伸过程中采用红外加温并进行惰性气体保护，然后经过固化加热以蒸发溶剂和深度环化，得到含有多层结构倾斜单体的聚酰亚胺厚膜。
  8. 一种聚酰亚胺厚膜，其特征在于，采用权利要求1至7任一项所述的制备方法制得。
  9. 一种量子碳基膜的制备方法，其特征在于，包括：
    B1：将多层采用权利要求1至7任一项所述的制备方法制得的聚酰亚胺厚膜进行层叠；
    B2：在对层叠的聚酰亚胺厚膜施压按合的同时进行热处理，热处理的温度低于聚酰亚胺厚膜开始热分解的温度，使得聚酰亚胺厚膜层与层之间产生结合，得到复合膜；
    B3：在对得到的复合膜进行按压的同时继续升温到聚酰亚胺厚膜开始热分解温度以上进行热处理，得到碳化复合膜；
    B4：在对碳化复合膜继续升温到2800～3000℃的同时向碳化复合膜中掺杂或注入纳米金属粒子，以在所述碳化复合膜的表面形成均匀的纳米量子点，形成具有多层石墨烯结构的量子碳基膜。
  10. 一种量子碳基膜，其特征在于，采用权利要求9所述的制备方法制得。
PCT/CN2019/079993 2019-01-21 2019-03-28 聚酰亚胺厚膜和量子碳基膜、及其制备方法 WO2020151079A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910055344.5 2019-01-21
CN201910055344.5A CN109776826B (zh) 2019-01-21 2019-01-21 一种聚酰亚胺厚膜和量子碳基膜、及其制备方法

Publications (1)

Publication Number Publication Date
WO2020151079A1 true WO2020151079A1 (zh) 2020-07-30

Family

ID=66501007

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/079993 WO2020151079A1 (zh) 2019-01-21 2019-03-28 聚酰亚胺厚膜和量子碳基膜、及其制备方法

Country Status (2)

Country Link
CN (1) CN109776826B (zh)
WO (1) WO2020151079A1 (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110862567A (zh) * 2019-10-30 2020-03-06 深圳丹邦科技股份有限公司 一种超柔韧高导电导热性柔性基材及其制备方法
CN110862076B (zh) * 2019-10-30 2021-09-28 深圳丹邦科技股份有限公司 化合物半导体柔性碳基膜及其制备方法
CN111129188A (zh) 2019-12-27 2020-05-08 湖北云邦科技有限公司 一种柔性铟镓氮多层结构太阳能光伏器件及其制备方法
CN112397775B (zh) * 2020-10-27 2021-12-03 广东东邦科技有限公司 Li3PS4固态电解质、固态混合电解质、全固态锂硫电池及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101168598A (zh) * 2007-10-08 2008-04-30 江阴市云达电子新材料有限公司 高导热性、低热膨胀系数的超厚聚酰亚胺薄膜的制备方法
CN103232818A (zh) * 2013-04-23 2013-08-07 深圳丹邦科技股份有限公司 一种热塑性聚酰亚胺胶膜、其双面基材及其制备方法
WO2017027456A1 (en) * 2015-08-12 2017-02-16 E. I. Du Pont De Nemours And Company Paste and process for forming a solderable polyimide–based polymer thick film conductor
CN106432723A (zh) * 2016-04-26 2017-02-22 安徽鑫柏格电子股份有限公司 一种剥离强度高的聚酰亚胺薄膜及其制备方法
WO2017112638A1 (en) * 2015-12-22 2017-06-29 E. I. Du Pont De Nemours And Company Polyimide-based polymer thick film compositions

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI439492B (zh) * 2011-09-14 2014-06-01 Mortech Corp 聚醯亞胺膜
CN109054018B (zh) * 2018-06-06 2021-05-14 华南理工大学 一种聚酰胺酸溶液及其制备方法
CN108794748B (zh) * 2018-06-06 2021-08-10 华南理工大学 一种低介电常数的聚酰亚胺薄膜及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101168598A (zh) * 2007-10-08 2008-04-30 江阴市云达电子新材料有限公司 高导热性、低热膨胀系数的超厚聚酰亚胺薄膜的制备方法
CN103232818A (zh) * 2013-04-23 2013-08-07 深圳丹邦科技股份有限公司 一种热塑性聚酰亚胺胶膜、其双面基材及其制备方法
WO2017027456A1 (en) * 2015-08-12 2017-02-16 E. I. Du Pont De Nemours And Company Paste and process for forming a solderable polyimide–based polymer thick film conductor
WO2017112638A1 (en) * 2015-12-22 2017-06-29 E. I. Du Pont De Nemours And Company Polyimide-based polymer thick film compositions
CN106432723A (zh) * 2016-04-26 2017-02-22 安徽鑫柏格电子股份有限公司 一种剥离强度高的聚酰亚胺薄膜及其制备方法

Also Published As

Publication number Publication date
CN109776826A (zh) 2019-05-21
CN109776826B (zh) 2020-09-29

Similar Documents

Publication Publication Date Title
WO2020151079A1 (zh) 聚酰亚胺厚膜和量子碳基膜、及其制备方法
JP7061199B2 (ja) 向上した熱伝導度を有するグラファイトシート用ポリイミドフィルムの製造方法
TWI714971B (zh) 聚醯亞胺膜、其製備方法、使用其製備的石墨片以及電子裝置
CN111788259B (zh) 包含基于含石墨烯的球形pi的填料的石墨片聚酰亚胺膜、其制造方法及使用其制造的石墨片
JP4119693B2 (ja) 絶縁材付グラファイトフィルムおよびその製造方法
JP2010003981A (ja) 厚み方向にグラファイトが配向した熱伝導シート
TWI768525B (zh) 聚醯亞胺薄膜、其製造方法及包含其的多層薄膜、可撓性金屬箔層壓板和電子部件
TWI765392B (zh) 聚醯亞胺薄膜、其製造方法及包含其的多層薄膜、可撓性金屬箔層壓板和電子部件
TWI772946B (zh) 聚醯亞胺薄膜之製造方法、由該方法製得的聚醯亞胺薄膜、及包含其的多層薄膜、可撓性金屬箔層壓板和電子部件
CN113563585B (zh) 一种聚酰亚胺及其在金属层叠板中的应用
CN113968971B (zh) 可溶性、低温快速酰亚胺化聚酰亚胺薄膜的制备方法
CN110626030A (zh) 一种高导热聚酰亚胺多层复合薄膜及其制备方法
TW201821360A (zh) 聚醯亞胺膜的製造方法與使用其之石墨膜的製造方法
CN114605153A (zh) 一种高导热石墨膜的制备方法
CN108586740B (zh) 一种含芴或芴酮结构的聚酰亚胺及其制备方法和应用
KR102077766B1 (ko) 그라파이트 필름, 그 제조방법 및 이를 포함하는 전자소자용 방열구조체
CN117430848B (zh) 一种添加无机助剂的导热型聚酰亚胺薄膜及其制备方法和应用
EP1606108A1 (en) Double-sided metallic laminate and method for manufacturing the same
JP2006095935A (ja) 高熱伝導性筐体及びグラファイトプリプレグ
JP2006269558A (ja) フレキシブル積層基板の製造方法
KR102473354B1 (ko) 저유전 폴리이미드 필름 및 이의 제조방법
JP4657649B2 (ja) グラファイトフィルムの製造方法
JP5384286B2 (ja) ポリイミド及びそれからなるポリイミドフィルム
TWI846160B (zh) 聚醯胺酸、聚醯亞胺膜、使用其的多層膜、可撓性覆金屬箔層壓板及電子部件
TWI810713B (zh) 聚醯亞胺薄膜、其製造方法、包含其的多層膜、可撓性覆金屬箔層壓板及電子部件

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19911257

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 14/09/2021)

122 Ep: pct application non-entry in european phase

Ref document number: 19911257

Country of ref document: EP

Kind code of ref document: A1