WO2022012078A1 - 一种自催化低介电聚酰亚胺材料及其制备方法 - Google Patents

一种自催化低介电聚酰亚胺材料及其制备方法 Download PDF

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WO2022012078A1
WO2022012078A1 PCT/CN2021/082191 CN2021082191W WO2022012078A1 WO 2022012078 A1 WO2022012078 A1 WO 2022012078A1 CN 2021082191 W CN2021082191 W CN 2021082191W WO 2022012078 A1 WO2022012078 A1 WO 2022012078A1
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low
autocatalytic
polyimide material
polyamic acid
dielectric
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French (fr)
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闵永刚
朋小康
廖松义
黄兴文
张诗洋
刘荣涛
赵晨
刘屹东
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Guangdong University of Technology
Dongguan South China Design and Innovation Institute
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Guangdong University of Technology
Dongguan South China Design and Innovation Institute
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    • 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
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • 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
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the invention relates to the technical field of low-dielectric materials, in particular to an autocatalytic low-dielectric polyimide material and a preparation method thereof.
  • the current domestic polyimide film production process mainly adopts the thermal imidization process, which uses a high temperature of about 400 °C to dehydrate and cyclize the polyamic acid. This process consumes a lot of energy, and the prepared membrane material is stable in batches. Poor performance and poor thermal properties. Therefore, reducing the dehydration and cyclization temperature of polyimide has become an urgent breakthrough in the current production of polyimide.
  • the present invention provides a self-catalytic low-dielectric polyimide material and a preparation method thereof in order to solve the technical problem that the existing low-dielectric material is unfavorable to use.
  • the invention provides a preparation method of an autocatalytic low-dielectric polyimide material, comprising the following steps:
  • the polyamic acid solution is prepared by reacting for a preset time
  • the ratio of the molar amount of the diamine monomer to the molar amount of the dibasic anhydride monomer is 1: (1-1.2); the sum of the mass of the diamine monomer and the dibasic anhydride monomer The mass ratio with the organic solvent is (0.5-2.5):10.
  • the organic solvent is one or more of N,N-dimethylacetamide, N,N-dimethylformamide and N-methylpyrrolidone.
  • dibasic anhydride monomer is one or more of 6FDA, 6FXDA, PFPDA, 3FDA, 3FXDA, 3FX3FXDA, and its molecular structural formula is as follows:
  • diamine monomers are 2,6-DAP, 2,5-DAP, 2,3-DAP, 3,4-DAP, 2,5-DAPM, 2,4-DAPM, 4, One or more of 6-DAPM or 4,5-DAPM, and its molecular structure is as follows:
  • step S4 the gradient imidization temperature range is 100-400°C.
  • the present invention also provides an autocatalytic low-dielectric polyimide material, and the autocatalytic low-dielectric polyimide material is prepared by the preparation method.
  • the present invention introduces a nitrogen-containing six-membered aromatic heterocyclic structure into the molecular structure of the polyimide, and utilizes the proton attraction effect of the lone pair of electrons of nitrogen to generate a catalytic effect, so that the dehydration and cyclization process of the polyamic acid is achieved.
  • Reduced temperature requirements In the present invention, a large amount of fluorine element is introduced into the polyimide, which can effectively reduce the dielectric constant of the material.
  • the preparation method of the invention is simple, and the thin film material with uniform and controllable thickness can be formed.
  • the material prepared by the invention has the characteristics of low dielectric constant and low imidization temperature.
  • first and second are only used for descriptive purposes, and should not be construed as indicating or implying relative importance or implying the number of indicated technical features. Thus, a feature defined as “first” or “second” may expressly or implicitly include one or more of that feature.
  • “plurality” means two or more, unless otherwise expressly and specifically defined.
  • the terms “installed”, “connected”, “connected”, “fixed” and other terms should be understood in a broad sense, for example, it may be a fixed connection or a detachable connection , or integrally connected; it can be a mechanical connection or an electrical connection; it can be a direct connection, or an indirect connection through an intermediate medium, or the internal communication between the two components.
  • installed e.g., it may be a fixed connection or a detachable connection , or integrally connected; it can be a mechanical connection or an electrical connection; it can be a direct connection, or an indirect connection through an intermediate medium, or the internal communication between the two components.
  • a first feature "on” or “under” a second feature may include the first and second features in direct contact, or may include the first and second features Not directly but through additional features between them.
  • the first feature being “above”, “over” and “above” the second feature includes the first feature being directly above and obliquely above the second feature, or simply denoting that the first feature is level above the second feature.
  • the first feature is “below”, “below” and “below” the second feature includes the first feature being directly below and diagonally below the second feature, or simply means that the first feature has a lower level than the second feature.
  • the invention provides a preparation method of an autocatalytic low-dielectric polyimide material, comprising the following steps:
  • the polyamic acid solution is prepared by reacting for a preset time
  • a nitrogen-containing six-membered aromatic heterocyclic structure is introduced into the molecular structure of the polyimide, and the proton attraction effect of the lone pair of electrons of nitrogen is used to produce a catalytic effect, so that the temperature requirement in the dehydration and cyclization process of the polyamic acid is reduced.
  • a large amount of fluorine element is introduced into the polyimide, which can effectively reduce the dielectric constant of the material.
  • the preparation method of the invention is simple, and the thin film material with uniform and controllable thickness can be formed.
  • the self-catalyzed low-dielectric polyimide material prepared by the invention has the characteristics of low dielectric constant, low imidization temperature and the like.
  • the ratio of the molar amount of the diamine monomer to the molar amount of the dibasic anhydride monomer is 1: (1-1.2); the diamine monomer and the dibasic anhydride monomer The ratio of the sum of the mass of the body to the mass of the organic solvent is (0.5-2.5):10.
  • the organic solvent is one or more of N,N-dimethylacetamide, N,N-dimethylformamide and N-methylpyrrolidone.
  • the described dibasic anhydride monomer is one or more of 6FDA, 6FXDA, PFPDA, 3FDA, 3FXDA, 3FX3FXDA, and its molecular structural formula is as follows:
  • the diamine monomer is 2,6-DAP, 2,5-DAP, 2,3-DAP, 3,4-DAP, 2,5-DAPM, 2,4 -One or more of DAPM, 4,6-DAPM or 4,5-DAPM, and its molecular structure is as follows:
  • step S4 the gradient imidization temperature ranges from 100 to 400°C.
  • the present invention also provides an autocatalytic low-dielectric polyimide material, and the autocatalytic low-dielectric polyimide material is prepared by the preparation method.
  • a nitrogen-containing six-membered aromatic heterocyclic structure is introduced into the molecular structure of the polyimide, and the proton attraction effect of the lone pair of electrons of nitrogen is used to produce a catalytic effect, so that the temperature requirement in the dehydration and cyclization process of the polyamic acid is reduced.
  • a large amount of fluorine element is introduced into the polyimide, which can effectively reduce the dielectric constant of the material.
  • the preparation method of the invention is simple, and the thin film material with uniform and controllable thickness can be formed.
  • the self-catalyzed low-dielectric polyimide material prepared by the invention has the characteristics of low dielectric constant, low imidization temperature and the like.
  • the average thickness of the polyimide film material obtained above is 15 ⁇ m, and the dielectric constant is 2.92@1MHz.
  • the variable temperature Fourier transform infrared spectroscopy test shows that this PAA film can be completely imidized at 300 ° C. There are considerable application prospects in the field of frequency flexible copper clad laminates.
  • the average thickness of the obtained polyimide film material is 15 ⁇ m, and the dielectric constant is 3.02@1MHz.
  • the variable temperature Fourier transform infrared spectroscopy test shows that the PAA film can be completely imidized at 270°C.
  • the average thickness of the obtained polyimide film material is 15 ⁇ m, and the dielectric constant is 2.88@1MHz.
  • the variable temperature Fourier transform infrared spectroscopy test shows that the PAA film can be completely imidized at 290 °C.

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

Abstract

一种自催化低介电聚酰亚胺材料的制备方法，包括以下步骤：将二元胺单体与二元酐单体先后溶解于有机溶剂中，其中，二元酐单体分批加入；在氮气或氩气气氛、室温环境下，经预设时间反应制得聚酰胺酸溶液；将聚酰胺酸溶液旋转涂布，得到聚酰胺酸薄膜；将聚酰胺酸薄膜在预设温度范围内经梯度亚胺化处理得到自催化低介电聚酰亚胺材料。通过在聚酰亚胺分子结构中引入含氮六元芳杂环结构，利用氮气的孤对电子的吸引质子作用，产生催化效果，使得聚酰胺酸脱水环化过程温度需求降低。通过在聚酰亚胺中引入大量的氟元素，可以有效降低材料介电常数。所得自催化低介电聚酰亚胺材料具备介电常数低、亚胺化温度低等特点。

Description

一种自催化低介电聚酰亚胺材料及其制备方法 技术领域
本发明涉及低介电材料技术领域，尤其涉及一种自催化低介电聚酰亚胺材料及其制备方法。
背景技术
随着5G高频通信技术的发展，对通信用材料的性能有了新的要求。在5G高频高速的工作条件下，传输线介质材料的合理选择及参数的设计对传输线的损耗具有决定性的影响，信号传输的完整性和准确性要求传输线介质材料具有低介电常数和低损耗的特性。适合高密度、高频和高速化集成电路应用的低介电低损耗挠性板(FPC)国产化材料正成为该行业的研发重点。由于聚酰亚胺薄膜柔软，尺寸稳定性好，介电性能优越，适于作带状电缆或软印刷电路的基材或覆盖层，成品体积小、质量轻、可靠性高、耐高温、抗辐射，在微电子领域愈发绽放光彩。但目前国内的聚酰亚胺薄膜生产过程主要还是采用热亚胺化工艺，利用400℃左右高温对聚酰胺酸进行脱水环化，这种工艺能耗高，而且制备出的膜材料批次稳定性差、热学性质较差。因此，降低聚酰亚胺脱水环化温度成了当前聚酰亚胺生产急需突破的一点。
发明内容
本发明为解决现有低介电材料不利于使用的技术问题，提供了一种自催化低介电聚酰亚胺材料及其制备方法。
本发明提供了一种自催化低介电聚酰亚胺材料的制备方法，包括以下步骤：
S1、将二元胺单体与二元酐单体先后溶解于有机溶剂中，其中，二元酐单体分批加入；
S2、在氮气或氩气气氛、室温环境下，经预设时间反应制得聚酰胺酸溶液；
S3、将聚酰胺酸溶液旋转涂布，得到聚酰胺酸薄膜；
S4、将聚酰胺酸薄膜在预设温度范围内经梯度亚胺化处理得到自催化低介电聚酰亚胺材料。
进一步地，所述二元胺单体的摩尔量与二元酐单体的摩尔量之比为1：(1～1.2)；所述二元胺单体和二元酐单体的质量之和与有机溶剂 的质量之比为(0.5～2.5)：10。
进一步地，所述的有机溶剂为N，N-二甲基乙酰胺、N，N-二甲基甲酰胺和N-甲基吡咯烷酮中的一种或多种。
进一步地，所述的所述二元酐单体为6FDA、6FXDA、PFPDA、3FDA、3FXDA、3FX3FXDA中的一种或多种，其分子结构式如下所示：
Figure PCTCN2021082191-appb-000001
进一步地，所述的二元胺单体为2，6-DAP、2，5-DAP、2，3-DAP、3，4-DAP、2，5-DAPM、2，4-DAPM、4，6-DAPM或4，5-DAPM中的一种或多种，其分子结构式如下所示：
Figure PCTCN2021082191-appb-000002
进一步地，步骤S4中，梯度亚胺化温度范围为100～400℃。
另一方面，本发明还提供一种自催化低介电聚酰亚胺材料，所述自催化低介电聚酰亚胺材料采用所述的制备方法制得。
本发明的有益效果是：本发明在聚酰亚胺分子结构中引入含氮六元芳杂环结构，利用氮气的孤对电子的吸引质子作用，产生催化效果， 使得聚酰胺酸脱水环化过程温度需求降低。本发明在聚酰亚胺中引入大量的氟元素，可以有效降低材料介电常数。本发明的制备方法简单，可形成厚度均匀可控的薄膜材料。本发明制备的材料具备介电常数低、亚胺化温度低等特点。
具体实施方式
下面详细描述本发明的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，旨在用于解释本发明，而不能理解为对本发明的限制。
在本发明的描述中，需要理解的是，术语“中心”、“纵向”、“横向”、“长度”、“宽度”、“厚度”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”“内”、“外”、“顺时针”、“逆时针”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。
此外，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本发明的描述中，“多个”的含义是两个或两个以上，除非另有明确具体的限定。
在本发明中，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”、“固定”等术语应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通。对于本领域的普通技术人员而言，可以根据具体情况理解上述术语在本发明中的具体含义。
在本发明中，除非另有明确的规定和限定，第一特征在第二特征之“上”或之“下”可以包括第一和第二特征直接接触，也可以包括第一和第二特征不是直接接触而是通过它们之间的另外的特征接触。而且，第一特征在第二特征“之上”、“上方”和“上面”包括第一特征在第二特 征正上方和斜上方，或仅仅表示第一特征水平高度高于第二特征。第一特征在第二特征“之下”、“下方”和“下面”包括第一特征在第二特征正下方和斜下方，或仅仅表示第一特征水平高度小于第二特征。
下面通过具体实施方式结合附图对本发明作进一步详细说明。
本发明提供了一种自催化低介电聚酰亚胺材料的制备方法，包括以下步骤：
S1、将二元胺单体与二元酐单体先后溶解于有机溶剂中，其中，二元酐单体分批加入；
S2、在氮气或氩气气氛、室温环境下，经预设时间反应制得聚酰胺酸溶液；
S3、将聚酰胺酸溶液旋转涂布，得到聚酰胺酸薄膜；
S4、将聚酰胺酸薄膜在预设温度范围内经梯度亚胺化处理得到自催化低介电聚酰亚胺材料。
本发明在聚酰亚胺分子结构中引入含氮六元芳杂环结构，利用氮气的孤对电子的吸引质子作用，产生催化效果，使得聚酰胺酸脱水环化过程温度需求降低。本发明在聚酰亚胺中引入大量的氟元素，可以有效降低材料介电常数。本发明的制备方法简单，可形成厚度均匀可控的薄膜材料。本发明制备的自催化低介电聚酰亚胺材料具备介电常数低、亚胺化温度低等特点。
在一个可选实施例中，所述二元胺单体的摩尔量与二元酐单体的摩尔量之比为1：(1～1.2)；所述二元胺单体和二元酐单体的质量之和与有机溶剂的质量之比为(0.5～2.5)：10。
在一个可选实施例中，所述的有机溶剂为N，N-二甲基乙酰胺、N，N-二甲基甲酰胺和N-甲基吡咯烷酮中的一种或多种。
在一个可选实施例中，所述的所述二元酐单体为6FDA、6FXDA、PFPDA、3FDA、3FXDA、3FX3FXDA中的一种或多种，其分子结构式如下所示：
Figure PCTCN2021082191-appb-000003
在一个可选实施例中，所述的二元胺单体为2，6-DAP、2，5-DAP、2，3-DAP、3，4-DAP、2，5-DAPM、2，4-DAPM、4，6-DAPM或4，5-DAPM中的一种或多种，其分子结构式如下所示：
Figure PCTCN2021082191-appb-000004
在一个可选实施例中，步骤S4中，梯度亚胺化温度范围为100～400℃。
另一方面，本发明还提供一种自催化低介电聚酰亚胺材料，所述自催化低介电聚酰亚胺材料采用所述的制备方法制得。
本发明在聚酰亚胺分子结构中引入含氮六元芳杂环结构，利用氮气的孤对电子的吸引质子作用，产生催化效果，使得聚酰胺酸脱水环化过程温度需求降低。本发明在聚酰亚胺中引入大量的氟元素，可以有效降低材料介电常数。本发明的制备方法简单，可形成厚度均匀可控的薄膜材料。本发明制备的自催化低介电聚酰亚胺材料具备介电常数低、亚胺化温度低等特点。
具体实施例如下：
实施例1
将10mmol 2，5-二氨基吡啶(2，5-DAP)和10mmol六氟二酐(6FDA)先后溶解于40mL N，N-二甲基乙酰胺溶剂中(六氟二酐分批加入)，在氮气气氛、室温下搅拌反应得到聚酰胺酸(PAA)溶液；将PAA溶液进行旋转涂布，得到PAA薄膜，然后经100℃、200℃、300℃梯度亚胺化后，得到低介电聚酰亚胺材料。
测试上述所得聚酰亚胺薄膜材料的平均厚度为15μm，介电常数为2.92@1MHz，变温傅立叶红外光谱测试显示这种PAA薄膜在300℃条件下即可完全亚胺化，在5G天线、高频柔性覆铜板领域有着可观的应用前景。
实施例2
将10mmol 4，6-二氨基嘧啶(4，6-DAPM)和10mmol 1，3-双(3，4-二羧基苯基)六氟丙烷二酐(PFPDA)先后溶解于40mL N，N-二甲基甲酰胺溶剂中，其中，双(3，4-二羧基苯基)六氟丙烷二酐(PFPDA)分批加入，在氩气气氛、室温下搅拌反应得到聚酰胺酸(PAA)溶液；将PAA溶液进行旋转涂布，得到PAA薄膜，然后经100℃、200℃、300℃梯度亚胺化后，得到低介电聚酰亚胺材料。
测试上述所得聚酰亚胺薄膜材料的平均厚度为15μm，介电常数为3.02@1MHz，变温傅立叶红外光谱测试显示这种PAA薄膜在270℃条件下即可完全亚胺化。
实施例3
将5mmol 3，4-二氨基吡啶(3，4-DAP)、5mmol 4，5-二氨基嘧啶(4，5-DAPM)和10mmol 4，4’-(1-苯基-2，2，2-三氟乙叉)二邻苯二甲酸酐(3FDA)先后溶解于40mL N-甲基吡咯烷酮溶剂中，其中，4，4’-(1-苯基-2，2，2-三氟乙叉)二邻苯二甲酸酐(3FDA)分批加入，在氩气气氛、室温下搅拌反应得到聚酰胺酸(PAA)溶液；将PAA溶液进行旋转涂布，得到PAA薄膜，然后经100℃、200℃、300℃梯度亚胺化后，得到低介电聚酰亚胺材料。
测试上述所得聚酰亚胺薄膜材料的平均厚度为15μm，介电常数为2.88@1MHz，变温傅立叶红外光谱测试显示这种PAA薄膜在290℃条件下即可完全亚胺化。
在本说明书的描述中，参考术语“一个实施方式”、“一些实施方式”、“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
以上内容是结合具体的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普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干简单推演或替换。

Claims (7)

  1. 一种自催化低介电聚酰亚胺材料的制备方法，其特征在于，包括以下步骤：
    S1、将二元胺单体与二元酐单体先后溶解于有机溶剂中，其中，二元酐单体分批加入；
    S2、在氮气或氩气气氛、室温环境下，经预设时间反应制得聚酰胺酸溶液；
    S3、将聚酰胺酸溶液旋转涂布，得到聚酰胺酸薄膜；
    S4、将聚酰胺酸薄膜在预设温度范围内经梯度亚胺化处理得到自催化低介电聚酰亚胺材料。
  2. 如权利要求1所述的一种自催化低介电聚酰亚胺材料的制备方法，其特征在于，所述二元胺单体的摩尔量与二元酐单体的摩尔量之比为1：(1～1.2)；所述二元胺单体和二元酐单体的质量之和与有机溶剂的质量之比为(0.5～2.5)：10。
  3. 如权利要求1所述的一种自催化低介电聚酰亚胺材料的制备方法，其特征在于，所述的有机溶剂为N，N-二甲基乙酰胺、N，N-二甲基甲酰胺和N-甲基吡咯烷酮中的一种或多种。
  4. 如权利要求1所述的一种自催化低介电聚酰亚胺材料的制备方法，其特征在于，所述的所述二元酐单体为6FDA、6FXDA、PFPDA、3FDA、3FXDA、3FX3FXDA中的一种或多种，其分子结构式如下所示：
    Figure PCTCN2021082191-appb-100001
  5. 如权利要求1所述的一种自催化低介电聚酰亚胺材料的制备方法，其特征在于，所述的二元胺单体为2，6-DAP、2，5-DAP、2，3-DAP、3，4-DAP、2，5-DAPM、2，4-DAPM、4，6-DAPM或4， 5-DAPM中的一种或多种，其分子结构式如下所示：
    Figure PCTCN2021082191-appb-100002
  6. 如权利要求1所述的一种自催化低介电聚酰亚胺材料的制备方法，其特征在于，步骤S4中，梯度亚胺化温度范围为100～400℃。
  7. 一种自催化低介电聚酰亚胺材料，其特征在于，所述自催化低介电聚酰亚胺材料采用权利要求1～6任一项所述的制备方法制得。
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