WO2022012076A1 - 一种低介电聚酰亚胺复合薄膜材料及其制备方法 - Google Patents

一种低介电聚酰亚胺复合薄膜材料及其制备方法 Download PDF

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WO2022012076A1
WO2022012076A1 PCT/CN2021/082189 CN2021082189W WO2022012076A1 WO 2022012076 A1 WO2022012076 A1 WO 2022012076A1 CN 2021082189 W CN2021082189 W CN 2021082189W WO 2022012076 A1 WO2022012076 A1 WO 2022012076A1
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low
film material
composite film
graphene quantum
quantum dots
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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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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
    • 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
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • 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
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Definitions

  • the invention relates to the field of photosensitive polyimide materials, in particular to a low-dielectric polyimide composite film material and a preparation method thereof.
  • polyimide As an engineering material with high and low temperature resistance, high strength, high modulus, low water absorption, radiation resistance and excellent insulation, polyimide has been widely used in the fields of microelectronics, information, atomic energy industry and aerospace. Applications. With the development of society and science and technology, especially the rapid development of aerospace, information energy, electrical and electronic industry and microelectronics industry in recent years, higher and updated requirements have been put forward for materials. Pure polyimide materials have special requirements. The field of functional materials, such as the field of optical, electrical and magnetic materials, is increasingly showing its deficiencies. With the gradual spread of 5G construction, the dielectric properties of traditional polyimide materials can no longer meet the high-frequency and high-speed operation requirements of 5G.
  • Doping inorganic fillers can effectively increase the free volume, reduce the molar polarizability, and then reduce the dielectric constant.
  • the size of inorganic fillers is generally large, and the effect of reducing the dielectric constant of polyimide materials is not ideal.
  • the present invention provides a low-dielectric polyimide composite film material and a preparation method thereof.
  • the invention provides a method for preparing a low-dielectric polyimide composite film material. adding in batches; reacting for a preset time to obtain a polyamic acid solution; using citric acid hydrothermal method to prepare graphene quantum dots, and then performing amidation reaction with diaminopyridine and graphene quantum dots to obtain aminopyridine-functionalized graphite Graphene quantum dots; the polyamic acid solution and the functionalized graphene quantum dots are stirred at room temperature to obtain a mixed solution; the mixed solution is spin-coated to obtain a polyamic acid composite film, which is then subjected to gradient imidization treatment within a certain temperature range. A low-dielectric polyimide composite film material was obtained.
  • the molar mass ratio of the diamine monomer and the dibasic anhydride monomer is 1: (1-1.2); the sum of the mass of the diamine monomer and the dibasic anhydride monomer and the organic
  • the mass ratio of the 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:
  • the temperature range of the graphene quantum dots prepared by the citric acid hydrothermal method is 160-240°C.
  • the diamine monomer is more than one of TFMOB, 3,3'-6FDAm, 3FDAm, TFMB, 4,4'-6FDAm or BDAF, and its molecular structural formula is as follows:
  • diaminopyridine is one or more of 2,3-diaminopyridine, 2,6-diaminopyridine, 2,5-diaminopyridine and 3,4-diaminopyridine.
  • the gradient imidization temperature range of the polyamic acid composite film is 100-400°C.
  • the present invention also provides a low-dielectric polyimide composite film material, and the low-dielectric polyimide composite film material is prepared by the preparation method.
  • the present invention adopts diaminopyridine to functionalize the graphene quantum dots, and the graphene quantum dots can be uniformly dispersed in the matrix by the salt-forming effect between the amino group and the carboxyl group in the polyamic acid.
  • the purpose is to effectively reduce the dielectric constant of polyimide.
  • the composite film material prepared by introducing pyridine-functionalized graphene quantum dots into polyimide has the characteristics of low dielectric constant, low imidization temperature, and energy saving.
  • the preparation method of the invention is simple, the used graphene quantum dots reach nanometer level, the specific surface area is large, and after modification, they can be uniformly dispersed in the polyimide matrix to form a thin film material with uniform and controllable thickness.
  • 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 means that the first feature is level higher than the second feature.
  • the first feature is “below”, “below” and “below” the second feature includes the first feature is 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 method for preparing a low-dielectric polyimide composite film material. adding in batches; reacting for a preset time to obtain a polyamic acid solution; using citric acid hydrothermal method to prepare graphene quantum dots, and then performing amidation reaction with diaminopyridine and graphene quantum dots to obtain aminopyridine-functionalized graphite Graphene quantum dots; the polyamic acid solution and the functionalized graphene quantum dots are stirred at room temperature to obtain a mixed solution; the mixed solution is spin-coated to obtain a polyamic acid composite film, which is then subjected to gradient imidization treatment within a certain temperature range. A low-dielectric polyimide composite film material was obtained.
  • amidation reaction of described diaminopyridine and graphene quantum dots comprises the following steps:
  • the graphene quantum dots are dispersed in a mixed solvent of thionyl chloride and toluene, refluxed for 12 hours in a temperature range of 60 to 100° C., washed with a tetrahydrofuran solution, and dried to obtain acyl chloride graphene quantum dots;
  • Graphene acyl chloride quantum dots are dispersed in tetrahydrofuran solution, add diaminopyridine, stir at room temperature, pass nitrogen or argon flow, react for 6 h, and dialyze the product and freeze-dry to obtain aminopyridine functionalized graphene quantum dots.
  • the graphene quantum dots are functionalized and modified by using diaminopyridine, and the salt-forming effect between the amino group and the carboxyl group in the polyamic acid can be used to make the graphene quantum dots uniformly disperse in the matrix, and the polyamide can be effectively reduced.
  • Dielectric constant of imine Dielectric constant of imine.
  • the composite film material prepared by introducing pyridine-functionalized graphene quantum dots into polyimide has the characteristics of low dielectric constant, low imidization temperature, and energy saving.
  • the preparation method of the invention is simple, the used graphene quantum dots reach nanometer level, the specific surface area is large, and after modification, they can be uniformly dispersed in the polyimide matrix to form a thin film material with uniform and controllable thickness.
  • the film has the characteristics of good heat resistance, low dielectric constant, low dielectric loss, low imidization temperature, and energy saving.
  • the molar mass ratio of the diamine monomer and the dibasic anhydride monomer is 1: (1-1.2); the ratio of the diamine monomer and the dibasic anhydride monomer is The ratio of the sum of the mass 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 temperature range of the graphene quantum dots prepared by the citric acid hydrothermal method is 160-240°C.
  • the diamine monomer is one or more of TFMOB, 3,3'-6FDAm, 3FDAm, TFMB, 4,4'-6FDAm or BDAF, and its molecular structure is as follows :
  • the diaminopyridine is 2,3-diaminopyridine, one of 2,6-diaminopyridine, 2,5-diaminopyridine and 3,4-diaminopyridine or more.
  • the gradient imidization temperature range of the polyamic acid composite film is 100-400°C.
  • the present invention also provides a low-dielectric polyimide composite film material, and the low-dielectric polyimide composite film material is prepared by the preparation method.
  • the graphene quantum dots are functionalized and modified by using diaminopyridine, and the salt-forming effect between the amino group and the carboxyl group in the polyamic acid can be used to make the graphene quantum dots uniformly disperse in the matrix, and the polyamide can be effectively reduced.
  • Dielectric constant of imine Dielectric constant of imine.
  • the composite film material prepared by introducing pyridine-functionalized graphene quantum dots into polyimide has the characteristics of low dielectric constant, low imidization temperature, and energy saving.
  • the preparation method of the invention is simple, the used graphene quantum dots reach nanometer level, the specific surface area is large, and after modification, they can be uniformly dispersed in the polyimide matrix to form a thin film material with uniform and controllable thickness.
  • the average thickness of the obtained polyimide composite film is 15 ⁇ m, the dielectric constant is 2.67@1MHz, the water absorption rate is 0.68%, and the thermal expansion coefficient is 27.6ppm/°C, which has considerable application prospects in the field of integrated circuits and 5G communications.
  • the polyimide film obtained above has an average thickness of 15 ⁇ m, a dielectric constant of 2.86@1MHz, a water absorption rate of 0.71%, and a thermal expansion coefficient of 28.5ppm/°C.
  • the polyimide film obtained above has an average thickness of 15 ⁇ m, a dielectric constant of 2.74@1MHz, a water absorption rate of 0.81%, and a thermal expansion coefficient of 26.3ppm/°C.
  • the polyimide film obtained above has an average thickness of 15 ⁇ m, a dielectric constant of 2.54@1MHz, a water absorption rate of 0.60%, and a thermal expansion coefficient of 29.1ppm/°C.

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Abstract

一种低介电聚酰亚胺复合薄膜材料及其制备方法，包括以下步骤：二元胺与二元酐反应制得聚酰胺酸溶液；柠檬酸水热法制得石墨烯量子点，并与二氨基吡啶进行酰胺化反应得到氨基吡啶功能化石墨烯量子点；将聚酰胺酸溶液与功能化石墨烯量子点室温混合，旋涂，并经梯度亚胺化处理得低介电聚酰亚胺复合薄膜材料。经功能化后的石墨烯量子点均匀分散在聚酰亚胺基体中，形成厚度均匀可控的薄膜材料。

Description

一种低介电聚酰亚胺复合薄膜材料及其制备方法 技术领域
本发明涉及光敏聚酰亚胺材料领域，尤其涉及一种低介电聚酰亚胺复合薄膜材料及其制备方法。
背景技术
聚酰亚胺作为一种具有耐高低温性、高强度、高模量、低吸水率、耐辐照和优异绝缘性的工程材料，在微电子、信息、原子能工业和航空航天等领域得到广泛的应用。随着社会和科学技术的发展，尤其近年来航空航天、信息能源、电子电气工业和微电子工业的快速发展，对材料提出了更高更新的要求，单纯的聚酰亚胺材料在要求有特殊功能的材料领域，如光、电、磁学材料领域，越来越显示出它的不足。随着5G建设的逐步铺开，传统聚酰亚胺材料的介电性能已无法满足5G高频高速的运行要求。通过掺杂无机填料可以有效增加自由体积，降低摩尔极化率，进而降低介电常数，但一般无机填料的尺寸较大，对聚酰亚胺材料介电常数的降低效果并不理想。
发明内容
本发明为解决现有聚酰亚胺不利于使用的技术问题，提供了一种低介电聚酰亚胺复合薄膜材料及其制备方法。
本发明提供了一种低介电聚酰亚胺复合薄膜材料的制备方法，包括以下步骤：先将二元胺单体和二元酐单体分别溶解于有机溶剂中其中，二元酐单体分批加入；经预设时间反应后制得聚酰胺酸溶液；利用柠檬酸水热法制得石墨烯量子点，然后用二氨基吡啶与石墨烯量子点进行酰胺化反应得到氨基吡啶功能化的石墨烯量子点；将聚酰胺酸溶液与功能化石墨烯量子点在室温进行搅拌得到混合溶液；将混合溶液旋转涂布，得到聚酰胺酸复合薄膜，然后再一定温度范围内经梯度亚胺化处理制得低介电聚酰亚胺复合薄膜材料。
进一步地，所述的二元胺单体和二元酐单体的摩尔质量之比为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 PCTCN2021082189-appb-000001
进一步地，所述的柠檬酸水热法制备石墨烯量子点温度范围为160～240℃。
进一步地，所述的二元胺单体为TFMOB、3，3’-6FDAm、3FDAm、TFMB、4，4’-6FDAm或BDAF中的一种以上，其分子结构式如下所示：
Figure PCTCN2021082189-appb-000002
进一步地，所述的二氨基吡啶为2，3-二氨基吡啶，2，6-二氨基吡啶、2，5-二氨基吡啶和3，4-二氨基吡啶中的一种或多种。
进一步地，所述的聚酰胺酸复合薄膜梯度亚胺化温度范围为100～400℃。
另一方面，本发明还提供一种低介电聚酰亚胺复合薄膜材料，所述低介电聚酰亚胺复合薄膜材料采用所述的制备方法制得。
本发明的有益效果是：本发明采用二氨基吡啶对石墨烯量子点进行功能化改性，利用氨基与聚酰胺酸中羧基之间的成盐作用可以使得石墨烯量子点在基体中达到均匀分散的目的，有效降低聚酰亚胺介电常数。另外，在聚酰亚胺中引入吡啶功能化的石墨烯量子点制备的复合薄膜材料，具有低介电常数、亚胺化温度低、节省能耗等特点。本发明的制备方法简单，所用的石墨烯量子点达到纳米级，比表面积大，经改性后可以均匀分散在聚酰亚胺基体中，形成厚度均匀可控的薄膜材料。
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。
本发明提供了一种低介电聚酰亚胺复合薄膜材料的制备方法，包括以下步骤：先将二元胺单体和二元酐单体分别溶解于有机溶剂中其中，二元酐单体分批加入；经预设时间反应后制得聚酰胺酸溶液；利用柠檬酸水热法制得石墨烯量子点，然后用二氨基吡啶与石墨烯量子点进行酰胺化反应得到氨基吡啶功能化的石墨烯量子点；将聚酰胺酸溶液与功能化石墨烯量子点在室温进行搅拌得到混合溶液；将混合溶液旋转涂布，得到聚酰胺酸复合薄膜，然后再一定温度范围内经梯度亚胺化处理制得低介电聚酰亚胺复合薄膜材料。
具体地，所述的二氨基吡啶与石墨烯量子点酰胺化反应包括如下步骤：
将石墨烯量子点分散于二氯亚砜和甲苯混合溶剂中，在60～100℃温度范围内回流12h，经四氢呋喃溶液清洗，干燥得到酰氯化石墨烯量子点；
将酰氯化石墨烯量子点分散在四氢呋喃溶液中，加入二氨基吡啶，室温搅拌、通入氮气或氩气流，反应6h，将产物进行透析、冷冻干燥得到氨基吡啶功能化石墨烯量子点。
本发明采用二氨基吡啶对石墨烯量子点进行功能化改性，利用氨基与聚酰胺酸中羧基之间的成盐作用可以使得石墨烯量子点在基体中达到均匀分散的目的，有效降低聚酰亚胺介电常数。另外，在聚酰亚胺中引入吡啶功能化的石墨烯量子点制备的复合薄膜材料，具有低介电常数、亚胺化温度低、节省能耗等特点。本发明的制备方法简单，所用的石墨烯量子点达到纳米级，比表面积大，经改性后可以均匀分散在聚酰亚胺基体中，形成厚度均匀可控的薄膜材料。
所述的低介电聚酰亚胺复合薄膜材料在集成电路、5G通信天线材料或柔性覆铜板领域中的应用。该薄膜具有耐热性良好，低介电常数、低介电损耗、亚胺化温度低、节省能耗等特点。
在一个可选实施例中，所述的二元胺单体和二元酐单体的摩尔质量之比为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 PCTCN2021082189-appb-000003
在一个可选实施例中，所述的柠檬酸水热法制备石墨烯量子点温度范围为160～240℃。
在一个可选实施例中，所述的二元胺单体为TFMOB、3，3’-6FDAm、3FDAm、TFMB、4，4’-6FDAm或BDAF中的一种以上，其分子结构式如下所示：
Figure PCTCN2021082189-appb-000004
在一个可选实施例中，所述的二氨基吡啶为2，3-二氨基吡啶，2，6-二氨基吡啶、2，5-二氨基吡啶和3，4-二氨基吡啶中的一种或多种。
在一个可选实施例中，所述的聚酰胺酸复合薄膜梯度亚胺化温度范围为100～400℃。
另一方面，本发明还提供一种低介电聚酰亚胺复合薄膜材料，所述低介电聚酰亚胺复合薄膜材料采用所述的制备方法制得。
本发明采用二氨基吡啶对石墨烯量子点进行功能化改性，利用氨基与聚酰胺酸中羧基之间的成盐作用可以使得石墨烯量子点在基体中达到均匀分散的目的，有效降低聚酰亚胺介电常数。另外，在聚酰亚胺中引入吡啶功能化的石墨烯量子点制备的复合薄膜材料，具有低介电常数、亚胺化温度低、节省能耗等特点。本发明的制备方法简单，所用的石墨烯量子点达到纳米级，比表面积大，经改性后可以均匀分散在聚酰亚胺基体中，形成厚度均匀可控的薄膜材料。
具体实施例如下：
实施例1
1.将10mmol 2，2’-双(三氟甲基)-4，4’-二氨基联苯(TFMB)和10mmol六氟二酐(6FDA)先后溶解于40mL N，N-二甲基乙酰胺溶剂中(二元酐单体分批加入)，在氮气气氛、室温下搅拌反应得到聚酰胺酸(PAA)溶液；
2.将2.0g柠檬酸溶解于10mL去离子水中，搅拌呈均匀溶液后，将溶液转移于内衬聚四氟乙烯水热反应釜中，经200℃反应8小时，得到棕色溶液，然后将棕色溶液用透析袋(截留分子量Da＝500)透析3天，得到石墨烯量子点溶液，然后经冷冻干燥3天后得到石墨烯 量子点粉末(GQDs)；
3.先将1g GQDs分散在100mL二氯亚砜和30mL苯溶液中，经过80℃回流12h，将回流产物通过四氢呋喃清洗，并干燥12h，得到酰氯化GQDs粉末；然后将100mg GQDs粉末分散在四氢呋喃溶液中，加入20mg 2，3-二氨基吡啶，在室温搅拌下，通入氮气流反应6h，将产物用透析袋(截留分子量Da＝500)透析3天，再将透析产物冷冻干燥3天后得到氨基吡啶功能化石墨烯量子点(FGQDs-1)；
4.在PAA溶液中加入1wt％的功能化石墨烯量子点(FGQDs-1)，搅拌得到混合溶液，将混合溶液进行旋转涂布，得到聚酰胺酸复合薄膜，然后经100℃、200℃、300℃、350℃、400℃梯度亚胺化后，得到低介电聚酰亚胺/石墨烯量子点复合薄膜。
测试上述所得聚酰亚胺复合薄膜的平均厚度为15μm，介电常数为2.67@1MHz，吸水率为0.68％，热膨胀系数为27.6ppm/℃，在集成电路及5G通信领域有着可观的应用前景。
实施例2
1.将10mmol 2，2-双(4-氨基苯基)六氟丙烷(4，4’-6FDAm)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(二元酐单体分批加入)，在氩气气氛、室温下搅拌反应生成聚酰胺酸(PAA)溶液；
2.将2.0g柠檬酸溶解于10mL去离子水中，搅拌呈均匀溶液后，将溶液转移于内衬聚四氟乙烯水热反应釜中，经200℃反应8小时，得到棕色溶液，然后将棕色溶液用透析袋(截留分子量Da＝500)透析3天，得到石墨烯量子点溶液，然后经冷冻干燥3天后得到石墨烯量子点粉末(GQDs)；
3.先将1g GQDs分散在100mL二氯亚砜和30mL苯溶液中，经过80℃回流12h，将回流产物通过四氢呋喃清洗，并干燥12h，得到酰氯化GQDs粉末；然后将100mg GQDs粉末分散在四氢呋喃溶液中，加入20mg 2，6-二氨基吡啶，在室温搅拌下，通入氩气流反应6h，将产物用透析袋(截留分子量Da＝500)透析3天，再将透析产物冷冻干燥3天后得到氨基吡啶功能化石墨烯量子点(FGQDs-2)；
4.在PAA溶液中加入1wt％的功能化石墨烯量子点(FGQDs-2)， 搅拌得到混合溶液，将混合溶液进行旋转涂布，得到聚酰胺酸复合薄膜，然后经100℃、200℃、300℃、350℃、400℃梯度亚胺化后，得到低介电聚酰亚胺/石墨烯量子点复合薄膜。
测试上述所得聚酰亚胺薄膜的平均厚度为15μm，介电常数为2.86@1MHz，，吸水率为0.71％，热膨胀系数为28.5ppm/℃。
实施例3
1.将10mmol 2，2-双(3-氨基苯基)六氟丙烷(3，3’-6FDAm)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(二元酐单体分批加入)，在氮气气氛、室温下搅拌反应生成聚酰胺酸(PAA)溶液；
2.将2.0g柠檬酸溶解于10mL去离子水中，搅拌呈均匀溶液后，将溶液转移于内衬聚四氟乙烯水热反应釜中，经200℃反应8小时，得到棕色溶液，然后将棕色溶液用透析袋(截留分子量Da＝500)透析3天，得到石墨烯量子点溶液，然后经冷冻干燥3天后得到石墨烯量子点粉末(GQDs)；
3.先将1g GQDs分散在100mL二氯亚砜和30mL苯溶液中，经过80℃回流12h，将回流产物通过四氢呋喃清洗，并干燥12h，得到酰氯化GQDs粉末；然后将100mg GQDs粉末分散在四氢呋喃溶液中，加入20mg 2，5-二氨基吡啶，在室温搅拌下，通入氮气流反应6h，将产物用透析袋(截留分子量Da＝500)透析3天，再将透析产物冷冻干燥3天后得到氨基吡啶功能化石墨烯量子点(FGQDs-3)；
4.在PAA溶液中加入1wt％的功能化石墨烯量子点(FGQDs-3)，搅拌得到混合溶液，将混合溶液进行旋转涂布，得到聚酰胺酸复合薄膜，然后经100℃、200℃、300℃、350℃、400℃梯度亚胺化后，得到低介电聚酰亚胺/石墨烯量子点复合薄膜。
测试上述所得聚酰亚胺薄膜的平均厚度为15μm，介电常数为2.74@1MHz，吸水率为0.81％，热膨胀系数为26.3ppm/℃。
实施例4
1.将10mmol 2，2-双[4-(4-氨基苯氧基)苯基]六氟丙烷(BDAF)和10mmol 9-三氟甲基-9-苯基氧杂蒽二酐(3FXDA)先后溶解于45mL N-甲基吡咯烷酮溶剂中(二元酐单体分批加入)，在氩气气氛、 室温下搅拌反应生成聚酰胺酸(PAA)溶液；
2.将2.0g柠檬酸溶解于10mL去离子水中，搅拌呈均匀溶液后，将溶液转移于内衬聚四氟乙烯水热反应釜中，经200℃反应8小时，得到棕色溶液，然后将棕色溶液用透析袋(截留分子量Da＝500)透析3天，得到石墨烯量子点溶液，然后经冷冻干燥3天后得到石墨烯量子点粉末(GQDs)；
3.先将1g GQDs分散在100mL二氯亚砜和30mL苯溶液中，经过80℃回流12h，将回流产物通过四氢呋喃清洗，并干燥12h，得到酰氯化GQDs粉末；然后将100mg GQDs粉末分散在四氢呋喃溶液中，加入20mg 3，4-二氨基吡啶，在室温搅拌下，通入氮气流反应6h，将产物用透析袋(截留分子量Da＝500)透析3天，再将透析产物冷冻干燥3天后得到氨基吡啶功能化石墨烯量子点(FGQDs-4)；
4.在PAA溶液中加入1wt％的功能化石墨烯量子点(FGQDs-4)，搅拌得到混合溶液，将混合溶液进行旋转涂布，得到聚酰胺酸复合薄膜，然后经100℃、200℃、300℃、350℃、400℃梯度亚胺化后，得到低介电聚酰亚胺/石墨烯量子点复合薄膜。
测试上述所得聚酰亚胺薄膜的平均厚度为15μm，介电常数为2.54@1MHz，吸水率为0.60％，热膨胀系数为29.1ppm/℃。
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 (9)

  1. 一种低介电聚酰亚胺复合薄膜材料的制备方法，其特征在于，包括以下步骤：先将二元胺单体和二元酐单体分别溶解于有机溶剂中其中，二元酐单体分批加入；经预设时间反应后制得聚酰胺酸溶液；利用柠檬酸水热法制得石墨烯量子点，然后用二氨基吡啶与石墨烯量子点进行酰胺化反应得到氨基吡啶功能化的石墨烯量子点；将聚酰胺酸溶液与功能化石墨烯量子点在室温进行搅拌得到混合溶液；将混合溶液旋转涂布，得到聚酰胺酸复合薄膜，然后再一定温度范围内经梯度亚胺化处理制得低介电聚酰亚胺复合薄膜材料。
  2. 如权利要求1所述的一种低介电聚酰亚胺复合薄膜材料的制备方法，其特征在于，所述的二元胺单体和二元酐单体的摩尔质量之比为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所述的一种低介电聚酰亚胺复合薄膜材料的制备方法，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所述的一种低介电聚酰亚胺复合薄膜材料的制备方法，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 PCTCN2021082189-appb-100001
  5. 如权利要求1所述的一种低介电聚酰亚胺复合薄膜材料的制备方法，其特征在于，所述的柠檬酸水热法制备石墨烯量子点温度范围为160～240℃。
  6. 如权利要求1所述的一种低介电聚酰亚胺复合薄膜材料的制 备方法，其特征在于，所述的二元胺单体为TFMOB、3，3’-6FDAm、3FDAm、TFMB、4，4’-6FDAm或BDAF中的一种以上，其分子结构式如下所示：
    Figure PCTCN2021082189-appb-100002
  7. 如权利要求1所述的一种低介电聚酰亚胺复合薄膜材料的制备方法，其特征在于，所述的二氨基吡啶为2，3-二氨基吡啶，2，6-二氨基吡啶、2，5-二氨基吡啶和3，4-二氨基吡啶中的一种或多种。
  8. 如权利要求1所述的一种低介电聚酰亚胺复合薄膜材料的制备方法，其特征在于，所述的聚酰胺酸复合薄膜梯度亚胺化温度范围为100～400℃。
  9. 一种低介电聚酰亚胺复合薄膜材料，其特征在于，所述低介电聚酰亚胺复合薄膜材料采用权利要求1～8任一项所述的制备方法制得。
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