CN114032060B - Polyimide composition, polyimide compound, preparation and application thereof - Google Patents

Polyimide composition, polyimide compound, preparation and application thereof Download PDF

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CN114032060B
CN114032060B CN202111421632.1A CN202111421632A CN114032060B CN 114032060 B CN114032060 B CN 114032060B CN 202111421632 A CN202111421632 A CN 202111421632A CN 114032060 B CN114032060 B CN 114032060B
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polyimide
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compound
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polyamic acid
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CN114032060A (en
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杨海滨
黎迈俊
郑爽
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Huangpu Institute of Materials
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives based on 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 C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2255/26—Polymeric coating
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

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Abstract

The invention provides a polyimide composition, a polyimide compound, preparation and application thereof, wherein the polyimide composition comprises the following components: a polyamic acid precursor of polyimide A, a polyamic acid precursor of polyimide B, a two-dimensional layered nano filler and an additive; the polyamic acid precursor of polyimide a and the polyamic acid precursor of polyimide B have specific structures. Through the cooperation of specific components, the polyimide composition can be dehydrated and cured to obtain a polyimide composite which has low dielectric loss, low dielectric constant, low thermal expansion coefficient and high bonding strength.

Description

Polyimide composition, polyimide compound, preparation and application thereof
Technical Field
The invention relates to the technical field of composite resin, in particular to a polyimide composition, a polyimide compound, and preparation and application thereof.
Background
With the development of 5G mobile communication technology, high frequency signal transmission is a main transmission mode, so that higher requirements are put on signal propagation speed and transmission efficiency of electronic components such as a printed circuit board, and high frequency signals transmitted in a circuit board of an electronic device are easily affected by dielectric properties of insulating materials around conductive lines, so that the insulating materials adopted in the circuit board of the electronic device must have low dielectric constant and low dielectric loss characteristics, so as to reduce dielectric loss for signal transmission, and improve efficiency and speed of high frequency signal transmission.
The copper-clad plate is a main material for preparing the circuit board, the traditional flexible copper-clad plate is generally divided into 3 layers of glue-type copper-clad plates and 2 layers of glue-free copper-clad plates, wherein the 3 layers of glue-type copper-clad plates consist of copper foil, adhesive and polyimide film, the 2 layers of glue-free copper-clad plates do not contain epoxy adhesive and consist of copper foil and polyimide film only, and the polyimide film and the copper foil are required to have high viscosity. The traditional 2-layer glue-free copper-clad plate or 3-layer glue-free copper-clad plate mainly adopts polyimide to prepare an insulating layer, and in order to meet the requirement of the copper-clad plate on low thermal expansion coefficient, polyimide with low thermal expansion coefficient and thermoplastic polyimide are often required to be adopted to prepare the insulating layer in a lamination mode, however, the traditional polyimide has the problems of higher dielectric constant and higher dielectric loss, so that the circuit board is difficult to be applied to a 5G communication line. In order to reduce the dielectric constant and dielectric loss of the copper-clad plate in the traditional technology, resin with low polar groups such as hydrocarbon resin is often adopted to prepare the insulating layer of the copper-clad plate, but the addition of the low polar groups is very easy to reduce the bonding performance of the insulating layer to copper or other insulating substrates, and the copper-clad plate with low dielectric loss, dielectric constant, low thermal expansion coefficient and high bonding strength is often difficult to obtain.
Thus, there is a need in the art for improvement.
Disclosure of Invention
Based on the above, the invention provides a polyimide composition and a polyimide compound which have low dielectric loss, low dielectric constant, low thermal expansion coefficient and high bonding strength, and preparation and application thereof.
The technical scheme of the invention is as follows.
In one aspect of the present invention, there is provided a polyimide composition comprising the following components:
a polyamic acid precursor of polyimide A, a polyamic acid precursor of polyimide B, a two-dimensional layered nano filler and an additive;
the polyimide A has a structure shown in a formula (1):
Figure BDA0003376795790000021
wherein, in each repeating unit of the polyimide A, at least one of R in the repeating unit 1 Is of the structure shown in formula (1-a):
Figure BDA0003376795790000022
r in each repeating unit of the polyimide A 2 Each independently selected from one of structures represented by formulae (1-b) to (1-d):
Figure BDA0003376795790000023
R 11 and R is 12 Each occurrence of which is independently selected from H, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom; r is R 13 Each occurrence of which is independently selected from a single bond, an ester group, and an oxygen atom;
the polyimide B has a structure shown in a formula (2):
Figure BDA0003376795790000031
wherein R in each repeating unit of the polyimide B 3 Each independently selected from one of structures represented by formulae (2-a) to (2-c):
Figure BDA0003376795790000032
R 21 each occurrence of which is independently selected from a single bond, an oxygen atom or a fluoroalkane subunit having 1 to 5 carbon atoms and being substituted with a fluorine atom;
R 4 selected from: a nitrogen-containing heteroaryl group having 5 to 10 ring atoms which is substituted or unsubstituted;
R 5 has a structure shown in formula (2-d):
Figure BDA0003376795790000033
r 'and R' are independently selected from substituted or unsubstituted aryl groups having 6 to 50 ring atoms or substituted or unsubstituted C 1 ～C 6 N is an integer of 1 to 30;
m, p and q represent the degree of polymerization, and x represents the site of attachment.
In some of these embodiments, at least one of the recurring units of polyimide A is further R 1 One selected from the following structures:
Figure BDA0003376795790000034
in some of these embodiments, R in each repeating unit of the polyimide B 4 Each independently selected from one of the structures shown below:
Figure BDA0003376795790000041
wherein Ar is 1 、Ar 2 、Ar 3 Ar and Ar 4 Each independently selected from a single bond and an aryl group having 6 to 12 ring atoms.
In some of these embodiments, R in each repeating unit of the polyimide B 3 Each independently selected from one of the structures shown below:
Figure BDA0003376795790000042
Figure BDA0003376795790000043
and/or
R in each repeating unit of the polyimide B 4 Each independently selected from one of the structures shown below:
Figure BDA0003376795790000044
Figure BDA0003376795790000051
in some of these embodiments, R 4 And R is R 5 The molar ratio of (2) is (30-50): (50-70).
In some of these embodiments, R 11 And R is 12 Each independently selected from methyl or trifluoromethyl; and/or
R 'and R' are independently selected from substituted or unsubstituted C 1 ～C 6 Is a hydrocarbon group.
In some of these embodiments, the structure of formula (1-a) is as follows:
Figure BDA0003376795790000052
and/or
R in each repeating unit of the polyimide A 2 Each independently selected from one of the following structures:
Figure BDA0003376795790000053
Figure BDA0003376795790000061
in some of these embodiments, the polyimide composition comprises the following components in parts by mass:
Figure BDA0003376795790000062
in some of these embodiments, the mass ratio of the polyamic acid precursor of the polyimide B to the two-dimensional layered nanofiller is 10 (0.1-5).
In some of these embodiments, the additive comprises a polyphenylene ether of formula (VI),
Figure BDA0003376795790000063
wherein Z represents an alkylene group having 1 to 3 carbon atoms or a single bond, x is selected from any one integer of 0 to 20, y is selected from any one integer of 0 to 20, and 1.ltoreq.x+y.ltoreq.30.
In another aspect of the present invention, there is also provided a method for preparing the polyimide composition as described above, comprising the steps of:
carrying out ring-opening polymerization reaction on a compound of formula (I) and a compound of formula (II) to obtain a polyamic acid precursor of the polyimide A;
mixing the two-dimensional layered nanofiller, the compound of formula (IV), the compound of formula (V) and an organic solvent to obtain a mixed solution;
performing ring-opening polymerization reaction on the compound of the formula (III) and the mixed solution to obtain a compound of the two-dimensional lamellar nano filler and a polyamic acid precursor of the polyimide B;
mixing the compound, the polyamic acid precursor of polyimide A and the additive to obtain the polyimide composition;
wherein the structures of the compound of formula (I), the compound of formula (II), the compound of formula (III), the compound of formula (IV) and the compound of formula (V) are as follows:
Figure BDA0003376795790000071
R 1 ～R 5 as described above for R 1 ～R 5 The same applies.
The invention also provides a polyimide composite which is prepared from the raw materials comprising the polyimide composition.
The invention further provides a copper-clad plate, which comprises an insulation base layer and copper foil arranged on the surface of the insulation base layer, wherein the preparation raw materials of the insulation base layer comprise the polyimide composition.
Further, the invention also provides a printed circuit board, which comprises the copper-clad plate.
The components of the polyimide composition provided by the invention comprise a polyamic acid precursor of polyimide A, a polyamic acid precursor of polyimide B, a two-dimensional layered nano filler and an additive, and the polyimide composition is dehydrated and cured to obtain a polyimide compound. The polyamic acid precursor of the polyimide A is converted into the polyimide A with a structure shown in a formula (1), and the polyimide A contains a large amount of trifluoromethyl groups and a specific mother ring structure, so that the dielectric constant, dielectric loss and thermal expansion coefficient of a polyimide compound can be reduced, and the polyimide A can be provided as basic performance of a polyimide insulating layer; the polyimide B is converted from a polyamic acid precursor of the polyimide B, and the polyimide B contains a siloxane structure with low polarity and low surface energy, so that the polyimide B can be endowed with the migration capability to the surface in a polyimide compound, the polyimide B can be subjected to phase separation and further enriched on the surface of the polyimide compound, meanwhile, the polyimide B is rich in a nitrogen-containing heterocyclic structure which can coordinate with metal so as to enhance the adhesion of the polyimide compound and a copper foil, and the siloxane structure further increases the binding force of the polyimide compound and the copper foil; the two-dimensional layered nano filler has high length-diameter ratio, can limit the free movement of polyimide chain segments and reduce free volume, so that the thermal expansion coefficient and dielectric loss of a polymer film can be further reduced, and the polyimide composition can be dehydrated and cured to obtain a polyimide composite with low dielectric loss, low dielectric constant, low thermal expansion coefficient and high bonding strength through cooperation of specific components.
Further, the additive comprises polyphenyl ether shown in a formula (VI), wherein the polyphenyl ether has extremely low dielectric constant and dielectric loss, and the polyphenyl ether can further reduce the dielectric constant and dielectric loss of the polyimide composite film by synergistic effect of the polyphenyl ether and other components.
Further, the invention also provides a copper-clad plate, which comprises an insulation base layer and a copper foil arranged on the surface of the insulation base layer, wherein the preparation raw materials of the insulation base layer comprise the polyimide composition. When the polyimide composition is used for preparing the copper-clad plate, the adhesion with the copper foil is excellent, the dielectric loss, the dielectric constant and the thermal expansion coefficient of the copper-clad plate can be reduced, a plurality of layers of polyimide layers are not needed to be laminated, and the copper-clad plate with low dielectric loss, low dielectric constant, low thermal expansion coefficient and high adhesion strength can be obtained by only preparing a layer of insulating base layer by adopting the polyimide composition. Therefore, the copper-clad plate is suitable for preparing high-performance printed circuit boards with high frequency, high speed and the like, thereby promoting the development of high-end integrated circuits.
Detailed Description
The present invention will be described more fully hereinafter in order to facilitate an understanding of the present invention, and preferred embodiments of the present invention are set forth. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the present invention, the same substituent may be independently selected from different groups when it appears multiple times. Where formula (2-d) contains a plurality of R 'and R ", then R' and R" may be independently selected from different groups.
In the present invention, "×" indicates a ligation site.
In the present invention, "substituted or unsubstituted" means that the defined group may or may not be substituted. When a defined group is substituted, it is understood to be optionally substituted with groups acceptable in the art, including but not limited to: c1-30 alkyl, heterocyclyl containing 3-20 ring atoms, aryl containing 5-20 ring atoms, heteroaryl containing 5-20 ring atoms.
In the present invention, when no attachment site is specified in a group, an optionally attachable site in the group is represented as an attachment site.
In the present invention, a single bond to which a substituent is attached extends through the corresponding ring, meaning that the substituent may be attached to an optional position on the ring, e.g
Figure BDA0003376795790000091
R in (2) is connected with any substitutable site of benzene ring; when a single bond is formed through two substituents on a ring, it is stated that the two substituents may be attached to an optional position on the ring and that the attachment positions of the two substituents are different. For example->
Figure BDA0003376795790000092
Since there is only one hydrogen atom on each unsubstituted carbon atom on the benzene ring, the two substituents will not be attached to the same carbon atom on the same benzene ring, in other words, the attachment sites of the two substituents to the ring will be different. Further, when R is H, this represents that hydrogen on the benzene ring is not substituted with other substituents.
In the present invention, when two groups are connected by a linkage, for example
Figure BDA0003376795790000093
In which R is selected from single bonds, i.e.represents two groups which are directly linked by a single bond without specific radical bonding, i.e. +.>
Figure BDA0003376795790000094
"alkanyl" in the present invention refers to the radical of an alkane that is formed after the loss of one hydrogen, e.g., methane that is formed after the loss of one hydrogen; "alkane subunit or alkylene" refers to a group formed by the loss of two hydrogens from an alkane, such as methane, which forms a methylene group by the loss of two hydrogens. Similarly, "fluoroalkanylene" refers to a group formed by the loss of two hydrogens from a fluoroalkane.
Based on the research experience of the person in the field of printed circuit boards for many years, the technical scheme of the invention is obtained after a great number of creative experimental researches.
The embodiment of the invention provides a polyimide composition, which comprises the following components:
a polyamic acid precursor of polyimide A, a polyamic acid precursor of polyimide B, a two-dimensional layered nano filler and an additive.
Polyimide a has a structure represented by formula (1):
Figure BDA0003376795790000095
m is the degree of polymerization, i.e. represents the number of repetitions of the repeating units in polyimide a, in other words, polyimide a is formed by the joining of m repeating units.
Wherein, in each repeating unit of polyimide A, at least one of R in the repeating unit 1 Is of the structure shown in formula (1-a).
Figure BDA0003376795790000101
R in each repeating unit of polyimide A 2 Each independently selected from one of structures represented by formulae (1-b) to (1-d):
Figure BDA0003376795790000102
R 11 and R is 12 Each occurrence of which is independently selected from H, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom; r is R 13 Each occurrence of which is independently selected from a single bond, an ester group, and an oxygen atom.
It will be appreciated that R in each repeat unit of polyimide A 2 R, which may be identical or different, R 2 In the same case, i.e. where polyimide A is formed by joining one type of repeating unit, R 2 When not identical, i.e. polyimide A is composed of several R 2 The different repeating units are linked and may be random without a specific arrangement.
Polyimide B has a structure represented by formula (2):
Figure BDA0003376795790000103
wherein R in each repeating unit of polyimide B 3 Each independently selected from one of structures represented by formulae (2-a) to (2-c):
Figure BDA0003376795790000104
Figure BDA0003376795790000111
R 21 each occurrence of which is independently selected from a single bond, an oxygen atom or a fluoroalkane subunit having 1 to 5 carbon atoms and being substituted with a fluorine atom;
R 4 a nitrogen-containing heteroaryl group having a cyclic origin of 5 to 10 selected from the group consisting of substituted and unsubstituted;
R 5 has a structure shown in formula (2-d):
Figure BDA0003376795790000112
r 'and R' are independently selected from substituted or unsubstituted aryl groups having 6 to 50 ring atoms or C 1 ～C 6 N is an integer of 1 to 30.
p and q represent the degree of polymerization, and x represents the site of attachment.
The polyimide composition is dehydrated and cured to obtain a polyimide compound, wherein a polyamic acid precursor of the polyimide A is converted into the polyimide A with a structure shown in a formula (1), and the polyimide A contains a large number of trifluoromethyl groups and a specific parent ring structure, so that the thermal expansion coefficient, dielectric constant and dielectric loss of the polyimide compound can be reduced; the polyimide B is converted from a polyamic acid precursor of the polyimide B, and the polyimide B contains a siloxane structure with low polarity and low surface energy, so that the polyimide B can be endowed with the migration capability to the surface in a polyimide compound, the polyimide B can be subjected to phase separation and further enriched on the surface of the polyimide compound, meanwhile, the polyimide B is rich in a nitrogen-containing heterocyclic structure which can coordinate with metal so as to enhance the adhesion of the polyimide compound and a copper foil, and the siloxane structure further increases the binding force of the polyimide compound and the copper foil; the two-dimensional layered nano filler has high length-diameter ratio, can limit the free movement of polyimide chain segments and reduce free volume, so that the thermal expansion coefficient and dielectric loss of a polymer film can be further reduced, and the polyimide composition can be dehydrated and cured to obtain a polyimide composite with low dielectric loss, low dielectric constant, low thermal expansion coefficient and high bonding strength through cooperation of specific components.
In the structure represented by the formula (2), p and q each represent a group containing R 4 And R is 5 The degree of polymerization of the repeating units of (2) may be random, and there is no particular arrangement in the structure represented by formula (2).
In some of these embodiments, at least one of the recurring units of polyimide A is further R 1 One selected from any one of the following structures:
Figure BDA0003376795790000121
it can be understood that in this case, the polyimide A having the structure represented by the formula (1) has R 1 Different repeat units.
In some of these embodiments, R in each repeating unit of polyimide B 4 Each independently selected from one of the structures shown below:
Figure BDA0003376795790000122
wherein Ar is 1 、Ar 2 、Ar 3 Ar and Ar 4 Independently selected from single bonds or cyclic precursorsAryl with the number of the sub-groups of 6 to 12.
It will be appreciated that when Ar in the above structure 1 、Ar 2 、Ar 3 Ar and Ar 4 Selected from single bonds, and Ar 1 、Ar 2 、Ar 3 Ar and Ar 4 The position is a single bond; the "number of ring atoms" is essentially defined as the number of atoms forming a ring in the group.
In some of these embodiments, the aryl group having 6 to 12 ring atoms is selected from the group consisting of: benzene, naphthalene and derivatives thereof.
In some of these embodiments, ar 1 、Ar 2 、Ar 3 Ar and Ar 4 Independently selected from single bonds or phenyl groups
In some of these embodiments, R in each repeating unit of polyimide B 4 Each independently selected from one of the structures shown below:
Figure BDA0003376795790000131
in some of these embodiments, R in each repeating unit of polyimide B 3 Each independently selected from one of the structures shown below:
Figure BDA0003376795790000132
preferably, R is used as R in the polyimide B 4 And R is R 5 Based on the sum of the molar masses R 5 The content of (2) is 40% or more.
Further, in the polyimide B, R 4 And R is R 5 The molar ratio of (2) is (30-50): (50-70).
Thus, the copper adhesion, solder resistance and heat resistance of the polyimide composition can be further improved.
It will be appreciated that the polyimide B contains R 4 Degree of polymerization p of repeating units of (2) and R-containing 5 The ratio of the repeating units of (2) is (30-50): (50-70).
In some of these embodiments, R 11 And R is 12 Each independently selected from H, methyl or trifluoromethyl.
In some of these embodiments, the structure of formula (1-a) is as follows:
Figure BDA0003376795790000141
in some of these embodiments, R in each repeat unit of polyimide A 2 Each independently selected from one of the following structures:
Figure BDA0003376795790000142
in some embodiments, R 'and R' are independently selected from substituted or unsubstituted C 1 ～C 6 Is a hydrocarbon group.
In some embodiments, the polyimide composition is prepared from the following raw materials in parts by weight:
Figure BDA0003376795790000143
Figure BDA0003376795790000151
the specific components are coordinated through specific proportions, so that dielectric loss, dielectric constant and thermal expansion coefficient of the polyimide composition are further reduced.
Further, the mass ratio of the polyamide acid precursor of the polyimide B to the two-dimensional lamellar nano filler is 10 (0.1-5); preferably, the mass ratio of the polyamic acid precursor of the polyimide B to the two-dimensional lamellar nano filler is 10 (0.5-5).
In some of these embodiments, the two-dimensional layered nanofiller may be a cationic two-dimensional layered material, primarily layered silicate, including but not limited to:montmorillonite, bentonite, beidellite, kaolin, sepiolite, attapulgite and vermiculite. Further, the interlayer metal cation in the two-dimensional layered nano filler is Li + 、Na + 、K + 、Ca 2+ 、Mg 2+ Or Ba (Ba) 2+ . More preferably, the two-dimensional layered nano filler is sodium montmorillonite and sodium bentonite.
The two-dimensional layered nano filler can also be an anionic two-dimensional layered material, and specifically one or more of binary metal hydroxide and multi-element metal hydroxide; preferably magnesium aluminum hydrotalcite, with interlayer anion of CO3 2- 。
The above additive comprises a polyphenylene ether represented by the formula (VI)
Figure BDA0003376795790000152
Wherein Z represents an alkylene group having 1 to 3 carbon atoms or a single bond, x is selected from any one integer of 0 to 20, y is selected from any one integer of 0 to 20, and 1.ltoreq.x+y.ltoreq.30.
The hydroxyl-containing polyphenylene ether represented by the above formula (VI) has extremely low dielectric constant, dielectric loss, and can further reduce the dielectric constant and dielectric loss of the polyimide composite film by synergistic effect with other components.
Preferably, the molecular weight of the hydroxyl group-containing polyphenylene ether is 1500 to 3000. The dielectric constant and dielectric loss of the polyimide composite film can be further reduced.
An embodiment of the present invention also provides a method for preparing the polyimide composition as described above, including the following steps S10 to S40.
Step S10, ring-opening polymerization reaction is carried out on the compound of the formula (I) and the compound of the formula (II) to obtain the polyamide acid precursor of the polyimide A.
The structures of the compounds of formula (I) and the compounds of formula (II) are shown as follows:
Figure BDA0003376795790000161
R 1 and R is 2 With R as above 1 And R is 2 The same applies.
In some of these embodiments, the molar amount ratio of the compound of formula (I) to the compound of formula (II) is from 1:9 to 9:1; further preferably 1:1.
in some embodiments, the ring-opening polymerization reaction temperature is 0 to 100 ℃; further preferably 1℃to 30 ℃.
In some examples, the ring-opening polymerization reaction is carried out for 1 to 72 hours; more preferably 5 to 24 hours.
In some of these embodiments, in step S10, the above ring-opening polymerization is performed in an organic solvent, further, in a polar solvent; preferably, the organic solvent is selected from any one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, sulfolane, butyrolactone, cresol or cyclohexanone; more preferably, the organic solvent is selected from at least one of N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
Further, the amount of the above-mentioned organic solvent is such that the solid content of the solution of the polyamic acid precursor of polyimide a prepared is 5 to 50% by weight; further, the solid content of the solution of the polyamic acid precursor of the polyimide A is 15 to 30 weight percent.
In some embodiments, when there is at least one R in each of the repeating units of polyimide A 1 Selected from one of the structures shown below:
Figure BDA0003376795790000171
at this time, in step S10, there is at least one R in the compound of formula (I) 1 One selected from the above structures, and a diamine compound represented by the formula (II).
And step S20, mixing the two-dimensional lamellar nano filler, the compound of the formula (IV), the compound of the formula (V) and the organic solvent to obtain a mixed solution.
In step S20, the organic solvent is at least one selected from dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, cyclohexanone, m-cresol, phenol, chlorophenol, toluene and xylene.
And S30, carrying out ring-opening polymerization reaction on the compound of the formula (III) and the mixed solution to obtain a compound of the two-dimensional lamellar nano filler and the polyamide acid precursor of the polyimide B.
In step S30, the compound of formula (III) and the mixture undergo ring-opening polymerization, and the compound of formula (III), formula (IV) and formula (V) undergo ring-opening polymerization to obtain a polyamic acid precursor of polyimide B, and the polyamic acid precursor of polyimide B is supported between the layers of the two-dimensional layered nanofiller to form a composite as a result of the ring-opening polymerization in the mixture containing the two-dimensional layered nanofiller.
It should be noted that, the step S10 and the step S20 may be performed sequentially without a specific sequence, and may be performed simultaneously; in other words, the step S10 of preparing the polyamic acid precursor of the polyimide a may be sequentially performed, or the steps S20 to 30 of preparing the composite of the two-dimensional layered nanofiller and the polyamic acid precursor of the polyimide B may be performed first, or both may be performed simultaneously.
Wherein the structures of the compound of formula (III), the compound of formula (IV) and the compound of formula (V) are as follows:
Figure BDA0003376795790000181
H 2 N-R 4 -NH 2 (IV)、H 2 N-R 5 -NH 2 (V)；
R 1 ～R 5 as described above for R 1 ～R 5 The same applies.
In some embodiments, in the step S20, the temperature of the mixture is 100-180 ℃ and the mixture is kept for 0.5-4 hours; further, in the step S30, the temperature of the ring-opening polymerization reaction is 140 to 180 ℃ and the time is 2 to 24 hours.
Further, the organic solvent is added in the step S20 in such an amount that the solid content of the obtained composite solution is 5 to 50 wt%; preferably, the solid content is 10-30 wt%.
Further, in the composite of the two-dimensional layered nanofiller and the polyamic acid precursor of polyimide B, the mass ratio of the two-dimensional layered nanofiller to the polyamic acid precursor of polyimide B is (0.1 to 5): 10; preferably (0.5 to 5): 10.
step S40, mixing the compound, the polyamide acid precursor of the polyimide A and the additive to obtain the polyimide composition.
In one embodiment of the present invention, there is also provided a polyimide composite produced using a raw material comprising the polyimide composition as described above.
The polyimide composite has the advantages of low dielectric loss, low dielectric constant, low thermal expansion coefficient and high bonding strength.
Further, the polyimide composite is obtained by dehydration curing of a raw material comprising the polyimide composition as described above.
In some embodiments, the dehydration curing temperature is: 300-360 ℃.
The invention further provides a copper-clad plate, which comprises an insulation base layer and a copper foil arranged on the surface of the insulation base layer, wherein the preparation raw materials of the insulation base layer comprise the polyimide composition.
When the polyimide composition is used for preparing the copper-clad plate, the adhesion with the copper foil is excellent, the dielectric loss, the dielectric constant and the thermal expansion coefficient of the copper-clad plate can be reduced, a plurality of polyimide layers are not needed to be laminated, and the copper-clad plate with low dielectric loss, low dielectric constant, low thermal expansion coefficient and high adhesion strength can be obtained by preparing a polyimide insulating base layer by adopting the polyimide composition. Therefore, the copper-clad plate is suitable for preparing high-performance printed circuit boards with high frequency, high speed and the like, thereby promoting the development of high-end integrated circuits.
Further, the insulating base layer is coated with copper foil on one or both sides.
In some embodiments, the copper-clad plate includes an insulation base layer and two copper foil layers respectively disposed on two sides of the insulation base layer.
Further, the thickness of the insulation base layer is 0.5 μm to 100 μm; the thickness of the copper foil layer is 2-100 μm, and in some embodiments, the preparation method of the copper-clad plate comprises the following steps S50-S60.
And S50, coating the solution of the polyimide composition on the surface of a copper foil, and then dehydrating and curing at 300-360 ℃ to form an insulating base layer on the surface of the copper foil, so as to obtain the intermediate copper plate.
It is understood that the copper foil has two surfaces, and that in the step of coating, a solution of the polyimide composition is coated on one of the surfaces of the copper foil.
The polyimide composition is dehydrated and cured at 300-360 ℃, the polyamic acid precursor of polyimide A and the polyamic acid precursor of polyimide B in the polyimide composition are converted into polyimide A and polyimide B, and the surface of the copper foil forms an insulating base layer of the polyimide composite.
Further, before the step of dehydrating and solidifying the copper intermediate plate at 300-360 ℃, the method further comprises the step of gradient heating: preferably, the temperature is heated to 300-360 ℃ in a gradient way at a heating rate of 1-4 ℃/min.
Further, the dehydration and solidification steps are performed under the protection of inert gas.
And step S60, placing another copper foil on one surface of the insulating base layer of the middle copper plate, which is far away from the copper foil, and hot-pressing to obtain the copper-clad plate.
In some of these embodiments, the process parameters of the hot press are: the pressure is 0.2 MPa-50 MPa, the temperature is 120-300 ℃ and the time is 0.1-30 min.
Preferably, the hot pressing process parameters are: the pressure is 0.2 MPa-20 MPa, the temperature is 150-260 ℃ and the time is 0.1-10 min.
Further, an embodiment of the invention also provides a printed circuit board, which comprises the copper-clad plate.
The printed circuit board has low dielectric loss, low dielectric constant, low thermal expansion coefficient, heat resistance and soldering resistance. The method is suitable for preparing high-performance printed circuit boards with high temperature resistance, aging resistance, integrated circuit packaging, high frequency, high speed and the like, thereby promoting the development of high-end integrated circuits.
The invention will be described in connection with specific embodiments, but the invention is not limited thereto, and it will be appreciated that the appended claims outline the scope of the invention, and those skilled in the art, guided by the inventive concept, will appreciate that certain changes made to the embodiments of the invention will be covered by the spirit and scope of the appended claims.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
(1) 2,2 '-bis (trifluoromethyl) -4,4' -biphenyldiamine (16.01 g, 0.05 mol) was added to N, N-dimethylacetamide (137 g), the solid was dissolved by stirring at room temperature, biphenyldianhydride (7.35 g, 0.025 mol) was added, and hexafluorodianhydride (6 FDA, 11.11g, 0.025 mol) was stirred at room temperature for 21 hours to form a polyamic acid precursor solution of polyamic acid A having a polymer solid content of 20% by weight.
(2) Sodium-based Monomotou (1.5 g), 2, 6-diaminopyridine (0.545 g, 0.005 mol), 1-3-bis (3-aminopropyl) -1-1-3-3-tetramethyldisiloxane (1.242 g, 0.005 mol) was added to N-methylpyrrolidone (20 g) and toluene (16 g), and heated to 150℃for 4h. Then, pyromellitic dianhydride (2.182 g, 0.010 mol) was added and heated to 180℃to react for 10 hours to form a polyamic acid precursor solution of polyimide B having a solid content of 10%.
(3) The polyamic acid precursor solution (50 g) of polyamic acid A, the polyamic acid precursor solution (18 g) of polyimide B, and the polyphenylene ether (Z is isopropylene (10 g)) represented by the formula (VI) with the molecular weight of 1600 were stirred at room temperature and mixed uniformly to obtain a polyimide composition.
(4) Uniformly coating the polyimide composition on the surface of a copper foil, and heating to 310 ℃ in a gradient way at a heating rate of 2 ℃/min to form a polyimide composite insulating layer with a thickness of 15 micrometers, thereby obtaining the glue-free single-sided copper-clad plate. And (3) bonding the surface of the prepared adhesive-free single-sided copper-clad plate with another copper foil by using the surface of the polyimide composite insulating layer, and pressing for 10min on a pressing machine at the temperature of 180 ℃ under the pressure of 1.0MPa to form the double-sided adhesive-free copper-clad plate.
Example 2
(1) 2,2 '-bis (trifluoromethyl) -4,4' -biphenyldiamine (16.01 g, 0.05 mol) was added to N, N-dimethylformamide (105 g), the solid was dissolved by stirring at room temperature, hexafluorodianhydride (15.10 g, 0.035 mol), and pyromellitic dianhydride (3.272 g,0.015 mol) were added, and stirring at room temperature was carried out for 22 hours to form a polyamic acid precursor solution of polyamic acid A having a polymer solids content of 18%.
(2) Magnesium aluminum hydrotalcite (1.4 g), 3, 5-diaminopyridine (0.545 g, 0.005 mol), and an aminopropyl polysiloxane (5.00 g, 0.005 mol) having a molecular weight of 1000 were added to N, N-dimethylformamide (30 g) and cyclohexanone (23 g), heated to 160℃for 3 hours, then biphenyl dianhydride (2.942 g,0.01 mol) was added, and heated to 150℃for 10 hours to form a polyamic acid precursor solution of polyimide B having a solid content of 15%.
(3) The polyamic acid precursor solution (55.6 g) of polyamic acid A, the polyamic acid precursor solution (10 g) of polyimide B, and the polyphenylene ether (Z is a single bond) represented by the formula (VI) with the molecular weight 2300 (5 g) were uniformly mixed to obtain a polyimide composition.
(4) Uniformly coating the polyimide composition on the surface of a copper foil, and heating to 320 ℃ in a gradient way at a heating rate of 1 ℃/min to form a polyimide composite insulating layer with a thickness of 15 micrometers, thereby obtaining the glue-free single-sided copper-clad plate. And (3) bonding the surface of the prepared adhesive-free single-sided copper-clad plate with another copper foil by using the surface of the polyimide composite insulating layer, and pressing for 15min on a pressing machine at the temperature of 200 ℃ under the pressure of 1.5MPa to form the double-sided adhesive-free copper-clad plate.
Example 3
(1) 2,2 '-bis (trifluoromethyl) -4,4' -biphenyldiamine (8.00 g, 0.025 mol), p-aminobenzoic acid (p-aminophenol) ester (5.706 g, 0.025 mol) was added to N-methylpyrrolidone (114 g), the solid was dissolved by stirring at room temperature, hexafluorodianhydride (22.21 g, 0.05 mol) was added, and stirring at room temperature was performed for 20 hours to form a polyamic acid precursor solution of polyamic acid A having a polymer solid content of 25%.
(2) Sodium bentonite (1.9 g), 4' -diaminobipyridine (0.931 g, 0.005 mol), and an aminopropyl polysiloxane (10.00 g, 0.005 mol) having a molecular weight of 2000 were added to cyclohexanone (16 g), heated to 150℃for 4 hours, and then hexafluorodianhydride (4.442 g,0.01 mol) was added thereto, heated to 160℃and reacted for 18 hours to form a polyamic acid precursor solution of polyimide B having a solid content of 20%.
(3) The polyamic acid precursor solution of polyamic acid a (40 g), the polyamic acid precursor solution of polyimide B (9 g), and polyphenylene ether (Z is isopropylidene) represented by formula (VI) having a molecular weight of 2000 (8 g) were stirred at room temperature and mixed uniformly to obtain a polyimide composition.
(4) Uniformly coating the polyimide composition on the surface of a copper foil, and heating to 310 ℃ in a gradient way at a heating rate of 1.5 ℃/min to form a polyimide composite insulating layer with a thickness of 15 micrometers, thereby obtaining the glue-free single-sided copper-clad plate. And (3) bonding the surface of the prepared adhesive-free single-sided copper-clad plate with another copper foil by using the surface of the polyimide composite insulating layer, and pressing for 15min on a pressing machine at the temperature of 190 ℃ under the pressure of 0.8MPa to form the double-sided adhesive-free copper-clad plate.
Example 4
(1) 2,2 '-bis (trifluoromethyl) -4,4' -biphenyldiamine (9.607 g, 0.03 mol), p-phenylenediamine (2.163 g, 0.02 mol) was added to N, N-dimethylformamide (136 g), the solid was dissolved by stirring at room temperature, hexafluorodianhydride ((22.21 g, 0.05 mol), pyromellitic dianhydride (10.906 g, 0.05 mol) was added, and stirring at room temperature for 20 hours to form a polyamic acid precursor solution of polyamic acid A having a polymer solids content of 20%.
(2) Magnesium aluminum hydrotalcite (1.6 g), 2, 5-bis (4-aminophenyl) pyridine (0.784 g, 0.003mol), 1, 3-diaminopropyl hexamethyldisiloxane (1.738 g, 0.007 mol) was added to N-methylpyrrolidone (30 g) and toluene (21 g), and heated to 180℃for 3h. Diphenyl ether dianhydride (3.102 g,0.01 mol) was added and heated to 180 ℃ to react for 16h to form a polyamic acid precursor solution of polyimide B having a solids content of 10%.
(3) The polyamic acid precursor solution (50 g) of polyamic acid A, the polyamic acid precursor solution (19 g) of polyimide B, and the polyphenylene ether (Z is a single bond) represented by the formula (VI) having a molecular weight of 3000 (15 g) were stirred at room temperature, and uniformly mixed to obtain a polyimide composition.
(4) Uniformly coating the polyimide composition on the surface of a copper foil, and heating to 360 ℃ in a gradient way at a heating rate of 2.5 ℃/min to form a polyimide composite insulating layer with a thickness of 15 micrometers, thereby obtaining the glue-free single-sided copper-clad plate. And (3) bonding the surface of the prepared adhesive-free single-sided copper-clad plate with another copper foil by using the surface of the polyimide composite insulating layer, and pressing for 8min on a pressing machine at the temperature of 210 ℃ under the pressure of 2.5MPa to form the double-sided adhesive-free copper-clad plate.
Example 5
(1) 2,2 '-bis (trifluoromethyl) -4,4' -biphenyldiamine (12.81 g, 0.04 mol), 2 '-dimethyl-4, 4' -biphenyldiamine (2.123 g,0.01 mol) was added to dimethyl sulfoxide (149 g), the solid was dissolved by stirring at room temperature, and hexafluorodianhydride (22.21 g, 0.05 mol) was added thereto, and stirring at room temperature was carried out for 24 hours, to form a polyamic acid precursor solution of polyamic acid A having a polymer solid content of 20%.
(2) Sodium-based Monomotou (1.7 g), 2- (4-aminophenyl) -5-amino-benzimidazole (0.45 g, 0.002 mol), a terminal aminopropyl polysiloxane (3.00 g,0.003 mol) having a molecular weight of 1000 was added to N-methylpyrrolidone (20 g) and toluene (16 g), and heated to 16℃for 3 hours. Triphenyl diether dianhydride (4.023 g, 0.010 mol) was added and heated to 170℃for 18h to form a polyamic acid precursor solution of polyimide B having a solids content of 10%.
(3) The polyamic acid precursor solution (50 g) of polyamic acid A, the polyamic acid precursor solution (11 g) of polyimide B having a molecular weight of 1000 and a polyphenylene ether (10 g) represented by the formula (VI) wherein Z is (methylene) were stirred at room temperature and mixed uniformly to obtain a polyimide composition.
(4) Uniformly coating the polyimide composition on the surface of a copper foil, and heating to 340 ℃ in a gradient way at a heating rate of 1 ℃/min to form a polyimide composite insulating layer with a thickness of 15 micrometers, thereby obtaining the glue-free single-sided copper-clad plate. And (3) bonding the surface of the prepared adhesive-free single-sided copper-clad plate with another copper foil by using the surface of the polyimide composite insulating layer, and pressing for 15min on a pressing machine at the temperature of 220 ℃ under the pressure of 1.5MPa to form the double-sided adhesive-free copper-clad plate.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that: in the step (2), sodium-based montmorillonite is not added, and other conditions are the same as in the example 1.
Comparative example 2
Comparative example 1 is substantially the same as example 1 except that: the replacement of the hexafluorodianhydride in step (1) of example 1 with an equimolar mass of diphenyl ether tetracarboxylic dianhydride was structured as follows:
Figure BDA0003376795790000231
other conditions were the same as in example 1.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that: the 1, 3-diaminopropyl hexamethyldisiloxane in step (2) of example 1 was replaced with equimolar 1, 10-diaminodecane.
Other conditions were the same as in example 1.
Comparative example 4
Comparative example 4 is substantially the same as example 1 except that: the 2, 6-diaminopyridine in step (2) of example 1 was replaced with equimolar m-phenylenediamine.
Other conditions were the same as in example 1.
Comparative example 5
Comparative example 5 is substantially the same as example 1 except that: example 5 step (2) was carried out without polyphenylene ether.
Other conditions were the same as in example 1.
Performance testing
The performance of the copper clad laminate products of the examples and comparative examples was tested, comprising the following steps:
1. determination of glass transition temperature: a dynamic thermo-mechanical performance analyzer, rheometric Scientific Inc, was used, heating rate 2 ℃/min, frequency 1Hz.
2. The Coefficient of Thermal Expansion (CTE) of the polyimide composite insulation layer on the copper clad laminate was measured: and adopting a static thermal mechanical analyzer (TMA Q400), wherein the test atmosphere is nitrogen, the temperature rising rate is 5 ℃/min, and the temperature interval is 20-200 ℃.
3. Determination of adhesive strength: for the copper clad laminate products of examples and comparative examples, peel strength (N/mm) at 90 ° stretching was tested using a tensile machine.
4. Measurement of the highest solder resistance temperature: after the copper-clad plate products of the examples and comparative examples were cured by heating the solder pot to a certain temperature, the copper-clad plate products were put into a solder bath and floated with the copper foil side down for 30 seconds, and whether or not there was an appearance change was confirmed. If the temperature is not changed, the temperature is continuously raised. And recording the highest temperature of the corresponding solder bath when the appearance of the copper-clad plate changes.
5. Measurement of dielectric constant and dielectric loss: the copper foil layers of the copper clad laminate products of examples and comparative examples were etched to obtain polyimide composite films, which were fixed in a separation dielectric resonator (SPDR), and dielectric constants and dielectric loss tangents at 10GHz were measured using a vector network analyzer (N5244A, agilent Technologies).
The test results are shown in table 1 below:
TABLE 1
Figure BDA0003376795790000251
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (13)

1. A polyimide composition comprising the following components:
a polyamic acid precursor of polyimide A, a polyamic acid precursor of polyimide B, a two-dimensional layered nano filler and an additive;
the polyimide A has a structure shown in a formula (1):
Figure FDA0004109359860000011
wherein, in each repeating unit of the polyimide A, at least one of R in the repeating unit 1 Is of the structure shown in formula (1-a):
Figure FDA0004109359860000012
r in each repeating unit of the polyimide A 2 Each independently selected from one of structures represented by formulae (1-b) to (1-d):
Figure FDA0004109359860000013
R 11 and R is 12 Each occurrence of which is independently selected from H, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom; r is R 13 Each occurrence of which is independently selected from a single bond, an ester group, and an oxygen atom;
the polyimide B has a structure shown in a formula (2):
Figure FDA0004109359860000021
wherein R in each repeating unit of the polyimide B 3 Each independently selected from one of structures represented by formulae (2-a) to (2-c):
Figure FDA0004109359860000022
R 21 each occurrence of which is independently selected from a single bond, an oxygen atom or a fluoroalkane subunit having 1 to 5 carbon atoms and being substituted with a fluorine atom;
r in each repeating unit of the polyimide B 4 Each independently selected from one of the structures shown below:
Figure FDA0004109359860000023
wherein Ar is 1 、Ar 2 、Ar 3 Ar and Ar 4 Each independently selected from a single bond or an aryl group having 6 to 12 ring atoms;
R 5 has a structure shown in formula (2-d):
Figure FDA0004109359860000031
r 'and R' are independently selected from substituted or unsubstituted aryl groups having 6 to 50 ring atoms or substituted or unsubstituted C 1 ～C 6 N is an integer of 1 to 30;
m, p and q represent the degree of polymerization, and x represents the site of attachment;
the additive comprises a polyphenylene ether represented by formula (VI):
Figure FDA0004109359860000032
wherein Z represents an alkylene group having 1 to 3 carbon atoms or a single bond, x is selected from any one integer of 0 to 20, y is selected from any one integer of 0 to 20, and 1.ltoreq.x+y.ltoreq.30.
2. The polyimide composition according to claim 1, wherein R is present in at least one of the repeating units of the polyimide A 1 One selected from the following structures:
Figure FDA0004109359860000033
3. the polyimide composition according to claim 1, wherein R in each repeating unit of the polyimide B 3 Each independently selected from at least one of the structures shown below:
Figure FDA0004109359860000034
Figure FDA0004109359860000041
4. the polyimide composition according to claim 1, wherein R in each repeating unit of the polyimide B 4 Each independently selected from one of the structures shown below:
Figure FDA0004109359860000042
Figure FDA0004109359860000051
5. the polyimide composition according to any one of claims 1 to 4, wherein R 4 And R is R 5 The molar ratio of (2) is (30-50): (50-70).
6. The polyimide composition according to any one of claims 1 to 4, wherein R 11 And R is 12 Each independently selected from methyl or trifluoromethyl.
7. The polyimide composition according to any one of claims 1 to 4, wherein R 'and R' are independently selected from the group consisting of substituted and unsubstituted C 1 ～C 6 Is a hydrocarbon group.
8. The polyimide composition according to any one of claims 1 to 4, wherein the structure of the formula (1-a) is as follows:
Figure FDA0004109359860000052
and/or
R in each repeating unit of the polyimide A 2 Each independently selected from one of the following structures:
Figure FDA0004109359860000053
9. the polyimide composition according to any one of claims 1 to 4, wherein the components of the polyimide composition comprise, in parts by mass:
Figure FDA0004109359860000061
10. the method for producing a polyimide composition according to any one of claims 1 to 9, comprising the steps of:
carrying out ring-opening polymerization reaction on a compound of formula (I) and a compound of formula (II) to obtain a polyamic acid precursor of the polyimide A;
mixing the two-dimensional layered nanofiller, the compound of formula (IV), the compound of formula (V) and an organic solvent to obtain a mixed solution;
performing ring-opening polymerization reaction on the compound of the formula (III) and the mixed solution to obtain a compound of the two-dimensional lamellar nano filler and a polyamic acid precursor of the polyimide B;
mixing the compound, the polyamic acid precursor of polyimide A and the additive to obtain the polyimide composition;
wherein the structures of the compound of formula (I), the compound of formula (II), the compound of formula (III), the compound of formula (IV) and the compound of formula (V) are as follows:
Figure FDA0004109359860000062
H 2 N-R 2 -NH 2 (II)、
Figure FDA0004109359860000063
H 2 N-R 4 -NH 2 (IV)、H 2 N-R 5 -NH 2 (V)；
R 1 ～R 5 r in the same claim 1 1 ～R 5 The same applies.
11. A polyimide composite prepared from a raw material comprising the polyimide composition according to any one of claims 1 to 9.
12. A copper-clad plate, characterized in that the copper-clad plate comprises an insulation base layer and a copper foil arranged on the surface of the insulation base layer, and the preparation raw material of the insulation base layer comprises the polyimide composition as claimed in any one of claims 1 to 9.
13. A printed circuit board comprising the copper-clad plate of claim 12.
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