CN116478400A - Polyimide and diamine monomer containing tetrabiphenyl derivative structure and preparation method thereof - Google Patents

Polyimide and diamine monomer containing tetrabiphenyl derivative structure and preparation method thereof Download PDF

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CN116478400A
CN116478400A CN202310089572.0A CN202310089572A CN116478400A CN 116478400 A CN116478400 A CN 116478400A CN 202310089572 A CN202310089572 A CN 202310089572A CN 116478400 A CN116478400 A CN 116478400A
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bis
compound
reaction
polyimide
diamine monomer
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张艺
贝润鑫
邓博
蒋星
刘四委
池振国
许家瑞
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Sun Yat Sen University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
    • C07C211/50—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/325—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups reduction by other means than indicated in C07C209/34 or C07C209/36
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/52—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention relates to the technical field of high-performance functional polyimide new materials, in particular to polyimide and diamine monomers containing a tetrabiphenyl derivative structure and a preparation method thereof. The novel polyimide film obtained by polymerizing the diamine monomer containing the tetrabasic benzene derivative structure with the commercial diamine and dianhydride monomer has the performance characteristics of high frequency, low loss factor, low dielectric constant, low thermal expansion coefficient, low water absorption, high strength, high modulus, high heat resistance and the like, and can be used as a high-performance insulating base material in the technical field of electronic packaging such as high-frequency signal transmission and the like.

Description

Polyimide and diamine monomer containing tetrabiphenyl derivative structure and preparation method thereof
Technical Field
The invention relates to the technical field of material science, in particular to the field of high-performance functional polyimide new materials, and relates to polyimide and diamine monomers containing a tetrabenzol derivative structure and a preparation method thereof.
Technical Field
Polyimide films are widely used in the fields of flexible circuit boards (FCCL) and the like due to the advantages of high strength, excellent insulating property, dielectric property, high dimensional stability, high temperature resistance and the like. The 5G communication uses a higher frequency band for information transmission, and conventional polyimide films such as Kapton (ODA-PMDA) have a higher dielectric constant (D) at high frequencies k :3.5,10 GHz) and higher dissipation factor (D f :0.015,10 ghz), resulting in high signal loss, which cannot meet the use requirements of high-frequency communication.
Chinese patent CN 109651631B introduces a certain amount of fatty chain structure into the main chain to reduce the loss factor of the polyimide film to 0.003-0.006, however, the introduction of fatty chain tends to cause the deterioration of the dimensional stability of the PI film, the increase of the thermal expansion coefficient and the deterioration of the temperature resistance, and is difficult to be applied to FCCL.
Japanese patent JP2018-80315A proposes to use a tetraphenyl structure to prepare a low-loss polyimide film, however, the dielectric constant of a simple structure is higher, the dielectric constant of a system in the patent is 3.47-3.57, the loss factor is 0.0027-0.0037, and the thermal expansion coefficient is not mentioned, so that the application requirement of FCCL is still not met.
In many structural designs, in order to reduce the dielectric constant of the polyimide film, large-volume low-polarization structures such as fluorene, triptycene, alicyclic ring, aliphatic chain and the like are introduced, however, the structures often bring about the problems of larger high-frequency loss factor, larger thermal expansion coefficient and the like; to reduce the loss factor, structures such as ester bonds may be introduced, however, such structures result in a larger dielectric constant. Therefore, it is a difficult research in the art how to obtain a high frequency low loss factor while reducing the dielectric constant of the polyimide film and maintaining excellent combination properties such as a low expansion coefficient.
In view of the foregoing, there is a need in the art for a polyimide film that has the performance characteristics of high frequency low dielectric constant, low loss factor, low water absorption, low thermal expansion coefficient, high strength and high modulus.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide polyimide containing a tetrabiphenyl derivative structure, which can overcome the problem that the prior polyimide cannot be simultaneously combined with the high-frequency loss factor, the dielectric constant, the thermal expansion coefficient and the like.
It is another object of the present invention to provide a method for producing the above polyimide.
It is still another object of the present invention to provide diamine monomers containing a tetraphenyl derivative structure which can be used as a starting material for synthesizing the above polyimide.
It is a further object of the present invention to provide a process for the preparation of diamine monomers containing a tetraphenyl derived structure.
The technical scheme of the invention is as follows:
a polyimide containing a tetrabenamine-derived structure having a repeating structural unit represented by the general formula (I):
wherein R is A Is tetravalent aromatic hydrocarbon radical, R B Is a divalent aromatic hydrocarbon group, x and y represent polymers of repeated structural units, and x is y=100:0-1:99; r in a tetrabiphenyl derived structure 1 ～R 8 Are identical or different from each other and are each independently selected from hydrogen, fluorine, C1-C10 alkyl, fluorinated C1-C10 alkyl, C1-C10 ester, C1-C10 alkoxy, fluorinated C1-C10 alkoxy, C6-C30 aryl or C6-C30 aryloxy, and R 1 ～R 8 At least one of the groups is a non-hydrogen group.
The preparation method of the polyimide containing the tetrabasic benzene derivative structure comprises the following steps: will containThe diamine monomer of the tetrabiphenyl derivative structure is dissolved in a solvent, and then R is added A Polymerizing the aromatic dianhydride monomer with the structure to obtain viscous polyamic acid glue solution, and heating and curing the glue solution after coating to obtain a polyimide film; alternatively, a diamine monomer containing the tetraphenyl structure and a catalyst containing R B The aromatic diamine monomer with the structure is dissolved in a solvent, and then R is added A Polymerizing the aromatic dianhydride monomer with the structure to obtain viscous polyamic acid glue solution, and heating and curing the glue solution after coating to obtain the polyimide film.
The beneficial effects of the invention are as follows:
1) The invention adopts diamine monomer with a tetrabiphenyl derivative structure shown in a general formula (II), obtains a rigid and hydrophobic tetrabiphenyl main structure through combination of multi-step Suzuki reaction, and simultaneously obtains the diamine monomer with the tetrabiphenyl derivative structure in R 1 ～R 8 Hydrogen, fluorine, C1-C10 alkyl, fluorinated C1-C10 alkyl, C1-C10 ester, C1-C10 alkoxy, fluorinated C1-C10 alkoxy, C6-C30 aryl or C6-C30 aryloxy are introduced at the position(s) and R 1 ～R 8 At least one group is a non-hydrogen group, the diamine monomer containing the tetrabasic benzene derivative structure has a rigid aromatic main chain structure, and the polyimide film obtained by polymerizing the diamine monomer, commercial diamine and commercial dianhydride has the advantages of high frequency, low loss factor, low thermal expansion coefficient, low water absorption, high strength, high modulus and the like, and R is used for maintaining the high frequency, low loss performance 1 ～R 8 The introduction of the groups further reduces the dielectric constant of the PI film.
2) The diamine monomer containing the tetralin derivative structure provided by the invention is prepared by the steps of a 、R b 、R c 、R d The polyimide film is introduced to be identical or different from each other, and is independently selected from fluorine, methyl, trifluoromethyl, tertiary butyl, oxymethyl, oxybutyl and the like, so that the advantages of low loss factor, low water absorption, high dimensional stability, high modulus and the like brought by maintaining a tetrabiphenyl structure of the polyimide film can be further ensured, and meanwhile, the advantages of low dielectric constant and the like can be brought by introducing low-polarity and hydrophobic alkyl groups such as methyl, fluoroalkyl groups such as trifluoromethyl and the like through side groups.
3) The polyimide provided by the invention has a structure shown in a general formula (I), and the polyimide film obtained by polymerizing diamine monomer containing a tetrabiphenyl derivative structure with commercial diamine and dianhydride has the following excellent comprehensive properties: the high-frequency low-dielectric constant, low-loss factor, low thermal expansion coefficient, low water absorption, high strength and high modulus can be used as a high-performance insulating base material to be applied to the technical field of electronic packaging such as high-frequency signal transmission and the like.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a diamine monomer compound according to example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance spectrum of a diamine monomer compound according to example 2 of the present invention;
FIG. 3 is a nuclear magnetic resonance spectrum of a diamine monomer compound of example 3 of the present invention;
FIG. 4 is a nuclear magnetic resonance spectrum of a diamine monomer compound according to example 5 of the present invention;
FIG. 5 is a nuclear magnetic resonance spectrum of a diamine monomer compound according to example 6 of the present invention;
FIG. 6 is a nuclear magnetic resonance spectrum of a diamine monomer compound according to example 7 of the present invention;
FIG. 7 is a nuclear magnetic resonance spectrum of a diamine monomer compound according to example 8 of the present invention;
FIG. 8 is a high resolution mass spectrum of the diamine monomer compound of example 5 of the present invention, wherein the upper half is the signal peak diagram of the measured compound, the lower half is the signal peak diagram of the physical theory of the compound, the ordinate Relative Abundance is the relative abundance, and the abscissa m/z is the ratio of proton number to charge number;
FIG. 9 is a high resolution mass spectrum of the diamine monomer compound of example 6 of the present invention, wherein the upper half is the signal peak diagram of the measured compound, the lower half is the signal peak diagram of the physical theory of the compound, the ordinate Relative Abundance is the relative abundance, and the abscissa m/z is the ratio of proton number to charge number;
FIG. 10 is a mechanical graph of a polyimide film according to the present invention of application example 2, in which Tensile Strength is taken as the ordinate and elongation at break is taken as the abscissa Elongation at break, five samples are tested in total, and the average value of the five data is as shown in Table 3;
FIG. 11 is a mechanical graph of a polyimide film according to the present invention of application example 6, in which Tensile Strength is taken as the ordinate and elongation at break is taken as the abscissa Elongation at break, and five samples are tested in total, and the average values of the five data are shown in Table 3.
Detailed Description
The invention relates to polyimide containing a tetrabasic benzene derivative structure, which has a repeated structural unit shown in a general formula (I):
wherein R is A Is tetravalent aromatic hydrocarbon radical, R B Is a divalent aromatic hydrocarbon group, x and y represent polymers of repeated structural units, and x is y=100:0-1:99; r in a tetrabiphenyl derived structure 1 ～R 8 Are identical or different from each other and are each independently selected from hydrogen, fluorine, C1-C10 alkyl, fluorinated C1-C10 alkyl, C1-C10 ester, C1-C10 alkoxy, fluorinated C1-C10 alkoxy, C6-C30 aryl or C6-C30 aryloxy, and R 1 ～R 8 At least one of the groups is a non-hydrogen group.
Preferably, the C1-C10 alkyl is selected from methyl, ethyl, propyl, butyl or tert-butyl; the fluorinated C1-C10 alkyl is selected from trifluoromethyl or pentafluoroethyl; the C6-C30 aryl is selected from trifluoromethyl phenyl or tert-butylphenyl; the C1-C10 ester group is selected from methyl ester group, phenyl ester group or tert-butyl phenyl ester group; the C1-C10 alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy; the alkoxy of the fluoro C1-C10 is selected from perfluorobutyl ethoxy, and the aryloxy of the C6-C30 is selected from tert-butylphenoxy or trifluoromethyl phenoxy.
Preferably, x is an integer from 2 to 1000 and y is an integer from 0 to 1000.
More preferably, the tetraphenyl derived structure is selected from the following structures:
wherein R is a 、R b 、R c 、R d Are identical to or different from each other and are each independently selected from fluorine, methyl, trifluoromethyl, tert-butyl, oxymethyl or oxybutyl.
Most preferably, the tetraphenyl derived structure is selected from at least one of the following structures:
preferably, R A At least one selected from the following structures:
preferably, R B At least one selected from the following structures:
the preparation method of polyimide containing the tetrabiphenyl derivative structure comprises the following steps: dissolving diamine monomer containing the tetralin derivative structure in solvent, and adding the monomer containing R A Polymerizing the aromatic dianhydride monomer with the structure to obtain viscous polyamic acid glue solution, and heating and curing the glue solution after coating to obtain a polyimide film; alternatively, a diamine monomer containing the tetraphenyl derivative structure and a catalyst containing R B The aromatic diamine monomer with the structure is dissolved in a solvent, and then R is added A Polymerizing the aromatic dianhydride monomer with the structure to obtain viscous polyamic acid glue solution, and heating and curing the glue solution after coating to obtain the polyimide film.
Preferably, the diamine monomer containing the tetrabenzene derivative structure is of a structure shown in a general formula (II):
Wherein R is 1 ～R 8 Are identical or different from each other and are each independently selected from hydrogen, fluorine, C1-C10 alkyl, fluorinated C1-C10 alkyl, C1-C10 ester, C1-C10 alkoxy, fluorinated C1-C10 alkoxy, C6-C30 aryl or C6-C30 aryloxy, and R 1 ～R 8 At least one of the groups is a non-hydrogen group.
Said composition comprising R A The aromatic dianhydride monomer of the structure may be commercially available, preferably at least one of the following aromatic dianhydride monomers: 3,3',4' -biphenyltetracarboxylic dianhydride, 2, 3',4' -biphenyltetracarboxylic dianhydride, 3',4,4' -benzophenone tetracarboxylic dianhydride, 4' -oxydiphthalic anhydride, 2, 3',4' -diphenyl ether tetracarboxylic dianhydride, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride, 4' -terephthaloyl diphthalic anhydride, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride, 3',4,4' -diphenyl sulfone tetracarboxylic dianhydride, 4' - (4, 4' -isopropyl diphenoxy) diphthalic anhydride, p-phenylene-bis-trimellitate dianhydride;
comprising R B The aromatic diamine monomer having a structure may be commercially available, and is preferably at least one of the following aromatic diamine monomers: para-phenylenediamine, meta-phenylenediamine, 4 '-diaminodiphenyl ether, 4' -diaminodiphenyl methane, 4 '-diaminotetrabiphenyl 4,4' -diamino-p-terphenyl, 1, 3-bis (4 '-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene 2,2' -bis (trifluoromethyl) -4,4 '-diaminophenyl ether, 2' -difluoro-4, 4 '-diaminobiphenyl, 2' -bis (trifluoromethyl) diaminobiphenyl, 4 '-diamino-2, 2' -dimethyl-1, 1 '-biphenyl, 2' -bis [4- (4-aminophenoxyphenyl) ]Propane, phenyl 4,4 '-diaminobenzoate, di-p-aminophenyl terephthalate, 4' -diaminodiphenyl sulfone, 3 '-diaminodiphenyl sulfone 4,4' -diaminobiphenyl, 2 2 '-diaminodiphenyl sulfide, 4' -bis (3-aminophenoxy) benzophenone, 3',5,5' -tetramethyl biphenylAmine, 4 '-bis (4-aminophenoxy) biphenyl, 4' -bis (3-aminophenoxy) diphenylsulfone, 2-bis [4- (4-aminophenoxy) phenyl ]]Hexafluoropropane.
The diamine monomer containing the tetrabenzene derivative structure comprises R B Aromatic diamine monomer of structure and containing R A The addition proportion of the structural aromatic dianhydride monomer can regulate the performance of the PI film, and preferably, the diamine monomer containing the tetrabenzol derivative structure and the diamine monomer containing R B The molar ratio of the structural aromatic diamine monomer is 10% -100%: 0 to 90%, more preferably 50 to 100%: 0-50%. Comprising R A The total molar ratio of the aromatic dianhydride monomer having a structure to the diamine monomer is 0.99 to 1.01, more preferably 0.995 to 1.005. The components of the dianhydride monomer can be combined and adjusted according to the performance requirements.
Preferably, the solvent is at least one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and gamma-butyrolactone; the solid content of the viscous polyamide acid glue solution is 5 to 30 weight percent, and the viscosity is 10000 to 200000 mPa.S; the coated substrate may be a glass plate, a metal support; the heating and solidifying mode is inert gas atmosphere, the heating rate is 1-5 ℃/min, the highest temperature is 300-500 ℃, the highest temperature and constant temperature time is 10-60 min, more preferably, the heating rate is 2-3 ℃/min, the highest temperature is 350-400 ℃, and the constant temperature time is 20-30 min.
The invention provides a diamine monomer containing a tetrabiphenyl derivative structure, which has the following structure:
the invention provides a preparation method of diamine monomer containing a tetrabenzene derivative structure, which comprises the following sequential steps: (1) Raw material A1 is subjected to Miyaura boric acid esterification reaction to prepare a compound A2;
(2) Carrying out Suzuki coupling reaction on A2 and excessive halide A3 to prepare new halide A4;
(3) A4 and phenylboronic acid or boric acid ester A5 with amino or nitro are subjected to Suzuki reaction to prepare a compound A6;
(4) A6 and phenylboronic acid or boric acid ester A7 with amino or nitro are subjected to Suzuki reaction to prepare a compound A8; (5) A8, preparing the target product of the general formula (II) through reduction;
the synthetic route is as follows:
wherein X is halogen; y is boric acid ester or boric acid; z is Z 1 、Z 2 Amino or nitro; when the compound A4 is available commercially, omitting the steps (1) and (2); when A5 is the same as A7, the steps (3) and (4) are combined into one step; when Z is 1 Z is as follows 2 When the amino group is amino, the step (5) is omitted, and A8 is the target product of the general formula (II); when Z is 1 Or Z is 2 Reducing A8 with nitro group in the step (5) to obtain the target product of the general formula (II); wherein R is 1 ～R 8 Are identical or different from each other and are each independently selected from hydrogen, fluorine, C1-C10 alkyl, fluorinated C1-C10 alkyl, C1-C10 ester, C1-C10 alkoxy, fluorinated C1-C10 alkoxy, C6-C30 aryl or C6-C30 aryloxy, and R 1 ～R 8 At least one of the groups is a non-hydrogen group.
Preferably, in the step (1), the compound A1 is added into a solvent under the protection of inert gas, pinacol diboronate, alkali and a palladium catalyst are added, the solvent is removed after the reaction, and the compound A2 is obtained through separation and purification.
In the step (2), under the protection of inert gas, adding the compound A2 into a solvent, adding a catalytic amount of a catalyst, adding alkali liquor, then adding the compound A3 for reaction, separating liquid after the reaction is finished, removing the solvent by rotary evaporation, and separating and purifying to obtain a compound A4;
in the steps (3) and (4), under the protection of inert gas, adding raw materials into a solvent, adding a catalytic amount of catalyst, adding alkali liquor, then adding a compound with amino or nitro for reaction, separating liquid after the reaction is finished, removing the solvent by rotary evaporation, and separating and purifying to obtain a corresponding product;
in the step (5), after removing air, raw materials are added, and the target product of the general formula (II) is prepared through reduction reaction.
Preferably, in the step (1), the solvent is one of dimethyl sulfoxide, DMF, dioxane and toluene, the palladium catalyst is one of [1,1 '-bis (diphenylphosphine) ferrocene ] palladium dichloride and [1,1' -bis (diphenylphosphine) ferrocene ] palladium dichloride dichloromethane complex, and the base is potassium carbonate, potassium phosphate or potassium acetate, more preferably potassium acetate. Preferably, the reaction temperature is 80 to 110 ℃, more preferably 90 to 100 ℃.
Preferably, in the steps (2), (3) and (4), the solvent is at least one of tetrahydrofuran, dioxane, toluene, ethanol and DMF, the catalyst is one of tetraphenylphosphine palladium and triphenylphosphine/palladium acetate, and the base is one of sodium carbonate, potassium phosphate, cesium fluoride, cesium carbonate, barium hydroxide and sodium hydroxide; preferably, the reaction temperature is 65 to 100 ℃, more preferably 70 to 80 ℃.
Preferably, in the step (5), the reduction reaction may be a Pd/C catalyzed hydrogen reduction reaction, a Fe/dilute hydrochloric acid reduction reaction, a stannous chloride/dilute hydrochloric acid reduction reaction, or a Pd/C catalyzed hydrazine hydrate reduction reaction.
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a diamine monomer containing a tetrabiphenyl derivative structure, and the synthetic route of the compound is shown as follows:
the preparation method of the compound comprises the following specific steps:
(1) 2.5-dibromo-1.4-dimethoxybenzene (5.92 g,20 mmol), dioxane 100mL, bisboronic acid pinacol ester (5.08 g,20 mmol), potassium acetate (2.94 g, 30 mmol), catalytic amount of [1,1' -bis (diphenylphosphine) ferrocene ] palladium dichloride, keeping argon atmosphere, reacting for 24h at 100 ℃, filtering and rotary evaporating to remove solvent after the reaction is finished, purifying by column chromatography to obtain white solid A,
(6.17g，90％)。
(2) In a 250mL double-necked flask, add intermediate A (6.17 g,18 mmol), tetrahydrofuran (150 mL), p-dibromobenzene (8.50 g,36 mmol), aqueous potassium carbonate (2M, 27 mL), catalytic amount of tetra-triphenylphosphine palladium, keep argon atmosphere, protect 80 ℃ for 24h, split after the reaction, remove solvent by rotary evaporation, purify by column chromatography to obtain white solid B (5.62 g, 84%)
(3) In a 250mL two-necked flask, an intermediate B (5.58 g,15 mmol), tetrahydrofuran (100 mL), para-aminophenylboric acid (6.16 g,45 mmol), an aqueous potassium carbonate solution (2M, 45 mL), a catalytic amount of tetrakis triphenylphosphine palladium, and a reaction at 80℃were added, the reaction was completed, the reaction was separated, the solvent was removed by rotary evaporation, and a beige solid (4.40 g, 74%) was obtained after purification by column chromatography. The nuclear magnetic hydrogen spectrum of the compound is shown in figure 1, and the high resolution mass spectrum HRMS m/z is [ m+H ] ] + calcd for C 26 H 24 N 2 O 2 ,397.19105,found 397.19095
Example 2
The procedure is as in example 1, andthe raw material is changed from 2.5-dibromo-1.4-dimethoxy benzene to 1, 4-dibromo-tetramethyl benzene, and finally the white solid target compound is prepared. The nuclear magnetic hydrogen spectrum of the compound is shown in figure 2, and the high resolution mass spectrum HRMS m/z is [ m+H ]] + calcd for C 28 H 28 N 2 ,393.23253,found 393.23239
Example 3
The experimental procedure of example 1 was followed, substituting 2.5-dibromo-1.4-dimethoxybenzene for 2.5-dibromo-1-trifluoromethylbenzene to prepare the compound. The nuclear magnetic hydrogen spectrum of the compound is shown in figure 3, and the high resolution mass spectrum HRMS m/z is [ m+H ]] + calcd for C 25 H 19 F 3 N 2 ,405.15731,found 405.15759。
Example 4
The compound can be prepared by changing the raw materials in the same way as in example 3, and the high resolution mass spectrum HRMS m/z is [ m+H ]] + calcd for C 25 H 22 N 2 ,351.18121,found 351.18144。
Example 5
The experimental procedure of example 1 was followed, substituting 2.5-dibromo-1.4-dimethoxybenzene for 2.5-dibromo-1.4-dimethylbenzene to prepare the compound. The nuclear magnetic hydrogen spectrum of the compound is shown in figure 5, and the high resolution mass spectrum HRMS m/z is [ m+H ]] + calcd for C 26 H 24 N 2 ,365.20123,found365.20132。
Example 6
The experimental procedure of example 1 was followed, substituting 2.5-dibromo-1.4-dimethoxybenzene for 1, 4-dibromo-2, 5-bistrifluoromethyl benzene to prepare the compound. The nuclear magnetic hydrogen spectrum of the compound is shown in figure 6, and the high resolution mass spectrum HRMS m/z is [ m+H ]] + calcd for C 26 H 18 F 6 N 2 ,473.14469,found 473.14438。
Example 7
The preparation route is shown as above, and the experimental procedure of example 1 is the same, wherein the raw material is changed from 2.5-dibromo-1.4-dimethoxybenzene to 2.5-dibromo-1.4-dimethylbenzene; in the second reaction step, the raw material is changed from 1, 4-dibromobenzene to 2, 5-dibromo-1, 4-dimethylbenzene, so as to prepare the compound. The nuclear magnetic spectrum of the compound is shown in figure 7, and the high resolution mass spectrum HRMS m/z: [ m+H ] ] + calcd for C 28 H 28 N 2 ,393.23253,found 393.23215。
Example 8
The compound was prepared as in example 7 by replacing 2.5-dibromo-1.4-dimethylbenzene with 2.5-dibromo-1.4-difluorobenzene. The nuclear magnetic diagram of the compound is shown in figure 8, and the high resolution mass spectrum HRMS m/z: [ m+H ]] + calcd for C 24 H 16 F 4 N 2 ,409.13224,found 409.13141。
Example 9
As in example 7, the compound can be synthesized by changing the raw materials, and the high resolution mass spectrum HRMS m/z is [ m+H ]] + calcd for C 26 H 24 N 2 ,365.20123,found 365.20131。
Example 10
As in example 2, the synthesis of the compound was carried out by changing the starting material, and the high resolution mass spectrum HRMS m/z: [ m+H ]] + calcd for C 24 H 16 F 4 N 2 ,409.13224,found 409.13261。
Example 11
As in example 7, the synthesis of the compound was carried out by changing the starting material, and the high resolution mass spectrum HRMS m/z: [ m+H ]] + calcd for C 28 H 16 F 12 N 2 ,609.11212,found 609.11235。
Example 12
As in example 1, the synthesis of the compound was carried out by changing the starting materials, and the high resolution mass spectrum HRMS m/z: [ m+H ]] + calcd for C 32 H 36 N 2 ,448.29930,found 448.29920。
Example 13
As in example 1, the synthesis of the compound was carried out by changing the starting materials, and the high resolution mass spectrum HRMS m/z: [ m+H ]] + calcd for C 32 H 36 N 2 O 2 ,481.48226,found 481.48245。
Application example 1
The embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:
(1) The diamine monomer compound (1.0514 g,3 mmol) obtained in example 4 was precisely weighed into a 30mL round bottom flask under nitrogen protection, anhydrous DMAc (17.40 g) was added, 3', 4' -biphenyltetracarboxylic dianhydride (BPDA) (0.8827 g,3 mmol) was added after stirring and dissolution, and the reaction was stirred for 24 hours to obtain a viscous polyamic acid solution.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, then 2 ℃/min is heated to 360 ℃, and the temperature is kept at 360 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
application example 2
The embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:
(1) The diamine monomer compound (1.1895 g,3 mmol) obtained in example 1 was precisely weighed into a 30mL round bottom flask under nitrogen protection, anhydrous DMAc (18.65 g) was added, 3', 4' -biphenyltetracarboxylic dianhydride (BPDA) (0.8827 g,3 mmol) was added after stirring and dissolution, and the reaction was stirred for 24 hours to obtain a viscous polyamic acid solution.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, then 2 ℃/min is heated to 360 ℃, and the temperature is kept at 360 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
application example 3
The embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:
(1) The diamine monomer compound (1.1776 g,3 mmol) obtained in example 2 was precisely weighed into a 30mL round bottom flask under nitrogen protection, anhydrous DMAc (18.54 g) was added, 3', 4' -biphenyltetracarboxylic dianhydride (BPDA) (0.8827 g,3 mmol) was added after stirring and dissolution, and the reaction was stirred for 24 hours to obtain a viscous polyamic acid solution.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, then 2 ℃/min is heated to 350 ℃, and the temperature is kept at 350 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
application example 4
The embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:
(1) The diamine monomer compound (1.2133 g,3 mmol) obtained in example 3 was precisely weighed into a 30mL round bottom flask under nitrogen protection, anhydrous DMAc (18.86 g) was added, 3', 4' -biphenyltetracarboxylic dianhydride (BPDA) (0.8827 g,3 mmol) was added after stirring and dissolution, and the reaction was stirred for 24 hours to obtain a viscous polyamic acid solution.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, then 2 ℃/min is heated to 360 ℃, and the temperature is kept at 360 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
application example 5
The embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:
(1) The diamine monomer compound (1.0935 g,3 mmol) obtained in example 9 was precisely weighed into a 30mL round bottom flask under nitrogen protection, anhydrous DMAc (17.78 g) was added, 3', 4' -biphenyltetracarboxylic dianhydride (BPDA) (0.8827 g,3 mmol) was added after stirring and dissolution, and the reaction was stirred for 24 hours to obtain a viscous polyamic acid solution.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, then 2 ℃/min is heated to 350 ℃, and the temperature is kept at 350 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
application example 6
The embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:
(1) The diamine monomer compound (1.0935 g,3 mmol) obtained in example 5 was precisely weighed into a 30mL round bottom flask under nitrogen protection, anhydrous DMAc (17.78 g) was added, 3', 4' -biphenyltetracarboxylic dianhydride (BPDA) (0.8827 g,3 mmol) was added after stirring and dissolution, and the reaction was stirred for 24 hours to obtain a viscous polyamic acid solution.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, then 2 ℃/min is heated to 350 ℃, and the temperature is kept at 350 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
application example 7
The embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:
(1) The diamine monomer compound (1.1776 g,3 mmol) obtained in example 7 was precisely weighed in a 30mL round bottom flask under nitrogen protection, anhydrous DMAc (18.54 g) was added, 3', 4' -biphenyltetracarboxylic dianhydride (BPDA) (0.8827 g,3 mmol) was added after stirring and dissolution, and the reaction was stirred for 24 hours to obtain a viscous polyamic acid solution.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, then 2 ℃/min is heated to 350 ℃, and the temperature is kept at 350 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
application example 8
The embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:
(1) The diamine monomer compound (1.3460 g,3 mmol) obtained in example 12 was precisely weighed in a 30mL round bottom flask under nitrogen protection, anhydrous DMAc (14.91 g) was added, 3', 4' -biphenyltetracarboxylic dianhydride (BPDA) (0.8827 g,3 mmol) was added after stirring and dissolution, and the reaction was stirred for 24 hours to obtain a viscous polyamic acid solution.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, then 2 ℃/min is heated to 350 ℃, and the temperature is kept at 350 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
application example 9
The embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:
(1) The diamine monomer compound (1.4173 g,3 mmol) obtained in example 6 was precisely weighed into a 30mL round bottom flask under nitrogen protection, anhydrous DMAc (15.39 g) was added, 3', 4' -biphenyltetracarboxylic dianhydride (BPDA) (0.8827 g,3 mmol) was added after stirring and dissolution, and the reaction was stirred for 24 hours to obtain a viscous polyamic acid solution.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, then 2 ℃/min is heated to 350 ℃, and the temperature is kept at 350 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
application example 10
The embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:
(1) The diamine monomer compound (1.2252 g,3 mmol) obtained in example 8 was precisely weighed into a 30mL round bottom flask under nitrogen protection, anhydrous DMAc (14.11 g) was added, 3', 4' -biphenyltetracarboxylic dianhydride (BPDA) (0.8827 g,3 mmol) was added after stirring and dissolution, and the reaction was stirred for 24 hours to obtain a viscous polyamic acid solution.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, then 2 ℃/min is heated to 360 ℃, and the temperature is kept at 360 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
application example 11
The embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:
(1) The diamine monomer compound (1.4420 g,3 mmol) obtained in example 13 was precisely weighed into a 30mL round bottom flask under nitrogen protection, anhydrous DMAc (13.17 g) was added, 3', 4' -biphenyltetracarboxylic dianhydride (BPDA) (0.8827 g,3 mmol) was added after stirring and dissolution, and the reaction was stirred for 24 hours to obtain a viscous polyamic acid solution.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, then heating to 300 ℃ at 2 ℃/min, and keeping the temperature at 300 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
application example 12
The embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:
(1) The diamine monomer compound (0.8089 g,2 mmol) obtained in example 3 was precisely weighed in a 30mL round bottom flask under nitrogen protection, 2' -bis (trifluoromethyl) diaminobiphenyl TFMB (0.6405, 2 mmol) was added with anhydrous DMAc (11.96 g), 3', 4' -biphenyltetracarboxylic dianhydride BPDA (1.1769 g,4 mmol) was added after stirring and dissolution, and the reaction was stirred for 24 hours to obtain a viscous polyamic acid solution.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, then 2 ℃/min is heated to 350 ℃, and the temperature is kept at 350 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
application example 13
The embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:
(1) The diamine monomer compound (0.7280 g,1.8 mmol) obtained in example 3 was precisely weighed in a 30mL round bottom flask under nitrogen protection, 2' -bis (trifluoromethyl) diaminobiphenyl TFMB (1.3450, 4.2 mmol) was added with anhydrous DMAc (15.35 g), 3', 4' -biphenyltetracarboxylic dianhydride BPDA (1.7653 g,6 mmol) was added after stirring and dissolution, and the reaction was stirred for 24 hours to obtain a viscous polyamic acid solution.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, then 2 ℃/min is heated to 350 ℃, and the temperature is kept at 350 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
application example 14
The embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:
(1) The diamine monomer compound (0.7851 g,2 mmol) obtained in example 2 was precisely weighed in a 30mL round bottom flask under nitrogen protection, 2' -bis (trifluoromethyl) diaminobiphenyl TFMB (0.6405 g,2 mmol) was added to anhydrous DMAc (14.74 g), 3', 4' -biphenyltetracarboxylic dianhydride BPDA (1.1769 g,4 mmol) was added after stirring and dissolution, and the reaction was stirred for 24 hours to obtain a viscous polyamic acid solution.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, then 2 ℃/min is heated to 350 ℃, and the temperature is kept at 350 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
application example 15
The embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:
(1) The diamine monomer compound (1.5702 g,4 mmol) obtained in example 2 was precisely weighed into a 30mL round bottom flask under nitrogen protection, anhydrous DMAc (13.34 g) was added, and after stirring and dissolution, 4'- (4, 4' -isopropyldiphenoxy) bis (phthalic anhydride) BPADA (0.4164 g,0.8 mmol) 3,3', 4' -biphenyltetracarboxylic dianhydride BPDA (0.9415 g,3.2 mmol) was added and stirred for 24 hours to obtain a viscous polyamic acid solution.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, then 2 ℃/min is heated to 350 ℃, and the temperature is kept at 350 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
application example 16
The embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:
(1) Diamine monomer Compound (0.8748 g,2.4 mmol) obtained in example 9 and 2,2' -bis [4- (4-aminophenoxyphenyl) ] propane BAPP (0.2463 g,0.6 mmol) were precisely weighed under nitrogen protection in a 30mL round bottom flask, and after stirring and dissolution, 3', 4' -benzophenone tetracarboxylic dianhydride BTDA (0.9667 g,3.0 mmol) was added thereto and stirred for reaction for 24 hours to obtain a viscous polyamic acid solution.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, then 2 ℃/min is heated to 350 ℃, and the temperature is kept at 350 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
application example 17
The embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:
(1) The diamine monomer compound (1.0935 g,3.0 mmol) obtained in example 5 was precisely weighed into a 30mL round bottom flask under nitrogen protection, anhydrous DMAc (18.21 g) was added, and after stirring and dissolution, 4' -oxydiphthalic anhydride ODPA (0.9306 g,3.0 mmol) was added and stirred for 24 hours to obtain a viscous polyamic acid solution.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, then 2 ℃/min is heated to 350 ℃, and the temperature is kept at 350 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
application example 18
The embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:
(1) The diamine monomer compound (1.4173 g,3.0 mmol) obtained in example 6 was precisely weighed out under nitrogen protection in a 30mL round bottom bottle, anhydrous DMAc (14.68 g) was added, 3', 4' -biphenyltetracarboxylic dianhydride BPDA (0.7061 g,2.4 mmol) and 4,4' - (hexafluoroisopropenyl) diphthalic anhydride 6FDA (0.2665 g,0.6 mmol) were added after stirring and dissolution, and the reaction was stirred for 24 hours to obtain a viscous polyamic acid solution.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, then 2 ℃/min is heated to 350 ℃, and the temperature is kept at 350 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
application example 19
The embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:
(1) The diamine monomer compound (1.4420 g,3 mmol) obtained in example 13 was precisely weighed into a 30mL round bottom flask under nitrogen protection, anhydrous DMAc (17.20 g) was added, 3', 4' -biphenyltetracarboxylic acid dianhydride BPDA (0.4413 g,1.5 mmol) and p-phenylene-bis-trimellitate dianhydride TAHQ (0.6875 g,1.5 mmol) were added after stirring and dissolution, and the reaction was stirred for 24 hours to obtain a viscous polyamic acid solution.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, then heating to 300 ℃ at 2 ℃/min, and keeping the temperature at 300 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
comparative example 1
The comparative example provides a polyimide film, the preparation method of which comprises the following steps:
(1) Diamine monomer 4,4' -diaminodiphenyl ether ODA (1.2014 g,6 mmol) is accurately weighed in a 30mL round bottom bottle under the protection of nitrogen, anhydrous DMAc (14.22 g) is added, pyromellitic anhydride PMDA (1.3087 g,6 mmol) is added after stirring and dissolving, and stirring reaction is carried out for 24 hours, so that viscous polyamic acid glue solution is obtained.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, and then the temperature is increased to 400 ℃ at 2 ℃/min, and the temperature is kept at 400 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
comparative example 2
The comparative example provides a polyimide film, the preparation method of which comprises the following steps:
(1) Diamine monomer p-phenylenediamine (0.7570 g,7 mmol) is accurately weighed into a 30mL round bottom bottle under the protection of nitrogen, anhydrous DMAc (15.96 g) is added, 3', 4' -biphenyl tetracarboxylic dianhydride (BPDA) (2.0595 g,7 mmol) is added after stirring and dissolving, and the mixture is stirred and reacted for 24 hours to obtain viscous polyamic acid glue solution.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, and then the temperature is increased to 400 ℃ at 2 ℃/min, and the temperature is kept at 400 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
comparative example 3
The comparative example provides a polyimide film, the preparation method of which comprises the following steps:
(1) Diamine monomer 2,2' -bis (trifluoromethyl) diaminobiphenyl TFMB (1.6011 g,5 mmol) was precisely weighed in a 30mL round bottom flask under the protection of nitrogen, anhydrous DMAc (14.00 g) was added, 3', 4' -biphenyltetracarboxylic dianhydride BPDA (1.4711 g,5 mmol) was added after stirring and dissolution, and the reaction was stirred for 24 hours to obtain a viscous polyamic acid solution.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, then 2 ℃/min is heated to 350 ℃, and the temperature is kept at 350 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
comparative example 4
The comparative example provides a polyimide film, the preparation method of which comprises the following steps:
(1) Diamine monomer 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyl (1.0614 g,5 mmol) was precisely weighed in a 30mL round bottom bottle under nitrogen protection, anhydrous DMAc (14.35 g) was added, 3', 4' -biphenyl tetracarboxylic dianhydride BPDA (1.4711 g,5 mmol) was added after stirring and dissolution, and the reaction was stirred for 24 hours to obtain a viscous polyamic acid solution.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, then 2 ℃/min is heated to 350 ℃, and the temperature is kept at 350 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
comparative example 5
The comparative example provides a polyimide film, the preparation method of which comprises the following steps:
(1) Diamine monomer 4,4' -diaminotetrabiphenyl (1.399 g,3 mmol) was precisely weighed in a 30mL round bottom bottle under the protection of nitrogen, anhydrous DMAc (17.03 g) was added, 3', 4' -biphenyltetracarboxylic dianhydride (BPDA) (0.8827 g,3 mmol) was added after stirring and dissolution, and the reaction was stirred for 24 hours to obtain a viscous polyamic acid solution.
(2) Coating the polyamic acid glue solution on a clean glass plate after vacuum defoaming, and heating and curing under a nitrogen atmosphere, wherein the curing program is 80 ℃ for 1h, and then the temperature is increased to 400 ℃ at 2 ℃/min, and the temperature is kept at 400 ℃ for 30min.
The repeating structural units of the polyimide film are as follows:
test results
The nuclear magnetic hydrogen spectrum test of the monomer is obtained by a AVANCE III 400.sup.400 nuclear magnetic resonance spectrometer test of Bruker company. The solvent used for the test was deuterated dimethyl sulfoxide (DMSO-d 6 ) Or deuterated chloroform (CDCl) 3 ) The concentration of the sample at the time of hydrogen spectrum test was about 4 mg.mL -1 。
The high-resolution mass spectrum test of the monomer is obtained through a QExactive hydrogenation test of a high-resolution orbitrap liquid chromatography-mass spectrometer of Sieimer, germany.
The test method of polyimide thin high-frequency dielectric constant and loss factor comprises the following steps: the vector network analyzer P5003A which is the Detech Keysight is adopted, the resonant cavity is a separation column dielectric resonant cavity (10 GHz) of the Poland QWED, the environmental humidity is controlled to be 50% RH, and the temperature is 25 ℃.
The water absorption test method comprises the following steps: vacuum drying film at 150deg.C for 12 hr, transferring to dryer, recovering to room temperature, and weighing to obtain W 0 Placing the film in water, soaking at 25deg.C for 12 hr, taking out, wiping clean surface water, and weighing W 1 . The water absorption rate is as follows: (W) 1 -W 0 )/W 0 *100％。
The test method of mechanical properties (tensile strength, elongation at break and elastic modulus) comprises the following steps: five bars were tested for each application example, with reference to national standard GB/T1040.1-2018, with the average of five values being the final result, as listed in table 3.
Thermal expansion coefficient test of polyimide film: using TA company D450 equipment, heating to 200 ℃ at 10 ℃/min, cooling to 50 ℃ at 10 ℃/min, heating to 400 ℃ at 10 ℃/min, and taking the linear expansion coefficient CTE as a temperature section of 100-200 ℃.
The composition of the high-frequency low-loss polyimide film containing tetrabasic benzene is shown in the following table 1. The mole% represents the respective mole ratios of the monomers in the entire diamine and dianhydride.
Polyimide films prepared in application examples and comparative examples were tested according to the above method, and the data obtained are shown in tables 2 and 3.
TABLE 1 monomer composition and ratio of polyimide films of the series listed in this patent
TABLE 2 comparative parameters of polyimide films prepared by application examples and comparative examples
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TABLE 3 mechanical Properties of films
Tensile Strength (MPa) Elastic membrane quantity (GPa) Elongation at break (%)
Application example 1 415 8.6 38.5
Application example 2 434 8.8 35.2
Application example 3 330 6.9 39.3
Application example 4 403 7.6 42.3
Application example 5 421 8.1 41.2
Application example 6 435 8.4 39.0
Application example 7 414 8.0 24.1
Application example 8 350 7.2 27.0
Application example 9 385 7.2 40.3
Application example 10 310 7.8 20.1
Application example 11 320 6.4 35.6
Application example 12 372 6.7 39.4
Application example 13 303 6.5 22.5
Application example 14 381 6.9 38.6
Application example 15 210 5.2 51.7
Application example 16 250 5.5 40.6
Application example 17 315 6.8 36.7
Application example 18 290 5.7 32.2
Application example 19 308 6.3 26.2
Comparative example 1 160 2.2 35.6
Comparative example 2 305 7.5 20.1
Comparative example 3 195 5.5 10.4
Comparative example 4 300 7.9 10.0
Comparative example 5 255 7.5 17.2
The advantages of the diamine monomer structure containing the tetrabasic benzene derivative structure in the high-frequency low-loss polyimide film designed by the invention can be clearly illustrated by the examples: the dielectric constant of the polyimide film is effectively reduced and excellent comprehensive performance is obtained by introducing groups such as methyl, trifluoromethyl, fluorine atoms, tertiary butyl and the like while the loss factor is low enough: has very low water absorption, low thermal expansion coefficient and excellent mechanical property. The specific data were analyzed as follows:
common polyimide films such as ODA-PMDA, PPD-BPDA and the like in the comparative example have loss factors as high as 0.00568-0.0130, and the loss factors in the examples are 0.00248-0.00581, most of the loss factors are lower than 0.0035, the loss factors are generally lower, and the use requirements of low loss factors in the field of high-frequency communication are met; for example, polyimide films polymerized from pure tetraphenylenediamine monomer and BPDA have a low loss factor 0.00262, but have a dielectric constant as high as 3.71, which cannot meet the low dielectric constant requirement in the high frequency communication field. On the basis, the dielectric constant is reduced from 3.71 to 3.05-3.60 by introducing methyl, trifluoromethyl, fluorine atom, tertiary butyl and other groups, and most of the dielectric constant is lower than 3.35. Meanwhile, the mechanical property tensile strength of the embodiment is 210-435 Mpa, the modulus is 5.2-8.8 Gpa, the elongation at break is 24.1-51.7%, the coefficient of thermal expansion CTE is-3.7-22.5, the water absorption is lower than 0.9%, and the composite material has excellent comprehensive properties, and is particularly suitable for being applied to the technical field of electronic packaging such as high-frequency signal transmission and the like as a high-performance insulating base material.

Claims (10)

1. A polyimide containing a tetrabenamine-derived structure having a repeating structural unit represented by the general formula (I):
wherein R is A Is tetravalent aromatic hydrocarbon radical, R B Is a divalent aromatic hydrocarbon group, x and y represent polymers of repeated structural units, and x is y=100:0-1:99; r in a tetrabiphenyl derived structure 1 ～R 8 Are identical or different from each other and are each independently selected from hydrogen, fluorine, C1-C10 alkyl, fluorinated C1-C10 alkyl, C1-C10 ester, C1-C10 alkoxy, fluorinated C1-C10 alkoxy, C6-C30 aryl or C6-C30 aryloxy, and R 1 ～R 8 At least one of the groups is a non-hydrogen group.
2. The polyimide containing a tetrabenamine derived structure according to claim 1, wherein: the C1-C10 alkyl is selected from methyl, ethyl, propyl, butyl or tertiary butyl; the fluorinated C1-C10 alkyl is selected from trifluoromethyl or pentafluoroethyl; the C6-C30 aryl is selected from trifluoromethyl phenyl or tert-butylphenyl; the C1-C10 ester group is selected from methyl ester group, phenyl ester group or tert-butyl phenyl ester group; the C1-C10 alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy; the alkoxy of the fluoro C1-C10 is selected from perfluorobutyl ethoxy, and the aryloxy of the C6-C30 is selected from tert-butylphenoxy or trifluoromethyl phenoxy.
3. The polyimide containing a tetrabenamine derived structure according to claim 1, wherein: the tetrabenzene derivative structure is selected from at least one of the following structures:
wherein R is a 、R b 、R c 、R d Are identical to or different from each other and are each independently selected from fluorine, methyl, trifluoromethyl, tert-butyl, oxymethyl or oxybutyl.
4. The polyimide containing a tetrabenamine derived structure according to claim 1, wherein: the tetrabenzene derivative structure is selected from at least one of the following structures:
preferably, R A At least one selected from the following structures:
preferably, R B At least one selected from the following structures:
5. the method for producing a polyimide having a tetraphenyl derivative structure according to claim 1 to 4, comprising the steps of: dissolving diamine monomer containing the tetralin derivative structure in solvent, and adding the monomer containing R A Polymerizing the aromatic dianhydride monomer with the structure to obtain viscous polyamic acid glue solution, and heating and curing the glue solution after coating to obtain a polyimide film; alternatively, a diamine monomer containing the tetraphenyl derivative structure and a catalyst containing R B The aromatic diamine monomer with the structure is dissolved in a solvent, and then R is added A Polymerizing the aromatic dianhydride monomer with the structure to obtain viscous polyamic acid glue solution, and heating and curing the glue solution after coating to obtain the polyimide film.
6. The method for producing a polyimide having a tetraphenyl derivative structure according to claim 5, wherein: the diamine monomer containing the tetrabasic benzene derivative structure is of a structure shown in a general formula (II):
wherein R is 1 ～R 8 Are identical or different from each other and are each independently selected from hydrogen, fluorine, C1-C10 alkyl, fluorinated C1-C10 alkyl, C1-C10 ester, C1-C10 alkoxy, fluorinated C1-C10 alkoxy, C6-C30 aryl or C6-C30 aryloxy, and R 1 ～R 8 At least one of the groups is a non-hydrogen group.
7. The method for producing a polyimide having a tetraphenyl derivative structure according to claim 5, wherein: said composition comprising R A The aromatic dianhydride monomer with the structure is selected from at least one of the following aromatic dianhydride monomers: 3,3',4' -biphenyltetracarboxylic dianhydride, 2, 3',4' -biphenyltetracarboxylic dianhydride, 3',4,4' -benzophenone tetracarboxylic dianhydride, 4' -oxydiphthalic anhydride, 2, 3',4' -diphenyl ether tetracarboxylic dianhydride, 2 ' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride, 4' -terephthaloyl diphthalic anhydride, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride, 3',4,4' -diphenyl sulfone tetracarboxylic dianhydride, 4' - (4, 4' -isopropyl diphenoxy) diphthalic anhydride, p-phenylene-bis-trimellitate dianhydride;
Comprising R B The aromatic diamine monomer with the structure is selected from at least one of the following aromatic diamine monomers: para-phenylenediamine, meta-phenylenediamine, 4 '-diaminodiphenyl ether, 4' -diaminodiphenyl methane, 4 '-diaminotetrabiphenyl 4,4' -diamino-p-terphenyl, 1, 3-bis (4 '-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene 2,2' -bis (trifluoromethyl) -4,4 '-diaminophenyl ether, 2' -difluoro-4, 4 '-diaminobiphenyl, 2' -bis (trifluoromethyl) diaminobiphenyl, 4 '-diamino-2, 2' -dimethyl-1, 1 '-biphenyl, 2' -bis [4- (4-amino) biphenylPhenoxyphenyl group]Propane, phenyl 4,4 '-diaminobenzoate, di-p-aminophenyl terephthalate, 4' -diaminodiphenyl sulfone, 3 '-diaminodiphenyl sulfone 4,4' -diaminobiphenyl, 2 2 '-diaminodiphenyl sulfide, 4' -bis (3-aminophenoxy) benzophenone, 3',5,5' -tetramethylbenzidine, 4 '-bis (4-aminophenoxy) biphenyl, 4' -bis (3-aminophenoxy) diphenylsulfone, 2-bis [4- (4-aminophenoxy) phenyl ]]Hexafluoropropane.
8. A diamine monomer containing a tetrabenamine derivative structure, which has the following structure:
9. a method for preparing diamine monomer containing a tetrabenamine derivative structure, which comprises the following sequential steps:
(1) Raw material A1 is subjected to Miyaura boric acid esterification reaction to prepare a compound A2;
(2) Carrying out Suzuki coupling reaction on A2 and excessive halide A3 to prepare new halide A4;
(3) A4 and phenylboronic acid or boric acid ester A5 with amino or nitro are subjected to Suzuki reaction to prepare a compound A6; (4) A6 and phenylboronic acid or boric acid ester A7 with amino or nitro are subjected to Suzuki reaction to prepare a compound A8; (5) A8, preparing the target product of the general formula (II) through reduction;
the synthetic route is as follows:
wherein X is halogen; y is boric acid ester or boric acid; z is Z 1 、Z 2 Amino or nitro; when the compound A4 is available commercially, omitting the steps (1) and (2); when A5 is the same as A7, the steps (3) and (4) are combined into one step; when Z is 1 Z is as follows 2 When the amino group is amino, the step (5) is omitted, and A8 is the target product of the general formula (II); when Z is 1 Or Z is 2 Reducing A8 with nitro group in the step (5) to obtain the target product of the general formula (II); wherein R is 1 ～R 8 Are identical or different from each other and are each independently selected from hydrogen, fluorine, C1-C10 alkyl, fluorinated C1-C10 alkyl, C1-C10 ester, C1-C10 alkoxy, fluorinated C1-C10 alkoxy, C6-C30 aryl or C6-C30 aryloxy, and R 1 ～R 8 At least one of the groups is a non-hydrogen group.
10. The method for producing a diamine monomer having a tetraphenyl derivative structure according to claim 9, wherein: in the step (1), under the protection of inert gas, adding the compound A1 into a solvent, adding pinacol diboronate, alkali and a palladium catalyst, removing the solvent after reaction, and separating and purifying to obtain a compound A2; in the step (2), under the protection of inert gas, adding the compound A2 into a solvent, adding a catalytic amount of a catalyst, adding alkali liquor, then adding the compound A3 for reaction, separating liquid after the reaction is finished, removing the solvent by rotary evaporation, and separating and purifying to obtain a compound A4; in the steps (3) and (4), under the protection of inert gas, adding raw materials into a solvent, adding a catalytic amount of catalyst, adding alkali liquor, then adding a compound with amino or nitro for reaction, separating liquid after the reaction is finished, removing the solvent by rotary evaporation, and separating and purifying to obtain a corresponding product; in the step (5), after removing air, adding raw materials, and preparing a target product of a general formula (II) through a reduction reaction;
Preferably, in the step (1), the solvent is one of dimethyl sulfoxide, dimethylformamide (DMF), dioxane and toluene, the palladium catalyst is one of [1,1 '-bis (diphenylphosphine) ferrocene ] palladium dichloride and [1,1' -bis (diphenylphosphine) ferrocene ] palladium dichloride dichloromethane complex, the alkali is potassium carbonate, potassium phosphate or potassium acetate, and the reaction temperature is 80-110 ℃; in the steps (2), (3) and (4), the solvent is at least one of tetrahydrofuran, dioxane, toluene, ethanol and DMF, the catalyst is one of triphenylphosphine palladium and triphenylphosphine/palladium acetate, the alkali is one of sodium carbonate, potassium phosphate, cesium fluoride, cesium carbonate, barium hydroxide and sodium hydroxide, and the reaction temperature is 65-100 ℃; in the step (5), the reduction reaction is hydrogen reduction reaction under Pd/C catalysis, reduction reaction under Fe/dilute hydrochloric acid, reduction reaction under stannous chloride/dilute hydrochloric acid or hydrazine hydrate reduction reaction under Pd/C catalysis.
CN202310089572.0A 2023-02-06 2023-02-06 Polyimide and diamine monomer containing tetrabiphenyl derivative structure and preparation method thereof Pending CN116478400A (en)

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