CN116478400B - Polyimide and diamine monomer containing quaternary phenyl derivative structure and preparation method thereof - Google Patents

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 quaternary phenyl derivative structure and preparation method thereof

Technical Field

The invention relates to the field of material science and technology, in particular to the field of high-performance functional polyimide new materials, and relates to a polyimide containing a quaternary phenyl derivative structure, a diamine monomer and a preparation method thereof.

Technical Background

Polyimide films are widely used in flexible printed circuit boards (FCCL) and other fields due to their high strength, excellent insulation performance, dielectric properties, high dimensional stability, high temperature resistance and other advantages. 5G communication uses higher frequency bands for information transmission. Traditional polyimide films such as Kapton (ODA-PMDA) have higher dielectric constants (D _k : 3.5, 10GHz) and higher loss factors (D _f : 0.015, 10GHz) at high frequencies, resulting in higher signal losses, which can no longer meet the use requirements of high-frequency communications.

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 chains will inevitably lead to poor dimensional stability of the PI film, increased thermal expansion coefficient, and poor temperature resistance, making it difficult to apply to FCCL.

Japanese patent JP2018-80315A proposes the use of a quaternary biphenyl structure to prepare a low-loss polyimide film. However, the dielectric constant of this structure alone is relatively high. The dielectric constant of the system in the patent is 3.47 to 3.57, the loss factor is 0.0027 to 0.0037, and the thermal expansion coefficient is not mentioned, which still cannot meet the application requirements of FCCL.

Among many structural designs, in order to reduce the dielectric constant of polyimide film, large volume and low polarization structures such as fluorene, triptycene, aliphatic ring, and aliphatic chain are introduced. However, such structures often bring problems such as large high-frequency loss factor and large thermal expansion coefficient. In order to reduce the loss factor, structures such as ester bonds can be introduced, but such structures lead to large dielectric constants. Therefore, how to reduce the dielectric constant of polyimide film while obtaining high-frequency low loss factor, while maintaining its excellent comprehensive performance such as low expansion coefficient, has become a research difficulty in this field.

In view of this, there is an urgent need in the art for a polyimide film that simultaneously possesses the performance characteristics of high frequency and low dielectric constant, low loss factor, low water absorption, low thermal expansion coefficient, high strength and high modulus.

Summary of the invention

In view of the shortcomings of the prior art, the object of the present invention is to provide a polyimide containing a quaternary phenyl derivative structure, which can overcome the problem that the existing polyimide cannot simultaneously achieve high-frequency loss factor, dielectric constant, thermal expansion coefficient, etc.

Another object of the present invention is to provide a method for preparing the polyimide.

Another object of the present invention is to provide a diamine monomer containing a quaternary phenyl derivative structure, which can be used as a raw material to synthesize the above-mentioned polyimide.

Another object of the present invention is to provide a method for preparing a diamine monomer containing a quaternary phenyl derivative structure.

The technical solution of the present invention is as follows:

A polyimide containing a quaternary phenyl derivative structure has a repeating structural unit represented by the general formula (I):

wherein _RA is a tetravalent aromatic hydrocarbon group, _RB is a divalent aromatic hydrocarbon group, x and y represent a polymer of repeating structural units, and x:y=100:0-1:99; _R1 - _R8 in the quaterphenyl derivative structure are the same as or different from each other, and are 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 at least one of _R1 - _R8 is a non-hydrogen group.

The preparation method of the polyimide containing a quaternary phenyl derivative structure comprises the following steps: dissolving a diamine monomer containing the quaternary phenyl derivative structure in a solvent, then adding an aromatic dianhydride monomer containing an _RA structure to polymerize to obtain a viscous polyamic acid glue solution, and heating and curing the solution after coating to obtain a polyimide film; or dissolving a diamine monomer containing the quaternary phenyl structure and an aromatic diamine monomer containing an _RB structure in a solvent, then adding an aromatic dianhydride monomer containing an _RA structure to polymerize to obtain a viscous polyamic acid glue solution, and heating and curing the solution after coating to obtain a polyimide film.

The beneficial effects of the present invention are:

1) The present invention adopts a diamine monomer containing a quaternary derivative structure represented by the general formula (II) to obtain a rigid and hydrophobic quaternary main structure through a combination of multiple Suzuki reactions, and simultaneously introduces 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 at the positions of R 1 to R 8, and at least one of R ₁ to R ₈ is a non-hydrogen group. The diamine monomer containing a quaternary derivative structure provided by the present invention has a rigid aromatic main chain structure, and the polyimide film obtained by polymerizing the diamine monomer with 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, etc., and while maintaining the high frequency low loss performance, the introduction of the R ₁ to R ₈ groups further reduces the dielectric constant of the PI film.

2) The diamine monomer containing a quaterphenyl derivative structure provided by the present invention can further ensure that the polyimide film maintains the advantages of low loss factor, low water absorption, high dimensional stability, high ^modulus , etc. brought by the quaterphenyl structure by introducing the same or different groups into ^Ra , Rb, ^Rc , and ^Rd , each independently selected from fluorine, methyl, trifluoromethyl, tert-butyl, oxymethyl, or oxybutyl. At the same time, low polarity and hydrophobic alkyl groups such as methyl and fluoroalkyl groups such as trifluoromethyl can be introduced through side groups to bring advantages such as low dielectric constant.

3) The structure of the polyimide provided by the present invention is shown in the general formula (I). The polyimide film obtained by polymerizing the diamine monomer containing a quaternary derivative structure with commercial diamine and dianhydride has the following excellent comprehensive properties: high frequency and low dielectric constant, low loss factor, low thermal expansion coefficient, low water absorption, high strength, and high modulus. It can be used as a high-performance insulating substrate in the field of electronic packaging technology such as high-frequency signal transmission.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is a hydrogen NMR spectrum of a diamine monomer compound of Example 1 of the present invention;

FIG2 is a hydrogen NMR spectrum of the diamine monomer compound of Example 2 of the present invention;

FIG3 is a hydrogen NMR spectrum of the diamine monomer compound of Example 3 of the present invention;

FIG4 is a hydrogen NMR spectrum of the diamine monomer compound of Example 5 of the present invention;

FIG5 is a hydrogen NMR spectrum of the diamine monomer compound of Example 6 of the present invention;

FIG6 is a hydrogen NMR spectrum of the diamine monomer compound of Example 7 of the present invention;

FIG7 is a hydrogen NMR spectrum of the diamine monomer compound of Example 8 of the present invention;

FIG8 is a high-resolution mass spectrum of the diamine monomer compound of Example 5 of the present invention, wherein the upper part is a peak diagram of the measured compound signal, the lower part is a peak diagram of the theoretical compound signal, the ordinate Relative Abundance is the relative abundance, and the abscissa m/z is the ratio of the number of protons/the number of charges;

FIG9 is a high-resolution mass spectrum of the diamine monomer compound of Example 6 of the present invention, wherein the upper part is a peak diagram of the measured compound signal, the lower part is a peak diagram of the theoretical compound signal, the ordinate Relative Abundance is the relative abundance, and the abscissa m/z is the ratio of the number of protons to the number of charges;

FIG10 is a mechanical curve diagram of the polyimide film of Application Example 2 of the present invention, wherein the ordinate TensileStrength is the tensile strength, and the abscissa Elongation at break is the elongation at break. A total of five samples were tested, and the average values of the five data are as listed in Table 3;

FIG11 is a mechanical curve diagram of the polyimide film of Application Example 6 of the present invention, wherein the ordinate TensileStrength is the tensile strength, and the abscissa Elongation at break is the elongation at break. A total of five samples were tested, and the average values of the five data are as listed in Table 3.

DETAILED DESCRIPTION

The present invention is a polyimide containing a quaternary phenyl derivative structure, having a repeating structural unit represented by the general formula (I):

wherein _RA is a tetravalent aromatic hydrocarbon group, _RB is a divalent aromatic hydrocarbon group, x and y represent a polymer of repeating structural units, and x:y=100:0-1:99; _R1 - _R8 in the quaterphenyl derivative structure are the same as or different from each other, and are 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 at least one of _R1 - _R8 is a non-hydrogen group.

Preferably, the C1-C10 alkyl group is selected from methyl, ethyl, propyl, butyl or tert-butyl; the fluorinated C1-C10 alkyl group is selected from trifluoromethyl or pentafluoroethyl; the C6-C30 aryl group is selected from trifluoromethylphenyl or tert-butylphenyl; the C1-C10 ester group is selected from methyl ester, phenyl ester or tert-butylphenyl ester; the C1-C10 alkoxy group is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy; the fluorinated C1-C10 alkoxy group is selected from perfluorobutylethoxy, and the C6-C30 aryloxy group is selected from tert-butylphenoxy or trifluoromethylphenoxy.

Preferably, x is an integer of 2 to 1000, and y is an integer of 0 to 1000.

More preferably, the quaternary phenyl derivative structure is selected from the following structures:

Wherein, ^Ra , ^Rb , ^Rc and ^Rd are the same as or different from each other, and are independently selected from fluorine, methyl, trifluoromethyl, tert-butyl, oxymethyl or oxybutyl.

Most preferably, the quaternary phenyl derivative structure is selected from at least one of the following structures:

Preferably, _RA is selected from at least one of the following structures:

Preferably, _RB is selected from at least one of the following structures:

The preparation method of a polyimide containing a quaternary phenyl derivative structure comprises the following steps: dissolving a diamine monomer containing the quaternary phenyl derivative structure in a solvent, then adding an aromatic dianhydride monomer containing an _RA structure to polymerize to obtain a viscous polyamic acid glue solution, and heating and curing the solution after coating to obtain a polyimide film; or dissolving a diamine monomer containing the quaternary phenyl derivative structure and an aromatic diamine monomer containing an _RB structure in a solvent, then adding an aromatic dianhydride monomer containing an _RA structure to polymerize to obtain a viscous polyamic acid glue solution, and heating and curing the solution after coating to obtain a polyimide film.

Preferably, the diamine monomer containing a quaternary phenyl derivative structure is a structure represented by the general formula (II):

Wherein, R ₁ -R ₈ are the same as or different from each other, and are 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 at least one of R ₁ -R ₈ is a non-hydrogen group.

The aromatic dianhydride monomer containing the _RA structure may be a commercially available product, preferably at least one of the following aromatic dianhydride monomers: 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride, 4,4'-phenylenedioxydiphthalic anhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 3,3',4,4'-diphenyl sulfonetetracarboxylic dianhydride, 4,4'-(4,4'-isopropyldiphenyloxy)phthalic anhydride, and p-phenylene-diphenyltrimethylol dianhydride;

The aromatic diamine monomer containing the R _B structure can be a commercially available product, preferably at least one of the following aromatic diamine monomers: p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4"-diaminoquaterphenyl, 4,4"-diaminoterphenyl, 1,3-bis(4'-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2'-bis(trifluoromethyl)-4,4'-diaminobenzene ether, 2,2'-difluoro-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)diaminobiphenyl, 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 2,2'-bis[4-(4-aminophenoxyphenyl)]propane, 4,4'-diaminobenzoic acid phenyl ester, di-p-aminophenyl terephthalate, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 2 2'-Diaminodiphenyl sulfide, 4,4-diaminodiphenyl sulfide, 4,4'-bis(3-aminophenoxy)benzophenone, 3,3',5,5'-tetramethylbenzidine, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)diphenyl sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane.

The addition ratio of the diamine monomer containing a quaternary phenyl derivative structure, the aromatic diamine monomer containing an _RB structure, and the aromatic dianhydride monomer containing an _RA structure can adjust the performance of the PI film. Preferably, the molar ratio of the diamine monomer containing a quaternary phenyl derivative structure to the aromatic diamine monomer containing an _RB structure is 10% to 100%: 0 to 90%, and more preferably 50% to 100%: 0 to 50%. The total molar ratio of the aromatic dianhydride monomer containing an _RA structure to the aforementioned diamine monomer is 0.99 to 1.01, and more preferably 0.995 to 1.005. The components of the dianhydride monomer can be combined and adjusted according to performance requirements.

Preferably, the solvent is at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide and γ-butyrolactone; the viscous polyamic acid glue has a solid content of 5wt% to 30wt% and a viscosity of 10000 to 200000 mPa·S; the coated substrate can be a glass plate or a metal carrier; the heating curing method is an inert gas atmosphere, a heating rate of 1 to 5°C/min, a maximum temperature of 300 to 500°C, and a constant temperature time of 10 to 60min. More preferably, the heating rate is 2 to 3°C/min, the maximum temperature is 350 to 400°C, and the constant temperature time is 20 to 30min.

The present invention provides a diamine monomer containing a quaternary phenyl derivative structure, which has the structure shown below:

The present invention provides a method for preparing a diamine monomer containing a quaternary phenyl derivative structure, comprising the following sequential steps: (1) preparing a compound A2 by Miyaura borate esterification reaction of a raw material A1;

(2) A2 and an excess of halide A3 undergo Suzuki coupling reaction to prepare a new halide A4;

(3) A4 is subjected to Suzuki reaction with phenylboronic acid or boric acid ester A5 having an amino group or a nitro group to prepare compound A6;

(4) A6 is subjected to Suzuki reaction with phenylboronic acid or boric acid ester A7 having an amino group or a nitro group to prepare compound A8; (5) A8 is reduced to obtain the target product of the general formula (II);

The synthesis path is as follows:

wherein X is a halogen; Y is a borate or a boric acid; Z ₁ and Z ₂ are amino or nitro groups; when compound A4 is commercially available, steps (1) and (2) are omitted; when A5 is the same as A7, steps (3) and (4) are combined into one step; when Z ₁ and Z ₂ are amino groups, step (5) is omitted, and A8 is the target product of general formula (II); when Z ₁ or Z ₂ has a nitro group, A8 is reduced by step (5) to obtain the target product of general formula (II); wherein R ₁ to R ₈ are the same or different and are 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 at least one of R ₁ to R ₈ is a non-hydrogen group.

Preferably, in step (1), under the protection of an inert gas, compound A1 is added to a solvent, and then diboric acid pinacol ester, a base, and a palladium catalyst are added. After the reaction, the solvent is removed, and compound A2 is obtained by separation and purification.

In step (2), under the protection of inert gas, compound A2 is added to a solvent, a catalytic amount of a catalyst is added, an alkali solution is added, and then compound A3 is added to react. After the reaction is completed, the liquids are separated, the solvent is removed by rotary evaporation, and compound A4 is obtained after separation and purification;

In steps (3) and (4), under the protection of inert gas, raw materials are added to the solvent, a catalytic amount of catalyst is added, an alkali solution is added, and then a compound with an amino group or a nitro group is added to react. After the reaction is completed, the liquids are separated, the solvent is removed by rotary evaporation, and the corresponding product is obtained after separation and purification;

In step (5), after removing the air, the raw materials are added and the target product of general formula (II) is prepared by reduction reaction.

Preferably, in step (1), the solvent is one of dimethyl sulfoxide, DMF, dioxane, and toluene, the palladium catalyst is one of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium, [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium 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°C, more preferably 90 to 100°C.

Preferably, in steps (2), (3) and (4), the solvent is at least one of tetrahydrofuran, dioxane, toluene, ethanol and DMF, the catalyst is one of tetrakistriphenylphosphine palladium and triphenylphosphine/palladium acetate, and the base is one of sodium carbonate, potassium carbonate, potassium phosphate, cesium fluoride, cesium carbonate, barium hydroxide and sodium hydroxide; preferably, the reaction temperature is 65 to 100°C, more preferably 70 to 80°C.

Preferably, in step (5), the reduction reaction may be a hydrogen reduction reaction under Pd/C catalysis, a reduction reaction under Fe/dilute hydrochloric acid, a reduction reaction under stannous chloride/dilute hydrochloric acid, or a hydrazine hydrate reduction reaction under Pd/C catalysis.

The following examples are provided for a better understanding of the present invention, but are not limited to the best mode of implementation, and do not limit the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior arts shall fall within the protection scope of the present invention.

If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in the field can be used. If no manufacturer is specified for the reagents or instruments used, they are all conventional reagent products that can be obtained commercially.

Example 1

This embodiment provides a diamine monomer containing a quaternary phenyl derivative structure, and the synthesis path of the compound is as follows:

The preparation method of the compound is specifically as follows:

(1) 2.5-dibromo-1.4-dimethoxybenzene (5.92 g, 20 mmol), 100 mL of dioxane, bipyraclostrobin (5.08 g, 20 mmol), potassium acetate (2.94 g 30 mmol), and a catalytic amount of [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride were added to a 250 mL two-necked flask. The mixture was kept under argon atmosphere and reacted at 100° C. for 24 h. After the reaction was completed, the solvent was removed by filtration and rotary evaporation. After purification by column chromatography, a white solid A was obtained.

(6.17 g, 90%).

(2) In a 250 mL double-necked flask, intermediate A (6.17 g, 18 mmol), tetrahydrofuran (150 mL), p-dibromobenzene (8.50 g, 36 mmol), potassium carbonate aqueous solution (2 M, 27 mL), and a catalytic amount of tetrakistriphenylphosphine palladium were added. The mixture was kept under argon atmosphere and reacted at 80° C. for 24 h. After the reaction was completed, the liquid was separated and the solvent was removed by rotary evaporation. After purification by column chromatography, a white solid B (5.62 g, 84%) was obtained.

(3) Add intermediate B (5.58 g, 15 mmol), tetrahydrofuran 100 mL, p-aminophenylboronic acid (6.16 g, 45 mmol), potassium carbonate aqueous solution (2 M, 45 mL), and catalytic amount of tetrakistriphenylphosphine palladium to a 250 mL two-necked flask, and react at 80°C for 24 h. After the reaction, separate the liquids, remove the solvent by rotary evaporation, and purify by column chromatography to obtain a beige solid, which is the target compound (4.40 g, 74%). The H NMR spectrum of the compound is shown in Figure 1. High-resolution mass spectrum HRMS m/z: [m+H] ⁺ calcd for C ₂₆ H ₂₄ N ₂ O ₂ ,397.19105, found 397.19095

Example 2

The same preparation steps as in Example 1 were used, except that the raw material was replaced by 1,4-dibromo-tetramethylbenzene instead of 2.5-dibromo-1.4-dimethoxybenzene, and the target compound as a white solid was finally prepared. The H NMR spectrum of the compound is shown in FIG2 . High resolution mass spectrum HRMS m/z: [m+H] ⁺ calcd for C ₂₈ H ₂₈ N ₂ ,393.23253, found 393.23239

Example 3

The same experimental steps as in Example 1 were used, except that the raw material was replaced by 2.5-dibromo-1,4-dimethoxybenzene with 2.5-dibromo-1-trifluoromethylbenzene to prepare the compound. The H NMR spectrum of the compound is shown in FIG3 , and the high resolution mass spectrum HRMS m/z: [m+H] ⁺ calcd for C ₂₅ H ₁₉ F ₃ N ₂ , 405.15731, found 405.15759.

Example 4

The same as Example 3, the raw materials were changed to prepare the compound, high resolution mass spectrum HRMS m/z: [m+H] ⁺ calculated for C ₂₅ H ₂₂ N ₂ , 351.18121, found 351.18144.

Example 5

The same experimental steps as in Example 1 were used, except that the raw material was replaced by 2.5-dibromo-1.4-dimethoxybenzene to prepare the compound. The H NMR spectrum of the compound is shown in FIG5 , and the high resolution mass spectrum HRMS m/z: [m+H] ⁺ calcd for C ₂₆ H ₂₄ N ₂ , 365.20123, found 365.20132.

Example 6

The same experimental steps as in Example 1 were used, except that the raw material was replaced by 1,4-dibromo-2,5-bistrifluoromethylbenzene from 2.5-dibromo-1.4-dimethoxybenzene to prepare the compound. The H NMR spectrum of the compound is shown in FIG6 , and the high resolution mass spectrum HRMS m/z: [m+H] ⁺ calcd for C ₂₆ H ₁₈ F ₆ N ₂ , 473.14469, found 473.14438.

Example 7

The preparation route is as shown above, and the experimental steps are the same as those in Example 1, except that the raw material is replaced by 2.5-dibromo-1.4-dimethoxybenzene with 2.5-dibromo-1.4-dimethylbenzene; in the second step, the raw material is replaced by 1,4-dibromobenzene with 2.5-dibromo-1.4-dimethylbenzene to prepare the compound. The NMR spectrum of the compound is shown in FIG7 , 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 same method as in Example 7 was used, except that 2.5-dibromo-1,4-dimethylbenzene was replaced with 2.5-dibromo-1,4-difluorobenzene to prepare the compound. The NMR spectrum of the compound is shown in FIG8 , 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

The same method as in Example 7 was used to synthesize the compound by changing the raw materials. High resolution mass spectrum HRMS m/z: [m+H] ⁺ calcd for C ₂₆ H ₂₄ N ₂ , 365.20123, found 365.20131.

Example 10

The same method as in Example 2 was used to synthesize the compound by changing the raw materials. High resolution mass spectrum HRMS m/z: [m+H] ⁺ calcd for C ₂₄ H ₁₆ F ₄ N ₂ , 409.13224, found 409.13261.

Embodiment 11

The same method as in Example 7 was used to synthesize the compound by changing the raw materials. 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

The same method as in Example 1 was used to synthesize the compound by changing the raw materials. High resolution mass spectrum HRMS m/z: [m+H] ⁺ calcd for _{C 32} H ₃₆ N ₂ , 448.29930, found 448.29920.

Embodiment 13

The same method as in Example 1 was used to synthesize the compound by changing the raw materials. 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

This embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, the diamine monomer compound (1.0514 g, 3 mmol) obtained in Example 4 was accurately weighed in a 30 mL round-bottom flask, anhydrous DMAc (17.40 g) was added, and after stirring to dissolve, 3,3',4,4'-biphenyltetracarboxylic dianhydride BPDA (0.8827 g, 3 mmol) was added, and the mixture was stirred for 24 h to obtain a viscous polyamic acid glue solution.

(2) After vacuum defoaming, the polyamic acid glue solution was coated on a clean glass plate and heated to cure in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 360°C at 2°C/min, and the temperature was maintained at 360°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Application Example 2

This embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, the diamine monomer compound (1.1895 g, 3 mmol) obtained in Example 1 was accurately weighed in a 30 mL round-bottom flask, anhydrous DMAc (18.65 g) was added, and after stirring to dissolve, 3,3',4,4'-biphenyltetracarboxylic dianhydride BPDA (0.8827 g, 3 mmol) was added, and the mixture was stirred for 24 h to obtain a viscous polyamic acid glue solution.

(2) After vacuum defoaming, the polyamic acid glue solution was coated on a clean glass plate and heated to cure in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 360°C at 2°C/min, and the temperature was maintained at 360°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Application Example 3

This embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, the diamine monomer compound (1.1776 g, 3 mmol) obtained in Example 2 was accurately weighed in a 30 mL round-bottom flask, anhydrous DMAc (18.54 g) was added, and after stirring to dissolve, 3,3',4,4'-biphenyltetracarboxylic dianhydride BPDA (0.8827 g, 3 mmol) was added, and the mixture was stirred for 24 h to obtain a viscous polyamic acid glue solution.

(2) The polyamic acid glue solution was vacuum defoamed and then coated on a clean glass plate. It was then heated and cured in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 350°C at 2°C/min, and the temperature was maintained at 350°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Application Example 4

This embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, the diamine monomer compound (1.2133 g, 3 mmol) obtained in Example 3 was accurately weighed in a 30 mL round-bottom flask, anhydrous DMAc (18.86 g) was added, and after stirring to dissolve, 3,3',4,4'-biphenyltetracarboxylic dianhydride BPDA (0.8827 g, 3 mmol) was added, and the mixture was stirred for 24 h to obtain a viscous polyamic acid glue solution.

(2) After vacuum defoaming, the polyamic acid glue solution was coated on a clean glass plate and heated to cure in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 360°C at 2°C/min, and the temperature was maintained at 360°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Application Example 5

This embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, the diamine monomer compound (1.0935 g, 3 mmol) obtained in Example 9 was accurately weighed in a 30 mL round-bottom flask, anhydrous DMAc (17.78 g) was added, and after stirring to dissolve, 3,3',4,4'-biphenyltetracarboxylic dianhydride BPDA (0.8827 g, 3 mmol) was added, and the mixture was stirred for 24 h to obtain a viscous polyamic acid glue solution.

(2) The polyamic acid glue solution was vacuum defoamed and then coated on a clean glass plate. It was then heated and cured in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 350°C at 2°C/min, and the temperature was maintained at 350°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Application Example 6

This embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, the diamine monomer compound (1.0935 g, 3 mmol) obtained in Example 5 was accurately weighed in a 30 mL round-bottom flask, anhydrous DMAc (17.78 g) was added, and after stirring to dissolve, 3,3',4,4'-biphenyltetracarboxylic dianhydride BPDA (0.8827 g, 3 mmol) was added, and the mixture was stirred for 24 h to obtain a viscous polyamic acid glue solution.

(2) The polyamic acid glue solution was vacuum defoamed and then coated on a clean glass plate. It was then heated and cured in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 350°C at 2°C/min, and the temperature was maintained at 350°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Application Example 7

This embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, the diamine monomer compound (1.1776 g, 3 mmol) obtained in Example 7 was accurately weighed in a 30 mL round-bottom flask, anhydrous DMAc (18.54 g) was added, and after stirring to dissolve, 3,3',4,4'-biphenyltetracarboxylic dianhydride BPDA (0.8827 g, 3 mmol) was added, and the mixture was stirred for 24 h to obtain a viscous polyamic acid glue solution.

(2) The polyamic acid glue solution was vacuum defoamed and then coated on a clean glass plate. It was then heated and cured in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 350°C at 2°C/min, and the temperature was maintained at 350°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Application Example 8

This embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, the diamine monomer compound (1.3460 g, 3 mmol) obtained in Example 12 was accurately weighed in a 30 mL round-bottom flask, anhydrous DMAc (14.91 g) was added, and after stirring to dissolve, 3,3',4,4'-biphenyltetracarboxylic dianhydride BPDA (0.8827 g, 3 mmol) was added, and the mixture was stirred for 24 h to obtain a viscous polyamic acid glue solution.

(2) The polyamic acid glue solution was vacuum defoamed and then coated on a clean glass plate. It was then heated and cured in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 350°C at 2°C/min, and the temperature was maintained at 350°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Application Example 9

This embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, the diamine monomer compound (1.4173 g, 3 mmol) obtained in Example 6 was accurately weighed in a 30 mL round-bottom flask, anhydrous DMAc (15.39 g) was added, and after stirring to dissolve, 3,3',4,4'-biphenyltetracarboxylic dianhydride BPDA (0.8827 g, 3 mmol) was added, and the mixture was stirred for 24 h to obtain a viscous polyamic acid glue solution.

(2) The polyamic acid glue solution was vacuum defoamed and then coated on a clean glass plate. It was then heated and cured in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 350°C at 2°C/min, and the temperature was maintained at 350°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Application Example 10

This embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, the diamine monomer compound (1.2252 g, 3 mmol) obtained in Example 8 was accurately weighed in a 30 mL round-bottom flask, anhydrous DMAc (14.11 g) was added, and after stirring to dissolve, 3,3',4,4'-biphenyltetracarboxylic dianhydride BPDA (0.8827 g, 3 mmol) was added, and the mixture was stirred for 24 h to obtain a viscous polyamic acid glue solution.

(2) After vacuum defoaming, the polyamic acid glue solution was coated on a clean glass plate and heated to cure in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 360°C at 2°C/min, and the temperature was maintained at 360°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Application Example 11

This embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, the diamine monomer compound (1.4420 g, 3 mmol) obtained in Example 13 was accurately weighed in a 30 mL round-bottom flask, anhydrous DMAc (13.17 g) was added, and after stirring to dissolve, 3,3',4,4'-biphenyltetracarboxylic dianhydride BPDA (0.8827 g, 3 mmol) was added, and the mixture was stirred for 24 h to obtain a viscous polyamic acid glue solution.

(2) The polyamic acid glue solution was vacuum defoamed and then coated on a clean glass plate. It was then heated and cured in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 300°C at 2°C/min, and the temperature was kept at 300°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Application Example 12

This embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, the diamine monomer compound (0.8089 g, 2 mmol) obtained in Example 3 and 2,2'-bis(trifluoromethyl)diaminobiphenyl TFMB (0.6405, 2 mmol) were accurately weighed in a 30 mL round-bottom flask, anhydrous DMAc (11.96 g) was added, and after stirring to dissolve, 3,3',4,4'-biphenyltetracarboxylic dianhydride BPDA (1.1769 g, 4 mmol) was added, and the reaction was stirred for 24 h to obtain a viscous polyamic acid glue solution.

(2) The polyamic acid glue solution was vacuum defoamed and then coated on a clean glass plate. It was then heated and cured in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 350°C at 2°C/min, and the temperature was maintained at 350°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Application Example 13

This embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, the diamine monomer compound (0.7280 g, 1.8 mmol) obtained in Example 3 and 2,2'-bis(trifluoromethyl)diaminobiphenyl TFMB (1.3450 g, 4.2 mmol) were accurately weighed in a 30 mL round-bottom flask, anhydrous DMAc (15.35 g) was added, and after stirring to dissolve, 3,3',4,4'-biphenyltetracarboxylic dianhydride BPDA (1.7653 g, 6 mmol) was added, and the mixture was stirred for 24 h to obtain a viscous polyamic acid glue solution.

(2) The polyamic acid glue solution was vacuum defoamed and then coated on a clean glass plate. It was then heated and cured in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 350°C at 2°C/min, and the temperature was maintained at 350°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Application Example 14

This embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, the diamine monomer compound (0.7851 g, 2 mmol) and 2,2'-bis(trifluoromethyl)diaminobiphenyl TFMB (0.6405 g, 2 mmol) prepared in Example 2 were accurately weighed in a 30 mL round-bottom flask, anhydrous DMAc (14.74 g) was added, and after stirring to dissolve, 3,3',4,4'-biphenyltetracarboxylic dianhydride BPDA (1.1769 g, 4 mmol) was added, and the reaction was stirred for 24 h to obtain a viscous polyamic acid glue solution.

(2) The polyamic acid glue solution was vacuum defoamed and then coated on a clean glass plate. It was then heated and cured in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 350°C at 2°C/min, and the temperature was maintained at 350°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Application Example 15

This embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, the diamine monomer compound (1.5702 g, 4 mmol) prepared in Example 2 was accurately weighed in a 30 mL round-bottom flask, anhydrous DMAc (13.34 g) was added, and after stirring to dissolve, 4,4'-(4,4'-isopropyldiphenyloxy)bis(phthalic anhydride) BPADA (0.4164 g, 0.8 mmol) and 3,3',4,4'-biphenyltetracarboxylic dianhydride BPDA (0.9415 g, 3.2 mmol) were added, and the mixture was stirred for 24 h to obtain a viscous polyamic acid glue solution.

(2) The polyamic acid glue solution was vacuum defoamed and then coated on a clean glass plate. It was then heated and cured in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 350°C at 2°C/min, and the temperature was maintained at 350°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Application Example 16

This embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, the diamine monomer compound (0.8748 g, 2.4 mmol) and 2,2'-bis[4-(4-aminophenoxyphenyl)]propane BAPP (0.2463 g, 0.6 mmol) prepared in Example 9 were accurately weighed in a 30 mL round-bottom flask, anhydrous DMAc (12.82 g) was added, and 3,3',4,4'-benzophenonetetracarboxylic dianhydride BTDA (0.9667 g, 3.0 mmol) was added after stirring to dissolve. The mixture was stirred for 24 h to obtain a viscous polyamic acid glue solution.

(2) The polyamic acid glue solution was vacuum defoamed and then coated on a clean glass plate. It was then heated and cured in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 350°C at 2°C/min, and the temperature was maintained at 350°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Application Example 17

This embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, the diamine monomer compound (1.0935 g, 3.0 mmol) obtained in Example 5 was accurately weighed in a 30 mL round-bottom flask, anhydrous DMAc (18.21 g) was added, and after stirring to dissolve, 4,4'-oxydiphthalic anhydride ODPA (0.9306 g, 3.0 mmol) was added, and the mixture was stirred for 24 h to obtain a viscous polyamic acid glue solution.

(2) The polyamic acid glue solution was vacuum defoamed and then coated on a clean glass plate. It was then heated and cured in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 350°C at 2°C/min, and the temperature was maintained at 350°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Application Example 18

This embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, the diamine monomer compound (1.4173 g, 3.0 mmol) obtained in Example 6 was accurately weighed in a 30 mL round-bottom flask, anhydrous DMAc (14.68 g) was added, and after stirring to dissolve, 3,3',4,4'-biphenyltetracarboxylic dianhydride BPDA (0.7061 g, 2.4 mmol) and 4,4'-(hexafluoroisopropylene) diphthalic anhydride 6FDA (0.2665 g, 0.6 mmol) were added, and the mixture was stirred for 24 h to obtain a viscous polyamic acid glue solution.

(2) The polyamic acid glue solution was vacuum defoamed and then coated on a clean glass plate. It was then heated and cured in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 350°C at 2°C/min, and the temperature was maintained at 350°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Application Example 19

This embodiment provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, the diamine monomer compound (1.4420 g, 3 mmol) obtained in Example 13 was accurately weighed in a 30 mL round-bottom flask, anhydrous DMAc (17.20 g) was added, and after stirring to dissolve, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride BPDA (0.4413 g, 1.5 mmol) and p-phenylene-diphenyltrimethylol dianhydride TAHQ (0.6875 g, 1.5 mmol) were added, and the mixture was stirred for 24 h to obtain a viscous polyamic acid glue solution.

(2) The polyamic acid glue solution was vacuum defoamed and then coated on a clean glass plate. It was then heated and cured in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 300°C at 2°C/min, and the temperature was kept at 300°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Comparative Example 1

This comparative example provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, accurately weigh the diamine monomer 4,4'-diaminodiphenyl ether ODA (1.2014 g, 6 mmol) in a 30 mL round-bottom flask, add anhydrous DMAc (14.22 g), stir to dissolve, then add pyromellitic anhydride PMDA (1.3087 g, 6 mmol), stir to react for 24 h, and obtain a viscous polyamic acid glue solution.

(2) The polyamic acid glue solution was vacuum defoamed and then coated on a clean glass plate. It was then heated and cured in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 400°C at 2°C/min, and the temperature was kept at 400°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Comparative Example 2

This comparative example provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, p-phenylenediamine (0.7570 g, 7 mmol) was accurately weighed in a 30 mL round-bottom flask, anhydrous DMAc (15.96 g) was added, and after stirring to dissolve, 3,3',4,4'-biphenyltetracarboxylic dianhydride BPDA (2.0595 g, 7 mmol) was added, and the mixture was stirred for 24 h to obtain a viscous polyamic acid glue solution.

(2) The polyamic acid glue solution was vacuum defoamed and then coated on a clean glass plate. It was then heated and cured in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 400°C at 2°C/min, and the temperature was kept at 400°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Comparative Example 3

This comparative example provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, accurately weigh the diamine monomer 2,2'-bis(trifluoromethyl)diaminobiphenyl TFMB (1.6011 g, 5 mmol) in a 30 mL round-bottom flask, add anhydrous DMAc (14.00 g), stir to dissolve, then add 3,3',4,4'-biphenyltetracarboxylic dianhydride BPDA (1.4711 g, 5 mmol), stir to react for 24 h, and obtain a viscous polyamic acid glue solution.

(2) The polyamic acid glue solution was vacuum defoamed and then coated on a clean glass plate. It was then heated and cured in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 350°C at 2°C/min, and the temperature was maintained at 350°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Comparative Example 4

This comparative example provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, accurately weigh the diamine monomer 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl (1.0614 g, 5 mmol) in a 30 mL round-bottom flask, add anhydrous DMAc (14.35 g), stir to dissolve, then add 3,3',4,4'-biphenyltetracarboxylic dianhydride BPDA (1.4711 g, 5 mmol), stir to react for 24 h, and obtain a viscous polyamic acid glue solution.

(2) The polyamic acid glue solution was vacuum defoamed and then coated on a clean glass plate. It was then heated and cured in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 350°C at 2°C/min, and the temperature was maintained at 350°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Comparative Example 5

This comparative example provides a polyimide film, and the preparation method thereof comprises the following steps:

(1) Under nitrogen protection, accurately weigh the diamine monomer 4,4"-diaminoquaternaryl (1.009 g, 3 mmol) in a 30 mL round-bottom flask, add anhydrous DMAc (17.03 g), stir to dissolve, then add 3,3',4,4'-biphenyltetracarboxylic dianhydride BPDA (0.8827 g, 3 mmol), stir to react for 24 h, and obtain a viscous polyamic acid glue solution.

(2) The polyamic acid glue solution was vacuum defoamed and then coated on a clean glass plate. It was then heated and cured in a nitrogen atmosphere. The curing procedure was 80°C for 1 h, then the temperature was increased to 400°C at 2°C/min, and the temperature was kept at 400°C for 30 min.

The repeating structural unit of the polyimide film is as follows:

Test Results

The H NMR spectrum of the monomer was obtained by using Bruker's AVANCE III 400 NMR spectrometer. The solvent used in the test was deuterated dimethyl sulfoxide (DMSO-d ₆ ) or deuterated chloroform (CDCl ₃ ), and the concentration of the sample during the H NMR test was about 4 mg·mL ^-1 .

The high-resolution mass spectrometry test of the monomer was obtained by the German Thermo Fisher high-resolution orbital trap liquid-mass spectrometer Q Exactive hydrogenation test.

The test method for the high-frequency dielectric constant and loss factor of polyimide film is as follows: the vector network analyzer P5003A of Keysight Technologies is used, the resonant cavity is the separated column dielectric resonant cavity (10GHz) of QWED of Poland, the environmental humidity is controlled at 50% RH, and the temperature is 25°C.

Test method for water absorption: dry the film in vacuum at 150℃ for 12h, transfer it to a dryer and restore it to room temperature, then weigh it to get W ₀ . Place the film in water at 25℃ for 12h, then take it out and wipe off the surface moisture, then weigh it to get W ₁ . Water absorption is: (W ₁ -W ₀ )/W ₀ *100%.

Test method for mechanical properties (tensile strength, elongation at break, elastic modulus): obtained by tensile machine test according to national standard GB/T 1040.1-2018, five specimens are tested for each application embodiment, and the average of the five values is the final result, as listed in Table 3.

Thermal expansion coefficient test of polyimide film: Use TA company D450 equipment, heat up to 200℃ at 10℃/min, then cool down to 50℃ at 10℃/min, and then heat up to 400℃ at 10℃/min. The linear expansion coefficient CTE takes the temperature range of 100-200℃.

The composition of the quaternary phenyl-containing high-frequency low-loss polyimide film is shown in the following Table 1. Mole % represents the molar ratio of each monomer in the total diamine and dianhydride.

The polyimide films prepared in the application examples and comparative examples were tested according to the above method, and the obtained data are shown in Table 2 and Table 3.

Table 1 Monomer composition and ratio of the series of polyimide films listed in this patent

Table 2. Parameter comparison of polyimide films prepared in the application examples and comparative examples

Table 3 Mechanical properties of films

Tensile strength(MPa) Elastic film 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 above examples clearly illustrate the advantages of the diamine monomer structure containing a quaternary derivative structure designed by the present invention in high-frequency and low-loss polyimide films: while having a sufficiently low loss factor, by introducing groups such as methyl, trifluoromethyl, fluorine atoms, and tert-butyl groups, the dielectric constant of the polyimide film is effectively reduced, and excellent comprehensive performance is obtained: it has very low water absorption, a low thermal expansion coefficient, and excellent mechanical properties. The specific data analysis is as follows:

The loss factors of common polyimide films such as ODA-PMDA and PPD-BPDA in the comparative examples are as high as 0.00568 to 0.0130, while the loss factors in the embodiments are 0.00248 to 0.00581, most of which are lower than 0.0035. The loss factors are generally low, which meets the use requirements of low loss factors in the field of high-frequency communications; for example, although the polyimide film polymerized by pure tetraphenyl diamine monomer and BPDA can have a low loss factor of 0.00262, its dielectric constant is as high as 3.71, which cannot meet the low dielectric constant requirements in the field of high-frequency communications. On this basis, by introducing methyl, trifluoromethyl, fluorine atom, tert-butyl and other groups, the dielectric constant is reduced from 3.71 to 3.05 to 3.60, most of which are lower than 3.35. At the same time, the mechanical properties of the embodiment include tensile strength of 210-435 MPa, modulus of 5.2-8.8 Gpa, elongation at break of 24.1%-51.7%, coefficient of thermal expansion CTE of -3.7-22.5, and water absorption of less than 0.9%. It has excellent comprehensive performance and is particularly suitable as a high-performance insulating substrate for use in electronic packaging technology fields such as high-frequency signal transmission.

Claims (13)

1. A polyimide containing a tetrabenamine-derived structure having a repeating structural unit represented by the general formula (I):

Wherein the method comprises the steps of Is tetravalent aromatic hydrocarbon, R _B is divalent aromatic hydrocarbon, x and y represent the polymerization degree of the repeated structural units, and x is y=100:0-1:99; tetradiphenyl derivative structureR ₁～R₈ in (a) is the same or different from each other and is independently selected from hydrogen, fluorine, C1-C10 alkyl, fluoro C1-C10 alkyl, C1-C10 ester group, C1-C10 alkoxy, fluoro C1-C10 alkoxy, C6-C30 aryl or C6-C30 aryloxy, and at least one of R ₁～R₈ is a non-hydrogen group.

2. The polyimide containing a tetrabenamine derived structure according to claim 1, wherein: the alkyl of C1-C10 is selected from methyl, ethyl, propyl and 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 ^a、R^b、R^c、R^d are the same 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:

5. The polyimide having a tetraphenyl derivative structure according to claim 4, wherein: the said process At least one selected from the following structures:

6. The polyimide having a tetraphenyl derivative structure according to claim 4, wherein: r _B is selected from at least one of the following structures:

7. The method for preparing polyimide containing a tetraphenyl derivative structure according to claim 1, comprising the steps of: dissolving diamine monomer containing the tetralin derivative structure in solvent, and then adding the diamine monomer containing the tetralin derivative structure 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; or dissolving diamine monomer containing the tetraphenyl derivative structure and aromatic diamine monomer containing R _B structure in solvent, and then adding the aromatic diamine monomer containing R _B structurePolymerizing 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.

8. The method for producing a polyimide having a tetraphenyl derivative structure according to claim 7, wherein: the diamine monomer containing the tetrabasic benzene derivative structure is of a structure shown in a general formula (II):

Wherein R ₁～R₈ are the same or different from each other and are each independently selected from hydrogen, fluorine, C1-C10 alkyl, fluoro C1-C10 alkyl, C1-C10 ester, C1-C10 alkoxy, fluoro C1-C10 alkoxy, C6-C30 aryl or C6-C30 aryloxy, and R ₁～R₈ has at least one group other than hydrogen.

9. The method for producing a polyimide having a tetraphenyl derivative structure according to claim 7, wherein: the said method includesThe 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;

The aromatic diamine monomer containing the R _B structure is selected from at least one of the following aromatic diamine monomers: 4,4 '-diamino-2, 2' -dimethyl-1, 1 '-biphenyl, 2' -bis [4- (4-aminophenoxyphenyl) ] propane phenyl 4,4 '-diaminobenzoate, di-p-aminophenyl terephthalate, 4' -diaminodiphenyl sulfone 4,4 '-diamino-2, 2' -dimethyl-1, 1 '-biphenyl, 2' -bis [4- (4-aminophenoxyphenyl) ] propane, phenyl 4,4 '-diaminobenzoate, di-p-aminophenyl terephthalate, 4' -diaminodiphenyl sulfone 3,3 '-diaminodiphenyl sulfone, 4' -diaminodiphenyl, 22 '-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.

10. A diamine monomer containing a tetrabenamine derivative structure, which has the following structure:

11. The process for the preparation of diamine monomer containing a tetrabenamine derived structure as claimed in claim 10, comprising the sequential steps of: (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 is reduced to prepare a target product of the general formula (II);

The synthetic route is as follows:

Wherein X is halogen; y is boric acid ester or boric acid; z ₁、Z₂ is 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 ₁ and Z ₂ are amino, omitting the step (5), wherein A8 is a target product of the general formula (II); when Z ₁ or Z ₂ carries nitro, reducing A8 by the step (5) to obtain a target product of the general formula (II); wherein R ₁～R₈ are the same or different from each other and are each independently selected from hydrogen, fluorine, C1-C10 alkyl, fluoro C1-C10 alkyl, C1-C10 ester, C1-C10 alkoxy, fluoro C1-C10 alkoxy, C6-C30 aryl or C6-C30 aryloxy, and R ₁～R₈ has at least one group other than hydrogen.

12. The method for producing a diamine monomer having a tetraphenyl derivative structure according to claim 11, 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, raw materials are added, and the target product of the general formula (II) is prepared through reduction reaction.

13. The method for producing a diamine monomer having a tetraphenyl derivative structure according to claim 12, wherein: 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, and the base 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.