CN113336998B - Preparation method of benzocyclobutene side group cross-linked polyimide film with low dielectric and low heat conduction and micropores - Google Patents
Preparation method of benzocyclobutene side group cross-linked polyimide film with low dielectric and low heat conduction and micropores Download PDFInfo
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Abstract
The invention provides a preparation method of a benzocyclobutene side group cross-linked polyimide film with a self-made micropore, wherein the polyimide film is low in dielectric and low in heat conduction. Firstly, synthesizing a diamine monomer C containing imide, then mixing the diamine monomer C with a diamine monomer D containing benzocyclobutene, and polymerizing under the action of an initiator to obtain polyimide powder containing benzocyclobutene active side groups. After purification and drying, dissolving the polymer in a polar solvent to form 1 to 30wt.% of a polymer solution, and uniformly coating the polymer solution on a flat glass plate; and then drying in an inert gas oven or a vacuum oven, removing the solvent, and performing thermocuring crosslinking in a temperature programming mode to form the benzocyclobutene side group crosslinking type polyimide film with the self-provided micropores and the thickness of 5-150 microns. The molecular chain of the cross-linked self-microporous polyimide provided by the invention contains a Ruger base structure, and the prepared film has the performance characteristics of low dielectric constant and low heat conduction, and has excellent mechanical property and heat-resistant stability, good dimensional stability and wide application prospect in the fields of high-frequency circuit boards and heat-insulating materials.
Description
Technical Field
The invention belongs to the technical field of polyimide materials, and particularly relates to a preparation method of a benzocyclobutene side group cross-linked polyimide film with a micropore and a low dielectric constant and a low heat conduction property.
Background
With the rapid development of the microelectronics industry, the miniaturization and integration of integrated circuits has led to smaller and smaller chip sizes. Since the delay of signal transmission greatly degrades the performance of the chip due to the reduction of the distance between the internal components of the chip, it is necessary to develop an insulating layer having a low dielectric constant. In addition, the requirements for heat insulation materials in the aerospace field are higher and higher, and materials with low thermal conductivity are required to be developed.
Polyimide (PI), which is a material having excellent high temperature resistance and insulation properties, is used as an ideal raw material for low dielectric materials, and also as a heat insulating material due to its low thermal conductivity. The polyimide with the self-made micropores has good thermal stability and film forming property, the self-made micropores are contained in the polymer, so that the polymer has a lower dielectric constant, and the twisted molecular structure reduces ordered accumulation among molecular chains, hinders heat transfer and reduces the heat conductivity coefficient. Lee et al prepared polyimide films with voids that reduced the dielectric constant (Lee Y J, huang J M, kuo S W, et al, low-dielectric, nanopous polyimide films prepared from PEO-POSS nanoparticles [ J ]. Polymer,2005,46 (23): 10056-10065.). CN112275147A discloses a preparation method of a self-micropore separation membrane. CN107469651A and CN110885556A disclose methods for preparing crosslinked polyimide films. The documents and the patents do not relate to the preparation of benzocyclobutene side group crosslinking type polyimide film with micropores and the application thereof in the fields of dielectric and heat conduction materials.
The invention provides a preparation method of benzocyclobutene side group crosslinked microporous polyimide, and the prepared benzocyclobutene side group crosslinked microporous polyimide well combines the characteristics of high performance and microporous structure of a polyimide material. The cross-linked polyimide film obtained by the invention has good mechanical property, good thermal stability, lower dielectric constant and low thermal conductivity coefficient, and has wide application prospect in the fields of microelectronics, heat preservation and insulation materials.
Disclosure of Invention
The invention mainly provides a preparation method of a benzocyclobutene side group cross-linked polyimide film with a self-made micropore, wherein the polyimide film is low in dielectric and low in heat conduction. The prepared cross-linked polyimide film has good mechanical property, good thermal stability, lower dielectric constant and thermal conductivity.
A preparation method of a benzocyclobutene side group cross-linked polyimide film with low dielectric and low heat conduction and a micropore. The method is characterized in that the specific synthesis process and preparation method are as follows:
(1) The molecular chain structure of the diamine monomer containing imide is shown as formula 1. The monomer C is obtained by reacting a diamine monomer B and a dianhydride monomer A. Wherein the amount of diamine B is 2.1 to 4 times the amount of dianhydride A during the reaction. The method comprises the following specific steps:
in N 2 In an atmosphere containing N 2 Adding diamine B into a flask with a breather pipe, a thermometer and a mechanical stirrer, adding a high-boiling point solvent (such as N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO) and the like), adding dianhydride A after the diamine B is completely dissolved, uniformly stirring, and reacting for 5-24 hours at 0-80 ℃; then adding a water-carrying agent, controlling the reaction temperature to be 150-200 ℃, and continuously carrying out reflux reaction for 2-80 hours to finally obtain the homogeneous diamine solution containing the imide. And (3) completely distilling out the water-carrying agent in the system, and after the reaction liquid is cooled, pouring the reaction liquid into the mixed liquid of ethanol and water which is stirred at a high speed to separate out a solid product. And (3) recrystallizing the solid product in N, N-Dimethylformamide (DMF), and drying the recrystallized product in vacuum at 50-180 ℃ for 2-48 hours to obtain the dried diamine monomer C containing imide.
(2) The molecular chain structure of the prepared self-contained microporous polyimide containing benzocyclobutene side groups is shown as a formula 2. The polymer is prepared from a diamine monomer C containing imide and a diamine monomer D containing benzocyclobutene serving as raw materials, and the self-prepared microporous polyimide containing benzocyclobutene side groups is prepared. The method comprises the following specific steps:
mixing the imide-containing diamine monomer C and the benzocyclobutene-containing diamine monomer D according to the mass ratio of 1. At N 2 Under protection, dissolving a mixture of diamine monomer C and diamine monomer D in an acidic solvent to prepare a solution with a solid content of 1-30 wt.%, adding a formaldehyde initiator, and stirring at-5-45 ℃ for 2-150 hours. After the reaction is finished, the reaction solution is poured into methanol stirred at a high speed, and a fibrous solid product is separated out. Fully washing the obtained fibrous solid product with methanol, filtering, naturally airing, and vacuum-drying the aired fibrous solid product at 50-180 ℃ for 2-48 hours to obtain a dried side containing benzocyclobuteneAnd a polyimide product E with micropores.
(3) Preparing the benzocyclobutene side group-containing cross-linked self-provided microporous polyimide film. The molecular chain structure is shown in formula 3.
First, the synthesized polyimide is dissolved in an aprotic polar solvent (e.g., N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), etc.) to prepare a polymer solution having a solid content of 1 to 30 wt.%. Then the polymer solution is evenly coated on flat glass, and the thickness of the coated solution layer is adjusted to be 5-150 microns after being dried. Then the plate glass coated with the polymer solution is put into an inert atmosphere oven or a vacuum oven for drying, and is dried according to the temperature programming modes of 1-5 hours at 40 ℃, 1-5 hours at 60 ℃, 1-5 hours at 80 ℃, 1-5 hours at 120 ℃ and 1-5 hours at 150 ℃ to remove the solvent; and then carrying out thermosetting crosslinking at 200 ℃ for 1-5 hours, at 250 ℃ for 1-5 hours and at 300 ℃ for 1-2 hours according to a temperature raising program, and cooling to obtain the benzocyclobutene side group crosslinked polyimide film with the micropores.
A method for preparing a benzocyclobutene side group crosslinking type polyimide film with pores by low dielectric and low heat conduction. The dianhydride A used in the step (1) of the method is 4,4' - (4, 4' -isopropyldiphenoxy) bis (phthalic anhydride) (BPADA), p-phenylene-ditrimellitic dianhydride (BTAH), pyromellitic dianhydride (PMDA), 4' - (hexafluoroisopropylidene) diphthalic anhydride (6 FDA), 1,4,5, 8-naphthalene tetracarboxylic anhydride (NTCDA), 3,4,9, 10-perylene tetracarboxylic dianhydride (PTCDA), triptycene-2, 3,6, 7-tetracarboxylic dianhydride (TTD), 9' -spirobifluorene-2, 2',2,7, 3,3' -tetracarboxylic dianhydride (SBDA), 3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), 3',4,4' -Diphenyl ether tetracarboxylic dianhydride (ODPA), 3', 4' -biphenyl tetracarboxylic dianhydride (BPDA), 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride (BDFDA), 4' -dinaphthalene-1, 1', 8' -tetracarboxylic dianhydride (BNTDA), 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (HPMDA), 5,6,7, 8-bicyclo [2.2.2] -2-heptenetetracarboxylic dianhydride (BTA), 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,3, 4-cyclopentanetetracarboxylic dianhydride (CPDA), 1,2,3, 4-tetramethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride (TCTD), 4,5,6, 7-bicyclo [2.2.1] heptanetetracarboxylic Dianhydride (DA), 2,3,5, 6-bicyclo [2.2.2] octanetetracarboxylic dianhydride (BODA), 2,3, 4-dicarboxytetracarboxylic dianhydride (BODA), and the like, 2R,5R,7S, 10S-naphthalene tetracarboxylic dianhydride (HNTDA), 6H,12H-5, 11-methylene dibenzo [ b, f ] [1,5] diazacyclo-2, 3,8, 9-tetracarboxylic dianhydride (TB-DA).
A preparation method of a benzocyclobutene side group cross-linked polyimide film with low dielectric and low heat conduction and a micropore. It is characterized in that the preparation method is characterized in that, the diamine B used in step (1) of the process is 5 (6) -amino-1- (4-aminophenyl) -1, 3-trimethylindane (DAPI), p-aminobenzoate (APAB), 2, 6-Diaminotoluene (DAP), 2, 5-dimethyl-1, 4-phenylenediamine (DPD), 4 '-diamino-3, 3' -dimethylbiphenyl (o-tolidine), 1 '-binaphthyl-2, 2' -diamine (AMA) as shown in formula 5 3,3 '-dimethylbipyridine (AMMA), 1, 5-Naphthalenediamine (NPD), 9' -spirobi [ 9H-fluorene ] -2,2 '-diamine (SBF), 3' -dimethyl-9, 9 '-spirobi [ 9H-fluorene ] -2,2' -diamine (CSBF), 6-amino-2- (3-aminophenyl) Benzimidazole (BIA), 9-bis (4-amino-3-methylphenyl) fluorene (BAMF), 9-bis (p-methylphenyl) fluorene (BMF); the aliphatic diamine B used is one or a mixture of more of 4,4' -diaminodiphenylethane (DDE), 4' - (cyclohexane-1, 4-diylbis (thio)) diphenylamine (SCHDA), 1, 4-bis [ 2-amino-4- (trifluoromethyl) phenyl ] piperazine (AFMT), 1-bis (4-aminophenyl) cyclohexane (BACH), 5' -isopropylidenebis (2-furfuryl) (DAF), 2-bis (4-aminophenyl) norbornane (BANB), 1, 4.
A method for preparing a benzocyclobutene side group crosslinking type polyimide film with pores by low dielectric and low heat conduction. Characterized in that the benzo cyclobutene-containing diamine D used in the step (2) of the method is D shown in a formula 6 1 、D 2 。
A preparation method of a benzocyclobutene side group cross-linked polyimide film with low dielectric and low heat conduction and a micropore. The method is characterized in that the high boiling point solvent used in the step (1) and the step (2) is any one or a mixture of N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc) and dimethyl sulfoxide (DMSO).
A preparation method of a benzocyclobutene side group cross-linked polyimide film with low dielectric and low heat conduction and a micropore. Characterized in that the amount of diamine B is 2.1 to 4 times the amount of dianhydride A in step (1).
A preparation method of a benzocyclobutene side group cross-linked polyimide film with low dielectric and low heat conduction and a micropore. The method is characterized in that in the step (1), the water-carrying agent is preferably any one of toluene, xylene or chlorobenzene or a mixture thereof. The reaction reflux temperature is controlled to be 150-200 ℃ when the water carrying agent carries water, and the continuous reflux time is 2-80 hours.
A preparation method of a benzocyclobutene side group cross-linked polyimide film with low dielectric and low heat conduction and a micropore. The method is characterized in that a solvent used for recrystallizing the diamine solid product in the step (1) is one or a mixture of N, N-dimethylformamide, N-dimethylacetamide and acetone. The treatment conditions when drying the recrystallized product were: in a vacuum oven, the temperature and the time are respectively 50-180 ℃ and 2-48 hours.
A method for preparing a benzocyclobutene side group crosslinking type polyimide film with pores by low dielectric and low heat conduction. The method is characterized in that the ratio of the content of the imide-containing diamine monomer C to the content of the benzocyclobutene-containing diamine monomer D in the step (2) is in the range of: 1; the reaction temperature is-5 ℃ to 45 ℃; the stirring time is 2 to 150 hours.
A method for preparing a benzocyclobutene side group crosslinking type polyimide film with pores by low dielectric and low heat conduction. The method is characterized in that the acidic solvent in the step (2) is one or a mixture of more of trifluoroacetic acid (TFA), polyphosphoric acid and hydrochloric acid. The formaldehyde Initiator (IV) is any of formalin, paraformaldehyde, hexamethylenetetramine (HMTA), and ethylene glycol dimethyl ether (DMM).
A method for preparing a benzocyclobutene side group crosslinking type polyimide film with pores by low dielectric and low heat conduction. The method is characterized in that the aprotic polar solvent in the step (3) is preferably any one of N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc) or a mixture thereof. The prepared polyimide solution has a solid content of 1-30%.
A preparation method of a benzocyclobutene side group cross-linked polyimide film with low dielectric and low heat conduction and a micropore. The method is characterized in that in the step (3), the flat plate is preferably a glass flat plate, and the thickness of the coated polymer solution layer after drying is controlled to be 5-150 micrometers.
A preparation method of a benzocyclobutene side group cross-linked polyimide film with low dielectric and low heat conduction and a micropore. The method is characterized in that the flat plate coated with the polymer solution in the step (3) is placed in an inert atmosphere oven or a vacuum oven, and is dried according to a temperature raising program of 1-5 hours at 40 ℃, 1-5 hours at 60 ℃, 1-5 hours at 80 ℃, 1-5 hours at 120 ℃ and 1-5 hours at 150 ℃ to remove the solvent; then the temperature program is used for 1 to 5 hours at 200 ℃,1 to 5 hours at 250 ℃ and 1 to 2 hours at 300 ℃ to carry out thermosetting crosslinking.
Examples
To further illustrate the present invention, some embodiments are described below, which are combined with specific operation procedures to describe some implementation methods of the present invention.
In the following examples, the synthesized polymers were structurally characterized using fourier transform infrared spectroscopy (FTIR).
Example 1:
synthesis of imide-containing diamine monomer C 1 . Adding aromatic diamine DPD (12.2571 g and 90 mmol) into a 500ml three-necked bottle under the protection of nitrogen, adding 240ml of NMP, adding aromatic dianhydride 6FDA (13.3271 g and 30 mmol) after DPD is completely dissolved, stirring at room temperature for reaction for 24 hours, adding 80ml of toluene as a water-carrying agent after the reaction is finished, and continuously stirring and heating at 180 ℃ for 24 hours to obtain a homogeneous imide-containing diamine solution. After toluene was completely distilled off, heating was stopped, and after natural cooling to room temperature, the reaction solution was poured into a mixture of methanol and water (2l, v 1 And (3) powder.
Preparation of self-contained microporous polyimide E containing benzocyclobutene side group 1 . The preparation is shown as formula 7, and the specific reaction process is as follows: 1g of the diamine monomer C prepared above 1 And 1g of a benzocyclobutene-containing diamine monomer D 1 After mixing, the mixture was charged into a nitrogen-protected three-necked flask, then 150ml of trifluoroacetic acid was added, and after complete dissolution, 2ml of dimethoxymethane (22.4 mmol) was added, and stirred at room temperature for 48 hours, then basified carefully with 2.5% aqueous ammonia solution, and the resulting solution was stirred to precipitate a white fibrous precipitate. The solid was filtered off and washed 3 times with water and then with methanol. The obtained fibrous precipitateDissolving the precipitate with chloroform, separating out in methanol, filtering, naturally drying, and vacuum drying at 120 deg.C for 24 hr to obtain polyimide E containing benzocyclobutene side group and having micropores 1 。
FTIR spectrum showed that the polymer was 1370cm -1 ，1716cm -1 ，1784cm -1 An absorption peak of the imide ring is shown nearby, and the polymer structure is in agreement with the expectation.
Preparing the benzocyclobutene side group-containing cross-linked self-provided microporous polyimide film. The molecular chain structure is shown as formula 8
Taking 3g of self-contained microporous polyimide E containing benzocyclobutene side groups 1 The powder is dissolved in NMP to prepare a polymer solution with solid content of 5wt.%, and the polymer solution is uniformly coated on a glass plate, and then dried in a vacuum oven according to a programmed heating mode of 1-5 hours at 40 ℃, 1-5 hours at 60 ℃, 1-5 hours at 80 ℃, 1-5 hours at 120 ℃ and 1-5 hours at 150 ℃ to remove the solvent. Then according to the temperature-rising program, the thermosetting crosslinking is carried out for 1-5 hours at the temperature of 200 ℃, 1-5 hours at the temperature of 250 ℃ and 1-2 hours at the temperature of 300 ℃, and the crosslinking type polyimide film with micropores is obtained after cooling. The film thickness was controlled at 45 μm.
Example 2
Synthesis of imide-containing diamine monomer C 2 . Adding aromatic diamine DPD (12.2571 g and 90 mmol) into a 500ml three-necked bottle under the protection of nitrogen, adding 240ml of NMP, adding aromatic dianhydride BPDA (8.8266 g and 30 mmol) after the DPD is completely dissolved, stirring at room temperature for reaction for 24 hours, adding 80ml of water-carrying agent toluene after the reaction is finished, and continuously stirring and heating at 180 ℃ for 24 hours to obtain a homogeneous imide-containing diamine solution. Stopping until toluene is completely distilled offAfter heating and natural cooling to room temperature, the reaction solution was poured into a mixture of methanol and water (2l, v =1) 2 And (3) powder.
Preparation of self-contained microporous polyimide E containing benzocyclobutene side group 2 . The preparation is shown as formula 9, and the specific reaction process is as follows: 1g of the diamine monomer C prepared above 2 And 1g of benzocyclobutene-containing diamine monomer D 1 After mixing well, it was put into a nitrogen-protected three-necked flask, then 150ml of trifluoroacetic acid was added, and after complete dissolution, 2ml of dimethoxymethane (22.4 mmol) was added, and stirred at room temperature for 48 hours, then carefully basified with 2.5% aqueous ammonia, and the resulting solution was stirred to precipitate a white fibrous precipitate. The solid was filtered off and washed 3 times with water and then with methanol. Dissolving the obtained fibrous precipitate with chloroform, separating out in methanol, filtering, naturally drying, and further drying at 120 deg.C under vacuum for 24 hr to obtain polyimide E containing benzocyclobutene side group and having micropores 2 。
FTIR spectrum showed that the polymer was 1375cm -1 ，1717cm -1 ，1788cm -1 An absorption peak of the imide ring is shown nearby, and the polymer structure is in agreement with the expectation.
Preparing the benzocyclobutene side group-containing cross-linked self-provided microporous polyimide film. The molecular chain structure is shown as a formula 10.
Taking 3g of self-contained microporous polyimide E containing benzocyclobutene side groups 2 Dissolving the powder in NMP to prepare a polymer solution with solid content of 5wt.%, uniformly coating the polymer solution on a glass plate, drying in a vacuum oven at the temperature of 40 ℃ for 1-5 hours, 60 ℃ for 1-5 hours, 80 ℃ for 1-5 hours, 120 ℃ for 1-5 hours and 150 ℃ for 1-5 hours, and removingAnd (3) a solvent. Then according to the temperature-rising program, the thermosetting crosslinking is carried out for 1-5 hours at the temperature of 200 ℃, 1-5 hours at the temperature of 250 ℃ and 1-2 hours at the temperature of 300 ℃, and the crosslinking type polyimide film with micropores is obtained after cooling. The film thickness was controlled at 52 μm.
Example 3
Synthesis of imide-containing diamine monomer C 3 . Adding aromatic diamine DPD (12.2571 g and 90 mmol) into a 500ml three-necked bottle under the protection of nitrogen, adding 200ml of NMP, adding fatty dianhydride CBDA (5.0733 g and 30 mmol) after DPD is completely dissolved, stirring at room temperature for reaction for 24 hours, adding 80ml of water-carrying agent toluene after the reaction is finished, and continuously stirring and heating at 180 ℃ for 24 hours to obtain a homogeneous imide-containing diamine solution. After toluene was completely evaporated, heating was stopped, and after cooling to room temperature naturally, the reaction solution was poured into a high-speed stirred mixture of methanol and water (2l, v 3 And (3) powder.
Preparation of self-contained microporous polyimide E containing benzocyclobutene side group 3 . The preparation is shown as formula 11, and the specific reaction process is as follows: 1g of the diamine monomer C prepared above 3 And 1g of a benzocyclobutene-containing diamine monomer D 2 After mixing, the mixture was charged into a nitrogen-protected three-necked flask, then 150ml of trifluoroacetic acid was added, and after complete dissolution, 2ml of dimethoxymethane (22.4 mmol) was added, and stirred at room temperature for 48 hours, then basified carefully with 2.5% aqueous ammonia solution, and the resulting solution was stirred to precipitate a white fibrous precipitate. The solid was filtered off and washed 3 times with water and then with methanol. Dissolving the obtained fibrous precipitate with chloroform, separating out in methanol, filtering, naturally drying, and further drying at 120 deg.C under vacuum for 24 hr to obtain polyimide E containing benzocyclobutene side group and having micropores 3 。
FTIR spectrum showed that the polymer was 1371cm -1 ，1716cm -1 ，1783cm -1 An absorption peak of the imide ring is shown nearby, and the polymer structure is in agreement with the expectation.
Preparing the benzocyclobutene side group-containing cross-linked self-provided microporous polyimide film. The molecular chain structure is shown as formula 12.
Taking 3g of self-microporous polyimide E containing benzocyclobutene side groups 3 Dissolving the powder in NMP to prepare a polymer solution with the solid content of 5wt.%, uniformly coating the polymer solution on a glass plate, and then drying in a vacuum oven according to the programmed heating modes of 1-5 hours at 40 ℃, 1-5 hours at 60 ℃, 1-5 hours at 80 ℃, 1-5 hours at 120 ℃ and 1-5 hours at 150 ℃ to remove the solvent. Then according to the temperature-rising program, the thermosetting crosslinking is carried out for 1-5 hours at the temperature of 200 ℃, 1-5 hours at the temperature of 250 ℃ and 1-2 hours at the temperature of 300 ℃, and the crosslinking type polyimide film with micropores is obtained after cooling. The film thickness was controlled at 48 μm.
Performance tests were conducted on the benzocyclobutene side-group crosslinked type self-microporous polyimide films of examples 1 to 3. Using a dielectric spectrometer and an impedance spectrometer to test the dielectric property of the film; the thermal conductivity of the film was tested using a thermal constant instrument; the glass transition temperature was tested using dynamic thermomechanical analysis (DMA).
The test results are shown in the following table.
| Performance of | Example 1 | Example 2 | Example 3 |
| Dielectric constant of | <2.8 | <2.8 | <2.9 |
| Coefficient of thermal conductivity (W/mK) | <0.015 | <0.012 | <0.012 |
| Tensile modulus, GPa (25 ℃ C.) | >1.0 | >1.0 | >1.0 |
| Tensile Strength, MPa (25 ℃ C.) | >60 | >60 | >60 |
| Glass transition temperature (. Degree. C.) | >380 | >390 | >380 |
Claims (4)
1. A preparation method of a benzocyclobutene side group crosslinking type polyimide film with a self-made micropore and low dielectric constant and low heat conduction is characterized by comprising the following steps:
(1) The method comprises the following steps of (1) synthesizing a diamine monomer containing imide, wherein the molecular chain structure of the diamine monomer is shown as a formula 1, the diamine monomer C containing imide is obtained by reacting a diamine monomer B with a dianhydride monomer A, the amount of the diamine monomer B is 2.1-4 times that of the dianhydride monomer A during reaction, and the method specifically comprises the following steps:
at N 2 In an atmosphere containing N 2 In a flask with a vent pipe, a thermometer and a mechanical stirrer, firstly adding a diamine monomer B, then adding a high-boiling-point solvent, after the diamine monomer B is completely dissolved, adding a dianhydride monomer A, uniformly stirring, and reacting for 5-24 hours at 0-80 ℃; adding a water-carrying agent, controlling the reaction temperature to be 150-200 ℃, continuously carrying out reflux reaction for 2-80 hours, finally obtaining a homogeneous diamine solution containing imide, completely evaporating the water-carrying agent in the system, pouring the reaction liquid into a mixed liquid of ethanol and water which are stirred at a high speed after the reaction liquid is cooled, separating out a solid product, recrystallizing the solid product in N, N-dimethylformamide, and carrying out vacuum drying on the recrystallized product at 50-180 ℃ for 2-48 hours to obtain a dried diamine monomer C containing imide;
the high boiling point solvent is selected from N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide;
(2) The preparation contains the micropore polyimide of oneself of benzocyclobutene lateral group, and its molecular chain structure is as shown by formula 2, the micropore polyimide E of oneself that contains benzocyclobutene lateral group uses diamine monomer C that contains imide and diamine monomer D that contains benzocyclobutene to prepare as the raw materials and obtains, and concrete step is:
the above-mentioned acyl group-containing compoundMixing an imine diamine monomer C and a benzocyclobutene-containing diamine monomer D according to a mass ratio of 1 2 Under protection, dissolving a mixture of a diamine monomer C containing imide and a diamine monomer D containing benzocyclobutene in an acidic solvent to prepare a solution with the solid content of 1-30 wt.%, then adding a formaldehyde initiator, stirring for 2-150 hours at-5-45 ℃, after the reaction is finished, pouring a reaction solution into methanol stirred at a high speed to separate out a fibrous solid product, fully washing the obtained fibrous solid product with methanol, filtering, naturally airing, and drying the aired fibrous solid product in vacuum at 50-180 ℃ for 2-48 hours to obtain the dry self-contained microporous polyimide E containing benzocyclobutene side groups;
(3) The molecular chain structure of the prepared benzocyclobutene side group crosslinked microporous polyimide film is shown as a formula 3,
firstly, dissolving synthesized polyimide E with micropores and containing benzocyclobutene side groups in an aprotic polar solvent to prepare a polymer solution with the solid content of 1-30 wt%, then uniformly coating the polymer solution on plate glass, adjusting the thickness of a coated solution layer to ensure that the dried thickness is 5-150 micrometers, then drying the plate glass coated with the polymer solution in an inert atmosphere oven or a vacuum oven, and drying the plate glass at 40 ℃ for 1-5 hours, 60 ℃ for 1-5 hours, 80 ℃ for 1-5 hours, 120 ℃ for 1-5 hours and 150 ℃ for 1-5 hours in a temperature programmed heating manner to remove the solvent; then carrying out thermocuring crosslinking at 200 ℃ for 1-5 hours, 250 ℃ for 1-5 hours and 300 ℃ for 1-2 hours according to a temperature raising program, and cooling to obtain the benzocyclobutene side group crosslinking type polyimide film with the micropores;
the aprotic polar solvent is selected from any one or the combination of at least two of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide;
wherein the dianhydride monomer A is 4,4' - (4, 4' -isopropyldiphenoxy) bis (phthalic anhydride) (BPADA), p-phenylene-ditrimellitic dianhydride (BTAH), pyromellitic dianhydride (PMDA), 4' - (hexafluoroisopropylidene) diphthalic anhydride (6 FDA), 1,4,5, 8-naphthalene tetracarboxylic anhydride (NTCDA), 3,4,9, 10-perylene tetracarboxylic dianhydride (PTCDA), triptycene-2, 3,6, 7-tetracarboxylic dianhydride (TTD), 9' -spirobifluorene-2, 2',3,3' -tetracarboxylic dianhydride (SBDA), 3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), 3', 4' -diphenyl ether tetracarboxylic dianhydride (ODPA), 3',4,4' -Biphenyltetracarboxylic dianhydride (BPDA), 9-bis (3, 4-dicarboxyphenyl) fluorenedianhydride (BDFDA), 4' -dinaphthalene-1, 1', 8' -tetracarboxylic dianhydride (BNTDA), 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (HPMDA), 5,6,7, 8-bicyclo [2.2.2] -2-heptylenetetracarboxylic dianhydride (BTA), 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,3, 4-cyclopentanetetracarboxylic dianhydride (CPDA), 1,2,3, 4-tetramethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride (TCTD), 4,5,6, 7-bicyclo [2.2.1] heptanetetracarboxylic dianhydride (BHDA), 2,3,5, 6-bicyclo [2.2.2] octanetetracarboxylic dianhydride (BODA), 2R,5R,7S, 10S-naphthalene tetracarboxylic dianhydride (HNTDA), 6H,12H-5, 11-methylene dibenzo [ b, f ] [1,5] diazacyclo-2, 3,8, 9-tetracarboxylic dianhydride (TB-DA);
the diamine monomer B is 5 (6) -amino-1- (4-aminophenyl) -1, 3-trimethylindane (DAPI), p-aminobenzoic acid p-aminophenyl ester (APAB), 2, 6-Diaminotoluene (DAP), 2, 5-dimethyl-1, 4-phenylenediamine (DPD), 4 '-diamino-3, 3' -dimethylbiphenyl (o-tolidine), 1 '-binaphthyl-2, 2' -diamine (AMA), 3 '-dimethylbipyridine (AMMA), 1, 5-Naphthalenediamine (NPD), 9' -spirobi [ 9H-fluorene ] -2,2 '-diamine (SBF) shown in formula 5 3,3' -dimethyl-9, 9 '-spirobi [ 9H-fluorene ] -2,2' -diamine (CSBF), 6-amino-2- (3-aminophenyl) Benzimidazole (BIA), 9-bis (4-amino-3-methylphenyl) fluorene (BAMF), 9-bis (p-tolyl) fluorene (BMF), 4 '-diaminodiphenylethane (DDE), 4' - (cyclohexane-1, 4-diylbis (thio)) diphenylamine (SCHDA), 1, 4-bis [ 2-amino-4- (trifluoromethyl) phenyl ] piperazine (AFMT), 1-bis (4-aminophenyl) cyclohexane (BACH), A mixture of one or more of 5,5' -isopropylidenebis (2-furfuryl) (DAF), 2-bis (4-aminophenyl) norbornane (BANB), 1,4, 3, 6-dianhydro-2, 5-di-O- (4-aminophenyl) -D-mannitol (DA-IM), 1, 3-bis (aminophenoxymethylene) -1, 2-trimethylpentane (BAMT), 3-bis (4-Aminophenyl) Quinuclidine (AQ), 1-bis (4-aminophenyl) -4-methylcyclohexane (BAME);
the diamine monomer D containing benzocyclobutene diamine is D shown in formula 6 1 、D 2 ，
2. The method for preparing benzocyclobutene film with low dielectric constant and low thermal conductivity and side group crosslinking type self-micropore polyimide film as claimed in claim 1, wherein the water carrying agent in step (1) is any one of toluene, xylene or chlorobenzene or a mixture thereof; the reaction reflux temperature of the water-carrying agent is controlled to be 150-200 ℃ when the water-carrying agent carries water, and the continuous reflux time is 2-80 hours.
3. The method for preparing benzocyclobutene side group crosslinked self-microporous polyimide film with low dielectric constant and low thermal conductivity according to claim 1, wherein the treatment conditions for drying the recrystallized product are as follows: in a vacuum oven, the temperature and the time are respectively 50-180 ℃ and 2-48 hours.
4. The method for preparing benzocyclobutene film with low dielectric constant and low thermal conductivity and side group crosslinking type self-micropore polyimide film as claimed in claim 1, wherein the acid solvent in the step (2) is one or a mixture of trifluoroacetic acid, polyphosphoric acid and hydrochloric acid; the formaldehyde initiator is any one of formalin, paraformaldehyde, hexamethylenetetramine and ethylene glycol dimethyl ether.
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