CN113336998A - 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 PDF

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CN113336998A
CN113336998A CN202110663689.6A CN202110663689A CN113336998A CN 113336998 A CN113336998 A CN 113336998A CN 202110663689 A CN202110663689 A CN 202110663689A CN 113336998 A CN113336998 A CN 113336998A
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benzocyclobutene
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庄永兵
陆健
张宇
万印华
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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, diamine monomer C containing imide is synthesized, then the diamine monomer C is mixed with diamine monomer D containing benzocyclobutene, and the mixture is polymerized under the action of an initiator to obtain polyimide powder containing benzocyclobutene active side group. After purification and drying, dissolving the polymer in a polar solvent to form 1-30 wt.% of 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 manner to form the benzocyclobutene side group crosslinking type polyimide film with the micropores in the self-made manner, wherein the thickness of the benzocyclobutene side group crosslinking type polyimide film is 5-150 micrometers. 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

Preparation method of benzocyclobutene side group cross-linked polyimide film with low dielectric and low heat conduction and micropores
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 components inside the chip, it is necessary to develop an insulating layer having a low dielectric constant. In addition, the requirements for heat insulating 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 porous polyimide films with reduced dielectric constant (Lee Y J, Huang J M, Kuo S W, et al, Low-dielectric, nanoporous polyimide films prepared from PEO-POSS nanoparticles [ J ]. Polymer,2005,46(23): 10056-. CN112275147A discloses a preparation method of a self-microporous separation membrane. CN107469651A and CN110885556A disclose methods for preparing crosslinked polyimide membranes. None of the above documents and patents relate to the preparation of benzocyclobutene side group crosslinked polyimide film with pores and its application in the field of dielectric and heat conducting 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 the reaction of a diamine monomer B and a dianhydride monomer A. Wherein the amount of the diamine B is 2.1 to 4 times the amount of the dianhydride A during the reaction. The method comprises the following specific steps:
Figure BDA0003115991820000011
in N2In an atmosphere containing N2Adding 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 ℃; and 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 the imide.
(2) The molecular chain structure of the prepared self-prepared 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:
Figure BDA0003115991820000021
mixing the imide-containing diamine monomer C and the benzocyclobutene-containing diamine monomer D according to the mass ratio of 1: 9-9: 1. In N2Under protection, dissolving a mixture of a diamine monomer C and a 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, pouring the reaction liquid into methanol stirred at a high speed to separate out a fibrous solid product. And 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 dry self-micropore polyimide product E containing benzocyclobutene side groups.
(3) Preparing the benzocyclobutene side group-containing cross-linked self-provided microporous polyimide film. The molecular chain structure is shown in formula 3.
Firstly, the synthesized polyimide is dissolved in an aprotic polar solvent (such as N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), and the like) to prepare a polymer solution with a solid content of 1-30 wt.%. And then uniformly coating the polymer solution on flat glass, and adjusting the thickness of the coated solution layer to make the dried thickness of the solution layer be 5-150 micrometers. Then, putting the plate glass coated with the polymer solution into an inert atmosphere oven or a vacuum oven for drying, and drying in a temperature programming 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; 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.
Figure BDA0003115991820000031
A preparation method of a benzocyclobutene side group cross-linked polyimide film with low dielectric and low heat conduction and a micropore. 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), 4,4'- (hexafluoroisopropylidene) diphthalic anhydride (6FDA), 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), 3,3',4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride (ODPA) shown in the formula 4, 3,3',4,4' -Biphenyltetracarboxylic dianhydride (BPDA), 9-bis (3, 4-dicarboxyphenyl) fluorenedianhydride (BDFDA), 4,4' -dinaphthalene-1, 1',8,8' -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 (BHDA), 2,3,5, 6-bicyclo [2.2.2] octane tetracarboxylic 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) or a mixture of a plurality of compounds thereof.
Figure BDA0003115991820000032
Figure BDA0003115991820000041
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 diamine B used in step (1) of the process is 5(6) -amino-1- (4-aminophenyl) -1,3, 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), 3,3 '-dimethylbipyridine (AMMA), 1, 5-Naphthalenediamine (NPD), 9' -spirobi [ 9H-fluorene ] -2,2 '-diamine (SBF), 3,3' -dimethyl-9 as shown in formula 5, one or more of 9 '-spirobi [ 9H-fluorene ] -2,2' -diamine (CSBF), 6-amino-2- (3-aminophenyl) Benzimidazole (BIA), 9-di (4-amino-3-methylphenyl) fluorene (BAMF), 9-di (p-methylphenyl) fluorene (BMF); the aliphatic diamine B used is 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), 1,4:3, 6-dianhydro-2, 5-bis-O- (4-aminophenyl) -D-mannitol (DA-IM), 1, 3-bis (aminophenoxymethylene) -1 as shown in formula 6, 2, 2-trimethylpentane (BAMT), 3-bis (4-Aminophenyl) Quinuclidine (AQ), 1-bis (4-aminophenyl) -4-methylcyclohexane (BAME).
Figure BDA0003115991820000042
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 benzo cyclobutene-containing diamine D used in the step (2) of the method is D shown in a formula 61、D2。
Figure BDA0003115991820000043
Figure BDA0003115991820000051
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. The method is characterized in that the amount of the diamine B in the step (1) is 2.1-4 times of that of the dianhydride A.
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 of the water-carrying agent is controlled to be 150-200 ℃ when the water-carrying agent is carried with 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 for drying the recrystallized product were: in a vacuum oven, the temperature and time are 50-180 ℃ and 2-48 hours respectively.
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 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: 9-9: 1; the reaction temperature is-5 ℃ to 45 ℃; the stirring time is 2-150 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 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 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 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 dried thickness of the coated polymer solution layer 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 rise 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 is raised to 200 ℃ for 1-5 hours, 250 ℃ for 1-5 hours, and 300 ℃ for 1-2 hours for thermal curing and crosslinking.
Examples
To further illustrate the present invention, some specific embodiments are described below, and some implementation methods of the present invention are described in conjunction with specific operation procedures.
In the following examples, the synthesized polymers were structurally characterized using fourier transform infrared spectroscopy (FTIR).
Example 1:
synthesis of imide-containing diamine monomer C1. Adding aromatic diamine DPD (12.2571g, 90mmol) into a 500ml three-necked bottle under the protection of nitrogen, adding NMP 240ml, adding aromatic dianhydride 6FDA (13.3271g, 30mmol) after DPD is completely dissolved, stirring at room temperature for reaction for 24 hours, and adding water-carrying agent A after the reaction is finished80ml of benzene were heated at 180 ℃ for 24 hours with continuous stirring to give a homogeneous imide-containing diamine solution. After toluene is completely evaporated, stopping heating, naturally cooling to room temperature, pouring the reaction liquid into a mixture (2L, V: V ═ 1:1) of methanol and water which is stirred at a high speed to obtain a precipitate, dissolving the obtained precipitate in DMF, separating out in methanol, filtering, naturally drying, and continuously drying at the temperature of 80 ℃ for 24 hours in vacuum to obtain the diamine monomer C containing imide1And (3) powder.
Preparation of self-contained microporous polyimide E containing benzocyclobutene side group1. The preparation is shown as formula 7, and the specific reaction process is as follows: 1g of the diamine monomer C prepared above1And 1g of a benzocyclobutene-containing diamine monomer D1After 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 (22.4mmol) 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 micropores1。
FTIR spectrum showed that the polymer was 1370cm-1，1716cm-1，1784cm-1An absorption peak of the imide ring is shown nearby, and the polymer structure is in agreement with the expectation.
Figure BDA0003115991820000061
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 groups1Dissolving the powder in NMP to prepare a polymer solution with the solid content of 5 wt.%, uniformly coating the polymer solution on a glass plate, and then uniformly coating the glass plate on the glass plate in a vacuum oven at 40 ℃ for 1-5 hours at 60 DEG CDrying at 1-5 hours, 80 ℃ for 1-5 hours, 120 ℃ for 1-5 hours, and 150 ℃ for 1-5 hours, and removing the solvent. And then carrying out thermosetting 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 crosslinked polyimide film with the micropores. The film thickness was controlled at 45 μm.
Figure BDA0003115991820000071
Example 2
Synthesis of imide-containing diamine monomer C2. Adding aromatic diamine DPD (12.2571g, 90mmol) into a 500ml three-necked bottle under the protection of nitrogen, adding 240ml of NMP, adding aromatic dianhydride BPDA (8.8266g, 30mmol) 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 is completely evaporated, stopping heating, naturally cooling to room temperature, pouring the reaction liquid into a mixture (2L, V: V ═ 1:1) of methanol and water which is stirred at a high speed to obtain a precipitate, dissolving the obtained precipitate in DMF, separating out in methanol, filtering, naturally drying, and continuously drying at the temperature of 80 ℃ for 24 hours in vacuum to obtain the diamine monomer C containing imide2And (3) powder.
Preparation of self-contained microporous polyimide E containing benzocyclobutene side group2. The preparation is shown as formula 9, and the specific reaction process is as follows: 1g of the diamine monomer C prepared above2And 1g of a benzocyclobutene-containing diamine monomer D1After 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 (22.4mmol) 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, precipitating in methanol, filtering, naturally drying, and collecting the filtrateContinuously drying for 24 hours at the temperature of 120 ℃ in vacuum to obtain the self-micropore polyimide E containing benzocyclobutene side group2。
FTIR spectrum showed 1375cm of the polymer-1，1717cm-1，1788cm-1An absorption peak of the imide ring is shown nearby, and the polymer structure is in agreement with the expectation.
Figure BDA0003115991820000081
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 groups2Dissolving the powder in NMP to prepare a polymer solution with a solid content of 5 wt.%, uniformly coating the polymer solution on a glass plate, and then drying in a vacuum oven at a 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, so as to remove the solvent. And then carrying out thermosetting 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 crosslinked polyimide film with the micropores. The film thickness was controlled at 52 μm.
Figure BDA0003115991820000082
Example 3
Synthesis of imide-containing diamine monomer C3. Adding aromatic diamine DPD (12.2571g and 90mmol) into a 500ml three-necked bottle under the protection of nitrogen, adding 200ml of NMP, adding aliphatic dianhydride CBDA (5.0733g and 30mmol) 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 is completely evaporated, stopping heating, naturally cooling to room temperature, pouring the reaction solution into high-speed stirring methanol and waterThe resulting precipitate was dissolved in DMF, and then precipitated in methanol, filtered, and naturally dried, followed by further drying at 80 ℃ under vacuum for 24 hours to obtain an imide-containing diamine monomer C3And (3) powder.
Preparation of self-contained microporous polyimide E containing benzocyclobutene side group3. The preparation is shown as formula 11, and the specific reaction process is as follows: 1g of the diamine monomer C prepared above3And 1g of a benzocyclobutene-containing diamine monomer D2After 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 (22.4mmol) 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 micropores3。
FTIR spectrum showed that the polymer was 1371cm-1，1716cm-1，1783cm-1An absorption peak of the imide ring is shown nearby, and the polymer structure is in agreement with the expectation.
Figure BDA0003115991820000091
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-contained microporous polyimide E containing benzocyclobutene side groups3Dissolving the powder in NMP to prepare a polymer solution with a solid content of 5 wt.%, uniformly coating the polymer solution on a glass plate, and then drying in a vacuum oven at a 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, so as to remove the solvent. Then heating the mixture for 1 to 5 hours at 200 ℃,1 to 5 hours at 250 ℃ and 300 hoursAnd (3) performing thermosetting crosslinking at the temperature of 1-2 hours, and cooling to obtain the crosslinked polyimide film with the micropores. The film thickness was controlled at 48 μm.
Figure BDA0003115991820000101
Performance tests were conducted on the benzocyclobutene side-group crosslinked type self-microporous polyimide films of examples 1 to 3. Using a dielectric and 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 <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 (13)

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 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 imide-containing monomer C is obtained by reacting a diamine monomer B with a dianhydride monomer A. Wherein the amount of the diamine B is 2.1 to 4 times the amount of the dianhydride A during the reaction. The method comprises the following specific steps:
Figure FDA0003115991810000011
in N2In an atmosphere containing N2Adding 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 water-carrying agent, controllingThe reaction temperature is 150-200 ℃, the reflux reaction is continued for 2-80 hours, and finally the homogeneous diamine solution containing the imide is obtained. 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 the imide.
(2) The molecular chain structure of the prepared self-prepared 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:
Figure FDA0003115991810000012
mixing the imide-containing diamine monomer C and the benzocyclobutene-containing diamine monomer D according to the mass ratio of 1: 9-9: 1. In N2Under protection, dissolving a mixture of a diamine monomer C and a 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, pouring the reaction liquid into methanol stirred at a high speed to separate out a fibrous solid product. And 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 dry self-micropore polyimide product E containing benzocyclobutene side groups.
(3) Preparing the benzocyclobutene side group cross-linked polyimide film with micropores. The molecular chain structure is shown in formula 3.
Firstly, the synthesized polyimide is dissolved in an aprotic polar solvent (such as N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), and the like) to prepare a polymer solution with a solid content of 1-30 wt.%. And then uniformly coating the polymer solution on flat glass, and adjusting the thickness of the coated solution layer to make the dried thickness of the solution layer be 5-150 micrometers. Then, putting the plate glass coated with the polymer solution into an inert atmosphere oven or a vacuum oven for drying, and drying in a temperature programming 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; 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.
Figure FDA0003115991810000021
。
2. The method according to claim 1, wherein the benzocyclobutene side group cross-linked polyimide film with low dielectric constant and low thermal conductivity is self-microporous. 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), 4,4'- (hexafluoroisopropylidene) diphthalic anhydride (6FDA), 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), 3,3',4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride (ODPA) shown in the formula 4, 3,3',4,4' -Biphenyltetracarboxylic dianhydride (BPDA), 9-bis (3, 4-dicarboxyphenyl) fluorenedianhydride (BDFDA), 4,4' -dinaphthalene-1, 1',8,8' -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 (BHDA), 2,3,5, 6-bicyclo [2.2.2] octane tetracarboxylic 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) or a mixture of a plurality of compounds thereof.
Figure FDA0003115991810000031
。
3. The method according to claim 1, wherein the benzocyclobutene side group cross-linked polyimide film with low dielectric constant and low thermal conductivity is self-microporous. Characterized in that the diamine B used in step (1) of the process is 5(6) -amino-1- (4-aminophenyl) -1,3, 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), 3,3 '-dimethylbipyridine (AMMA), 1, 5-Naphthalenediamine (NPD), 9' -spirobi [ 9H-fluorene ] -2,2 '-diamine (SBF), 3,3' -dimethyl-9 as shown in formula 5, one or more of 9 '-spirobi [ 9H-fluorene ] -2,2' -diamine (CSBF), 6-amino-2- (3-aminophenyl) Benzimidazole (BIA), 9-di (4-amino-3-methylphenyl) fluorene (BAMF), 9-di (p-methylphenyl) fluorene (BMF); the aliphatic diamine B used is 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), 1,4:3, 6-dianhydro-2, 5-bis-O- (4-aminophenyl) -D-mannitol (DA-IM), 1, 3-bis (aminophenoxymethylene) -1 as shown in formula 6, 2, 2-trimethylpentane (BAMT), 3-bis (4-Aminophenyl) Quinuclidine (AQ), 1-bis (4-aminophenyl) -4-methylcyclohexane (BAME).
Figure FDA0003115991810000041
。
4. A low dielectric constant of claim 1,A preparation method of a benzocyclobutene side group cross-linked polyimide film with micropores is provided. Characterized in that the benzo cyclobutene-containing diamine D used in the step (2) of the method is D shown in a formula 61、D2。
Figure FDA0003115991810000042
。
5. The method according to claim 1, wherein the benzocyclobutene side group cross-linked polyimide film with low dielectric constant and low thermal conductivity is self-microporous. 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).
6. The method according to claim 1, wherein the benzocyclobutene side group cross-linked polyimide film with low dielectric constant and low thermal conductivity is self-microporous. The method is characterized in that the amount of the diamine B in the step (1) is 2.1-4 times of that of the dianhydride A.
7. The method according to claim 1, wherein the benzocyclobutene side group cross-linked polyimide film with low dielectric constant and low thermal conductivity is self-microporous. 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 of the water-carrying agent is controlled to be 150-200 ℃ when the water-carrying agent is carried with water, and the continuous reflux time is 2-80 hours.
8. The method according to claim 1, wherein the benzocyclobutene side group cross-linked polyimide film with low dielectric constant and low thermal conductivity is self-microporous. 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 for drying the recrystallized product were: in a vacuum oven, the temperature and time are 50-180 ℃ and 2-48 hours respectively.
9. The method according to claim 1, wherein the benzocyclobutene side group cross-linked polyimide film with low dielectric constant and low thermal conductivity is self-microporous. 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: 9-9: 1; the reaction temperature is-5 ℃ to 45 ℃; the stirring time is 2-150 hours.
10. The method according to claim 1, wherein the benzocyclobutene side group cross-linked polyimide film with low dielectric constant and low thermal conductivity is self-microporous. 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).
11. The method according to claim 1, wherein the benzocyclobutene side group cross-linked polyimide film with low dielectric constant and low thermal conductivity is self-microporous. 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%.
12. The method according to claim 1, wherein the benzocyclobutene side group cross-linked polyimide film with low dielectric constant and low thermal conductivity is self-microporous. The method is characterized in that in the step (3), the flat plate is preferably a glass flat plate, and the dried thickness of the coated polymer solution layer is controlled to be 5-150 micrometers.
13. The method according to claim 1, wherein the benzocyclobutene side group cross-linked polyimide film with low dielectric constant and low thermal conductivity is self-microporous. 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 rise 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 is raised to 200 ℃ for 1-5 hours, 250 ℃ for 1-5 hours, and 300 ℃ for 1-2 hours for thermal curing and crosslinking.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114634619A (en) * 2022-03-16 2022-06-17 中国科学院过程工程研究所 Polyimide, preparation method thereof and gas separation membrane
CN115536666A (en) * 2022-10-12 2022-12-30 中国科学院宁波材料技术与工程研究所 Dianhydride monomer containing benzo-bisnorbornene cyclobutane structure and preparation method and application thereof
CN115583889A (en) * 2022-10-26 2023-01-10 波米科技有限公司 Diamine, liquid crystal aligning agent, and preparation method and application thereof
CN116333354A (en) * 2023-02-23 2023-06-27 深圳大学 Benzocyclobutene-based intrinsic crosslinked polyimide film and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107469651A (en) * 2017-08-22 2017-12-15 中国海洋大学 A kind of preparation method and applications of high flux crosslinked polyimide solvent resistant NF membrane
CN108503647A (en) * 2018-04-09 2018-09-07 华南理工大学 Dant monomer of a kind of benzocyclobutene sealing end and preparation method thereof and curing
CN110885556A (en) * 2019-11-07 2020-03-17 安徽国风塑业股份有限公司 Heat-conducting cross-linked polyimide film and preparation method thereof
CN112275147A (en) * 2020-09-01 2021-01-29 中国科学院山西煤炭化学研究所 Self-polymerization microporous polyimide gas separation membrane and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107469651A (en) * 2017-08-22 2017-12-15 中国海洋大学 A kind of preparation method and applications of high flux crosslinked polyimide solvent resistant NF membrane
CN108503647A (en) * 2018-04-09 2018-09-07 华南理工大学 Dant monomer of a kind of benzocyclobutene sealing end and preparation method thereof and curing
CN110885556A (en) * 2019-11-07 2020-03-17 安徽国风塑业股份有限公司 Heat-conducting cross-linked polyimide film and preparation method thereof
CN112275147A (en) * 2020-09-01 2021-01-29 中国科学院山西煤炭化学研究所 Self-polymerization microporous polyimide gas separation membrane and preparation method and application thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114634619A (en) * 2022-03-16 2022-06-17 中国科学院过程工程研究所 Polyimide, preparation method thereof and gas separation membrane
CN115536666A (en) * 2022-10-12 2022-12-30 中国科学院宁波材料技术与工程研究所 Dianhydride monomer containing benzo-bisnorbornene cyclobutane structure and preparation method and application thereof
CN115536666B (en) * 2022-10-12 2024-01-26 中国科学院宁波材料技术与工程研究所 Dianhydride monomer containing benzobisnorbornene cyclobutane structure and preparation method and application thereof
CN115583889A (en) * 2022-10-26 2023-01-10 波米科技有限公司 Diamine, liquid crystal aligning agent, and preparation method and application thereof
CN115583889B (en) * 2022-10-26 2023-09-19 波米科技有限公司 Diamine, liquid crystal aligning agent, and preparation method and application thereof
CN116333354A (en) * 2023-02-23 2023-06-27 深圳大学 Benzocyclobutene-based intrinsic crosslinked polyimide film and preparation method thereof

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