CN118027809A - Polyimide varnish and preparation method thereof - Google Patents
Polyimide varnish and preparation method thereof Download PDFInfo
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- CN118027809A CN118027809A CN202410213065.8A CN202410213065A CN118027809A CN 118027809 A CN118027809 A CN 118027809A CN 202410213065 A CN202410213065 A CN 202410213065A CN 118027809 A CN118027809 A CN 118027809A
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- polyimide varnish
- crosslinking type
- dianhydride
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- 239000002966 varnish Substances 0.000 title claims abstract description 47
- 239000004642 Polyimide Substances 0.000 title claims abstract description 38
- 229920001721 polyimide Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000004132 cross linking Methods 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 20
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 15
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 15
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 239000002981 blocking agent Substances 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 150000003254 radicals Chemical class 0.000 claims abstract description 8
- 239000004952 Polyamide Substances 0.000 claims abstract description 6
- 229920002647 polyamide Polymers 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 5
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
- -1 3-aminophenoxy Chemical group 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 2
- RFSCGDQQLKVJEJ-UHFFFAOYSA-N 2-methylbutan-2-yl benzenecarboperoxoate Chemical compound CCC(C)(C)OOC(=O)C1=CC=CC=C1 RFSCGDQQLKVJEJ-UHFFFAOYSA-N 0.000 claims description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 2
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 claims description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 2
- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 claims description 2
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 claims description 2
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 20
- 239000010949 copper Substances 0.000 abstract description 18
- 229910052802 copper Inorganic materials 0.000 abstract description 18
- 239000004020 conductor Substances 0.000 abstract description 13
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000003973 paint Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 4
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 125000002883 imidazolyl group Chemical group 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000012970 tertiary amine catalyst Substances 0.000 description 3
- 229920006259 thermoplastic polyimide Polymers 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004972 Polyurethane varnish Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention belongs to the field of high polymer materials, and discloses polyimide varnish which is mainly prepared by imidizing polymerization reaction of thermosetting polyamide acid precursor solution capped by a crosslinking type end capping agent, N-vinylimidazole, a free radical initiator and an imidization accelerator; the thermosetting polyamic acid precursor solution blocked by the crosslinking type blocking agent is obtained by polymerizing aromatic diamine and aromatic dianhydride in aprotic solvent to obtain the thermosetting polyamic acid precursor solution, and then adding the crosslinking type blocking agent to react. The polyimide varnish has moderate viscosity, good adhesiveness and film forming property, and excellent binding property with copper conductors. The preparation method of the polyimide varnish has the advantages of simple operation, low cost and high imidization film forming rate.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to polyimide varnish and a preparation method thereof.
Background
The driving motor is a core component of the new energy electric automobile. At present, the flat wire motor has become the mainstream development trend of the new energy electric automobile motor because of the advantages of high power density, high integration level, low cost, high efficiency and the like. The flat wire motor improves the groove fullness rate of the motor and simultaneously greatly improves the temperature resistance requirement of the insulating varnish for the enameled wire. Polyimide insulating varnish is an insulating material technical solution for high-voltage flat-wire motors by virtue of excellent high-temperature resistance and flame retardance.
The paint film adhesion of the enamelled wire refers to the firm degree of the combination between the bare copper wire and the paint film of the enamelled wire, and is one of the most important performance indexes of the enamelled wire. If there is a problem with the adhesion of the wire film to the wire, there is a great problem with the insulation between the wires.
The structure of enamelled copper flat wire: the inner layer is a copper flat wire conductor, and according to different performance requirements and application fields of the enamelled copper flat wire conductor, two or three layers of insulating paint films are coated outside the copper flat wire conductor, and the paint films specifically comprise a primer layer, a corona-resistant or low-dielectric paint layer and a top paint layer. The primer layer provides a tight bond between the bare copper wire and the paint film.
Patent document CN115424770a discloses a high-voltage load wire. The high-voltage load wire comprises a conductor, and a double-layer structure of a high-adhesion layer and a surge-resistant layer, wherein the high-adhesion layer and the surge-resistant layer are positioned near the conductor, and the double-layer structure is formed by covering the outer periphery of the conductor and the surge-resistant layer positioned on the surface of the high-adhesion layer. The varnish for forming the high adhesion layer includes one of a polyester imide varnish, a polyamide imide varnish, a polyimide varnish, a polyamide varnish, a polyvinyl formal varnish, a polyurethane varnish, and a polyester varnish. The most preferred high adhesion layer is polyimide varnish in terms of high temperature resistance, but this patent does not relate to the specific components of the high adhesion layer varnish.
Patent document CN103596360a discloses a flexible glue-free circuit board substrate and a method for manufacturing the same. The flexible glue-free circuit board base material comprises 0.5% -2% of vinyl imidazole compound and thermoplastic polyimide glue, wherein the vinyl imidazole compound accounts for 0.5% -2% of the mass of the liquid thermoplastic polyimide glue. Under the action of heat or plasma, vinyl imidazole breaks the vinyl double bond, forms a bond with amido in the thermoplastic polyimide adhesive, and the imidazole group after bonding forms a coordination bond with copper, so that good bonding force between copper and a high polymer film is ensured, but heat treatment (170-220 ℃ for 1-2 h) or plasma treatment is not suitable for a wire enamel application process.
Therefore, a polyimide varnish having a high bonding force with a copper conductor is still required due to the simple manufacturing process.
Disclosure of Invention
The invention aims to solve the technical problems and overcome the defects and shortcomings in the background art, and provides polyimide varnish which is simple in manufacturing process and has excellent binding force with a copper conductor and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
A polyimide varnish is mainly prepared from thermosetting polyamic acid precursor solution blocked by a crosslinking type blocking agent, N-vinylimidazole, a free radical initiator and an imidization accelerator through imidization polymerization reaction; the thermosetting polyamic acid precursor solution blocked by the crosslinking type blocking agent is obtained by polymerizing aromatic diamine and aromatic dianhydride in an aprotic solvent to obtain the thermosetting polyamic acid precursor solution, and then adding the crosslinking type blocking agent for reaction.
According to the invention, the rapid crosslinking of the end capping agent containing carbon-carbon unsaturated double bond and N-vinylimidazole is ensured by introducing the free radical initiator, an imidazole group is connected into a PI structure by free radical polymerization, and a coordination bond is formed by the imidazole group and copper, so that the tight combination of varnish and copper conductor is ensured; by introducing the imidization accelerator, the imidization film forming rate and film forming property of the varnish are improved; the N-vinyl imidazole reacts with a crosslinking type end-capping agent containing carbon-carbon unsaturated double bonds through a free radical polymerization reaction so as to be grafted onto a polyimide molecular chain; the polyimide varnish finally obtained has excellent binding force with the copper conductor.
The polyimide varnish preferably has a solid content of 25 to 35% and a viscosity of 80 to 250 Pa.S at 23+ -2deg.C of the thermosetting polyamic acid precursor solution blocked by the crosslinking type blocking agent.
Preferably, the aromatic diamine monomer is selected from at least one of 4,4 '-diaminodiphenyl ether (4, 4-ODA), 3,4' -diaminodiphenyl ether (3, 4-ODA), p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 4 '-bis (3-aminophenoxy) diphenylsulfone, and 4,4' -diaminodiphenylmethane.
Preferably, the aromatic dianhydride monomer is selected from 1,2,4, 5-pyromellitic dianhydride (PMDA), 3', 4' -benzophenone tetracarboxylic dianhydride, 3', at least one of 4,4' -biphenyltetracarboxylic dianhydride, 4' -oxydiphthalic anhydride, 3', 4' -diphenyl sulfone tetracarboxylic dianhydride and bisphenol A dianhydride;
Preferably, the aprotic solvent is selected from at least one of N, N '-dimethylformamide, N' -dimethylacetamide and N-methylpyrrolidone.
Preferably, the crosslinking type end-capping agent is an end-capping agent with carbon-carbon unsaturated double bonds, and is selected from at least one of maleic anhydride and norbornene dianhydride.
Preferably, the free radical initiator is a peroxide free radical initiator, and is at least one selected from benzoyl peroxide, cyclohexanone peroxide, lauroyl peroxide, tert-amyl peroxybenzoate, tert-butyl hydroperoxide, dicumyl peroxide and cumene perhydro, and the dosage of the free radical initiator is 0.1-1% of the total weight of the crosslinking end-capping agent and N-vinylimidazole.
Preferably, the imidization accelerator is a tertiary amine catalyst, more preferably a heterocyclic tertiary amine catalyst and/or an aliphatic tertiary amine catalyst, and most preferably one or more of pyridine and its derivatives, picoline and its derivatives, beta-pyrroline, lutidine, quinoline, isoquinoline, imidazole, triethylamine, triethanolamine and N, N-dimethylethanolamine; the addition amount of the imidization accelerator is 2-4% of the total weight of the aromatic diamine and the aromatic dianhydride.
Preferably, the molar ratio of the aromatic diamine to the aromatic dianhydride is 100:95-99, the molar ratio of the crosslinking end-capping agent to the aromatic diamine is 100:2-10, and the molar ratio of the crosslinking end-capping agent to the N-vinylimidazole is 100:50-100.
Based on one general inventive concept, the invention also provides a preparation method of polyimide varnish, which comprises the following steps:
(1) Adding a solvent and an aromatic diamine monomer into a reaction container, adding aromatic dianhydride into the reaction container in batches after the aromatic diamine monomer is dissolved for polymerization reaction, and then adding a crosslinking type end capping agent into the reaction container for end capping reaction to obtain a thermosetting polyamide acid precursor solution capped by the crosslinking type end capping agent; in the process, the viscosity and the solid content of the polyamic acid precursor solution are regulated and controlled by the addition amount of the aromatic dianhydride and the addition amount of the solvent;
(2) Adding a thermosetting polyamide acid precursor solution blocked by a crosslinking type blocking agent into a reaction container, sequentially adding N-vinylimidazole, a peroxide free radical initiator and an imidization accelerator, and uniformly stirring and mixing to obtain the polyimide varnish.
In the above preparation method of polyimide varnish, preferably, in the step (1), the polymerization reaction temperature is 40-80 ℃ and the reaction time is 2-8 hours; the temperature of the end capping reaction is 10-40 ℃ and the reaction time is 1-4 h.
Preferably, in the step (2), the stirring temperature is 0 to 5 ℃ and the stirring time is 0.5 to 2 hours.
Compared with the prior art, the invention has the beneficial effects that:
1. The polyimide varnish provided by the invention has moderate viscosity, good adhesiveness and film forming property and excellent binding property with copper conductors.
2. The polyimide varnish provided by the invention has higher solid content (25-35%) and proper viscosity (100-250 Pa.S), can reduce the number of lacquering tracks of the copper flat wire, and reduces the production cost.
3. The preparation method provided by the invention is simple to operate, low in cost and high in imidization film forming rate.
Detailed Description
The present invention will be described more fully hereinafter with reference to the preferred embodiments for the purpose of facilitating understanding of the present invention, but the scope of the present invention is not limited to the following specific embodiments.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1:
a preparation method of polyimide varnish comprises the following steps:
(1) Preparation of maleic anhydride terminated thermosetting polyamic acid precursor solution: 6007.20g of ODA (4, 4 '-diaminodiphenyl ether) was dissolved in DMAc (N, N' -dimethylacetamide) and 6478.16g of PMDA (pyromellitic dianhydride) was added thereto in portions to conduct polymerization, reacted at 80℃for 8 hours, then 58.83g of maleic anhydride was added thereto, and further end-capped at 35℃for 4 hours; the total amount of the added solvent DMAc is 37632.59g, and the solid content of the polyamic acid precursor solution is adjusted to 25%;
(2) Preparing polyimide varnish: to the reaction vessel were added 56.472g of N-vinylimidazole, 1.15g of dicumyl peroxide and 125g of pyridine, and the mixture was stirred at 5℃for 1 hour to effect imidization and polymerization, and the mixture was uniformly mixed.
Examples 2 to 3:
The preparation process of the thermosetting polyamic acid precursor solution of examples 2 to 3 and the preparation process of the polyimide varnish were carried out with reference to preparation example 1, and the specific charging ratio and the reaction process are shown in table 1.
Comparative examples 1 to 4:
The preparation process of the thermosetting polyamic acid precursor solution of comparative examples 1 to 4 and the preparation process of the polyimide varnish were carried out with reference to preparation example 1, and the specific charging ratio and the reaction process are shown in table 1.
Table 1: examples 1 to 3 and comparative examples 1 to 3 were fed in proportion and reaction process
The following properties of examples 1 to 3 and comparative examples 1 to 4 were measured and evaluated. The results are shown in Table 2.
Solid content (wt%): a clean weighing dish was taken, the weight was designated m 0, about 3.0g of the sample solution was placed on the weighing dish, the weight was designated m 1, then the weighing dish was placed in an oven at 180℃for heat preservation for 60 minutes, and then the weight after heat treatment was measured, and the weight was designated m 2. The solid content (wt%) was calculated by the formula (m 2-m0)/(m1-m0). Times.100%. 3 samples were taken and averaged.
Viscosity (pa·s): the sample was placed in a 250ml plastic container and incubated in a constant temperature sink at 23 ℃. When the temperature of the sample reached 23.+ -. 2 ℃ measured using a digital thermometer, the viscosity of the sample was measured using a rotational viscometer in Pa.S. Test 3 times and average.
Storage stability, viscosity variable (η%): the sample is put in a 250ml plastic container and is placed in a refrigeration house below 5 ℃ for storage for 3 months, the initial viscosity is eta 0, the viscosity after three months is eta 3, the viscosity variable is = |1-eta 3/η0 |100%, the viscosity variable is less than 15%, and the storage stability is considered to be good.
Film forming performance: the sample was coated on a glass substrate by a film coater, and then the substrate was placed in a thermal circulation oven for imidization film formation. The state of the formed film was visually evaluated. Films without powdering, cracking and swelling were rated o, otherwise rated x.
Manufacturing an enamelled flat wire: and manufacturing the enameled flat wire by using the polyimide varnish. The specific method comprises the following steps: copper is cast, extended, wiredrawn and softened to obtain a copper flat wire with the thickness of 2.50 mm and 4.00mm, polyimide varnish manufactured by the method is coated on the peripheral surface of the copper flat wire through a die, baked to form a film under the conditions that the inlet temperature of a baking oven is 100 ℃ and the outlet temperature is 450 ℃, and painted for multiple times to form a paint film with the total thickness of 0.12-0.13 mm.
Adhesion: referring to GB/T4074.3-2008, a 400mm enameled rectangular wire is cut into a test sample at a middle position for one circle until a copper conductor is reached, and after 15% of the test sample is stretched, the insulation is tested for the distance of losing adhesion.
TABLE 2 film Properties of examples 1-3 and comparative examples 1-4
As can be seen from Table 2, examples 1 to 3 have good film forming property and storage stability uniformly with comparative examples 1 to 4, and examples 1 to 3 have better adhesion than comparative examples 1 to 4.
Claims (10)
1. A polyimide varnish is characterized in that the polyimide varnish is mainly prepared from thermosetting polyamic acid precursor solution blocked by a crosslinking type blocking agent, N-vinylimidazole, a free radical initiator and an imidization accelerator through imidization polymerization reaction; the thermosetting polyamic acid precursor solution blocked by the crosslinking type blocking agent is obtained by polymerizing aromatic diamine and aromatic dianhydride in an aprotic solvent to obtain the thermosetting polyamic acid precursor solution, and then adding the crosslinking type blocking agent for reaction.
2. The polyimide varnish according to claim 1, wherein the solid content of the thermosetting polyamic acid precursor solution blocked by the crosslinking blocking agent is 25% to 35%, and the viscosity at 23.+ -. 2 ℃ is 80 to 250 Pa.S.
3. The polyimide varnish according to claim 1, wherein the aromatic diamine monomer is at least one selected from the group consisting of 4,4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 4 '-bis (3-aminophenoxy) diphenylsulfone and 4,4' -diaminodiphenylmethane;
the aromatic dianhydride monomer is selected from 1,2,4, 5-pyromellitic dianhydride, 3', 4' -benzophenone tetracarboxylic dianhydride and 3,3', at least one of 4,4' -biphenyltetracarboxylic dianhydride, 4' -oxydiphthalic anhydride, 3', 4' -diphenyl sulfone tetracarboxylic dianhydride and bisphenol A dianhydride;
The aprotic solvent is at least one selected from the group consisting of N, N '-dimethylformamide, N' -dimethylacetamide and N-methylpyrrolidone.
4. The polyimide varnish according to claim 1, wherein the crosslinking type end-capping agent is at least one selected from the group consisting of maleic anhydride and norbornene dianhydride.
5. The polyimide varnish according to claim 1, wherein the free radical initiator is at least one selected from the group consisting of benzoyl peroxide, cyclohexanone peroxide, lauroyl peroxide, t-amyl peroxybenzoate, t-butyl hydroperoxide, dicumyl peroxide and cumene perhydro-hydride, and the amount of the free radical initiator is 0.1 to 1% of the total weight of the crosslinking type end-capping agent and the N-vinylimidazole.
6. The polyimide varnish according to claim 1, wherein the imidization accelerator is one or more of pyridine and its derivatives, picoline and its derivatives, β -pyrroline, lutidine, quinoline, isoquinoline, imidazole, triethylamine, triethanolamine and N, N-dimethylethanolamine; the addition amount of the imidization accelerator is 2-4% of the total weight of the aromatic diamine and the aromatic dianhydride.
7. The polyimide varnish according to any one of claims 1 to 6, wherein the molar ratio of the aromatic diamine to the aromatic dianhydride is 100:95 to 99, the molar ratio of the crosslinking type end-capping agent to the aromatic diamine is 100:2 to 10, and the molar ratio of the crosslinking type end-capping agent to the N-vinylimidazole is 100:50 to 100.
8. A method for producing the polyimide varnish according to any one of claims 1 to 7, comprising the steps of:
(1) Adding a solvent and an aromatic diamine monomer into a reaction container, adding aromatic dianhydride into the reaction container in batches after the aromatic diamine monomer is dissolved for polymerization reaction, and then adding a crosslinking type end capping agent into the reaction container for end capping reaction to obtain a thermosetting polyamide acid precursor solution capped by the crosslinking type end capping agent;
(2) Adding a thermosetting polyamide acid precursor solution blocked by a crosslinking type blocking agent into a reaction container, sequentially adding N-vinylimidazole, a peroxide free radical initiator and an imidization accelerator, and uniformly stirring and mixing to obtain the polyimide varnish.
9. The method for producing a polyimide varnish according to claim 8, wherein in the step (1), the polymerization reaction is carried out at a temperature of 40 to 80 ℃ for a reaction time of 2 to 8 hours; the temperature of the end capping reaction is 10-40 ℃ and the reaction time is 1-4 h.
10. The method for producing a polyimide varnish according to claim 8, wherein in the step (2), the stirring temperature is 0 to 5℃and the stirring time is 0.5 to 2 hours.
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