CN116162197B - A photothermal dual-curable resin containing a benzocyclobutene structure and its preparation method and application - Google Patents
A photothermal dual-curable resin containing a benzocyclobutene structure and its preparation method and application Download PDFInfo
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- CN116162197B CN116162197B CN202310176291.9A CN202310176291A CN116162197B CN 116162197 B CN116162197 B CN 116162197B CN 202310176291 A CN202310176291 A CN 202310176291A CN 116162197 B CN116162197 B CN 116162197B
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- 229920005989 resin Polymers 0.000 title claims abstract description 66
- 239000011347 resin Substances 0.000 title claims abstract description 66
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical group C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 32
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 25
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 16
- DTGDMPJDZKDHEP-UHFFFAOYSA-N 4-ethenylbicyclo[4.2.0]octa-1(6),2,4-triene Chemical compound C=CC1=CC=C2CCC2=C1 DTGDMPJDZKDHEP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000009977 dual effect Effects 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 39
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 239000003999 initiator Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000012986 chain transfer agent Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 8
- -1 diethyl hexyl peroxydicarbonate Chemical compound 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000011229 interlayer Substances 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 5
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 4
- ZOKCNEIWFQCSCM-UHFFFAOYSA-N (2-methyl-4-phenylpent-4-en-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)CC(=C)C1=CC=CC=C1 ZOKCNEIWFQCSCM-UHFFFAOYSA-N 0.000 claims description 3
- ZHUWXKIPGGZNJW-UHFFFAOYSA-N 6-methylheptyl 3-sulfanylpropanoate Chemical compound CC(C)CCCCCOC(=O)CCS ZHUWXKIPGGZNJW-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 239000005456 alcohol based solvent Substances 0.000 claims description 2
- 239000003759 ester based solvent Substances 0.000 claims description 2
- 239000005453 ketone based solvent Substances 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 claims 2
- 230000000379 polymerizing effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 10
- 238000002329 infrared spectrum Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 239000005022 packaging material Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000004377 microelectronic Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001029 thermal curing Methods 0.000 description 3
- ULWDYECGHQQXMV-UHFFFAOYSA-N 3-ethyl-3-(3-ethyloctan-3-ylperoxy)octane Chemical compound C(C)C(CCCCC)(CC)OOC(CCCCC)(CC)CC ULWDYECGHQQXMV-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000003541 multi-stage reaction Methods 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229940090181 propyl acetate Drugs 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007158 vacuum pyrolysis Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
- C08F222/08—Maleic anhydride with vinyl aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明公开了一种含苯并环丁烯结构的可光热双重固化树脂及其制备方法和应用。该含苯并环丁烯结构的可光热双重固化树脂是以4‑乙烯基苯并环丁烯、苯乙烯、马来酸酐、二乙烯基苯为单体经聚合得到共聚物，再加入丙烯酸羟基酯，经开环反应制得。该含苯并环丁烯结构的可光热双重固化树脂可以进行光热双重固化，且固化时间较短，并具有较好的热稳定性、耐化学性、力学和电学性能。
The invention discloses a photothermal dual curable resin containing a benzocyclobutene structure, and a preparation method and application thereof. The photothermal dual curable resin containing a benzocyclobutene structure is prepared by polymerizing 4-vinylbenzocyclobutene, styrene, maleic anhydride, and divinylbenzene as monomers to obtain a copolymer, and then adding hydroxy acrylate to obtain a copolymer through a ring-opening reaction. The photothermal dual curable resin containing a benzocyclobutene structure can be photothermally dual cured, and the curing time is short, and has good thermal stability, chemical resistance, mechanical and electrical properties.
Description
Technical Field
The invention belongs to the technical field of cured resin, and particularly relates to photo-thermal dual-cured resin containing a benzocyclobutene structure, and a preparation method and application thereof.
Background
Benzocyclobutene (BCB) resin, which is a novel active resin, can be formed into either a thermoplastic resin or a thermosetting resin, and has excellent heat stability, molding processability, low dielectric constant, low thermal expansion coefficient, and the like. Based on these excellent properties, BCB resins have been widely used in the fields of military, aerospace, microelectronics industry, and the like.
Rapid vacuum pyrolysis is a relatively mature method for synthesizing BCB. The method mainly comprises the steps that organic molecules pass through a high-temperature region (550-800 ℃) within a short time (about 10 -2 s) to remove certain small molecules in the molecules to perform a ring closing reaction, the reaction is greatly influenced by vacuum degree and pyrolysis temperature, and route conditions are severe, so that the cost of benzocyclobutene is high, and the development and application of the benzocyclobutene are greatly limited.
With the development of very large scale integrated circuits, multi-chip modules and the like, the requirements for medium materials are also increasing, and the materials have not only excellent dielectric properties, but also excellent thermal stability, water resistance and the like. The single BCB resin material has failed to meet the requirements of these applications in terms of performance, and other groups need to be introduced to improve the performance of BCB resins. At present, the main stream method is to introduce structures such as silane, siloxane, silsesquioxane and polyimide, but all the problems of complicated synthetic method and high price caused by the need of modifying benzocyclobutene through multi-step reaction are faced.
The benzocyclobutene functionalized cage-type polysilsesquioxane and the resin thereof are synthesized by Chinese patent CN 107325287A, the prepared resin has excellent thermal stability, mechanical property and electrochemical property, is suitable for being used as an interlayer dielectric film or packaging material in the fields of microelectronics industry, national defense aviation and aerospace and the like, but has long synthetic route, consumes a large amount of toluene in the separation and purification process to cause pollution, and uses noble metal catalyst platinum in the preparation process, so that the cost is high.
Chinese patent CN 105778096a uses silane or siloxane substituted benzocyclobutene monomer and siloxane monomer to make hydrolytic copolymerization to prepare an organic silicon resin using siloxane as main chain and benzocyclobutene as side chain. The benzocyclobutene-containing organic silicon resin has good thermal stability, low dielectric constant and mechanical property after thermal curing, and higher refractive index, can be used as high-performance resin or packaging material in the fields of electric industry, large-scale integrated circuit, microelectronics industry, aerospace and the like, but is synthesized through multi-step reaction, and has complex post-treatment and higher energy consumption due to complex thermal curing process.
Chinese patent CN 109180492B synthesizes a rosin benzocyclobutene monomer capable of free radical polymerization, has excellent thermal stability, water resistance and dielectric property, strengthens the reprocessing and utilization of rosin, reduces the use of petrochemical resources, but has lower glass transition temperature and general mechanical strength.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide the photo-thermal dual-curing resin containing the benzocyclobutene structure, and the preparation method and the application thereof.
In order to achieve the technical purpose and the technical effect, the invention is realized by the following technical scheme:
A photo-thermal dual-curing resin containing a benzocyclobutene structure is prepared by polymerizing 4-vinylbenzocyclobutene, styrene, maleic anhydride and divinylbenzene as monomers to obtain a copolymer, adding hydroxyl acrylate and carrying out ring opening reaction, wherein the structural formula of the photo-thermal dual-curing resin is shown as the following formula (I):
Wherein a, b, c, d is an integer of 1 to 100, a+b+c+d is an integer of 4 to 300, e is an integer of 1 to 7, and R 2 is a methyl group or a hydrogen atom.
The invention further provides a preparation method of the photo-thermal dual-curing resin containing the benzocyclobutene structure, which comprises the following steps:
(1) 4-vinylbenzocyclobutene, styrene, maleic anhydride and divinylbenzene are taken as monomers for polymerization reaction, and the molar ratio of the four monomers is 1-10:1-10;
(2) Adding hydroxyl acrylate into the system after the reaction in the step (1), and carrying out ring opening reaction under the action of a catalyst to obtain the photo-thermal dual-curing resin containing the benzocyclobutene structure, wherein the molar ratio of the hydroxyl acrylate to the maleic anhydride is 0.5-1:1.
The reaction in the step (1) is carried out in a solvent, wherein the solvent is at least one selected from water, an alcohol solvent, an ester solvent, a ketone solvent, an aromatic hydrocarbon solvent, N-methylpyrrolidone and N, N-dimethylformamide, and the dosage of the solvent is 1-10 times of the total mass of the four monomers.
Further, in the step (1), a chain transfer agent and an initiator are added, wherein the chain transfer agent is at least one of tert-butyl alcohol, tert-dodecyl mercaptan, mercaptoethanol, mercaptoacetic acid, isooctyl 3-mercaptopropionate, 2, 4-diphenyl-4-methyl-1-pentene and tert-butyl methacrylate, the amount of the chain transfer agent is 0.1% -5% of the total mass of the four monomers, the initiator is at least one of azodiisobutyronitrile, dibenzoyl peroxide, diethyl hexyl peroxide, potassium persulfate, ammonium persulfate, potassium persulfate-sodium hypophosphite, potassium persulfate-sodium hydrogen sulfite, boron trifluoride diethyl ether and trifluoromethanesulfonic acid, and the amount of the initiator is 0.1% -5% of the total mass of the four monomers.
Further, the catalyst in the step (2) is at least one selected from triethylamine, 4-dimethylaminopyridine, ethanolamine, ethylenediamine and potassium carbonate, and the dosage of the catalyst is 0.1% -5% of the total mass of the four monomers.
Further, the reaction time of the step (1) is 1-3 hours, the reaction temperature is 20-80 ℃, the reaction time of the step (2) is 3-5 hours, and the reaction temperature is 80-150 ℃.
The invention also provides application of the photo-thermal dual-curing resin containing the benzocyclobutene structure in an interlayer dielectric film or packaging material, and specifically comprises the steps of uniformly mixing the photo-thermal dual-curing resin containing the benzocyclobutene structure with an initiator, and curing to obtain the interlayer dielectric film or packaging material.
The beneficial effects of the invention are as follows:
The resin containing the benzocyclobutene structure is obtained through two-step reaction, wherein the first-step reaction is to polymerize four monomers of 4-vinylbenzocyclobutene, styrene, maleic anhydride and divinylbenzene through cations or free radicals to obtain a copolymer, wherein a proper chain transfer agent is added to effectively adjust and control the molecular weight, and the second-step reaction is to carry out ring opening reaction on hydroxyl acrylate and anhydride bonds on a main chain, and introduce photo-curable acryloyloxy groups on side chains of the copolymer.
The benzocyclobutene structure on the side chain of the copolymer can be thermally cured, the introduced acryloyloxy group can be photo-cured, and the double bond of divinylbenzene on the side chain can be subjected to crosslinking curing reaction under the condition of light or heat. In addition, the resin formed by copolymerization of styrene and maleic anhydride has better thermal stability, mechanical property and electrical property. The introduction of divinylbenzene and 4-vinylbenzocyclobutene monomers can further enhance the thermal stability of the resin and further reduce its dielectric constant.
The resin containing the benzocyclobutene structure can be subjected to photo-thermal dual curing, and the dual curing system has the obvious advantages that the thermal curing can help to cure non-planar parts, the photo-curing can improve the crosslinking density, the fullness and the glossiness of materials and provide excellent chemical resistance, and the resin containing the benzocyclobutene structure has shorter curing time, can greatly improve the production efficiency, can reduce the surface pollution in the production process of the surfaces of parts after application, and can improve the yield.
Drawings
Fig. 1 to 5 are infrared spectra of the benzocyclobutene structure-containing photo-thermal dual-curable resins obtained in examples 1 to 5, respectively.
Detailed Description
The following description of the embodiments of the present invention will be made more apparent and fully by reference to the accompanying drawings, in which it is shown, by way of illustration, only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a photo-thermal dual-curing resin containing a benzocyclobutene structure, which is prepared by polymerizing 4-vinylbenzocyclobutene, styrene, maleic anhydride and divinylbenzene serving as monomers to obtain a copolymer, adding hydroxyl acrylate and carrying out ring opening reaction, wherein the structural formula of the photo-thermal dual-curing resin is shown as the following formula (I):
Wherein a, b, c, d is an integer of 1 to 100, a+b+c+d is an integer of 4 to 300, e is an integer of 1 to 7, and R 2 is a methyl group or a hydrogen atom.
The preparation method of the photo-thermal dual-curing resin containing the benzocyclobutene structure comprises the following steps:
(1) Adding a priming solvent into a four-neck flask, installing a mechanical stirrer and a condenser tube, introducing nitrogen to deoxidize for 20 minutes, then stirring and heating to a proper temperature, slowly dripping four monomer solutions of maleic anhydride, styrene, 4-vinylbenzocyclobutene and divinylbenzene, a chain transfer agent and an initiator by using a constant pressure dropping funnel, and after dripping, preserving heat for reacting for a period of time, and monitoring the reaction progress by infrared spectrum;
The dropwise adding time in the step (1) is 1-5 hours, the thermal insulation reaction time is 1-3 hours, and the reaction temperature is 20-80 ℃;
(2) And (3) adding metered (methyl) hydroxyl acrylate and a catalyst into the system after the reaction in the step (1), regulating to a proper temperature, continuing the reaction, monitoring the reaction progress through infrared spectrum, and removing the reaction solvent in vacuum after the reaction is finished, thereby obtaining the colorless to pale yellow photo-thermal dual-curing resin containing the benzocyclobutene structure.
The synthetic route of the photo-thermal dual-curing resin containing the benzocyclobutene structure is as follows:
Wherein a, b, c, d is an integer of 1 to 100, a+b+c+d is an integer of 4 to 300, e is an integer of 1 to 7, R 2 is a methyl group or a hydrogen atom;
The reaction time of the step (2) is 3-5 hours, and the reaction temperature is 80-150 ℃.
The solvent in the step (1) is at least one selected from water, alcohol solvents, ester solvents, ketone solvents, aromatic hydrocarbon solvents, N-methyl pyrrolidone and N, N-dimethylformamide, and the dosage of the solvent is 1-10 times of the total mass of the four monomers.
Wherein the chain transfer agent in the step (1) is at least one selected from tertiary butanol, tertiary dodecyl mercaptan, mercaptoethanol, thioglycollic acid, isooctyl 3-mercaptopropionate, 2, 4-diphenyl-4-methyl-1-pentene and tert-butyl methacrylate, the amount of the chain transfer agent is 0.1-5% of the total mass of the four monomers, the initiator is at least one selected from azodiisobutyronitrile, dibenzoyl peroxide, diethyl hexyl peroxide, potassium persulfate, ammonium persulfate, potassium persulfate-sodium hypophosphite, potassium persulfate-sodium hydrogen sulfite, boron trifluoride diethyl ether and trifluoromethanesulfonic acid, and the amount of the initiator is 0.1-5% of the total mass of the four monomers.
Wherein the catalyst in the step (2) is at least one of triethylamine, 4-dimethylaminopyridine, ethanolamine, ethylenediamine and potassium carbonate, and the dosage of the catalyst is 0.1% -5% of the total mass of the four monomers.
The invention also provides application of the photo-thermal dual-curing resin containing the benzocyclobutene structure in an interlayer dielectric film or packaging material, and specifically comprises the steps of uniformly mixing the photo-thermal dual-curing resin containing the benzocyclobutene structure with an initiator, and curing to obtain the interlayer dielectric film or packaging material.
Example 1
200ML of dry butanone was added to a 1000mL three-necked round bottom flask, a mechanical stirrer and reflux condenser were fitted, and nitrogen was purged for 20 minutes, then the stirrer was turned on and heated to 60 ℃. 10.4 g of styrene, 9.8 g of maleic anhydride, 13.0 g of 4-vinylbenzocyclobutene, 13.0 g of divinylbenzene, 2g of azo-diisobutyronitrile as an initiator and 1g of mercaptoethanol as a chain transfer agent are dissolved in 200mL of anhydrous butanone, transferred into a constant pressure dropping funnel, slowly dropped into a three-necked flask for reaction (about 2 hours after the completion of the dropping), and the reaction is carried out for 2 hours after the completion of the dropping.
After the polymerization was completed, 11.6 g of hydroxyethyl acrylate and 0.5 g of triethylamine as a catalyst were added to a three-necked flask, and the temperature was raised to 100℃for reaction for 5 hours. And after the reaction is finished, removing the solvent in vacuum, and discharging the material when the material is hot, thus obtaining the photo-thermal dual-curing resin containing the benzocyclobutene structure.
The number average molecular weight Mn of the benzocyclobutene-structure-containing photo-thermal dual-curable resin obtained in example 1 was 2710 daltons, the infrared spectrum thereof was shown in fig. 1, and the spectrum analysis thereof was shown in table 1.
TABLE 1
Example 2
200ML of xylene was added to a 1000mL three-necked round bottom flask, equipped with a mechanical stirrer and reflux condenser, deoxygenated with nitrogen for 20 minutes, and then the stirrer was turned on and heated to 30 ℃. 10.4 g of styrene, 9.8 g of maleic anhydride, 13.0 g of 4-vinylbenzocyclobutene, 13.0 g of divinylbenzene, 2 g of benzoyl peroxide as an initiator and 1 g of t-butyl methacrylate as a chain transfer agent are dissolved in 200mL of xylene, and then transferred to a constant pressure dropping funnel, slowly dropped into a three-necked flask for reaction (about 1 hour after the dropping), and the reaction is carried out for 2 hours after the dropping.
After the polymerization was completed, 13.1 g of hydroxyethyl methacrylate and 1 g of triethylamine as a catalyst were added to a three-necked flask, and the temperature was raised to 130℃for reaction for 5 hours. And after the reaction is finished, removing the solvent in vacuum, and discharging the material when the material is hot, thus obtaining the photo-thermal dual-curing resin containing the benzocyclobutene structure.
The number average molecular weight Mn of the benzocyclobutene structure-containing photo-thermal dual-curable resin obtained in example 2 was 2617 daltons, and the infrared spectrum thereof is shown in FIG. 2.
Example 3
200ML of anhydrous toluene was added to a 1000mL three-necked round bottom flask, a mechanical stirrer and a reflux condenser were mounted, and nitrogen was purged for 20 minutes, then the stirrer was turned on and heated to 20 ℃. 10.4 g of styrene, 9.8 g of maleic anhydride, 13.0 g of 4-vinylbenzocyclobutene, 13.0 g of divinylbenzene, 0.5g of trifluoromethanesulfonic acid as an initiator and 1g of t-butyl methacrylate as a chain transfer agent are dissolved in 200mL of anhydrous toluene, and then transferred into a constant pressure dropping funnel, slowly dropped into a three-necked flask for reaction (about 1 hour after the completion of the dropping), and the reaction is carried out for 2 hours after the completion of the dropping.
After the polymerization reaction was completed, 13 g of hydroxypropyl acrylate and 1 g of 4-dimethylaminopyridine as a catalyst were added to a three-necked flask, and the temperature was raised to 120℃for reaction for 5 hours. And after the reaction is finished, removing the solvent in vacuum, and discharging the material when the material is hot, thus obtaining the photo-thermal dual-curing resin containing the benzocyclobutene structure.
The number average molecular weight Mn of the photo-thermal dual curable resin containing benzocyclobutene structure obtained in example 3 was 4936 daltons, and the infrared spectrum thereof is shown in FIG. 3.
Example 4
200ML of propyl acetate was added to a 1000mL three-necked round bottom flask, equipped with a mechanical stirrer and reflux condenser, and purged with nitrogen for 20 minutes, then the stirrer was turned on and heated to 80 ℃. 10.4 g of styrene, 9.8 g of maleic anhydride, 6.5 g of 4-vinylbenzocyclobutene, 13.0 g of divinylbenzene, 2 g of diethyl hexyl peroxydicarbonate serving as an initiator and 1g of tert-dodecyl mercaptan serving as a chain transfer agent are dissolved in 200mL of propyl acetate and transferred to a constant pressure dropping funnel, and the mixture is slowly added dropwise into a three-necked flask for reaction (about 2 hours after the dropwise addition), and the mixture is kept at a temperature for 2 hours after the dropwise addition.
After the polymerization was completed, 14.4 g of hydroxypropyl methacrylate and 2 g of triethylamine as a catalyst were added to a three-necked flask, and the temperature was raised to 100℃for 5 hours. And after the reaction is finished, removing the solvent in vacuum, and discharging the material when the material is hot, thus obtaining the photo-thermal dual-curing resin containing the benzocyclobutene structure.
The number average molecular weight Mn of the photo-thermal dual curable resin containing benzocyclobutene structure obtained in example 4 was 5104 daltons, and the infrared spectrum thereof is shown in FIG. 4.
Example 5
200ML of dry butanone was added to a 1000mL three-necked round bottom flask, equipped with a mechanical stirrer and reflux condenser, deoxygenated with nitrogen for 20 minutes, and then the stirrer was turned on and heated to 80 ℃. 10.4 g of styrene, 4.9 g of maleic anhydride, 13.0 g of 4-vinylbenzocyclobutene, 13.0 g of divinylbenzene, 1 g of boron trifluoride diethyl ether as an initiator and 1 g of tert-butyl methacrylate as a chain transfer agent are dissolved in 200mL of anhydrous butanone, transferred to a constant pressure dropping funnel, slowly added dropwise into a three-necked flask for reaction (about 2 hours after the completion of the dropwise addition), and the mixture is kept for reaction for 2 hours after the completion of the dropwise addition.
After the polymerization was completed, 7.2 g of hydroxypropyl methacrylate and 2 g of triethylamine as a catalyst were added to a three-necked flask, and the temperature was raised to 100℃for 5 hours. And after the reaction is finished, removing the solvent in vacuum, and discharging the material when the material is hot, thus obtaining the photo-thermal dual-curing resin containing the benzocyclobutene structure.
The number average molecular weight Mn of the photo-thermal dual curable resin containing benzocyclobutene structure obtained in example 5 was 1630 daltons, and the infrared spectrum thereof is shown in FIG. 5.
Example 6
200ML of anhydrous toluene was added to a 1000mL three-necked round bottom flask, a mechanical stirrer and a reflux condenser were mounted, and nitrogen was purged for 20 minutes, then the stirrer was turned on and heated to 80 ℃. 22 g of styrene, 4.9 g of maleic anhydride, 13.0 g of 4-vinylbenzocyclobutene, 13.0 g of divinylbenzene, 1.5 g of diethyl hexyl peroxydicarbonate serving as an initiator and 1g of tert-dodecyl mercaptan serving as a chain transfer agent are dissolved in 200mL of anhydrous butanone, and then transferred into a constant pressure dropping funnel, slowly dropped into a three-necked flask for reaction (about 2 hours after the completion of the dropping), and the reaction is carried out for 2 hours after the completion of the dropping.
After the polymerization was completed, 7.2 g of hydroxypropyl methacrylate and 2 g of triethylamine as a catalyst were added to a three-necked flask, and the temperature was raised to 100℃for 5 hours. And after the reaction is finished, removing the solvent in vacuum, and discharging the material when the material is hot, thus obtaining the photo-thermal dual-curing resin containing the benzocyclobutene structure.
The number average molecular weight Mn of the benzocyclobutene structure-containing photo-thermal dual-curable resin obtained in example 6 was 5880 daltons.
Application performance test:
Curing to form a film
1. And (3) in the photo-curing process, 95 parts of the resin obtained in the examples 1-6, 2.5 parts of ITX initiator (Basoff) and 2.5 parts of 907 initiator (Basoff) are mixed and stirred uniformly, poured into a polytetrafluoroethylene mould, subjected to vacuum bubble removal in a vacuum drying oven at 70 ℃, and then irradiated under an ultraviolet lamp with the power of 2KW until the film is completely cured.
2. And (3) the heat curing process, namely putting the photo-cured film (with the polytetrafluoroethylene die) into an oven for curing in 5 stages, wherein the temperature is slowly increased to 180 ℃ for 5 hours in the first stage, 200 ℃ for 5 hours in the second stage, 220 ℃ for 3 hours in the third stage, 240 ℃ for 3 hours in the fourth stage, and 160 ℃ for 5 hours in the fifth stage, and obtaining the photo-thermal dual-cured film.
Evaluation method
1. Refractive index of cured film
The refractive index of the cured film was measured using a 2WAJ monocular Abbe refractometer according to the method prescribed by the national standard "determination of refractive index of plastics GB/T39691-2020".
2. Hardness of cured film
The pencil hardness of the cured films was tested according to the method specified in the national Standard GB/T6739-2006 paint and varnish pencil method for determining film hardness.
3. Dielectric constant Dk and dielectric loss Df of cured film
The dielectric properties (specifically, the test dielectric constant Dk and the dielectric loss Df) of the cured films of the above examples were tested according to the split dielectric resonator (splite post dielectric resonator, abbreviated SPDR) method, in which the test frequency was 5GHz.
4. Thermogravimetric analysis of cured films
The glass transition temperature Tg of the cured films was measured using a Metler DSC 3-differential scanning calorimeter according to the method prescribed in Dynamic Mechanical Analysis (DMA) for glass transition temperature test method of Polymer-based composite of national Standard GB/T40396-2021.
Table 1 below shows the test results of the cured films of the respective examples.
TABLE 1
As is clear from Table 1 above, the cured films obtained using the resins of the examples of the present invention were excellent in dielectric properties, low in both dielectric constant Dk and dielectric loss Df, high in Tg, high in heat resistance, and excellent in refractive index and hardness.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all modifications or equivalent arrangements using the teachings of this invention, or direct or indirect application in other related arts, are included within the scope of this invention.
Claims (10)
1. A photo-thermal dual-curing resin containing a benzocyclobutene structure is characterized in that 4-vinylbenzocyclobutene, styrene, maleic anhydride and divinylbenzene are taken as monomers to be polymerized to obtain a copolymer, and hydroxy acrylate is added to the copolymer to be subjected to ring opening reaction to obtain the photo-thermal dual-curing resin, wherein the structural formula of the photo-thermal dual-curing resin is shown as the following formula (I):
Wherein a, b, c, d is an integer of 1 to 100, a+b+c+d is an integer of 4 to 300, e is an integer of 1 to 7, and R 2 is a methyl group or a hydrogen atom.
2. A method for preparing the photo-thermal dual curable resin containing benzocyclobutene structure of claim 1, comprising the steps of:
(1) 4-vinylbenzocyclobutene, styrene, maleic anhydride and divinylbenzene are taken as monomers for polymerization reaction;
(2) Adding hydroxyl acrylate into the system after the reaction in the step (1), and carrying out ring opening reaction under the action of a catalyst to obtain the photo-thermal dual-curing resin containing the benzocyclobutene structure.
3. The method for producing a photo-thermal dual curable resin containing benzocyclobutene structure of claim 2, wherein the reaction of step (1) is carried out in a solvent.
4. The method for preparing a photo-thermal dual-curable resin containing a benzocyclobutene structure according to claim 3, wherein the solvent is at least one selected from the group consisting of water, alcohol solvents, ester solvents, ketone solvents, aromatic hydrocarbon solvents, N-methylpyrrolidone and N, N-dimethylformamide, and the amount of the solvent is 1-10 times of the total mass of the four monomers.
5. The method for producing a photo-thermal dual curable resin having a benzocyclobutene structure according to claim 2, wherein a chain transfer agent and an initiator are added in the step (1).
6. The preparation method of the photo-thermal dual-curing resin containing the benzocyclobutene structure, which is characterized in that the chain transfer agent is at least one of tertiary butyl alcohol, tertiary dodecyl mercaptan, mercaptoethanol, mercaptoacetic acid, isooctyl 3-mercaptopropionate, 2, 4-diphenyl-4-methyl-1-pentene and tertiary butyl methacrylate, the amount of the chain transfer agent is 0.1% -5% of the total mass of four monomers, the initiator is at least one of azobisisobutyronitrile, dibenzoyl peroxide, diethyl hexyl peroxydicarbonate, potassium persulfate, ammonium persulfate, potassium persulfate-sodium hypophosphite, potassium persulfate-sodium hydrogen sulfite, boron trifluoride diethyl ether and trifluoromethanesulfonic acid, and the amount of the initiator is 0.1% -5% of the total mass of four monomers.
7. The preparation method of the photo-thermal dual-curing resin containing the benzocyclobutene structure, which is disclosed in claim 2, is characterized in that the catalyst in the step (2) is at least one selected from triethylamine, 4-dimethylaminopyridine, ethanolamine, ethylenediamine and potassium carbonate, and the dosage of the catalyst is 0.1% -5% of the total mass of the four monomers.
8. The method for preparing the photo-thermal dual-curable resin containing the benzocyclobutene structure according to claim 2, wherein the reaction time of the step (1) is 1-3 hours, the reaction temperature is 20-80 ℃, the reaction time of the step (2) is 3-5 hours, and the reaction temperature is 80-150 ℃.
9. Use of the benzocyclobutene-containing photo-thermal dual cure resin of claim 1 in interlayer dielectric films or encapsulation materials.
10. The use of the benzocyclobutene structure-containing photo-thermal dual-curing resin of claim 9, wherein the benzocyclobutene structure-containing photo-thermal dual-curing resin of claim 1 and an initiator are uniformly mixed and cured to obtain an interlayer dielectric film or an encapsulation material.
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