CN117327004A - Benzocyclobutene-terminated diester bisimide monomer and preparation and curing methods thereof - Google Patents
Benzocyclobutene-terminated diester bisimide monomer and preparation and curing methods thereof Download PDFInfo
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- CN117327004A CN117327004A CN202311271049.6A CN202311271049A CN117327004A CN 117327004 A CN117327004 A CN 117327004A CN 202311271049 A CN202311271049 A CN 202311271049A CN 117327004 A CN117327004 A CN 117327004A
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- benzocyclobutene
- bisimide
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- 239000000178 monomer Substances 0.000 title claims abstract description 34
- 150000005690 diesters Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000001723 curing Methods 0.000 title abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 20
- 229920001721 polyimide Polymers 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000004642 Polyimide Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000007711 solidification Methods 0.000 claims abstract description 4
- 230000008023 solidification Effects 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 24
- -1 benzocyclobutene imide Chemical class 0.000 claims description 19
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 150000003949 imides Chemical class 0.000 claims description 11
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002250 absorbent Substances 0.000 claims description 9
- 230000002745 absorbent Effects 0.000 claims description 9
- 150000002989 phenols Chemical class 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- ZSDKRCVZMXLSPK-UHFFFAOYSA-N bicyclo[4.2.0]octa-1(6),2,4-trien-5-amine Chemical compound NC1=CC=CC2=C1CC2 ZSDKRCVZMXLSPK-UHFFFAOYSA-N 0.000 claims description 7
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 150000001263 acyl chlorides Chemical class 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 7
- 238000010345 tape casting Methods 0.000 abstract description 3
- 238000009835 boiling Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 9
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical group C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 229920003230 addition polyimide Polymers 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000010136 thermoset moulding Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Indole Compounds (AREA)
Abstract
The invention relates to a preparation and curing method of benzocyclobutene-terminated diester bisimide monomer, which has the chemical structural general formula as follows:wherein R is: the monomer can be dissolved in dichloromethane with a low boiling point solvent, has excellent processing performance, can be directly heated, melted, solidified and molded or prepared into a polyimide film by a tape casting method, and the polyimide material obtained after solidification has excellent thermal stability, high transparency and excellent dielectric performance.
Description
Technical Field
The invention relates to a preparation and curing method of benzocyclobutene-terminated diester bisimide monomer, belonging to the field of high polymer materials.
Background
Polyimide is a polymer with main chain containing imide ring, and the rigid imide structure endows polyimide with unique performance, so that the polyimide has excellent heat resistance, excellent mechanical, electric, irradiation and solvent resistance and other performances. The polyimide is prepared by two modes of condensation type and addition type. The condensation type polyimide is prepared by a one-step chlorobenzene/m-cresol solvent method, or a two-step method: the polyamic acid is first formed in N, N-dimethylacetamide/N-methylpyrrolidone/N, N-dimethylformamide solvent and then imidized by heating (about 300 ℃) or chemically imidized by acetic anhydride/acetyl chloride/thionyl chloride reagent. The method can lead the film to have larger shrinkage rate due to the escape of moisture in the thermal imidization or chemical imidization process. The preparation of the addition type polyimide is environment-friendly, does not generate small molecules, and is simple and convenient to thermoset molding.
The benzocyclobutene group has excellent processability, can be thermally opened at more than 200 ℃ and can be subjected to [4+4] addition with the benzocyclobutene group to form an eight-membered ring, so that a dimer or a high polymer is formed. No catalyst is needed in the reaction process, no small molecules are produced, and the product is pure and has small shrinkage. Thus, benzocyclobutene groups can be used to prepare addition polyimide materials, and thus it would be highly advantageous to invent a benzocyclobutene-terminated diester bisimide monomer, a method of preparing and curing the monomer.
Disclosure of Invention
The invention aims to provide a benzocyclobutene-terminated diester bisimide monomer, a preparation method and a curing method thereof, wherein the monomer is soluble in a low-boiling-point solvent methylene dichloride, has excellent processability, can be directly heated, melted, cured and molded or prepared into a polyimide film by a tape casting method, and has the advantages that only heating is needed in the curing process, and no small molecules are released. The polyimide material obtained after curing has excellent thermal stability, high transparency and excellent dielectric property.
A benzocyclobutene-terminated diester bisimide monomer has a chemical structural formula as follows:
wherein R is:
preferably R is:
the preparation method of the invention comprises the following steps: (1) Adding 4-aminobenzocyclobutene and trimellitic anhydride into an organic solvent to react to prepare the benzocyclobutene imide containing carboxyl, wherein the structural formula is as follows:
(2) Adding the benzocyclobutene imide containing carboxyl, thionyl chloride and acid absorbent prepared in the step (1) into an organic solvent to react to prepare the benzocyclobutene imide containing acid chloride, wherein the structural formula of the benzocyclobutene imide is as follows:
(3) Adding the benzocyclobutene imide containing the acyl chloride prepared in the step (2), a phenolic compound and an acid absorbent into an organic solvent, reacting, and separating reaction products to obtain a benzocyclobutene-terminated diester bisimide monomer, wherein the structural general formula is as follows:
wherein R is:
the preparation method of the invention comprises the following steps: the organic solvent is glacial acetic acid, toluene or tetrahydrofuran. The acid absorbent is pyridine or triethylamine. Wherein the molar ratio of the reaction in the step (1) is as follows: 4-aminobenzocyclobutene: trimellitic anhydride: solvent = 1:1:40-50, reaction at 120 ℃ for 20-28h. The molar ratio of the reaction in the step (2) is as follows: the imide prepared in (1): thionyl chloride: acid absorbent: solvent = 1:3:1:40-50, reaction at 60 ℃ for 4-6h. The molar ratio of the reaction in the step (3) is as follows: (2) acid chloride prepared: phenolic compounds: acid absorbent: solvent = 2:1:2:50-100, at 60 ℃ for 20-28h, wherein the phenolic compound used preferably has the structure:
and (3) after the reaction in the step (3), adding anhydrous methanol with the volume of 3-4 times into the reactant, precipitating white solid, and carrying out suction filtration to obtain the product.
The invention also provides a method for curing benzocyclobutene-terminated diester bisimide monomer, which is characterized by comprising the following steps of: it is formed by directly heating, melting, solidifying and forming or dissolving in solvent, then rotating and coating film on the substrate to solidify, and then making cross-linking solidification at 250-280 deg.C so as to obtain the polyimide material.
The monomer prepared by the invention can be dissolved in a low boiling point solvent methylene dichloride, has excellent processing performance, and can be directly heated, melted, solidified and molded or prepared into a polyimide film by a tape casting method. The preparation method is simple, easy to control, high in reaction conversion rate and simple in purification after reaction; the prepared imide can directly form a polyimide material through thermal ring-opening addition polymerization, is environment-friendly, and does not generate small molecules. The polyimide material prepared by the invention has the characteristics of excellent thermal stability, high transparency, excellent dielectric property and the like, and can be used as a thermosetting polymer material to be applied to the fields of 5G communication, microelectronics, packaging materials and the like.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of benzocyclobutene-terminated bisester bisimide monomers prepared by the process of the invention.
FIG. 2 is a DSC chart of benzocyclobutene-terminated diester bisimide monomers prepared by the process of the invention.
FIG. 3 is a TGA spectrum of benzocyclobutene terminated diester bisimide monomers prepared by the process of the present invention.
Detailed Description
A process for preparing benzocyclobutene-terminated diester bisimide monomers comprising the steps of:
(1) Adding 4-aminobenzocyclobutene and trimellitic anhydride into an anhydrous reagent according to the following molar ratio: 4-aminobenzocyclobutene: trimellitic anhydride: reagent=1:1:40-50, reacting for 20-28h at 120 ℃, and the structural formula of the prepared benzocyclobutene imide containing carboxyl is:
(2) Adding the imide, thionyl chloride and pyridine prepared in the step (1) into an anhydrous reagent, wherein the molar ratio of the added imide, thionyl chloride and pyridine is as follows: the imide prepared in (1): thionyl chloride: pyridine: reagent=1:3:1:40-50, reacting for 4-6 hours at 60 ℃, and the prepared benzocyclobutene containing acyl chloride has the structural formula:
(3) Adding the acyl chloride prepared in the step (2) into an anhydrous reagent, wherein the molar ratio of various phenolic compounds to pyridine is as follows: (2) acid chloride prepared: phenolic compounds: pyridine: reagent=2:1:2:50-100, at 60 ℃ for 20-28h, wherein the phenolic compound used has the following structure:
(4) And (3) adding 3-4 times of anhydrous methanol into the reactant in the step (3) to separate out white solid, and carrying out suction filtration to obtain the product. It has the following chemical formula:
wherein R is:
specific examples of benzocyclobutene-terminated diester bisimide monomers of the invention are listed below:
the structures of the four embodiments are listed below, respectively:
(Compound BBIA-BPA bis (2, 3-dihydro-1, 3-dioxo-2- (bicyclo [4.2.0] oct-1, 3, 5-trien-3-yl) -1H-isoindole-5-carboxylic acid) bisphenol A ester
(Compound BBIA-BPS bis (2, 3-dihydro-1, 3-dioxo-2- (bicyclo [4.2.0] oct-1, 3, 5-trien-3-yl) -1H-isoindole-5-carboxylic acid) bisphenol S ester
(Compound BBIA-BPAF bis (2, 3-dihydro-1, 3-dioxo-2- (bicyclo [4.2.0] oct-1, 3, 5-trien-3-yl) -1H-isoindole-5-carboxylic acid) bisphenol AF ester
(Synthesis of the Compound BBIA-DBA bis (2, 3-dihydro-1, 3-dioxo-2- (bicyclo [4.2.0] oct-1, 3, 5-trien-3-yl) -1H-isoindole-5-carboxylic acid) 2,2' -diallylbisphenol A ester) [ example 1 ] Synthesis of benzocyclobutene-terminated diester bisimide monomers of the invention 1
Compound BBIA-BPA bis (2, 3-dihydro-1, 3-dioxo-2- (bicyclo [4.2.0] oct-1, 3, 5-trien-3-yl) -1H-isoindole-5-carboxylic acid) bisphenol A ester
1.904g (16.0 mmol) of 4-aminobenzocyclobutene and 3.070g (16.0 mmol) of trimellitic anhydride are placed in a 200mL round-bottomed flask. 40mL of glacial acetic acid was added under nitrogen. Stirring and refluxing for 24 hours at 120 ℃, cooling to room temperature, adding 120mL of deionized water, precipitating yellow solid, decompressing and filtering, and washing with deionized water for three times to obtain the benzocyclobutene imide containing carboxyl. As shown in fig. 1, the nuclear magnetic hydrogen spectrogram of the present invention is analyzed as follows:
1 H NMR(400MHz,DMSO):13.75(s,1H),8.41(d,J＝7.7Hz,1H),8.30(s,1H),8.07(d,J＝7.7Hz,1H),7.23(s,2H),7.15(s,1H),3.20(s,4H)。
1.173g (4.00 mmol) of the above product, 20mL of toluene and two drops of N, N-dimethylformamide were taken in a 200mL round bottom flask. 1.0mL (1.64 g,13.8 mmol) of thionyl chloride was added to the ice-water bath under nitrogen. After 10min, pyridine 0.5mL (0.49 g,6.2 mmol) was added and the mixture was refluxed for 4h at 60 ℃. Cooling to room temperature, and removing the solvent by rotary evaporation to obtain the benzocyclobutene imide containing the acyl chloride.
To the above round bottom flask with acid chloride was added 0.457g (2.00 mmol) bisphenol A. Under nitrogen, 20mL of anhydrous tetrahydrofuran, 0.5mL (0.49 g,6.2 mmol) of pyridine were added sequentially, and the mixture was refluxed with stirring at 65℃for 24 hours. Cooling to room temperature, adding 60mL of anhydrous methanol, stirring for 0.5h, precipitating a large amount of white solid, carrying out vacuum filtration, washing 3 times with the anhydrous methanol to obtain 1.146g of compound BBIA-BPA, wherein the yield is 73.5%, and the appearance is white solid. The DSC profile of example 1 in FIG. 2 shows that the present invention is solidified by melting. The TGA profile of example 1 in fig. 3 shows that the thermal stability after molding of the present invention is very good.
1 H NMR(400MHz,CDCl 3 ):8.76(s,2H),8.63(d,J＝7.7Hz,2H),8.19-8.02(m,2H),7.35(d,J＝8.2Hz,4H),7.24-7.05(m,10H),3.24(s,8H),1.75(s,6H).
The reaction flow chart is as follows:
EXAMPLE 2 Synthesis of the benzocyclobutene-terminated bisester bisimide monomer of the invention Compound BBIA-BPS
The synthesis of the carboxylic benzocyclobutene-containing imides is the same as in example 1.
The synthesis of acid chlorides is the same as in example 1.
To the above round bottom flask with acid chloride was added 0.501g (2.00 mmol) bisphenol S. Under nitrogen, 20mL of anhydrous tetrahydrofuran, 0.5mL (0.49 g,6.2 mmol) of pyridine were added sequentially, and the mixture was refluxed with stirring at 65℃for 24 hours. Cooling to room temperature, adding 60mL of anhydrous methanol, stirring for 0.5h, precipitating a large amount of white solid, carrying out vacuum filtration, and washing 3 times with the anhydrous methanol to obtain the compound BBIA-BPS1.396g, wherein the yield is 87.1%, and the appearance is white solid.
1 H NMR(400MHz,CDCl 3 ):8.74(s,2H),8.62(d,J＝7.6Hz,2H),8.19-7.94(m,6H),7.48(d,J＝8.3Hz,4H),7.21(s,4H),7.09(s,2H),3.24(s,8H).
The reaction flow chart is as follows:
EXAMPLE 3 Synthesis of benzocyclobutene-terminated diester bisimide monomers of the invention 3
Compound BBIA-BPAF
The synthesis of the carboxylic benzocyclobutene-containing imides is the same as in example 1.
The synthesis of acid chlorides is the same as in example 1.
To the above round bottom flask with acid chloride was added 0.672g (2.00 mmol) bisphenol AF. Under nitrogen, 20mL of anhydrous tetrahydrofuran, 0.5mL (0.49 g,6.2 mmol) of pyridine were added sequentially, and the mixture was refluxed with stirring at 65℃for 24 hours. Cooling to room temperature, adding 60mL of absolute methanol, stirring for 0.5h, precipitating a large amount of white solid, carrying out vacuum filtration, washing 3 times with the absolute methanol to obtain 1.513g of a compound BBIA-BPAF, wherein the yield is 85.3%, and the appearance is white solid.
1 H NMR(400MHz,CDCl 3 ):8.77(s,2H),8.64(d,J＝7.8Hz,2H),8.12(d,J＝7.6Hz,2H),7.55(d,J＝8.5Hz,4H),7.34(d,J＝8.4Hz,4H),7.21(s,4H),7.10(s,2H),3.25(s,8H). 19 F NMR(376MHz,CDCl 3 ):-63.79.
The reaction flow chart is as follows:
EXAMPLE 4 Synthesis of benzocyclobutene-terminated diester bisimide monomers of the invention 4
Compound BBIA-DBA
The synthesis of the carboxylic benzocyclobutene-containing imides is the same as in example 1.
The synthesis of acid chlorides is the same as in example 1.
To the above round bottom flask with acid chloride was added 0.684g (2.22 mmol) of DBA. Under nitrogen, 20mL of anhydrous tetrahydrofuran, 0.5mL (0.49 g,6.2 mmol) of pyridine were added sequentially, and the mixture was refluxed with stirring at 65℃for 24 hours. Cooling to room temperature, adding 60mL of absolute methanol, stirring for 0.5h, precipitating a large amount of white solid, carrying out vacuum filtration, washing 3 times with the absolute methanol to obtain 0.800g of compound BBIA-DBA, wherein the yield is 46.3%, and the appearance is white solid.
1 H NMR(400MHz,CDCl 3 ):8.74(s,2H),8.61(d,J＝7.8Hz,2H),8.10(d,J＝7.8Hz,2H),7.24-6.93(m,12H),5.88(td,J＝16.5,6.4Hz,2H),5.16-4.71(m,4H),3.35(d,J＝6.5Hz,4H),3.24(s,8H),1.73(s,6H).
The reaction flow chart is as follows:
example 5 solidification of BBIA-BPA prepared according to the invention example 1
A certain mass of powder of benzocyclobutene-terminated diester bisimide monomer BBIA-BPA is taken on a glass substrate with a clean surface, and the powder is heated to 250 ℃ to be melted into light yellow low-viscosity liquid. Spreading while hot, then placing into an oven for curing under nitrogen atmosphere, heating at 270 ℃ for 1.5 hours and 300 ℃ for 0.5 hour to obtain a yellowish transparent cured film with smooth surface. DSC curing behavior analysis: the BBIA-BPA has a melting point of 244℃and a crosslinking curing temperature of 272 ℃. Thermogravimetric analysis: the initial decomposition temperature (weight loss 5%) was 445℃and the residual carbon content at 800℃was 37%.
Curing flow chart:
Claims (10)
1. a benzocyclobutene-terminated diester bisimide monomer has a chemical structural formula as follows:
wherein R is:
2. a benzocyclobutene-terminated diester bisimide monomer according to claim 1, wherein R is:
3. a method for preparing benzocyclobutene-terminated diester bisimide monomers, comprising the steps of: (1) Adding 4-aminobenzocyclobutene and trimellitic anhydride into an organic solvent to react to prepare the benzocyclobutene imide containing carboxyl, wherein the structural formula is as follows:
(2) Adding the benzocyclobutene imide containing carboxyl, thionyl chloride and acid absorbent prepared in the step (1) into an organic solvent to react to prepare the benzocyclobutene imide containing acid chloride, wherein the structural formula of the benzocyclobutene imide is as follows:
(3) Adding the benzocyclobutene imide containing the acyl chloride prepared in the step (2), a phenolic compound and an acid absorbent into an organic solvent, reacting, and separating reaction products to obtain a benzocyclobutene-terminated diester bisimide monomer, wherein the structural general formula is as follows:
wherein R is:
4. the method for preparing benzocyclobutene-terminated diester bisimide monomers of claim 3, wherein the organic solvent is glacial acetic acid, toluene or tetrahydrofuran.
5. The method for preparing benzocyclobutene-terminated diester bisimide monomers of claim 3, wherein the acid absorber is pyridine or triethylamine.
6. A process for the preparation of benzocyclobutene-terminated diester bisimide monomers of claim 3, wherein the molar ratio of step (1) is: 4-aminobenzocyclobutene: trimellitic anhydride: solvent = 1:1:40-50, reaction at 120 ℃ for 20-28h.
7. A process for the preparation of benzocyclobutene-terminated diester bisimide monomers of claim 3, wherein the molar ratio of the step (2) reactions is: the imide prepared in (1): thionyl chloride: acid absorbent: solvent = 1:3:1:40-50, reaction at 60 ℃ for 4-6h.
8. A process for the preparation of benzocyclobutene-terminated diester bisimide monomers of claim 3, wherein the molar ratio of the step (3) reaction is: (2) acid chloride prepared: phenolic compounds: acid absorbent: solvent = 2:1:2:50-100, at 60 ℃ for 20-28h, wherein the phenolic compound used has the structure:
9. the method for producing benzocyclobutene-terminated diester bisimide monomers as claimed in claim 3, wherein after the reaction in step (3), 3-4 times by volume of anhydrous methanol is added to the reactants, white solid is precipitated, and the product is obtained by suction filtration.
10. A method for curing benzocyclobutene-terminated diester bisimide monomers, which is characterized by comprising the following steps: it is formed by directly heating, melting, solidifying and forming or dissolving in solvent, then rotating and coating film on the substrate to solidify, and then making cross-linking solidification at 250-280 deg.C so as to obtain the polyimide material.
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