CN103086851B - Containing simple thermosetting resin, the preparation method and application of fluorenes and benzocyclobutene structural unit - Google Patents
Containing simple thermosetting resin, the preparation method and application of fluorenes and benzocyclobutene structural unit Download PDFInfo
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- CN103086851B CN103086851B CN201310039644.7A CN201310039644A CN103086851B CN 103086851 B CN103086851 B CN 103086851B CN 201310039644 A CN201310039644 A CN 201310039644A CN 103086851 B CN103086851 B CN 103086851B
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- benzocyclobutene
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Abstract
The invention belongs to high-performance polymer and manufacture field, be specifically related to a kind of simple thermosetting resin, the preparation method and application that contain fluorenes and benzocyclobutene structural unit.Described monomer has following structural formula:
be by bisphenol fluorene and 4-bromine benzocyclobutene under the existence of cuprous salt, imidazole ligands and mineral alkali, in solvent, there is etherification reaction obtain monomer.Monomer has good film-forming properties, and the organic film obtained, through being heating and curing, can obtaining and have high heat resistance, low water-intake rate and low specific inductivity and the higher solid film of planeness, this film in a nitrogen atmosphere, 5% weight loss temperature (T
d5%) be 468.5 DEG C, at the carbon yields of 1000 DEG C up to 37.6%.Be applicable to be used as in the field such as aerospace and national defence high-temperature-resistant adhesive and the electric industry packaged material as electronic devices and components.
Description
Technical field
The invention belongs to high-performance polymer manufacturing technology field, be specifically related to a kind of simple thermosetting resin, the preparation method and application that contain fluorenes and benzocyclobutene structural unit.The thermosetting resin containing fluorenes and benzocyclobutene structural unit of, low water absorption heat-resisting for the preparation of height and low-k.
Background technology
The pi-conjugated quantum yield of fluorene-containing polymers Yin Qigao and the modifiability of molecular structure, as electroluminescent organic material, organic thin film solar material and biological detection material, be widely used in organic photoelectric functional material field.On the other hand, because fluorenes has larger free volume, take bisphenol fluorene as the thermotolerance of the epoxy resin Yin Qigao of structural unit and good processibility, and enjoy the favor of aerospace field and electric industry.Enter the nineties in last century, along with the development of microelectronics industry, based on the manufacture of 90 nano chips of copper interconnection technology in the urgent need to the heat-stable material of low-k, the Dow Chemical Company develops multiple dielectric materials for this reason, except famous SILK, bisphenol fluorene trifluoro vinyl ether resin is also furtherd investigate.This fluorine-containing bisphenol fluorene after thermofixation, obtain film there are excellent thermotolerance and dielectric properties (WO9015043).But, because [2+2] cycloaddition reaction that trifluoro vinyl ether is at high temperature occurred often is carried out not exclusively, cause thermotolerance and the dielectric properties instability of film.
Known, benzocyclobutene (Benzocyclobutene, BCB) resin has high temperature tolerance, chemical stability, excellent electric property, low rate of moisture absorption and good mechanical property etc., and easy homogeneous film formation, planeness is high.The synthesis of benzocyclobutane ene derivative from Finklesteln reported first in 1909, its relevant applied research development rapidly, be widely used in space flight and aviation abroad, microelectronics, military, the field such as civilian, have developed a series of high temperature material based on benzocyclobutene, high-performance dielectric film material, matrix material, high performance adhesive, the materials such as nonlinear optical material, the own benzocyclobutane olefine resin that all uses of the computer liquid crystal display screen that IBM Corporation and COMPAQ company as the U.S. produce does packaged material, the Dow Chemical Company develops siliceous benzocyclobutene, after pre-polymerization process, the oligopolymer obtained has good film-forming properties.Through being heating and curing further, obtain the solid film that specific inductivity can reach 2.5.In national defense industry, the application of benzocyclobutane olefine resin can reduce the volume of military electronic component and device greatly, is conducive to weapon miniaturization, and significantly improves stability and the reliability of electronic devices and components, has great significance to the modernization of national defense.By the impact of the factors such as raw material, China relatively lags behind to this resinoid development & application research, researches and develops high performance benzocyclobutane olefine resin, has important realistic meaning to the development of China's new and high technology.
Based on the demand of microelectronics industry, particularly towards the integrated circuit technology below 65 nanometers, specific inductivity is less than to the demand of the material of 2.8, research and development good heat resistance, specific inductivity is low and to have the high performance material of good workability extremely urgent.In view of the excellent properties of bisphenol fluorene and benzocyclobutene class material, both advantages are combined, be expected to the material obtaining excellent performance.The present invention is just based on such thinking, benzocyclobutene is introduced containing in fluorene compound, synthesize a series of thermosetting monomer containing fluorenes and benzocyclobutene structural unit, these compounds can be used as high-performance resin matrix or the packaged material of class of super heat-resistant, low water absorption and low-k, are applied to the fields such as microelectronics industry, aerospace and national defence.
Summary of the invention
The present invention aims to provide a kind of preparation method containing the thermosetting resin of fluorenes and benzocyclobutene structural unit, the benzocyclobutene resin property of preparation is excellent, is suitable for being used as high-performance resin matrix or packaged material in the fields such as microelectronics industry, aerospace and national defence.
The thermosetting resin containing fluorenes and benzocyclobutene structural unit of the present invention, monomer whose has following chemical structure of general formula:
Wherein R
1, R
2, R
3be respectively H, F, CH
3, CF
3and phenyl; R
1, R
2and R
3can identical also can be different.
Of the present inventionly to prepare in accordance with the following methods containing fluorenes and benzocyclobutene thermosetting resin: with 4-bromine benzocyclobutene and bisphenol fluorene for raw material, under the existence of cuprous salt, imidazole ligands and mineral alkali, etherification reaction occurs in a solvent and obtains.
Bisphenol fluorene of the present invention has following structure:
Wherein R
1, R
2, R
3be respectively H, F, CH
3, CF
3and phenyl; R
1, R
2and R
3can identical also can be different.
Cuprous salt of the present invention is cuprous chloride, cuprous bromide or cuprous iodide, preferably uses cuprous chloride.
Imidazole ligands of the present invention is 1-Methylimidazole, 1,2 dimethylimidazole, N-butyl imidazole or N-isopropylimdazole.
Mineral alkali of the present invention is alkali-metal oxyhydroxide, phosphoric acid salt or carbonate, preferably uses salt of wormwood to be alkali.
Solvent of the present invention is toluene, dioxane, DMF, DMF, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, hexamethylphosphoramide or tetramethylene sulfone.
The mol ratio of 4-bromine benzocyclobutene of the present invention and bisphenol fluorene is 2 ~ 5:1.
The mol ratio of 4-bromine benzocyclobutene of the present invention and cuprous salt, imidazole ligands and mineral alkali is 1 ~ 5:0.1 ~ 1:0.1 ~ 1:1 ~ 5.
Etherification reaction temperature of the present invention is 80-160 DEG C, and the reaction times is 5-30 hour.
Simple thermosetting resin containing fluorenes and benzocyclobutene structural unit of the present invention can be used for preparing thermosetting resin or film, by filling with mould or passing through wiring solution-forming spin coating or drip to be coated with film forming, the intensification of employing stage is heating and curing, obtain highly cross-linked thermosetting resin or film, or solidify with the resin alloy of other benzocyclobutene monomers or unsaturated double-bond; The described simple thermosetting resin containing fluorenes and benzocyclobutene structural unit is 1:0.05 ~ 80 with other benzocyclobutene monomers or unsaturated double-bond resin alloy mass ratio; Described stage program of being heating and curing that heats up is 150 ~ 200 DEG C of pre-treatment 0.5 ~ 4 hour, 210 ~ 260 DEG C of thermofixations 1 ~ 8 hour, 260 ~ 330 DEG C of thermal treatment 1 ~ 4 hour; Described organic solution is toluene, trimethylbenzene, phenyl ether, trichloromethane, acetone, N, N-METHYLFORMAMIDE, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), one or several the mixing in N-Methyl pyrrolidone.
The polymers exhibit of solidification gained goes out good temperature tolerance, good dielectric properties (specific inductivity k<2.7), extremely low rate of moisture absorption, high chemical stability and higher second-order transition temperature.Can be used for modification other benzocyclobutane olefine resin or unsaturated polyesters simultaneously, while good mechanical property and dielectric properties being kept, improve its resistance toheat.Thermosetting resin of the present invention can the matrix material such as doping carbon fiber, prepare high performance composite, the resin obtained after solidification has excellent thermostability and mechanical property, is applied in the fields such as microelectronics industry, aerospace and national defence and is used as high-performance resin matrix or packaged material.
Embodiment:
Below by embodiment, the present invention is specifically described; what be necessary to herein means out is that the present embodiment is only further described for the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
One, the preparation of serial bisphenol fluorene raw material
The synthesis of two (the fluoro-4-hydroxy phenyl of the 3-) fluorenes of embodiment 19,9-
Under nitrogen protection; 36.2 grams of Fluorenones are added, 90.1 grams of adjacent fluorophenols, 0.3 milliliter of β-mercaptopropionic acid and 100 milliliters of toluene in reaction unit; stir at 30 DEG C after 0.5 hour; in reaction system, slowly drip 5 milliliters of vitriol oils, be warming up to 55 DEG C of reactions 5 hours after dropwising, be cooled to room temperature; product is poured into water; have solid to separate out, in toluene, recrystallization obtains fluorine-containing bisphenol fluorene white crystal, productive rate 92%.Fusing point, 220-221 DEG C (document, USP5304688,219-221 DEG C).Mass spectrum (EI-MS) characterizes m/z:386.11 (100.0%), and 387.12 (27.3%), 388.12 (4.0%).
The synthesis of two (the 3-trifluoromethyl-4-hydroxy phenyl) fluorenes of embodiment 29,9-
Under nitrogen protection; 18.2 grams of Fluorenones are added in reaction unit; 64.8 grams of o-trifluoromethyl phenol; 0.4 milliliter of β-mercaptopropionic acid and 80 milliliters of toluene; stir at 30 DEG C after 0.5 hour; slowly 4 milliliters of vitriol oils are dripped in reaction system; 55 DEG C of reactions 6 hours are warming up to after dropwising; be cooled to room temperature, product saturated sodium bicarbonate solution neutralizes, and is washed to neutrality; organic phase is revolved and is steamed to obtain solid crude product; fluorine-containing bisphenol fluorene white crystal can be obtained, productive rate 85% by column chromatography (petrol ether/ethyl acetate, 4:1).Mass spectrum (EI-MS) characterizes m/z:486.11 (100.0%), and 487.11 (29.5%), 488.11 (4.5%)
The synthesis of two (4-hydroxy phenyl) fluorenes of embodiment 32,7-bis-(trifluoromethyl)-9,9-
Under argon shield, in reaction unit, add 8.2 gram 2,7-bis-bromo-9; two (4-hydroxy phenyl) fluorenes of 9-(is prepared according to document: R.Grisorio etc., Macromolecules2011,44; 7977 – 7986), 2 gram three (dibenzalacetone) two palladium (i.e. Pd
2(dba)
3), 4.23 grams of cuprous iodides, 32 milliliters of fluorosulfonyl methyl difluoroacetates and 100 milliliters of N; dinethylformamide; react 12 hours at 100 DEG C, be cooled to room temperature, product is poured into water; solid is had to separate out; in toluene, recrystallization obtains two (4-hydroxy phenyl) fluorenes of 2,7-bis-(trifluoromethyl) 9,9-; white crystal, productive rate 86%.Mass spectrum (EI-MS) characterizes m/z:486.11 (100.0%), and 487.11 (29.5%), 488.11 (4.5%)
The synthesis of two (2, the 6-dimethyl-4-hydroxy phenyl) fluorenes of embodiment 49,9-
Under nitrogen protection, in reaction unit, add 36.2 grams of Fluorenones, 122 gram 2; 6-xylenol; 0.3 milliliter of β-mercaptopropionic acid and 100 milliliters of toluene, stir at 30 DEG C after 0.5 hour, in reaction system, slowly drip 5 milliliters of vitriol oils; 55 DEG C of reactions 5 hours are warming up to after dropwising; be cooled to room temperature, product is poured into water, and has solid to separate out; in toluene, recrystallization obtains fluorine-containing bisphenol fluorene white crystal, productive rate 87%.Mass spectrum (EI-MS) characterizes m/z:406.19 (100.0%), and 407.20 (31.7%), 408.20 (5.3%)
Prepared by the simple thermosetting resin two, containing fluorenes and benzocyclobutene structural unit
The synthesis of two (the 4-benzocyclobutane thiazolinyl phenyl ether base) fluorenes of embodiment 59,9-
Under argon shield; 17.5 gram 9 is added in reaction unit; two (4-hydroxy phenyl) fluorenes of 9-; 36.6 grams of 4-bromine benzocyclobutenes, 1.95 grams of cuprous iodides, 6.15 grams of N-butyl imidazole; 13.86 gram salt of wormwood; 100 milliliters of toluene, are warming up to 140 DEG C of reactions 16 hours, are cooled to room temperature; product chloroform extraction; dilute hydrochloric acid washs, and saturated sodium bicarbonate neutralizes, and is washed to neutrality; organic phase revolves steaming can obtain solid crude product; white solid product can be obtained, productive rate 62% by column chromatography (petrol ether/ethyl acetate, 6:1).Proton nmr spectra
1h-NMR result (300MHz, CDCl
3, ppm) and δ 7.76 (d, J=7.3Hz, 2H), 7.37 (dd, J=14.9,7.5Hz, 4H), 7.28 (d, J=10.7Hz, 2H), 7.12 (d, J=8.7Hz, 4H), 6.98 (d, J=7.9Hz, 2H), 6.81 (t, J=10.7Hz, 6H), 6.73 (s, 2H), 3.12 (s, 8H).Mass spectrum (EI/MS) characterizes m/z:486.11 (100.0%), and 487.11 (29.5%), 488.11 (4.5%).
The synthesis of two (the 4-benzocyclobutane thiazolinyl phenyl ether base) fluorenes of embodiment 69,9-
With embodiment 4; under argon shield; 14.3 gram 9 is added in reaction unit; two (4-hydroxy phenyl) fluorenes of 9-, 22.3 grams of 4-bromine benzocyclobutenes, 0.86 gram of cuprous chloride; 4.95 grams of N-butyl imidazole; 11.25 grams of salt of wormwood, 80 milliliters of toluene, are warming up to 120 DEG C of reactions 20 hours; be cooled to room temperature; product chloroform extraction, dilute hydrochloric acid washs, and saturated sodium bicarbonate neutralizes; be washed to neutrality; organic phase revolves steaming can obtain solid crude product, can obtain white solid product, productive rate 57% by methylene dichloride/normal hexane recrystallization.
The synthesis of two (the 3-fluoro-4-benzocyclobutane thiazolinyl phenyl ether base) fluorenes of embodiment 79,9-
Under argon shield; 7.78 gram 9 is added in reaction unit; two (the fluoro-4-hydroxy phenyl of the 3-) fluorenes of 9-; 13.38 grams of 4-bromine benzocyclobutenes, 0.68 gram of cuprous chloride, 2.36 grams of N-isopropylimdazoles; 5.86 gram salt of wormwood; 50 milliliters of N-Methyl pyrrolidone, are warming up to 120 DEG C of reactions 16 hours, are cooled to room temperature; product chloroform extraction; dilute hydrochloric acid washs, and saturated sodium bicarbonate neutralizes, and is washed to neutrality; organic phase revolves steaming can obtain solid crude product; white solid product can be obtained, productive rate 53% by column chromatography (petrol ether/ethyl acetate, 6:1).Mass spectral characteristi (MALDI-TOF): 590.211
The synthesis of two (2, the 6-dimethyl-4-benzocyclobutane thiazolinyl phenyl ether base) fluorenes of embodiment 89,9-
Under argon shield; 4.06 gram 9 is added in reaction unit; two (2, the 6-dimethyl-4-hydroxy phenyl) fluorenes of 9-, 7.43 grams of 4-bromine benzocyclobutenes; 0.32 gram of cuprous chloride; 1.36 grams of N-isopropylimdazoles, 6.36 grams of cesium carbonates, 50 milliliters of toluene; be warming up to 120 DEG C of reactions 16 hours; be cooled to room temperature, product chloroform extraction, dilute hydrochloric acid washs; saturated sodium bicarbonate neutralizes; be washed to neutrality, organic phase revolves steaming can obtain solid crude product, by column chromatography (petrol ether/ethyl acetate; 6:1) white solid product can be obtained, productive rate 51%.Mass spectral characteristi (MALDI-TOF): 611.292
The synthesis of two (3-trifluoromethyl-4-benzocyclobutane thiazolinyl phenyl ether base) fluorenes of embodiment 99,9-
Under argon shield; 9.73 gram 9 is added in reaction unit; 9-bis-(3-trifluoromethyl-4-hydroxy phenyl) fluorenes; 15.68 grams of 4-bromine benzocyclobutenes; 0.73 gram of cuprous chloride, 1.52 grams of N-butyl imidazole, 8.86 grams of potassiumphosphates; 60 milliliters of toluene; be warming up to 140 DEG C of reactions 15 hours, be cooled to room temperature, product dilute hydrochloric acid washs; saturated sodium bicarbonate neutralizes; be washed to neutrality, organic phase revolves steaming can obtain solid crude product, by column chromatography (petrol ether/ethyl acetate; 6:1) white solid product can be obtained, productive rate 51%.Mass spectral characteristi (MALDI-TOF): 691.201
The synthesis of two (3-trifluoromethyl-4-benzocyclobutane thiazolinyl phenyl ether base) fluorenes of embodiment 109,9-
With embodiment 9; under argon shield; 9.73 gram 9 is added in reaction unit; 9-bis-(3-trifluoromethyl-4-hydroxy phenyl) fluorenes, 15.68 grams of 4-bromine benzocyclobutenes, 1.65 grams of cuprous iodides; 1.59 grams of N-butyl imidazole; 13.32 grams of cesium carbonates, 60 milliliters of toluene, are warming up to 140 DEG C of reactions 10 hours; be cooled to room temperature; product dilute hydrochloric acid washs, and saturated sodium bicarbonate neutralizes, and is washed to neutrality; organic phase revolves steaming can obtain solid crude product; white solid product can be obtained, productive rate 54% by column chromatography (petrol ether/ethyl acetate, 6:1).
Three, thermosetting resin cured containing fluorenes and benzocyclobutene structural unit
Embodiment 11
Getting 0.6 gram of embodiment 5 product is dissolved in 5 milliliters of dichlorobenzene toluene, be spun to film forming on ITO conductive glass substrate, then put in vacuum drying oven, stage elevated cure, 210 DEG C × 1 hour, 220 DEG C × 1 hour, 240 DEG C × 1 hour, 260 DEG C × 1 hour, 280 DEG C × 1 hour, 300 DEG C × 1 hour, after completion of cure, highly cross-linked resin film can be obtained.It is as shown in the table for specific performance:
Embodiment 11
Getting 2.5 grams of embodiment 8 products is dissolved in 5 milliliters of dichlorobenzene; be spun to ITO conductive glass substrate film forming; under nitrogen protection, stage elevated cure: 180 DEG C of thermal treatment 1 hour, 220 DEG C × 1 hour; 230 DEG C × 1 hour; 240 DEG C × 1 hour, 260 DEG C × 1 hour, 280 DEG C × 1 hour; 300 DEG C of thermal treatment 1 hour, can obtain highly cross-linked resin film after completion of cure.
Specific performance is as shown in the table:
Embodiment 12
Getting 2.5 grams of embodiment 9 products is dissolved in 5 milliliters of dichlorobenzene; be spun to film forming on ITO conductive glass substrate, under nitrogen protection, stage elevated cure: 180 DEG C of thermal treatment 1 hour; 210 DEG C × 1 hour; 220 DEG C × 1 hour, 230 DEG C × 1 hour, 240 DEG C × 1 hour; 260 DEG C × 1 hour; 280 DEG C × 1 hour, 300 DEG C of thermal treatment 1 hour, can obtain highly cross-linked thermosetting resin after completion of cure.
Specific performance is as shown in the table:
Claims (14)
1. contain the simple thermosetting resin of fluorenes and benzocyclobutene structural unit, it is characterized in that, this monomer has following chemical structure of general formula:
Wherein,
R
1for F, CH
3, CF
3, and R
2, R
3be respectively H, F, CH
3or CF
3; Or R
1for H, and R
2for F, CH
3or CF
3; And R
3for H or F; R
1, R
2and R
3identical or different.
2. simple thermosetting resin as claimed in claim 1, is characterized in that, R
1for CF
3, and R
2for H, F, CH
3or CF
3.
3. simple thermosetting resin as claimed in claim 1, is characterized in that, described monomer is two (3-trifluoromethyl-4-benzocyclobutane thiazolinyl phenyl ether base) fluorenes of 9,9-.
4. a polymkeric substance for solidification, is characterized in that, described polymkeric substance solidify to form containing the simple thermosetting resin of fluorenes and benzocyclobutene structural unit as claimed in claim 1, and the specific inductivity k of described polymkeric substance is less than <2.7.
5. the polymkeric substance of solidification as claimed in claim 4, is characterized in that, the specific inductivity k of described polymkeric substance is less than≤and 2.61.
6. the polymkeric substance of solidification as claimed in claim 4, it is characterized in that, the specific inductivity k of described polymkeric substance is≤2.58.
7. the polymkeric substance of solidification as claimed in claim 4, it is characterized in that, the specific inductivity k of described polymkeric substance is 2.38.
8. one kind contains the preparation method of the simple thermosetting resin of fluorenes and benzocyclobutene heat structure unit as claimed in claim 1, it is characterized in that, with 4-bromine benzocyclobutene and bisphenol fluorene for raw material, under the existence of cuprous salt, imidazole ligands and mineral alkali, occur to obtain for etherification reaction 5-30 hour in 80-160 DEG C and organic solvent:
Described bisphenol fluorene has following structure:
Wherein R
1, R
2, R
3definition is with claim 1;
Described cuprous salt is cuprous chloride, cuprous bromide or cuprous iodide;
Described imidazole ligands is 1-Methylimidazole, 1,2 dimethylimidazole, N-butyl imidazole or N-isopropylimdazole;
Described mineral alkali is alkali-metal oxyhydroxide, phosphoric acid salt or carbonate;
Described 4-bromine benzocyclobutene and the mol ratio of bisphenol fluorene are 2 ~ 5:1;
Described 4-bromine benzocyclobutene and the mol ratio of cuprous salt, imidazole ligands and mineral alkali are 1 ~ 5:0.1 ~ 1:0.1 ~ 1:1 ~ 5.
9. contain the preparation method of the simple thermosetting resin of fluorenes and benzocyclobutene heat structure unit as claimed in claim 8, it is characterized in that, described cuprous salt is cuprous chloride; Described mineral alkali is salt of wormwood.
10. as described in claim 8 or 9, contain the preparation method of the simple thermosetting resin of fluorenes and benzocyclobutene structural unit, it is characterized in that, described organic solvent is toluene, dioxane, DMF, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, hexamethylphosphoramide or tetramethylene sulfone.
11. one kind as claimed in claim 1 containing the simple thermosetting resin of fluorenes and benzocyclobutene structural unit for the preparation of the application of thermosetting resin.
12. as claimed in claim 11 containing the application of the simple thermosetting resin of fluorenes and benzocyclobutene structural unit, it is characterized in that, described simple thermosetting resin is by filling with mould or by wiring solution-forming spin coating or a painting film forming, being heating and curing, obtaining highly cross-linked thermosetting resin or film; Or solidify with other benzocyclobutene monomers or unsaturated double-bond resin alloy; The resin alloy weight ratio of described simple thermosetting resin and other benzocyclobutene monomers or unsaturated double-bond is 1:0.05 ~ 80.
13. as claimed in claim 12 containing the application of the thermosetting resin of fluorenes and benzocyclobutene structural unit, it is characterized in that, the described employing stage elevated cure that is heating and curing: 150 ~ 200 DEG C of pre-treatment 0.5 ~ 4 hour, 210 ~ 260 DEG C of thermofixations 1 ~ 8 hour, 260 ~ 330 DEG C of thermal treatment 1 ~ 4 hour.
14. as claimed in claim 12 containing the application of the thermosetting resin of fluorenes and benzocyclobutene structural unit, it is characterized in that, the organic solution that described wiring solution-forming adopts is toluene, trimethylbenzene, phenyl ether, trichloromethane, acetone, N, one or several mixing in dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone.
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| CN103755735B (en) * | 2014-01-21 | 2017-02-01 | 中国科学院上海有机化学研究所 | Curable fluorine-containing polyarylether |
| CN104311401B (en) * | 2014-09-12 | 2016-06-29 | 中国科学院上海有机化学研究所 | Containing benzocyclobutene and the thermosetting monomer of Freon C318 unit, preparation method and application thereof |
| CN105152881B (en) * | 2015-06-23 | 2018-06-29 | 复旦大学 | Benzocyclobutene monomer, preparation method and application containing adamantane Yu trans-1,1,2,2,3,4-Hexafluorocyclobutane structure |
| CN107325277B (en) * | 2016-04-28 | 2020-01-03 | 江苏和成新材料有限公司 | Polyphenylene ether resin and use thereof |
| CN114231221B (en) * | 2021-12-29 | 2023-05-12 | 深圳市纽菲斯新材料科技有限公司 | Insulating adhesive film and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4927907A (en) * | 1989-05-30 | 1990-05-22 | Shell Oil Company | Bisbenzocyclobutene/bisimide/free radical polymerization inhibitor composition |
| WO1997005184A1 (en) * | 1995-07-28 | 1997-02-13 | The Dow Chemical Company | 2,7-aryl-9-substituted fluorenes and 9-substituted fluorene oligomers and polymers |
| CN101302154A (en) * | 2008-06-23 | 2008-11-12 | 西南科技大学 | Acrylic ester type benzocyclobutene monomer and preparation thereof |
| CN101445437A (en) * | 2007-11-30 | 2009-06-03 | 赛拓有限责任公司 | Improved process for the catalytic synthesis of diaryl ethers |
| CN102391202A (en) * | 2011-09-09 | 2012-03-28 | 复旦大学 | Benzocyclobutene functional groups-contained benzoxazine monomer and synthetic method and use thereof |
-
2013
- 2013-01-31 CN CN201310039644.7A patent/CN103086851B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4927907A (en) * | 1989-05-30 | 1990-05-22 | Shell Oil Company | Bisbenzocyclobutene/bisimide/free radical polymerization inhibitor composition |
| WO1997005184A1 (en) * | 1995-07-28 | 1997-02-13 | The Dow Chemical Company | 2,7-aryl-9-substituted fluorenes and 9-substituted fluorene oligomers and polymers |
| CN101445437A (en) * | 2007-11-30 | 2009-06-03 | 赛拓有限责任公司 | Improved process for the catalytic synthesis of diaryl ethers |
| CN101302154A (en) * | 2008-06-23 | 2008-11-12 | 西南科技大学 | Acrylic ester type benzocyclobutene monomer and preparation thereof |
| CN102391202A (en) * | 2011-09-09 | 2012-03-28 | 复旦大学 | Benzocyclobutene functional groups-contained benzoxazine monomer and synthetic method and use thereof |
Non-Patent Citations (2)
| Title |
|---|
| Synthesis and characterization of poly(arylene ether ketone) with sulfonated fluorene pendants for proton exchange membrane;Xueya Shang,Shaoming Fang,Yuezhong Meng;《Journal of membrane science》;20070315;第297卷;90-97 * |
| 含芴基二胺单体及其聚酰亚胺的合成与表征;尚雪亚等;《化工新型材料》;20101215;第38卷(第12期);44-46 * |
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