CN103086851A - Thermosetting resin monomer containing fluorene and benzocyclobutene construction unit as well as preparation method and application thereof - Google Patents
Thermosetting resin monomer containing fluorene and benzocyclobutene construction unit as well as preparation method and application thereof Download PDFInfo
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- CN103086851A CN103086851A CN2013100396447A CN201310039644A CN103086851A CN 103086851 A CN103086851 A CN 103086851A CN 2013100396447 A CN2013100396447 A CN 2013100396447A CN 201310039644 A CN201310039644 A CN 201310039644A CN 103086851 A CN103086851 A CN 103086851A
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Abstract
The invention belongs to the filed of high-performance polymer preparation, and particularly relates to a thermosetting resin monomer containing fluorene and benzocyclobutene construction unit as well as a preparation method and application thereof. The constitutional formula of the monomer is shown in the description; and the monomer is obtained through etherification reaction between bisphenol fluorine and 4-bromobenzocyclobutene in a solvent in the presence of cuprous salt, imidazole ligand and inorganic base. The monomer has very good film formation property, and a solid film with high heat resistance, low water absorbing capacity, low specific inductive capacity and high flatness can be obtained through thermal curing of the obtained organic film. In the atmosphere of nitrogen, 5% weight loss temperature (Td 5%) of the film is 468.5 DEG C, and the carbon yield at 1000 DEG C is up to 37.6%. The monomer is suitable for serving as a high-temperature resistant bonding agent in the fields of aerospace, national defense and the like and an encapsulating material of electronic devices and components in an electric industry.
Description
Technical field
The invention belongs to high-performance polymer manufacturing technology field, be specifically related to a kind of thermosetting resin monomer, preparation method and application that contain fluorenes and benzocyclobutene structural unit.The thermosetting resin that contains fluorenes and benzocyclobutene structural unit of, low water absorption heat-resisting for the preparation of height and low-k.
Background technology
The quantum yield of pi-conjugated fluorene-containing polymers Yin Qigao and the modifiability of molecular structure as electroluminescent organic material, organic thin film solar material and biological detection material, are widely used in the organic photoelectric functional material field.On the other hand, because fluorenes has larger free volume, the thermotolerance of the epoxy resin Yin Qigao take bisphenol fluorene as structural unit and good processibility, and enjoy the favor of aerospace field and electric industry.Enter the nineties in last century, development along with microelectronics industry, based on the manufacturing of 90 nano chips of the copper interconnection technology heat-stable material in the urgent need to low-k, the Dow Chemical Company has developed multiple dielectric materials for this reason, except famous SILK, bisphenol fluorene trifluoro vinyl ether resin is also furtherd investigate.This fluorine-containing bisphenol fluorene is through after thermofixation, and the film that obtains has excellent thermotolerance and dielectric properties (WO9015043).But, because [2+2] cycloaddition reaction that trifluoro vinyl ether at high temperature occurs often carries out not exclusively causing the thermotolerance of film and dielectric properties unstable.
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 even film forming, and planeness is high.from Finklesteln reported first in 1909 benzocyclobutane ene derivative synthetic, its relevant applied research development rapidly, be widely used in abroad space flight and aviation, microelectronics, military, the field such as civilian, a series of high temperature materials based on benzocyclobutene have been developed, the high-performance dielectric film material, matrix material, high performance adhesive, the materials such as nonlinear optical material, the computer liquid crystal display screen of producing as the IBM Corporation of the U.S. and COMPAQ company oneself all use the benzocyclobutane olefine resins to do packaged material, the Dow Chemical Company develops siliceous benzocyclobutene, after processing through pre-polymerization, the oligopolymer that obtains has good film-forming properties.Through further being heating and curing, obtaining specific inductivity and can reach 2.5 solid film.In national defense industry, the application of benzocyclobutane olefine resin can be dwindled the volume of military electronic devices and components greatly, is conducive to the weapon miniaturization, and has significantly improved stability and the reliability of electronic devices and components, and the modernization of national defense is had great significance.Be subjected to the impact of the factors such as raw material, China relatively lags behind to this resinoid exploitation and applied research, researches and develops high performance benzocyclobutane olefine resin, and the development of China's new and high technology is had important realistic meaning.
Based on the demand of microelectronics industry, particularly towards the integrated circuit technology below 65 nanometers to the demand of specific inductivity less than 2.8 material, the research and development good heat resistance, specific inductivity is low and it is extremely urgent to have a high performance material of good workability.In view of the excellent properties of bisphenol fluorene and benzocyclobutene class material, both advantage is combined, be expected to obtain the material of excellent performance.The present invention just is being based on such thinking, benzocyclobutene is introduced contained in fluorene compound, synthesize a series of thermosetting monomers that contain 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 who contains 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 that contains fluorenes and benzocyclobutene structural unit of the present invention, monomer whose has following chemical structure of general formula:
R wherein
1, R
2, R
3Be respectively H, F, CH
3, CF
3And phenyl; R
1, R
2And R
3Can be identical also can be different.
Of the present inventionly contain fluorenes and the benzocyclobutene thermosetting resin prepares in accordance with the following methods: take 4-bromobenzene and cyclobutene and bisphenol fluorene as raw material, under the existence of cuprous salt, imidazole ligands and mineral alkali, etherification reaction occurs obtain in solvent.
Bisphenol fluorene of the present invention has following structure:
R wherein
1, R
2, R
3Be respectively H, F, CH
3, CF
3And phenyl; R
1, R
2And R
3Can be 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 the 1-Methylimidazole, 1,2 dimethylimidazole, N-butyl imidazole or N-isopropylimdazole.
Mineral alkali of the present invention is alkali-metal oxyhydroxide, and phosphoric acid salt or carbonate preferably use 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-bromobenzene of the present invention and cyclobutene and bisphenol fluorene is 2 ~ 5:1.
The mol ratio of 4-bromobenzene of the present invention and cyclobutene 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 ℃, and the reaction times is 5-30 hour.
The thermosetting resin monomer that contains fluorenes and benzocyclobutene structural unit of the present invention can be used for preparing thermosetting resin or film, by filling with mould or by the wiring solution-forming spin coating or drip and 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 thermosetting resin monomer that contains 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 ℃ of pre-treatment 0.5 ~ 4 hour, 210 ~ 260 ℃ of thermofixations 1 ~ 8 hour, 260 ~ 330 ℃ 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), the mixing of one or several in N-Methyl pyrrolidone.
The polymkeric substance that solidifies gained shows temperature tolerance preferably, 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 simultaneously modification other benzocyclobutane olefine resin or unsaturated polyesters, when can keep good mechanical property and dielectric properties, improve its resistance toheat.Thermosetting resin of the present invention can the doping carbon fiber etc. matrix material, the preparation high performance composite, the resin that obtains after curing has good thermostability and mechanical property, is applied to be used as high-performance resin matrix or packaged material in the fields such as microelectronics industry, aerospace and national defence.
Embodiment:
Below by embodiment, the present invention is carried out concrete description; be necessary to be pointed out that at this present embodiment only is used for the present invention and further illustrates; 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
Embodiment 19, two (the 3-fluoro-4-hydroxy phenyl) fluorenes of 9-synthetic
Under nitrogen protection; add 36.2 gram Fluorenones in reaction unit, the adjacent fluorophenol of 90.1 grams, 0.3 milliliter of β-mercaptopropionic acid and 100 milliliters of toluene; stir after 0.5 hour under 30 ℃; slowly drip 5 milliliters of vitriol oils in reaction system, be warming up to 55 ℃ of reactions 5 hours after dropwising, be cooled to room temperature; product is poured into water; have solid to separate out, recrystallization gets fluorine-containing bisphenol fluorene white crystal, productive rate 92% in toluene.Fusing point, 220-221 ℃ (document, USP5304688,219-221 ℃).Mass spectrum (EI-MS) characterizes m/z:386.11 (100.0%), 387.12 (27.3%), 388.12 (4.0%).
Embodiment 29, two (the 3-trifluoromethyl-4-hydroxy phenyl) fluorenes of 9-synthetic
Under nitrogen protection; add 18.2 gram Fluorenones in reaction unit; 64.8 gram o-trifluoromethyl phenol; 0.4 milliliter β-mercaptopropionic acid and 80 milliliters of toluene; stir after 0.5 hour under 30 ℃; slowly drip 4 milliliters of vitriol oils in reaction system; be warming up to 55 ℃ of reactions 6 hours after dropwising; be cooled to room temperature, product neutralizes with saturated sodium bicarbonate solution, is washed to neutrality; organic phase is revolved and is steamed to get solid crude product; (petrol ether/ethyl acetate 4:1) can get fluorine-containing bisphenol fluorene white crystal, productive rate 85% by column chromatography.Mass spectrum (EI-MS) characterizes m/z:486.11 (100.0%), 487.11 (29.5%), 488.11 (4.5%)
Embodiment 32,7-two (trifluoromethyl)-9, two (4-hydroxy phenyl) fluorenes of 9-synthetic
Under argon shield, add 8.2 grams 2 in reaction unit, 7-two bromo-9; two (4-hydroxy phenyl) fluorenes of 9-(prepare according to document: R.Grisorio etc., Macromolecules2011,44; 7977 – 7986), 2 gram three (dibenzalacetone) two palladiums (are Pd
2(dba)
3), 4.23 gram cuprous iodides, 32 milliliters of fluorosulfonyl methyl difluoroacetates and 100 milliliters of N; dinethylformamide; reaction is 12 hours under 100 ℃, is cooled to room temperature, and product is poured into water; there is solid to separate out; recrystallization gets 2,7-two (trifluoromethyl) 9 in toluene, two (4-hydroxy phenyl) fluorenes of 9-; white crystal, productive rate 86%.Mass spectrum (EI-MS) characterizes m/z:486.11 (100.0%), 487.11 (29.5%), 488.11 (4.5%)
Embodiment 49, two (2, the 6-dimethyl-4-hydroxy phenyl) fluorenes of 9-synthetic
Under nitrogen protection, add 36.2 gram Fluorenones in reaction unit, 122 grams 2; the 6-xylenol; 0.3 milliliter β-mercaptopropionic acid and 100 milliliters of toluene stir after 0.5 hour under 30 ℃, slow 5 milliliters of vitriol oils of dropping in the reaction system; be warming up to 55 ℃ of reactions 5 hours after dropwising; be cooled to room temperature, product is poured into water, and has solid to separate out; recrystallization gets fluorine-containing bisphenol fluorene white crystal, productive rate 87% in toluene.Mass spectrum (EI-MS) characterizes m/z:406.19 (100.0%), 407.20 (31.7%), 408.20 (5.3%)
Two, contain the thermosetting resin monomer preparation of fluorenes and benzocyclobutene structural unit
Embodiment 59, two (the 4-benzocyclobutane thiazolinyl phenyl ether base) fluorenes of 9-synthetic
Under argon shield; add 17.5 grams 9 in reaction unit; two (4-hydroxy phenyl) fluorenes of 9-; 36.6 gram 4-bromobenzene and cyclobutene, 1.95 gram cuprous iodides, 6.15 gram N-butyl imidazole; 13.86 gram salt of wormwood; 100 milliliters of toluene are warming up to 140 ℃ of reactions 16 hours, are cooled to room temperature; the product chloroform extraction; the dilute hydrochloric acid washing, the saturated sodium bicarbonate neutralization is washed to neutrality; organic phase is revolved steaming can get solid crude product; (petrol ether/ethyl acetate 6:1) can get white solid product, productive rate 62% by column chromatography.Proton nmr spectra
1H-NMR result (300MHz, CDCl
3, ppm) 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%), 487.11 (29.5%), 488.11 (4.5%).
Embodiment 69, two (the 4-benzocyclobutane thiazolinyl phenyl ether base) fluorenes of 9-synthetic
With embodiment 4; under argon shield; add 14.3 grams 9 in reaction unit; two (4-hydroxy phenyl) fluorenes of 9-, 22.3 gram 4-bromobenzene and cyclobutenes, 0.86 gram cuprous chloride; 4.95 gram N-butyl imidazole; 11.25 gram salt of wormwood, 80 milliliters of toluene are warming up to 120 ℃ of reactions 20 hours; be cooled to room temperature; the product chloroform extraction, dilute hydrochloric acid washing, saturated sodium bicarbonate neutralization; be washed to neutrality; organic phase is revolved steaming can get solid crude product, can get white solid product by methylene dichloride/normal hexane recrystallization, productive rate 57%.
Embodiment 79, two (the 3-fluoro-4-benzocyclobutane thiazolinyl phenyl ether base) fluorenes of 9-synthetic
Under argon shield; add 7.78 grams 9 in reaction unit; two (the 3-fluoro-4-hydroxy phenyl) fluorenes of 9-; 13.38 gram 4-bromobenzene and cyclobutene, 0.68 gram cuprous chloride, 2.36 gram N-isopropylimdazoles; 5.86 gram salt of wormwood; 50 milliliters of N-Methyl pyrrolidone are warming up to 120 ℃ of reactions 16 hours, are cooled to room temperature; the product chloroform extraction; the dilute hydrochloric acid washing, the saturated sodium bicarbonate neutralization is washed to neutrality; organic phase is revolved steaming can get solid crude product; (petrol ether/ethyl acetate 6:1) can get white solid product, productive rate 53% by column chromatography.Mass spectral characteristi (MALDI-TOF): 590.211
Embodiment 89, two (2, the 6-dimethyl-4-benzocyclobutane thiazolinyl phenyl ether base) fluorenes of 9-synthetic
Under argon shield; add 4.06 grams 9 in reaction unit; two (2, the 6-dimethyl-4-hydroxy phenyl) fluorenes of 9-, 7.43 gram 4-bromobenzene and cyclobutenes; 0.32 gram cuprous chloride; 1.36 gram N-isopropylimdazole, 6.36 gram cesium carbonates, 50 milliliters of toluene; be warming up to 120 ℃ of reactions 16 hours; be cooled to room temperature, product chloroform extraction, dilute hydrochloric acid washing; the saturated sodium bicarbonate neutralization; be washed to neutrality, organic phase is revolved steaming can get solid crude product, by column chromatography (petrol ether/ethyl acetate; 6:1) can get white solid product, productive rate 51%.Mass spectral characteristi (MALDI-TOF): 611.292
Embodiment 99, two (3-trifluoromethyl-4-benzocyclobutane thiazolinyl phenyl ether base) fluorenes of 9-synthetic
Under argon shield; add 9.73 grams 9 in reaction unit; 9-two (3-trifluoromethyl-4-hydroxy phenyl) fluorenes; 15.68 gram 4-bromobenzene and cyclobutene; 0.73 the gram cuprous chloride, 1.52 gram N-butyl imidazole, 8.86 gram potassiumphosphates; 60 milliliters of toluene; be warming up to 140 ℃ of reactions 15 hours, be cooled to room temperature, product washs with dilute hydrochloric acid; the saturated sodium bicarbonate neutralization; be washed to neutrality, organic phase is revolved steaming can get solid crude product, by column chromatography (petrol ether/ethyl acetate; 6:1) can get white solid product, productive rate 51%.Mass spectral characteristi (MALDI-TOF): 691.201
Embodiment 109, two (3-trifluoromethyl-4-benzocyclobutane thiazolinyl phenyl ether base) fluorenes of 9-synthetic
With embodiment 9; under argon shield; add 9.73 grams 9 in reaction unit; 9-two (3-trifluoromethyl-4-hydroxy phenyl) fluorenes, 15.68 gram 4-bromobenzene and cyclobutenes, 1.65 gram cuprous iodides; 1.59 gram N-butyl imidazole; 13.32 the gram cesium carbonate, 60 milliliters of toluene are warming up to 140 ℃ of reactions 10 hours; be cooled to room temperature; product washs with dilute hydrochloric acid, and the saturated sodium bicarbonate neutralization is washed to neutrality; organic phase is revolved steaming can get solid crude product; (petrol ether/ethyl acetate 6:1) can get white solid product, productive rate 54% by column chromatography.
Three, contain the thermosetting resin cured of fluorenes and benzocyclobutene structural unit
Embodiment 11
Getting 0.6 gram embodiment 5 products is dissolved in 5 milliliters of dichlorobenzene toluene, be spun to film forming on ITO conductive glass substrate, then put in vacuum drying oven, the stage heats up and solidifies, 210 ℃ * 1 hour, 220 ℃ * 1 hour, 240 ℃ * 1 hour, 260 ℃ * 1 hour, 280 ℃ * 1 hour, 300 ℃ * 1 hour, can get highly cross-linked resin film after completion of cure.It is as shown in the table for specific performance:
Embodiment 11
Getting 2.5 gram embodiment 8 products is dissolved in 5 milliliters of dichlorobenzene; be spun to ITO conductive glass substrate film forming; under nitrogen protection, the stage heat up to solidify: 180 ℃ of thermal treatment 1 hour, 220 ℃ * 1 hour; 230 ℃ * 1 hour; 240 ℃ * 1 hour, 260 ℃ * 1 hour, 280 ℃ * 1 hour; 300 ℃ of thermal treatment 1 hour can get highly cross-linked resin film after completion of cure.
Specific performance is as shown in the table:
Embodiment 12
Getting 2.5 gram embodiment 9 products is dissolved in 5 milliliters of dichlorobenzene; be spun to film forming on ITO conductive glass substrate, under nitrogen protection, the stage heat up to solidify: 180 ℃ of thermal treatment 1 hour; 210 ℃ * 1 hour; 220 ℃ * 1 hour, 230 ℃ * 1 hour, 240 ℃ * 1 hour; 260 ℃ * 1 hour; 280 ℃ * 1 hour, 300 ℃ of thermal treatment 1 hour can get highly cross-linked thermosetting resin after completion of cure.
Specific performance is as shown in the table:
Claims (8)
1. contain the thermosetting resin monomer of fluorenes and benzocyclobutene structural unit, it is characterized in that, this monomer has following chemical structure of general formula:
R wherein
1, R
2, R
3Be respectively H, F, CH
3, CF
3Or phenyl; R
1, R
2And R
3Identical or different.
2. preparation method who contains as claimed in claim 1 the thermosetting resin monomer of fluorenes and benzocyclobutene heat structure unit, it is characterized in that, take 4-bromobenzene and cyclobutene and bisphenol fluorene as raw material, under the existence of cuprous salt, imidazole ligands and mineral alkali, etherification reaction occurs in 80-160 ℃ and organic solvent made in 5-30 hour:
Described bisphenol fluorene has following structure:
R wherein
1, R
2, R
3Definition is cuprous chloride, cuprous bromide or cuprous iodide with cuprous salt claimed in claim 1;
Described imidazole ligands is the 1-Methylimidazole, 1,2 dimethylimidazole, N-butyl imidazole or N-isopropylimdazole;
Described mineral alkali is alkali-metal oxyhydroxide, phosphoric acid salt or carbonate;
The mol ratio of described 4-bromobenzene and cyclobutene and bisphenol fluorene is 2 ~ 5:1;
The mol ratio of described 4-bromobenzene and cyclobutene and cuprous salt, imidazole ligands and mineral alkali is 1 ~ 5:01 ~ 1:01 ~ 1:1 ~ 5.
3. contain as claimed in claim 2 the preparation method of the thermosetting resin monomer of fluorenes and benzocyclobutene heat structure unit, it is characterized in that, described cuprous salt is cuprous chloride; Described mineral alkali is salt of wormwood.
4. as containing the preparation method of the thermosetting resin monomer of fluorenes and benzocyclobutene structural unit as described in claim 2 and 3, it is characterized in that, described organic solvent is toluene, dioxane, N, dinethylformamide, DMF, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, hexamethylphosphoramide or tetramethylene sulfone.
5. one kind contains the thermosetting resin monomer of fluorenes and benzocyclobutene structural unit as claimed in claim 1 for the preparation of the application of thermosetting resin.
6. contain as claimed in claim 5 the application of the thermosetting resin monomer of fluorenes and benzocyclobutene structural unit, it is characterized in that, described thermosetting resin monomer obtains highly cross-linked thermosetting resin or film by filling with mould or by the wiring solution-forming spin coating or drip and be coated with film forming, being heating and curing; Or solidify with other benzocyclobutene monomers or unsaturated double-bond resin alloy; The resin alloy weight ratio of described thermosetting resin monomer and other benzocyclobutene monomers or unsaturated double-bond is 1:0.05 ~ 80.
7. contain as claimed in claim 6 the application of the thermosetting resin of fluorenes and benzocyclobutene structural unit, it is characterized in that, the described employing stage that is heating and curing heat up to solidify: 150 ~ 200 ℃ of pre-treatment 0.5 ~ 4 hour, 210 ~ 260 ℃ of thermofixations 1 ~ 8 hour, 260 ~ 330 ℃ of thermal treatment 1 ~ 4 hour.
8. contain as claimed in claim 6 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, the mixing of one or several in dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone.
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| CN105152881A (en) * | 2015-06-23 | 2015-12-16 | 复旦大学 | Benzocyclobutene monomer containing adamantane and hexafluorocyclobutane structures, and preparation method and application thereof |
| CN107325277A (en) * | 2016-04-28 | 2017-11-07 | 江苏和成新材料有限公司 | Polyphenylene oxide resin and its application |
| CN114231221A (en) * | 2021-12-29 | 2022-03-25 | 深圳市纽菲斯新材料科技有限公司 | Insulating adhesive film and preparation method and application thereof |
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| CN104311401A (en) * | 2014-09-12 | 2015-01-28 | 中国科学院上海有机化学研究所 | Benzocyclobutene-perfluorocyclobutane unit-containing thermosetting monomer and its preparation method and use |
| CN105152881A (en) * | 2015-06-23 | 2015-12-16 | 复旦大学 | Benzocyclobutene monomer containing adamantane and hexafluorocyclobutane structures, and preparation method and application thereof |
| CN107325277A (en) * | 2016-04-28 | 2017-11-07 | 江苏和成新材料有限公司 | Polyphenylene oxide resin and its application |
| 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 |
| CN114231221A (en) * | 2021-12-29 | 2022-03-25 | 深圳市纽菲斯新材料科技有限公司 | Insulating adhesive film and preparation method and application thereof |
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