CN117510853A - Polyphenylsulfone resin and preparation method and application thereof - Google Patents
Polyphenylsulfone resin and preparation method and application thereof Download PDFInfo
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- CN117510853A CN117510853A CN202311559340.3A CN202311559340A CN117510853A CN 117510853 A CN117510853 A CN 117510853A CN 202311559340 A CN202311559340 A CN 202311559340A CN 117510853 A CN117510853 A CN 117510853A
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- polyphenylsulfone resin
- biphenol
- double
- tetramethyl
- polyphenylsulfone
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- 239000011347 resin Substances 0.000 title claims abstract description 85
- 229920005989 resin Polymers 0.000 title claims abstract description 85
- 229920000491 Polyphenylsulfone Polymers 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 35
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims abstract description 29
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- 229920001955 polyphenylene ether Polymers 0.000 claims description 15
- 229930185605 Bisphenol Natural products 0.000 claims description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000002798 polar solvent Substances 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 18
- 230000007547 defect Effects 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000000113 differential scanning calorimetry Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 229920012287 polyphenylene sulfone Polymers 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WBODDOZXDKQEFS-UHFFFAOYSA-N 1,2,3,4-tetramethyl-5-phenylbenzene Chemical group CC1=C(C)C(C)=CC(C=2C=CC=CC=2)=C1C WBODDOZXDKQEFS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- -1 diaryl thionyl chloride Chemical compound 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229960001802 phenylephrine Drugs 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Substances ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
Classifications
-
- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
Abstract
The invention discloses a polyphenylsulfone resin and a preparation method and application thereof, and relates to the technical field of high polymer materials. The polyphenylsulfone resin disclosed by the invention comprises the following structural units in percentage by mol: 3,3', 5' -tetramethyl-4, 4' -biphenol: 35 to 50mol percent of double-end hydroxyl polyphenyl ether: 1 to 15mol percent of 4,4' -dichloro diphenyl sulfone: 45-55 mol percent. According to the invention, by introducing structural units of 3,3', 5' -tetramethyl-4, 4' -biphenol and dihydroxyl polyphenyl ether in a specific proportion, the obtained polyphenylsulfone resin has excellent high temperature resistance and dielectric property, the glass transition temperature is more than 250 ℃, the dielectric constant is less than 3.2, the defect that the conventional polyphenylsulfone resin cannot adapt to the application scene requirements of higher temperature resistance and lower dielectric property is overcome, and the polyphenylsulfone resin is suitable for the fields of medical appliances, aerospace, electronic devices and automobiles.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polyphenylsulfone resin and a preparation method and application thereof.
Background
The polyphenylsulfone resin (polyphenylene sulfone, PPSU) is a non-crystalline thermoplastic engineering plastic formed by polycondensation of diaryl thionyl chloride and aromatic rings, has a slightly amber-colored high transparent body in appearance, has excellent mechanical property, electrical property, irradiation resistance, combustion performance and hydrolysis resistance, and has high transparency, so that the polyphenylsulfone resin is widely applied to various fields of medical appliances, aerospace, electronic devices, automobiles and the like.
The polyphenylsulfone resin widely applied in the current market is prepared from 4,4 '-dichlorodiphenyl sulfone and 4,4' -biphenol through salifying polycondensation, and has good comprehensive performance, but the heat resistance and dielectric property are improved according to the prior art, the glass transition temperature only reaches about 220 ℃, the dielectric constant is higher, and the application scene requirements of higher temperature resistance and lower dielectric property, such as high-glass transition temperature high-frequency high-speed electronic base materials, high-temperature-resistant electronic devices, high-temperature-resistant wire insulation coating materials and the like, can not be met at about 3.6.
The prior art discloses a high-performance polyphenylsulfone resin, a preparation method and application thereof, and provides an application scene that an amide group-containing aromatic bisphenol monomer, biphenol and 4,4' -dichloro diphenyl sulfone with specific structures are adopted to prepare hydrophilic polyphenylsulfone resin by copolymerization, the glass transition temperature of the resin is up to 280 ℃, but the dielectric constant is more than 4.0, the dielectric performance cannot be considered, and the low dielectric requirement cannot be met.
Disclosure of Invention
The present invention aims to solve at least one of the above technical problems in the prior art. Therefore, the invention aims to provide a high-temperature-resistant low-dielectric polyphenylsulfone resin, which is characterized in that 3,3', 5' -tetramethyl-4, 4' -biphenol and a dihydroxyl polyphenyl ether structural unit are introduced in a specific proportion, so that the glass transition temperature of the polyphenylsulfone resin is increased, and the dielectric constant of the polyphenylsulfone resin is reduced.
The second aspect of the invention provides a preparation method of the polyphenylsulfone resin.
The third aspect of the invention provides an application of the polyphenylsulfone resin.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a polyphenylsulfone resin comprising structural units of the following monomers in mole percent:
3,3', 5' -tetramethyl-4, 4' -biphenol: 35 to 50mol percent,
double-end hydroxyl polyphenyl ether: 1 to 15mol percent,
4,4' -dichlorodiphenyl sulfone: 45-55 mol percent.
The invention reduces the dielectric constant of the polyphenylsulfone resin while improving the glass transition temperature of the polyphenylsulfone resin by introducing the structural units of 3,3', 5' -tetramethyl-4, 4' -biphenol and dihydroxyl polyphenyl ether into the polyphenylsulfone resin in specific mole percent.
Wherein, the main chain of the 3,3', 5' -tetramethyl-4, 4 '-biphenol contains a tetramethyl biphenyl structure, and the movement between polymer chain segments can be limited and the glass transition temperature of the polymer can be effectively improved by controlling the specific mole percent of the structural units formed in the polymer, so that the glass transition temperature of the polyphenylsulfone resin can be obviously improved by introducing the structural units of the 3,3',5 '-tetramethyl-4, 4' -biphenol with a certain mole percent; the two ends of the molecular chain of the dihydroxyl polyphenyl ether contain high-activity phenolic hydroxyl groups, and can be subjected to condensation reaction with 4,4' -dichlorodiphenyl sulfone to form polyphenylsulfone, and meanwhile, the dihydroxyl polyphenyl ether belongs to an intrinsic low-dielectric polymer, so that the dielectric constant of polyphenylsulfone resin can be effectively reduced and the dielectric property can be improved by introducing the structural units of the dihydroxyl polyphenyl ether and controlling the mole percentage of the structural units.
In some embodiments of the invention, the mole percent of 3,3', 5' -tetramethyl-4, 4' -biphenol is from 40 to 48 mole percent
In some embodiments of the invention, the mole percent of 3,3', 5' -tetramethyl-4, 4' -biphenol is from 40 to 45 mole percent.
In some embodiments of the invention, the mole percent of 3,3', 5' -tetramethyl-4, 4' -biphenol is from 44 to 45 mole percent.
In some examples of the invention, the mole percent of 3,3', 5' -tetramethyl-4, 4' -biphenol is 40 mole percent, 42.5 mole percent, 45 mole percent, 47.5 mole percent.
In some embodiments of the invention, the molar percentage of the double-ended hydroxyl polyphenylene ether is 2 to 10 mole percent.
In some embodiments of the invention, the molar percentage of the double-ended hydroxyl polyphenylene ether is 5 to 10 mole percent.
In some embodiments of the invention, the molar percentage of the double-ended hydroxyl polyphenylene ether is 5 to 6%.
In some examples of the invention, the mole percent of the double-ended hydroxyl polyphenylene ether is 5 mole percent, 2.5 mole percent, 7.5 mole percent, 10 mole percent.
In some embodiments of the invention, the percentage of 4,4' -dichlorodiphenyl sulfone is 50 mole%.
In some embodiments of the invention, the double-ended hydroxyl polyphenylene ether has a number average molecular weight of 800 to 8000.
In some embodiments of the invention, the double-ended hydroxyl polyphenylene ether has a number average molecular weight of 1000 to 3000.
In some embodiments of the invention, the double-ended hydroxyl polyphenylene ether has a number average molecular weight of 1500 to 2500.
The double-end hydroxyl polyphenyl ether with low molecular weight is selected, so that the high temperature resistance and dielectric property of the polyphenylsulfone resin are further improved.
In some embodiments of the invention, the double-ended hydroxyl polyphenylene ether has a structure as shown in formula 1:
wherein the Y substituent is At least one of (a) and (b); m and n are integers from 0 to 50, and n > m.
The double-end hydroxyl polyphenyl ether with a specific structure is selected, so that the glass transition temperature of the polyphenylsulfone resin is further improved, and the dielectric constant of the polyphenylsulfone resin is reduced.
In some embodiments of the invention, the Y substituent is
In some embodiments of the invention, the sum of m and n is an integer from 0 to 50.
In some embodiments of the invention, the sum of m and n is an integer from 1 to 30.
The second aspect of the present invention provides a preparation method of the above polyphenylsulfone resin, comprising the steps of:
mixing and dissolving 4,4' -dichloro diphenyl sulfone, bisphenol monomer and aprotic polar solvent, adding salifying agent and water-carrying agent, and carrying out salifying reaction and polymerization reaction to obtain polyphenylsulfone resin;
the bisphenol monomer is 3,3', 5' -tetramethyl-4, 4' -biphenol and double-end hydroxyl polyphenyl ether.
In some embodiments of the invention, the 4,4' -dichlorodiphenyl sulfone is used in a molar ratio to bisphenol monomer of (0.7 to 1.3): 1.
In some embodiments of the invention, the bisphenol monomer is used in a molar ratio to the salt former of 1 (0.8 to 1.6).
In some embodiments of the invention, the 4,4' -dichlorodiphenyl sulfone is used in a 1:1 molar ratio to bisphenol monomer.
In some embodiments of the invention, the bisphenol monomer is used in a molar ratio to the salt former of 1 (1 to 1.5).
In some embodiments of the invention, the bisphenol monomer is used in a molar ratio of 1 (1.2-1.3) to the salt former.
In some embodiments of the invention, the salt forming reaction temperature is 120 to 180 ℃.
In some embodiments of the invention, the salt forming reaction is at a temperature of 130 to 170 ℃.
In some embodiments of the invention, the salt forming reaction is at a temperature of 160 to 170 ℃.
In some examples of the invention, the salt forming reaction is at a temperature of 125 ℃, 130 ℃, 140 ℃, 160 ℃, 165 ℃.
In some embodiments of the invention, the polymerization temperature is 160 to 250 ℃.
In some embodiments of the invention, the polymerization temperature is 160 to 230 ℃.
In some embodiments of the invention, the polymerization reaction temperature is 220 to 230 ℃.
In some examples of the invention, the polymerization reaction is at a temperature of 225 ℃, 235 ℃, 180 ℃, 160 ℃.
In some embodiments of the invention, the salification reaction time is from 1 to 5 hours.
In some embodiments of the invention, the salification reaction time is 2 to 4 hours.
In some embodiments of the invention, the polymerization time is1 to 5 hours.
In some embodiments of the invention, the polymerization time is 2 to 4 hours.
In some embodiments of the invention, the polymerization reaction is further followed by precipitation, washing, and drying.
In some embodiments of the invention, the solvent temperature used for the washing is 50-100 ℃.
In some embodiments of the invention, the temperature of the solvent is 70-90 ℃.
In some embodiments of the invention, the temperature of the solvent is 75-85 ℃.
In some examples of the invention, the temperature of the solvent is 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃.
In some examples of the invention, the solvent is deionized water.
In some embodiments of the invention, the salification, polymerization reactions are carried out under an inert atmosphere.
In some embodiments of the invention, the inert atmosphere is a nitrogen atmosphere.
In some embodiments of the present invention, the method for preparing a polyphenylsulfone resin includes the steps of:
adding aprotic polar solvent into a nitrogen-filled reaction system, and then adding 4,4 '-dichlorodiphenyl sulfone, 3',5 '-tetramethyl-4, 4' -biphenol and double-end hydroxyl polyphenyl ether in sequence, stirring and heating to 80-90 ℃ to enable the monomers to be completely dissolved; adding a salifying agent and a water-carrying agent into the system, and heating to form a salt reaction under the protection of nitrogen; after the salification reaction is finished, continuing to heat for polymerization reaction; after the polymerization reaction is finished, the polymerized viscous material is precipitated in deionized water, filtered and dried, and the solid product is crushed, washed with deionized water and dried to obtain the faint yellow high temperature resistant low dielectric polyphenylsulfone resin.
In some embodiments of the invention, the aprotic polar solvent is at least one of sulfolane, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylacetamide.
In some embodiments of the invention, the salt former is one or both of sodium carbonate and potassium carbonate.
In some embodiments of the invention, the water-carrying agent is at least one of toluene, xylene, mesitylene, chlorobenzene.
The third aspect of the invention provides application of the polyphenylsulfone resin in the fields of medical appliances, aerospace, electronic devices and automobiles.
The polyphenylsulfone resin obtained by the invention has high glass transition temperature and low dielectric constant, combines high temperature resistance and dielectric property, overcomes the defect that the existing polyphenylsulfone resin cannot adapt to the application scene requirements of higher temperature resistance and lower dielectric property, is suitable for the fields of medical appliances, aerospace, electronic devices and automobiles, and is especially suitable for the fields of high-frequency high-speed electronic substrates, high-temperature-resistant electronic devices, high-temperature-resistant wire cladding materials and the like.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, by introducing structural units of 3,3', 5' -tetramethyl-4, 4' -biphenol and dihydroxyl polyphenyl ether in a specific proportion, the obtained polyphenylsulfone resin has excellent high temperature resistance and dielectric property, the glass transition temperature (Tg) is more than 250 ℃, and the dielectric constant is less than 3.2.
(2) According to the invention, the glass transition temperature of the obtained polyphenylsulfone resin is up to 263.61 ℃ and the dielectric constant is as low as 3.13 by further controlling the mole percentage of structural units of 3,3', 5' -tetramethyl-4, 4' -biphenol and dihydroxyl polyphenyl ether and the structure or number average molecular weight of the dihydroxyl polyphenyl ether.
(3) The polyphenylsulfone resin obtained by the invention combines high temperature resistance and dielectric property, overcomes the defect that the existing polyphenylsulfone resin cannot meet the application scene requirements of higher temperature resistance and lower dielectric property, is suitable for the fields of medical appliances, aerospace, electronic devices and automobiles, and is especially suitable for the fields of high-frequency high-speed electronic substrates, high-temperature-resistant electronic devices, high-temperature-resistant wire cladding materials and the like.
Drawings
FIG. 1 is an infrared spectrum of a polyphenylsulfone resin in example 1 of the present invention.
FIG. 2 is a nuclear magnetic resonance spectrum of a polyphenylsulfone resin in example 1 of the present invention.
FIG. 3 is a differential scanning calorimetry chart of the polyphenylsulfone resin in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or apparatus used in the examples and comparative examples were either commercially available from conventional sources or may be obtained by prior art methods unless specifically indicated. Unless otherwise indicated, assays or testing methods are routine in the art.
The following examples of the present invention and comparative examples are described below with respect to some of the raw materials used therein:
double-end hydroxyl polyphenyl ether A has a number average molecular weight of 1500, is obtained from the university of Guangdong academy of sciences of chemical industry, and has the following structure:
wherein m+n is10 to 15.
Double-end hydroxyl polyphenyl ether B has a number average molecular weight of 2500, is from a Saber basic innovation plastics company, and has the brand SA9000 and the following structure:
wherein m+n is 18 to 23.
The purity of 3,3', 5' -tetramethyl-4, 4' -biphenol was >99.0%, and the same species were used in the examples and comparative examples of the present invention, which were obtained from the institute of chemical industry, the university of Guangdong.
4,4' -dichlorodiphenyl sulfone with purity >99.0%, hebei Xulong chemical Co., ltd, the same kind was used for the examples and comparative examples of the present invention.
The performance test of the polyphenylsulfone resins obtained in the following examples and comparative examples of the present invention is illustrated below:
infrared analysis (FT-IR): testing by using a Nicolet iS10 Fourier transform infrared spectrometer of Nicolet company in the United states and a KBr tabletting method; the test range was 4000 to 400 wavenumbers with a resolution of 4 wavenumbers.
Nuclear magnetic analysis (NMR): a suitable amount of sample is weighed and dissolved in chloroform at room temperature by using a B400-2 nuclear magnetic resonance apparatus of Bruker company, switzerland, and TMS is used as an internal standard, and the scanning frequency is 500MHz.
Inherent viscosity test: preparing a solution with the mass concentration of 0.01g/mL by taking DMAc as a solvent, wherein the test temperature is 30+/-0.1 ℃, and the inherent viscosity eta is calculated by adopting an NCY type Ubbelohde viscometer with the inner diameter of 0.7mm and the specific logarithmic viscosity eta of Shanghai Sierda scientific instruments Co., ltd., by adopting the following formula:
wherein: t represents the polymer solution run-off time; t is t 0 Represents the pure solvent run-off time; c represents the mass concentration of the solution.
Differential scanning calorimetric analysis (DSC): the heat absorption and release curves of PPSU resins were measured using a type 200F3 differential scanning calorimeter from NETZSCH, germany; the test conditions were: n (N) 2 Atmosphere, flow rate of 50mL/min, heating rate of 10 ℃/min; the test range is 40-320 ℃.
Dielectric analysis: the dielectric constant and dielectric loss of the material are tested by adopting a KEYSIGHT E5080B (9 kHz-20 GHz) vector network analyzer manufactured by De technology (China) limited company, adopting a resonant cavity method for testing with reference to the standard GB/T29306.2-2012 and adopting a 10GHz point scan.
Example 1
The embodiment provides a polyphenylsulfone resin, comprising the following monomer structural units in mole percent: 3,3', 5' -tetramethyl-4, 4' -biphenol: 45mol% of double-end hydroxyl polyphenyl ether B:5mol%, 4' -dichlorodiphenyl sulfone: 50mol%.
The preparation method of the polyphenylsulfone resin of the above example 1 can be referred to as follows:
5.75g (0.020 mol) of 4,4 '-dichlorodiphenyl sulfone, 4.35g (0.018 mol) of 3,3',5 '-tetramethyl-4, 4' -biphenol, 5.00g (0.002 mol) of double-end hydroxyl polyphenyl ether B and 40.00g of sulfolane are added into a four-neck flask with a mechanical stirring device, a thermometer, a water separator and a water condensing tube under the nitrogen atmosphere, 3.45g (0.025 mol) of anhydrous potassium carbonate and 35.00g of xylene are added after the solution is heated and stirred for dissolution, the reaction time is 2 hours, and the solution is continuously heated to 225 ℃ for polymerization reaction for 3 hours; stopping heating, pouring the reaction solution into deionized water for precipitation, filtering, drying, crushing, washing the powder with 80 ℃ deionized water for 3 times, and vacuum drying at 100 ℃ for 6 hours to obtain pale yellow polyphenylsulfone resin.
Example 2
The embodiment provides a polyphenylsulfone resin, comprising the following monomer structural units in mole percent: 3,3', 5' -tetramethyl-4, 4' -biphenol: 47.5mol% of double-ended hydroxyl polyphenylene ether B:2.5mol%, 4' -dichlorodiphenyl sulfone: 50mol%.
The preparation method of the polyphenylsulfone resin of the above example 2 can be referred to as follows:
5.75g (0.020 mol) of 4,4 '-dichlorodiphenyl sulfone, 4.60g (0.019 mol) of 3,3',5 '-tetramethyl-4, 4' -biphenol, 2.50g (0.001 mol) of double-end hydroxyl polyphenyl ether B,40.00g N-methyl pyrrolidone, 3.73g (0.027 mol) of anhydrous potassium carbonate and 45.00g of toluene are added into a four-neck flask with a mechanical stirring device, a thermometer, a water separator and a water condensation pipe under a nitrogen atmosphere, and then the four-neck flask is stirred at 125 ℃ for salifying reaction, and the reaction is continued to be carried out by heating to 235 ℃ for 2 hours; stopping heating, pouring the reaction solution into deionized water for precipitation, filtering, drying, crushing, washing the powder with 90 ℃ deionized water for 3 times, and vacuum drying at 100 ℃ for 6 hours to obtain pale yellow polyphenylsulfone resin.
Example 3
The embodiment provides a polyphenylsulfone resin, comprising the following monomer structural units in mole percent: 3,3', 5' -tetramethyl-4, 4' -biphenol: 42.5mol% of double-ended hydroxyl polyphenylene ether B:7.5mol%, 4' -dichlorodiphenyl sulfone: 50mol%.
The preparation method of the polyphenylsulfone resin of the above example 3 can be referred to as follows:
5.75g (0.020 mol) of 4,4 '-dichlorodiphenyl sulfone, 4.11g (0.017 mol) of 3,3',5 '-tetramethyl-4, 4' -biphenol, 4.50g (0.003 mol) of double-end hydroxyl polyphenyl ether A,35.00g of dimethyl sulfoxide, heating, stirring and dissolving, adding 2.97g (0.028 mol) of anhydrous sodium carbonate and 35.00g of toluene, stirring at 140 ℃ for salifying reaction, reacting for 4 hours, and continuously heating to 180 ℃ for polymerization reaction for 3 hours; stopping heating, pouring the reaction solution into deionized water for precipitation, filtering, drying, crushing, washing the powder with the deionized water at 75 ℃ for 3 times, and vacuum drying at 100 ℃ for 6 hours to obtain the pale yellow polyphenylsulfone resin.
Example 4
The embodiment provides a polyphenylsulfone resin, comprising the following monomer structural units in mole percent: 3,3', 5' -tetramethyl-4, 4' -biphenol: 40mol% of double-end hydroxyl polyphenyl ether B:10mol%, 4' -dichlorodiphenyl sulfone: 50mol%.
The preparation method of the polyphenylsulfone resin of the above example 4 can be referred to as follows:
5.75g (0.020 mol) of 4,4 '-dichlorodiphenyl sulfone, 3.88g (0.016 mol) of 3,3',5 '-tetramethyl-4, 4' -biphenol, 6.00g (0.004 mol) of double-end hydroxyl polyphenyl ether A,50.00g of N, N-dimethylacetamide are added into a four-neck flask with a mechanical stirrer, a thermometer, a water separator and a water condensing tube, the mixture is stirred at 130 ℃ for salification reaction for 4 hours, and the mixture is continuously heated to 160 ℃ for polymerization reaction for 4 hours; stopping heating, pouring the reaction solution into deionized water for precipitation, filtering, drying, crushing, washing the powder with deionized water at 85 ℃ for 3 times, and vacuum drying at 100 ℃ for 6 hours to obtain pale yellow polyphenylsulfone resin.
Comparative example 1
The comparative example provides a polyphenylsulfone resin comprising structural units of the following monomers in mole percent: 4,4' -dichlorodiphenyl sulfone: 50mol%, 4' -biphenol: 50mol%.
The preparation method of the polyphenylsulfone resin of the comparative example 1 comprises the following steps:
5.75g (0.020 mol) of 4,4 '-dichlorodiphenyl sulfone, 3.72g (0.020 mol) of 4,4' -biphenol and 40.00g of sulfolane are added into a four-neck flask with a mechanical stirring device, a thermometer, a water knockout drum and a water condensing tube under the nitrogen atmosphere, 3.45g (0.025 mol) of anhydrous potassium carbonate and 35.00g of dimethylbenzene are added after the materials are heated, stirred and dissolved, and the materials are stirred at 165 ℃ for salification reaction for 2 hours, and then the materials are continuously heated to 225 ℃ for polymerization reaction for 3 hours; stopping heating, pouring the reaction solution into deionized water for precipitation, filtering, drying, crushing, washing the powder with 80 ℃ deionized water for 3 times, and vacuum drying at 100 ℃ for 6 hours to obtain white polyphenylsulfone resin.
Comparative example 2
The comparative example provides a polyphenylsulfone resin comprising structural units of the following monomers in mole percent: 4,4' -dichlorodiphenyl sulfone: 50mol%, 3', 5' -tetramethyl-4, 4' -biphenol: 50mol%.
The preparation method of the polyphenylsulfone resin of the comparative example 2 comprises the following steps:
5.75g (0.020 mol) of 4,4 '-dichlorodiphenyl sulfone, 4.84g (0.020 mol) of 3,3',5 '-tetramethyl-4, 4' -biphenol, 35.00g of dimethyl sulfoxide, heating, stirring and dissolving, adding 2.97g (0.028 mol) of anhydrous sodium carbonate and 35.00g of toluene, stirring at 140 ℃ for salifying reaction, reacting for 4 hours, and continuously heating to 180 ℃ for polymerization reaction for 3 hours; stopping heating, pouring the reaction solution into deionized water for precipitation, filtering, drying, crushing, washing the powder with the deionized water at 75 ℃ for 3 times, and vacuum drying at 100 ℃ for 6 hours to obtain the pale yellow polyphenylsulfone resin.
Result detection
The polyphenylene sulfone resins obtained in the above examples and comparative examples were subjected to intrinsic viscosity, glass transition temperature and dielectric properties test, and the test results are shown in table 1.
TABLE 1 polyphenylene sulfone resin Performance alignment Table for examples and comparative examples
As can be seen from Table 1, the polyphenylsulfone resin obtained by introducing the structural units of 3,3', 5' -tetramethyl-4, 4 '-biphenol and double-end hydroxyl polyphenyl ether has high temperature resistance and excellent dielectric property, the glass transition temperature of the polyphenylsulfone resin is more than 250 ℃, the maximum glass transition temperature is 270 ℃, the dielectric constant is reduced to 3.2 or below, and the obtained polyphenylsulfone resin can realize the glass transition temperature of 263.61 ℃ and the dielectric constant of 3.13 simultaneously by adjusting the mole percentages of the structural units of 3,3',5 '-tetramethyl-4, 4' -biphenol and double-end hydroxyl polyphenyl ether.
The polyphenylsulfone resin of comparative example 1 contains only structural units of 4,4 '-dichlorodiphenyl sulfone and 4,4' -biphenol, has a low glass transition temperature of only 219.88 ℃ and less than 220 ℃, and has a dielectric constant of 3.64 and poor dielectric properties.
In comparative example 2, only the structural unit of 3,3', 5' -tetramethyl-4, 4' -biphenol was introduced, and although the high temperature resistance was improved, the dielectric constant was still large and the dielectric performance was poor.
FIG. 1 is an infrared spectrum of a polyphenylsulfone resin in example 1 of the present invention. As can be seen from FIG. 1, at 1383cm -1 Where s=o asymmetric stretching vibration of the sulfone group exists; at 1232cm -1 The telescopic vibration of the phenylephrine ether bond Ar-O-Ar exists; at 1150cm -1 Symmetrical telescopic vibration of sulfonyl exists at the position; at 2921cm -1 、2857cm -1 There is stretching vibration of methyl C-H on benzene ring; at 1470cm -1 There is a c=c backbone vibration of the benzene ring.
FIG. 2 is a nuclear magnetic resonance spectrum of a polyphenylsulfone resin in example 1 of the present invention. Wherein, H (7.84-7.86 ppm), H (7.26-7.31 ppm) and H (6.88-6.90 ppm) respectively correspond to three proton hydrogens on the benzene rings of the 3,3', 5' -tetramethyl-4, 4' -biphenol; h (6.47 ppm) corresponds to the proton hydrogen on the benzene ring of the double-ended hydroxyl polyphenylene ether repeating unit; h (1.99-2.31 ppm) corresponds to proton hydrogen on methyl; h (1.57 ppm) corresponds to the protic hydrogen on the isopropylidene group of TMBPA units in the double-ended hydroxy polyphenylene ether.
As can be seen from a combination of FIGS. 1 and 2, the polyphenylsulfone resin obtained in example 1 of the present invention does contain structural units of 3,3', 5' -tetramethyl-4, 4' -biphenol and double-ended hydroxyl polyphenylene ether.
FIG. 3 is a differential scanning calorimetry chart of the polyphenylsulfone resin in example 1 of the present invention. The glass transition temperature of the polyphenylsulfone resin in example 1 was 263.61 ℃according to DSC test results.
In summary, the polyphenylsulfone resin obtained by introducing the structural units of 3,3', 5' -tetramethyl-4, 4' -biphenol and dihydroxyl polyphenyl ether in a specific proportion has excellent high temperature resistance and dielectric property, the glass transition temperature (Tg) of the polyphenylsulfone resin is more than 250 ℃, the dielectric constant of the polyphenylsulfone resin is less than 3.2, the defect that the conventional polyphenylsulfone resin cannot adapt to the application scene requirements of higher temperature resistance and lower dielectric property is overcome, and the polyphenylsulfone resin is suitable for the fields of medical appliances, aerospace, electronic devices and automobiles, in particular for the fields of high-frequency high-speed electronic substrates, high-temperature-resistant electronic devices, high-temperature-resistant wire cladding materials and the like.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. A polyphenylsulfone resin comprising structural units derived from the following monomers in mole percent:
3,3', 5' -tetramethyl-4, 4' -biphenol: 35 to 50mol percent,
double-end hydroxyl polyphenyl ether: 1 to 15mol percent,
4,4' -dichlorodiphenyl sulfone: 45-55 mol percent.
2. The polyphenylsulfone resin according to claim 1, wherein the mole percentage of 3,3', 5' -tetramethyl-4, 4' -biphenol is 40 to 45mol%;
and/or, the mole percentage of the double-end hydroxyl polyphenyl ether is 5-10 mol%.
3. The polyphenylsulfone resin according to claim 1, wherein said double-ended hydroxyl polyphenylene ether has a number average molecular weight of 800 to 8000.
4. The polyphenylsulfone resin according to claim 1 or 3, wherein the double-ended hydroxyl polyphenylene ether has a structure represented by formula 1:
wherein the Y substituent is At least one of (a) and (b); m and n are integers from 0 to 50, and n > m.
5. A method for producing a polyphenylsulfone resin according to any one of claims 1 to 4, comprising the steps of:
mixing and dissolving 4,4' -dichloro diphenyl sulfone, bisphenol monomer and aprotic polar solvent, adding salifying agent and water-carrying agent, and carrying out salifying reaction and polymerization reaction to obtain polyphenylsulfone resin;
the bisphenol monomer is 3,3', 5' -tetramethyl-4, 4' -biphenol and double-end hydroxyl polyphenyl ether.
6. The preparation method according to claim 5, wherein the molar ratio of the 4,4' -dichlorodiphenyl sulfone to the bisphenol monomer is (0.7-1.3): 1;
and/or the dosage mole ratio of the bisphenol monomer and the salifying agent is1 (0.8-1.6).
7. The preparation method according to claim 5 or 6, wherein the salification reaction temperature is 120-180 ℃;
and/or the polymerization temperature is 160-250 ℃.
8. The preparation method according to claim 5, wherein the polymerization reaction is further followed by precipitation, washing and drying;
and/or the solvent temperature used for the washing is 50-100 ℃;
and/or the salt forming reaction and the polymerization reaction are carried out under inert atmosphere.
9. The method according to claim 5, wherein the aprotic polar solvent is at least one of sulfolane, N-methylpyrrolidone, dimethyl sulfoxide, and N, N-dimethylacetamide;
and/or the salt forming agent is one or two of sodium carbonate and potassium carbonate.
10. Use of the polyphenylsulfone resin according to any one of claims 1 to 4 in the fields of medical devices, aerospace, electronic devices, automobiles.
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