CN1032758C - Polyether sulfone containing diazonaphthalene structure and preparing process - Google Patents
Polyether sulfone containing diazonaphthalene structure and preparing process Download PDFInfo
- Publication number
- CN1032758C CN1032758C CN 93109180 CN93109180A CN1032758C CN 1032758 C CN1032758 C CN 1032758C CN 93109180 CN93109180 CN 93109180 CN 93109180 A CN93109180 A CN 93109180A CN 1032758 C CN1032758 C CN 1032758C
- Authority
- CN
- China
- Prior art keywords
- polyethersulfone
- reaction
- naphthyridine
- high temperature
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 5
- 239000004695 Polyether sulfone Substances 0.000 title claims description 19
- 229920006393 polyether sulfone Polymers 0.000 title claims description 19
- MBENGEYDAUUYCZ-UHFFFAOYSA-N 1-diazo-2h-naphthalene Chemical group C1=CC=C2C(=[N+]=[N-])CC=CC2=C1 MBENGEYDAUUYCZ-UHFFFAOYSA-N 0.000 title 1
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 3
- 239000002798 polar solvent Substances 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical group N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 238000000710 polymer precipitation Methods 0.000 claims description 3
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 15
- 239000011347 resin Substances 0.000 abstract description 15
- 125000001174 sulfone group Chemical group 0.000 abstract description 9
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- 229920000090 poly(aryl ether) Polymers 0.000 abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 229930185605 Bisphenol Natural products 0.000 abstract 1
- 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 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000009477 glass transition Effects 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 238000003672 processing method Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 229920002492 poly(sulfone) Polymers 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000001226 reprecipitation Methods 0.000 description 3
- 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 description 2
- YYZIUYKVJGFWIZ-UHFFFAOYSA-N 4-(1-hydroxy-2H-1,8-naphthyridin-4-yl)phenol Chemical compound ON1CC=C(C2=CC=CN=C12)C1=CC=C(C=C1)O YYZIUYKVJGFWIZ-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PZDAAZQDQJGXSW-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)benzene Chemical group C1=CC(F)=CC=C1C1=CC=C(F)C=C1 PZDAAZQDQJGXSW-UHFFFAOYSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000007891 compressed tablet Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The present invention discloses novel high temperature resistant polyarylether sulphone resin shown in the formula (I) and a method for preparing the resin. Novel bisphenol monomers shown in the formula (II) and bihalogen monomers X-Ar-X are used as raw material, wherein X can be fluorine and chlorine, and Ar of at least one kind of the bihalogen monomers contains-SO2-radicals. Salts of alkaline metal or alkaline earth metal are used as catalysts, and the high temperature resistant polyarylether sulphone resin is prepared in non protonic polar solvent through high temperature polymerization. The glass transition temperature of the polymer is as high as 295 DEG C, and the inherent viscosity reaches 0.40 to 0.45. The polymer has the characteristics of favorable toughness, high intensity, high temperature resistance, strong heat plasticity, wide application prospect, etc. and is suitable for a plurality of processing methods.
Description
The invention belongs to the synthetic of a kind of novel fire resistant polyaryl ether sulphone resin.
Polyether sulphone is the heat-proof macromolecule material of a class high comprehensive performance.According to English Patent BP1078234 and A.G.Farnham et.al., J.Polym.Sci., A-1,5,2375 (1967) reports, industrialized the earliest kind is polysulfones (PSF), this resin be by dihydroxyphenyl propane and 4,4 '-dichloro diphenyl sulfone is through progressively being polymerized:
Because Tg=195 ℃ of its second-order transition temperature can only be at 150 ℃ of following life-time service as structured material.Thereafter, English Patent BP1016245, U.S. Pat 4008203 has successively been reported the synthetic method of another kind polyethersulfone resin (PES).PES contains following repeated structural unit:
Tg=225 ℃ of its second-order transition temperature improves 30 ℃ than PSF, and its range of application has been expanded greatly than PSF, but usually also can only be at 180～200 ℃ of following life-time service as structured material.PES can adopt nucleophilic substitution progressively polymerization and electrophilic substitution progressively two kinds of methods of polymerization are synthetic:
Swiss Patent CH491981, U.S. Pat 4008203 and S.M.Cohen et al., J.Polym.Sci., A-1,4,722 (1966); J.B.Rose, Polymer, 15 (7), 456 (1974) etc. all had research and report to PES.Yet existing polyether sulphone product can only be at life-time service below 200 ℃.In recent years,, organic polymer material has been proposed requirements at the higher level, wished on the basis that guarantees excellent comprehensive performance, to improve its thermotolerance as far as possible along with development of high-tech.This point has been subjected to the attention of polymer science circle, and the high performance heat resistant macromolecular material has become an important research and development field.
The objective of the invention is from Molecular Structure Design, synthesize a kind of novel polyethersulfone that contains the naphthyridine structure, its second-order transition temperature is 295 ℃, to satisfy the heat-resisting demand of life-time service more than 260 ℃.
Content of the present invention is to be raw material with the two halogen monomers of our up-to-date novel biphenol monomer of succeeding in developing that contains the naphthyridine structure and the aromatic series that is activated, synthesized a kind of polyethersulfone that contains the naphthyridine structure, it is characterized in that the repeated structural unit that constitutes this material is:
R wherein
1, R
2Be hydrogen atom, methyl, phenyl.
Concrete synthetic method content of the present invention is the biphenol monomer and 4 to contain the naphthyridine structure, 4 '-dihalo-sulfobenzide monomer is a raw material, in polar solvent, be catalyzer with the salt of basic metal or alkaline-earth metal, at high temperature carry out polymerization, carry out azeotropic dehydration in the reaction, reaction is a precipitation agent with ethanol or methyl alcohol after finishing, and stirs down polymer precipitation is come out, filtering separation obtains polymkeric substance.
The biphenol monomer that the present invention adopts contains the naphthyridine structure, and its general structure is:
R wherein
1, R
2Be hydrogen atom, methyl, phenyl.
Two halogen monomers that the present invention adopts are 4,4 '-the dihalo-sulfobenzide, wherein halogen is arbitrary halogen, particularly fluorine or chlorine.
Polymeric reaction temperature of the present invention is controlled at 120-240 ℃, and polymerization reaction time is 12-40 hour.The equation of polyreaction can be expressed as:
If adopt two kinds of two halogen monomers simultaneously: 4,4 '-dihalo-sulfobenzide and 4,4 '-the dihalo-benzophenone, then contain simultaneously in the main polymer chain-SO
2-and-the CO-unit structure.
Polymerization process can be divided into two stages.Fs is the dehydration pre-polymerization stage, adopts toluene or dimethylbenzene azeotropic dehydration.This stage mainly generates oligopolymer, and system viscosity changes less, has large quantity of moisture to be removed.To be with the water entrainer to steam, and heat up, reaction enters subordinate phase.Subordinate phase mainly is to react between the oligopolymer, generates superpolymer, and system viscosity progressively increases.Treat that viscosity enlarges markedly, reach after the requirement, stop heating, progressively cool termination reaction.Reaction is a precipitation agent with ethanol or methyl alcohol after finishing, and stirs down polymer precipitation is come out, and filtering separation obtains polymkeric substance.Again with chloroform with polymer dissolution, with ethanol or methyl alcohol reprecipitation twice, with the polymer filtration drying, white purified high molecular weight polyether sulphone resin.
The structure of polymkeric substance is confirmed through infrared spectra and nmr analysis.Being the limiting viscosity that solvent is measured polymkeric substance with the chloroform, is 0.3～0.8 polyethersulfone resin by changing monomer ratio and polymerization time, can making limiting viscosity.
The high temperature resistant polyethersulfone resin of synthetic novel high polymer amount according to the present invention has excellent heat-resistant stability, and second-order transition temperature Tg=295 ℃, improve 70 ℃ than PES, be the highest polyaryl ether sulphone resin of present use temperature.This novel polyether sulphone resin can pass through solution-cast film forming or hotting mask compressed tablet, carries out the test of electrical property, mechanical property etc.The result shows that the limiting viscosity of this resin is greater than 0.45, and best can be the good thermoplastic resin of toughness greater than 0.5.Toughness judges with reference to U.S. Pat P4,320,224, and into about the thick film of 0.2mm, 180 ℃ of foldings are at least five times repeatedly with the solution casting legal system, and flawless is considered as toughened resin.This resin excellent combination property has very high intensity, excellent electric insulation, radiation resistance, burning is from characteristics such as breath property, and can carry out the solution casting film forming, compression molding, extrude, multiple mode such as injection processes.
Most preferred embodiment
Embodiment 1. is under nitrogen protection, with 285.9g (1.2 moles) 1-hydroxyl-4-(4-hydroxy phenyl) naphthyridine, 344.6g (1.2 moles) 4,4 '-dichloro diphenyl sulfone, 248.8g (1.8 moles) anhydrous K
2CO
3, 1700ml N,N-DIMETHYLACETAMIDE and 400ml toluene joins in the reactor that agitator, thermometer, reflux water-dividing device and nitrogen inlet are housed, stir, the heat temperature raising reaction, under 145 ℃, azeotropic reflux dewatering 5 hours has big water gaging to be steamed separation removal.Then, steam most of toluene.Temperature is raised to 165-170 ℃, keeps refluxing on a small quantity, continues reaction 18 hours.Reaction system is by the light yellow brown that changes into gradually, and system viscosity obviously increases.After reaction finishes, add N,N-DIMETHYLACETAMIDE reaction mixture is diluted, filter.Polymers soln under high-speed stirring, with ethanol as precipitation agent, with the polymkeric substance precipitating, filter, drain.Again with chloroform dissolving, ethanol reprecipitation.Repeat once to obtain polymkeric substance, this polymkeric substance 80 ℃ of vacuum-dryings 24 hours, is obtained purified polyaryl ether sulphone resin, its limiting viscosity is 0.47, and second-order transition temperature Tg is 295 ℃.
Embodiment 2. is under nitrogen protection; with 285.9g (1.2 moles) 1-hydroxyl-4-(4-hydroxy phenyl) naphthyridine, 258.4g (0.9 mole) 4; 4 '-dichloro diphenylsulfone, 65.46g (0.3 mole) 4,4 '-difluorodiphenyl base ketone, 248.8g (1.8 moles) anhydrous K
2CO
3, 1600ml N,N-DIMETHYLACETAMIDE and 400ml toluene joins in the reactor, stir and be warming up to 150 ℃, azeotropic reflux dewatering 5 hours, steam large quantity of moisture and most of toluene, 180 ℃ keep down refluxing, reacted 20 hours, to brown, system viscosity obviously increases reaction system by pale yellow.After reaction finished, through precipitation, reprecipitation obtained polymkeric substance.It 80 ℃ of vacuum-dryings 24 hours, is obtained limiting viscosity and is 0.53 the good polyethersulfone ketone copolymer resin of toughness.
Claims (5)
1. polyethersulfone that contains the naphthyridine structure is characterized in that the repeated structural unit that constitutes this polyethersulfone is:
R wherein
1, R
2Be hydrogen atom, methyl, phenyl.
2. one kind is reaction solvent with non-proton type polar solvent, salt with basic metal or alkaline-earth metal is the method that Preparation of Catalyst contains the polyethersulfone of naphthyridine structure, it is characterized in that it being biphenol monomer and 4 to contain the naphthyridine structure, 4 '-dihalo-sulfobenzide monomer is a raw material, at high temperature carry out polyreaction, temperature of reaction is 120-240 ℃, reaction times is 12-40 hour, carry out azeotropic dehydration in the reaction, after reaction finishes, add precipitation agent, stir down polymer precipitation is come out, filtering separation obtains polymkeric substance.
3. the preparation method that contains the polyethersulfone of naphthyridine structure according to claim 2 is characterized in that with toluene or dimethylbenzene as azeotropy dehydrant.
4. the preparation method that contains the polyethersulfone of naphthyridine structure according to claim 3 is characterized in that with methyl alcohol or ethanol as precipitation agent.
5. the preparation method that contains the polyethersulfone of naphthyridine structure according to claim 4, it is characterized in that if adopt 4,4 simultaneously '-dihalo-sulfobenzide and 4,4 '-two kinds of two halogen monomers of dihalo-benzophenone, then contain simultaneously in the main polymer chain-SO
2-and-the CO-unit structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93109180 CN1032758C (en) | 1993-07-26 | 1993-07-26 | Polyether sulfone containing diazonaphthalene structure and preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93109180 CN1032758C (en) | 1993-07-26 | 1993-07-26 | Polyether sulfone containing diazonaphthalene structure and preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1098113A CN1098113A (en) | 1995-02-01 |
| CN1032758C true CN1032758C (en) | 1996-09-11 |
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ID=4987514
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93109180 Expired - Lifetime CN1032758C (en) | 1993-07-26 | 1993-07-26 | Polyether sulfone containing diazonaphthalene structure and preparing process |
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| Country | Link |
|---|---|
| CN (1) | CN1032758C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004096418A1 (en) * | 2003-05-01 | 2004-11-11 | Tsinghua University | Hollow fiber ultrafilter membrane with poly(phthalazinone ether fulfone), poly(phthalazinone ether ketone) or poly(phthalazinone ether sulfone ketone) and preparation thereof |
| CN100443543C (en) * | 2005-09-09 | 2008-12-17 | 大连理工大学 | Method for interface modification of continuous fibre reinforced polyarylether resin-base composite materials containing diazacyclo group |
| KR101637267B1 (en) * | 2010-12-02 | 2016-07-08 | 현대자동차 주식회사 | Poly(arylene ether) copolymer having cation-exchange group, process of manufacturing the same, and use thereof |
| CN102831964A (en) * | 2012-07-27 | 2012-12-19 | 河南华泰特种电缆有限公司 | Heterocycle biphenyl polyether sulfone insulting special cable |
| CN114479062A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Polyaryletherketone containing naphthalene structure and preparation method thereof |
-
1993
- 1993-07-26 CN CN 93109180 patent/CN1032758C/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| CN1098113A (en) | 1995-02-01 |
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