CN103642031A - High-fluidity polyphenylenesulfoneketone resin and industrial production technology thereof - Google Patents
High-fluidity polyphenylenesulfoneketone resin and industrial production technology thereof Download PDFInfo
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- CN103642031A CN103642031A CN201310609135.3A CN201310609135A CN103642031A CN 103642031 A CN103642031 A CN 103642031A CN 201310609135 A CN201310609135 A CN 201310609135A CN 103642031 A CN103642031 A CN 103642031A
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- benzophenone
- polyphenylene ether
- ether sulfone
- dihalo
- ketone resin
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- 239000011347 resin Substances 0.000 title claims abstract description 32
- 229920005989 resin Polymers 0.000 title claims abstract description 32
- 238000005516 engineering process Methods 0.000 title claims abstract description 11
- 238000009776 industrial production Methods 0.000 title abstract description 3
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 239000007787 solid Substances 0.000 claims abstract description 25
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 150000003457 sulfones Chemical group 0.000 claims abstract description 6
- 150000002576 ketones Chemical group 0.000 claims abstract description 3
- 239000012965 benzophenone Substances 0.000 claims description 24
- 229920001955 polyphenylene ether Polymers 0.000 claims description 19
- -1 sulfone ketone Chemical class 0.000 claims description 19
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 16
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical group O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000004305 biphenyl Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 10
- 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 description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- DSNHSQKRULAAEI-UHFFFAOYSA-N 1,4-Diethylbenzene Chemical compound CCC1=CC=C(CC)C=C1 DSNHSQKRULAAEI-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical group C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 210000003097 mucus Anatomy 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 229920006393 polyether sulfone Polymers 0.000 claims description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000005323 carbonate salts Chemical class 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 3
- YXMYPHLWXBXNFF-UHFFFAOYSA-N (2-chlorophenyl)-(4-chlorophenyl)methanone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1Cl YXMYPHLWXBXNFF-UHFFFAOYSA-N 0.000 claims description 2
- QSWKFJLPMWWZJE-UHFFFAOYSA-N (4-chlorophenyl)-(2-fluorophenyl)methanone Chemical compound FC1=CC=CC=C1C(=O)C1=CC=C(Cl)C=C1 QSWKFJLPMWWZJE-UHFFFAOYSA-N 0.000 claims description 2
- QRFMXBKGNQEADL-UHFFFAOYSA-N 1,1'-biphenyl;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.C1=CC=CC=C1C1=CC=CC=C1 QRFMXBKGNQEADL-UHFFFAOYSA-N 0.000 claims description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000003021 water soluble solvent Substances 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 9
- 150000008365 aromatic ketones Chemical class 0.000 abstract description 7
- 238000007334 copolymerization reaction Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 229920006260 polyaryletherketone Polymers 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract description 3
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 abstract 2
- 229920000491 Polyphenylsulfone Polymers 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 17
- 125000001174 sulfone group Chemical group 0.000 description 14
- 125000000468 ketone group Chemical group 0.000 description 13
- 239000004721 Polyphenylene oxide Substances 0.000 description 11
- 229920000570 polyether Polymers 0.000 description 11
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229920000090 poly(aryl ether) Polymers 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- ZHUXSAKDWNNBCQ-UHFFFAOYSA-N (3-fluorophenyl)-(4-fluorophenyl)methanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=CC(F)=C1 ZHUXSAKDWNNBCQ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 150000001492 aromatic hydrocarbon derivatives Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Polyethers (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention discloses a high-fluidity polyphenylenesulfoneketone (PPSUK) resin. Aromatic ketone monomers (especially heterogeneous aromatic ketone monomers) are introduced into a PPSU polymer to carry out copolymerization reactions so as to obtain the PPSUK resin, whose main chain comprises a random copolymerization structure composed of poly(aryl ether sulfone) and poly(aryl ether ketone), wherein the mole ratio of poly(aryl ether sulfone) group to poly(aryl ether ketone) group is in a range of (5 to 9):1. The industrial production technology comprises two phases, namely a salt forming phase and a polymerization phase; wherein the solid content of the system in the salt forming phase is 20% to 25%, and the solid content in the polymerization phase is 35% to 45%. The processing temperature and molding temperature of the PPSUK resin is usually not higher than 350 DEG C; the PPSUK resin has a high fluidity, is easy to process, and has an excellent solvent-resistant performance, so the product application area is enlarged.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of high-flow polyphenylene ether sulfone ketone resin PPSUK and industrialized producing technology thereof.
Background technology
Polyether sulphone is a kind of high performance engineering plastics, because they have thermotolerance, hot water resistance, creep resistance, dimensional stability, shock-resistance, chemical proofing, the excellent over-all properties such as nontoxic, fire-retardant, thus for a long time electronics, electrical equipment, machinery, automobile, medical apparatus, food-processing and not the field such as stickness paint be widely used.
Industrial important polyether sulphone comprises polyethersulfone (PES) and biphenyl polyether sulfone (PPSU), all has very high second-order transition temperature (~ 220 ℃).In use, because polyether sulphone has higher melt viscosity, be not easy the product of molding structure complexity, and in moulding product, have bubble, the defect such as hollow, therefore in the urgent need to improving its processing fluidity, can keep its excellent thermal characteristics and don't the impact transparency, expand its range of application simultaneously.In addition, polyether sulphone is more responsive to some chemical solvents, and pressure embrittlement problem easily occurs.
Copolymerization is a kind of effective ways that change molecular structure, if Chinese patent CN200910217764 is by biphenyl sulfone ether and polyethersulfone terpolymer, can change the Tg of polymkeric substance.American documentation literature US20100310804A1 discloses a kind of method of ketone group containing polyether sulphone, it is to take sulfobenzide as solvent, the mixture of sodium carbonate and salt of wormwood is salt forming agent, 275 ℃ of polyreactions, later stage adds end-capping reagent, anti-depolymerizing agent etc., prepared fusing point from the PPSK of 319 ~ 360 ℃, but unexposed its industrial process.Chinese patent literature CN102757561A discloses a kind of ketone group containing polyethersulfone resin, mol ratio containing sulfone monomer and ketone group containing monomer is 9:1 ~ 1:1, and it is to take tetramethylene sulfone as solvent, and toluene is a minute aqua, potassium hydroxide solution is salt forming agent, but unexposed its industrialized preparing process.
In actual production and application, the polyether sulphone that does not add ketone group monomer is amorphous, and because the viscosity of itself is higher, thereby processing temperature surpasses 360 ℃ conventionally, reaches 380 ℃ or higher, therefore in some industry, can not apply.Add ternary or the multi-component copolymer polyether sulphone of ketone group monomer to occur regular phenomenon, have fixing fusing point, because the introducing of ketone group has increased the regularity of molecule, its mobility is also improved.When ketone group containing monomer ratio be greater than sulfuryl monomer and ketone group monomer sum 30% time, the cycle that polyreaction can be more difficult, polymerization is produced is longer, thereby can cause the higher problem of product color and fusing point, especially when ketone group containing monomer ratio be greater than sulfuryl monomer and ketone group monomer sum 40% time, at the temperature lower than 240 ℃, polyreaction occurs hardly.When ketone group containing monomer ratio be greater than sulfuryl monomer and ketone group monomer sum 25% time, the Tm of the random copolymers of gained is greater than 350 ℃, its processing temperature of the product of gained can reach 380 ℃ or higher equally, thereby causes processing difficulties, is difficult to be widely used.In addition, the transparency of its product also has certain decline.Therefore, controlling ketone group containing monomer ratio in the reasonable scope, is the scheme of developing the polyaryletherketone simple possible of high workability, easy processing, chemical solvent resistance energy and radiance.
Many employings of technique system solid content of existing production polyaryl ether sulphone resin is left and right in 20 ~ 25% scopes, produces one ton of polyaryl ether sulphone resin and need to add 3 tons of tetramethylene sulfone.There is following defect in this kind of technique: under (1) identical device condition, the production capacity of polyether sulphone is low; (2) due to tetramethylene sulfone unstable at high temperature, thereby make the rate of recovery of tetramethylene sulfone in whole technical process only in 80% left and right, that is to say that 1 ton of polyether sulphone of every production will lose 600.00KG tetramethylene sulfone, increase production of resins cost.If directly improve the solid content of polymerization system, if design system solid content is in 30 ~ 40% scopes, we find that speed of response is not accelerated along with the increase of concentration in tetramethylene sulfone system, increase speed of response along with concentration declines on the contrary, when solid content is 30 ~ 35% time, speed of response is dropped by nearly half, and increases production cost.
Summary of the invention
The object of the invention is to overcome above-mentioned prior art defect, a kind of high workability, easy processing, chemical solvent resistance polyphenylene ether sulfone ketone resin are provided.
A kind of high-flow polyphenylene ether sulfone ketone resin of the present invention, its structural formula is
Wherein Ar representative
;
A:(b+c wherein)=5 ~ 9:1,0≤c≤0.1b.
Preferably, 0.75<a<0.9,0.1<b<0.25,0<c<0.05.
Work as c=0, a/b >=99 o'clock, are biphenyl bis-phenol, benzene sulfone and Benzophenone membered copolymer, and molecular structure is close to PPSU, and molecule macroscopic properties and polyphenylene ether sulfone are suitable.
Work as c=0, during 1 < a/b < 99, molecular structure is polyethersulfone ketone multipolymer.
Another object of the present invention is to provide a kind of industrialized producing technology of the above-mentioned high-flow polyphenylene ether sulfone ketone resin that improves production capacity, reduces production costs, and comprises the following steps:
(1) salt-forming reaction
With 4,4'-'-biphenyl diphenol, 4,4'-dichloro diphenyl sulfone, 4,4'-dihalo-benzophenone and 3,4'-dihalo-benzophenone are reaction monomers,
In the reactor of nitrogen filled protection, in non-proton intensive polar solvent, add in turn 4, 4'-'-biphenyl diphenol, 4, 4'-dichloro diphenyl sulfone, 4, 4'-dihalo-benzophenone, system solid content is 20 ~ 45%, and start stirring heating, until temperature, reach after 65 ~ 80 ℃, continue to be stirred to after the whole dissolvings of monomer, be warmed up to 100 ℃ adds than added 4 in system again, the alkaline carbonate salt forming agent of 4'-'-biphenyl diphenol mole number excessive 5 ~ 20%, and add subsequently a minute aqua, under agitation continue to heat up, system starts salt-forming reaction, temperature is controlled between 190 ~ 220 ℃, until system aquifer yield, reach after theoretical value, discharge water and minute aqua, system is increased the temperature between 230 ~ 240 ℃ again,
Solid content in salt-forming reaction stage system is 20% ~ 25%.
(2) polyreaction
Above-mentioned reaction mixture is proceeded to and is full of nitrogen and has been warming up in the reactor of 220 ℃ ~ 240 ℃, beginning is stirred with the stirring velocity of 50 ~ 70 turn/min, constant temperature strengthened stirring velocity to 70 ~ 90 after 0.5 ~ 1.0 hour turn/min, add 3,4'-dihalo-benzophenone, continue constant temperature and within 0.5 ~ 1.0 hour, arrive setting viscosity, obtain polymerization mucus; Wherein, 4,4'-dichloro diphenyl sulfone, 4, it is identical with 4,4'-'-biphenyl diphenol mole number that the monomer molar of 4'-dihalo-benzophenone and 3,4'-dihalo-benzophenone is counted sum;
Wherein, the solid content in polymerization stage system is 35 ~ 45%;
(3) aftertreatment
After stopped reaction, polymkeric substance mucus is ground into powder through water cooling, filters and obtain containing polymkeric substance, water-soluble solvent and salt; And then the powder containing polymkeric substance is removed to desolventizing and salt with deionized water boiling washing again, drier, obtain multiple copolymer.
Described 4,4'-dihalo-benzophenone is contraposition aromatic ketone monomer, and its structural formula is
wherein, X=F or Cl, Y=F or Cl, be specially 4,4'-difluoro benzophenone, 4, the chloro-4'-fluorine of 4'-dichloro benzophenone or 4-benzophenone.
Described 3,4'-dihalo-benzophenone is position aromatic ketone monomer between isomery, and its structural formula is
, wherein, X=F or Cl, Y=F or Cl, be specially the fluoro-4'-fluorine of 3-benzophenone, the chloro-4'-chlorobenzophenone of 3-, the fluoro-4'-chlorobenzophenone of 3-or the chloro-4'-fluorine of 3-benzophenone.
Described non-proton strong polar organic solvent is tetramethylene sulfone, sulfobenzide, dimethyl sulfoxide (DMSO), N,N-dimethylacetamide or N-Methyl pyrrolidone, preferably tetramethylene sulfone.
Described alkaline carbonate salt forming agent is Na
2cO
3or K
2cO
3or the mixture of its different ratios, preferred domestic Na
2cO
3.
Described minute aqua be containing the aromatic hydrocarbon derivative of alkyl, comprises toluene, dimethylbenzene, trimethylbenzene, durene, ethylbenzene, p-Diethylbenzene, a kind of in diethylbenzene or mixture that these are several partially.Described minute aqua preferably 200 ° of C of 160 ° of C< boiling point < and density is less than the organic minute aqua of hypotoxicity of water, is specially sym-trimethylbenzene, hemimellitol, a trimethylbenzene, p-Diethylbenzene, the mixture of one or more in diethylbenzene or durene partially.Adopt high boiling minute aqua, reaction heat-up rate is obviously faster than the heat-up rate that adopts lower boiling dimethylbenzene for minute aqua, can shorten 1 ~ 2 hour single batch of reaction time in industrial production, reduces production energy consumption, reduces material local temperature.
The present invention in 200 ~ 210 ° of C, completes prepolymerisation stage at salt-forming stage system temperature simultaneously, at salt-forming stage, forms low-molecular-weight performed polymer, and number and the residing concentration of monomer of performed polymer molecular chain are directly related.Increase pre-polymerization scale of construction increase along with monomer concentration, monomer concentration step-down after performed polymer is increased to a certain degree in system, cause later stage polymerization velocity to weaken, there is the too high speed of response of solid content slack-off phenomenon on the contrary, therefore, the present invention is preferred, and at salt-forming reaction stage system solid content, controlling is 20% ~ 25%, at polymerization stage system solid content, controlling is 35 ~ 45%, thereby guarantees the concentration of polymerization stage monomer.Polymerization stage high solids content is conducive to polyreaction, can greatly reduce the consumption of crucial solvent sulfolane, reduces energy consumption, cost-saving.
The present invention compared with prior art, has following beneficial effect:
1) the invention provides a kind of aromatic ketone monomer of introducing in PPSU polymkeric substance, especially isomery aromatic ketone monomer copolymerization, aromatic ketone monomer accounts for 10 ~ 25% of fragrant sulfone monomer molar total amount, on the polyphenylene ether sulfone ketone resin molecular backbone chain preparing, contain polyether sulphone and polyaryletherketone random copolymerization structure, wherein
group with
the mol ratio of group is between 5 ~ 9:1, and the fusing point of resulting product is between 305 ~ 340 ℃, and its machine-shaping temperature is not conventionally higher than 350 ℃; Melting index, between 28.0 ~ 36g/10min, has higher mobility, is easy to processing, can be widely used in various thin-gage goods;
2) the present invention, by being controlled to the solid content of salt phase and polymerization stage, can greatly reduce the consumption of crucial solvent sulfolane,
Improve production capacity nearly 1/3rd.In 40% solid content, 1 ton of polyaryl ether sulphone resin of every production only needs, with 1.5 tons of tetramethylene sulfone, by the rate of recovery of tetramethylene sulfone 80%, to compare and directly lose less 300KG tetramethylene sulfone with 25% solid content technique, has greatly saved cost;
3) pattern of process using of the present invention two stills series connection, after salify completes, proceeds to polymeric kettle after steaming whole minute aquas again,
The production cycle of technique and the system production cycle of 25% solid content of producing are stage by stage basically identical, and two still tandem process can improve one times of production capacity, can realize production capacity and maximize;
4) the present invention adopts high boiling minute aqua energy Reaction time shorten, improves production capacity;
5) salt forming agent of the present invention adopts the Na that produce China's Mainland
2cO
3, save purchase cost; In addition excessive Na
2cO
3form with powder is present in system, and hydrolysis alkalescence is obviously than KOH, NaOH and K
2cO
3system is low, a little less than the toxic side effect of system, and adopts domestic Na
2cO
3the polyether sulphone product of explained hereafter and use import Na
2cO
3for the product that salt forming agent is produced is distinguished without color and luster;
6) the prepared polymkeric substance of the present invention has excellent solvent resistance, has expanded product applications, is especially applicable to application
In various petrochemicals; The prepared polymkeric substance of the present invention also has excellent resistance to x radiation x performance, can be widely used in medicine equipment goods and food, health rank goods; The prepared polymkeric substance of the present invention has excellent impact resistance and high-temperature behavior, can be applicable to motor car engine periphery goods, is particularly useful for automobile oil pipe.
Embodiment
Below by embodiment, further illustrate the present invention, following examples are the concrete embodiment of the present invention, but embodiments of the present invention are not subject to the restriction of following embodiment.
Embodiment 1
In 300 liters of stainless steel cauldrons of logical nitrogen tube and condensation water trap and high-efficiency stirrer are housed, first add to start to stir after 75.00 KG tetramethylene sulfone and be warming up to 80 ℃, add in turn 31.5 KG 4, 4'-dichloro diphenyl sulfone, 2.5KG 4, 4'-difluoro benzophenone, 22.50 KG 4, 4'-'-biphenyl diphenol, after monomer all dissolves, when being warming up to 100 ℃, in system, add 14.0 KG sodium carbonate again, add subsequently 60.0 liters of durenes, under continuing to stir, be warming up to 200 ℃, salt-forming reaction starts, the water generating in system and durene azeotropic, in prolong, starting has water coolant to drip, layering in water trap, treat upper strata durene from muddiness become clarification continue again to reflux 20 minutes complete to guarantee salt-forming reaction, salt-forming stage 1 hour, the system solid content in salt-forming reaction stage is 25%, after completing, salify steams whole durenes, be warming up to again 230 ℃, squeeze into and utilize in advance purity nitrogen to replace and to be warming up in 200 liters of stainless steel cauldrons of 230 ℃, the stirring velocity that beginning turns with per minute 60 stirs, and constant temperature adds 160.0g 3,4'-difluoro benzophenone after 1.0 hours, strengthening stirring velocity to per minute 80 turns, continue constant temperature and within 0.5 ~ 1.0 hour, arrive setting viscosity, obtain polymerization mucus, the system solid content of polymerization stage is 35%, by the directly cooling rear pulverizing of film forming on Stainless Steel Band water cooler of polymerization mucus, then add new deionized water to boil 1 hour in the powder after filtering, 8 ~ 10 times so repeatedly, until in water chloride ion content below 5ppm.By the polymkeric substance vacuum-drying after filtering to moisture weight content lower than 0.5%, obtain polyphenylene ether sulfone ketone (PPSUK) virgin resin.
Gained PPSUK resin melting index M I=28.5 g/10min (350.0 ℃, 5KG).
Fusing point is: 319 ℃
Embodiment 2
With embodiment 1, except adding the amount of 4,4'-dichloro diphenyl sulfone, be that the amount of 29.75KG and 4,4'-difluoro benzophenone is 3.75KG, p-Diethylbenzene replaces durene, and the system solid content of polymerization stage is 40%, and other conditions are identical.
Gained PPSUK resin melting index M I=36.2 g/10min (350.0 ℃, 5KG);
Fusing point is: 315 ℃
Embodiment 3
With embodiment 1, except adding the amount of 4,4'-dichloro diphenyl sulfone, be 29.75KG and 4, the amount of 4'-difluoro benzophenone is 3.65KG, 3, and the amount of 4'-difluoro benzophenone is 260.0 g, and diethylbenzene replaces outside durene partially, the system solid content of polymerization stage is 38%, and other conditions are identical.
Gained PPSUK resin melting index M I=36.0 g/10min (350.0 ℃, 5KG);
Fusing point is: 315 ℃
Embodiment 4
With embodiment 1, the amount that is 5.0KG, 3,4 ￠-difluoro benzophenone except the amount of 4, the 4'-dichloro diphenyl sulfone amount that is 28.0KG and 4,4'-difluoro benzophenone is outside 400.0 g, and the system solid content of polymerization stage is 40%, and other conditions are identical.
Gained PPSUK resin melting index M I=32.2 g/10min (350.0 ℃, 5KG).
Fusing point is: 310 ℃
Embodiment 5
With embodiment 1, the amount that is 28.0KG and 4,4'-difluoro benzophenone except the amount of 4,4'-dichloro diphenyl sulfone is 5.0KG, 3, and the amount of 4'-difluoro benzophenone is outside 300.0 g, and the system solid content of polymerization stage is 39%, and other conditions are identical.
Gained PPSUK resin melting index M I=32.0 g/10min (350.0 ℃, 5KG).
Fusing point is: 310 ℃.
Claims (10)
1. a high-flow polyphenylene ether sulfone ketone resin, its structural formula is
Wherein Ar representative
;
A:(b+c wherein)=5 ~ 9:1,0≤c≤0.1b.
2. high-flow polyphenylene ether sulfone ketone resin according to claim 1, it is characterized in that, 0.75<a<0.9,0.1<b<0.25,0<c<0.05.
3. high-flow polyphenylene ether sulfone ketone resin according to claim 1, is characterized in that, works as c=0, a/b >=99
Time, be biphenyl bis-phenol, benzene sulfone and Benzophenone membered copolymer, molecule macroscopic properties and polyphenylene ether sulfone are suitable.
4. high-flow polyphenylene ether sulfone ketone resin according to claim 1, is characterized in that, works as c=0, and during 1 < a/b < 99, molecular structure is polyethersulfone ketone multipolymer.
5. the industrialized producing technology of the high-flow polyphenylene ether sulfone ketone resin described in claim 1 ~ 4 any one, is characterized in that, comprises the following steps:
(1) salt-forming reaction
With 4,4'-'-biphenyl diphenol, 4,4'-dichloro diphenyl sulfone, 4,4'-dihalo-benzophenone and 3,4'-dihalo-benzophenone are reaction monomers,
In the reactor of nitrogen filled protection, in non-proton intensive polar solvent, add in turn 4, 4'-'-biphenyl diphenol, 4, 4'-dichloro diphenyl sulfone, 4, 4'-dihalo-benzophenone, and start stirring heating, until temperature, reach after 65 ~ 80 ℃, continue to be stirred to after the whole dissolvings of monomer, be warmed up to 100 ℃ adds than added 4 in system again, the alkaline carbonate salt forming agent of 4'-'-biphenyl diphenol mole number excessive 5 ~ 20%, and add subsequently a minute aqua, under agitation continue to heat up, system starts salt-forming reaction, temperature is controlled between 190 ~ 220 ℃, until system aquifer yield, reach after theoretical value, discharge water and minute aqua, system is increased the temperature between 230 ~ 240 ℃ again, solid content in salt-forming reaction stage system is 20% ~ 25%,
(2) polyreaction
Above-mentioned reaction mixture is proceeded to and is full of nitrogen and has been warming up in the reactor of 220 ℃ ~ 240 ℃, beginning is stirred with the stirring velocity of 50 ~ 70 turn/min, constant temperature strengthened stirring velocity to 70 ~ 90 after 0.5 ~ 1.0 hour turn/min, add 3,4'-dihalo-benzophenone, continue constant temperature and within 0.5 ~ 1.0 hour, arrive setting viscosity, obtain polymerization mucus; Wherein, 4,4'-dichloro diphenyl sulfone, 4, it is identical with 4,4'-'-biphenyl diphenol mole number that the monomer molar of 4'-dihalo-benzophenone and 3,4'-dihalo-benzophenone is counted sum;
Wherein, the solid content in polymerization stage system is 35 ~ 45%;
(3) aftertreatment
After stopped reaction, polymkeric substance mucus is ground into powder through water cooling, filters and obtain containing polymkeric substance, water-soluble solvent and salt; And then the powder containing polymkeric substance is removed to desolventizing and salt with deionized water boiling washing again, drier, obtain multiple copolymer.
6. the industrialized producing technology of high-flow polyphenylene ether sulfone ketone resin according to claim 5, is characterized in that, described 4, and 4'-dihalo-benzophenone is 4,4'-difluoro benzophenone, 4, the chloro-4'-fluorine of 4'-dichloro benzophenone or 4-benzophenone.
7. the Industrialized synthesis method of high-flow polyphenylene ether sulfone ketone resin according to claim 5, it is characterized in that, described 3,4'-dihalo-benzophenone is the fluoro-4'-fluorine of 3-benzophenone, the chloro-4'-chlorobenzophenone of 3-, the fluoro-4'-chlorobenzophenone of 3-or the chloro-4'-fluorine of 3-benzophenone.
8. the industrialized producing technology of high-flow polyphenylene ether sulfone ketone resin according to claim 5, it is characterized in that, described non-proton strong polar organic solvent is tetramethylene sulfone, sulfobenzide, dimethyl sulfoxide (DMSO), N,N-dimethylacetamide or N-Methyl pyrrolidone, preferably tetramethylene sulfone.
9. the industrialized producing technology of high-flow polyphenylene ether sulfone ketone resin according to claim 5, is characterized in that, described alkaline carbonate salt forming agent is Na
2cO
3or K
2cO
3or the mixture of its different ratios, preferred domestic Na
2cO
3.
10. the industrialized producing technology of high-flow polyphenylene ether sulfone ketone resin according to claim 5, it is characterized in that, described minute aqua is to comprise toluene, dimethylbenzene, trimethylbenzene, durene, ethylbenzene, diethylbenzene or the mixture of one or more in diethylbenzene partially, preferably 200 ° of C of 160 ° of C< boiling point < and density are less than the organic minute aqua of hypotoxicity of water, are specially sym-trimethylbenzene, hemimellitol, a trimethylbenzene, p-Diethylbenzene, the mixture of one or more in diethylbenzene or durene partially.
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| CN103613763A (en) * | 2013-11-27 | 2014-03-05 | 江门市优巨新材料有限公司 | High-fluidity polyphenylene ether sulfone ketone resin and industrial synthesis method thereof |
| CN104497300A (en) * | 2014-12-17 | 2015-04-08 | 江门市优巨新材料有限公司 | High-liquidity poly(phenylene ether sulfone ketone) resin and preparation method thereof |
| CN104497301A (en) * | 2014-12-17 | 2015-04-08 | 江门市优巨新材料有限公司 | High-fluidity polysulfone ketone resin and production process thereof |
| WO2022042814A1 (en) * | 2020-08-24 | 2022-03-03 | Basf Se | Polyphenylene sulfone |
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Cited By (4)
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| CN103613763A (en) * | 2013-11-27 | 2014-03-05 | 江门市优巨新材料有限公司 | High-fluidity polyphenylene ether sulfone ketone resin and industrial synthesis method thereof |
| CN104497300A (en) * | 2014-12-17 | 2015-04-08 | 江门市优巨新材料有限公司 | High-liquidity poly(phenylene ether sulfone ketone) resin and preparation method thereof |
| CN104497301A (en) * | 2014-12-17 | 2015-04-08 | 江门市优巨新材料有限公司 | High-fluidity polysulfone ketone resin and production process thereof |
| WO2022042814A1 (en) * | 2020-08-24 | 2022-03-03 | Basf Se | Polyphenylene sulfone |
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