CN110591095A - Synthetic method of polyphenylene sulfide and polysulfone thioether block polymer - Google Patents
Synthetic method of polyphenylene sulfide and polysulfone thioether block polymer Download PDFInfo
- Publication number
- CN110591095A CN110591095A CN201910852911.XA CN201910852911A CN110591095A CN 110591095 A CN110591095 A CN 110591095A CN 201910852911 A CN201910852911 A CN 201910852911A CN 110591095 A CN110591095 A CN 110591095A
- Authority
- CN
- China
- Prior art keywords
- reaction
- heating
- temperature
- kettle
- polysulfone
- 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.)
- Pending
Links
- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 65
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 65
- 229920000642 polymer Polymers 0.000 title claims abstract description 48
- 229920002492 poly(sulfone) Polymers 0.000 title claims abstract description 46
- 150000003568 thioethers Chemical class 0.000 title claims abstract description 26
- 238000010189 synthetic method Methods 0.000 title claims description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 213
- 238000000034 method Methods 0.000 claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 23
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 22
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 162
- 238000010438 heat treatment Methods 0.000 claims description 87
- 239000000463 material Substances 0.000 claims description 81
- 229910052757 nitrogen Inorganic materials 0.000 claims description 81
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims description 47
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims description 47
- 238000001816 cooling Methods 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 32
- 238000001914 filtration Methods 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000012295 chemical reaction liquid Substances 0.000 claims description 22
- 239000012752 auxiliary agent Substances 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 19
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 11
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 11
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 9
- 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 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 7
- 239000001632 sodium acetate Substances 0.000 claims description 7
- 235000017281 sodium acetate Nutrition 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000007867 post-reaction treatment Methods 0.000 claims description 6
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical group ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 5
- CMVQZRLQEOAYSW-UHFFFAOYSA-N 1,2-dichloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1Cl CMVQZRLQEOAYSW-UHFFFAOYSA-N 0.000 claims description 5
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims 8
- 239000011541 reaction mixture Substances 0.000 claims 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 8
- 125000000101 thioether group Chemical group 0.000 abstract description 5
- 239000002798 polar solvent Substances 0.000 abstract description 4
- 239000011780 sodium chloride Substances 0.000 abstract description 4
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 125000001174 sulfone group Chemical group 0.000 abstract description 3
- ODPYDILFQYARBK-UHFFFAOYSA-N 7-thiabicyclo[4.1.0]hepta-1,3,5-triene Chemical group C1=CC=C2SC2=C1 ODPYDILFQYARBK-UHFFFAOYSA-N 0.000 abstract description 2
- 229920001400 block copolymer Polymers 0.000 abstract description 2
- 239000000155 melt Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 229920002994 synthetic fiber Polymers 0.000 abstract 1
- -1 sulfide sulfone Chemical class 0.000 description 7
- 229920000412 polyarylene Polymers 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 150000003457 sulfones Chemical class 0.000 description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- RWCMHQZUYWBVAE-UHFFFAOYSA-N OS(=O)(=O)S(=O)(=O)S(O)(=O)=O Chemical compound OS(=O)(=O)S(=O)(=O)S(O)(=O)=O RWCMHQZUYWBVAE-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0245—Block or graft polymers
-
- 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
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/025—Preparatory processes
- C08G75/0254—Preparatory processes using metal sulfides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention relates to a method for synthesizing polyphenylene sulfide and polysulfone thioether block polymer, which comprises the steps of synthesizing oligomers in three stages respectively to finally obtain a block copolymer of n phenylene sulfide groups and m sulfone groups, wherein the synthesis method comprises the steps of synthesizing micromolecule oligomers in stages, then chain extending the micromolecule oligomers into high polymer with high molecular weight, removing NaCl generated in reaction synthesis firstly out of a reaction system, and enabling the NaCl generated in the later synthesis to react in the direction beneficial to the generation of the high polymer, the synthetic material is the high polymer formed by introducing polysulfone thioether group blocks into polyphenylene sulfide groups, the melt index is 100 ~ 300 at 315 ℃, the thermal deformation temperature is higher than 240 ℃, the film drawing treatment can be carried out, and the high polymer can be dissolved in a part of strong polar solvent, so that the film can be processed easily.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of preparation of high molecular polymers, in particular to a preparation method of polyarylene sulfide sulfone.
[ background of the invention ]
The polyarylene sulfide sulfone (PASS) is an excellent engineering plastic, has good ductility, excellent mechanical and electrical properties, good dimensional stability, chemical corrosion resistance, radiation resistance, flame retardance and the like, and good film processability.
The polyphenylene sulfide and polysulfone sulfide block polymer is a chemical modified material which introduces sulfone groups on the basis of polyphenylene sulfide, and the introduction of polar sulfone groups enables the chemically modified polyphenylene sulfide new material to have a higher glass transition temperature which is as high as 180-220 ℃, so that the polyphenylene sulfide new material can be used for a long time in a higher temperature environment to keep the stability of physicochemical properties, can be dissolved in part of extremely strong solution, and has the properties which are not possessed by the original polyphenylene sulfide material. Therefore, compared with the polyphenylene sulfide material without modification, the polyphenylene sulfide and polysulfone sulfide block polymer after chemical modification is a material which is easier to process into a film.
Meanwhile, in some reactions for generating high polymers, a large amount of NaCl exists in the reaction solution and is always present in the reaction system, which is not favorable for the reaction in the direction of generating high polymers.
[ summary of the invention ]
The invention provides a chemically modified high polymer based on polyphenylene sulfide, and provides a synthetic method of a polyphenylene sulfide and polysulfone sulfide block high polymer, which has simpler preparation process and higher reaction efficiency.
The invention relates to a method for synthesizing polyphenylene sulfide and polysulfone thioether block polymer, which comprises the following steps:
the method comprises the following steps: in a 5L pressure autoclave, the following materials were charged:
Na2S·3H2O 300～360g；
1500-6000 g of N-methylpyrrolidine (NMP);
the materials and the corresponding auxiliary agents are put into a reaction kettle, and nitrogen N is introduced into the reaction kettle2Controlling the temperature at 140-200 ℃, and dehydrating for 3H;
step two: cooling to 120 ℃, and adding materials:
600-720 g of 4, 4' -dichlorodiphenyl sulfone (DCDPS);
heating for reaction, introducing nitrogen to replace air in the reaction kettle, pressurizing by using the nitrogen until P is 0.1-2.0 mPa, starting heating reaction in a closed system, heating the system to 180 ℃, reacting for 2H at a constant temperature, and heating to 200-230 ℃ for reacting for 3H; the above reaction is exothermic;
step three: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering to remove salt while the solution is hot, obtaining polysulfone thioether oligomer at the moment, and taking reaction solution A for next synthesis;
step four: in a 5L reactor, the following materials were charged:
Na2S·3H2O 450～550g；
1200-6000 g of N-methylpyrrolidone (NMP);
the materials and the corresponding auxiliary agents are put into a reaction kettle, and nitrogen N is introduced into the reaction kettle2Controlling the temperature at 140-200 ℃, and dehydrating for 3H;
step five: cooling to T less than or equal to 150 ℃, and adding materials:
530-650 g of p-Dichlorobenzene (DPCB);
heating for reaction: introducing nitrogen N2To the reaction kettle with nitrogen N2Pressurizing until P is 0.1-2.0 mPa, heating to 200-230 ℃ for 2H reaction, carrying out exothermic reaction, and controlling the temperature;
step six: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering while the solution is hot to remove salt to obtain polyphenylene sulfide (PPS) oligomer reaction liquid B for next synthesis;
step seven: in a 10L pressure reactor, the following materials were charged:
when the total amount of the reaction liquid A and the reaction liquid B is 7000g, the following components are mixed:
performing dehydration reaction, introducing nitrogen, controlling the temperature at 140-200 ℃, and dehydrating for 2-3H;
the first stage reaction: introducing nitrogen to replace air in the reaction kettle, pressurizing by using the nitrogen until P is 0.1-2.0 mPa, sealing the system, starting heating reaction, controlling the temperature at 220-225 ℃, and carrying out heat preservation reaction for 2H; pressurizing and pressing 10g of chain extension auxiliary agent under continuous stirring;
and (3) heating reaction in the second stage: heating the system to 230-245 ℃, reacting for 2H at constant temperature, heating to 250-265 ℃, reacting for 2H, cooling to 100 ℃ after the reaction is finished, relieving the pressure of the system, and opening the reaction kettle to obtain polyphenylene sulfide and polysulfone thioether block polymer;
the molecular formula of the obtained high polymer of the polyphenylene sulfide sulfone and polysulfone sulfide block is as follows:
according to the above obtained product, post-reaction treatment was carried out: pouring the reaction solution into 20kg of deionized water, and separating out a large amount of strip-shaped solids; pulverizing the solid, washing with deionized water for 7 times, washing with deionized water at high temperature of 130 deg.C under pressure for 2 times, and filtering; drying the obtained solid powder at 120 deg.C to obtain dried solid powder with water content of below 0.35%.
More particularly, the invention relates to a method for synthesizing polyphenylene sulfide and polysulfone thioether block polymer, which comprises the following steps, wherein
The method comprises the following steps: in a 5L pressure autoclave, the following materials were charged:
putting the materials into a reaction kettle, wherein LiCl is used as a catalyst, sodium acetate and NaOH are used as auxiliaries, and introducing nitrogen N into the reaction kettle2Controlling the temperature at 140-200 ℃, and dehydrating for 3H;
step two: cooling to 120 ℃, and adding materials:
1000-3000 g of N-methylpyrrolidine (NMP);
600-720 g of 4, 4' -dichlorodiphenyl sulfone (DCDPS);
heating for reaction, introducing nitrogen to replace air in the reaction kettle, pressurizing by using the nitrogen until P is 0.1-2.0 mPa, starting heating reaction in a closed system, heating the system to 180 ℃, reacting for 2H at a constant temperature, and heating to 200-230 ℃ for reacting for 3H; the above reaction is exothermic;
step three: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering to remove salt while the solution is hot, obtaining polysulfone thioether oligomer at the moment, and taking reaction solution A for next synthesis;
step four: in a 5L reactor, the following materials were charged:
Na2S·3H2O 450～550g；
1200-6000 g of N-methylpyrrolidone (NMP);
the materials and the corresponding auxiliary agents are put into a reaction kettle, and nitrogen N is introduced into the reaction kettle2Controlling the temperature at 140-200 ℃, and dehydrating for 3H;
step five: cooling to T less than or equal to 150 ℃, and adding materials:
530-650 g of p-Dichlorobenzene (DPCB);
heating for reaction: introducing nitrogen N2To the reaction kettle with nitrogen N2Pressurizing until P is 0.1-2.0 mPa, heating to 200-230 ℃ for 2H reaction, carrying out exothermic reaction, and controlling the temperature;
step six: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering while the solution is hot to remove salt to obtain polyphenylene sulfide (PPS) oligomer reaction liquid B for next synthesis;
step seven: in a 10L pressure reactor, the following materials were charged:
when the total amount of the reaction liquid A and the reaction liquid B is 7000g, the following components are mixed:
performing dehydration reaction, introducing nitrogen, controlling the temperature at 140-200 ℃, and dehydrating for 2-3H;
the first stage reaction: introducing nitrogen to replace air in the reaction kettle, pressurizing by using the nitrogen until P is 0.1-2.0 mPa, sealing the system, starting heating reaction, controlling the temperature at 220-225 ℃, and carrying out heat preservation reaction for 2H; pressurizing and pressing 10g of chain extension auxiliary agent under continuous stirring; the chain extension auxiliary agent can be trichlorobenzene, mononitrodichlorobenzene, dinitrochlorobenzene and the like.
And (3) heating reaction in the second stage: heating the system to 230-245 ℃, reacting for 2H at constant temperature, heating to 250-265 ℃, reacting for 2H, cooling to 100 ℃ after the reaction is finished, relieving the pressure of the system, and opening the reaction kettle to obtain polyphenylene sulfide and polysulfone thioether block polymer;
the molecular formula of the obtained high polymer of the polyphenylene sulfide sulfone and polysulfone sulfide block is as follows:
according to the above obtained product, post-reaction treatment was carried out: pouring the reaction solution into 20kg of deionized water, and separating out a large amount of strip-shaped solids; pulverizing the solid, washing with deionized water for 7 times, washing with deionized water at high temperature of 130 deg.C under pressure for 2 times, and filtering; drying the obtained solid powder at 120 deg.C to obtain dried solid powder with water content of below 0.35%.
Still more particularly, the invention relates to a method for synthesizing polyphenylene sulfide and polysulfone thioether block polymer, comprising the following steps, wherein
The method comprises the following steps: in a 5L pressure autoclave, the following materials were charged:
putting the materials into a reaction kettle, wherein LiCl is used as a catalyst, sodium acetate and NaOH are used as auxiliaries, and introducing nitrogen N into the reaction kettle2Controlling the temperature at 140-200 ℃, and dehydrating for 3H;
step two: cooling to 120 ℃, and adding materials:
1000-3000 g of N-methylpyrrolidine (NMP);
600-720 g of 4, 4' -dichlorodiphenyl sulfone (DCDPS);
heating for reaction, introducing nitrogen to replace air in the reaction kettle, pressurizing by using the nitrogen until P is 0.1-2.0 mPa, starting heating reaction in a closed system, heating the system to 180 ℃, reacting for 2H at a constant temperature, and heating to 200-230 ℃ for reacting for 3H; the above reaction is exothermic;
step three: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering to remove salt while the solution is hot, obtaining polysulfone thioether oligomer at the moment, and taking reaction solution A for next synthesis;
step four: in a 5L reactor, the following materials were charged:
the materials are put into a reaction kettle, LiCl and NaOH are taken as auxiliary agents, and nitrogen N is introduced into the reaction kettle2Controlling the temperature at 140-200 ℃, and dehydrating for 3H;
step five: cooling to T less than or equal to 150 ℃, and adding materials:
100-2000 g of N-methylpyrrolidone (NMP);
530-650 g of p-Dichlorobenzene (DPCB);
heating for reaction: introducing nitrogen N2To the reaction kettle with nitrogen N2Pressurizing until P is 0.1-2.0 mPa, heating to 200-230 ℃ for 2H reaction, carrying out exothermic reaction, and controlling the temperature;
step six: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering while the solution is hot to remove salt to obtain polyphenylene sulfide (PPS) oligomer reaction liquid B for next synthesis;
step seven: in a 10L pressure reactor, the following materials were charged:
when the total amount of the reaction liquid A and the reaction liquid B is 7000g, the following components are mixed:
performing dehydration reaction, introducing nitrogen, controlling the temperature at 140-200 ℃, and dehydrating for 2-3H;
the first stage reaction: introducing nitrogen to replace air in the reaction kettle, pressurizing by using the nitrogen until P is 0.1-2.0 mPa, sealing the system, starting heating reaction, controlling the temperature at 220-225 ℃, and carrying out heat preservation reaction for 2H; pressurizing and pressing 10g of chain extension auxiliary agent under continuous stirring; the chain extension auxiliary agent can be trichlorobenzene, mononitrodichlorobenzene, dinitrochlorobenzene and the like.
And (3) heating reaction in the second stage: heating the system to 230-245 ℃, reacting for 2H at constant temperature, heating to 250-265 ℃, reacting for 2H, cooling to 100 ℃ after the reaction is finished, relieving the pressure of the system, and opening the reaction kettle to obtain polyphenylene sulfide and polysulfone thioether block polymer;
the molecular formula of the obtained high polymer of the polyphenylene sulfide sulfone and polysulfone sulfide block is as follows:
according to the above obtained product, post-reaction treatment was carried out: pouring the reaction solution into 20kg of deionized water, and separating out a large amount of strip-shaped solids; pulverizing the solid, washing with deionized water for 7 times, washing with deionized water at high temperature of 130 deg.C under pressure for 2 times, and filtering; drying the obtained solid powder at 120 deg.C to obtain dried solid powder with water content of below 0.35%.
More specifically, the synthesis method comprises the following steps:
the method comprises the following steps: in a 5L pressure autoclave, the following materials were charged:
the above materials are put into a reaction kettle, wherein Na is contained in the materials2S·3H2O is used as main material, NMP provides reaction environment, NMP may be replaced by high boiling point ketone polar solvent such as cyclohexanone, 1, 3-dimethyl-2-imidazolidinone, etc., nitrogen N is introduced into the reactor after feeding2Controlling the temperature at 140-200 ℃, and dehydrating for 3H;
step two: cooling to 120 ℃, and adding materials:
1100g of N-methylpyrrolidine (NMP);
4, 4' -dichlorodiphenyl sulfone (DCDPS)660 g;
heating for reaction, introducing nitrogen to replace air in the reaction kettle, pressurizing by using the nitrogen until P is 0.3mPa, starting heating reaction by a closed system, heating the system to 180 ℃, reacting for 2H at a constant temperature, and heating to 215-220 ℃ for reacting for 3H; the above reaction is exothermic;
step three: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering to remove salt while the solution is hot, obtaining polysulfone thioether oligomer at the moment, and taking reaction solution A for next synthesis;
step four: in a 5L reactor, the following materials were charged:
the materials are put into a reaction kettle, LiCl and NaOH are taken as auxiliary agents, and nitrogen N is introduced into the reaction kettle2Controlling the temperature at 140-200 ℃, and dehydrating for 3H;
step five: cooling to T less than or equal to 150 ℃, and adding materials:
500g of N-methylpyrrolidine (NMP);
580g of p-Dichlorobenzene (DPCB);
heating for reaction: introducing nitrogen into the reaction kettle, pressurizing to 0.30mPa by using the nitrogen, heating to 215-220 ℃ for reacting for 2H, carrying out exothermic reaction, and controlling the temperature;
step six: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering while the solution is hot to remove salt to obtain polyphenylene sulfide (PPS) oligomer reaction liquid B for next synthesis;
step seven: in a 10L pressure reactor, the following materials were charged:
carrying out dehydration reaction, introducing nitrogen, controlling the temperature at 140-200 ℃, and dehydrating for 3H;
the first stage reaction: introducing nitrogen to replace air in the reaction kettle, pressurizing the reaction kettle to 0.30mPa by using the nitrogen, sealing the system, starting heating to react, controlling the temperature to be 220-225 ℃, and carrying out heat preservation reaction for 2H; 10g of chain extension assistant was pressed in under pressure with continuous stirring. The chain extension auxiliary agent can be trichlorobenzene, mononitrodichlorobenzene, dinitrochlorobenzene and the like.
And (3) heating reaction in the second stage: and (3) heating the system to 240 ℃, reacting for 2H at constant temperature, heating to 250 ℃, reacting for 2H, cooling to 100 ℃ after the reaction is finished, relieving the pressure of the system, and opening the reaction kettle to obtain the polyphenylene sulfide and polysulfone thioether block polymer.
The molecular formula of the obtained polyphenylene sulfide sulfone in the high polymer of the polysulfone sulfide block is as follows:
according to the above obtained product, post-reaction treatment was carried out: pouring the reaction solution into 20kg of deionized water, and separating out a large amount of strip-shaped solids; pulverizing the solid, washing with deionized water for 7 times, washing with deionized water at high temperature of 130 deg.C under pressure for 2 times, and filtering; drying the obtained solid powder at 120 deg.C to obtain dried solid powder with water content of below 0.35%.
The molecular formula of the polyphenylene sulfide and polysulfone thioether block polymer obtained by the synthesis method is shown in the specificationStructurally, it isAndinstead of polysulfone sulfideBoth the structure and the polymerization mode are completely different. The chemical property, the mechanical property and the application scene of the high polymer modified material of polyphenylene sulfide synthesized by the invention are substantially different and greatly different from those of unmodified polyphenylene sulfide.
[ detailed description ] embodiments
The present invention will be described in further detail with reference to specific embodiments thereof.
The invention relates to a method for synthesizing polyphenylene sulfide and polysulfone thioether block polymer, which comprises the following steps:
the method comprises the following steps: in a 5L pressure autoclave, the following materials were charged:
the above materials are put into a reaction kettle, wherein Na is contained in the materials2S·3H2O is used as main material, NMP provides reaction environment, NMP may be replaced by high boiling point ketone polar solvent such as cyclohexanone, 1, 3-dimethyl-2-imidazolidinone, etc. after feeding, nitrogen N is introduced into the reactor2Controlling the temperature at 140-200 ℃, and dehydrating for 3H;
step two: cooling to 120 ℃, and adding materials:
1100g of N-methylpyrrolidine (NMP);
4, 4' -dichlorodiphenyl sulfone (DCDPS)660 g;
heating for reaction, introducing nitrogen to replace air in the reaction kettle, pressurizing by using the nitrogen until P is 0.3mPa, starting heating reaction by a closed system, heating the system to 180 ℃, reacting for 2H at a constant temperature, and heating to 215-220 ℃ for reacting for 3H; the above reaction is exothermic;
step three: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering to remove salt while the solution is hot, obtaining polysulfone thioether oligomer at the moment, and taking reaction solution A for next synthesis;
step four: in a 5L reactor, the following materials were charged:
the materials are put into a reaction kettle, and nitrogen N is introduced into the reaction kettle2Temperature ofControlling the temperature to be 140-200 ℃, and dehydrating for 3H;
step five: cooling to T less than or equal to 150 ℃, and adding materials:
500g of N-methylpyrrolidine (NMP);
580g of p-Dichlorobenzene (DPCB);
heating for reaction: introducing nitrogen into the reaction kettle, pressurizing to P & lt 0.3mPa by using the nitrogen, heating to 215-220 ℃ for reacting for 2H, carrying out exothermic reaction, and controlling the temperature;
step six: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering while the solution is hot to remove salt to obtain polyphenylene sulfide (PPS) oligomer reaction liquid B for next synthesis;
step seven: in a 10L pressure reactor, the following materials were charged:
carrying out dehydration reaction, introducing nitrogen, controlling the temperature at 140-200 ℃, and dehydrating for 3H;
the first stage reaction: introducing nitrogen to replace air in the reaction kettle, pressurizing the reaction kettle to 0.30mPa by using the nitrogen, sealing the system, starting heating to react, controlling the temperature to be 220-225 ℃, and carrying out heat preservation reaction for 2H; pressurizing and pressing 10g of chain extension auxiliary agent under continuous stirring; the chain extension auxiliary agent can be trichlorobenzene, mononitrodichlorobenzene, dinitrochlorobenzene and the like.
And (3) heating reaction in the second stage: heating the system to 240 ℃, reacting for 2H at constant temperature, heating to 250 ℃, reacting for 2H, cooling to 100 ℃ after the reaction is finished, relieving the pressure of the system, and opening the reaction kettle to obtain polyphenylene sulfide and polysulfone thioether block polymer;
the molecular formula of the obtained polyphenylene sulfide sulfone in the high polymer of the polysulfone sulfide block is as follows:
according to the above obtained product, post-reaction treatment was carried out: pouring the reaction solution into 20kg of deionized water, and separating out a large amount of strip-shaped solids; pulverizing the solid, washing with deionized water for 7 times, washing with deionized water at high temperature of 130 deg.C under pressure for 2 times, and filtering; drying the obtained solid powder at 120 deg.C to obtain dried solid powder with water content of below 0.35%.
We are a different material from the so-called polyarylene sulfide sulfone materials in other prior patent products because of the first: the structures of the prepared material and the prior polyarylene sulfide sulfone are completely different, and the structure isThe block copolymers of (A) are, as it were, those prepared by the so-called polyarylene sulfide sulfonesPolymer, second: the synthesis method comprises the steps of synthesizing small molecular oligomers in sections, and then chain extending the small molecular oligomers into high polymers with high molecular weight, so that the small molecular oligomers have application value, and the third step is as follows: NaCl (salt) produced during the synthesis of two-stage oligomer is first removed from the reaction system to react in the direction favorable to the formation of high polymer during subsequent synthesis
Preparing a high molecular weight poly (aryl sulfide sulfone) product in a specific mode, wherein the product contains m sulfosulfone groupsAnd n phenylene sulfide groupsThe block polymer of (1). Polysulfone thioether group block high polymer is introduced into polyphenylene sulfide groups, the block polymer is light gray to white powder, the melt index is 100-300 at 315 ℃, the thermal deformation temperature is more than 240 ℃, and film drawing treatment can be carried out. And because the polyphenylene sulfide group has polarity, the modified polyphenylene sulfide material can be dissolved in a part of strong polar solvent, so that the modified polyphenylene sulfide material is easy to process into a film.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A synthetic method of polyphenylene sulfide and polysulfone thioether block polymer comprises the following steps:
the method comprises the following steps: in a 5L pressure autoclave, the following materials were charged:
Na2S·3H2O 300~360g；
n-methylpyrrolidine (NMP) 1500 ~ 6000 g;
putting the materials and the corresponding auxiliary agents into a reaction kettle, introducing nitrogen N2 into the reaction kettle, controlling the temperature at 140 ℃ to ~ 200 ℃ and dehydrating for 3H;
step two: cooling to 120 ℃, and adding materials:
600 ~ 720g of 4, 4' -dichlorodiphenyl sulfone (DCDPS);
heating for reaction, introducing nitrogen to replace air in the reaction kettle, pressurizing to P =0.1 ~ 2.0.0 mPa by using the nitrogen, starting heating for reaction in a closed system, heating the system to 180 ℃, reacting for 2H at a constant temperature, and heating to 200 ~ 230 ℃, reacting for 3H, wherein the reaction is exothermic;
step three: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering to remove salt while the solution is hot, obtaining polysulfone thioether oligomer at the moment, and taking reaction solution A for next synthesis;
step four: in a 5L reactor, the following materials were charged:
Na2S·3H2O 450~550g；
1200 g of N-methylpyrrolidine (NMP) 1200 ~ 6000;
putting the materials and the corresponding auxiliary agents into a reaction kettle, introducing nitrogen N2 into the reaction kettle, controlling the temperature at 140 ℃ to ~ 200 ℃ and dehydrating for 3H;
step five: cooling to T less than or equal to 150 ℃, and adding materials:
p-Dichlorobenzene (DPCB) 530 ~ 650 g;
heating reaction, namely introducing nitrogen N2 into a reaction kettle, pressurizing to P =0.1 ~ 2.0.0 mPa by using nitrogen N2, heating to 200 ~ 230 ℃ for 2H reaction, carrying out exothermic reaction, and controlling the temperature;
step six: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering while the solution is hot to remove salt to obtain polyphenylene sulfide (PPS) oligomer reaction liquid B for next synthesis;
step seven: in a 10L pressure reactor, the following materials were charged:
when the total amount of the reaction liquid A and the reaction liquid B is 7000g, the following components are mixed:
100 ~ 6900g of reaction solution A;
100 ~ 6900g of reaction solution B;
caprolactam 30 ~ 200 g;
LiCl 30~200g；
performing dehydration reaction, introducing nitrogen, controlling the temperature at 140 ℃ and ~ 200 ℃ and dehydrating for 3H;
the first stage reaction, namely introducing nitrogen to replace the air in the reaction kettle, pressurizing the air to P =0.1 ~ 2.0.0 mPa by using the nitrogen, closing the system, starting heating the reaction system, controlling the temperature to be 220 ~ 225 ℃, keeping the temperature for reaction for 2H, and pressurizing and pressing 10g of chain extension auxiliary agent under continuous stirring;
and (3) heating the system to 230 ~ 245 ℃, reacting for 2H at constant temperature, heating to 250 ~ 265 ℃ for 2H, cooling to 100 ℃ after the reaction is finished, decompressing the system, and opening the reaction kettle to obtain the polyphenylene sulfide and polysulfone sulfide block polymer.
2. The method for synthesizing polyphenylene sulfide and polysulfone sulfide block polymer according to claim 1, comprising the steps of:
the method comprises the following steps: in a 5L pressure autoclave, the following materials were charged:
Na2S·3H2O 300~360g；
n-methylpyrrolidine (NMP) 1500 ~ 6000 g;
LiCl 20~40g；
sodium acetate 45 ~ 55 g;
NaOH 3~8 g；
putting the materials into a reaction kettle, wherein LiCl is used as a catalyst, sodium acetate and NaOH are used as auxiliaries, introducing nitrogen N2 into the reaction kettle, controlling the temperature to be 140 ℃ and ~ 200 ℃ and dehydrating for 3H;
step two: cooling to 120 ℃, and adding materials:
1000 ~ 3000g of N-methylpyrrolidine (NMP);
600 ~ 720g of 4, 4' -dichlorodiphenyl sulfone (DCDPS);
heating for reaction, introducing nitrogen to replace air in the reaction kettle, pressurizing to P =0.1 ~ 2.0.0 mPa by using the nitrogen, starting heating for reaction in a closed system, heating the system to 180 ℃, reacting for 2H at a constant temperature, and heating to 200 ~ 230 ℃, reacting for 3H, wherein the reaction is exothermic;
step three: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering to remove salt while the solution is hot, obtaining polysulfone thioether oligomer at the moment, and taking reaction solution A for next synthesis;
step four: in a 5L reactor, the following materials were charged:
Na2S·3H2O 450~550g；
1200 g of N-methylpyrrolidine (NMP) 1200 ~ 6000;
putting the materials and the corresponding auxiliary agents into a reaction kettle, introducing nitrogen N2 into the reaction kettle, controlling the temperature at 140 ℃ to ~ 200 ℃ and dehydrating for 3H;
step five: cooling to T less than or equal to 150 ℃, and adding materials:
p-Dichlorobenzene (DPCB) 530 ~ 650 g;
heating reaction, namely introducing nitrogen N2 into a reaction kettle, pressurizing to P =0.1 ~ 2.0.0 mPa by using nitrogen N2, heating to 200 ~ 230 ℃ for 2H reaction, carrying out exothermic reaction, and controlling the temperature;
step six: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering while the solution is hot to remove salt to obtain polyphenylene sulfide (PPS) oligomer reaction liquid B for next synthesis;
step seven: in a 10L pressure reactor, the following materials were charged:
when the total amount of the reaction liquid A and the reaction liquid B is 7000g, the following components are mixed:
100 ~ 6900g of reaction solution A;
100 ~ 6900g of reaction solution B;
caprolactam 30 ~ 200 g;
LiCl 30~200g；
performing dehydration reaction, introducing nitrogen, controlling the temperature at 140 ℃ and ~ 200 ℃ and dehydrating for 3H;
the first stage reaction, namely introducing nitrogen to replace the air in the reaction kettle, pressurizing the air to P =0.1 ~ 2.0.0 mPa by using the nitrogen, closing the system, starting heating the reaction system, controlling the temperature to be 220 ~ 225 ℃, keeping the temperature for reaction for 2H, and pressurizing and pressing 10g of chain extension auxiliary agent under continuous stirring;
and (3) heating the system to 230 ~ 245 ℃, reacting for 2H at constant temperature, heating to 250 ~ 265 ℃ for 2H, cooling to 100 ℃ after the reaction is finished, decompressing the system, and opening the reaction kettle to obtain the polyphenylene sulfide and polysulfone sulfide block polymer.
3. The method for synthesizing polyphenylene sulfide and polysulfone sulfide block polymer according to claim 1, comprising the steps of:
the method comprises the following steps: in a 5L pressure autoclave, the following materials were charged:
Na2S·3H2O 300~360g；
n-methylpyrrolidine (NMP) 1500 ~ 6000 g;
LiCl 20~40g；
sodium acetate 45 ~ 55 g;
NaOH 3~8 g；
putting the materials into a reaction kettle, wherein LiCl is used as a catalyst, sodium acetate and NaOH are used as auxiliaries, introducing nitrogen N2 into the reaction kettle, controlling the temperature to be 140 ℃ and ~ 200 ℃ and dehydrating for 3H;
step two: cooling to 120 ℃, and adding materials:
1000 ~ 3000g of N-methylpyrrolidine (NMP);
600 ~ 720g of 4, 4' -dichlorodiphenyl sulfone (DCDPS);
heating for reaction, introducing nitrogen to replace air in the reaction kettle, pressurizing to P =0.1 ~ 2.0.0 mPa by using the nitrogen, starting heating for reaction in a closed system, heating the system to 180 ℃, reacting for 2H at a constant temperature, and heating to 200 ~ 230 ℃, reacting for 3H, wherein the reaction is exothermic;
step three: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering to remove salt while the solution is hot, obtaining polysulfone thioether oligomer at the moment, and taking reaction solution A for next synthesis;
step four: in a 5L reactor, the following materials were charged:
Na2S·3H2O 450~550g；
1200 g of N-methylpyrrolidine (NMP) 1200 ~ 6000;
LiCl 40~60g；
NaOH 3~6g；
putting the materials into a reaction kettle, wherein LiCl and NaOH are used as auxiliary agents, introducing nitrogen N2 into the reaction kettle, controlling the temperature at 140 ℃ to ~ 200 ℃ and dehydrating for 3H;
step five: cooling to T less than or equal to 150 ℃, and adding materials:
100 ~ 2000g of N-methylpyrrolidine (NMP);
p-Dichlorobenzene (DPCB) 530 ~ 650 g;
heating reaction, namely introducing nitrogen N2 into a reaction kettle, pressurizing to P =0.1 ~ 2.0.0 mPa by using nitrogen N2, heating to 200 ~ 230 ℃ for 2H reaction, carrying out exothermic reaction, and controlling the temperature;
step six: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering while the solution is hot to remove salt to obtain polyphenylene sulfide (PPS) oligomer reaction liquid B for next synthesis;
step seven: in a 10L pressure reactor, the following materials were charged:
when the total amount of the reaction liquid A and the reaction liquid B is 7000g, the following components are mixed:
100 ~ 6900g of reaction solution A;
100 ~ 6900g of reaction solution B;
caprolactam 30 ~ 200 g;
LiCl 30~200g；
performing dehydration reaction, introducing nitrogen, controlling the temperature at 140 ℃ and ~ 200 ℃ and dehydrating for 3H;
the first stage reaction, namely introducing nitrogen to replace the air in the reaction kettle, pressurizing the air to P =0.1 ~ 2.0.0 mPa by using the nitrogen, closing the system, starting heating the reaction system, controlling the temperature to be 220 ~ 225 ℃, keeping the temperature for reaction for 2H, and pressurizing and pressing 10g of chain extension auxiliary agent under continuous stirring;
and (3) heating the system to 230 ~ 245 ℃, reacting for 2H at constant temperature, heating to 250 ~ 265 ℃ for 2H, cooling to 100 ℃ after the reaction is finished, decompressing the system, and opening the reaction kettle to obtain the polyphenylene sulfide and polysulfone sulfide block polymer.
4. The method for synthesizing polyphenylene sulfide and polysulfone sulfide block polymer according to claim 1, comprising the steps of:
the method comprises the following steps: in a 5L pressure autoclave, the following materials were charged:
Na2S·3H2O 330g；
2200g of N-methylpyrrolidine (NMP);
LiCl 30g；
50g of sodium acetate;
NaOH 5 g；
putting the materials into a reaction kettle, introducing nitrogen N2 into the reaction kettle, controlling the temperature at 140 ℃ to ~ 200 ℃ and dehydrating for 3H;
step two: cooling to 120 ℃, and adding materials:
1100g of N-methylpyrrolidine (NMP);
4, 4' -dichlorodiphenyl sulfone (DCDPS)660 g;
heating for reaction, introducing nitrogen to replace air in the reaction kettle, pressurizing to P =0.3mPa by using the nitrogen, starting heating for reaction by a closed system, heating the system to 180 ℃, reacting for 2H at a constant temperature, and heating to 215-220 ℃ for reacting for 3H; the above reaction is exothermic;
step three: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering to remove salt while the solution is hot, obtaining polysulfone thioether oligomer at the moment, and taking reaction solution A for next synthesis;
step four: in a 5L reactor, the following materials were charged:
Na2S·3H2O 492g；
2000g of N-methylpyrrolidine (NMP);
LiCl 50g；
NaOH 5g；
putting the materials into a reaction kettle, introducing nitrogen N2 into the reaction kettle, controlling the temperature at 140 ℃ to ~ 200 ℃ and dehydrating for 3H;
step five: cooling to T less than or equal to 150 ℃, and adding materials:
500g of N-methylpyrrolidine (NMP);
580g of p-Dichlorobenzene (DPCB);
heating for reaction: introducing nitrogen into the reaction kettle, pressurizing to P =0.30mPa by using the nitrogen, heating to 215-220 ℃ for reacting 2H, carrying out exothermic reaction, and controlling the temperature;
step six: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering while the solution is hot to remove salt to obtain polyphenylene sulfide (PPS) oligomer reaction liquid B for next synthesis;
step seven: in a 10L pressure reactor, the following materials were charged:
4000g of reaction liquid A;
3000g of a reaction solution B;
60g of caprolactam;
LiCl 80g；
performing dehydration reaction, introducing nitrogen, controlling the temperature at 140 ℃ and ~ 200 ℃ and dehydrating for 3H;
the first stage reaction, namely introducing nitrogen to replace the air in the reaction kettle, pressurizing the reaction kettle to P =0.30mPa by using the nitrogen, closing the system, starting heating the reaction kettle, controlling the temperature at 220 ~ 225 ℃, keeping the temperature for reaction for 2H, and pressurizing and pressing 10g of chain extension assistant under continuous stirring;
and (3) heating reaction in the second stage: and (3) heating the system to 240 ℃, reacting for 2H at constant temperature, heating to 250 ℃, reacting for 2H, cooling to 100 ℃ after the reaction is finished, relieving the pressure of the system, and opening the reaction kettle to obtain the polyphenylene sulfide and polysulfone thioether block polymer.
5. The method for synthesizing the polyphenylene sulfide and polysulfone sulfide block polymer as claimed in claim 1 ~ 4, wherein the reaction mixture is subjected to a post-reaction treatment by pouring the reaction mixture into 20kg of deionized water to precipitate a large amount of solid in the form of strands, washing, filtering, and drying.
6. The method for synthesizing polyphenylene sulfide and polysulfone thioether block polymer according to claim 5, wherein the strip-shaped solid is crushed and then washed, and the washing process comprises: the solid is crushed and washed with deionized water for 7 times, and then washed with deionized water at high temperature of 130 ℃ under pressure for 2 times and filtered.
7. The method for synthesizing polyphenylene sulfide and polysulfone sulfide block polymer according to claim 6, wherein the solid powder obtained by washing and filtering is dried at 120 ℃ to obtain a dry solid powder having a moisture content of 0.35% or less.
8. The method for synthesizing the polyphenylene sulfide and polysulfone sulfide block polymer according to claim 1 ~ 4, wherein the chain extension assistant is trichlorobenzene, mononitrodichlorobenzene or dinitrochlorobenzene.
9. The method for synthesizing the polyphenylene sulfide and polysulfone thioether block polymer according to claim 4, wherein the synthesized material is a functional film material with very good toughness, has excellent electrical and mechanical properties, and can be used in the industries of electronics, automobiles, household appliances, aerospace and military industry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910852911.XA CN110591095A (en) | 2019-09-10 | 2019-09-10 | Synthetic method of polyphenylene sulfide and polysulfone thioether block polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910852911.XA CN110591095A (en) | 2019-09-10 | 2019-09-10 | Synthetic method of polyphenylene sulfide and polysulfone thioether block polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110591095A true CN110591095A (en) | 2019-12-20 |
Family
ID=68858481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910852911.XA Pending CN110591095A (en) | 2019-09-10 | 2019-09-10 | Synthetic method of polyphenylene sulfide and polysulfone thioether block polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110591095A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63125531A (en) * | 1986-11-14 | 1988-05-28 | Dainippon Ink & Chem Inc | Carbon fiber-reinforced resin composition |
| US4960841A (en) * | 1986-11-20 | 1990-10-02 | Dainippon Ink And Chemicals, Inc. | Polyphenylene sulfide/polyphenylene sulfide sulfone block copolymer |
| JPH05148363A (en) * | 1991-11-28 | 1993-06-15 | Tosoh Corp | Polythioether thioether thioether sulfone and its production |
| JPH0822919B2 (en) * | 1987-05-11 | 1996-03-06 | 大日本インキ化学工業株式会社 | Method for producing polyphenylene sulfide / polyphenylene sulfide sulfone block copolymer |
| CN1896120A (en) * | 2006-06-29 | 2007-01-17 | 四川大学 | Preparation of polyarylphenyl resin by phase-transferring catalyst |
| CN103172864A (en) * | 2013-04-23 | 2013-06-26 | 四川大学 | Preparation method of organic acid salt catalytic polyarylene sulfide |
| CN103467741A (en) * | 2013-09-22 | 2013-12-25 | 四川大学 | Polyphenylene sulfide and preparation method thereof |
| CN105585712A (en) * | 2014-10-23 | 2016-05-18 | 中国石油化工股份有限公司 | Polyphenylene sulfide microspheres as well as preparation method and application thereof |
| CN106832283A (en) * | 2017-03-10 | 2017-06-13 | 四川中科兴业高新材料有限公司 | A kind of new method for preparing polyaryl thioether sulfone |
-
2019
- 2019-09-10 CN CN201910852911.XA patent/CN110591095A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63125531A (en) * | 1986-11-14 | 1988-05-28 | Dainippon Ink & Chem Inc | Carbon fiber-reinforced resin composition |
| US4960841A (en) * | 1986-11-20 | 1990-10-02 | Dainippon Ink And Chemicals, Inc. | Polyphenylene sulfide/polyphenylene sulfide sulfone block copolymer |
| JPH0822919B2 (en) * | 1987-05-11 | 1996-03-06 | 大日本インキ化学工業株式会社 | Method for producing polyphenylene sulfide / polyphenylene sulfide sulfone block copolymer |
| JPH05148363A (en) * | 1991-11-28 | 1993-06-15 | Tosoh Corp | Polythioether thioether thioether sulfone and its production |
| CN1896120A (en) * | 2006-06-29 | 2007-01-17 | 四川大学 | Preparation of polyarylphenyl resin by phase-transferring catalyst |
| CN103172864A (en) * | 2013-04-23 | 2013-06-26 | 四川大学 | Preparation method of organic acid salt catalytic polyarylene sulfide |
| CN103467741A (en) * | 2013-09-22 | 2013-12-25 | 四川大学 | Polyphenylene sulfide and preparation method thereof |
| CN105585712A (en) * | 2014-10-23 | 2016-05-18 | 中国石油化工股份有限公司 | Polyphenylene sulfide microspheres as well as preparation method and application thereof |
| CN106832283A (en) * | 2017-03-10 | 2017-06-13 | 四川中科兴业高新材料有限公司 | A kind of new method for preparing polyaryl thioether sulfone |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101313011B (en) | Polyarylene sulfide and process for production thereof | |
| JP4296526B2 (en) | Method for producing polyarylene sulfide resin | |
| JP4256506B2 (en) | Process for producing polyarylene sulfide | |
| JP4953020B2 (en) | Method for producing polyarylene sulfide resin | |
| CN109535426B (en) | Polyphenylene sulfide resin synthesis process | |
| US5071949A (en) | Process for preparation of polyphenylene-sulfide resins in the absence of specific polymerization assistants | |
| CN101215379A (en) | Polyarylene amide sulfides polymers and preparation method thereof | |
| US7569656B2 (en) | Process for production of polyarylene sulfide | |
| WO2013041062A1 (en) | Process for preparing polysulfone | |
| JP2007314803A (en) | Manufacturing process for polyarylene sulfide | |
| JP3603359B2 (en) | Method for producing polyarylene sulfide | |
| JP7194189B2 (en) | High molecular weight polyphenylene sulfide resin and its production method and use | |
| JPH02302436A (en) | Production of polyarylene sulfide | |
| CN110591095A (en) | Synthetic method of polyphenylene sulfide and polysulfone thioether block polymer | |
| CN105713199B (en) | A kind of high-purity polyphenylene sulfide resin production process | |
| JP2019119810A (en) | Polyphenylene sulfide resin composition and manufacturing method therefor | |
| CN101864077B (en) | Polyarylene sulfide ketone and preparation method thereof | |
| CN111286027B (en) | Production method of polyphenylene sulfide with low covalent bonding chlorine | |
| JPS63125531A (en) | Carbon fiber-reinforced resin composition | |
| JP2012072222A (en) | Cyclic polyphenylene sulfide mixture, and method for producing the same | |
| JP3797446B2 (en) | Process for producing polyarylene sulfide | |
| EP0261988B1 (en) | Aromatic sulphide amide polymers and a process for the production thereof | |
| CN104817716B (en) | The production method of crystal type Polymer Synthesizing method for recovering solvents and polyphenylene sulfide | |
| US5171831A (en) | Producing high molecular weight poly(arylene sulfide) polymers by adding second polar solvent prior to termination of polymerization | |
| JPS6248727A (en) | Production of polyarylene thioether having high melt crystallization temperature |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191220 |
|
| RJ01 | Rejection of invention patent application after publication |