CN114015047B - S-containing polymer and preparation method thereof - Google Patents
S-containing polymer and preparation method thereof Download PDFInfo
- Publication number
- CN114015047B CN114015047B CN202111432287.1A CN202111432287A CN114015047B CN 114015047 B CN114015047 B CN 114015047B CN 202111432287 A CN202111432287 A CN 202111432287A CN 114015047 B CN114015047 B CN 114015047B
- Authority
- CN
- China
- Prior art keywords
- solvent
- sodium
- potassium
- lithium
- sulfur
- 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.)
- Active
Links
Images
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
- C08G75/025—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
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0277—Post-polymerisation treatment
- C08G75/0281—Recovery or purification
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention relates to a preparation method of a sulfur-containing polymer, belonging to the field of high polymer synthesis. The invention provides a preparation method of an S-containing polymer, which comprises the following steps: 1) the raw materials of sulfur-containing monomer, dihalogenated monomer and the like are subjected to blending reaction by adopting a series-type microchannel reactor to obtain a sulfur-containing polymer solution; 2) feeding the sulfur-containing polymer solution obtained in the step 1) into another group of parallel microchannel reactors, and reacting the sulfur-containing polymer solution with the end group control agent solution at 240-280 ℃ to obtain a sulfur-containing polymer mixed solution; 3) and purifying to obtain the product, namely the S-containing polymer. The invention introduces the microchannel reactor into the preparation process of the S-containing polymer for the first time, and can prepare the polymer with narrow molecular weight distribution; and the proportion of the reaction and the molecular weight and molecular weight distribution of the sulfur-containing polymer can be controlled by controlling the feeding amount and feeding speed of the sulfur-containing monomer and the dihalogenated monomer and the number of reaction modules of the microchannel reactor.
Description
Technical Field
The invention relates to a preparation method of a sulfur-containing polymer, belonging to the field of high polymer synthesis.
Background
Sulfur-containing compounds polyarylene sulfides such as polyphenylene sulfide, polyphenylene sulfide ketone and polyphenylene sulfide sulfone are widely used in the automotive, aerospace and electronic arts because of their high temperature resistance, corrosion resistance, excellent electrical properties, mechanical properties and dimensional stability. In industrial production, the main methods for producing polyarylene sulfide at present are as follows: sodium sulfide and dihalogenated aromatic compound are subjected to solution polycondensation at high temperature and high pressure, for example, Philips company prepares sodium sulfide and p-dichlorobenzene by pressure reaction in nitrogen and polar solvent NMP (US 33544129), and the method has high energy consumption and long reaction period; CN1793202A Deyang science and technology Limited company uses sodium sulfide and p-dichlorobenzene as raw materials to synthesize fiber-grade polyphenylene sulfide resin by pressurization, adopts a kettle-type reactor, has general efficiency, low recovery rates of a solvent and a catalyst, does not carry out post-end capping treatment on a product, and has poor processing stability of the product; chinese patent CN1143652A reports that in a polar solvent, sulfur is used as a raw material to synthesize a tough polyphenylene sulfide resin under pressure, a reducing agent is needed in the reaction process, the process is complex, reaction byproducts are more, the product is not easy to purify, and the solvent is recovered by dehydration and rectification, which is high in energy consumption and uneconomical.
Disclosure of Invention
The invention aims to provide a method for producing an ultra-high-efficiency low-energy-consumption S-containing polymer aiming at the defects of the prior art, which is characterized in that a sulfur-containing monomer, a dihalogenated monomer, alkali, an end group control agent, a solvent leaching agent, a catalyst leaching agent and the like are adopted as raw materials, and solution polycondensation reaction is carried out through a microchannel reactor under the action of a catalyst, so that the high-performance ultra-high-efficiency low-energy-consumption S-containing polymer is prepared.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the present invention is to provide a method for preparing an S-containing polymer, comprising the steps of:
1) carrying out dehydration reaction on 32-248 parts of sulfur-containing monomer, 0.5-50 parts of catalyst, 0.5-50 parts of alkali and 100-400 parts of solvent at 150-220 ℃ to prepare a sulfur-containing reaction solution; dissolving 114-677 parts of dihalogenated monomer by 100-200 parts of solvent to prepare monomer solution; then, carrying out blending reaction on the sulfur-containing reaction solution and the monomer solution in a series-type microchannel reactor (a first group) at 165-260 ℃ to obtain a sulfur-containing polymer solution;
2) sending the sulfur-containing polymer solution obtained in the step 1) into another group of parallel microchannel reactors (a second group), and reacting with the end group control agent solution at 240-280 ℃ to obtain a sulfur-containing polymer mixed solution;
3) filtering or carrying out closed flash evaporation on the sulfur-containing polymer mixed solution obtained in the step 2) at a high temperature of 100-210 ℃, recovering part of the solvent in the mixed solution, and then respectively adding 100-500 parts of solvent leaching agent and 200-1000 parts of catalyst leaching agent to leach the rest of the solvent and the catalyst; and purifying to obtain the product, namely the S-containing polymer.
Further, in step 2), the end group control agent is:
Further, in step 1), the sulfur-containing monomer is selected from:
any one of the above.
Further, in step 1), the dihalo-aromatic compound has a structural formula of X-Ar-X, wherein X ═ F, Cl or Br,
Further, in the step 1), the sulfur-containing reaction solution and the monomer solution are subjected to a blending reaction for 5-1800 s at 165-260 ℃ in a series-type microchannel reaction to obtain a sulfur-containing polymer solution.
Further, in the step 1), the sulfur-containing reaction solution and the monomer solution are fed into the series-type microchannel reactor through a high-pressure metering pump, and the feeding speed is 15-1500 g/min.
Further, in the step 1), the number of reaction modules of the series-connection type microchannel reactor is 1-100 (preferably 10-60) groups, and the diameter of the microchannel is 1-10000 micrometers (preferably 5-500 micrometers).
Further, in the step 1), a sulfur-containing monomer, a catalyst, alkali and a solvent are subjected to dehydration reaction for 0.5-3 hours at 150-220 ℃ under the protection of inert gas to prepare a sulfur-containing reaction solution.
Further, in the step 2), the number of reaction modules of the parallel microchannel reactor is 1-20, and the diameter of the microchannel is 1-20000 micrometers (preferably 100-600 micrometers).
Further, in the step 2), the solution of the end group control agent is a solution prepared from 0.01-10 parts of the end group control agent and 5-50 ml of a solvent.
Further, in the step 3), the method for adding the solvent leaching agent to leach the residual solvent comprises the following steps: adding a leaching agent, and leaching the residual solvent for 2-5 times under the conditions of 10-150 ℃ and 0.5-40 MPa in a closed condition; and feeding the leached mixed gas into a gas-liquid separator through a filter screen to separate leaching agent from solvent.
Further, the solvent purity after adding a solvent leaching agent for leaching the residual solvent is more than or equal to 97.5 percent, the solvent is directly sent into a solvent recovery tank to be mixed with the solvent recovered by high-temperature filtration or closed flash evaporation, and the solvent can be directly applied to preparing subsequent products without purification or refining; the obtained leaching agent enters a closed circulation system, is recycled by a pump and is sent to a leaching agent recycling storage tank for recycling.
Further, in the step 3), the method for leaching the catalyst comprises the following steps: the solid crude product obtained after leaching the residual solvent adopts a catalyst leaching agent to recover and separate the catalyst; the liquid after leaching is subjected to multi-effect evaporation, the liquid is recycled as a next batch of catalyst leaching agent, and the solid is the recycled catalyst and can be directly used without post-treatment.
Further, in steps 1) to 3), the solvent is selected from: formamide, acetamide, N, N, N ', N' -tetramethylurea, N, N-dimethylformamide, N, N-dimethylacetamide, isoquinoline, N-phenylmorpholine, sulfolane, 2, 4-dimethylsulfolane, 1-methyl-3-propylimidazole bromide salt, 1-methyl-3-isopropylimidazole bromide salt, 1, 3-dipropylimidazolium bromide salt, dimethylsulfone, 2, 4-dimethylsulfolane, diphenylsulfone, hexamethylphosphoric triamide, dimethylformamide, epsilon-caprolactam, N-methylcaprolactam, N, any one of N-dimethylpropylurea, 1, 3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, N-cyclohexylpyrrolidone, or 2-pyrrolidone.
Further, in the step 1), the catalyst is LiCl or CeCl 2 Lithium oxalate, sodium oxalate, potassium oxalate, zinc oxalate, lithium malonate, sodium malonate, potassium malonate, zinc malonate, lithium succinate, sodium succinate, potassium succinate, lithium adipate, sodium adipate, potassium adipate, zinc adipate, lithium terephthalate, sodium terephthalate, potassium terephthalate, zinc terephthalate, lithium formate, sodium formate, potassium formate, zinc formate, lithium acetate, sodium acetate, potassium acetate, zinc acetate, lithium benzoate, sodium benzoate, potassium benzoate, zinc benzoate, lithium ethylenediamine tetraacetate, sodium ethylenediamine tetraacetate, potassium ethylenediamine tetraacetate, zinc ethylenediamine tetraacetate, lithium ethylenediamine tetraacetate, trisodium ethylenediamine tetraacetate, tripotassium ethylenediamine tetraacetate, lithium phosphate, sodium phosphate, potassium phosphate, lithium tartrate, sodium tartrate, potassium tartrate, sodium malonate, potassium malonate, zinc oxalate, zinc malonate, potassium oxalate, sodium oxalate, potassium, Sodium lactate, lithium sorbate, sodium sorbatePotassium sorbate, lithium lysinate, sodium lysinate, potassium lysinate, lithium cystinate, sodium cystinate, potassium cystinate, lithium citrate, sodium citrate, potassium citrate, zinc citrate, lithium 6-aminocaproate, sodium 6-aminocaproate, potassium 6-aminocaproate, zinc 6-aminocaproate, lithium nitrilotriacetate, sodium nitrilotriacetate, potassium nitrilotriacetate, zinc nitrilotriacetate, lithium hydroxyacetate, sodium hydroxyacetate, potassium hydroxyacetate, zinc hydroxyacetate, lithium gluconate, sodium gluconate, potassium gluconate, zinc gluconate, lithium diethylenetriaminepentacarboxylate, sodium diethylenetriaminepentacarboxylate, potassium diethylenetriaminepentacarboxylate, lithium heptonate, sodium heptonate, potassium heptonate, lithium glycollate, sodium glycocholate, potassium cholate, zinc cholate, lithium dioctylsuccinate, sodium dioctylsuccinate, potassium dioctylsuccinate, sodium dioctylsuccinate, Lithium ethylenediamine tetramethylene phosphate, sodium ethylenediamine tetramethylene phosphate, potassium ethylenediamine tetramethylene phosphate, lithium alginate, sodium alginate, potassium alginate, zinc alginate, lithium p-aminobenzenesulfonate, sodium sulfanilate, potassium p-aminobenzenesulfonate, zinc p-aminobenzenesulfonate, lithium p-methylbenzenesulfonate, sodium p-methylbenzenesulfonate, potassium p-methylbenzenesulfonate, zinc p-methylbenzenesulfonate, 15-crown-5, 18-crown-6, sodium stearate, potassium stearate, zinc stearate, sodium ethylenediamine tetramethylene phosphate, sodium diethylenetriamine pentamethylene phosphonate, or sodium aminomethylene trimetaphosphate.
Further, in step 1), the base is any one of lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium acetate, lithium bicarbonate, sodium bicarbonate, or potassium bicarbonate.
Further, in the step 3), the solvent leaching agent is any one of dichloromethane, chloroform, dichloroethane, acetone, butanone, pentanone, cyclohexanone, dioxane, tetrahydrofuran, diethyl ether, carbon dioxide, sulfur hexafluoride, difluoromethylene difluoride, trifluoromethane, tetrafluoromethane, tetrafluorodichloromethane, hexafluoroethane, tetrafluoroethane, hexafluoropropane or perfluorocyclobutane.
Further, in step 3), the catalyst leaching agent is any one of methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerol, isopropanol, isobutanol, tert-butanol, n-pentanol, isopentanol, n-hexanol, n-heptanol, n-octanol, or isooctanol.
The second technical problem to be solved by the present invention is to provide a sulfur-containing polymer, which is obtained by the above-mentioned method.
Furthermore, the sulfur-containing polymer has narrow molecular weight distribution, and the molecular weight distribution is 1.56-1.7.
Further, the sulfur-containing polymer has a halogen content of 250ppm or less.
The third technical problem to be solved by the present invention is to provide a post-treatment method of a sulfur-containing polymer, comprising the steps of:
(1) first recovery of solvent: in the process of preparing the S-containing polymer by adopting the method disclosed by the prior art, 240-1500 parts of the mixed solution of the sulfur-containing reaction product before post-treatment is subjected to high-temperature filtration or closed flash evaporation at 150-210 ℃, part of the solvent in the mixed solution of the reaction product is recovered, and the recovered solvent is conveyed to a solvent recovery tank;
(2) recovering the solvent wrapped in the resin by an extraction method: adding the material subjected to primary solvent recovery into a high-pressure leaching kettle, adding 100-500 parts of leaching agent, and leaching the residual solvent for 2-5 times under the conditions of 10-150 ℃ and 0.5-40 MPa in a closed manner; feeding the leached mixed gas into a 2-stage gas-liquid separator through a filter screen to separate a leaching agent from a solvent, automatically liquefying the solvent after the solvent passes through the 2-stage gas-liquid separator to obtain a high-purity solvent with the purity of more than or equal to 97.5%, directly feeding the high-purity solvent into a solvent recovery tank to be mixed with the recovered solvent in the step (1), and directly applying the solvent to preparation of subsequent products without purification or refining; the leaching agent enters a closed circulation system after passing through a 2-stage gas-liquid separator, and is recycled by a pump and sent to a leaching agent recycling storage tank for recycling;
(3) recovering the catalyst: recovering and separating the catalyst from the solid crude product obtained after the treatment in the step (2) by adopting 200-1000 parts of catalyst leaching agent; the liquid after leaching is subjected to multi-effect evaporation, the liquid is recycled to be used as a next batch of catalyst leaching agent, and the solid is a recycled catalyst and can be directly used without post-treatment; and (3) carrying out countercurrent washing and solid-liquid separation on the leached solid resin crude product for 3-6 times by adopting desalted water or washing water of the product of the last batch, and drying the separated water-containing sulfur-containing compound to obtain a sulfur-containing polymer (polyarylene sulfide substance).
Further, the solvent leaching agent is any one of dichloromethane, chloroform, dichloroethane, acetone, butanone, pentanone, cyclohexanone, dioxane, tetrahydrofuran, diethyl ether, carbon dioxide, sulfur hexafluoride, difluorodichloromethane, trifluoromethane, tetrafluoromethane, tetrafluorodichloromethane, hexafluoroethane, tetrafluoroethane, hexafluoropropane or perfluorocyclobutane.
Further, the catalyst leaching agent is any one of methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerol, isopropanol, isobutanol, tert-butanol, n-pentanol, isoamyl alcohol, n-hexanol, n-heptanol, n-octanol or isooctanol.
In the invention, the raw materials are in parts by weight except for special specifications.
The invention has the beneficial effects that:
1. according to the invention, the microchannel reactor is introduced into the preparation process of the S-containing polymer for the first time, so that the polymer with narrow molecular weight distribution (the molecular weight distribution is 1.56-1.7) can be prepared; and the proportion of the reaction and the molecular weight distribution of the sulfur-containing polymer can be controlled by controlling the feeding amount and the feeding speed of the sulfur-containing reaction solution and the dihalogenated monomer solution and the number of reaction modules of the microchannel reactor.
2. Because of the adoption of the microchannel reactor, the reaction efficiency is higher, the time is saved, and the heat release and the mass transfer of materials in the reaction process can be better controlled.
3. Compared with the traditional technical method, the method has the advantages that the reaction is carried out in two stages, the end group of the product can be more effectively controlled, the end-capping efficiency is higher by using the method of the microchannel reactor, the melt processing stability of the product is more excellent, the halogen content of the product is favorably reduced, the high-quality resin variety with ultralow halogen content (the halogen content of the obtained product can be 190ppm at least) is prepared, and the halogen-free or low-halogen requirements are met.
4. In the solvent recovery process, a combination mode of flash evaporation (or thermal filtration) and leaching is adopted, so that the solvent recovery rate is greatly improved to 98-99%, the purity is more than or equal to 97.5%, rectification and purification are not needed, the energy consumption is greatly reduced, and the cost is reduced.
5. The catalyst is recovered in a step-by-step and sectional mode, and is finally recovered and separated along with the catalyst leaching agent in a multi-effect evaporation mode, so that the catalyst is low in energy consumption and high in purity.
Description of the drawings:
FIG. 1 is a graph showing the results of infrared tests on the S-containing polymer obtained in example 1 of the present invention.
FIG. 2 is a chart showing DSC (differential scanning calorimetry) results of the S-containing polymer obtained in example 1 of the present invention.
FIG. 3 shows the IR characterization of the S-containing polymer obtained in example 2 of the present invention.
FIG. 4 shows DSC results of the S-containing polymer obtained in example 2 of the present invention.
FIG. 5 shows the results of IR characterization of the S-containing polymer obtained in example 3 of the present invention.
FIG. 6 shows DSC results of the S-containing polymer obtained in example 3 of the present invention.
Detailed Description
The present invention is described in detail below by way of examples, it being necessary to point out here that the examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as one skilled in the art may, in light of the above teachings, make insubstantial modifications and adaptations to the invention.
Example 1
(1) 50g of CeCl 2 Adding 50g of sodium carbonate, 400g of solvent isoquinoline and 178g of water-containing sodium sulfide into a pre-reaction kettle, performing dehydration reaction for 0.5h at the temperature of 220 ℃ under the protection of nitrogen to obtain a dehydrated pre-reaction solution, and keeping the temperature constant; 147g of p-dichlorobenzene and 100g of solvent isoquinoline are added into a pre-mixer, and after the dihalogenated monomer is dissolved, the pre-reaction solution and the monomer solution in the pre-mixer are respectively fed into the series-connection micro-channel by adopting a high-pressure metering pumpIn a reactor (module number: 50 groups), controlling the feeding molar ratio of the pre-reaction solution to the monomer solution in the pre-mixer to be 1:1.01(S monomer: dihalogenated monomer), the feeding speed to be 40g/min, and polymerizing for about 1400S at the temperature of 260 ℃ to obtain a sulfur-containing compound solution with a certain molecular weight and molecular weight distribution;
(2) then the obtained sulfur-containing compound solution is sent to another group of parallel microchannel reactors (the number of modules is 10), 0.5g of terminal group control agent thiophenol dissolved in 50ml of solvent isoquinoline is sent to the parallel microchannel reactors through a high-pressure metering pump to react with the obtained sulfur-containing compound, the reaction temperature is 265 ℃, and S-containing compound mixed solution is prepared;
(3) filtering the mixed solution containing the S compound at 150 ℃ at high temperature, recovering part of the solvent in the mixed solution, adding the obtained solid material into a high-pressure leaching kettle, adding 500g of acetone, and leaching the residual solvent for 5 times at 100 ℃ and 1MPa in a closed condition; feeding the leached mixed gas into a 2-stage gas-liquid separator through a filter screen to separate a leaching agent from a solvent, automatically liquefying the solvent after passing through the 2-stage gas-liquid separator to obtain a high-purity solvent with the purity of 98.2%, directly feeding the high-purity solvent into a solvent recovery tank to be mixed with the solvent recovered after high-temperature filtration in the step (3), and directly applying the solvent to preparation of subsequent products without purification or refining; the acetone enters a closed circulation system after passing through a 2-stage gas-liquid separator, is recycled by a pump and is sent to an extracting agent recycling storage tank for recycling;
(4) recovering and separating the catalyst from the solid crude product obtained after the treatment of the step (3) by adopting 1000g of catalyst leaching agent ethanol; the liquid after leaching is subjected to multi-effect evaporation, the liquid is recycled to be used as a next batch of catalyst leaching agent, and the solid is a recycled catalyst and can be directly used without post-treatment; carrying out countercurrent washing and solid-liquid separation on the leached solid resin crude product for 3 times by adopting desalted water or washing water of the product of the last batch, and drying the separated water-containing sulfur-containing compound to obtain the ultra-efficient low-energy-consumption S-containing polymer; the yield was 94%, the intrinsic viscosity [ η ] was 0.36, the weight average molecular weight was 61000, the molecular weight distribution was 1.61 (DMF was used as solvent, the mobile phase was also DMF, the prepared resin concentration was 2mg/ml, the sample injection rate was 0.200ml/min), the solvent recovery was 98.9%, the catalyst recovery was 97.3%, the melt index was 82g/10min, and the chloride ion content was 210 ppm.
The structure of the ultra-efficient low-energy-consumption S-containing polymer prepared by the invention is verified by infrared spectrum test, and is shown in figure 1; the glass transition temperature and melting point of the S-containing polymer were measured by Differential Scanning Calorimetry (DSC) and the results are shown in fig. 2: the melting point is 292.1 ℃, and the S-containing polymer obtained by the invention is proved to have better thermal property.
Example 2
(1) Adding 30g of lithium chloride, 5g of sodium hydroxide, 350g of solvent N-methyl pyrrolidone and 117g of water-containing sodium hydrosulfide into a pre-reaction kettle, performing dehydration reaction for 1h at the temperature of 200 ℃ under the protection of nitrogen to obtain a dehydrated pre-reaction solution, and keeping the temperature constant; 287g of 4, 4' -dichlorodiphenyl sulfone and 100g of solvent N-methylpyrrolidone are added into a pre-mixer, after the dihalogenated monomer is dissolved, the pre-reaction solution and the monomer solution in the pre-mixer are respectively fed into a series-type microchannel reactor (the number of modules is 40 groups) by adopting a high-pressure metering pump, the feeding molar ratio of the pre-reaction solution to the monomer solution in the pre-mixer is controlled to be 1:1.02(S monomer: dihalogenated monomer), the feeding speed is 50g/min, the polymerization is about 1100S, and the temperature is 190 ℃, so that the sulfur-containing compound solution with certain molecular weight and molecular weight distribution is obtained;
(2) then sending the obtained sulfur-containing compound solution to another group of parallel microchannel reactors (the number of modules is 8), and reacting 1g of end group control agent phenol dissolved in 40g of solvent N-methyl pyrrolidone with the obtained sulfur-containing compound by a high-pressure metering pump at the temperature of 200 ℃ to prepare ultra-high efficiency low energy consumption mixed solution of the S-containing compound;
(3) carrying out high-temperature flash evaporation on the reaction product mixed solution at 150 ℃, recovering part of the solvent in the reaction product mixed solution, adding the solid material into a high-pressure leaching kettle, adding 450g of dioxane, and leaching the residual solvent for 5 times under the conditions of 150 ℃ of temperature and 0.5MPa of pressure in a closed condition; feeding the leached mixed gas into a 2-stage gas-liquid separator through a filter screen to separate a leaching agent from a solvent, automatically liquefying the solvent after passing through the 2-stage gas-liquid separator to obtain a high-purity solvent with the purity of 97.8%, directly feeding the high-purity solvent into a solvent recovery tank to be mixed with the recovered solvent subjected to high-temperature flash evaporation in the step (3), and directly applying the solvent to preparation of subsequent products without purification or refining; the dioxane enters a closed circulation system after passing through a 2-stage gas-liquid separator, and is recycled by a pump and sent to a leaching agent recycling storage tank for recycling;
(4) recovering and separating the catalyst from the solid crude product obtained after the treatment of the step (3) by adopting 900g of catalyst leaching agent isopropanol; the liquid after leaching is subjected to multi-effect evaporation, the liquid is recycled to be used as a next batch of catalyst leaching agent, and the solid is a recycled catalyst and can be directly used without post-treatment; carrying out countercurrent washing and solid-liquid separation on the leached solid resin crude product for 5 times by adopting desalted water or washing water of the product of the last batch, and drying the separated water-containing sulfur-containing compound to obtain the ultra-efficient low-energy-consumption compound polyarylene sulfide sulfone; the yield was 99%, the intrinsic viscosity [. eta. ] -0.62, the weight average molecular weight was 76200, the molecular weight distribution was 1.56, the solvent recovery was 98.1%, the catalyst recovery was 97.9%, and the chloride ion content was 190 ppm; the infrared characterization is detailed in FIG. 3, and the DSC analysis is shown in FIG. 4: the glass transition temperature is 223.2 ℃, and the thermal property is better.
Example 3
(1) Adding 50g of sodium acetate, 45g of potassium carbonate, 350g of solvent N-methylpyrrolidone and 117g of water-containing sodium hydrosulfide into a pre-reaction kettle, and carrying out dehydration reaction for 1h at the temperature of 195 ℃ under the protection of nitrogen to obtain a dehydrated pre-reaction solution, and keeping the temperature constant; adding 4, 4' -difluorobenzophenone 218g and N-methylpyrrolidone 100g as a solvent into a pre-mixer, after the dihalogenated monomer is dissolved, respectively feeding the pre-reaction solution and the monomer solution in the pre-mixer into a series-connection type microchannel reactor (the number of modules: 80 groups) by adopting a high-pressure metering pump, controlling the feeding molar ratio of the pre-reaction solution to the monomer solution in the pre-mixer to be 1:0.99(S monomer: dihalogenated monomer), the feeding speed to be 350g/min, polymerizing for about 1800S, and controlling the temperature to be 240 ℃, thus obtaining a sulfur-containing compound solution with a certain molecular weight and molecular weight distribution;
(2) then sending the obtained sulfur-containing compound solution to another group of parallel microchannel reactors (the number of modules is 10), and reacting 1g of end group control agent bromobenzene dissolved in 40g of solvent N-methyl pyrrolidone with the obtained sulfur-containing compound by a high-pressure metering pump at the temperature of 260 ℃ to prepare ultra-high efficiency low energy consumption mixed solution of the S-containing compound;
(3) filtering the reaction product mixed solution at 140 ℃ to recover part of the solvent in the reaction product mixed solution, adding the solid material into a high-pressure leaching kettle, adding 450g of sulfur hexafluoride, and leaching the residual solvent for 4 times at 50 ℃ and 35MPa under a closed condition; conveying the leached mixed gas into a 2-stage gas-liquid separator through a filter screen to separate a leaching agent from a solvent, automatically liquefying the solvent after passing through the 2-stage gas-liquid separator to obtain a high-purity solvent with the purity of 99.1%, directly conveying the high-purity solvent into a solvent recovery tank to be mixed with the recovered solvent subjected to high-temperature filtration in the step (3), and directly applying the solvent to preparing subsequent products without further purification or refining; the sulfur hexafluoride enters a closed circulation system after passing through a 2-stage gas-liquid separator, is recycled by a pump and is sent to a leaching agent recycling storage tank for recycling;
(4) recovering and separating the catalyst from the solid crude product obtained after the treatment of the step (3) by adopting 700g of catalyst leaching agent ethylene glycol; the liquid after leaching is subjected to multi-effect evaporation, the liquid is recycled to be used as a next catalyst leaching agent, and the solid is a recycled catalyst and can be directly used without aftertreatment; carrying out countercurrent washing and solid-liquid separation on the leached solid resin crude product for 5 times by adopting desalted water or washing water of the product of the last batch, and drying the separated water-containing sulfur-containing compound to obtain the ultra-efficient low-energy-consumption compound polyarylene sulfide ketone; the yield was 96%, the intrinsic viscosity [. eta. ] -0.82, the weight average molecular weight was 57000, the molecular weight distribution was 1.65, the solvent recovery rate was 99.0%, the catalyst recovery rate was 98.3%, and the halogen ion content was 250 ppm; the infrared characterization is detailed in FIG. 5, and the DSC analysis is shown in FIG. 6: the melting point is 346 ℃, and the thermal property is better.
Example 4
(1) Adding 20g of sodium acetate, 18g of sodium amine trimethophorum phosphate, 36g of potassium bicarbonate, 400g of solvent N-cyclohexylpyrrolidone and 142g of para-phenyl dithiol into a pre-reaction kettle, performing dehydration reaction for 1 hour at the temperature of 215 ℃ under the protection of nitrogen to obtain dehydrated pre-reaction solution, and keeping the temperature constant; adding 4, 4' -bis (4-fluorobenzoyl) m-phenylenediamine 218g and N-cyclohexylpyrrolidone 200g as a solvent into a pre-mixer, after the dihalogenated monomer is dissolved, respectively feeding the pre-reaction solution and the monomer solution in the pre-mixer into a series-type microchannel reactor (number of modules: 60) by adopting a high-pressure metering pump, controlling the feeding molar ratio of the pre-reaction solution to the monomer solution in the pre-mixer to be 1:0.99(S monomer: dihalogenated monomer), the feeding speed to be 80g/min, polymerizing for about 1800S, and controlling the temperature to be 230 ℃, thus obtaining a sulfur-containing compound solution with a certain molecular weight and molecular weight distribution;
(2) then sending the obtained sulfur-containing compound solution to another group of parallel microchannel reactors (the number of modules is 6), and reacting 2g of end group control agent p-fluorotoluene dissolved in 50g of solvent N-cyclohexylpyrrolidone with the obtained sulfur-containing compound by a high-pressure metering pump at the temperature of 250 ℃ to obtain ultra-efficient low-energy-consumption S-containing compound mixed solution;
(3) filtering the reaction product mixed solution at 140 ℃ at high temperature, recovering part of the solvent in the reaction product mixed solution, adding the solid material into a high-pressure leaching kettle, adding 450g of tetrahydrofuran, and leaching the residual solvent for 5 times at 90 ℃ and 0.6MPa under a closed condition; feeding the leached mixed gas into a 2-stage gas-liquid separator through a filter screen to separate a leaching agent from a solvent, automatically liquefying the solvent after passing through the 2-stage gas-liquid separator to obtain a high-purity solvent with the purity of 99.2%, directly feeding the high-purity solvent into a solvent recovery tank to be mixed with the recovered solvent filtered at high temperature in the step (3), and directly applying the solvent to preparation of subsequent products without purification or refining; tetrahydrofuran enters a closed circulation system after passing through a 2-stage gas-liquid separator, is recycled by a pump and is sent to a leaching agent recycling storage tank for recycling;
(4) recovering and separating the catalyst from the solid crude product obtained after the treatment of the step (3) by adopting 950g of catalyst leaching agent methanol; the liquid after leaching is subjected to multi-effect evaporation, the liquid is recycled to be used as a next batch of catalyst leaching agent, and the solid is a recycled catalyst and can be directly used without post-treatment; carrying out 6 times of countercurrent water washing and solid-liquid separation on the leached solid resin crude product by adopting desalted water or washing water of the product of the last batch, and drying the separated water-containing sulfur-containing compound to obtain the ultra-efficient low-energy-consumption compound polyarylene sulfide amide; the yield was 96%, the intrinsic viscosity [. eta. ] -0.56, the weight-average molecular weight was 51400, the molecular weight distribution was 1.70, the solvent recovery rate was 98.6%, the catalyst recovery rate was 98.0%, and the fluorine ion content was 220 ppm.
Comparative example 1
The same procedure as in example 1 was followed, except that: the materials adopted in the comparative example 1 are various raw materials for preparing polyarylate, other process parameters are similar to those of the example 1, the weight average molecular weight of the obtained product is 35000-41000, and the molecular weight distribution is 8.9-11.6; when a traditional kettle type reactor is adopted, the weight average molecular weight of the obtained polyarylate product is 39000-51000, and the molecular weight distribution is 2-3.5; it follows that not all polymer preparations incorporating microchannel reactors achieve the result of producing materials with narrow molecular weight distributions.
Claims (25)
1. A method for preparing an S-containing polymer, comprising the steps of:
1) carrying out dehydration reaction on 32-248 parts of sulfur-containing monomer, 0.5-50 parts of catalyst, 0.5-50 parts of alkali and 100-400 parts of solvent at 150-220 ℃ for 0.5-3 h under the protection of inert gas to prepare a sulfur-containing reaction solution; dissolving 114-677 parts of dihalogenated monomer by 100-200 parts of solvent to prepare monomer solution; then, carrying out blending reaction on the sulfur-containing reaction solution and the monomer solution in a series-type microchannel reactor at 165-260 ℃ to obtain a sulfur-containing polymer solution;
2) feeding the sulfur-containing polymer solution obtained in the step 1) into another group of parallel microchannel reactors, and reacting the sulfur-containing polymer solution with the end group control agent solution at 240-280 ℃ to obtain a sulfur-containing polymer mixed solution;
3) filtering or carrying out closed flash evaporation on the sulfur-containing polymer mixed solution obtained in the step 2) at a high temperature of 100-210 ℃, recovering part of the solvent in the mixed solution, and then respectively adding 100-500 parts of solvent leaching agent and 200-1000 parts of catalyst leaching agent to leach the rest of the solvent and the catalyst; and purifying to obtain the product, namely the S-containing polymer.
2. The method of claim 1, wherein in step 1), the sulfur-containing monomer is selected from the group consisting of:
3. The method of claim 1, wherein the dihalo-monomer in step 1) has the formula X-Ar-X, wherein X-F, Cl or Br,
4. The method of claim 1 or 2, wherein in step 2), the end-group controlling agent is:
5. The process according to claim 1 to 3, wherein the S-containing polymer is a copolymer of a propylene polymer and a propylene polymer,
in the step 1), the sulfur-containing reaction solution and the monomer solution are reacted in a series-type micro-channel, and are subjected to a blending reaction for 5-1800 s at 165-260 ℃ to obtain a sulfur-containing polymer solution.
6. The process according to any one of claims 1 to 3, wherein in the step 1), the sulfur-containing reaction solution and the monomer solution are fed into the cascade type microchannel reactor by a high-pressure metering pump at a feed rate of 15 to 1500 g/min.
7. The method according to any one of claims 1 to 3, wherein in the step 1), the number of reaction modules of the series-type microchannel reactor is 1 to 100, and the diameter of the microchannel is 1 to 10000. mu.m.
8. The method according to claim 7, wherein in step 1), the number of reaction modules of the series-type microchannel reactor is 10-60 groups, and the diameter of the microchannel is 5-500 μm.
9. The method according to any one of claims 1 to 3, wherein in the step 2), the number of reaction modules of the parallel microchannel reactor is 1 to 20, and the diameter of the microchannel is 1 to 20000 μm.
10. The method of claim 9, wherein the diameter of the microchannel in step 2) is 100 to 600 μm.
11. The method for preparing S-containing polymer according to any one of claims 1 to 3, wherein the solution of the end-group controlling agent in the step 2) is a solution of 0.01 to 10 parts of the end-group controlling agent and 5 to 50ml of a solvent.
12. The process according to claim 1 to 3, wherein the S-containing polymer is a copolymer of a propylene polymer and a propylene polymer,
in the step 3), the method for adding the solvent leaching agent to carry out residual solvent leaching comprises the following steps: adding a leaching agent, and leaching the residual solvent for 2-5 times under the conditions of 10-150 ℃ and 0.5-40 MPa in a closed condition; and feeding the leached mixed gas into a gas-liquid separator through a filter screen to separate leaching agent from solvent.
13. The process according to claim 12 for preparing an S-containing polymer,
the solvent purity after adding the solvent leaching agent for leaching the residual solvent is more than or equal to 97.5 percent, the solvent is directly sent into a solvent recovery tank to be mixed with the solvent recovered by high-temperature filtration or closed flash evaporation, and the solvent can be directly applied to preparing subsequent products without purification or refining; the obtained leaching agent enters a closed circulation system, is recycled by a pump and is sent to a leaching agent recycling storage tank for recycling.
14. A process for producing an S-containing polymer according to any one of claims 1 to 3,
in the step 3), the method for leaching the catalyst comprises the following steps: the solid crude product obtained after leaching the residual solvent adopts a catalyst leaching agent to recover and separate the catalyst; and (3) performing multi-effect evaporation on the liquid after leaching, recovering the liquid to be used as a next catalyst leaching agent, and recovering the solid to be a recovered catalyst, so that the solid can be directly used without aftertreatment.
15. The process according to claim 1 to 3, wherein the S-containing polymer is a copolymer of a propylene polymer and a propylene polymer,
in step 1) to step 3), the solvent is selected from: formamide, acetamide, N, N, N ', N' -tetramethylurea, N, N-dimethylformamide, N, N-dimethylacetamide, isoquinoline, N-phenylmorpholine, sulfolane, 2, 4-dimethylsulfolane, 1-methyl-3-propylimidazole bromide salt, 1-methyl-3-isopropylimidazole bromide salt, 1, 3-dipropylimidazolium bromide salt, dimethylsulfone, 2, 4-dimethylsulfolane, diphenylsulfone, hexamethylphosphoric triamide, dimethylformamide, epsilon-caprolactam, N-methylcaprolactam, N, any one of N-dimethylpropylurea, 1, 3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, N-cyclohexylpyrrolidone, or 2-pyrrolidone.
16. The method according to any one of claims 1 to 3, wherein the catalyst in step 1) is LiCl or CeCl 2 Lithium oxalate, sodium oxalate, potassium oxalate, zinc oxalate, lithium malonate, sodium malonate, potassium malonate, zinc malonate, lithium succinate, sodium succinate, potassium succinate, lithium adipate, sodium adipate, potassium adipate, zinc adipate, lithium terephthalate, sodium terephthalate, potassium terephthalate, zinc terephthalate, lithium formate, sodium formate, potassium formate, zinc formate, lithium acetate, sodium acetate, potassium acetate, zinc acetate, lithium benzoate, sodium benzoate, potassium benzoate, zinc benzoate, lithium ethylenediamine tetraacetate, sodium ethylenediamine tetraacetate, potassium ethylenediamine tetraacetate, zinc ethylenediamine tetraacetate, lithium ethylenediamine tetraacetate, trisodium ethylenediamine tetraacetate, tripotassium ethylenediamine tetraacetate, lithium phosphate, sodium phosphate, potassium phosphate, lithium tartrate, sodium tartrate, potassium tartrate, sodium malonate, potassium malonate, zinc oxalate, zinc malonate, potassium oxalate, sodium oxalate, potassium, Sodium lactate, lithium sorbate, sodium sorbate, potassium sorbate, lithium lysinate, sodium lysinate, potassium lysinate, lithium cystinate, sodium cystinate, potassium cystinate, lithium citrate, sodium citrate, potassium citrate, zinc citrate, lithium 6-aminohexanoate, sodium 6-aminohexanoate, potassium 6-aminohexanoate, zinc 6-aminohexanoate, lithium nitrilotriacetate, sodium nitrilotriacetate, potassium nitrilotriacetate, zinc nitrilotriacetate, lithium hydroxyacetate, sodium hydroxyacetate, potassium hydroxyacetate, zinc hydroxyacetate, lithium gluconate, sodium gluconate, potassium gluconate, zinc gluconate, lithium diethylenetriaminepentacarboxylate, sodium diethylenetriaminepentacarboxylate, potassium diethylenetriaminepentacarboxylate, lithium heptonate, sodium heptonate, potassium heptonate, lithium choledocarbonate, sodium glycocholate, potassium glycocholate, zinc glycocholate, dioctyl succinate, IIAt least one of sodium octyl succinate, potassium dioctyl succinate, lithium ethylenediamine tetramethylene phosphate, sodium ethylenediamine tetramethylene phosphate, potassium ethylenediamine tetramethylene phosphate, lithium alginate, sodium alginate, potassium alginate, zinc alginate, lithium p-aminobenzenesulfonate, sodium p-aminobenzenesulfonate, potassium p-aminobenzenesulfonate, zinc p-aminobenzenesulfonate, lithium p-methylbenzenesulfonate, sodium p-methylbenzenesulfonate, potassium p-methylbenzenesulfonate, zinc p-methylbenzenesulfonate, 15-crown-5, 18-crown-6, sodium stearate, potassium stearate, zinc stearate, sodium diethylenetriamine pentamethylene phosphonate or sodium amine trimetaphosphate.
17. The method according to any one of claims 1 to 3, wherein in the step 1), the base is any one of lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium acetate, lithium bicarbonate, sodium bicarbonate, or potassium bicarbonate.
18. The method according to any one of claims 1 to 3, wherein in the step 3), the solvent leaching agent is any one of dichloromethane, chloroform, dichloroethane, acetone, butanone, pentanone, cyclohexanone, dioxane, tetrahydrofuran, diethyl ether, carbon dioxide, sulfur hexafluoride, difluorodichloromethane, trifluoromethane, tetrafluoromethane, tetrafluorodichloromethane, hexafluoroethane, tetrafluoroethane, hexafluoropropane or perfluorocyclobutane.
19. The method according to any one of claims 1 to 3, wherein in the step 3), the catalyst leaching agent is any one of methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerol, isopropanol, isobutanol, tert-butanol, n-pentanol, isoamyl alcohol, n-hexanol, n-heptanol, n-octanol or isooctyl alcohol.
20. An S-containing polymer, characterized in that it is obtainable by a process according to any one of claims 1 to 19.
21. The S-containing polymer of claim 20, wherein the sulfur-containing polymer has a narrow molecular weight distribution of 1.56 to 1.7.
22. An S-containing polymer according to claim 20, wherein said sulfur-containing polymer has a halogen content of 250ppm or less.
23. A method for post-treating S-containing polymers, characterized in that it comprises the following steps:
(1) first recovery of solvent: in the process of preparing the S-containing polymer by adopting the method disclosed by the prior art, 240-1500 parts of the mixed solution of the sulfur-containing reaction product before post-treatment is subjected to high-temperature filtration or closed flash evaporation at 150-210 ℃, part of the solvent in the mixed solution of the reaction product is recovered, and the recovered solvent is conveyed to a solvent recovery tank;
(2) recovering the solvent wrapped in the resin by an extraction method: adding the material subjected to primary solvent recovery into a high-pressure leaching kettle, adding 100-500 parts of leaching agent, and leaching the residual solvent for 2-5 times under the conditions of 10-150 ℃ and 0.5-40 MPa in a closed manner; feeding the leached mixed gas into a 2-stage gas-liquid separator through a filter screen to separate a leaching agent from a solvent, automatically liquefying the solvent after the solvent passes through the 2-stage gas-liquid separator to obtain a high-purity solvent with the purity of more than or equal to 97.5%, directly feeding the high-purity solvent into a solvent recovery tank to be mixed with the recovered solvent in the step (1), and directly applying the solvent to preparation of subsequent products without purification or refining; the leaching agent enters a closed circulation system after passing through a 2-stage gas-liquid separator, is recycled by a pump and is sent to a leaching agent recycling storage tank for recycling;
(3) recovering the catalyst: recovering and separating the catalyst from the solid crude product obtained after the treatment in the step (2) by adopting 200-1000 parts of catalyst leaching agent; the liquid after leaching is subjected to multi-effect evaporation, the liquid is recycled to be used as a next batch of catalyst leaching agent, and the solid is a recycled catalyst and can be directly used without post-treatment; and (3) carrying out countercurrent washing and solid-liquid separation on the leached solid resin crude product for 3-6 times by using desalted water or washing water of the product of the last batch, and drying the separated water-containing sulfur-containing compound to obtain the S-containing polymer.
24. The method of claim 23, wherein the solvent extraction agent is any one of dichloromethane, chloroform, dichloroethane, acetone, butanone, pentanone, cyclohexanone, dioxane, tetrahydrofuran, diethyl ether, carbon dioxide, sulfur hexafluoride, difluorodichloromethane, trifluoromethane, tetrafluoromethane, tetrafluorodichloromethane, hexafluoroethane, tetrafluoroethane, hexafluoropropane or perfluorocyclobutane.
25. The method of claim 23, wherein the catalyst leaching agent is any one of methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerol, isopropanol, isobutanol, t-butanol, n-pentanol, isoamyl alcohol, n-hexanol, n-heptanol, n-octanol, or isooctanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111432287.1A CN114015047B (en) | 2021-11-29 | 2021-11-29 | S-containing polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111432287.1A CN114015047B (en) | 2021-11-29 | 2021-11-29 | S-containing polymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114015047A CN114015047A (en) | 2022-02-08 |
| CN114015047B true CN114015047B (en) | 2022-09-23 |
Family
ID=80067561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111432287.1A Active CN114015047B (en) | 2021-11-29 | 2021-11-29 | S-containing polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114015047B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115466388B (en) * | 2022-09-16 | 2023-09-08 | 华南理工大学 | Polythiourea compound and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7442360B2 (en) * | 2004-04-27 | 2008-10-28 | Velocys, Inc. | Hydrogen peroxide production in microchannel reactors |
| KR102251793B1 (en) * | 2018-10-19 | 2021-05-13 | 주식회사 엘지화학 | Process for separation and recovering polyarylene sulfide |
| CN111100286B (en) * | 2018-10-26 | 2022-09-23 | 成都锦颜科技有限公司 | Green high-purity polyarylether and preparation method thereof |
-
2021
- 2021-11-29 CN CN202111432287.1A patent/CN114015047B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114015047A (en) | 2022-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8680230B2 (en) | Production process of poly(arylene sulfide) whose content of terminal halogen group has been reduced | |
| US8530605B2 (en) | Poly(arylene sulfide) and production process thereof | |
| CN108602954B (en) | Method for producing granular polyarylene sulfide, method for increasing average particle diameter of granular polyarylene sulfide, method for improving particle strength of granular polyarylene sulfide, and granular polyarylene sulfide | |
| US5635587A (en) | Process for manufacturing polyarylene sulfide | |
| JPS63289025A (en) | Improved manufacture of poly(p-phenylenesulfide) | |
| CN103172864A (en) | Preparation method of organic acid salt catalytic polyarylene sulfide | |
| CN114015047B (en) | S-containing polymer and preparation method thereof | |
| CN115572389B (en) | Method for preparing high-reactivity polyphenylene sulfide resin and product thereof | |
| CN115335435A (en) | Polyarylene sulfide and method for producing same | |
| CN110121521B (en) | Process for producing granular polyarylene sulfide and granular polyarylene sulfide | |
| EP3617250B1 (en) | Method for preparing polyarylene sulfide | |
| CN117362646A (en) | High Wen Benzheng-resistant ultralow-dielectric polyarylether, foaming material and preparation thereof | |
| CN114349953B (en) | Environment-friendly ether-containing elastomer and preparation method thereof | |
| CN114249894B (en) | Ether-containing polymer containing active group and preparation method and application thereof | |
| US11661482B2 (en) | Separation and purification method of polyarylene sulfide | |
| CN115960354A (en) | Purification method of polyarylether and high-purity polyarylether | |
| US11597800B2 (en) | Separation and recovery method of polyarlene sulfide | |
| US11427683B2 (en) | Preparation method of polyarylene sulfide | |
| CN115746302B (en) | Material recycling process in polyphenylene sulfide production process | |
| CN110256664B (en) | Preparation method of poly (arylene ether nitrile) resin | |
| US11414521B2 (en) | Preparation method of polyarylene sulfide | |
| CN117384380A (en) | Method for synthesizing polyphenylene sulfide by pressurizing inert gas without aid | |
| CN115151597A (en) | Method for producing polyarylene sulfide | |
| CN118652422A (en) | High-purity high-temperature-resistant anti-aging low-dielectric polyphenyl ether and preparation method thereof | |
| KR20200036327A (en) | Method for praparing polyarylene sulfide |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |