CN102352033B - Method for preparing powdered resin - Google Patents
Method for preparing powdered resin Download PDFInfo
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- CN102352033B CN102352033B CN 201110271160 CN201110271160A CN102352033B CN 102352033 B CN102352033 B CN 102352033B CN 201110271160 CN201110271160 CN 201110271160 CN 201110271160 A CN201110271160 A CN 201110271160A CN 102352033 B CN102352033 B CN 102352033B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/14—Powdering or granulating by precipitation from solutions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/06—Treatment of polymer solutions
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- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/46—Post-polymerisation treatment, e.g. recovery, purification, drying
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/06—Polysulfones; Polyethersulfones
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Abstract
The invention provides a method for preparing powdered resin, which comprises the following steps of: (1) performing polymerization reaction, and directly reducing the temperature at a speed of 2 to 50 DEG C/min for 1 to 60 minutes to precipitate polymer from a reaction system so as to form polymer colloidal solution; and stirring at a speed of 10 to 3,000 revolutions/minute in the process to prevent agglomeration; (2) when the temperature of the system is reduced to be between 130 and 250 DEG C, adding a certain amount of poor solvent into the mixture to make a polymerization product system and the poor solvent form a suspension liquid mixture; (3) removing mother solution from suspension polymer by a centrifuging, filtering or leaching method, and performing filtering separation to obtain a required polymer crude product; and (4) extracting and refining salt and impurities in the polymer at a high temperature for multiple times by using a solvent or boiling water, and drying to obtain a product. The treatment method has the advantages that: polymer powder with a uniform size is obtained through process control; materials are quickly discharged, and the viscosity of resin is prevented from being changed in the discharging process; and the problem that the materials are adhered to the wall of a reaction kettle is solved, and production efficiency is improved.
Description
Technical field
The present invention relates to a kind of method for preparing powdex, particularly a kind of preparation method of high-performance powder resin.
Background technology
Advantages such as that many resins such as polyaryletherketone resin have is high temperature resistant, HS, radiation hardness because of its polymeric reaction temperature is everlasting more than 300 ℃, need be used high-temperature solvent such as sulfobenzide etc., and other solvents all can't adapt to.No matter adopt which kind of solvent to synthesize, after polycondensation finishes, all need and isolate, reaction solvent, inorganic salt, residual monomer and other compounds are therefrom removed the reaction product washing.Wherein, the most difficult what remove is alkali metal halide, alkaline earth metal halide.Residual in the polymkeric substance have high-content by product or solvent can cause final product in the various extrusion die plastics of moulding, to have technical disadvantages; Form striped from the teeth outwards like high-content by product or solvent; Cause the peculiar smell puzzlement, cause the mechanical property of bubble and material to reduce.In addition; Some by product has genotoxic potential and possibly cause Health cost; Owing to these reasons, common volatile constituent in the polymkeric substance is removed to is lower than 0.1% residual content, in some cases; Also will be removed to residual content, so aftertreatment needs the washing of very many times and high amounts of solvents usually in the ppm scope.
To the technologic improvement of product postprocessing, mainly contain the following aspects: 1, suitable solvent capable of using washs polymkeric substance, also can adopt the mode of elevated temperature and pressure to wash (WO 02/096974, CN 200510082627.7); 2, (US 5357040, and US 5288834, and EP-A-0297363), but, owing to its desired LV needs a large amount of reaction solvents, above-mentioned solvent must expensively be removed through before reaction mixture cured, filtering separating inorganic salts; 3, removing reaction solvent (DE-A-4301543) through spraying drying will remove the complete heating evaporation of solvent, also is very expensive; 4, in addition a kind of is through outgasing in the forcing machine, but can not remove reaction solvent fully, and under 350 ℃ ~ 420 ℃ conventional processing temperature, extruding the required overstand of the machine degassing, causes polymkeric substance to receive pyrolytic damage.
Chinese patent 200610005142.2 discloses a kind of technology of wet pulverization, adopts the wet pulverization reaction mixture, then through in the pressurization withdrawal device, extracting and filter the product of wet pulverization.Still there are problems in this post-treating method, as pulverizing or grinding, material transfer to shredder, is transferred to washing container from shredder, and is further transferred to the high expense of aspects such as moisture eliminator, problems such as product loss and pollution.In addition, the separated aftertreatment technology step in this equipment and space is dangerous, and promptly the dried ingredients by the reactor drum ejecta forms dangerous dust-air mixture, causes unnecessary explosion hazard.Adopt this kind technology in producing at present mostly.
How to control the aftertreatment technology condition, can avoid polymkeric substance to pulverize process, it is controlled both to have reached size of particles, can improve again simultaneously and boil the material effect, improves the product quality and becomes an important goal in research.The shortcoming that energy expenditure is big, treatment effect is bad that original resin aftertreatment technology exists.
Summary of the invention
The objective of the invention is to overcome provides the post-treating method that a kind of production efficiency is high, energy consumption is saved, production cost is low, through to the control aftertreatment technology, obtains the toner of specified particle diameter size.
The aftertreatment technology of preparation toner according to the invention comprises the steps: (1) at first directly cooling after polyreaction finishes, and polymkeric substance precipitates to separate out from reaction system and obtains the gluey liquid of polymkeric substance; Cooling rate is preferably 2 ~ 50 ℃/min, and temperature fall time is 1 ~ 60min; Strengthen stirring velocity and make the gluey liquid homodisperse of polymkeric substance, stirring velocity is preferably 10 ~ 3000 commentaries on classics/min; (2) cool to 130 ~ 250 ℃ when system, in this mixture, add a certain amount of poor solvent again, make polymerisate system and poor solvent form the suspension liquid mixture; (3), obtain needed polymer crude product with the suspended substance solid-liquid separation; (4) thick product is made with extra care drying.
Said performance resins comprises poly aryl ether ketone, polyarylether class, polysulfones; The solvent that polyreaction adopts is a sulfobenzide; The mixture of one or more in DMSO 99.8MIN., METHYL SULFONYL METHANE., diethylammonium sulfone, diethyl sulfoxide, di-isopropyl sulfone, sulfobenzide, tetramethylene sulfone or the tetramethyl-sulfone, reaction system solids content are 5% ~ 60% by weight percentage.
The aftertreatment technology of said preparation toner; Adopt temperature reduction technology, cooling rate is 2 ~ 50 ℃/min, more preferably 5 ~ 30 ℃; Cool to 130 ~ 250 ℃; Temperature fall time is 1 ~ 60min, and air-cooled, water-cooled that cooling method is taked can also be employed in the extraneous cold oil cooling method of input in the jacket of polymerization deep fat.
The aftertreatment technology of said preparation toner, the poor solvent that in system, adds are water, ethanol, acetone, YLENE, toluene or tetramethylene sulfone, and the volume ratio of the solvent of adding and polymerization solvent for use is 1:2 ~ 3:1, is preferably 1:1 ~ 2:1.
Said polyreaction stirring rake is anchor formula, oar formula, turbine type, push type, frame, scrapes wall type, high-shear formula, disc type, gear piece formula, helical-ribbon type stirring arm, planetary stirring rake; Or multilayer stirring rake; The blade of stirring rake is double leaf, multiple-blade; Flat leaf, hinged joint, curved leaf, or adopt multi-form stirring rake combination.
The mixing speed scope is 10 ~ 1000 commentaries on classics/min before the cooling of said polyreaction, and the mixing speed scope is 10-3000 commentaries on classics/min in the last handling process, more preferably in the last handling process mixing speed greater than the polyreaction rotating speed.
Polymer crude product is removed mother liquor with the method for centrifugal, filtration or leaching, and thick product is made with extra care salt in the polymkeric substance and impurity are at high temperature multiple extraction with boiling water or solvent, and obtains product after the drying.Resulting toner grain size is evenly distributed, and size of particles is 50 ~ 500um.
The method for preparing powdex according to the invention, its advantage is following:
1) original disintegrating process is polymkeric substance in big water gaging the ecto-entad cooling is separated out, and crude product is vesicular, wherein includes a lot of solvents, needs use a large amount of water treatments, the product tap density that obtains little; And polymkeric substance is separated out from solution naturally in the technology according to the invention, and the product tap density is big, and water consumption or quantity of solvent are controlled in the discharging process; Solvent is dense in the mother liquor of filtration back; Significantly reduced the waste of solvent, practiced thrift energy consumption, also can improve greatly and boil material efficient;
2) reduce pulverising step, thereby avoided crushing process can introduce that a large amount of smog, the kibblers of generation produces problems such as a large amount of noises in iron contamination, the crushing process, can improve workshop condition greatly; In the reaction kettle all polymkeric substance all deposition separate out, direct water flushing avoided the residual of product in the reaction kettle, also avoided a large amount of loaded down with trivial details engineering of reaction kettle being cleaned after the repeatedly polymerization;
3) the aftertreatment time short, polymer viscosity changes very for a short time in last handling process, has improved the homogeneity of product;
4) solid content generally can not surpass 15% in original technology; Otherwise because product viscosity is very big, polymkeric substance can not be emitted from reaction kettle smoothly, and the solid content of polymkeric substance improves greatly in the technology of the present invention; Can reach 60%; Can not influence discharging, so the solvent usage quantity is few, thereby further reaches the purpose of practicing thrift cost;
Therefore, discharging technology according to the invention has not only improved production efficiency greatly, has improved productive rate, has improved the quality of product, has saved energy consumption, has reduced production cost, has improved workshop condition simultaneously, has the effect of achieving many things at one stroke.
Description of drawings
Fig. 1 is the micro-amplification picture of the product particle of toner aftertreatment technology according to the invention;
Fig. 2 is the micro-amplification picture of the product particle of the said toner aftertreatment technology of original technology.
Embodiment
Below introduce specific embodiment and come the present invention is described further, but these specific embodiments are not to limit the invention.
Embodiment 1 (solid content about 15%)
Polymerization process:
In the four-hole reaction kettle that TM, logical nitrogen tube, condensation water trap, anchor stirrer are housed; Add refining tetramethylene sulfone 50Kg earlier; Add 4 of 6.67Kg then; 4 ' difluoro benzophenone and 3.303Kg Resorcinol when treating that it all dissolves and treating that temperature is raised to 80 ℃, add 3.498Kg (excessive 2%) Na
2CO
3, add 2Kg YLENE again after, stir, heating, treat that temperature rises to 150 ℃; System begins azeotropic, and YLENE and water condensation are arranged in the water trap, the upper strata refluxing xylene, and lower layer of water is constantly emitted; When treating that water is recovered to theoretical amount, upper strata YLENE begins clear, continues to reflux 20 minutes again, begins from system, to steam YLENE then; System temperature is constantly risen by heating, reach 263 ~ 265 ℃ to temperature after, keep constant temperature, system viscosity carries out viscosity with polyreaction and constantly increases; After treating 1.5 hours, viscosity reaches stopped reaction after the stationary value, and this moment, mixing speed was 50 commentaries on classics/min.
The discharging process:
Stop heating, adopt in reaction heat supply oil oven to add the cooling oil cooling, cooling rate is 5 ℃/min; Liquid precipitates gradually and separates out in the reaction kettle, slowly becomes gel, strengthens the stirring dynamics; Mixing speed is transferred to 100 commentaries on classics/min, and stirring rake produces the effect of high shear, and gel is disperseed; Make it be unlikely to agglomerating, cool to 130 ℃ and in reaction kettle, add water 25L, solution becomes suspended substance gradually.
Suspended substance is emitted spinning.Discharging process 30 minutes.Tetramethylene sulfone content is 70% in the test mother liquor.Poach polymkeric substance 5 times is used the 300L deionized water at every turn, each boiling time 40 minutes, and the F ion content is 0.2mg/L in the detection solution, and the refining completion of product is described.Oven dry, the test product property.Sampling uses viscometer test characteristic viscosity to be 0.72dl/g.Record product and melt to refer to be 100g/10min.Recording size distribution D50 is 200um.
Embodiment 2 (solid content about 30%)
Polymerization process:
In the four-hole reaction kettle that TM, logical nitrogen tube, condensation water trap, paddle stirrer are housed; Add refining tetramethylene sulfone 20Kg earlier; 4,4 ' difluoro benzophenone and the 3.303Kg Resorcinol (can get polymkeric substance 8.64Kg, solid content is about 30%) that add 6.67Kg then; When treating that it all dissolves and treating that temperature is raised to 80 ℃, add 3.498g (excessive 2%) Na
2CO
3, continue to heat up again, add 2Kg YLENE again after, stir, heating; Treat that temperature rises to 150 ℃, system begins azeotropic, and YLENE and water condensation are arranged in the water trap, the upper strata refluxing xylene; Lower layer of water is constantly emitted, and when treating that water is recovered to theoretical amount, upper strata YLENE begins clear, continues to reflux 20 minutes again; Begin from system, to steam YLENE then, system temperature is constantly risen by heating, reach 260 ~ 262 ℃ to temperature after, keep constant temperature; System viscosity carries out viscosity with polyreaction and constantly increases, and after 1.5 hours, treats that viscosity reaches stopped reaction after the stationary value, and this moment, rotating speed of agitator was 80 commentaries on classics/min.
The discharging process:
Stop heating, in reaction heat supply oil oven, add the cooling oil cooling, cooling rate is 20 ℃/min, and liquid precipitates gradually and separates out in the reaction kettle; Slowly become gel, strengthen the stirring dynamics, rotating speed of agitator is transferred to 220 commentaries on classics/min; Stirring rake produces the effect of high shear, and gel is disperseed, and makes it be unlikely to agglomerating; Cool to 180 ℃, in reaction kettle, add water (about 30L), solution becomes suspended substance gradually.
Suspended substance is emitted spinning.Discharging process 6 minutes.Tetramethylene sulfone content is 58% in the test mother liquor.Poach polymkeric substance 6 times is used the 300L deionized water at every turn, each boiling time 40 minutes.The F ion content is 0.3 mg/L in the detection solution, and product is refining to be accomplished.Oven dry, the test product property.Sampling uses viscometer test characteristic viscosity to be 0.85dl/g, melts to refer to 71g/10min.Test size distribution D50 is 300um.
Embodiment 3 (solid content about 15%) polymerization process:
In the four-hole reaction kettle that TM, logical nitrogen tube, condensation water trap, propeller agitator are housed; Add refining tetramethylene sulfone 50Kg earlier; 4,4 ' difluoro benzophenone and the 3.303Kg Resorcinol (can get polymkeric substance 8.64Kg, solid content is about 15%) that add 6.67Kg then; When treating that it all dissolves and treating that temperature is raised to 80 ℃, add 3.498Kg (excessive 2%) Na
2CO
3, continue to heat up again, add 2Kg YLENE again after, stir, heating; Treat that temperature rises to 150 ℃, system begins azeotropic, and YLENE and water condensation are arranged in the water trap, the upper strata refluxing xylene; Lower layer of water is constantly emitted, and when treating that water is recovered to theoretical amount, upper strata YLENE begins clear, continues to reflux 20 minutes again; Begin from system, to steam YLENE then, system temperature is constantly risen by heating, reach 263 ℃ to temperature after, keep constant temperature; System viscosity carries out viscosity with polyreaction and constantly increases, and continue to keep 1 hour 40 minutes, treats that viscosity reaches stopped reaction after the stationary value.This moment, stirring rake speed was 200 commentaries on classics/min.
The discharging process:
Stop heating, in reaction heat supply oil oven, add the cooling oil cooling, cooling rate is 30 ℃/min, and liquid precipitates gradually and separates out in the reaction kettle; Slowly become gel, strengthen the stirring dynamics, the stirring rake speed setting is 500 commentaries on classics/min; Stirring rake produces the effect of high shear, and gel is disperseed, and makes it be unlikely to agglomerating; Cool to 240 ℃, in reaction kettle, add tetramethylene sulfone 50L, solution becomes suspended substance gradually.
Suspended substance is emitted spinning, discharging process 4 minutes.The content of tetramethylene sulfone is 99% in the mother liquor.Poach polymkeric substance 5 times is used the 300L deionized water at every turn, each boiling time 40 minutes, and the F ion content is 0.35 mg/L in the detection solution, product is refining to be accomplished.Oven dry, the test product property.Limiting viscosity is 0.9dl/g, melts to refer to be 45g/10min.D50 is 150um.
Embodiment 4 (solid content about 26%)
Polymerization process:
In the four-hole reaction kettle that TM, logical nitrogen tube, condensation water trap, powerful combined impeller are housed; Add refining tetramethylene sulfone 25Kg earlier; 4,4 ' difluoro benzophenone and the 3.303g Resorcinol (can get polymkeric substance 8.64g, solid content is about 26%) that add 6.67g then; When treating that it all dissolves and treating that temperature is raised to 80 ℃, add 3.5Kg (excessive 2%) Na
2CO
3, continue to heat up again, add 4L YLENE again after, stir, heating; Treat that temperature rises to 150 ℃, system begins azeotropic, and YLENE and water condensation are arranged in the water trap, the upper strata refluxing xylene; Lower layer of water is constantly emitted, and when treating that water is recovered to theoretical amount, upper strata YLENE begins clear, continues to reflux 20 minutes again; Begin from system, to steam YLENE then, system temperature is constantly risen by heating, reach 265 ℃ to temperature after, keep constant temperature; System viscosity carries out viscosity with polyreaction and constantly increases, and treats after 2 hours that viscosity reaches stopped reaction after the stationary value, and this moment, stirring rake speed was 95 commentaries on classics/min.
The discharging process:
Stop heating, add cooling oil to reaction oil bath chuck, cooling rate is 48 ℃/min, and liquid precipitates gradually and separates out in the reaction kettle; Slowly become gel, strengthen the stirring dynamics, rotating speed of agitator is adjusted to 100 commentaries on classics/min; Stirring rake produces the effect of high shear, and gel is disperseed, and makes it be unlikely to agglomerating; Cool to 200 ℃, in reaction kettle, add tetramethylene sulfone 59L, solution becomes suspended substance gradually.
Suspended substance is emitted, spinning, discharging process 5 minutes, tetramethylene sulfone content is 100% in the mother liquor.Poach polymkeric substance 5 times is used the 300L deionized water at every turn, each boiling time 40 minutes, and the F ion content is 0.35 mg/L in the detection solution, product is refining to be accomplished.Oven dry, the test product property.The test product viscosity is 1.0dl/g.Melt finger 16g/10min, product size distribution D50 is 250um.
Embodiment 5 (solid content about 15%)
Polymerization process:
In the four-hole reaction kettle that TM, logical nitrogen tube, condensation water trap, double-deck cloverleaf propeller agitator are housed; Add refining tetramethylene sulfone 50Kg earlier; 4,4 ' difluoro benzophenone and the 3.303Kg Resorcinol (can get polymkeric substance 8.64Kg, solid content is about 15%) that add 6.67Kg then; When treating that it all dissolves and treating that temperature is raised to 80 ℃, add 3.498Kg (excessive 2%) Na
2CO
3, continue to heat up again, add 2Kg YLENE again after, stir, heating; Treat that temperature rises to 150 ℃, system begins azeotropic, and YLENE and water condensation are arranged in the water trap, the upper strata refluxing xylene; Lower layer of water is constantly emitted, and when treating that water is recovered to theoretical amount, upper strata YLENE begins clear, continues to reflux 20 minutes again; Begin from system, to steam YLENE then, system temperature is constantly risen by heating, reach 267 ~ 270 ℃ to temperature after, keep constant temperature; System viscosity carries out viscosity with polyreaction and constantly increases, and treats that viscosity reaches stopped reaction after the stationary value, and this moment, stirring rake speed was 150 commentaries on classics/min.
The discharging process:
Stop heating, with the high-power fan cooling, cooling rate is 4 ℃/min, and liquid precipitates gradually and separates out in the reaction kettle; Slowly become gel, strengthen the stirring dynamics, rotating speed of agitator is adjusted to 400 commentaries on classics/min; Stirring rake produces the effect of high shear, and gel is disperseed, and makes it be unlikely to agglomerating; Cool to 130 ℃, in reaction kettle, add ethanol 50L, solution becomes suspended substance gradually.
Suspended substance is emitted spinning.Discharging process 55 minutes.Tetramethylene sulfone content is 45% in the mother liquor, uses the 300L deionized water at every turn, and each boiling time 40 minutes boils 5 times, and the F ion content is 0.4 mg/L in the detection solution, and the refining completion of product is described.Oven dry, the test product property, tested viscosity is 0.95dl/g, melts to refer to that test is 30g/10min, size distribution D50 is 180um.
Embodiment 6 (solid content about 30%)
Polymerization process:
In the four-hole reaction kettle that TM, logical nitrogen tube, condensation water trap, duplicate rows star whisking appliance are housed; Add refining tetramethylene sulfone 20Kg earlier; 4,4 ' difluoro benzophenone and the 3.303Kg Resorcinol (can get polymkeric substance 8.64Kg, solid content is about 30%) that add 6.67Kg then; When treating that it all dissolves and treating that temperature is raised to 80 ℃, add 3.498Kg (excessive 2%) Na
2CO
3, continue to heat up again, add 2Kg YLENE again after, stir, heating; Treat that temperature rises to 150 ℃, system begins azeotropic, and YLENE and water condensation are arranged in the water trap, the upper strata refluxing xylene; Lower layer of water is constantly emitted, and when treating that water is recovered to theoretical amount, upper strata YLENE begins clear, continues to reflux 20 minutes again; Begin from system, to steam YLENE then, system temperature is constantly risen by heating, reach 267 ℃ to temperature after, keep constant temperature; System viscosity carries out viscosity with polyreaction and constantly increases, and treats that viscosity reaches stopped reaction after the stationary value, and this moment, stirring rake speed was 40 commentaries on classics/min.
The discharging process:
Stop heating, in reaction heat supply oil oven, add the cooling oil cooling, cooling rate is 25 ℃/min, and liquid precipitates gradually and separates out in the reaction kettle; Slowly become gel, strengthen the stirring dynamics, stirring rake speed is 50 commentaries on classics/min; Stirring rake produces the effect of high shear, and gel is disperseed, and makes it be unlikely to agglomerating; Cool to 130 ℃, in reaction kettle, add ethanol 30L, solution becomes suspended substance gradually.
Suspended substance is emitted spinning, discharging process 10 minutes.Tetramethylene sulfone content is 46% in the mother liquor.Each 300L water of using, each boiling time 40 minutes boils material 4 times, and the F ion content is 0.2 mg/L in the detection solution, and product is refining to be accomplished.Oven dry, the test product property.Logarithmic ratio concentration viscosity is 1.02dl/g, melts to refer to be 14g/10min, and size distribution D50 is 270um.
Embodiment 7 (solid content about 30%)
Polymerization process:
In the four-hole reaction kettle that TM, logical nitrogen tube, condensation water trap, four layers of paddle stirrer are housed; Add refining tetramethylene sulfone 20Kg earlier; 4,4 ' difluoro benzophenone and the 3.303Kg Resorcinol (can get polymkeric substance 8.64Kg, solid content is about 30%) that add 6.67Kg then; When treating that it all dissolves and treating that temperature is raised to 80 ℃, add 3.498Kg (excessive 2%) Na
2CO
3, continue to heat up again, add 2Kg YLENE again after, stir, heating; Treat that temperature rises to 150 ℃, system begins azeotropic, and YLENE and water condensation are arranged in the water trap, the upper strata refluxing xylene; Lower layer of water is constantly emitted, and when treating that water is recovered to theoretical amount, upper strata YLENE begins clear, continues to reflux 20 minutes again; Begin from system, to steam YLENE then, system temperature is constantly risen by heating, reach 265 ℃ to temperature after, keep constant temperature; System viscosity carries out viscosity with polyreaction and constantly increases, and treats that viscosity reaches stopped reaction after the stationary value, and this moment, rotating speed of agitator was 95 commentaries on classics/min.
The discharging process:
Stop heating, in reaction heat supply oil oven, add cooling oil, cooling rate is 30 ℃/min, and liquid precipitates gradually and separates out in the reaction kettle; Slowly become gel, strengthen the stirring dynamics, stirring velocity becomes 100 commentaries on classics/min; Stirring rake produces the effect of high shear, and gel is disperseed, and makes it be unlikely to agglomerating; Cool to 180 ℃, in reaction kettle, add YLENE 30L, solution becomes suspended substance gradually.
Suspended substance is emitted spinning, discharging process 5 minutes.The content of tetramethylene sulfone is 50% in the mother liquor.Each 300L water of using, each boiling time 40 minutes boils material 5 times, and the F ion content is 0.2 mg/L in the detection solution, and product is refining to be accomplished.Oven dry, the test product property.The test logarithmic specific concentration viscosity is 1.2dl/g.Test melts to refer to be 9g/10min, and test product particle diameter D50 is 200um.
Embodiment 8 (solid content about 37%)
Polymerization process:
In the four-hole reaction kettle that TM, logical nitrogen tube, condensation water trap, oar formula and turbine type combined impeller are housed; Add refining tetramethylene sulfone 15Kg earlier; 4,4 ' difluoro benzophenone and the 3.303Kg Resorcinol (can get polymkeric substance 8.64Kg, solid content is about 37%) that add 6.67Kg then; When treating that it all dissolves and treating that temperature is raised to 80 ℃, add 3.498Kg (excessive 2%) Na
2CO
3, continue to heat up again, add 2Kg YLENE again after, stir, heating; Treat that temperature rises to 150 ℃, system begins azeotropic, and YLENE and water condensation are arranged in the water trap, the upper strata refluxing xylene; Lower layer of water is constantly emitted, and when treating that water is recovered to theoretical amount, upper strata YLENE begins clear, continues to reflux 20 minutes again; Begin from system, to steam YLENE then, system temperature is constantly risen by heating, reach 267 ℃ to temperature after, keep constant temperature; System viscosity carries out viscosity with polyreaction and constantly increases, and after 1 hour, treats that viscosity reaches stopped reaction after the stationary value, and this moment, stirring rake speed was 110 commentaries on classics/min.
The discharging process:
Stop heating, in reaction heat supply oil oven, add the cooling oil cooling, cooling rate is 20 ℃/min, and liquid precipitates gradually and separates out in the reaction kettle; Slowly become gel, strengthen the stirring dynamics, rotating speed of agitator is adjusted to 280 commentaries on classics/min; Stirring rake produces the effect of high shear, and gel is disperseed, and makes it be unlikely to agglomerating; Cool to 160 ℃, in reaction kettle, add YLENE 35L, solution becomes suspended substance gradually.
Suspended substance is emitted spinning, discharging process 9 minutes.Tetramethylene sulfone content is 23% in the mother liquor.Polymkeric substance is used the 300L deionized water with poach 6 times at every turn, and each boiling time 40 minutes detects that the F ion content is 0.2mg/L in the solution, and the refining completion of product be described.Oven dry, the test product property.Tested viscosity is 0.8dl/g.Product melts to refer to be 85g/10min.Size distribution D50 is 350um.
Embodiment 9 (solid content about 40%)
Polymerization process:
In the four-hole reaction kettle that TM, logical nitrogen tube, condensation water trap, gear piece formula impeller agitator are housed; Add refining tetramethylene sulfone 13Kg earlier; 4,4 ' difluoro benzophenone and the 3.303Kg Resorcinol (can get polymkeric substance 8.64Kg, solid content is about 40%) that add 6.67Kg then; When treating that it all dissolves and treating that temperature is raised to 80 ℃, add 3.498Kg (excessive 2%) Na
2CO
3, continue to heat up again, add 2Kg YLENE again after, stir, heating; Treat that temperature rises to 150 ℃, system begins azeotropic, and YLENE and water condensation are arranged in the water trap, the upper strata refluxing xylene; Lower layer of water is constantly emitted, and when treating that water is recovered to theoretical amount, upper strata YLENE begins clear, continues to reflux 20 minutes again; Begin from system, to steam YLENE then, system temperature is constantly risen by heating, reach 260 ℃ to temperature after, keep constant temperature; System viscosity carries out viscosity with polyreaction and constantly increases, and after 1 hour, treats that viscosity reaches stopped reaction after the stationary value.This moment agitator speed 800 commentaries on classics/min.
The discharging process:
Stop heating, in the heating oil oven, add the cooling deep fat, liquid precipitates gradually and separates out in the about 15 ℃/min of cooling rate in the still, reaction kettle, slowly becomes gel, strengthens the stirring dynamics, and rotating speed of agitator is adjusted to 2800 commentaries on classics/min.Stirring rake produces the effect of high shear, and gel is disperseed, and makes it be unlikely to agglomerating, cools to 200 ℃, in reaction kettle, adds water 20L, and solution becomes suspended substance gradually.
Suspended substance is emitted spinning.Discharging process 12 minutes.Tetramethylene sulfone content is 45% in the mother liquor, with 300L water boil polymkeric substance 4 times, detects that the F ion content is 0 mg/L in the solution, and the refining completion of product be described.Oven dry, the test product property.Sample characteristics of for example viscosity is 0.65dl/g.Product melts to refer to be 150g/10min, and test size distribution D50 is 50um.
Embodiment 10 (solid content about 30%)
Polymerization process:
In the four-hole reaction kettle that TM, logical nitrogen tube, condenser tube, grid agitator are housed, feed high pure nitrogen, add refining sulfobenzide 5Kg earlier; After the heating for dissolving, add 1.72Kg 4,4 ' difluoro benzophenones successively; 726g '-biphenyl diphenol and 426g Resorcinol, wherein, 4; 4 '-difluoro benzophenone/(Resorcinol+'-biphenyl diphenol)=1:1 (mol ratio) all need be treated after each the feeding in raw material to add a kind of material again after its dissolving; With pre-dry soda ash light crushing screening, accurately weighing 954g powder yellow soda ash joins rapidly in the reaction system, continues to stir 30 minutes down at 150 ℃; Make phenol and yellow soda ash reaction in the system form sodium salt, then temperature of reaction is elevated to 190 ℃, the sodium salt of generation is subsequently with 4; 4 '-difluoro benzophenone polymerization reaction take place reacted after 30 minutes, and the temperature with reaction system in 10 minutes is elevated to 300 ℃; Speed of response is accelerated, and viscosity increases; React after 1 hour, when system viscosity changes when little, temperature of reaction is elevated to 325 ℃, in reaction system, add the 10g Resorcinol more once more, reaction system viscosity increases sharply, and strengthens stirring velocity simultaneously, reacts to stop heating after 1.5 hours.This moment agitator speed 85 commentaries on classics/min.
The discharging process:
Stop heating, in reaction heat supply oil oven, add cooling oil, and blow reaction kettle with high-power fan, the liquid cooling rate is about 25 ℃/minute in the reaction kettle; Deposition is separated out gradually, slowly becomes gel, strengthens the stirring dynamics, and agitator speed is adjusted to 95 commentaries on classics/min; Stirring rake produces the effect of high shear, and gel is disperseed, and makes it be unlikely to agglomerating; Cool to 130 ℃, in reaction kettle, add ethanol 20L, solution becomes suspended substance gradually.
Suspended substance is emitted spinning.Discharging process 12 minutes.Containing sulfobenzide in the mother liquor is 20%, boils polymkeric substance 4 times with 100L ethanol, uses 300L poach polymkeric substance 6 times again, and the F ion content is 0 mg/L in the detection solution, and the refining completion of product is described.Oven dry, the test product property.Sample characteristics of for example viscosity is 0.75dl/g.Melt and refer to that test is 15g/min.Test size distribution D50 is 500um.
Embodiment 11 (solid content about 5%)
Polymerization process:
In the four-hole reaction kettle that TM, logical nitrogen tube, condenser tube, grid agitator are housed, feed high pure nitrogen, add refining sulfobenzide 30Kg earlier; After the heating for dissolving, add 1.72Kg 4,4 ' difluoro benzophenones successively; 726g '-biphenyl diphenol and 426g Resorcinol, wherein, 4; 4 '-difluoro benzophenone/(Resorcinol+'-biphenyl diphenol)=1:1 (mol ratio) all need be treated after each the feeding in raw material to add a kind of material again after its dissolving; With pre-dry soda ash light crushing screening, accurately weighing 954g powder yellow soda ash joins rapidly in the reaction system, continues to stir 30-50 minute down at 150-160 ℃; Make phenol and yellow soda ash reaction in the system form sodium salt, then temperature of reaction is elevated to 190 ℃, the sodium salt of generation is subsequently with 4; 4 '-difluoro benzophenone polymerization reaction take place reacted after 30 minutes, and the temperature with reaction system in 10 minutes is elevated to 300 ℃; Speed of response is accelerated, and viscosity increases; React after 1 hour, when system viscosity changes when little, temperature of reaction is elevated to 325 ℃, in reaction system, add the 10g Resorcinol more once more, reaction system viscosity increases sharply, and strengthens stirring velocity simultaneously, reacts to stop heating after 1.5 hours.This moment agitator speed 12 commentaries on classics/min.
The discharging process:
Stop heating, in reaction heat supply oil oven, add cooling oil, and blow reaction kettle with high-power fan, the liquid cooling rate is about 20 ℃/min in the reaction kettle; Deposition is separated out gradually, slowly becomes gel, strengthens the stirring dynamics, and agitator speed is adjusted to 40 commentaries on classics/min; Stirring rake produces the effect of high shear, and gel is disperseed, and makes it be unlikely to agglomerating; Cool to 180 ℃, in reaction kettle, add YLENE 40L, solution becomes suspended substance gradually.
Suspended substance is emitted spinning.Discharging process 10 minutes.Containing sulfobenzide in the mother liquor is 20%, boils polymkeric substance 6 times with 300L ethanol, uses 300L poach polymkeric substance 5 times again, and the F ion content is 0 mg/L in the detection solution, and the refining completion of product is described.Oven dry, the test product property.Sample characteristics of for example viscosity is 0.76dl/g.Melt and refer to be 14g/min.Test size distribution D50 is 250um.
Embodiment 12 (solid content about 30%)
Polymerization process:
In the four-hole reaction kettle that TM, logical nitrogen tube, condensation water trap, paddle stirrer are housed; Add refining tetramethylene sulfone 32.5Kg earlier, add 4,4 ' dichloro diphenyl sulfone and the 7.5Kg4 of 8.61Kg then; 4 ' dihydroxy diphenylsulphone (can get polymkeric substance 13.92Kg; Solid content is about 30%), when treating that it all dissolves and treating that temperature is raised to 80 ℃, add 3.498Kg (excessive 2%) Na
2CO
3, continue to heat up again, add 2Kg YLENE again after, stir, heating; Treat that temperature rises to 150 ℃, system begins azeotropic, and YLENE and water condensation are arranged in the water trap, the upper strata refluxing xylene; Lower layer of water is constantly emitted, and when treating that water is recovered to theoretical amount, upper strata YLENE begins clear, continues to reflux 20 minutes again; Begin from system, to steam YLENE then, system temperature is constantly risen by heating, reach 240 ℃ to temperature after, keep constant temperature; System viscosity carries out viscosity with polyreaction and constantly increases, and after 1 hour, treats that viscosity reaches stopped reaction after the stationary value, and this moment, agitator speed was 95 commentaries on classics/min.
The discharging process:
Stop heating, in reaction heat supply oil oven, add cooling oil, cooling rate is 30 ℃/min; Liquid precipitates gradually and separates out in the reaction kettle, slowly becomes gel, strengthens the stirring dynamics; Agitator speed is 100 commentaries on classics/min, and stirring rake produces the effect of high shear, and gel is disperseed; Make it be unlikely to agglomerating, in reaction kettle, add YLENE 40L, solution becomes suspended substance gradually.
Suspended substance is emitted, spinning, discharging process 3 minutes, tetramethylene sulfone content is 30% in the mother liquor, with water boil polymkeric substance 5 times, each about 300L of water consumption detects that the F ion content is 0.2 mg/L in the solution, the refining completion of product.Oven dry, the test product property.Particle diameter test distribution D50 is 400um.Sample characteristics of for example viscosity is 0.85dl/g.Melt and refer to that test is 25g/10min.(melt and refer to that test condition is 370 ℃, 5Kg pressure.）
Embodiment 13 (solid content about 60%)
Polymerization process:
In the four-hole reaction kettle that TM, logical nitrogen tube, condensation water trap, paddle stirrer are housed; Add refining tetramethylene sulfone 9Kg earlier, add 4,4 ' dichloro diphenyl sulfone and the 7.5Kg 4 of 8.61Kg then; 4 ' dihydroxy diphenylsulphone (can get polymkeric substance 13.92Kg; Solid content is about 60%), when treating that it all dissolves and treating that temperature is raised to 80 ℃, add 3.498g (excessive 2%) Na
2CO
3, continue to heat up again, add 2Kg YLENE again after, stir, heating; Treat that temperature rises to 150 ℃, system begins azeotropic, and YLENE and water condensation are arranged in the water trap, the upper strata refluxing xylene; Lower layer of water is constantly emitted, and when treating that water is recovered to theoretical amount, upper strata YLENE begins clear, continues to reflux 20 minutes again; Begin from system, to steam YLENE then, system temperature is constantly risen by heating, reach 240 ℃ to temperature after, keep constant temperature; System viscosity carries out viscosity with polyreaction and constantly increases, and after 1 hour, treats that viscosity reaches stopped reaction after the stationary value, and this moment, agitator speed was 95 commentaries on classics/min.
The discharging process:
Stop heating, in reaction heat supply oil oven, add cooling oil, cooling rate is 25 ℃/min, and liquid precipitates gradually and separates out in the reaction kettle; Slowly become gel, strengthen the stirring dynamics, agitator speed is 100 commentaries on classics/min; Stirring rake produces the effect of high shear, and gel is disperseed, and makes it be unlikely to agglomerating; Cool to 130 ℃, in reaction kettle, add acetone 20L, solution becomes suspended substance gradually.
Suspended substance is emitted spinning, discharging process 10 minutes.Tetramethylene sulfone content is 30% in the mother liquor.With water boil polymkeric substance 6 times, each about 300L of water consumption detects that the F ion content is 0.2 mg/L in the solution, the refining completion of product.Oven dry, the test product property, particle diameter test distribution D50 is 500um, sample characteristics of for example viscosity is 0.88dl/g.Melt and refer to be 22g/10min.(melt and refer to that test condition is 370 ℃, 5Kg pressure.）
Embodiment 14 (solid content about 27%)
Polymerization process:
In the four-hole reaction kettle that TM, logical nitrogen tube, condensation water trap, anchor stirrer are housed; Add refining tetramethylene sulfone 32.5Kg earlier, add 4,4 ' dichloro diphenyl sulfone and the 5.58Kg4 of 8.61Kg then; 4 ' '-biphenyl diphenol (can get polymkeric substance 12Kg; Solid content is about 27%), when treating that it all dissolves and treating that temperature is raised to 80 ℃, add 3.498Kg (excessive 2%) Na
2CO
3, continue to heat up again, add 2Kg YLENE again after, stir, heating; Treat that temperature rises to 150 ℃, system begins azeotropic, and YLENE and water condensation are arranged in the water trap, the upper strata refluxing xylene; Lower layer of water is constantly emitted, and when treating that water is recovered to theoretical amount, upper strata YLENE begins clear, continues to reflux 20 minutes again; Begin from system, to steam YLENE then, system temperature is constantly risen by heating, reach 240 ℃ to temperature after, keep constant temperature; System viscosity carries out viscosity with polyreaction and constantly increases, and after 1 hour, treats that viscosity reaches stopped reaction after the stationary value, and this moment, rotating speed of agitator was 75 commentaries on classics/min.
The discharging process:
Stop heating, in reaction heat supply oil oven, add cooling oil, cooling rate is 15 ℃/min; Liquid precipitates gradually and separates out in the reaction kettle, slowly becomes gel, strengthens the stirring dynamics; Stirring rake speed is 85 commentaries on classics/min, and stirring rake produces the effect of high shear, and gel is disperseed; Make it be unlikely to agglomerating, in reaction kettle, add YLENE 30L, solution becomes suspended substance gradually.
Suspended substance is emitted spinning.Discharging process 8 minutes.Sampling respectively before and after the discharging, the data of test product viscosity are respectively 0.80 dl/g, and tetramethylene sulfone content is 30% in the mother liquor, with 300L water boil polymkeric substance 5 times, detects that the F ion content is 0.3 mg/L in the solution, explain that product makes with extra care completion.Oven dry, the test product property.Particle diameter test distribution D50 is 450um.The specimen limiting viscosity is 0.80dl/g, and at 370 ℃, test melts to refer to be 36g/min under the 5Kg condition.
Above embodiment has just listed partial reaction embodiment, actually includes, but are not limited to this.
Comparative Examples 1
Polymerization method is identical with embodiment 1, and different is to adopt following mode discharging.Polymkeric substance mucus is injected cold water, after treating fully to cool off, pulverize and filter with kibbler.Discharging process 50 minutes.Filtrated stock tetramethylene sulfone content is 25%.The gained powder is added water, boiled 1 hour, refilter, boil repeatedly 8 times, solvent and by-product salt in material are all removed.Powder after making in baking oven 130 ℃ the oven dry 12 hours, make moisture content be lower than 0.5%.The specimen limiting viscosity be 0.72dl/g. at 400 ℃, test is melted and is referred to be 100g/min under the 5Kg condition.The product size distribution is that D50 is 800um.
Comparative Examples 2
Polymerization method is identical with embodiment 10, and different is to adopt following mode discharging in polymerization reaction late stage.Polymkeric substance mucus is injected cold water, after treating fully to cool off, pulverize and filter with kibbler.Discharging process 90 minutes.The gained powder is added ethanol, boil 4 times, refilter, boil repeatedly 9 times with deionized water, solvent and by-product salt in material are all removed.Powder after making in baking oven 130 ℃ the oven dry 12 hours, make moisture content be lower than 0.5%.The specimen limiting viscosity be 0.75dl/g. at 400 ℃, test is melted and is referred to be 15g/min under the 5Kg condition.The product size distribution is that D50 is 1000um.
Comparative Examples 3
Polymerization method is identical with embodiment 13, and different is to adopt following mode discharging in polymerization reaction late stage.Polymkeric substance mucus is injected cold water, after treating fully to cool off, pulverize and filter with kibbler.Discharging process 70 minutes.The gained powder is added deionized water boil repeatedly 8 times, solvent and by-product salt in material are all removed.Powder after making in baking oven 130 ℃ the oven dry 12 hours, make moisture content be lower than 0.5%.The specimen limiting viscosity be 0.89dl/g. at 370 ℃, test is melted and is referred to be 23g/min under the 5Kg condition.The product size distribution is that D50 is 1500um.
Comparative Examples 4
Polymerization method is identical with embodiment 14, and different is to adopt following mode discharging in polymerization reaction late stage.Polymkeric substance mucus is injected cold water, after treating fully to cool off, pulverize and filter with kibbler.Discharging process 120 minutes.The gained powder is added deionized water boil repeatedly 9 times, solvent and by-product salt in material are all removed.Powder after making in baking oven 140 ℃ the oven dry 12 hours, make moisture content be lower than 0.5%.Test final sample limiting viscosity is 0.79dl/g.At 370 ℃, test melts to refer to be 40g/min under the 5Kg condition.The product size distribution is that D50 is 1200um.Sample thief tested viscosity before and after the discharging.
We adopt the relative merits of embodiment and two kinds of methods of following data contrast:
Each embodiment product data contrast table of table 1
| ? | Tg（℃） | Tm（℃） | Product property viscosity (dl/g) | Tap density ρ (g/ml) | Td(℃) |
| Embodiment 1 | 144 | 337 | 0.72 | 0.21 | 583 |
| Embodiment 2 | 143 | 337 | 0.85 | 0.31 | 584 |
| Embodiment 3 | 143 | 337 | 0.9 | 0.20 | 580 |
| Embodiment 4 | 143 | 337 | 1.0 | 0.18 | 581 |
| Embodiment 5 | 143 | 337 | 0.95 | 0.35 | 584 |
| Embodiment 6 | 145 | 337 | 1.02 | 0.30 | 590 |
| Embodiment 7 | 143 | 337 | 1.2 | 0.21 | 583 |
| Embodiment 8 | 143 | 337 | 0.8 | 0.18 | 584 |
| Embodiment 9 | 142 | 338 | 0.65 | 0.25 | 588 |
| Embodiment 10 | 146 | 337 | 0.75 | 0.35 | 590 |
| Embodiment 11 | 148 | 340 | 0.76 | 0.4 | 590 |
| Embodiment 12 | 220 | - | 0.85 | 0.30 | 550 |
| Embodiment 13 | 222 | - | 0.88 | 0.32 | 553 |
| Embodiment 14 | 220 | - | 0.8 | 0.5 | 550 |
| Comparative Examples 1 | 143 | 337 | 0.72 | 0.11 | 583 |
| Comparative Examples 2 | 148 | 340 | 0.75 | 0.15 | 585 |
| Comparative Examples 3 | 220 | - | 0.89 | 0.16 | 548 |
| Comparative Examples 4 | 222 | - | 0.79 | 0.18 | 551 |
Each embodiment product data contrast table of table 2
| ? | Reaction system | Solid content | Solubilization dosage (L) | Discharging time (min) | The product cleaning number of times | Melt finger (g/10min) | Particle diameter D50 (um) |
| Embodiment 1 | TMS | 15% | Add water 25L | 30 | 5 | 100 | 200 |
| Embodiment 2 | TMS | 30% | Add water 30L | 6 | 6 | 71 | 300 |
| Embodiment 3 | TMS | 15% | Add TMS50L | 4 | 5 | 45 | 150 |
| Embodiment 4 | TMS | 26% | Add TMS59L | 5 | 5 | 16 | 250 |
| Embodiment 5 | TMS | 15% | Add ethanol 50L | 55 | 5 | 30 | 180 |
| Embodiment 6 | TMS | 30% | Add ethanol 30L | 10 | 4 | 14 | 270 |
| Embodiment 7 | TMS | 15% | YLENE 30L | 5 | 5 | 9 | 200 |
| Embodiment 8 | TMS | 37% | YLENE 35L | 9 | 6 | 85 | 350 |
| Embodiment 9 | TMS | 40% | Water 20L | 12 | 4 | 150 | 50 |
| Embodiment 10 | Sulfobenzide PAEK | 30% | Ethanol 20L | 12 | 6 | 15 | 500 |
| Embodiment 11 | Sulfobenzide PAEK | 5% | YLENE 40L | 10 | 6 | 14 | 250 |
| Embodiment 12 | TMS、PES | 30% | YLENE 40L | 3 | 5 | 25 | 400 |
| Embodiment 13 | TMS、PES | 60% | Acetone 20L | 10 | 6 | 22 | 500 |
| Embodiment 14 | TMS、PPSU | 27% | YLENE 30L | 8 | 5 | 36 | 450 |
| Comparative Examples 1 | TMS | 15% | Pulverize | 50 | 8 | 100 | 800 |
| Comparative Examples 2 | Sulfobenzide PAEK | 30% | Pulverize | 90 | 9 | 15 | 1000 |
| Comparative Examples 3 | TMS、PES | 60% | Pulverize | 70 | 8 | 23 | 1500 |
| Comparative Examples 4 | TMS、PPSU | 27% | Pulverize | 120 | 9 | 40 | 1200 |
For beneficial effect of the present invention further is described, do a contrast with Comparative Examples 4 with embodiment 14, like table 1
Table 3 embodiment 14 and Comparative Examples 4 contrasts
| ? | Discharging time (min) | Viscosity (dl/g) before the discharging | Resin viscosity (dl/g) after discharging is accomplished | The still wall is stained with the material situation |
| Embodiment 14 | 8 | 0.8 | 0.82 | Be stained with material 50 grams (account for gross product amount 0.4%) |
| Comparative Examples 4 | 120 | 0.65 | 0.85 | Be stained with material 500 grams (account for gross product amount 4%) |
The logarithmic specific concentration viscosity testing method adopts as follows: dissolving 0.2g polymkeric substance in 98% the 20ml vitriol oil, test its logarithmic specific concentration viscosity with Ubbelohde viscometer down at 25 ℃; The F particle content adopts the test of fluoride measurement appearance, and content of fluoride ion is qualified less than 2mg/L; The tap density testing method adopts the 10ml graduated cylinder accurately to measure 10ml powdered sample, compacting, weigh.Calculate m=ρ V according to formula, thereby calculate tap density ρ.
Product (embodiment 1 ~ 11, Comparative Examples 1 ~ 2) test melting index method after refining adopts as follows: according to ASTM D1238-04 standard; Test condition is at 400 ℃; Under the 5Kg pressure, toner through the gravimetric value of standard capillary, was averaged and is represented with g/10min in 10 minutes.(embodiment 12,13,14, Comparative Examples 3 and Comparative Examples 4 adopt same procedure at 370 ℃, the test down of 5Kg pressure); The laser particle size analyzer test is adopted in the product particle size analysis, and the cumulative particle sizes percentile of getting D50 and be sample reaches 50% o'clock pairing particle diameter.
The Tg of polymkeric substance, Tm adopt differential scanning calorimetry (DSC) test; Test condition: under nitrogen protection; Polymkeric substance is elevated to 400 degree from room temperature with 20 ℃/min of speed for the first time; Cooling rate with 50 ℃/min is reduced to room temperature again, and the heat-up rate with 20 ℃/min is elevated to 400 ℃ again, with the numerical evaluation of the heating curve second time.The heat decomposition temperature of polymkeric substance adopts the thermogravimetic analysis (TGA) test, and polymkeric substance is elevated to 800 ℃ with 5 ℃/min speed, the heat decomposition temperature of test 5%.
Table 1, table 2 are each embodiment and the contrast of Comparative Examples product data, and table 3 is embodiment 14 and Comparative Examples 4 contrasts.
The product that makes such as Fig. 1, shown in Figure 2, Fig. 2 is consistent with the magnification of Fig. 1, from figure, sees; In the microscopically test of same magnification, the relatively more even and subglobular of product particle of adopting new technology and obtaining is that natural sedimentation obtains; Density is big, and the product type that adopts disintegrating process to obtain is similar to ribbon, and there are a large amount of spaces and hole in the centre; Therefore include a lot of solvents, this is to cause both in treating process, the reason than big difference to be arranged.
Above embodiment is not that product of the present invention is done any restriction, every according to technical spirit of the present invention or composition components or content to any trickle modification, equivalent variations and modification that above embodiment did, all belong in the scope of technical scheme of the present invention.
Claims (8)
1. a method for preparing powdex comprises the steps: (1) at first directly cooling after polyreaction finishes, and polymkeric substance precipitates to separate out from reaction system and obtains the gluey liquid of polymkeric substance; Cooling rate is 2 ~ 50 ℃/min, and temperature fall time is 1 ~ 60min; Strengthen stirring velocity and make the gluey liquid homodisperse of polymkeric substance; (2) cool to 130 ~ 250 ℃ when system, add a certain amount of poor solvent, make polymeric system and poor solvent form the suspension liquid mixture; (3), obtain the thick product of needed polymer powder with the suspended substance solid-liquid separation; (4) thick product is made with extra care drying;
Wherein, said resin is selected from poly aryl ether ketone, polyarylether class, polysulfones; Said poor solvent is water, ethanol, acetone, YLENE or tetramethylene sulfone, and the volume ratio of the poor solvent of adding and polymerization solvent for use is 1:2 ~ 3:1.
2. according to the said method for preparing powdex of claim 1; It is characterized in that; The solvent that polyreaction adopts is a sulfobenzide; The mixture of one or more in DMSO 99.8MIN., METHYL SULFONYL METHANE., diethylammonium sulfone, diethyl sulfoxide, di-isopropyl sulfone, tetramethylene sulfone or the tetramethyl-sulfone, reaction system solids content are 5% ~ 60% by weight percentage.
3. according to the said method for preparing powdex of claim 1, it is characterized in that that cooling method is taked is air-cooled, water-cooled or be employed in the cooling method of the extraneous cold oil of input in the jacket of polymerization deep fat.
4. according to the said method for preparing powdex of claim 3, it is characterized in that, the temperature reduction technology that is adopted, cooling rate is 5 ~ 30 ℃/min.
5. according to the said method for preparing powdex of claim 1, it is characterized in that the volume ratio of poor solvent that in system, adds and polymerization solvent for use is 1:1 ~ 2:1.
6. according to the said method for preparing powdex of claim 1; It is characterized in that; Stirring rake is anchor formula, oar formula, turbine type, push type, frame, scrapes wall type, high-shear formula, disc type, gear piece formula, helical-ribbon type stirring arm, planetary stirring rake, multilayer stirring rake or adopt multi-form stirring rake combination that stirrer paddle is double leaf, multiple-blade, flat leaf, hinged joint or curved leaf.
7. according to the said method for preparing powdex of claim 1; It is characterized in that; Polyreaction mixing speed scope is 10 ~ 1000 commentaries on classics/min, and the mixing speed scope is 10 ~ 3000 commentaries on classics/min in the last handling process, and the mixing speed in the last handling process is greater than the mixing speed in the polymerization process.
8. according to the said method for preparing powdex of claim 1; It is characterized in that; The thick product of polymer powder is removed mother liquor with the method for centrifugal, filtration or leaching, and thick product is made with extra care salt in the polymkeric substance and impurity are at high temperature multiple extraction with boiling water or ethanol, and obtains product after the drying.
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| CN103254421B (en) * | 2013-01-18 | 2015-07-01 | 山东浩然特塑有限公司 | High pressure synthesis method for aromatic polysulfone resin |
| CN103515634B (en) * | 2013-09-27 | 2016-02-03 | 南通汉瑞新材料科技有限公司 | A kind of synthesis of vanadium redox battery amberplex and preparation method |
| CN110655666B (en) * | 2019-10-30 | 2023-01-20 | 中山大学 | Polyaryletherketone powder and preparation method thereof |
| CN111363139B (en) * | 2020-05-13 | 2023-06-06 | 浙江帕尔科新材料有限公司 | Post-treatment method of polyaryletherketone polymer |
| CN111682209A (en) * | 2020-05-22 | 2020-09-18 | 浙江中科玖源新材料有限公司 | Binder for lithium ion battery, preparation method of binder and lithium ion battery |
| CN112126086B (en) * | 2020-08-06 | 2022-08-16 | 湖南华曙高科技股份有限公司 | Drying method of nylon powder suspension for selective laser sintering |
| CN114225496B (en) * | 2021-12-07 | 2023-04-11 | 明士(北京)新材料开发有限公司 | Purification method and purification device for high-performance polymer resin |
| CN114920960B (en) * | 2022-06-09 | 2023-06-16 | 吉林大学 | Preparation method of superfine powder of polyaryletherketone resin or composite material thereof |
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| CN101338105A (en) * | 2008-08-14 | 2009-01-07 | 济南大学 | Method for preparing fluor-containing powder resin fro coating |
| WO2010103019A1 (en) * | 2009-03-13 | 2010-09-16 | Akzo Nobel Coatings International B.V. | Powder coating extrusion process |
| CN102107127B (en) * | 2011-01-11 | 2015-04-22 | 西安蓝晓科技新材料股份有限公司 | Technology for granulating powder |
-
2011
- 2011-09-14 CN CN 201110271160 patent/CN102352033B/en not_active Expired - Fee Related
- 2011-12-08 WO PCT/CN2011/002051 patent/WO2013037097A1/en active Application Filing
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| Publication number | Publication date |
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| WO2013037097A1 (en) | 2013-03-21 |
| CN102352033A (en) | 2012-02-15 |
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