CN107936243A - The technique that semi-continuous process produces polyether ketone ketone - Google Patents
The technique that semi-continuous process produces polyether ketone ketone Download PDFInfo
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- CN107936243A CN107936243A CN201711286358.5A CN201711286358A CN107936243A CN 107936243 A CN107936243 A CN 107936243A CN 201711286358 A CN201711286358 A CN 201711286358A CN 107936243 A CN107936243 A CN 107936243A
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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
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4043—(I) or (II) containing oxygen other than as phenol or carbonyl group
- C08G65/405—(I) or (II) containing oxygen other than as phenol or carbonyl group in ring structure, e.g. phenolphtalein
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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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
- C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
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Abstract
The invention belongs to macromolecule synthesising technology field, and in particular to a kind of technique of semi-continuous process production polyether ketone ketone.The present invention first using equimolar than diphenyl ether and and/the paraphthaloyl chloride generation preferable prepolymer of mobility, then by the prepolymer of the good fluidity of generation and it is remaining between/paraphthaloyl chloride quantitatively fed in double-screw reactor by feeder.Acted on by the Strong shear of double-screw reactor, mixed material, increase the collision probability of active end group, accelerate polymerization rate, prepare the polyether ketone ketone of high inherent viscosity in a short time.
Description
Technical field
The invention belongs to macromolecule synthesising technology field, and in particular to a kind of technique of semi-continuous process production polyether ketone ketone.
Background technology
Polyether ketone ketone (PEKK) resin is a kind of special engineering plastics with excellent properties, belongs to the one of poly(aryl ether ketone)
Kind, the chemical constitution of the mutual proper alignment of phenyl ring ehter bond ketone group in its molecular structure, imparts the chemical bond that numberator height is stablized
Characteristic, makes it have excellent mechanical performance, radiation resistance, high temperature resistant, chemical resistance and good electrical insulating property
And fire resistance, can be by extruding, being molded, the processing method such as being molded and be processed shaping, it is in aerospace, electronics electricity
There is high application demand in terms of gas, automobile and oil.
The synthetic method of the polyether ketone ketone of document report is different using nucleophilic displacement of fluorine synthetic method with polyether-ether-ketone, it is more
Prepared using the method for parental materials.
Document report using electrophilic method prepare poly(aryl ether ketone) technique its be mainly the following mode：1) with HF/BF3
Poly(aryl ether ketone), such as patent are prepared for dicyandiamide solution：US3516966, US3441538, US3442857, EP0124275,
US3442857.But patent US3956240 is proposed using diphenyl ether as monomer, with HF/BF3Poly- virtue is prepared for dicyandiamide solution
Poly(aryl ether ketone) prepared by ether ketone is unstable, since unknown side reaction result in crosslinking phenomena hair during melt molding
It is raw.Poly(aryl ether ketone) prepared by this method is unstable, since unknown side reaction result in crosslinking during melt molding
Phenomenon occurs.And since HF/BF3 system corrosivity is larger, and when post-processing, these corrosive more difficult recycling of solvent,
More difficult industrialized production.2) patent US4396755 reports one kind using diphenyl ether, terephthalic acid (TPA) as monomer, using perfluor alkane
Base sulfonic acid is a kind of method of the solvent using phosphorus pentachloride as catalyst preparation polyether ketone ketone.Due to perfluoro alkyl sulfonic acid system cost
Higher, preparing poly(aryl ether ketone) using such a mode, not only cost is too high but also higher to equipment requirement, it is more difficult to industrialized production.
3) " precipitation method " prepare poly(aryl ether ketone).Patent US20120263953 describes one kind and prepares poly(aryl ether ketone) using " precipitation method "
Method, using conventional catalyst, adds controlling agent, is then reacted under high velocity agitation, when its molecular weight reaches certain journey
It will be precipitated out after degree from solvent, form tiny particle, then the monomer in solvent continues to react shape with fine particle
Into the poly(aryl ether ketone) of high molecular weight.Final product is granular poly(aryl ether ketone), after reaction, it is not necessary at special equipment
Catalyst solution, directly can be just complexed, required poly(aryl ether ketone) has just been obtained after filtering by reason with less amount of water.But use this
Kind of method needs substantial amounts of organic solvent, polymerisation inefficiency, and more demanding to mixing speed, industrially more difficult reality
It is existing.4) lewis acid/lewis base of Raychem exploitations is total to catalyzed preparation of poly aryl ether ketone (WO8403891)；5) E.I.Du Pont Company
Two-step synthesis method (US4816556)；6) substep of (the CN 101812170B) of Chongqing Aorima High-performance Polymer Co., Ltd.
High glass-transition temperature polyether ketone ketone prepared by charging method.Above in the technique of numerous electrophilic methods synthesis poly(aryl ether ketone), very
Just it is being capable of the mainly three kinds latter of commercialization.But nonetheless, since poly(aryl ether ketone) is compared with being insoluble in general organic solvent,
Its polymer be not in polymerization system in the form of true solution existing for, but in polymerization system add lewis base it is same
Lewis acid collective effect makes polymer form complex system in the solution, and on the one hand this complex system has enough activity
End group enables to polymeric chain sustainable growth；On the other hand this complex system due to be with existing for gel state so that its
Reaction kettle middle and later periods polymerization speed is particularly slow, generally requires longer time and can be only achieved the required degree of polymerization, and due to
Reaction system is with existing for gel state so that post-processes special trouble, gathers often over after reaction two or three times
Many polyether ketone ketone gels for not allowing easy to clean to get off will be assembled by closing reaction kettle surface, seriously affect leading for polymerization reaction kettle
Heat so that be not easily controlled reaction temperature in the polymerisation in later stage, cause the molecular weight distribution of generated polymer wide.
Industrialized polyether ketone ketone production is intermittent production technology at present, although the manufacturer having been reported, such as France
The companies such as Arkema, U.S. Cytec, India Gharda realize small-scale industrialized production, but its average annual yield is less than
1000 tons/year, since there are problem above, making it difficult to realize large-scale industrialization continuous production polyether ketone ketone.At present, work
The batch process production technology generally used in industry is primarily present problems with：
(1) reaction kettle is difficult to handle high-viscosity material system so that and the phase can not stir the material of gel state after the reaction,
Polymerization time is caused to become and due to the more difficult collision of active end group, it is difficult to prepare the polyether ketone ketone polymer of higher molecular weight
(general characteristic viscosity is less than 1.0dL/g), which limits the application of prepared polyether ketone ketone polymer；
(2) production cycle is grown, and equipment service efficiency is low, when producing polyether ketone ketone using reaction kettle half-continuous process, due to
The material of gel state is more intractable so that it needs longer time to handle reaction mass after the completion of reaction, causes its life
The production cycle is up to 6-20h；
(3) polymerization reaction kettle needs frequently cleaning, and reaction kettle often synthesizes a collection of polyether ketone ketone all can be in polymerization reaction kettle table
As soon as face covers a layer relatively viscous material, rear thickness can reach 1cm two or three times, on the one hand seriously affect the heat conduction effect of reaction kettle
Fruit, on the other hand since the presence of residual material destroys the rate of charge of next batch materials, in preparation of industrialization polyether ketone ketone
When need frequently cleaning polymerization reaction kettle, seriously affected production efficiency；
(4) current industrialized production is batch production technique, its production automation degree is low.
Double-screw reactor is widely used in the polymer industry production of aromatic polyamide, (such as CN101798385A,
CN1546552), but the present invention is different from the continuously or semi-continuously polymerization technique of aromatic polyamide, it is in the synthesis process
It can be prepared without catalyst, but electrophilic method needs to add the catalyst of friedel-crafts reaction during preparing poly(aryl ether ketone), such as
Aluminum trichloride (anhydrous), anhydrous ferric trichloride, boron trifluoride, anhydrous zinc dichloride, anhydrous Antimony pentachloride, anhydrous stannous chloride etc..
The content of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of semi-continuous process production polyether ketone ketone technique,
Polymerization rate is fast, prepares the polyether ketone ketone of high inherent viscosity in a short time.
The technique of semi-continuous process production polyether ketone ketone of the present invention, comprises the following steps：
(1) solvent is added into prepolymerization kettle, after cooling, adds lewis acid and lewis base；
(2) aromatic diacid chlorides monomer is added into mixing kettle A, adds solvent, stirring forms homogeneous phase solution；
(3) the obtained partial materials of mixing kettle A are added into mixture B, then by the aromatic series of active hydrogen
Compound is added into mixing kettle B, is uniformly mixed and is formed homogeneous phase solution；
(4) material obtained in mixing kettle B in step (3) is added into the prepolymerization kettle in step (1), reaction obtains pre-
Polymers；
(5) obtained prepolymer is fed in double-screw reactor, side spout adds remaining thing in mixing kettle A
Material, carries out polymerisation；
(6) polymer extruded from double screw extruder is crushed acid at the same time at head to drench, then filters, wash, do
It is dry, obtain product.
Wherein：
Solvent is dichloromethane, 1,2- dichloroethanes, o-dichlorohenzene, nitrobenzene, tetrachloroethanes, carbon disulfide or nitro first
Any one or a few in alkane；The quality sum of solvent for use is aromatic diacid chlorides and the aromatic compound of active hydrogen
0.5~10 times of the quality sum of thing.
Aromatic diacid chlorides are paraphthaloyl chloride and m-phthaloyl chloride；The aromatic compound of active hydrogen is two
Phenylate.
Lewis base is dimethylformamide, dimethylacetylamide, diphenyl sulphone (DPS), triphenylphosphine oxide, nitropropane, ring fourth
Any one in sulfone, dimethyl sulfoxide (DMSO), dimethyl sulfone, 1-methyl-2-pyrrolidinone, anhydrous lithium chloride or anhydrous sodium chloride, Louis
This base amount is 1~8 times of the mole that aromatic diacid chlorides monomer is total in step (2)；
Lewis acid is aluminum trichloride (anhydrous), anhydrous ferric trichloride, boron trifluoride, anhydrous zinc dichloride, anhydrous phosphoric
Any one in antimony or anhydrous stannous chloride；Its dosage is that the sum of all carbonyl total moles contents add in polymerized monomer system
The mole of lewis base has added the amount of catalytic action, and the amount for playing catalytic action is that acyl chlorides mole contains in polymerized monomer system
0.05~1 times of amount.
Cooling is to be cooled between -5 DEG C to -30 DEG C in step (1).
Partial material accounts in mixing kettle A the 75%~95% of obtained all materials quality in step (3).
Step (4) is：At -5 DEG C~-35 DEG C, the material obtained in mixing kettle B is added to the pre-polymerization in step (1)
In kettle, at -5 DEG C~-35 DEG C keep 1~2 it is small when, then heat to 20~30 DEG C, the reaction was continued 1~2 it is small when, obtain pre-polymerization
Thing.
The temperature control of double-screw reactor is at 20~60 DEG C in step (5), in double-screw reactor during the reaction of material
Between be 10~50 minutes；Constantly exclude to generate during the reaction by the method vacuumized in step (5) polymerization process
Low molecular weight substance.
It is to use concentration as 3wt%~6wt% that double screw extruder, which finds time as 3~50min, acid leaching, in step (6)
Aqueous hydrochloric acid solution carry out sour leaching, drying temperature is 160~180 DEG C.
Preferably, the technique of semi-continuous process production polyether ketone ketone of the present invention, step are as follows：
(1) under the dry condition, solvent is added into prepolymerization kettle, between being cooled to -5 DEG C to -30 DEG C after, to prepolymerization kettle
In lewis acid and lewis base is added portionwise；
(2) under the dry condition, m-phthaloyl chloride and paraphthaloyl chloride are added into mixing kettle A, Ran Hou
Solvent is added in mixing kettle A, stirring forms homogeneous phase solution；
(3) under the dry condition, the 75%~95% of the obtained materials of mixing kettle A is added to mixing by diaphragm pump
In kettle B, then diphenyl ether is added in mixing kettle B, and be mixed uniformly；
(4) at -5 DEG C~-35 DEG C, the obtained materials of mixing kettle B are added in the prepolymerization kettle in step (1), -5
DEG C~-35 DEG C at keep 1~2 it is small when, then heat to 20~30 DEG C, the reaction was continued 1~2 it is small when, obtain prepolymer；
(5) obtained prepolymer is fed in double-screw reactor, side spout adds remaining thing in mixing kettle A
Material, residence time of the reaction system in double-screw reactor are 10~50 minutes, and polymerization temperature is controlled at 20~60 DEG C；
(6) polymer extruded from double screw extruder is crushed at head while sprays the hydrochloric acid of 3wt%~6wt%
Aqueous solution, is then filtered, and dries it in 160~180 DEG C of driers after obtained polymer is washed with deionized again
It is dry, obtain product.
It is highly preferred that the technique of semi-continuous process production polyether ketone ketone of the present invention, step are as follows：
(1) under the dry condition, the solvent measured is then added into prepolymerization kettle, is cooled between -5 to -30 DEG C
Afterwards, the lewis acid and lewis base measured is then added portionwise into reaction system.
(2) under the dry condition, the m-phthaloyl chloride measured and paraphthaloyl chloride are added to mixing kettle A
In, then added in mixing kettle with m-phthaloyl chloride and the solvent of paraphthaloyl chloride equivalent.
(3) under the dry condition, the 75%~95% of the monomer mixed solution of mixing kettle A will be added extremely by diaphragm pump
In mixing kettle B, the diphenyl ether measured is then added in mixing kettle B, and is mixed uniformly.
(4) under conditions of relative low temperature, preferably between -5~-35 DEG C, by diaphragm pump by the monomer of mixing kettle B kinds
Mixed liquor is added in prepolymerization kettle, and control, which adds speed, makes reaction temperature be maintained at low-temperature condition, and monomer will be pre- after adding
In poly- kettle reaction system kept under low-temperature condition 1~2 it is small when, then slowly heating, by temperature of reaction system liter in prepolymerization kettle
Up to 20~30 DEG C, the reaction was continued 1~2 it is small when prepare prepolymer.
(5) obtained prepolymer will be quantitatively fed in double-screw reactor by feeder, side spout is quantitatively adding
Remaining m-phthaloyl chloride and paraphthaloyl chloride mixed liquor, reaction system are stopped in double-screw reactor in mixing kettle A
It is 10~50 minutes to stay the time, and preferably 20~40 minutes, polymerization temperature was controlled at 20~60 DEG C, preferably 30~50 DEG C, thing
Expect that residence time in double-screw reactor can be adjusted by varying the shape of screw speed and screw rod, reacting
During the low molecular weight substance that generates, as hydrogen chloride can constantly be excluded by the method vacuumized, be so conducive to improve
Polycondensation reaction speed and the inherent viscosity for improving polymer.
(6) by the polymer extruded from double screw extruder crushed at head and meanwhile spray 3%~6% hydrochloric acid it is water-soluble
Liquid, is then filtered, and dries it i.e. in 160~180 DEG C of driers after obtained polymer is washed with deionized again
It can obtain block type polyethylene-ketone-ketone resin.
Compared with prior art, the present invention has the following advantages：
The present invention first using equimolar than diphenyl ether and/paraphthaloyl chloride generation the preferable pre-polymerization of mobility
Thing, then by the prepolymer of the good fluidity of generation and it is remaining between/paraphthaloyl chloride quantitatively feeds twin-screw by feeder
In reactor.Acted on by the Strong shear of double-screw reactor, mixed material, increase the collision probability of active end group, accelerated poly-
Reaction rate is closed, prepares the polyether ketone ketone of high inherent viscosity in a short time.
Brief description of the drawings
Fig. 1 is the process flow chart of the technique of semi-continuous process production polyether ketone ketone of the present invention.
Embodiment
With reference to embodiment, the present invention will be further described.
Embodiment 1
Semi-continuous process produces the technique of polyether ketone ketone, comprises the following steps：
(1) 500kg dichloromethane is added into prepolymerization kettle, -5 DEG C is cooled to, is then added in batches into prepolymerization kettle
210kg anhydrous Aluminum chlorides and 50kg dimethylformamides are reacted, and obtain reaction solution；
(2) 42.63kg paraphthaloyl chlorides, 18.27kg m-phthaloyl chlorides are added in mixing kettle A, then added
The dichloromethane of 60kg is dissolved, and obtains mixed liquor after mixing；
(3) liquid in 96.72Kg mixing kettles A is added into mixing kettle B by diaphragm pump, then in mixing kettle B
51.06kg diphenyl ether is added, obtains mixed liquor after mixing；
(4) liquid in mixing kettle B is slowly added dropwise into prepolymerization kettle by diaphragm pump, keeps pre-polymerization temperature in the kettle not high
In -5 DEG C, monomer reaction system in prepolymerization kettle is kept under low-temperature condition after adding 1.5 it is small when, then slowly heat up,
Temperature of reaction system in prepolymerization kettle is increased to 25 DEG C, the reaction was continued 1.5 it is small when obtain prepolymer.
(5) obtained prepolymer in step 4 is quantitatively fed in double-screw reactor by feeder, side spout is quantitative
Remaining m-phthaloyl chloride and paraphthaloyl chloride mixed liquor in mixing kettle A is added, prepolymer is fed with the addition of mixed liquor
When ratio be 23:1.At 40 DEG C, the control that finds time is polymerize after 30min, extrusion for reaction temperature control in twin-screw
Thing, polymer is crushed at the head of double-screw reactor, while is sprayed with the hydrochloric acid solution that concentration is 5wt%
Leaching, filtered, deionized water washing are dried after at 170 DEG C, obtain polyether ketone ketone crude product.
Embodiment 2
Semi-continuous process produces the technique of polyether ketone ketone, comprises the following steps：
(1) 500kg dichloromethane is added into prepolymerization kettle, -5 DEG C is cooled to, is then added in batches into prepolymerization kettle
210kg anhydrous Aluminum chlorides and 50kg dimethylformamides are reacted, and obtain reaction solution；
(2) 36.54kg paraphthaloyl chlorides, 24.36 m-phthaloyl chlorides are added in mixing kettle A, then added
The dichloromethane of 60kg is dissolved, and obtains mixed liquor after mixing；
(3) liquid in 96.72Kg mixing kettles A is added into mixing kettle B by diaphragm pump, then in mixing kettle B
51.06kg diphenyl ether is added, obtains mixed liquor after mixing；
(4) liquid in mixing kettle B is slowly added dropwise into prepolymerization kettle by diaphragm pump, keeps pre-polymerization temperature in the kettle not high
In -5 DEG C, monomer reaction system in prepolymerization kettle is kept under low-temperature condition after adding 1 it is small when, then slowly heating, general
Temperature of reaction system is increased to 30 DEG C in prepolymerization kettle, the reaction was continued 1 it is small when obtain prepolymer.
(5) obtained prepolymer in step 4 is quantitatively fed in double-screw reactor by feeder, side spout is quantitative
Remaining m-phthaloyl chloride and paraphthaloyl chloride mixed liquor in mixing kettle A is added, prepolymer is fed with the addition of mixed liquor
When ratio be 23:1.At 40 DEG C, the control that finds time is polymerize after 30min, extrusion for reaction temperature control in twin-screw
Thing, polymer is crushed at the head of double-screw reactor, while is sprayed with the hydrochloric acid solution that concentration is 6wt%
Leaching, filtered, deionized water washing are dried after at 180 DEG C, obtain polyether ketone ketone crude product.
Embodiment 3
Semi-continuous process produces the technique of polyether ketone ketone, comprises the following steps：
(1) 500kg dichloromethane is added into prepolymerization kettle, -5 DEG C is cooled to, is then added in batches into prepolymerization kettle
210kg anhydrous Aluminum chlorides and 50kg dimethylformamides are reacted, and obtain reaction solution；
(2) 30.45kg paraphthaloyl chlorides, 30.45kg m-phthaloyl chlorides are added in mixing kettle A, then added
The dichloromethane of 60kg is dissolved, and obtains mixed liquor after mixing；
(3) liquid in 96.72Kg mixing kettles A is added into mixing kettle B by diaphragm pump, then in mixing kettle B
51.06kg diphenyl ether is added, obtains mixed liquor after mixing；
(4) liquid in mixing kettle B is slowly added dropwise into prepolymerization kettle by diaphragm pump, keeps pre-polymerization temperature in the kettle not high
In -5 DEG C, monomer reaction system in prepolymerization kettle is kept under low-temperature condition after adding 2 it is small when, then slowly heating, general
Temperature of reaction system is increased to 20 DEG C in prepolymerization kettle, the reaction was continued 2 it is small when obtain prepolymer.
(5) obtained prepolymer in step 4 is quantitatively fed in double-screw reactor by feeder, side spout is quantitative
Remaining m-phthaloyl chloride and paraphthaloyl chloride mixed liquor in mixing kettle A is added, prepolymer is fed with the addition of mixed liquor
When ratio be 23:1.At 40 DEG C, the control that finds time is polymerize after 30min, extrusion for reaction temperature control in twin-screw
Thing, polymer is crushed at the head of double-screw reactor, while is sprayed with the hydrochloric acid solution that concentration is 3wt%
Leaching, filtered, deionized water washing are dried after at 160 DEG C, obtain polyether ketone ketone crude product.
The obtained polymer of embodiment 1-3 is tested after purification by following steps：
Obtained polyether ketone ketone crude product 60Kg is added in the first stirred tank, add 1200Kg aqueous formic acids with
The mass ratio of the mixed solution of acetylacetone,2,4-pentanedione, wherein aqueous formic acid and acetylacetone,2,4-pentanedione is 3.8:1, aqueous formic acid concentration
95%, 105 DEG C are warming up to, and sealing is stirred at reflux washing 8h, most solutions is removed through centrifuging, material is put into the second stirring
In kettle, 4h is washed with 75% aqueous formic acid stirring at normal temperature of 600kg concentration, is centrifuged, material uses 1200Kg in the 3rd stirred tank
Water room temperature washs 4h, and centrifugation, in double cone dryer after the dry 10h of 130 DEG C of normal pressure, then obtains after negative pressure -0.085MPa dryings 4h
To the polyether-ether-ketone of purifying.
Inherent viscosity uses dark type viscometer, with dense H2SO4Make solvent, be configured to the solution of 0.5g/L, in steady temperature T
Four-point method is used at=25 ± 0.1 DEG C, measures the inherent viscosity of polymer.The glass transition temperature and fusing point of polymer use
Differential scan calorimeter (DSC) is tested, and under nitrogen atmosphere, programming rate is 10 DEG C/min, 40~380 DEG C of temperature elevating range.
1 distinct methods of table prepare the physical property of polyether ketone ketone
Claims (10)
- A kind of 1. technique of semi-continuous process production polyether ketone ketone, it is characterised in that：Comprise the following steps：(1) solvent is added into prepolymerization kettle, after cooling, adds lewis acid and lewis base；(2) aromatic diacid chlorides monomer is added into mixing kettle A, adds solvent, stirring forms homogeneous phase solution；(3) the obtained partial materials of mixing kettle A are added into mixture B, then by the aromatic compound of active hydrogen Add into mixing kettle B, be uniformly mixed and form homogeneous phase solution；(4) material obtained in mixing kettle B in step (3) is added into the prepolymerization kettle in step (1), reaction obtains pre-polymerization Thing；(5) obtained prepolymer being fed in double-screw reactor, side spout adds remaining material in mixing kettle A, into Row polymerisation；(6) polymer extruded from double screw extruder is crushed acid at the same time at head to drench, then filtered, washed, is dry, obtaining To product.
- 2. the technique of semi-continuous process production polyether ketone ketone according to claim 1, it is characterised in that：Solvent is dichloromethane In alkane, 1,2- dichloroethanes, o-dichlorohenzene, nitrobenzene, tetrachloroethanes, carbon disulfide or nitromethane any one or it is several Kind；The quality sum of solvent for use is the 0.5 of the quality sum of the aromatic compound of aromatic diacid chlorides and active hydrogen ~10 times.
- 3. the technique of semi-continuous process production polyether ketone ketone according to claim 1, it is characterised in that：Aromatic diacid chlorides are Paraphthaloyl chloride and m-phthaloyl chloride；The aromatic compound of active hydrogen is diphenyl ether.
- 4. the technique of semi-continuous process production polyether ketone ketone according to claim 1, it is characterised in that：Lewis base is diformazan Base formamide, dimethylacetylamide, diphenyl sulphone (DPS), triphenylphosphine oxide, nitropropane, sulfolane, dimethyl sulfoxide (DMSO), dimethyl sulfone, Any one in 1-methyl-2-pyrrolidinone, anhydrous lithium chloride or anhydrous sodium chloride, lewis base dosage are fragrance in step (2) 1~8 times of the total mole of race's diacid chloride monomer；Lewis acid for aluminum trichloride (anhydrous), anhydrous ferric trichloride, boron trifluoride, anhydrous zinc dichloride, anhydrous Antimony pentachloride or Any one in anhydrous stannous chloride；Its dosage is that the sum of all carbonyl total moles contents add Louis in polymerized monomer system The mole of this alkali has added the amount of catalytic action, and the amount for playing catalytic action is acyl chlorides molar content in polymerized monomer system 0.05~1 times.
- 5. the technique of semi-continuous process production polyether ketone ketone according to claim 1, it is characterised in that：Cooling in step (1) To be cooled between -5 DEG C to -30 DEG C.
- 6. the technique of semi-continuous process production polyether ketone ketone according to claim 1, it is characterised in that：Part in step (3) Material accounts in mixing kettle A the 75%~95% of obtained all materials quality.
- 7. the technique of semi-continuous process production polyether ketone ketone according to claim 1, it is characterised in that：Step (4) is：- 5 DEG C~-35 DEG C at, the material obtained in mixing kettle B is added in the prepolymerization kettle in step (1), is protected at -5 DEG C~-35 DEG C Hold 1~2 it is small when, then heat to 20~30 DEG C, the reaction was continued 1~2 it is small when, obtain prepolymer.
- 8. the technique of semi-continuous process production polyether ketone ketone according to claim 1, it is characterised in that：Double spiral shells in step (5) The temperature control of bar reactor is at 20~60 DEG C, and the reaction time of material is 10~50 minutes in double-screw reactor；Step (5) The low molecular weight substance generated during the reaction is constantly excluded by the method vacuumized in polymerization process.
- 9. the technique of semi-continuous process production polyether ketone ketone according to claim 1, it is characterised in that：Double spiral shells in step (6) It is to use concentration to carry out sour leaching for the aqueous hydrochloric acid solution of 3wt%~6wt% that bar extruder, which finds time as 3~50min, acid leaching, Drying temperature is 160~180 DEG C.
- 10. according to the technique of any semi-continuous process production polyether ketone ketone of claim 1-9, it is characterised in that：Step is such as Under：(1) under the dry condition, solvent is added into prepolymerization kettle, between being cooled to -5 DEG C to -30 DEG C after, into prepolymerization kettle point Criticize and add lewis acid and lewis base；(2) under the dry condition, m-phthaloyl chloride and paraphthaloyl chloride are added into mixing kettle A, then mixed Solvent is added in kettle A, stirring forms homogeneous phase solution；(3) under the dry condition, the 75%~95% of the obtained materials of mixing kettle A is added to mixing kettle B by diaphragm pump In, then diphenyl ether is added in mixing kettle B, and be mixed uniformly；(4) at -5 DEG C~-35 DEG C, the obtained materials of mixing kettle B are added in the prepolymerization kettle in step (1), -5 DEG C~- At 35 DEG C keep 1~2 it is small when, then heat to 20~30 DEG C, the reaction was continued 1~2 it is small when, obtain prepolymer；(5) obtained prepolymer is fed in double-screw reactor, side spout adds remaining material in mixing kettle A, instead It is 10~50 minutes to answer residence time of the system in double-screw reactor, and polymerization temperature is controlled at 20~60 DEG C；(6) by the polymer extruded from double screw extruder crushed at head and meanwhile spray 3wt%~6wt% hydrochloric acid it is water-soluble Liquid, is then filtered, it is dried in 160~180 DEG C of driers after obtained polymer is washed with deionized again, is obtained To product.
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| CN113174037A (en) * | 2021-04-26 | 2021-07-27 | 江阴市博生新材料科技有限公司 | Linear high heat-resistant oxidized polyaryletherketone ketone and preparation method thereof |
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