CN107778503A - A kind of continuous preparation method of soluble poly aromatic ether ketone film - Google Patents
A kind of continuous preparation method of soluble poly aromatic ether ketone film Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/12—Spreading-out the material on a substrate, e.g. on the surface of a liquid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
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- 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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Abstract
The present invention provides a kind of continuous preparation method of soluble poly aromatic ether ketone film, belongs to method for manufacturing thin film technical field.This method is post-processed the PAEK solution that soluble poly aromatic ether ketone resin powder or reaction obtain, the soluble poly aromatic ether ketone resin after being handled；Then the soluble poly aromatic ether ketone resin after processing is dissolved in solvent, scratched after defoaming in substrate, pass through solution casting method film forming, the 2.00m/min of pulling speed 0.02, warm area 14 is dried, each warm area length is 0.2 10.0m, 20 240 DEG C of drying temperature, 50 200 DEG C of hot blast temperature, the 800m3/h of wind speed 0, obtain soluble poly aromatic ether ketone film.Its tensile strength 80 of film 100MPa that the preparation method of the present invention obtains；Modulus of elasticity 2.1Gpa~3.5Gpa, elongation at break position 67%~106%.
Description
Technical field
The invention belongs to method for manufacturing thin film technical field, and in particular to a kind of serialization of soluble poly aromatic ether ketone film
Preparation method.
Background technology
Polyaryletherketone film is a kind of high added value polymeric material, have good heat resistance, dimensional stability and
High-strength and high-modulus performance.Polyaryletherketone film prepared by high temperature method uses extrusion the tape casting, pulling method or film blowing method due to needing,
When passing through Screw Extrusion, discharging opening temperature is up to 350-380 DEG C, and even more high, energy consumption is higher, the requirement to process equipment also compared with
Height, domestic rare company can prepare can steady production process equipment.
The content of the invention
The invention aims to solve, the preparation method of existing polyaryletherketone film is harsh to equipment requirement, cost
High technical problem, and a kind of continuous preparation method of soluble poly aromatic ether ketone film is provided.
The present invention provides a kind of continuous preparation method of soluble poly aromatic ether ketone film, and this method includes：
Step 1：The PAEK solution that soluble poly aromatic ether ketone resin powder or reaction are obtained is dilute using good solvent
Release, stir, obtain PAEK weak solution, then add poor solvent, through the isolated separation of solid and liquid of one-step or two-step
Product afterwards, by the solid dissolving in product in good solvent, then add precipitating reagent and precipitated, it is solvable after being handled
Property ketone-grouped resin；
Step 2：Soluble poly aromatic ether ketone resin after the processing that step 1 is obtained is dissolved in solvent, after defoaming
Scratched in substrate, pass through solution casting method film forming, pulling speed 0.02-2.00m/min, drying warm area 1-4, each warm area length
Spend for 0.2-10.0m, 20-240 DEG C of drying temperature, 50-200 DEG C of hot blast temperature, wind speed 0-800m3/h, obtain soluble poly virtue
Ether ketone film.
Preferably, described good solvent is selected from dimethyl sulfoxide (DMSO), DMF, N, N- dimethylacetamides
Amine, 1-METHYLPYRROLIDONE, N- cyclohexyl pyrrolidones, sulfolane, dichloromethane, chloroform, dichloroethanes or trichloroethanes
It is one or more of.
Preferably, described poor solvent and precipitating reagent are in water, methanol, ethanol, formic acid, acetic acid and isopropanol
It is one or more of.
Preferably, it is 1 that described poor solvent, which is selected from water and methanol according to mass ratio,：The mixed solution of 4 mixing, or
Water and ethanol are 1 according to mass ratio：The mixed solution of 4 mixing.
Preferably, described precipitating reagent is selected from water and acetic acid according to mass ratio 1：The mixed solution of 1 mixing.
Preferably, it is described use good solvent dilute after polymer solid content for 2~15%.
Preferably, described poor solvent addition is the 2-300% of PAEK weak solution quality；Described precipitation
Agent dosage is 0.5-20 times of PAEK weak solution quality.
Preferably, the structural formula of described soluble poly aromatic ether ketone resin is as shown in formula I or formula II：
In formula I or II, a>0, m>0, n>0, m+n=1 ,-O-Ar-O- and-O-Ar '-O can be with identical or different ,-O-Ar-
O- and-O-Ar '-O- is respectively that biphenol monomer HO-Ar-OH and HO-Ar '-OH form main polymer chain after nucleophilic condensation polymerization
Group；Ar " is the substituted rear remaining aromatic moieties of halogen atom in double halides X-Ar "-X.
Preferably, described substrate is PET or aluminium strip.
Preferably, the solvent of the step 2 is selected from DMF, DMA, tetrahydrochysene furan
Mutter, the one or more in 1-METHYLPYRROLIDONE, chloroform, dichloromethane 1,2- dichloroethanes, 1,1,2- trichloroethanes.
Beneficial effects of the present invention
The present invention provides a kind of continuous preparation method of soluble poly aromatic ether ketone film, and this method is first using after special
Handling process, branched in polymer and low polymer is removed, it is special to obtain the linear polyaryletherketone film of HMW
Material, then again by solution casting method film forming, by the technological parameter in adjusting method, it is good to obtain thin polymer film flatness,
Transparency is higher, while while keeping high heat-resisting, improves tensile strength, stretch modulus, elongation at break of film etc.,
And it can easily realize prepared by serialization wide cut.Test result indicates that：Its stretching of the film that the preparation method of the present invention obtains is strong
Spend 80-100MPa；Modulus of elasticity 2.1Gpa~3.5Gpa, elongation at break position 67%~106%.
Brief description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of the phenolphthalein polyaryletherketone of comparative example；
Fig. 2 is the GPC curves of the phenolphthalein polyaryletherketone of comparative example；
Fig. 3 is the nucleus magnetic hydrogen spectrum figure for the phenolphthalein polyaryletherketone that the post-processing approach of the embodiment of the present invention 1 obtains；
Fig. 4 is the GPC curves for the phenolphthalein polyaryletherketone that the post-processing approach of the embodiment of the present invention 1 obtains.
Embodiment
The present invention provides a kind of continuous preparation method of soluble poly aromatic ether ketone film, and this method includes：
Step 1：The PAEK solution that soluble poly aromatic ether ketone resin powder or reaction are obtained is dilute using good solvent
Release, stir, obtain PAEK weak solution, then add poor solvent, through the isolated separation of solid and liquid of one-step or two-step
Product afterwards, by the solid dissolving in product in good solvent, then add precipitating reagent and precipitated, it is solvable after being handled
Property ketone-grouped resin；
Step 2：Soluble poly aromatic ether ketone resin after the processing that step 1 is obtained is dissolved in solvent, after defoaming
Scratched in substrate, pass through solution casting method film forming, pulling speed 0.02-2.00m/min, drying warm area 1-4, each warm area length
Spend for 0.2-10.0m, 20-240 DEG C of drying temperature, 50-200 DEG C of hot blast temperature, wind speed 0-800m3/h, obtain soluble poly virtue
Ether ketone film.
According to the present invention, the polymer that soluble poly aromatic ether ketone resin powder or reaction obtain is diluted using good solvent,
PAEK weak solution is obtained, described dilution temperature is not particularly limited, according to the type of soluble poly aromatic ether ketone resin
Determine, preferably room temperature, after stirring, then add poor solvent, the production after the isolated separation of solid and liquid of one-step or two-step
Thing, by the solid dissolving in product in good solvent, described solution temperature is not particularly limited, according to soluble poly aromatic ether ketone
Depending on the type of resin, preferably solution temperature is 40-80 DEG C, then adds precipitating reagent and is precipitated, solvable after being handled
Property ketone-grouped resin.
According to the present invention, described good solvent is preferably selected from dimethyl sulfoxide (DMSO) (DMSO), DMF
(DMF), DMAC N,N' dimethyl acetamide (DMAc), 1-METHYLPYRROLIDONE (NMP), N- cyclohexyl pyrrolidones (NCP), sulfolane
(TMS), dichloromethane (CH2Cl2), chloroform (CHCl3), the one or more of dichloroethanes (DCE) and trichloroethanes (TCE).
According to the present invention, described poor solvent is preferably selected from one in water, methanol, ethanol, formic acid, acetic acid and isopropanol
Kind is several, and more preferably water and methanol are 1 according to mass ratio：The mixed solution of 4 mixing, or water and ethanol are according to mass ratio
For 1：The mixed solution of 4 mixing.
According to the present invention, described precipitating reagent is preferably selected from one kind in water, methanol, ethanol, formic acid, acetic acid and isopropanol
Or it is several, water and acetic acid are more preferably selected from according to mass ratio 1：The mixed solution of 1 mixing.
According to the present invention, it is described diluted using good solvent after the solid content of polymer be preferably 2~15%, more preferably
For 3-10%；Described poor solvent addition is preferably the 2-300% of PAEK weak solution quality；It is described by product
Solid be re-dissolved in good solvent, the addition of described good solvent is 2-49 times of PAEK weak solution quality, institute
The dosage for the precipitating reagent stated is preferably 0.5-20 times of PAEK weak solution quality, more preferably 1-10 times.
According to the present invention, the structural formula of described soluble poly aromatic ether ketone resin is as shown in formula I or formula II：
In formula I or II, a>0, m>0, n>0, m+n=1 ,-O-Ar-O- and-O-Ar '-O can be with identical or different ,-O-Ar-
O- and-O-Ar '-O- is respectively that biphenol monomer HO-Ar-OH and HO-Ar '-OH form main polymer chain after nucleophilic condensation polymerization
Group；Described HO-Ar-OH and HO-Ar '-OH independences selected from hydroquinones, '-biphenyl diphenol (4,4'- dihydroxybiphenyl),
Dihydroxy benzophenone (4,4'- dihydroxy benzophenones), dihydroxydiphenylsulisomer (4,4' dihydroxydiphenyl sulfone), 4,4'- dihydroxy two
Phenylate, 4,4'- dihydroxy diphenyl sulfide, bisphenol-A (2,2- double (4- hydroxy phenyls) propane), ((hexafluoro is different by 4,4'- for hexafluoro bisphenol-a
Propylidene) bis-phenol), bis-phenol P (4,4'- (1,4- phenylenes diisopropyl) biphenol), phenolphthalein (double (the 4- hydroxy phenyls) -1 of 3,3-
(3H)-isobenzofuranone), phenolphthalin (2- [double (4- hydroxyphenyls) methyl] benzoic acid), double (4- hydroxy phenyls) benzos of 3,3'-
The double triptycene diphenol of pyrrolones, bisphenol fluorene (9,9- bis- (4- hydroxy phenyls) fluorenes), 6,13-, 2,5- triptycenes diphenol, 5,5 '-it is bis-
Double (4- hydroxyphenoxies) -4 '-(2,3,4,5, the 6- five phenyl) hexichol of (2-4- (hydroxy phenyl)-benzimidazole), 2,6-
Ketone, (1-12 C) -3,6- pairs of (4- hydroxy benzoyls) carbazoles of N- saturations and unsaturated alkyl substitution, N- expoxy propane base -
Double (4- hydroxy benzoyls) carbazoles of 3,6-, N- trifluoromethyls -3,6- double (4- hydroxy benzoyls) carbazole, N- phenyl -3,6-
Double (4- hydroxy benzoyls) carbazoles, N- (4- trifluoromethyls) -3,6- double (4- hydroxy benzoyls) carbazole, N- (4- second
Alkenyl phenyl) double (4- hydroxy benzoyls) carbazoles of -3,6-, N- (4- ethynyl phenyls) -3,6- be double (4- hydroxy benzoyls)
Double (4- hydroxy benzoyls) carbazoles of carbazole, N- (4- cyano-phenyls) -3,6-.
Ar " is that the substituted rear remaining aromatic moieties of halogen atom, X-Ar "-X are 4,4 '-two in double halides X-Ar "-X
Fluorine benzophenone, 4,4 '-difluorodiphenyl sulfone, 1,4- bis- (4- fluoro benzoyls) benzene, 1- phenyl -4,4 '-difluorodiphenyl phosphine ketone, 4,
4 '-dichlorobenzophenone, 4,4 '-dichloro diphenyl sulfone, 1,4- bis- (4- chlorobenzene formacyls) benzene, 1- phenyl -4,4 '-dichloro phosphine
Ketone.
Invented according to instinct, after described processing method can by the adjustment of number of processes to the crosslinking component in resin and
Linear low molecule, cyclic oligomer carry out selective removal, and number of processes is no more than four times.
To be invented according to instinct, the number-average molecular weight of described soluble poly aromatic ether ketone resin is preferably 20~200kDa, point
Son amount distribution preferably 1.4~2.20.
According to the present invention, described post-processing approach both can directly operate in the last handling process of resins synthesis,
Linear PAEK tree can be finally given to carrying out after-treatment using the ketone-grouped resin after the processing of general purification process
Fat material.The material is suitable as film PP Pipe Compound, and realizes continuous production.
According to the present invention, the soluble poly aromatic ether ketone resin after processing obtained above is dissolved in solvent, preferably normal
Temperature is lower to be dissolved, and the solid content of casting solution is 5-40%, is scratched after defoaming in substrate, by solution casting method film forming,
Pulling speed 0.02-2.00m/min, preferably 0.5-1.00m/min, drying warm area 1-4, each warm area length is 0.2-
10.0m, preferably 2-4m, preferably 20-240 DEG C of drying temperature, 40-180 DEG C, preferably 50-200 DEG C of hot blast temperature, 70-
180 DEG C, wind speed 0-800m3/ h, preferably 150-450m3/ h, obtain soluble poly aromatic ether ketone film.
Casting film fluid solid content, pulling speed in solution casting method film forming process of the present invention, drying temperature, hot blast temperature
Degree and wind speed are that these parameters are influenced each other and restricted an important factor for influenceing the film quality.The content shadow of solvent first
The state of polymer is rung, when initial, polymer is using solution state as mobility, as solvent is gradual in surface evaporation, solid content
Increase, when solid content is in 50-70%, mobility extreme difference, it is possible to which as film base, film base can separate with base material, enter traveling one
Walk drying.By taking temperature and wind speed as an example, when the timing of pulling speed one, wind speed is small, and when temperature is low, the time for obtaining film base is just grown,
And wind speed is big, when temperature is high, the time of film base is obtained with regard to short.The time for forming film base should not be long, can not be too short.Time mistake
Length can increase equipment investment, and energy consumption is bigger；Time is too short, then is easily destroyed the flatness of film base, and fold, injustice occurs, is not easy
In final winding.Therefore, the film of high quality is obtained, need to be by above-mentioned process parameter control in the reasonable scope.
According to the present invention, described solvent is preferably selected from DMF, DMA, tetrahydrochysene furan
Mutter, the one or more in 1-METHYLPYRROLIDONE, chloroform, dichloromethane 1,2- dichloroethanes, 1,1,2- trichloroethanes.It is described
Substrate be preferably PET or aluminium strip.
According to the present invention, 5-100 μm of described film thickness, faint yellow, light brown or water white transparency, through solution curtain coating system
Standby film base, the solid content of film base is 70-95%, and reachable 99% after being further dried, after gained film drying, solvent is low
In 1.0%.High-performance polyarylether ketone film, its tensile strength 80- are obtained using solution casting method serialization technology of preparing
100MPa；Modulus of elasticity 2.1Gpa~3.5Gpa, elongation at break position 67%~106%.
With reference to specific embodiment, the present invention will be further described in detail, and the raw material being related in embodiment is
It is commercially available.
Comparative example 1
It is as follows using the phenolphthalein polyaryletherketone of commercialization, structural formula：
Polymer number-average molecular weight is 36kDa, molecular weight distribution 2.40；The nuclear magnetic spectrogram of polymer is as shown in figure 1, GPC
Curve is as shown in Figure 2.
Above-mentioned polymer is dissolved in DMF solvent, the solid content of polymeric casting film liquid is 25%, by solution casting method into
Film, base material aluminium band etc., pulling speed 0.03m/min, warm area 3 is dried, each warm area length is 2.0m, drying temperature
Degree is respectively 40 DEG C, 80 DEG C and 120 DEG C, 150 DEG C of hot blast temperature, wind speed 180m3/ h, obtains film.
Test result indicates that：30 μm of 1 gained film thickness of comparative example, after tested：Tensile strength 73.4MPa, stretch modulus
1.9GPa, elongation at break 8.0%.
Embodiment 1
The phenolphthalein polyaryletherketone solution (theoretical yield 360g) prepared by polycondensation reaction need not carry out salt-removal steps, use
9kgDMF is diluted to solid content 4.0%, and mechanical agitation obtains uniform solution, and mixed liquor (water and the methanol of water, methanol is slowly added dropwise
Mass ratio 1:4) 1500g, solution gradually become white, until there is a small amount of sediment to separate out.After separation of solid and liquid, solid separation is removed
Go, solution continues that mixed liquor (water and the ethanol mass ratio 1 of water, ethanol is slowly added dropwise:4) 100g, occur a large amount of precipitations in solution.
After separation of solid and liquid, dissolved again with 2700g DMF, solution is heated to 40 DEG C, again in 10kg water and the precipitating reagent (water of acetic acid
With quality of acetic acid ratio 1:1) precipitated in, boiling 5-7 times, after drying, obtain polymer 290g, its nuclear magnetic spectrogram is as shown in Figure 3.
Number-average molecular weight is 68kDa, molecular weight distribution 1.75；GPC curves are as shown in Figure 4.
Above-mentioned polymer is dissolved in DMF under room temperature condition, the solid content of casting solution is 25%, by solution casting method into
Film, base material select PET, pulling speed 0.03m/min, dry warm area 3, and each warm area length is 2.0m, drying temperature
Respectively 40 DEG C, 80 DEG C and 120 DEG C, 150 DEG C of hot blast temperature, wind speed 180m3/ h, obtains film.
Test result indicates that：30 μm, tensile strength 96.2MPa, stretch modulus 2.2GPa of 1 gained film thickness of embodiment,
Elongation at break is 106%.Elongation at break improves 12.3 times.
Solvent for use and precipitated liquid are through being evaporated under reduced pressure recoverable.
Embodiment 2
300g bisphenol A type polyaromatic ether ketone resins accurately are weighed, are dissolved in 7.5kg chloroformic solutions, solid content is
4.05%, mechanical agitation, it is to be dissolved completely after, thereto 3 batches add 1.8L methanol (each 0.6L), solution gradually becomes white,
Until there are a large amount of sediments to separate out, after separation of solid and liquid, jelly is heated to 80 DEG C, is dissolved with 2kg DMAc, existed again again
Precipitated in 5kg water, after drying, obtained polymer 262g, its number-average molecular weight is 55kDa, molecular weight distribution 2.20.
Above-mentioned polymer is dissolved in tetrahydrofuran under room temperature condition, the solid content of casting solution is 40%, passes through solution stream
Prolong method film forming, base material dries warm area 3 from PET fractal films etc., pulling speed 0.50m/min, and each warm area length is
2.0m, drying temperature are respectively 40 DEG C, 60 DEG C and 80 DEG C, 70 DEG C of hot blast temperature, wind speed 150m3/ h, obtains film.
Test result indicates that：60 μm, tensile strength 91.5MPa, stretch modulus 2.1Gpa of 2 gained film thickness of embodiment,
Elongation at break is 75%, and elongation at break improves 8.4 times.Solvent for use and precipitated liquid are through being evaporated under reduced pressure recoverable.
Embodiment 3
Wherein n=0.4, m=0.6.
350g phenolphthalein-bisphenol fluorene type polyether sulphone sulfone copolymer resins accurately is weighed, it is molten to be dissolved in 3.2kg tetrahydrofurans
In liquid, solid content 10%, mechanical agitation, it is to be dissolved completely after, 650ml methanol is added portionwise thereto, solution gradually becomes
In vain, until there are a large amount of sediments to separate out, after separation of solid and liquid, dissolved with 1.5kg DMF, precipitated again in 3.5kg methanol again,
After drying, the polymer 315g obtained, its number-average molecular weight are 82kDa, molecular weight distribution 2.17.
Above-mentioned polymer is dissolved in 1-METHYLPYRROLIDONE under room temperature condition, the solid content of casting solution is 5%, by molten
Liquid the tape casting film forming, base material aluminium band, pulling speed 0.03m/min dry warm area 4, and each warm area length is
2.0m, drying temperature are respectively 60 DEG C, 80 DEG C, 80 DEG C and 120 DEG C, 170 DEG C of hot blast temperature, wind speed 380m3/ h, obtains film.
Test result indicates that：15 μm, tensile strength 86.3MPa, stretch modulus 2.2GPa of 3 gained film thickness of embodiment,
Elongation at break is 85%, and elongation at break improves 13.1 times.Solvent for use and precipitated liquid are through being evaporated under reduced pressure recoverable.
Embodiment 4
Wherein n=0.7, m=0.3.
350g phenolphthalein-phthalazone type poly (arylene ether nitrile) ketone copolymer resins accurately is weighed, is dissolved in 5kg N- methyl
In pyrrolidone solution, solid content 6.54%, mechanical agitation, it is to be dissolved completely after, thereto in two batches add 500ml second
Alcohol, solution gradually become white, until there is a large amount of sediments to separate out, after separation of solid and liquid, are dissolved with 1kg NMP, existed again again
Precipitated in 3.5kg ethanol, after drying, obtained polymer 327g, its number-average molecular weight is 75kDa, molecular weight distribution 2.10.
Above-mentioned polymer is dissolved in 1-METHYLPYRROLIDONE under room temperature condition, the solid content of casting solution is 18%, is passed through
Solution casting method film forming, base material select PET mould release membrances, pulling speed 0.20m/min, dry warm area 4, each warm area length
It is respectively 100 DEG C, 140 DEG C, 140 DEG C and 180 DEG C to spend for 2.0m, drying temperature, 180 DEG C of hot blast temperature, wind speed 350m3/ h, is obtained
To film.
Test result indicates that：32 μm, tensile strength 95.5MPa, stretch modulus 3.5Gpa of 4 gained film thickness of embodiment,
Elongation at break is 67%, and elongation at break improves 7.4 times.Solvent for use and precipitated liquid are through being evaporated under reduced pressure recoverable.
Embodiment 5
Wherein n=0.5, m=0.5.
300g phenolphthalin type PAEK copolymer resinses accurately are weighed, are dissolved in 3kg DMAc solution, solid content
For 9.1%, mechanical agitation, it is to be dissolved completely after, add 600ml ethanol in two batches thereto, solution gradually becomes white, until having
A large amount of sediments separate out, and after separation of solid and liquid, are dissolved again with 750g DMAc, again in 3kg ethanol/waters (ethanol and water quality ratio
4:1) precipitated in, after drying, obtained polymer 280g, its number-average molecular weight is 67kDa, molecular weight distribution 1.76.
Above-mentioned polymer is dissolved in DMAc under room temperature condition, the solid content of casting solution is 15%, passes through solution casting method
Film forming, base material select PET mould release membrances, pulling speed 1.0m/min, dry warm area 4, and each warm area length is 4.0m, is dried
Dry temperature is respectively 100 DEG C, 120 DEG C, 120 DEG C and 150 DEG C, 180 DEG C of hot blast temperature, wind speed 450m3/ h, obtains film.
Test result indicates that：28 μm, tensile strength 79.6MPa, stretch modulus 2.6Gpa of 5 gained film thickness of embodiment,
Elongation at break is 81%, and elongation at break improves 7.0 times.Solvent for use and precipitated liquid are through being evaporated under reduced pressure recoverable.
Claims (10)
1. a kind of continuous preparation method of soluble poly aromatic ether ketone film, it is characterised in that this method includes：
Step 1：The PAEK solution that soluble poly aromatic ether ketone resin powder or reaction obtain is diluted using good solvent, stirred
Mix uniformly, obtain PAEK weak solution, then add poor solvent, the production after the isolated separation of solid and liquid of one-step or two-step
Thing, by the solid dissolving in product in good solvent, then add precipitating reagent and precipitated, the soluble poly virtue after being handled
Ether ketone resin；
Step 2：Soluble poly aromatic ether ketone resin after the processing that step 1 is obtained is dissolved in solvent, in substrate after defoaming
Upper blade coating, by solution casting method film forming, pulling speed 0.02-2.00m/min, drying warm area 1-4, each warm area length is
0.2-10.0m, 20-240 DEG C of drying temperature, 50-200 DEG C of hot blast temperature, wind speed 0-800m3/h, obtain soluble poly aromatic ether ketone
Film.
A kind of 2. continuous preparation method of soluble poly aromatic ether ketone film according to claim 1, it is characterised in that institute
The good solvent stated is selected from dimethyl sulfoxide (DMSO), N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE, N-
Cyclohexyl pyrrolidone, sulfolane, dichloromethane, chloroform, the one or more of dichloroethanes or trichloroethanes.
A kind of 3. continuous preparation method of soluble poly aromatic ether ketone film according to claim 1, it is characterised in that institute
One or more of the poor solvent and precipitating reagent stated in water, methanol, ethanol, formic acid, acetic acid and isopropanol.
A kind of 4. continuous preparation method of soluble poly aromatic ether ketone film according to claim 3, it is characterised in that institute
It is 1 that the poor solvent stated, which is selected from water and methanol according to mass ratio,：The mixed solution of 4 mixing, or water and ethanol are according to mass ratio
For 1：The mixed solution of 4 mixing.
A kind of 5. continuous preparation method of soluble poly aromatic ether ketone film according to claim 3, it is characterised in that institute
The precipitating reagent stated is selected from water and acetic acid according to mass ratio 1：The mixed solution of 1 mixing.
A kind of 6. continuous preparation method of soluble poly aromatic ether ketone film according to claim 1, it is characterised in that institute
State use good solvent dilute after polymer solid content for 2~15%.
A kind of 7. continuous preparation method of soluble poly aromatic ether ketone film according to claim 1, it is characterised in that institute
The poor solvent addition stated is the 2-300% of PAEK weak solution quality；Described precipitating reagent dosage is that PAEK is dilute
0.5-20 times of solution quality.
A kind of 8. continuous preparation method of soluble poly aromatic ether ketone film according to claim 1, it is characterised in that institute
The structural formula for the soluble poly aromatic ether ketone resin stated is as shown in formula I or formula II：
In formula I or II, a>0, m>0, n>0, m+n=1 ,-O-Ar-O- and-O-Ar '-O can with identical or different ,-O-Ar-O- and-
O-Ar '-O- are respectively the base that biphenol monomer HO-Ar-OH and HO-Ar '-OH form main polymer chain after nucleophilic condensation polymerization
Group；Ar " is the substituted rear remaining aromatic moieties of halogen atom in double halides X-Ar "-X.
A kind of 9. continuous preparation method of soluble poly aromatic ether ketone film according to claim 1, it is characterised in that institute
The substrate stated is PET or aluminium strip.
A kind of 10. continuous preparation method of soluble poly aromatic ether ketone film according to claim 1, it is characterised in that
The solvent of the step 2 is selected from N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, tetrahydrofuran, N- crassitudes
One or more in ketone, chloroform, dichloromethane 1,2- dichloroethanes, 1,1,2- trichloroethanes.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110183647A (en) * | 2019-06-18 | 2019-08-30 | 吉林大学 | A kind of carbon nano-tube/poly ether ketone composite material and preparation method and application |
| CN111363139A (en) * | 2020-05-13 | 2020-07-03 | 浙江帕尔科新材料有限公司 | Post-treatment method of polyaryletherketone polymer |
| CN111499890A (en) * | 2020-05-13 | 2020-08-07 | 浙江帕尔科新材料有限公司 | Polyaryletherketone polymer hollow micro powder and preparation method thereof |
| CN114901733A (en) * | 2019-12-27 | 2022-08-12 | 三菱化学株式会社 | Member for composite material, moving body, and method for producing film for composite material |
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| CN101948568A (en) * | 2010-09-16 | 2011-01-19 | 电子科技大学 | Method for preparing poly(arylene ether nitrile) resin powder |
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| CN101948568A (en) * | 2010-09-16 | 2011-01-19 | 电子科技大学 | Method for preparing poly(arylene ether nitrile) resin powder |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110183647A (en) * | 2019-06-18 | 2019-08-30 | 吉林大学 | A kind of carbon nano-tube/poly ether ketone composite material and preparation method and application |
| CN114901733A (en) * | 2019-12-27 | 2022-08-12 | 三菱化学株式会社 | Member for composite material, moving body, and method for producing film for composite material |
| CN111363139A (en) * | 2020-05-13 | 2020-07-03 | 浙江帕尔科新材料有限公司 | Post-treatment method of polyaryletherketone polymer |
| CN111499890A (en) * | 2020-05-13 | 2020-08-07 | 浙江帕尔科新材料有限公司 | Polyaryletherketone polymer hollow micro powder and preparation method thereof |
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