CN107778503B - Continuous preparation method of soluble polyaryletherketone film - Google Patents
Continuous preparation method of soluble polyaryletherketone film Download PDFInfo
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Abstract
The invention provides a continuous preparation method of a soluble polyaryletherketone film, belonging to the technical field of film preparation methods. Carrying out post-treatment on soluble polyaryletherketone resin powder or polyaryletherketone solution obtained by reaction to obtain treated soluble polyaryletherketone resin; then dissolving the treated soluble polyaryletherketone resin in a solvent, defoaming, then blade-coating on a substrate, and forming a film by a solution casting method, wherein the traction speed is 0.02-2.00m/min, the drying temperature zones are 1-4, the length of each temperature zone is 0.2-10.0m, the drying temperature is 20-240 ℃, the hot air temperature is 50-200 ℃, and the air speed is 0-800m3/h, so as to obtain the soluble polyaryletherketone film. The tensile strength of the film obtained by the preparation method is 80-100 MPa; the elastic modulus is 2.1Gpa to 3.5Gpa, and the elongation at break is 67 percent to 106 percent.
Description
Technical Field
The invention belongs to the technical field of film preparation methods, and particularly relates to a continuous preparation method of a soluble polyaryletherketone film.
Background
The polyaryletherketone film is a high value-added polymer material, and has good heat resistance, dimensional stability, high strength and high modulus. The polyaryletherketone film prepared by the high-temperature method needs an extrusion casting method, a stretching method or a film blowing method, and when the polyaryletherketone film is extruded by a screw, the temperature of a discharge port is as high as 350-.
Disclosure of Invention
The invention aims to solve the technical problems of strict requirements on equipment and high cost of the existing preparation method of the polyaryletherketone film, and provides a continuous preparation method of a soluble polyaryletherketone film.
The invention provides a continuous preparation method of a soluble polyaryletherketone film, which comprises the following steps:
the method comprises the following steps: diluting soluble polyaryletherketone resin powder or polyaryletherketone solution obtained by reaction with a good solvent, uniformly stirring to obtain polyaryletherketone dilute solution, then adding a poor solvent, carrying out one-step or two-step separation to obtain a product after solid-liquid separation, dissolving the solid in the product in the good solvent, and then adding a precipitator for precipitation to obtain the treated soluble polyaryletherketone resin;
step two: dissolving the treated soluble polyaryletherketone resin obtained in the step one in a solvent, defoaming, then blade-coating on a substrate, and forming a film by a solution casting method, wherein the traction speed is 0.02-2.00m/min, the drying temperature zones are 1-4, the length of each temperature zone is 0.2-10.0m, the drying temperature is 20-240 ℃, the hot air temperature is 50-200 ℃, and the air speed is 0-800m3/h, so that the soluble polyaryletherketone film is obtained.
Preferably, the good solvent is selected from one or more of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, N-cyclohexylpyrrolidone, sulfolane, dichloromethane, chloroform, dichloroethane or trichloroethane.
Preferably, the poor solvent and the precipitant are selected from one or more of water, methanol, ethanol, formic acid, acetic acid and isopropanol.
Preferably, the poor solvent is selected from water and methanol according to a mass ratio of 1:4, or mixing water and ethanol according to a mass ratio of 1:4 mixing the mixed solution.
Preferably, the precipitating agent is selected from water and acetic acid according to the mass ratio of 1:1 mixed solution.
Preferably, the solid content of the polymer diluted by the good solvent is 2-15%.
Preferably, the adding amount of the poor solvent is 2-300% of the mass of the polyaryletherketone dilute solution; the dosage of the precipitant is 0.5-20 times of the mass of the polyaryletherketone dilute solution.
Preferably, the structural formula of the soluble polyaryletherketone resin is shown as formula I or formula II:
in the formula I or II, a is 0, m is 0, n is 0, m + n is 1, -O-Ar-O-and-O-Ar ' -O can be same or different, -O-Ar-O-and-O-Ar ' -O-are groups which form a polymer main chain after nucleophilic polycondensation reaction of bisphenol monomers HO-Ar-OH and HO-Ar ' -OH; ar 'is double halogen X-Ar' -the aromatic ring part left after the halogen atom in X is replaced.
Preferably, the substrate is a PET or aluminum tape.
Preferably, the solvent of the second step is one or more selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, N-methylpyrrolidone, chloroform, 1, 2-dichloroethane and 1,1, 2-trichloroethane.
The invention has the advantages of
The invention provides a continuous preparation method of a soluble polyaryletherketone film, which comprises the steps of firstly adopting a special post-treatment process to remove branching and low-molecular polymers in the polymers to obtain a special material of a high-molecular-weight linear polyaryletherketone film, then forming the film by a solution casting method, adjusting process parameters in the method to obtain the polymer film with good flatness and higher transparency, simultaneously keeping high heat resistance, improving the tensile strength, tensile modulus, breaking elongation and the like of the film, and conveniently realizing continuous wide-width preparation. The experimental results show that: the tensile strength of the film obtained by the preparation method is 80-100 MPa; the elastic modulus is 2.1Gpa to 3.5Gpa, and the elongation at break is 67 percent to 106 percent.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of phenolphthalein polyaryletherketone of a comparative example;
FIG. 2 is a GPC curve of a phenolphthalein polyaryletherketone of a comparative example;
FIG. 3 is a nuclear magnetic hydrogen spectrum of phenolphthalein polyaryletherketone obtained by the post-treatment method of example 1 of the present invention;
FIG. 4 is a GPC chart of phenolphthalein polyaryletherketone obtained by the post-treatment method of example 1 of the present invention.
Detailed Description
The invention provides a continuous preparation method of a soluble polyaryletherketone film, which comprises the following steps:
the method comprises the following steps: diluting soluble polyaryletherketone resin powder or polyaryletherketone solution obtained by reaction with a good solvent, uniformly stirring to obtain polyaryletherketone dilute solution, then adding a poor solvent, carrying out one-step or two-step separation to obtain a product after solid-liquid separation, dissolving the solid in the product in the good solvent, and then adding a precipitator for precipitation to obtain the treated soluble polyaryletherketone resin;
step two: dissolving the treated soluble polyaryletherketone resin obtained in the step one in a solvent, defoaming, then blade-coating on a substrate, and forming a film by a solution casting method, wherein the traction speed is 0.02-2.00m/min, the drying temperature zones are 1-4, the length of each temperature zone is 0.2-10.0m, the drying temperature is 20-240 ℃, the hot air temperature is 50-200 ℃, and the air speed is 0-800m3/h, so that the soluble polyaryletherketone film is obtained.
According to the invention, soluble polyaryletherketone resin powder or a polymer obtained by reaction is diluted by a good solvent to obtain a polyaryletherketone dilute solution, wherein the dilution temperature is not particularly limited and is determined according to the type of the soluble polyaryletherketone resin, preferably room temperature, after uniform stirring, a poor solvent is added, a product obtained after solid-liquid separation is obtained through one-step or two-step separation, the solid in the product is dissolved in the good solvent, the dissolution temperature is not particularly limited and is determined according to the type of the soluble polyaryletherketone resin, preferably the dissolution temperature is 40-80 ℃, and then a precipitator is added for precipitation to obtain the treated soluble polyaryletherketone resin.
According to the invention, the good solvent is preferably selected from the group consisting of dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP),N-Cyclohexylpyrrolidone (NCP), sulfolane (TMS), dichloromethane (CH)2Cl2) Chloroform (CHCl)3) One or more of Dichloroethane (DCE) and Trichloroethane (TCE).
According to the present invention, the poor solvent is preferably one or more selected from the group consisting of water, methanol, ethanol, formic acid, acetic acid and isopropanol, and more preferably water and methanol in a mass ratio of 1:4, or mixing water and ethanol according to a mass ratio of 1:4 mixing the mixed solution.
According to the invention, the precipitant is preferably one or more selected from water, methanol, ethanol, formic acid, acetic acid and isopropanol, more preferably water and acetic acid in a mass ratio of 1:1 mixed solution.
According to the invention, the solid content of the polymer diluted by the good solvent is preferably 2-15%, and more preferably 3-10%; the adding amount of the poor solvent is preferably 2-300% of the mass of the polyaryletherketone dilute solution; the solid in the product is re-dissolved in a good solvent, the addition amount of the good solvent is 2-49 times of the mass of the polyaryletherketone dilute solution, and the dosage of the precipitant is preferably 0.5-20 times of the mass of the polyaryletherketone dilute solution, and more preferably 1-10 times.
According to the invention, the structural formula of the soluble polyaryletherketone resin is shown as a formula I or a formula II:
in the formula I or II, a is 0, m is 0, n is 0, m + n is 1, -O-Ar-O-and-O-Ar ' -O can be same or different, -O-Ar-O-and-O-Ar ' -O-are groups which form a polymer main chain after nucleophilic polycondensation reaction of bisphenol monomers HO-Ar-OH and HO-Ar ' -OH; the HO-Ar-OH and HO-Ar '-OH are independently selected from hydroquinone, biphenol (4,4' -dihydroxybiphenyl), dihydroxybenzophenone (4,4 '-dihydroxybenzophenone), dihydroxybiphenyl sulfone (4,4' -dihydroxybiphenyl sulfone), 4 '-dihydroxydiphenyl ether, 4' -dihydroxybiphenyl sulfide, bisphenol A (2, 2-bis (4-hydroxyphenyl) propane), hexafluorobisphenol A (4,4'- (hexafluoroisopropylidene) bisphenol), bisphenol P (4,4' - (1, 4-phenylenediisopropyl) diphenol), phenolphthalein (3, 3-bis (4-hydroxyphenyl) -1(3H) -isobenzofuranone), phenolphthalein (2- [ bis (4-hydroxyphenyl) methyl ] benzoic acid), 3,3' -bis (4-hydroxyphenyl) phthalimidine, bisphenol fluorene (9, 9-bis (4-hydroxyphenyl) fluorene), 6, 13-bistriprienediol, 2, 5-triptycenediol, 5 ' -bis (2-4- (hydroxyphenyl) -benzimidazole), 2, 6-bis (4-hydroxyphenoxy) -4 ' - (2,3,4,5, 6-pentaphenylphenyl) benzophenone, N-saturated and unsaturated alkyl-substituted (1-12C) -3, 6-bis (4-hydroxybenzoyl) carbazole, N-glycidylalkyl-3, 6-bis (4-hydroxybenzoyl) carbazole, N-trifluoromethyl-3, 6-bis (4-hydroxybenzoyl) carbazole, N-phenyl-3, 6-bis (4-hydroxybenzoyl) carbazole, N- (4-trifluoromethylphenyl) -3, 6-bis (4-hydroxybenzoyl) carbazole, N- (4-vinylphenyl) -3, 6-bis (4-hydroxybenzoyl) carbazole, N- (4-ethynylphenyl) -3, 6-bis (4-hydroxybenzoyl) carbazole, N- (4-cyanophenyl) -3, 6-bis (4-hydroxybenzoyl) carbazole.
Ar ' is the aromatic ring part left after the halogen atom in the double halogen compound X-Ar ' -X is replaced, and X-Ar ' -X is 4,4' -difluorobenzophenone, 4' -difluorodiphenyl sulfone, 1, 4-bis (4-fluorobenzoyl) benzene, 1-phenyl-4, 4' -difluorodiphenyl phosphine ketone, 4' -dichlorobenzophenone, 4' -dichlorodiphenyl sulfone, 1, 4-bis (4-chlorobenzoyl) benzene and 1-phenyl-4, 4' -dichlorodiphenyl phosphine ketone.
According to the invention, the cross-linking component and linear low-molecular and cyclic oligomer in the resin can be selectively removed by adjusting the treatment times after the treatment method, and the treatment times are not more than four times.
According to the invention, the number average molecular weight of the soluble polyaryletherketone resin is preferably 20-200 kDa, and the molecular weight distribution is preferably 1.4-2.20.
According to the invention, the post-treatment method can be directly operated in the post-treatment process of resin synthesis, and can also be used for carrying out secondary treatment on the polyaryletherketone resin treated by a common purification method to finally obtain the linear polyaryletherketone resin material. The material is suitable for being used as a special material for films and realizes continuous production.
According toThe invention dissolves the processed soluble polyaryletherketone resin in a solvent, preferably at normal temperature, the solid content of the casting solution is 5-40%, the casting solution is defoamed, blade-coated on a substrate, and film-formed by a solution casting method, the traction rate is 0.02-2.00m/min, preferably 0.5-1.00m/min, the drying temperature zones are 1-4, the length of each temperature zone is 0.2-10.0m, preferably 2-4m, the drying temperature is 20-240 ℃, preferably 40-180 ℃, the hot air temperature is 50-200 ℃, preferably 70-180 ℃, and the air speed is 0-800m3H, preferably 150-450m3And h, obtaining the soluble polyaryletherketone film.
The solid content, the traction speed, the drying temperature, the hot air temperature and the air speed of the casting solution in the solution casting method film forming process method are important factors influencing the quality of the film, and the parameters influence and restrict each other. Firstly, the content of the solvent influences the state of the polymer, the polymer is in a solution state as fluidity at the beginning, the solid content is gradually increased along with the evaporation of the solvent on the surface, when the solid content is 50-70%, the fluidity is extremely poor, a film blank can be formed, and the film blank can be separated from the base material for further drying. Taking temperature and wind speed as examples, when the traction speed is fixed, the wind speed is small, when the temperature is low, the time for obtaining the film blank is long, and when the wind speed is large, when the temperature is high, the time for obtaining the film blank is short. The time for forming the film blank should not be too long, nor too short. The equipment investment is increased and the energy consumption is larger if the time is too long; if the time is too short, the flatness of the film blank is easily damaged, wrinkles and unevenness occur, and the final winding is not easy to realize. Therefore, to obtain a high quality film, the above process parameters need to be controlled within a reasonable range.
According to the invention, the solvent is preferably one or more selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, N-methylpyrrolidone, chloroform, 1, 2-dichloroethane dichloromethane and 1,1, 2-trichloroethane. The substrate is preferably a PET or aluminum tape.
According to the invention, the film has the thickness of 5-100 μm, is light yellow, light brown or colorless and transparent, is prepared into a film blank through solution casting, the solid content of the film blank is 70-95%, the solid content can reach 99% after further drying, and the solvent content of the obtained film is lower than 1.0% after drying. Adopting a solution casting continuous preparation technology to obtain a high-performance polyaryletherketone film with the tensile strength of 80-100 MPa; the elastic modulus is 2.1Gpa to 3.5Gpa, and the elongation at break is 67 percent to 106 percent.
The present invention is further illustrated by reference to the following specific examples, in which the starting materials are all commercially available.
Comparative example 1
The structural formula of the commercial phenolphthalein polyaryletherketone is as follows:
the number average molecular weight of the polymer is 36kDa, and the molecular weight distribution is 2.40; the NMR spectrum of the polymer is shown in FIG. 1, and the GPC curve is shown in FIG. 2.
Dissolving the polymer in DMF solvent, wherein the solid content of the polymer casting solution is 25%, forming a film by a solution casting method, the substrate material is an aluminum strip or the like, the traction rate is 0.03m/min, the drying temperature zones are 3, the length of each temperature zone is 2.0m, the drying temperature is 40 ℃, 80 ℃ and 120 ℃, the hot air temperature is 150 ℃, and the air speed is 180m3And/h, obtaining the film.
The experimental results show that: the film obtained in comparative example 1, having a thickness of 30 μm, was tested: tensile strength 73.4MPa, tensile modulus 1.9GPa, and elongation at break 8.0%.
Example 1
The phenolphthalein polyaryletherketone solution (theoretical yield is 360g) prepared by polycondensation does not need a desalting step, is diluted to solid content of 4.0% by 9kg of DMF, is mechanically stirred to obtain a uniform solution, 1500g of mixed solution of water and methanol (mass ratio of water to methanol is 1:4) is slowly dripped, and the solution gradually becomes white until a small amount of precipitate is separated out. After solid-liquid separation, the solid is separated and removed, 100g of mixed solution of water and ethanol (the mass ratio of water to ethanol is 1:4) is continuously and slowly dropped into the solution, and a large amount of precipitate appears in the solution. After solid-liquid separation, the solution was dissolved again in 2700g of DMF, the solution was heated to 40 ℃ and precipitated again in 10kg of a precipitant of water and acetic acid (water and acetic acid in a mass ratio of 1:1), and the resulting solution was boiled in water 5 to 7 times and dried to obtain 290g of a polymer, the nuclear magnetic spectrum of which is shown in FIG. 3. The number average molecular weight is 68kDa, and the molecular weight distribution is 1.75; the GPC curve is shown in FIG. 4.
Dissolving the polymer in DMF at room temperature, wherein the solid content of the casting solution is 25%, forming a film by a solution casting method, selecting PET as a substrate material, drawing at a speed of 0.03m/min, drying at 40 deg.C, 80 deg.C and 120 deg.C, hot air at 150 deg.C and air at 180m, wherein the length of each temperature zone is 2.0m, and the drying temperature is 40 deg.C, 80 deg.C and 120 deg.C respectively3And/h, obtaining the film.
The experimental results show that: the film obtained in example 1 had a thickness of 30 μm, a tensile strength of 96.2MPa, a tensile modulus of 2.2GPa, and an elongation at break of 106%. The elongation at break is improved by 12.3 times.
The solvent and the precipitation solution can be recycled by reduced pressure distillation.
Example 2
Accurately weighing 300g of bisphenol A type polyaryletherketone resin, dissolving the bisphenol A type polyaryletherketone resin in 7.5kg of chloroform solution, wherein the solid content is 4.05 percent, mechanically stirring, adding 1.8L of methanol (0.6L each time) into 3 batches of the bisphenol A type polyaryletherketone resin after complete dissolution, gradually turning the solution white until a large amount of precipitate is separated out, after solid-liquid separation, heating the jelly to 80 ℃, dissolving the jelly again with 2kg of DMAc, precipitating in 5kg of water again, and drying to obtain 262g of polymer, wherein the number average molecular weight of the polymer is 55kDa, and the molecular weight distribution is 2.20.
Dissolving the polymer in tetrahydrofuran at room temperature, wherein the solid content of the casting solution is 40%, forming a film by solution casting method, selecting PET (polyethylene terephthalate) release film as a base material, drawing at 0.50m/min, drying at 3 temperature regions, wherein each temperature region has a length of 2.0m, drying at 40 deg.C, 60 deg.C and 80 deg.C, hot air at 70 deg.C, and air speed of 150m3And/h, obtaining the film.
The experimental results show that: the film obtained in example 2 had a thickness of 60 μm, a tensile strength of 91.5MPa, a tensile modulus of 2.1GPa, an elongation at break of 75% and an elongation at break increased by 8.4 times. The solvent and the precipitation solution can be recycled by reduced pressure distillation.
Example 3
Wherein n is 0.4 and m is 0.6.
350g of phenolphthalein-bisphenol fluorene type polyarylethersulfone copolymer resin is accurately weighed and dissolved in 3.2kg of tetrahydrofuran solution, the solid content is 10%, the mechanical stirring is carried out, 650ml of methanol is added in batches after the complete dissolution, the solution gradually turns white until a large amount of precipitates are separated out, after solid-liquid separation, 1.5kg of DMF is used for dissolution again, the precipitates are precipitated in 3.5kg of methanol again, and after drying, 315g of polymer is obtained, the number average molecular weight of the polymer is 82kDa, and the molecular weight distribution is 2.17.
Dissolving the polymer in N-methylpyrrolidone at room temperature, wherein the solid content of the casting solution is 5%, forming a film by a solution casting method, the base material is an aluminum belt, the traction speed is 0.03m/min, 4 drying temperature zones are provided, the length of each temperature zone is 2.0m, the drying temperature is 60 ℃, 80 ℃ and 120 ℃, the hot air temperature is 170 ℃, and the air speed is 380m3And/h, obtaining the film.
The experimental results show that: the film obtained in example 3 had a thickness of 15 μm, a tensile strength of 86.3MPa, a tensile modulus of 2.2GPa, an elongation at break of 85% and an elongation at break improved by 13.1 times. The solvent and the precipitation solution can be recycled by reduced pressure distillation.
Example 4
Wherein n is 0.7 and m is 0.3.
350g of phenolphthalein-phthalazinone type polyarylethernitrilone copolymer resin is accurately weighed and dissolved in 5kg of N-methylpyrrolidone solution, the solid content is 6.54 percent, the mechanical stirring is carried out, after the complete dissolution, 500ml of ethanol is added into the solution in two batches, the solution gradually turns white until a large amount of precipitates are separated out, after solid-liquid separation, 1kg of NMP is used for dissolution again, the precipitates are precipitated in 3.5kg of ethanol again, and after drying, 327g of polymer is obtained, the number average molecular weight of the polymer is 75kDa, and the molecular weight distribution is 2.10.
Dissolving the polymer in N-methylpyrrolidone at room temperature, wherein the solid content of the casting solution is 18%, forming a film by a solution casting method, the base material is a PET release film, the traction rate is 0.20m/min, 4 drying temperature zones are provided, the length of each temperature zone is 2.0m, the drying temperature is respectively 100 ℃, 140 ℃ and 180 ℃, the hot air temperature is 180 ℃, and the air speed is 350m3And/h, obtaining the film.
The experimental results show that: the film obtained in example 4 had a thickness of 32 μm, a tensile strength of 95.5MPa, a tensile modulus of 3.5GPa, an elongation at break of 67% and an elongation at break increased by 7.4 times. The solvent and the precipitation solution can be recycled by reduced pressure distillation.
Example 5
Wherein n is 0.5 and m is 0.5.
Accurately weighing 300g of phenolphthalein type polyaryletherketone copolymer resin, dissolving the phenolphthalein type polyaryletherketone copolymer resin in 3kg of DMAc solution, wherein the solid content is 9.1%, mechanically stirring, adding 600ml of ethanol into the solution in two batches after the solution is completely dissolved, gradually turning the solution white until a large amount of precipitates are separated out, dissolving the solution again with 750g of DMAc after solid-liquid separation, precipitating the solution in 3kg of ethanol/water (the mass ratio of ethanol to water is 4:1), and drying to obtain 280g of polymer, wherein the number average molecular weight of the polymer is 67kDa, and the molecular weight distribution is 1.76.
Dissolving the polymer in DMAc at room temperature, wherein the solid content of the casting solution is 15%, forming a film by a solution casting method, selecting a PET release film as a base material, drawing at a speed of 1.0m/min, drying at 4 temperature zones, wherein the length of each temperature zone is 4.0m, the drying temperature is 100 ℃, 120 ℃, 150 ℃, the hot air temperature is 180 ℃, and the air speed is 450m3And/h, obtaining the film.
The experimental results show that: the film obtained in example 5 had a thickness of 28 μm, a tensile strength of 79.6MPa, a tensile modulus of 2.6GPa, an elongation at break of 81% and an elongation at break increased by 7.0 times. The solvent and the precipitation solution can be recycled by reduced pressure distillation.
Claims (10)
1. A continuous preparation method of a soluble polyaryletherketone film is characterized by comprising the following steps:
the method comprises the following steps: diluting soluble polyaryletherketone resin powder or polyaryletherketone solution obtained by reaction with a good solvent, uniformly stirring to obtain polyaryletherketone dilute solution, then adding a poor solvent, carrying out one-step or two-step separation to obtain a product after solid-liquid separation, dissolving the solid in the product in the good solvent, and then adding a precipitator for precipitation to obtain the treated soluble polyaryletherketone resin;
step two: dissolving the treated soluble polyaryletherketone resin obtained in the step one in a solvent, wherein the solid content of the casting solution is 5-40%, defoaming, then blade-coating on a substrate, forming a film by a solution casting method, wherein the traction rate is 0.02-2.00m/min, 1-4 drying temperature zones are provided, the length of each temperature zone is 0.2-10.0m, the drying temperature is 20-240 ℃, the hot air temperature is 50-200 ℃, and the air speed is 0-800m3/h, so as to obtain the soluble polyaryletherketone film.
2. The continuous preparation method of the soluble polyaryletherketone film as claimed in claim 1, wherein the good solvent is selected from one or more of dimethylsulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, N-cyclohexylpyrrolidone, sulfolane, dichloromethane, chloroform, dichloroethane and trichloroethane.
3. The continuous process for preparing a soluble polyaryletherketone film as claimed in claim 1, wherein said poor solvent and precipitating agent are selected from one or more of water, methanol, ethanol, formic acid, acetic acid and isopropanol.
4. The continuous preparation method of the soluble polyaryletherketone film as claimed in claim 3, wherein the poor solvent is selected from water and methanol at a mass ratio of 1:4, or mixing water and ethanol according to a mass ratio of 1:4 mixing the mixed solution.
5. The continuous preparation method of the soluble polyaryletherketone film as claimed in claim 3, wherein the precipitating agent is selected from water and acetic acid according to a mass ratio of 1:1 mixed solution.
6. The continuous preparation method of the soluble polyaryletherketone film as claimed in claim 1, wherein the solid content of the polymer diluted with the good solvent is 2-15%.
7. The continuous preparation method of soluble polyaryletherketone film as claimed in claim 1, wherein the amount of said poor solvent is 2-300% of the weight of the diluted solution of polyaryletherketone; the dosage of the precipitant is 0.5-20 times of the mass of the polyaryletherketone dilute solution.
8. The continuous preparation method of the soluble polyaryletherketone film as claimed in claim 1, wherein the structural formula of the soluble polyaryletherketone resin is represented by formula I or formula II:
in the formula I or II, a is 0, m is 0, n is 0, m + n is 1, -O-Ar-O-and-O-Ar ' -O can be same or different, -O-Ar-O-and-O-Ar ' -O-are groups which form a polymer main chain after nucleophilic polycondensation reaction of bisphenol monomers HO-Ar-OH and HO-Ar ' -OH; ar 'is double halogen X-Ar' -the aromatic ring part left after the halogen atom in X is replaced.
9. The continuous process for preparing soluble polyaryletherketone film as claimed in claim 1, wherein said substrate is PET or aluminum tape.
10. The continuous preparation method of the soluble polyaryletherketone film as claimed in claim 1, wherein the solvent in the second step is one or more selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, N-methylpyrrolidone, chloroform, 1, 2-dichloroethane and 1,1, 2-trichloroethane.
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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 |
| CN105348512A (en) * | 2015-11-09 | 2016-02-24 | 吉林大学 | Polyarylether materials containing imide side groups and preparation method therefor |
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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 |
| CN105348512A (en) * | 2015-11-09 | 2016-02-24 | 吉林大学 | Polyarylether materials containing imide side groups and preparation method therefor |
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