CN110437428B - High-dyne-value active polyester, polyester film and preparation method thereof - Google Patents

High-dyne-value active polyester, polyester film and preparation method thereof Download PDF

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CN110437428B
CN110437428B CN201910732735.6A CN201910732735A CN110437428B CN 110437428 B CN110437428 B CN 110437428B CN 201910732735 A CN201910732735 A CN 201910732735A CN 110437428 B CN110437428 B CN 110437428B
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polyester
parts
active
dyne
sodium
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CN110437428A (en
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张刚
张雨
杨杰
严光明
王晗
吴喆夫
胡全
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Sichuan University
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
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    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
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    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
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    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
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    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
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    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
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    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/12—Applications used for fibers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

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  • Polymers & Plastics (AREA)
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  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
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  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention relates to high-dyne-value active polyester, a polyester film and a preparation method thereof, belonging to the field of polymer synthesis. The invention provides a high-dyne-value active polyester, which is prepared from the following raw materials in parts by weight: 1 to 290 parts of aromatic diphenol monomer, 455 parts of aromatic diformyl chloride 203-. The invention adopts the copolymerization of the diphenol monomer containing active methoxyl, carboxyl and sulfonic group, the aromatic diphenol monomer and the aromatic diformyl chloride monomer, effectively improves the surface activity of the obtained polyester, improves the dyne value of the polyester, greatly improves the interface bonding strength of the obtained polyester and other composite phases, and is beneficial to preparing functional composite membrane materials.

Description

High-dyne-value active polyester, polyester film and preparation method thereof
Technical Field
The invention relates to high-dyne-value active polyester, a polyester film and a preparation method thereof, belonging to the field of polymer synthesis.
Background
The polyester has better thermal property, mechanical property and processing property when being used as engineering plastics; the traditional polyester mainly comprises PET (glass transition temperature 69 ℃, melting point 255-; when the material is used as a film material, the molecular chain is inert (relatively high in chemical stability), so that the material is poor in interface bonding with other phases during subsequent applications such as compounding, coating and pattern layer, the interlaminar shear strength is low, and phenomena such as peeling or severe coating shrinkage are easily caused.
Disclosure of Invention
Aiming at the defects, the invention provides the high-dyne-value active polyester, the polyester film and the preparation method thereof, and the obtained high-dyne-value active polyester has excellent heat resistance, processability, mechanical strength, flame retardance and extremely excellent surface activity, can be used for preparing high-performance and functional polyester fibers and polyester films, and has wide application prospect.
The first technical problem to be solved by the invention is to provide a high-dyne-value active polyester, wherein the starting materials of the polyester comprise the following components:
Figure BDA0002161159510000011
wherein the structural formula of the diphenol monomer containing the active group is as follows:
Figure BDA0002161159510000021
Figure BDA0002161159510000022
at least one of (1).
Further, the aromatic diphenol monomer has a formula:
Figure BDA0002161159510000023
Figure BDA0002161159510000024
at least one of;
the aromatic dicarboxylic acid chloride has the structural formula:
Figure BDA0002161159510000031
Figure BDA0002161159510000032
at least one of (1).
Further, the polymeric molecular stabilizer is any one of aniline, benzylamine, 4-aminobenzenesulfone, 4-aminobenzophenone, 4-aminodiphenyl ether, 4-aminobenzenesulfide, benzidine, naphthylamine, ethylamine, propylamine, butylamine, n-hexylamine, cyclohexylamine, or dicyclohexylamine.
Further, the catalyst is any one of 15-crown-5, 18-crown-6, dioctyl sodium succinate, zinc citrate, sodium tartrate, sodium gluconate, sodium nitrilotriacetate, sodium sorbate, sodium ethylene diamine tetracetate, sodium glycocholate, sodium terephthalate, sodium stearate, tetrabutyl ammonium bromide, benzyl triethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride, sodium dodecyl benzene sulfonate, sodium p-methyl benzene sulfonate, sodium alginate or sodium dodecyl sulfonate.
Further, the base is any one of lithium hydroxide, sodium hydroxide, calcium hydroxide, potassium hydroxide, barium hydroxide, aluminum hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, barium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, barium bicarbonate, ammonia water, trimethylamine, triethylamine, tri-tert-butylamine, pyridine, or piperazine.
Further, the organic solvent is any one of 1, 2-dichloroethane, 1,2, 2-tetrachloroethane, dichloromethane, chloroform, carbon tetrachloride, cyclohexane, cyclohexanone, chlorobenzene, m-dichlorobenzene, or 1,2, 4-trichlorobenzene.
The second technical problem to be solved by the present invention is to provide a method for preparing the above high dyne value active polyester, which comprises the following steps:
(1) preparation of active group-containing polyester:
sequentially adding 1-290 parts of aromatic diphenol monomer, 0.1-20 parts of catalyst and 80-200 parts of alkali into a reaction kettle filled with 150-1000 parts of water, and stirring and dissolving at-10-20 ℃; dissolving 203-455 parts of aromatic diformyl chloride into a dissolving kettle filled with 300-2000 parts of organic solvent to obtain aromatic diformyl chloride solution; dropwise adding the aromatic diformyl chloride solution into the reaction kettle, adding 0.1-450 parts of diphenol monomer containing the active group when the aromatic diformyl chloride solution is added in an amount of 1/3-2/3, and stirring and reacting at the temperature of-5-25 ℃ for 1-12 hours after all materials are added to obtain polyester resin containing the active group; adding 0.1-20 parts of dissolved polymeric molecular stabilizer into the reaction kettle, and continuously stirring for reaction for 0.5-3 hours to obtain a mixed solution of a crude polyester product containing active groups;
(2) purification of the polyester containing reactive groups:
standing and layering the obtained mixed solution of the crude polyester product containing the active groups, and then separating out an aqueous solution layer; adding 150-2000 parts of desalted water into the reaction kettle, sequentially stirring, washing, standing for layering, and separating out an aqueous solution layer, and circulating for at least 3 times to obtain a primarily purified polymer solution;
(3) curing and granulating the polyester containing the active group:
adding 0-2000 parts of organic solvent into the preliminarily purified polymer solution for dilution, and conveying the diluted solution to an atomization granulation tower through a metering pump for solidification and granulation to obtain purified high-dyne-value active polyester; wherein the temperature of the atomizing granulation tower is controlled to be 20-160 ℃, and the vacuum degree is-0.05 to-0.09 MPa.
Further, in the method, the solid material obtained through solidification and granulation is reserved, and the solvent steam is collected to a solvent recovery tank after being condensed for recycling.
The third technical problem to be solved by the invention is to provide a high-dyne-value active polyester film, which is prepared by adopting the following method: the active polyester with high dyne value and the processing aid are extruded and granulated to obtain film-grade active polyester granules, and then the granules are used for preparing the active polyester film with high dyne value by the conventional film-making method.
In the invention, the processing aid can be added with other aids such as an antioxidant, an ultraviolet absorber or a light stabilizer according to actual requirements.
Further, the high dyne value active polyester film is prepared by adopting the following process: extruding and granulating 100 parts of high-dyne-value active polyester, 0.1-50 parts of antioxidant, 0.1-30 parts of ultraviolet absorbent and 0.1-30 parts of light stabilizer by using a double screw to prepare a film-grade high-dyne-value active polyester resin granule; drying the granules at the temperature of 80-120 ℃ for 4-12 hours, and then extruding and casting the granules in a casting machine set to prepare a membrane with the thickness of 1-3 mm, wherein the processing temperature of the casting machine set is 230-340 ℃, the feeding speed is 0.5-10 kg/min, and the screw rotating speed is 30-150 r/min; and then clamping the membrane on a clamp in a two-way membrane drawing machine, preheating by hot air, preheating at the temperature of 80-210 ℃ for 1-10 min, transversely drawing by 2-20 times at the drawing rate of 10-300 mm/min, and longitudinally drawing by 2-20 times to prepare the membrane with uniform thickness.
Further, the antioxidant used in the preparation method of the high dyne value active polyester film is any one of phosphorous acid S-9228, antioxidant 1076, antioxidant MB, aluminum dihydrogen phosphate, sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate, 2, 5-di-tert-butylhydroquinone, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid or 1,3,5, tris (3, 5-di-tert-butyl-4-hydroxybenzyl) S-triazine-2, 4, 6- (1H, 3H, 5H) trione.
Further, the ultraviolet absorbent used in the method for preparing the dyne-value-high active polyester film is any one of phenyl ortho-hydroxybenzoate, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone or 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-phenyl) -5-chlorobenzotriazole.
Further, the light stabilizer used in the method for preparing the high dyne-value active polyester film is any one of tris (1, 2,2, 6, 6-pentamethylpiperidinyl) phosphite, 4-benzoyloxy-2, 2, 6, 6-tetramethylpiperidine, 2,4, 6-tris (2 '-n-butoxyphenyl) -1, 3, 5-triazine, hexamethylphosphoric triamide, 2, 2' -thiobis (4-tert-octylphenoloxy) nickel or resorcinol monobenzoate.
The fourth technical problem to be solved by the invention is to provide a method for improving the surface activity of polyester, which comprises the following steps: copolymerizing diphenol monomer containing active group with aromatic diphenol monomer and aromatic diacid chloride monomer to prepare polyester; wherein the structural formula of the diphenol monomer containing the active group is as follows:
Figure BDA0002161159510000051
Figure BDA0002161159510000052
at least one of (1).
The fifth technical problem to be solved by the present invention is to point out the application of the high dyne value active polyester in the preparation of functional composite materials, namely, the high dyne value active polyester is blended with other polymers to prepare the functional composite materials.
The invention has the following advantages:
1. the polyester resin adopted in the invention has simple polymerization process flow, mild condition and easy control; in the whole reaction process, except the byproduct salt, no other harmful substances are generated, so that the method is environment-friendly;
2. the invention adopts the diphenol monomer containing active methoxyl, carboxyl and sulfonic group to copolymerize with the aromatic diphenol monomer and the aromatic diformyl chloride monomer, thus effectively improving the surface activity of the obtained polyester, improving the dyne value of the polyester, greatly improving the interface bonding strength of the obtained polyester and other composite phases and being beneficial to preparing functional composite membrane materials;
3. the invention adopts the standing chromatography water washing method to wash and remove the water-soluble by-product generated in the polymerization process at one time; by adopting atomization and solidification granulation processes, the solvent and the polymer resin can be thoroughly separated at one time, so that the obtained resin has high purity and high solvent recovery efficiency; the whole process flow is short, the required equipment is few, the energy consumption in the product washing process is greatly reduced, the production cost is reduced, and the market competitiveness of the product is improved;
4. the obtained resin can be used for special engineering plastics and high-performance polymer composite materials and for preparing high-light-transmittance, heat-resistant and flame-retardant parts, fibers and film products.
Drawings
FIG. 1 is an infrared spectrum of a polyester resin obtained in examples 1 to 5.
FIG. 2 is a nuclear magnetic representation of the polyester resins obtained in examples 1 to 5.
Detailed Description
In order to improve the surface activity of polyester and maintain excellent thermal property, mechanical property and processability of the polyester, the invention performs multi-component copolymerization on diphenol monomer containing active reaction groups, traditional diphenol and diacyl chloride, and obtains a series of high-dyne value and high-temperature resistant polyester resins containing active elements by molecular design and optimized regulation of the types and the proportions of reaction monomers.
The present invention is described in detail below by way of examples, it should be noted that the examples are only for the purpose of further illustration, and are not to be construed as limiting the scope of the present invention, and that those skilled in the art can make insubstantial modifications and adaptations of the present invention based on the teachings of the present invention described above.
Example 1
(1) Preparation of polyesters containing reactive groups
Adding 176.7kg of bisphenol A, 51.2kg of bisphenol B, 10kg of hexadecyl trimethyl ammonium chloride and 100kg of potassium hydroxide into a reaction kettle filled with 1000kg of water in sequence, and stirring and dissolving at-10 ℃; dissolving 162.4kg of isophthaloyl dichloride and 40.6kg of terephthaloyl chloride in a dissolving kettle filled with 300kg of dichloromethane, dropwise adding an acyl chloride solution in the dissolving kettle into the reaction kettle (dropwise adding in the stirring process), adding 8kg of carboxyl-containing 1, 1-bis (4-hydroxyphenyl) -1-phenylmethane after the acyl chloride solution is dropwise added by 1/3 (namely, 1/3 of the total amount of the acyl chloride solution is dropwise added), and stirring and reacting at the temperature of-5 ℃ for 12 hours to obtain the high-viscosity polyester resin containing active groups; adding 0.1kg of dissolved cyclohexylamine into the reaction kettle, and continuously stirring for reaction for 0.5h to obtain a crude product of the high-dyne-value active polyester;
(2) purification of polyesters containing reactive groups
Standing and layering the polymer mixed solution, then separating an aqueous solution layer, adding 500kg of desalted water into the reaction kettle, stirring, washing, standing and layering, separating the aqueous solution layer, and repeating the steps for 6 times to obtain a preliminarily purified polymer solution;
(3) curing and pelletizing of polyesters containing reactive groups
Adding 600kg of dichloromethane into the polymer solution after primary purification for dilution, conveying the diluted solution to an atomizing and granulating tower through a metering pump for solidification and granulation, controlling the temperature of the atomizing and granulating tower at 50 ℃ and the vacuum degree at-0.06 MPa; conveying the solid material to a film workshop for later use through a pipeline, condensing solvent steam, and collecting the condensed solvent steam to a solvent recovery tank for recycling; the obtained resin has intrinsic viscosity of 0.91g/dL and infrared spectrum of 3040cm, as shown in FIG. 1-1The vibration absorption peak of benzene ring C-H is 2960cm-1，2860cm-1Nearby is-CH31735cm for stretching vibration absorption-1Absorption peak near-COO-, 1690cm-1An absorption peak of 1590cm near-COOH-1,1540cm-1,1500cm-1The neighborhood is a skeleton absorption peak of a benzene ring, a nuclear magnetic spectrum is shown in figure 2, deuterated chloroform is used as a solvent, and the attribution of each peak is respectively marked in the figure.
(4) Preparation of high dyne active polyester film
100kg of the resin, 0.1kg of antioxidant phosphorous acid S-9228, 1kg of ultraviolet absorbent 2, 4-dihydroxy benzophenone, 0.1kg of light stabilizer hexamethylphosphoric triamide are extruded and granulated by a double screw to prepare a film-grade high-dyne value active polyester resin granule, the granule is dried at the temperature of 80 ℃ for 12 hours and then extruded and casted in a casting machine set to prepare a film with the thickness of 1mm, and the processing temperature of the casting machine set is as follows: 230 ℃ in the first section, 250 ℃ in the second section, 270 ℃ in the third section, 280 ℃ in the fourth section, 290 ℃ in the fifth section, 290 ℃ in the sixth section, 300 ℃ in the seventh section, 310 ℃ in the eighth section, 310 ℃ in the ninth section, 300 ℃ in the neck mold, 2kg/min in feeding speed and 70r/min in screw speed, then clamping the membrane on a clamp in a two-way membrane drawing machine, preheating the membrane by hot air, transversely drawing 6 times at the drawing speed of 100mm/min after preheating the membrane for 1min at the temperature of 180 ℃, and longitudinally drawing 20 times to prepare a film with uniform thickness, wherein the thickness of the obtained film is about 9 mu m, and the dyne value of the obtained film is 52.
Example 2
(1) Preparation of polyesters containing reactive groups
171kg of bisphenol A, 51.2kg of bisphenol B, 1kg of sodium ethylene diamine tetracetate and 120kg of triethylamine are sequentially added into a reaction kettle filled with 800kg of water and stirred and dissolved at 10 ℃; dissolving 101.5kg of isophthaloyl dichloride and 101.5kg of terephthaloyl chloride in a dissolving kettle filled with 2000kg of chloroform, dropwise adding an acyl chloride solution in the dissolving kettle into the reaction kettle, adding 16kg of carboxyl-containing 1, 1-bis (4-hydroxyphenyl) -1-phenylmethane after the acyl chloride solution is dropwise added by 2/3, stirring and reacting at the temperature of 5 ℃ for 1 hour to obtain high-viscosity polyester resin containing active groups, adding 0.2kg of dissolved aniline in the reaction kettle, and continuously stirring and reacting for 1 hour to obtain a crude product of the active polyester with the high dyne value;
(2) purification of polyesters containing reactive groups
Standing and layering the polymer mixed solution, then separating an aqueous solution layer, adding 800kg of desalted water into the reaction kettle, stirring, washing, standing and layering, separating the aqueous solution layer, and repeating the steps for 5 times to obtain a preliminarily purified polymer solution;
(3) curing and pelletizing of polyesters containing reactive groups
Adding 1000kg chloroform into the polymer solution after primary purification for dilution, conveying the diluted solution to an atomization and granulation tower through a metering pump for solidification and granulation, and controlling the temperature of the atomization and granulation towerThe temperature is 60 ℃, and the vacuum degree is-0.07 MPa; conveying the solid material to a film workshop for later use through a pipeline, condensing solvent steam, and collecting the condensed solvent steam to a solvent recovery tank for recycling; the obtained resin has intrinsic viscosity of 0.86g/dL, infrared spectrum of 3064cm and shown in FIG. 1-1The vibration absorption peak of benzene ring C-H is 2965cm-1，2880cm-1Nearby is-CH31745cm for telescopic vibration absorption-1Absorption peak near-COO-, 1696cm-1An absorption peak of 1611cm near-COOH-1,1505cm-1The neighborhood is a skeleton absorption peak of a benzene ring, a nuclear magnetic spectrum is shown in figure 2, deuterated chloroform is used as a solvent, and the attribution of each peak is respectively marked in the figure.
(4) Preparation of high dyne active polyester film
Extruding and granulating 100kg of the resin, 1kg of antioxidant aluminum dihydrogen phosphate, 0.1kg of ultraviolet absorbent 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole and 5kg of light stabilizer 4-benzoyloxy-2, 2, 6, 6-tetramethylpiperidine by using a double screw extruder to prepare a film level dyne value active polyester resin granule, drying the granule at the temperature of 120 ℃ for 4 hours, extruding and casting the granule in a casting machine set to prepare a film with the thickness of 2mm, wherein the processing temperature of the casting machine set is as follows: 230 ℃ in the first section, 250 ℃ in the second section, 280 ℃ in the third section, 290 ℃ in the fourth section, 300 ℃ in the fifth section, 300 ℃ in the sixth section, 310 ℃ in the seventh section, 320 ℃ in the eighth section, 320 ℃ in the ninth section, 310 ℃ in the neck mold, 3kg/min in feeding speed and 90r/min in screw rotation speed, then clamping the membrane on a clamp in a two-way membrane drawing machine, preheating the membrane by hot air, firstly transversely drawing 10 times at the drawing speed of 120mm/min after preheating for 2min at the temperature of 190 ℃, then longitudinally drawing 20 times to prepare a film with uniform thickness, wherein the obtained film thickness is about 10 mu m, and the dyne value is 52.
Example 3
(1) Preparation of polyesters containing reactive groups
Adding 125kg of bisphenol S, 108.8kg of bisphenol B, 5kg of sodium glycocholate and 130kg of sodium hydroxide into a reaction kettle filled with 900kg of water in sequence, and stirring and dissolving at 15 ℃; dissolving 101.5kg of isophthaloyl dichloride, 155.5kg of 4, 4' -diphenyl thioether diformyl chloride into a dissolving kettle filled with 900kg of carbon tetrachloride, dropwise adding an acyl chloride solution in the dissolving kettle into the reaction kettle, adding 16kg of carboxyl-containing 1, 1-bis (4-hydroxyphenyl) -1-phenylmethane and 8.9kg of sulfonic acid-containing 1, 1-bis (4-hydroxyphenyl) -1-phenylmethane after the acyl chloride solution is dropwise added by 1/3, stirring and reacting at the temperature of 15 ℃ for 6h to obtain high-viscosity polyester resin containing active groups, adding 5kg of dissolved benzylamine into the reaction kettle, and continuously stirring and reacting for 2h to obtain a crude product of the high dyne value active polyester;
(2) purification of polyesters containing reactive groups
Standing and layering the polymer mixed solution, then separating an aqueous solution layer, adding 700kg of desalted water into the reaction kettle, stirring, washing, standing and layering, separating the aqueous solution layer, and repeating the steps for 4 times to obtain a preliminarily purified polymer solution;
(3) curing and pelletizing of polyesters containing reactive groups
Adding 500kg of carbon tetrachloride into the polymer solution after primary purification for dilution, conveying the diluted solution to an atomizing and granulating tower through a metering pump for solidification and granulation, and controlling the temperature of the atomizing and granulating tower at 90 ℃ and the vacuum degree at-0.08 MPa; conveying the solid material to a film workshop for later use through a pipeline, condensing solvent steam, and collecting the condensed solvent steam to a solvent recovery tank for recycling; the obtained resin has intrinsic viscosity of 0.78g/dL, infrared spectrum of 3050cm as shown in FIG. 1-1The vibration absorption peak of benzene ring C-H is 2965cm-1，2873cm-1Nearby is-CH31746cm for telescopic vibration absorption-1Absorption peak near-COO-, 1692cm-1An absorption peak of 1611cm near-COOH-1,1505cm-1The vicinity is a skeleton absorption peak of benzene ring, 1207cm-1,1050cm-1The vicinity is the vibration absorption peak of the sulfonic acid group, the nuclear magnetic spectrum is shown in figure 2, deuterated chloroform is used as a solvent, and the attribution of each peak is respectively indicated in the figure.
(4) Preparation of high dyne active polyester film
Extruding and granulating 100kg of the resin, 2kg of antioxidant 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, 0.1kg of ultraviolet absorbent 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole and 2kg of light stabilizer tris (1, 2,2, 6, 6-pentamethylpiperidinyl) phosphite by using a twin screw extruder to prepare a film grade high-dyne value active polyester resin granule, drying the granule at the temperature of 100 ℃ for 8 hours, and extruding and casting the granule in a casting machine set to prepare a film with the thickness of 1.5mm, wherein the processing temperature of the casting machine set is as follows: 230 ℃ in the first section, 240 ℃ in the second section, 250 ℃ in the third section, 260 ℃ in the fourth section, 270 ℃ in the fifth section, 280 ℃ in the sixth section, 290 ℃ in the seventh section, 290 ℃ in the eighth section, 280 ℃ in the ninth section, 275 ℃ in the neck mold, 1.5kg/min of feeding speed and 60r/min of screw speed, then clamping the membrane on a clamp in a two-way membrane drawing machine, preheating the membrane by hot air, transversely drawing the membrane by 20 times at the drawing speed of 40mm/min after preheating the membrane for 5min at the temperature of 120 ℃, and then longitudinally drawing the membrane by 10 times to prepare a thin film with uniform thickness, wherein the thickness of the obtained film is about 15 mu m, and the dyne value of the obtained film is 56.
Example 4
(1) Preparation of polyesters containing reactive groups
Adding 55kg of hydroquinone, 22kg of resorcinol, 51.2kg of bisphenol B, 13kg of sodium p-toluenesulfonate and 80kg of piperazine into a reaction kettle filled with 500kg of water in sequence, and stirring and dissolving at 10 ℃; dissolving 101.5kg of isophthaloyl dichloride and 210.5kg of pyrimidine thioether-containing diformyl chloride into a dissolving kettle filled with 2000kg of chlorobenzene, dropwise adding an acyl chloride solution in the dissolving kettle into the reaction kettle, adding 16kg of carboxyl-containing 1, 1-bis (4-hydroxyphenyl) -1-phenylethane and 15.3kg of methoxyl-containing 1, 1-bis (4-hydroxyphenyl) -1-phenylmethane after 2/3 is dropwise added into the acyl chloride solution, stirring and reacting at the temperature of 10 ℃ for 6 hours to obtain high-viscosity polyester resin containing active groups, adding 0.5kg of dissolved dicyclohexylamine into the reaction kettle, and continuously stirring and reacting for 1 hour to obtain a crude product of the high-dyne value active polyester;
(2) purification of polyesters containing reactive groups
Standing and layering the polymer mixed solution, then separating an aqueous solution layer, adding 1000kg of desalted water into the reaction kettle, stirring, washing, standing and layering, separating the aqueous solution layer, and repeating the steps for 6 times to obtain a preliminarily purified polymer solution;
(3) curing and pelletizing of polyesters containing reactive groups
Adding 1500kg of chlorobenzene into the preliminarily purified polymer solution for dilution, conveying the diluted solution to an atomizing and granulating tower through a metering pump for solidification and granulation, and controlling the temperature of the atomizing and granulating tower at 120 ℃ and the vacuum degree at-0.085 MPa; conveying the solid material to a film workshop for later use through a pipeline, condensing solvent steam, and collecting the condensed solvent steam to a solvent recovery tank for recycling; the obtained resin has intrinsic viscosity of 0.80g/dL, infrared spectrum of 3055cm as shown in FIG. 1-1The vibration absorption peak of benzene ring C-H is 2965cm-1，2873cm-1Nearby is-CH31748cm for telescopic vibration absorption-1Absorption peak near-COO-, 1691cm-1Near the absorption peak of-COOH at 1610cm-1,1503cm-1The absorption peak of the skeleton of benzene ring is 1073cm-1The neighborhood is the vibration absorption peak of methoxyl, the nuclear magnetic spectrum is shown in figure 2, deuterated chloroform is used as a solvent, and the attribution of each peak is respectively indicated in the figure.
(4) Preparation of high dyne active polyester film
100kg of the resin, 6kg of antioxidant 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, 0.4kg of ultraviolet absorbent 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole and 8kg of light stabilizer resorcinol monobenzoate are extruded and granulated by a twin screw to prepare a film level dyne value active polyester resin granule, the granule is dried at the temperature of 110 ℃ for 10 hours and then extruded and cast in a casting machine to prepare a film with the thickness of 1mm, and the processing temperature of the casting machine is as follows: 230 ℃ in the first section, 240 ℃ in the second section, 250 ℃ in the third section, 260 ℃ in the fourth section, 270 ℃ in the fifth section, 280 ℃ in the sixth section, 290 ℃ in the seventh section, 300 ℃ in the eighth section, 315 ℃ in the ninth section, 305 ℃ in the neck mold, 4kg/min in feeding speed and 95r/min in screw speed, then clamping the membrane on a clamp in a two-way membrane drawing machine, preheating the membrane by hot air, firstly transversely drawing 8 times at the drawing speed of 210mm/min after preheating the membrane for 3min at the temperature of 170 ℃, then longitudinally drawing 12 times to prepare a film with uniform thickness, wherein the obtained film thickness is about 16 mu m and the dyne value is 54.
Example 5
(1) Preparation of polyesters containing reactive groups
Sequentially adding 93kg of biphenol, 68.4kg of bisphenol A, 19.2kg of bisphenol B, 18-crown-60.2 kg of bisphenol B and 200kg of barium hydroxide into a reaction kettle filled with 650kg of water, and stirring and dissolving at 0 ℃; dissolving 162.4kg of isophthaloyl dichloride and 40.6kg of terephthaloyl chloride in a dissolving kettle filled with 1200kg of dichloromethane, dropwise adding an acyl chloride solution in the dissolving kettle into the reaction kettle, adding 24kg of carboxyl-containing 1, 1-bis (4-hydroxyphenyl) -1-phenylethane and 18.5kg of sulfonic acid-containing 1, 1-bis (4-hydroxyphenyl) -1-phenylethane after 2/3 is dropwise added into the acyl chloride solution, stirring and reacting at the temperature of 10 ℃ for 8 hours to obtain polyester resin containing active groups, adding 0.9kg of dissolved dicyclohexylamine with high viscosity into the reaction kettle, and continuously stirring and reacting for 1.5 hours to obtain a crude product of the active polyester with the dyne value;
(2) purification of polyesters containing reactive groups
Standing and layering the polymer mixed solution, then separating an aqueous solution layer, adding 1200kg of desalted water into the reaction kettle, stirring, washing, standing and layering, separating the aqueous solution layer, and repeating the steps for 3 times to obtain a preliminarily purified polymer solution;
(3) curing and pelletizing of polyesters containing reactive groups
Adding 2000kg of dichloromethane into the preliminarily purified polymer solution for dilution, conveying the diluted solution to an atomizing and granulating tower through a metering pump for solidification and granulation, controlling the temperature of the atomizing and granulating tower at 45 ℃ and the vacuum degree at-0.08 MPa; conveying the solid material to a film workshop for later use through a pipeline, condensing solvent steam, and collecting the condensed solvent steam to a solvent recovery tank for recycling; the obtained resin has intrinsic viscosity of 0.91g/dL, infrared spectrum of 3042cm and shown in FIG. 1-1The vibration absorption peak of benzene ring C-H is 2958cm-1，2873cm-1Nearby is-CH31739cm for stretching vibration absorption-1Absorption peak near-COO-, 1696cm-1An absorption peak of-COOH, 1612cm-1,1505cm-1The vicinity is a skeleton absorption peak of a benzene ring, 1208cm-1,1058cm-1Vibration having sulfonic acid group in the vicinity thereofThe dynamic absorption peak and the nuclear magnetic spectrum are shown in figure 2, the deuterated chloroform is used as a solvent, and the attribution of each peak is respectively marked in the figure.
(4) Preparation of high dyne active polyester film
100kg of the resin, 0.6kg of antioxidant 1076, 1kg of ultraviolet absorbent 2-hydroxy-4-n-octoxy benzophenone and 1kg of light stabilizer 2, 2' -thiobis (4-tert-octylphenoxy) nickel are subjected to twin-screw extrusion granulation to prepare a film grade dyne value active polyester resin granule, the granule is dried at the temperature of 100 ℃ for 10 hours and then is subjected to extrusion casting in a casting machine set to prepare a film with the thickness of 1mm, and the processing temperature of the casting machine set is as follows: 230 ℃ in the first section, 240 ℃ in the second section, 250 ℃ in the third section, 260 ℃ in the fourth section, 280 ℃ in the fifth section, 290 ℃ in the sixth section, 300 ℃ in the seventh section, 310 ℃ in the eighth section, 325 ℃ in the ninth section, 315 ℃ in the neck mold, 6kg/min in feeding speed and 135r/min in screw speed, then clamping the membrane on a clamp in a two-way membrane drawing machine, preheating the membrane by hot air, firstly transversely drawing 10 times at the drawing speed of 160mm/min after preheating for 2min at the temperature of 200 ℃, then longitudinally drawing 10 times to prepare a film with uniform thickness, wherein the obtained film thickness is about 10 mu m, and the dyne value is 56.
Comparative example 1
The preparation method of the polyester containing the active group is the same as the steps (1) to (3) of the example 1, except that in the step (1), bisphenol A, bisphenol B and 1, 1-bis (4-hydroxyphenyl) -1-phenylmethane containing carboxyl are added into water together with alkali and a catalyst; as a result, a high-viscosity polyester resin cannot be obtained; the intrinsic viscosity of the resin obtained after purification, solidification and granulation is 0.22 g/dL. The resulting resin, when melted or formulated into a solution, could not be formed into a polyester film and thus its dyne value could not be detected.

Claims (10)

1. A high dyne value active polyester is characterized in that the starting material of the polyester consists of the following components:
Figure FDA0002737040160000011
wherein the structural formula of the diphenol monomer containing the active group is as follows:
Figure FDA0002737040160000012
Figure FDA0002737040160000013
at least one of;
and, the high dyne value active polyester is prepared by the following method:
(1) preparation of active group-containing polyester:
sequentially adding 1-290 parts of aromatic diphenol monomer, 0.1-20 parts of catalyst and 80-200 parts of alkali into a reaction kettle filled with 150-1000 parts of water, and stirring and dissolving at-10-20 ℃; dissolving 203-455 parts of aromatic diformyl chloride into a dissolving kettle filled with 300-2000 parts of organic solvent to obtain aromatic diformyl chloride solution; dropwise adding the aromatic diformyl chloride solution into the reaction kettle, adding 0.1-450 parts of diphenol monomer containing the active group when the aromatic diformyl chloride solution is added in an amount of 1/3-2/3, and stirring and reacting at the temperature of-5-25 ℃ for 1-12 hours after all materials are added to obtain polyester resin containing the active group; adding 0.1-20 parts of dissolved polymeric molecular stabilizer into the reaction kettle, and continuously stirring for reaction for 0.5-3 hours to obtain a mixed solution of a crude polyester product containing active groups;
(2) purification of the polyester containing reactive groups:
standing and layering the obtained mixed solution of the crude polyester product containing the active groups, and then separating out an aqueous solution layer; adding 150-2000 parts of desalted water into the reaction kettle, sequentially stirring, washing, standing for layering, and separating out an aqueous solution layer, and circulating for at least 3 times to obtain a primarily purified polymer solution;
(3) curing and granulating the polyester containing the active group:
adding 0-2000 parts of organic solvent into the preliminarily purified polymer solution for dilution, and conveying the diluted solution to an atomization granulation tower through a metering pump for solidification and granulation to obtain purified high-dyne-value active polyester; wherein the temperature of the atomizing granulation tower is controlled to be 20-160 ℃, and the vacuum degree is-0.05 to-0.09 MPa.
2. The high dyne reactive polyester of claim 1, wherein the aromatic diphenol monomer has the formula:
Figure FDA0002737040160000021
Figure FDA0002737040160000022
at least one of;
the aromatic dicarboxylic acid chloride has the structural formula:
Figure FDA0002737040160000031
Figure FDA0002737040160000032
at least one of (1).
3. The high dyne active polyester of claim 1 or 2, characterized in that,
the polymeric molecular stabilizer is any one of aniline, benzylamine, 4-aminobenzenesulfone, 4-aminobenzophenone, 4-aminodiphenyl ether, 4-aminobenzenesulfide, benzidine, naphthylamine, ethylamine, propylamine, butylamine, n-hexylamine, cyclohexylamine or dicyclohexylamine; or:
the catalyst is any one of 15-crown-5, 18-crown-6, dioctyl sodium succinate, zinc citrate, sodium tartrate, sodium gluconate, sodium nitrilotriacetate, sodium sorbate, sodium ethylene diamine tetracetate, ethylene diamine tetracetanyl sodium phosphate, sodium glycocholate, sodium terephthalate, sodium stearate, tetrabutylammonium bromide, benzyl triethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride, sodium dodecyl benzene sulfonate, sodium p-methyl benzene sulfonate, sodium alginate or sodium dodecyl sulfonate; or:
the alkali is any one of lithium hydroxide, sodium hydroxide, calcium hydroxide, potassium hydroxide, barium hydroxide, aluminum hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, barium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, barium bicarbonate, ammonia water, trimethylamine, triethylamine, tri-tert-butylamine, pyridine or piperazine; or:
the organic solvent is any one of 1, 2-dichloroethane, 1,2, 2-tetrachloroethane, dichloromethane, chloroform, carbon tetrachloride, cyclohexane, cyclohexanone, chlorobenzene, m-dichlorobenzene or 1,2, 4-trichlorobenzene.
4. The method for preparing high dyne value active polyester of any one of claims 1 to 3, characterized in that the preparation method comprises the following steps:
(1) preparation of active group-containing polyester:
sequentially adding 1-290 parts of aromatic diphenol monomer, 0.1-20 parts of catalyst and 80-200 parts of alkali into a reaction kettle filled with 150-1000 parts of water, and stirring and dissolving at-10-20 ℃; dissolving 203-455 parts of aromatic diformyl chloride into a dissolving kettle filled with 300-2000 parts of organic solvent to obtain aromatic diformyl chloride solution; dropwise adding the aromatic diformyl chloride solution into the reaction kettle, adding 0.1-450 parts of diphenol monomer containing the active group when the aromatic diformyl chloride solution is added in an amount of 1/3-2/3, and stirring and reacting at the temperature of-5-25 ℃ for 1-12 hours after all materials are added to obtain polyester resin containing the active group; adding 0.1-20 parts of dissolved polymeric molecular stabilizer into the reaction kettle, and continuously stirring for reaction for 0.5-3 hours to obtain a mixed solution of a crude polyester product containing active groups;
(2) purification of the polyester containing reactive groups:
standing and layering the obtained mixed solution of the crude polyester product containing the active groups, and then separating out an aqueous solution layer; adding 150-2000 parts of desalted water into the reaction kettle, sequentially stirring, washing, standing for layering, and separating out an aqueous solution layer, and circulating for at least 3 times to obtain a primarily purified polymer solution;
(3) curing and granulating the polyester containing the active group:
adding 0-2000 parts of organic solvent into the preliminarily purified polymer solution for dilution, and conveying the diluted solution to an atomization granulation tower through a metering pump for solidification and granulation to obtain purified high-dyne-value active polyester; wherein the temperature of the atomizing granulation tower is controlled to be 20-160 ℃, and the vacuum degree is-0.05 to-0.09 MPa.
5. The method of claim 4, wherein the solid material obtained by solidification and granulation is ready for use, and the solvent vapor is collected to a solvent recovery tank after condensation for recycling.
6. A high dyne value active polyester film is characterized in that the polyester film is prepared by adopting the following method: extruding and granulating the active polyester with the high dyne value and the processing aid to obtain film-grade active polyester granules, and preparing the granules into the active polyester film with the high dyne value by using the conventional film-making method; wherein the high-dyne-value active polyester is the active polyester disclosed in any one of claims 1-3, or is prepared by the preparation method disclosed in claim 4 or 5.
7. The high dyne active polyester film of claim 6, wherein said high dyne active polyester film is prepared by the following method: extruding and granulating 100 parts of high-dyne-value active polyester, 0.1-50 parts of antioxidant, 0.1-30 parts of ultraviolet absorbent and 0.1-30 parts of light stabilizer by using a double screw to prepare a film-grade high-dyne-value active polyester resin granule; drying the granules at the temperature of 80-120 ℃ for 4-12 hours, and then extruding and casting the granules in a casting machine set to prepare a membrane with the thickness of 1-3 mm, wherein the processing temperature of the casting machine set is 230-340 ℃, the feeding speed is 0.5-10 kg/min, and the screw rotating speed is 30-150 r/min; and then clamping the membrane on a clamp in a two-way membrane drawing machine, preheating by hot air, preheating at the temperature of 80-210 ℃ for 1-10 min, transversely drawing by 2-20 times at the drawing rate of 10-300 mm/min, and longitudinally drawing by 2-20 times to prepare the membrane with uniform thickness.
8. The high dyne active polyester film of claim 7, wherein the antioxidant is any one of phosphite S-9228, antioxidant 1076, antioxidant MB, aluminum dihydrogen phosphate, sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate, 2, 5-di-tert-butylhydroquinone, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid or 1,3,5, tris (3, 5-di-tert-butyl-4-hydroxybenzyl) S-triazine-2, 4, 6- (1H, 3H, 5H) trione; or:
the ultraviolet absorbent is any one of phenyl ortho-hydroxybenzoate, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2, 4-dihydroxy benzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxy benzophenone or 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-phenyl) -5-chlorinated benzotriazole; or:
the light stabilizer is any one of tris (1, 2,2, 6, 6-pentamethylpiperidinyl) phosphite, 4-benzoyloxy-2, 2, 6, 6-tetramethylpiperidine, 2,4, 6-tris (2 '-n-butoxyphenyl) -1, 3, 5-triazine, hexamethylphosphoric triamide, 2, 2' -thiobis (4-tert-octylphenoloxy) nickel or resorcinol monobenzoate.
9. A method for improving the surface activity of polyester is characterized by comprising the following steps: copolymerizing diphenol monomer containing active group with aromatic diphenol monomer and aromatic diacid chloride monomer to prepare polyester; wherein the structural formula of the diphenol monomer containing the active group is as follows:
Figure FDA0002737040160000051
Figure FDA0002737040160000052
at least one of;
the method comprises the following steps:
(1) sequentially adding 1-290 parts of aromatic diphenol monomer, 0.1-20 parts of catalyst and 80-200 parts of alkali into a reaction kettle filled with 150-1000 parts of water, and stirring and dissolving at-10-20 ℃; dissolving 203-455 parts of aromatic diformyl chloride into a dissolving kettle filled with 300-2000 parts of organic solvent to obtain aromatic diformyl chloride solution; dropwise adding the aromatic diformyl chloride solution into the reaction kettle, adding 0.1-450 parts of diphenol monomer containing the active group when the aromatic diformyl chloride solution is added in an amount of 1/3-2/3, and stirring and reacting at the temperature of-5-25 ℃ for 1-12 hours after all materials are added to obtain polyester resin containing the active group; adding 0.1-20 parts of dissolved polymeric molecular stabilizer into the reaction kettle, and continuously stirring for reaction for 0.5-3 hours to obtain a mixed solution of a crude polyester product containing active groups;
(2) standing and layering the obtained mixed solution of the crude polyester product containing the active groups, and then separating out an aqueous solution layer; adding 150-2000 parts of desalted water into the reaction kettle, sequentially stirring, washing, standing for layering, and separating out an aqueous solution layer, and circulating for at least 3 times to obtain a primarily purified polymer solution;
(3) adding 0-2000 parts of organic solvent into the preliminarily purified polymer solution for dilution, and conveying the diluted solution to an atomization granulation tower through a metering pump for solidification and granulation to obtain purified dyne-value-high active polyester; wherein the temperature of the atomizing granulation tower is controlled to be 20-160 ℃, and the vacuum degree is-0.05 to-0.09 MPa.
10. The application of the high-dyne-value active polyester in preparing a functional composite material is characterized in that the high-dyne-value active polyester is blended with other polymers to prepare the functional composite material, and the high-dyne-value active polyester is the active polyester disclosed by any one of claims 1-3 or prepared by the preparation method disclosed by claim 4 or 5.
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