CN108424511B - Method for preparing water-based polyester resin by using printing and dyeing slurry residues and application - Google Patents
Method for preparing water-based polyester resin by using printing and dyeing slurry residues and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/127—Acids containing aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Abstract
The invention discloses a method for preparing waterborne polyester resin by using printing and dyeing slurry residues and application thereof. The invention relates to a method for producing water-based polyester resin from terephthalic acid mixed organic acid precipitated from printing and dyeing alkali decrement wastewater or printing and dyeing desizing wastewater, which is used in the fields of polyester resin materials, water-based polyester resin coatings, water-based polyester resin adhesives and the like. The resources are circulated, and the waste is changed into valuable. By utilizing the principle and the condition, a multipurpose application path of the terephthalic acid mixed organic acid can be developed. The method for preparing the complete waterborne polyester resin also improves the manufacturing process characteristics of the traditional waterborne polyester resin adopting alkali to neutralize acid carboxyl, has no solvent VOC, produces a complete green and environment-friendly waterborne polyester resin product, and has great social benefit and economic benefit.
Description
Technical Field
The invention belongs to the field of textile printing and dyeing wastewater treatment, and particularly relates to a method for preparing waterborne polyester resin by using printing and dyeing slurry residues and application thereof.
Background
A large number of textile printing and dyeing enterprises exist in part of our country, the enterprises have processing lines of dyeing and finishing alkali decrement production and dyeing and finishing desizing process, and thousands of tons of terylene and chemical fiber cotton fabrics enter the subsequent printing and dyeing process after being subjected to decrement and desizing from the dyeing and finishing processing lines every day. During the processing process of alkali decrement and desizing, a large amount of decrement terephthalic acid (PTA) and mixed organic acid are precipitated, namely white slurry residue (white mud). But the organic substance is infusible and insoluble, the synthesis temperature is high, the product has high crystal point and large viscosity, and the application of the use process is limited. The alkali decrement byproduct of dyeing and finishing waste water and the desizing residue waste in the national printing and dyeing industry have the discharge amount of at least about 10-30 ten thousand tons every year, and are very huge quantities. Because the recovered PTA is not well applied and discharged, the PTA completely enters a sewage system, so that the COD is greatly increased, and a local environment system is polluted.
The terephthalic acid is mainly used for producing polyester, and then synthesizing polyester resin, high-grade paint, high-grade adhesive, plasticizer, other high-grade engineering materials and the like. The acid-out terephthalic acid mixed organic acid in the printing and dyeing wastewater has low purity which is lower than the polyester grade, and brings printing and dyeing materials, so that transparent products cannot be produced, and the refining is very difficult, thereby restricting the bottleneck of recycling. The mixed saturated polyester resin is produced by esterification polymerization of terephthalic acid mixed acid and dihydric alcohol, a mixed polyester high molecular material is generated through linear polycondensation and reticular crosslinking, and industrial production products of saturated polyester and unsaturated polyester are changed through technical modification, so that the method is an innovative technical method.
According to the technical characteristics of innovative materials, the development of products such as water-based saturated polyester resin materials, water-based polyester resin adhesives, water-based polyester resin coatings and the like is a direction of complete innovation and development. The production technology of the water-based saturated polyester resin has certain advancement at home and abroad, the domestic technology and grade quality are a certain distance away from the world level, the water-based polyester resin material is produced by utilizing the recovered waste material of the printing and dyeing wastewater, the traditional production process route is innovated and reformed, the method for neutralizing organic acid carboxyl by using alkali is distinguished, the organic solvent is not used for dilution at all, a brand new water-based saturated polyester resin product is innovated, no VOC (volatile organic compound) component pollution is generated in the process and the product, a green product is produced, and the requirements of green and environment-friendly production and use are met.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for preparing water-based polyester resin by using printing and dyeing slurry residues and application thereof.
A method for manufacturing water-based polyester resin by using printing and dyeing slurry residues comprises the following steps:
1) acid-out extracting wet organic acid solid containing terephthalic acid from printing and dyeing alkali decrement waste water and printing and dyeing desizing waste water;
2) directly mixing the wet organic acid solid obtained in the step 1) with dihydric alcohol or polyhydric alcohol, stirring and pulping, and adding the mixture into an esterification synthesis reactor after pulping, wherein the molar ratio of carboxyl of the wet organic acid solid to hydroxyl in alcohol is 1: 2-3;
3) dehydrating under the inert gas atmosphere; then the organic acid and alcohol are subjected to esterification reaction;
4) the esterification synthesis waste heat of a reaction kettle is utilized, the vacuum pumping is carried out for devolatilization, the unreacted excessive alcohol is removed, the vacuum degree is kept between 0.01Mpa and 0.05Mpa, and the time is 10 to 30 minutes; and then cooling the hydroxyl-terminated polyester product generated by esterification to below 140 ℃ to obtain the water-based polyester resin.
Preferably, the step 1) is specifically:
filtering the printing and dyeing alkali decrement wastewater and the printing and dyeing desizing wastewater to remove insoluble mechanical impurities, adding acid, mixing, stirring and carrying out acid precipitation, and controlling the pH value of the acid precipitation wastewater to be 2-5; centrifugally separating out organic acid solids, washing with clear water until the pH value of the washing water is 6-7, and repeatedly centrifugally dewatering to obtain the organic acid solids with the water content of 40-70% by mass.
Preferably, the acid added for acid precipitation is "98%" sulfuric acid.
Preferably, the molar ratio of the carboxyl groups of the mixed acid to the hydroxyl groups of the alcohol is preferably 1: 2.1 to 2.5.
Preferably, the dihydric alcohol is one or more of ethylene glycol, propylene glycol, neopentyl glycol, butanediol and polyhydric alcohol.
Preferably, the step 3) is specifically: replacing the esterification synthesis reactor with nitrogen; controlling the temperature rise speed to be 2-4 ℃/min, and reacting for 30-60 min; continuously evaporating water from the tower top, closing an outlet valve of a cooling system of the reactor communicated with the atmosphere after the water is distilled for 1-2 hours, heating the reactor at the speed of 30-50 ℃/h, continuing heating the reactor for 2-3 hours after the temperature in the reactor reaches 170-; then the temperature is continuously increased at the speed of 10-30 ℃/h, the reaction is carried out at the temperature of 220-260 ℃, and the reaction is stopped when the temperature at the top of the tower automatically decreases and no liquid is evaporated or the temperature at the top of the tower drops below 150 ℃. The final reaction temperature of the preferable synthesis method is 30-40 ℃ lower than that of the traditional esterification reaction of terephthalic acid and dihydric alcohol, so that the reaction energy consumption can be reduced, and the influence on subsequent trial due to overhigh polymerization degree of resin can be avoided.
Further, the step 3) is specifically: before the temperature rise reaction, extracting air in the kettle, purging for three times by using nitrogen, heating at the speed of raising the temperature by 2-4 ℃ per minute, reacting for 40-45min, wherein the temperature at the top of the reaction kettle reaches 100 ℃ or above, continuously evaporating added water from the top of the reaction kettle, slightly raising the temperature of the reaction kettle after distilling water for 1-2 hours, and closing an outlet valve of a cooling system of the reactor communicated with the atmosphere; the reactor is continuously heated at the speed of 30-50 ℃/hour to ensure that the temperature in the reactor reaches 190 ℃ for 170-3 hours, the reaction is slowly heated for 2-3 hours, the temperature at the top of the tower is controlled by the reflux at the top of the tower, the pressure of the reaction kettle is 0.03-0.5Mpa, the moisture generated by esterification is timely discharged, the reaction is continuously carried out at the temperature of 220-260 ℃ at the temperature of 10-30 ℃/hour, no liquid is evaporated when the temperature at the top of the tower automatically drops, or the reaction is stopped when the temperature at the top of the tower drops below 150 ℃.
The invention also discloses application of the water-based polyester resin prepared by the method, and the water-based polyester resin is used for preparing a water-based saturated polyester resin material, a water-based polyester resin adhesive or a water-based polyester resin coating.
The invention also discloses a resin slurry taking the waterborne polyester resin prepared by the method as a main component, and the preparation method comprises the following steps:
1) proportioning water and water into water-based polyester resin, wherein the mass ratio of the water-based polyester resin to the water is 3: 4-6, pressing the water-based polyester resin to a superfine grinding machine through a feeding pump, grinding the water-based polyester resin to translucent slurry, and storing the translucent slurry as a basic main material of a polyester prepolymer;
2) adding a curing agent into a basic main material of a polyester prepolymer, wherein the curing agent is one or more of waterborne phenolic resin, waterborne amino resin, waterborne epoxy resin, waterborne polyurethane resin, waterborne acetal resin, waterborne acrylic resin and waterborne fluorine-containing silicone resin, and the mass ratio of the basic main material of the prepolymer to the curing agent is 5: 1-5; adding 1-10 wt% of polyester resin functional auxiliary agent, and adjusting the pH value of the resin slurry to be within 7-9.
The invention also discloses an application method of the resin slurry, which comprises the steps of coating, dipping and mixing the resin slurry into the interior or the surface of a coated and dipped object, slowly dehydrating at low temperature before baking and curing, wherein the dehydration temperature is lower than 60 ℃, so that bubbles are avoided, when the moisture is completely removed, the temperature of the coated adhesive object is quickly raised to 120-200 ℃, and the baking time is 5-60 minutes, so as to achieve the purpose of thermosetting network crosslinking.
Compared with the prior art, the invention has the beneficial effects that:
the method is characterized by comprising the steps of (1) chemically synthesizing mixed polyester by using terephthalic acid obtained by carrying out acid precipitation on printing and dyeing alkali reduction wastewater, organic acid mixture obtained by carrying out acid precipitation on printing and dyeing desizing wastewater and other polybasic acids and dihydric alcohol or other polyhydric alcohols, and then crushing or directly diluting and grinding the polyester into semitransparent pulp by using water to prepare the water-based mixed polyester resin, so that the novel innovation of preparing the water-based polyester by recycling resources is realized.
The completely aqueous polyester resin produced by the new process has the advantages of increased molar ratio and dosage of terephthalic acid, high crystallization point, improved strength, good heat resistance, wide application range, no solvent VOC, aqueous environmental protection and green product.
And thirdly, the novel aqueous polyester resin has the advantages of large consumption of low-price terephthalic acid, low cost, good economic benefit, cyclic utilization of printing and dyeing acid precipitation pulp residue resources, waste recycling and remarkable social and economic benefits.
In conclusion, the polyester mixed by the acid-out terephthalic acid from the printing and dyeing alkali decrement wastewater, the acid-out organic acid mixture from the printing and dyeing desizing wastewater and other polybasic acids, and the dihydric alcohol or other polyhydric alcohols are chemically synthesized into the organic acid, so that the industry of the water-based paint and the water-based adhesive can be changed, the blank of the technology and variety in the manufacturing and using method of the water-based polyester resin is filled, the performance conditions can reach and exceed the level of solvent-based polyester products, and the method is worthy of great popularization and advocation for use.
Detailed Description
The invention aims to provide a method for preparing water-based polyester resin by using printing and dyeing slurry residues.
Adding organic acid such as terephthalic acid extracted by acid precipitation from printing and dyeing alkali decrement wastewater and printing and dyeing desizing wastewater and dihydric alcohol or polyhydric alcohol and polybasic acid in a storage tank into an alkyd mixing container according to a required proportion, stirring and mixing to prepare pulp, and stirring and mixing the organic acid and the dihydric alcohol according to a reaction required proportion of 1: 2-3mol, wherein the optimal proportion is 1: 2.1-2.5 mol; the dihydric alcohol can be ethylene glycol, propylene glycol, neopentyl glycol, butanediol, polyalcohol, etc. The diol is slightly excessive, and the esterification synthesis is more sufficient.
In order to further adjust the performance of the polyester resin, other dibasic acid can be added, the dibasic acid can be compounded and synthesized by adipic acid, sebacic acid or most commonly used aromatic dibasic acid phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, tribasic acid and the like according to the required proportion, the proportion of the common terephthalic acid can be 30-70 percent or more, and the proportion of the other dibasic acid can be 20-50 percent. The variety of the polyester resin synthesized by adding the polybasic acid and the polyhydric alcohol is more diversified, and the performance is more comprehensive.
Grinding the mixture of organic acid and dihydric alcohol mixed in an alkyd mixer into fine slurry by using colloid, adding the fine slurry into an esterification synthesis reactor, wherein the esterification reactor is additionally provided with a stirring paddle, a dehydration distillation tower, a condenser, a reflux meter, a product discharge valve, an electric heater, a condensed polyhydric alcohol storage tank, a distilled condensed water storage tank, a vacuum system, a nitrogen bottle and other auxiliary functional structure devices; starting to raise the temperature for esterification synthesis. Before the temperature rise reaction, the air in the kettle is pumped out and is purged for three times by nitrogen. Heating at the speed of 2-4 ℃ per minute, reacting for about 40 minutes, wherein the temperature of the materials in the reaction kettle is about 130 ℃, the temperature of the top of the reaction kettle reaches 100 ℃ or above, the added water is continuously distilled out from the top of the reaction kettle, and the temperature of the reaction kettle slightly rises after the water is distilled out for 1-2 hours, namely, an outlet valve of a cooling system of the reactor communicated with the atmosphere is closed. The temperature of the reactor is continuously increased at the speed of 30-50 ℃/hour, the temperature in the kettle reaches about 180 ℃, the pressure in the kettle is about 0.01MPa, and the esterification reaction slowly starts. Slowly heating to react for 2-3 h, controlling the temperature at the top of the tower by using the reflux at the top of the tower, controlling the pressure to be about 0.03-0.5Mpa, and timely discharging the water generated by esterification. And then the temperature rise speed is kept at 10-30 ℃/h, the reaction is carried out for 2-3 h under the condition that the kettle temperature is 220-260 ℃, and no liquid is evaporated when the temperature at the top of the tower automatically drops, which indicates that the esterification reaction is finished. (or the overhead temperature falls below 150 ℃ C.) the reaction is stopped. The pressure may be 0.1MPa or more (0.3 to 0.5MPa at the maximum).
After the esterification reaction is finished, the residual heat of esterification synthesis of the reaction kettle is utilized, a vacuum pump is started to evacuate and devolatilize, the unreacted redundant dihydric alcohol is removed, the vacuum degree is not too high and is less than 30 minutes, the vacuum degree is controlled, the deep polycondensation of the esterification product is prevented, the excessive high-polymerization product is prevented from being generated, and the gelation can not be generated absolutely. Then cooling the end hydroxyl polyester product generated by esterification to below 140 ℃, discharging, granulating and packaging. Obtaining various low molecular weight polyester products with acid value less than 10 NaOHmg/l. The esterification production process is controlled by computer automation and intelligence.
Example 1
A 1200L stainless steel reaction kettle, wherein a pilot material 900KG (containing water) is printing and dyeing alkali decrement de-sizing slag; wherein the content of terephthalic acid is more than 97 percent; carrying out acid precipitation by using 98% sulfuric acid to obtain wet organic acid solid;
the acid precipitation method comprises the following steps: adding acid, mixing, stirring and carrying out acid precipitation, and controlling the pH value of the acid precipitation wastewater to be 2-5; centrifugally separating out organic acid solids, washing with clear water until the pH value of the washing water is 6-7, and repeatedly centrifugally dewatering to obtain the organic acid solids with the water content of 40-70% by mass.
The molar ratio of organic acid to glycol is 1: 2.8, and esterification reaction is carried out, wherein the reaction process is as follows: before the temperature rise reaction, the air in the kettle is pumped out and is purged for three times by nitrogen. Heating at the speed of 2-4 ℃ per minute, reacting for about 40 minutes, wherein the temperature of materials in the reaction kettle is about 130 ℃, the temperature of the top of the reaction kettle reaches 100 ℃ or above, dehydrating, continuously evaporating added water at the top of the reaction kettle, and slightly increasing the temperature of the reaction kettle after distilling water for 1-2 hours, namely closing an outlet valve of a cooling system of the reaction kettle and communicating the temperature with the atmosphere. The temperature of the reactor is continuously increased at the speed of 30-50 ℃/hour, the temperature in the kettle reaches about 180 ℃, the pressure in the kettle is about 0.01MPa, and the esterification reaction slowly starts. Slowly heating to react for 2-3 h, controlling the temperature at the top of the tower by using the reflux at the top of the tower, controlling the pressure to be about 0.03-0.5Mpa, and timely discharging the water generated by esterification. And then the temperature rise speed is kept at 10-30 ℃/h, the reaction is carried out for 2-3 h under the condition that the kettle temperature is 220-260 ℃, and no liquid is evaporated when the temperature at the top of the tower automatically drops, which indicates that the esterification reaction is finished. (or the overhead temperature falls below 150 ℃ C.) the reaction is stopped. The pressure may be 0.1MPa or more (0.3 to 0.5MPa at the maximum).
Controlling the final temperature of 230 ℃ and 260 ℃, the reaction pressure of 0.5Mpa and the total reaction time of 12 h; the pilot product mixed organic acid glycol ester 300KG is obtained, the acid value is 3KOHmg/L, and the color is grey milky white.
And uniformly mixing 70% of the powdery mixed organic acid glycol ester and 30% of the amino resin, or adding 70% of purified water in the total amount, grinding by a colloid mill, coating, impregnating, spraying, carrying out compression molding, and baking at 140 ℃ for 40 minutes to obtain an amino resin modified mixed polyester resin sample.
Example 2
Compared with the embodiment 1, the method is characterized in that the ratio of the organic acid to the glycol is 1: 2.1mol, the reaction temperature is 230 ℃ and 260 ℃, the reaction pressure is 0.5Mpa, and the total reaction time is 12 h; the pilot product is 300KG, the acid value is 3KOHmg/L, and the color is milky white.
And uniformly mixing 70% of the powdery mixed organic acid glycol ester and 30% of polyurethane resin, adding 70% of purified water in the total amount, grinding by a colloid mill, coating, dipping, spraying, carrying out compression molding, and baking at 140 ℃ for 40 minutes to obtain a polyurethane modified mixed polyester resin sample.
Example 3
Compared with the embodiment 1, the method is characterized in that the ratio of the organic acid to the glycol is 1: 2.5mol, the reaction temperature is 230 ℃ and 260 ℃, the reaction pressure is 0.5Mpa, and the total reaction time is 12 h; the pilot product is 300KG, the acid value is 3KOHmg/L, and the color is milky white.
And uniformly mixing 70% of the powdery mixed organic acid glycol ester and 30% of phenolic resin, adding 70% of purified water in the total amount, grinding by a colloid mill, coating, impregnating, spraying, carrying out compression molding, and baking at 140 ℃ for 40 minutes to obtain a phenolic resin modified mixed polyester resin sample.
The degree of polymerization of the pilot product (based on bis-ethylene terephthalate) obtained in examples 1-3 was tested to be about 2; can be stably dispersed in water (resin: water ratio of 3: 4-6) for a long time.
The content of terephthalic acid in the printing, dyeing and desizing wastewater is more than 60 percent, and other components are mainly acrylic acid mixed organic acid. The method of example 1 was used as a raw material, and 900KG (containing water) of a stainless steel reaction kettle of 1200L was used as a raw material, the ratio of organic acid to ethylene glycol was 1: 2.5mol, the pilot plant product was 280KG, the acid value was 3KOHmg/L, and the color was milky white.
The main component of the product obtained by the invention is the terephthalic acid bis-glycol ester, the main component of the product obtained by the embodiment is the terephthalic acid bis-glycol ester, the clear water is proportioned in a certain proportion, the mass ratio of the terephthalic acid bis-glycol ester to the water is 3: 4-6 generally, and the slurry has good fluidity and high solid content when the proportioning is optimal. The semi-transparent slurry is ground into semi-transparent slurry by a superfine grinder pressed by a feeding pump, the fineness of the solid ester reaches submicron or nanometer, the solid ester is basically dissolved or suspended in the water-based polyester slurry product and has the best intersolubility, and the slurry product does not generate layering when being stored for a long time. The material is used as basic main material of polyester prepolymer of water-based polyester resin, water-based polyester adhesive, water-based polyester coating and the like.
The basic main material of the prepolymer using the waterborne polyester as the main component is added with curing agents of different varieties and mass proportions, stirred, homogenized, heated and netted for crosslinking and curing. The curing agent is generally less than 30% as the main crosslinking component. The best curing agent classes that can be used are: aqueous phenolic resin, aqueous amino resin, aqueous epoxy resin and aqueous polyurethane resin; also usable are organic substances having an activity to react with a hydroxyl group or a carboxyl group, such as aqueous acetal resins, aqueous acrylic resins, and aqueous fluorosilicone resins. The curing agent resin must be water-soluble, or water-based emulsion, or water suspension, and have good compatibility with the basic main material water-based polyester resin prepolymer, and cannot carry water-soluble organic solvents and other organic auxiliaries which cause VOC residues. The mass ratio of the aqueous polyester resin prepolymer to the curing agent is generally 5: 1-5, preferably 5: 1-2. The better ratio can be calculated by that the MOL equivalent of the active functionality of the waterborne polyester resin prepolymer to the curing agent is 1: 1-1.05.
Polyester resin functional auxiliary agents with different properties are required to be added into polyester resin in different use occasions. The main functional auxiliary agents of the polyester resin are: reinforcing agent, tackifier, emulsifier, leveling agent, penetrant, softening agent, pigment, flame retardant and the like, wherein the optimal addition amount is 1-10%. Other auxiliary agents comprise water repellent agents, anti-aging agents, weather-proof agents, light-retaining agents, fillers and the like, and the functions of the polyester resin are changed by chemical synthesis and blending according to the reaction principle and the function requirement and according with the compatibility mechanism and by adjusting the proportion.
Finally, the pH value of the resin slurry is required to be adjusted, the pH value is required to be controlled within 7-9, the optimal pH value is within 7.0-7.5, the neutral property of the slurry is kept to be slightly alkaline, hydrolysis is prevented, the resin quality is stable, and the storage period is prolonged.
According to the embodiment of the invention, glycol is used as polyhydric alcohol, the typical polyester synthesized by reaction is mainly terephthalic acid bis-glycol ester, the melting point of the synthesized terephthalic acid bis-glycol ester product mixture is a solid with the temperature of less than or equal to 110 ℃, and the product is a white waxy solid with low melting point and is soluble in water. The product of the recycled printing and dyeing pulp residue is slightly gray, the appearance is solid before no compound processing, and the product can be crushed into solid powder subsequently; or adding water to compound and react to prepare the water-based polyester resin in a slurry state or shaping according to the requirement of service performance. The tool can adopt related manufacturing and construction processes such as direct dipping, coating, spraying, film plastic hot pressing, baking and the like.
The best method for the curing and using process is to use baking for heat curing. The resin is coated, impregnated and mixed into the coated and impregnated object or the surface, the coating needs to be thin, and the workpiece needs not to be too thick. The low-temperature slow dehydration is carried out by a conveyor belt in a short time before baking and curing, the dehydration temperature is not more than 60-90 ℃, and the generation of bubbles is avoided. When the water is removed completely, the temperature of the adhesive-coated object is rapidly raised to 200 ℃ at 120-. The baking time is 5-60 minutes, the optimal time is 5-20 minutes, the curing and baking temperature and time of the polyester resin are adjusted according to needs to achieve thermosetting network crosslinking, and the phenomena that the polyester resin is over-cured, embrittled, carbonized and decomposed during baking and the molding quality of the resin is influenced are prevented.
The saturated polyester resin prepared by using printing and dyeing pulp residue terephthalic acid as a main material can be crosslinked and cured at a daily temperature, for example, unsaturated carboxylic acid anhydride with double bonds or alkyd organic materials without double bonds and the like are added in advance in the esterification synthesis reaction process for grafting synthesis to prepare unsaturated polyester resin or saturated polyester resin, and the compatibility of the unsaturated polyester resin and the saturated polyester resin with water is poor. Or grinding with water, or adding diluent, adding curing catalyst at normal temperature, and curing. The unsaturated polyester resin curing catalyst comprises: acidic and basic substances, ammonia and amine substances, peroxides, metal compounds, and the like. Commonly used are: sulfonic acid, sulfuric acid, NaOH, ammonia water, organic amine, hydrogen peroxide, methyl ethyl ketone peroxide, cobalt naphthenate and the like are selected according to the variety of the resin, and curing and crosslinking can be realized at normal temperature. The curing catalyst is used in an amount of usually 0.1 to 10%, preferably 0.1 to 5%. The curing reaction speed is high, and the A resin and the B resin can be used in a temporary mixing way.
Through experimental exploration, a 500 ton/year pilot-scale production model device of the water-based polyester resin is established, and a design scheme for feasibility operation analysis is completed. Can be developed into a strip which comprises: the method comprises the steps of slurry residue recovery, polyester resin synthesis, compound engineering material preparation, PTA of a terminal product and a slurry residue PTA mixture derived from various brand-new green environment-friendly industrial chains, innovations and fills up resource product industrial structures in China and Shaoxing areas, creates good basic conditions for recycling, saves petroleum product resources, changes waste into valuables and creates huge social benefits and economic benefits.
Claims (7)
1. A method for manufacturing water-based polyester resin by using printing and dyeing slurry residues is characterized by comprising the following steps:
1) acid-out extracting wet organic acid solid mainly containing terephthalic acid from printing and dyeing alkali decrement wastewater and printing and dyeing desizing wastewater;
the step 1) is specifically as follows: filtering the printing and dyeing alkali decrement wastewater and the printing and dyeing desizing wastewater to remove insoluble mechanical impurities, adding acid, mixing, stirring and carrying out acid precipitation, and controlling the pH value of the acid precipitation wastewater to be 2-5; centrifugally separating out organic acid solids, washing with clear water until the pH value of the washing water is 6-7, and then repeatedly centrifugally dewatering to obtain organic acid solids with the water content of 40-70% by mass;
2) directly mixing the wet organic acid solid obtained in the step 1) with dihydric alcohol, stirring and pulping, and adding the mixture into an esterification synthesis reactor after pulping, wherein the molar ratio of carboxyl of the wet organic acid solid to hydroxyl in alcohol is 1: 2-3;
3) dehydrating under the inert gas atmosphere; then the organic acid and alcohol are subjected to esterification reaction;
the step 3) is specifically as follows: replacing the esterification synthesis reactor with nitrogen; controlling the temperature rise speed to be 2-4 ℃/min, and reacting for 30-60 min; continuously evaporating water from the tower top, closing an outlet valve of a cooling system of the reactor communicated with the atmosphere after the water is distilled for 1-2 hours, heating the reactor at the speed of 30-50 ℃/h, continuing heating the reactor for 2-3 hours after the temperature in the reactor reaches 170-; then continuously heating at the speed of 10-30 ℃/h, reacting at the temperature of 220-260 ℃, and stopping the reaction when the temperature at the tower top automatically drops and no liquid is evaporated out or the temperature at the tower top drops below 150 ℃;
4) utilizing esterification synthesis waste heat of a reaction kettle, vacuumizing and devolatilizing to remove unreacted redundant alcohol, and keeping the vacuum degree at 0.01-0.05 MPa for 10-30 minutes; and then cooling the hydroxyl-terminated polyester product generated by esterification to below 140 ℃ to obtain the water-based polyester resin.
2. The method for producing an aqueous polyester resin from textile printing sludge according to claim 1, wherein the acid added for acid precipitation is 98% sulfuric acid.
3. The process for producing an aqueous polyester resin from the textile printing sludge according to claim 1, wherein the molar ratio of the carboxyl group of the wet organic acid solid to the hydroxyl group of the alcohol is 1: 2.1 to 2.5.
4. The method for producing an aqueous polyester resin using a printing and dyeing sludge as described in claim 1, wherein the glycol is one or more of ethylene glycol, propylene glycol, neopentyl glycol and butanediol.
5. The method for producing an aqueous polyester resin using printing and dyeing sludge according to claim 1, wherein the step 3) is specifically:
before the temperature rise reaction, extracting air in the kettle, purging for three times by using nitrogen, heating at the speed of raising the temperature by 2-4 ℃ per minute, reacting for 40-45min, wherein the temperature at the top of the reaction kettle reaches 100 ℃ or above, continuously evaporating added water from the top of the reaction kettle, slightly raising the temperature of the reaction kettle after distilling water for 1-2 hours, and closing an outlet valve of a cooling system of the reactor communicated with the atmosphere; the reactor is continuously heated at the speed of 30-50 ℃/hour to ensure that the temperature in the reactor reaches 190 ℃ for 170-3 hours, the reaction is slowly heated for 2-3 hours, the temperature at the top of the tower is controlled by the reflux at the top of the tower, the pressure of the reaction kettle is 0.03-0.5Mpa, the moisture generated by esterification is timely discharged, the reaction is continuously carried out at the temperature of 220-260 ℃ at the temperature of 10-30 ℃/hour, no liquid is evaporated when the temperature at the top of the tower automatically drops, or the reaction is stopped when the temperature at the top of the tower drops below 150 ℃.
6. A resin paste comprising as a main component the aqueous polyester resin prepared by the method of claim 1, characterized by being prepared by the following steps:
1) proportioning water and water into water-based polyester resin, wherein the mass ratio of the water-based polyester resin to the water is 3: 4-6, pressing the water-based polyester resin to a superfine grinding machine through a feeding pump, grinding the water-based polyester resin to translucent slurry, and storing the translucent slurry as a basic main material of a polyester prepolymer;
2) adding a curing agent into a basic main material of a polyester prepolymer, wherein the curing agent is one or more of waterborne phenolic resin, waterborne amino resin, waterborne epoxy resin, waterborne polyurethane resin, waterborne acetal resin, waterborne acrylic resin and waterborne fluorine-containing silicone resin, and the mass ratio of the basic main material of the prepolymer to the curing agent is 5: 1-5; adding 1-10 wt% of polyester resin functional auxiliary agent, and adjusting the pH value of the resin slurry to be within 7-9.
7. Use of the resin syrup according to claim 6, wherein: coating, dipping and mixing the resin slurry into the interior or the surface of the coated and dipped object, slowly dehydrating at low temperature before baking and curing, wherein the dehydration temperature is lower than 60 ℃, avoiding generating air bubbles, and when the moisture is completely removed, rapidly heating the coated adhesive object to 120 ℃ and 200 ℃, and baking for 5-60 minutes to achieve the purpose of thermosetting reticular crosslinking.
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| CN101503510A (en) * | 2009-03-09 | 2009-08-12 | 嘉兴市清河高力绝缘有限公司 | Preparation of water-soluble polyester resin for silicon steel sheet insulation processing |
| WO2010119317A1 (en) * | 2009-04-14 | 2010-10-21 | Basf Coatings Japan Ltd. | Aqueous mid-coat paint composition |
| CN104231879A (en) * | 2014-09-16 | 2014-12-24 | 北京高盟燕山科技有限公司 | Water-based polyester primer for enhancing printing and aluminum plating and preparation method of water-based polyester primer |
| CN106277576A (en) * | 2016-08-11 | 2017-01-04 | 上海凯鑫分离技术股份有限公司 | A kind of polyester fiber alkali processes the integrated conduct method of waste water |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503510A (en) * | 2009-03-09 | 2009-08-12 | 嘉兴市清河高力绝缘有限公司 | Preparation of water-soluble polyester resin for silicon steel sheet insulation processing |
| WO2010119317A1 (en) * | 2009-04-14 | 2010-10-21 | Basf Coatings Japan Ltd. | Aqueous mid-coat paint composition |
| CN104231879A (en) * | 2014-09-16 | 2014-12-24 | 北京高盟燕山科技有限公司 | Water-based polyester primer for enhancing printing and aluminum plating and preparation method of water-based polyester primer |
| CN106277576A (en) * | 2016-08-11 | 2017-01-04 | 上海凯鑫分离技术股份有限公司 | A kind of polyester fiber alkali processes the integrated conduct method of waste water |
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