CN109485835B - Method for synthesizing water-soluble polyester by composite and concerted catalysis method - Google Patents
Method for synthesizing water-soluble polyester by composite and concerted catalysis method Download PDFInfo
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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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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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
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Abstract
The invention provides a method for synthesizing water-soluble polyester by a composite and concerted catalysis method. The effective component content of the water-soluble polyester prepared by the invention is 99.12-99.19%; the appearance is yellowish particles, and the color is good; the melting point Tm is 145.9-147 ℃, and the glass transition temperature Tg is 42.0-44.5 ℃. The pH value (20% water solution, 25 ℃) of the water-soluble polyester prepared by the invention is 6.1-6.9; 10-25% polyester water solution, which is homogeneous liquid without delamination after being placed in a sealed condition and an environment at 25 ℃ for one month.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and relates to a method for synthesizing water-soluble polyester by a composite and concerted catalysis method.
Background
The water-soluble polyester is modified polyester, which is an ionic copolyester introducing ionic structural units into polyethylene terephthalate (PET) molecular chains, and the modified water-soluble polyester has been widely applied to the fields of chemical fibers, printing ink, coating, adhesives and the like due to excellent moisture absorption performance and ionic conductivity, and has wide application prospects.
Meanwhile, the water-soluble polyester does not need strong alkali desizing due to the excellent biodegradation characteristic, thereby effectively reducing the sewage treatment difficulty and saving the wastewater treatment cost. With the increasing demand of sea-island superfine composite fibers in the textile field, the improvement of the living standard of human beings and the enhancement of environmental awareness, the research and development of high-tech and pollution-free water-soluble polyester attract worldwide attention.
Chinese patent (2016104527319) proposes the direct esterification of terephthalic acid and/or isophthalic acid, ethylene glycol, SIPE and Polyethylene Adipate (PAE) to form water-soluble polyesters.
Chinese patent (2017114789702) proposes a preparation method for synthesizing water-soluble polyester resin using polyhydric alcohol, dihydric alcohol, SIPA and the like.
The water-soluble polyester prepared by the prior art has the following technical problems:
(1) the content of active ingredients is generally below 96 percent, and the solubility is poor;
(2) the aqueous solution of the polyester is unstable and is easy to separate during storage;
(3) the intrinsic viscosity is high, so that the permeability of the slurry is poor, the adhesion of the polyester yarn is poor, and the application performance is poor.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a method for synthesizing water-soluble polyester by a composite and concerted catalysis method, so as to realize the following purposes:
(1) the content of the effective components is improved to more than 99.1 percent, so that the product is dissolved in water at the temperature of 95 ℃ for no more than 30 minutes;
(2) the aqueous solution of the polyester is stable and is not easy to delaminate after being placed for one month;
(3) the water-soluble polyester with proper intrinsic viscosity is synthesized by selecting proper materials, adjusting the material proportion and determining process parameters, so that the adhesion of the polyester yarns is improved, and the service performance is improved.
In order to solve the defects in the prior art, the invention provides a method for synthesizing water-soluble polyester by a composite and concerted catalysis method, which realizes the following purposes:
in order to realize the purpose, the invention adopts the following technical scheme:
a method for synthesizing water-soluble polyester by a composite and concerted catalysis method is characterized in that: the method comprises esterification, feeding, pre-polycondensation and post-polycondensation.
And (3) performing esterification, namely adding Ethylene Glycol (EG), terephthalic acid (PTA), polyethylene glycol (PEG), ethylene glycol Adipate (AE) and a catalyst cobalt acetate.
The mass of the ethylene glycol is 50-55% of that of the terephthalic acid; the mass of the polyethylene glycol is 8.2-10.4% of that of the terephthalic acid; the mass of the adipic acid glycol ester is 5.7-7.1% of that of the terephthalic acid; the mass of the cobalt acetate is 0.002-0.0037 percent of that of the terephthalic acid.
And in the step of feeding, the temperature of the material obtained after esterification is reduced to 220-225 ℃, and SIPE (diethylene glycol isophthalate-5-sodium sulfonate) solution, ethylene glycol titanium, sodium acetate and trimethyl phosphate are added.
The mass of the SIPE solution is 16.5-18.75% of that of the terephthalic acid; the mass of the ethylene glycol titanium is 0.025-0.038% of that of the terephthalic acid; the mass of the sodium acetate is 0.05-0.07% of that of the terephthalic acid; the mass of trimethyl phosphate is 0.006-0.0075% of that of terephthalic acid.
The pre-polycondensation is carried out at the reaction temperature of 230-235 ℃; the absolute pressure in the kettle is 500-600Pa, and the kettle is kept for 45-60 minutes.
The post-polycondensation is carried out at the reaction temperature of 245-260 ℃ and the absolute pressure in the kettle of 50-100 Pa.
The esterification is carried out at the reaction temperature of 230 ℃ to 240 ℃ for 150 minutes to 200 minutes.
And (3) after-polycondensation, when the power of the motor is observed to be 20% higher than that in normal operation, the stirring speed is reduced, and the viscosity of the materials in the polycondensation kettle is sampled and analyzed to be higher than 0.350dl/g, stirring is continued for 10-20 minutes, and the reaction is finished.
The SIPE solution with the content of 40.04-40.21%; the saponification value is 126.11-126.65 mgKOH/g, the acid value is 0.38-0.62 mgKOH/g, the iron content is 1.6-4.6ppm, the water content is 0.24-0.47%, and the sulfate radical content is 156.48-231.47 ppm.
Determining the reaction end point of the esterification reaction of PTA and EG, wherein firstly, the water amount obtained by esterification reaches more than 98% of a theoretical calculated value according to two process parameters; firstly, the change condition of the temperature at the top of the fractionating tower is observed, and the temperature of the fraction at the top of the fractionating tower is reduced from higher temperature to 100 ℃ and is in a descending trend after being stabilized for a period of time. After the two index values reach the required values at the same time, the esterification reaction can be preliminarily judged to be ended.
Compared with the prior art, the invention has the following technical effects:
(1) the effective component content of the water-soluble polyester prepared by the invention is 99.12-99.19%; the appearance is yellowish particles, and the color is good; the melting point Tm is 145.9-147 ℃, and the glass transition temperature Tg is 42.0-44.5 ℃.
(2) The pH value (20% water solution, 25 ℃) of the water-soluble polyester prepared by the invention is 6.1-6.9; 10-25% polyester water solution, which is homogeneous liquid without delamination after being placed in a sealed condition and an environment at 25 ℃ for one month.
(3) The water-soluble polyester prepared by the invention has the intrinsic viscosity of 0.380-0.393 dl/g, the molecular weight of 8000-12000 and the viscosity (20 percent of aqueous solution, 25 ℃) of 10.9-13.8 mPa.s; the polyester yarn adhesion force was 195.1N.
The breaking strength of the pure film is 29.17N/mm; the number of times of flexing resistance of serosa is more than 10000.
(4) The polyester prepared by the invention can be dissolved by 100 percent within 20-24min at 95 ℃.
(5) The reaction time is generally 580-600 minutes from the esterification to the completion of the polycondensation reaction.
Detailed Description
Example 1 Synthesis of Water-soluble polyester by Complex and concerted catalysis
The method comprises the following steps:
(1) esterification
Putting EG50 kg into an esterification kettle, starting stirring, and slowly adding PTA100 kg, PEG8.2 kg, ethylene glycol adipate 6.5kg and cobalt acetate 2 g;
filling nitrogen into the esterification kettle to remove air in the esterification kettle, releasing pressure when the pressure (gauge pressure) in the esterification kettle is 0.02MPa, starting heating, and heating to 235 ℃ within 60 minutes. The reaction temperature was controlled at 235 ℃ and the reaction was carried out at this temperature for 150 minutes. When the distilled water reaches 30Kg and the temperature of the rectifying column of the esterification kettle drops below 100 ℃ and continues to be in a descending trend, the esterification is finished.
(2) Charging of
The temperature of the esterification kettle is reduced to 220 ℃, 16.5 kg of 40.18 percent SIPE, 25 g of ethylene glycol titanium, 60 g of sodium acetate and 6 g of trimethyl phosphate are added, the mixture is continuously stirred for 25 minutes, the materials are pressed into the polycondensation kettle by nitrogen (the tightness of the polycondensation kettle is checked before material pressing), and a feeding valve is closed.
(3) Prepolycondensation
And starting the temperature of the polycondensation kettle, starting a vacuum pump, heating the polycondensation kettle to 230 ℃ within 15 minutes, gradually increasing the opening of a vacuum valve, and enabling the absolute pressure in the polycondensation kettle to reach 500Pa within 25 minutes. Keeping the temperature of the kettle at 230 ℃ and the absolute pressure in the kettle at 500Pa for 50 minutes;
(4) post-condensation polymerization
After 50 minutes of low vacuum polycondensation, the vacuum system was switched and the vacuum was switched to the high vacuum system. And (3) heating the polycondensation kettle to make the absolute pressure in the polycondensation kettle reach 100Pa within 25 minutes, and heating the polycondensation kettle to 250 ℃ within 30 minutes. The reaction was continued at a pot temperature of 250 ℃ and an absolute pressure in the pot of 100 Pa. When the power of the motor is higher than that in normal operation by 30 percent, the stirring speed is reduced, and the viscosity of the materials in the polycondensation kettle is sampled and analyzed to be higher than 0.360dl/g, the stirring is continued for 10 minutes, and the reaction is finished.
Discharging under the protection of nitrogen, cooling and crushing.
The quality index analysis of the prepared water-soluble polyester is shown in the following table 1:
TABLE 1
Example 2A method for preparing water-soluble polyester from a concentrate of wastewater from a tri-monomer production process
The preparation process of example 1 was used, with the following modifications:
(1) esterification
Putting EG50 kg into an esterification kettle, starting stirring, slowly adding PTA100 kg, PEG9.0 kg, glycol adipate 5.7 kg and cobalt acetate 3 g, filling nitrogen into the esterification kettle to remove air in the kettle until the pressure (gauge pressure) in the esterification kettle is 0.03MPa, releasing pressure, starting heating, and heating to 235 ℃ within 70 minutes. The reaction temperature was controlled at 235 ℃ and the reaction was carried out at this temperature for 160 minutes. When the distilled water reaches 30Kg, the temperature of the rectifying column of the reaction kettle drops below 100 ℃ and continues to be in a downward trend, the esterification is finished.
(2) Charging of
The temperature of the esterification kettle is reduced to 220 ℃, 18.5 kg of 40.18 percent SIPE, 35 g of ethylene glycol titanium, 50 g of sodium acetate and 7 g of trimethyl phosphate are added, the mixture is continuously stirred for 25 minutes, the materials are pressed into the polycondensation kettle by nitrogen (the tightness of the polycondensation kettle is checked before material pressing), and a feeding valve is closed.
(3) Prepolycondensation
And starting the temperature of the polycondensation kettle, starting a vacuum pump, heating the polycondensation kettle to 230 ℃ within 15 minutes, gradually increasing the opening of a vacuum valve, and enabling the absolute pressure in the polycondensation kettle to reach 600Pa within 25 minutes. The temperature of the kettle is 230 ℃ and the absolute pressure in the kettle is 600Pa for 50 minutes.
(4) Post-condensation polymerization
After 50 minutes of low vacuum polycondensation, the vacuum system was switched and the vacuum was switched to the high vacuum system. And (3) heating the polycondensation kettle to make the absolute pressure in the polycondensation kettle reach 60Pa within 25 minutes, and heating the polycondensation kettle to 255 ℃ within 25 minutes. The reaction is continued at a kettle temperature of 255 ℃ and an absolute pressure in the kettle of 60 Pa. When the power of the motor is higher than that in normal operation by 30 percent, the stirring speed is reduced, and the viscosity of the materials in the polycondensation kettle is sampled and analyzed to be higher than 0.360dl/g, the stirring is continued for 15 minutes, and the reaction is finished.
Discharging under the protection of nitrogen, cooling and crushing.
The quality index analysis of the prepared water-soluble polyester is shown in the following table 2.
TABLE 2
Example 3A method for preparing water-soluble polyester from a concentrate of wastewater from a tri-monomer production process
The procedure of example 1 was followed with the following modifications:
(1) esterification
Putting EG58 kg into an esterification kettle, starting stirring, slowly adding PTA110 kg, PEG9.3 kg, glycol adipate 7.3 kg and cobalt acetate 3.5 g, filling nitrogen into the esterification kettle to remove air in the kettle until the pressure (gauge pressure) in the esterification kettle is 0.02MPa, releasing pressure, starting heating, and heating to 235 ℃ within 80 minutes. The reaction temperature was controlled at 240 ℃ and the reaction was carried out at this temperature for 180 minutes. When the distilled water reaches 33.5Kg, the temperature of the rectifying column of the reaction kettle drops below 100 ℃ and continues to be in a descending trend, the esterification is finished.
(2) Charging of
The temperature of the esterification kettle is reduced to 225 ℃, 18.5 kg of 40.18 percent SIPE, 35 g of ethylene glycol titanium, 70 g of sodium acetate and 8 g of trimethyl phosphate are added, the mixture is continuously stirred for 25 minutes, the materials are pressed into the polycondensation kettle by nitrogen (the tightness of the polycondensation kettle is checked before material pressing), and a feeding valve is closed.
(3) Prepolycondensation
And (3) starting to heat the polycondensation kettle, starting a vacuum pump, heating the polycondensation kettle to 235 ℃ within 30 minutes, gradually increasing the opening of a vacuum valve, and enabling the absolute pressure in the polycondensation kettle to reach 600Pa within 30 minutes. The temperature in the kettle is 235 ℃ and the absolute pressure in the kettle is 600Pa for 50 minutes.
(4) Post-condensation polymerization
After 50 minutes of low vacuum polycondensation, the vacuum system was switched and the vacuum was switched to the high vacuum system. The absolute pressure in the polycondensation kettle is 50Pa within 30 minutes, the polycondensation kettle is heated up to 255 ℃ within 30 minutes. The reaction was continued at a pot temperature of 255 ℃ and an absolute pressure in the pot of 50 Pa. When the power of the motor is higher than that in normal operation by 30 percent, the stirring speed is reduced, and the viscosity of the materials in the polycondensation kettle is sampled and analyzed to be higher than 0.360dl/g, the stirring is continued for 20 minutes, and the reaction is finished.
Discharging under the protection of nitrogen, cooling and crushing.
The quality index analysis of the prepared water-soluble polyester is as follows 3:
TABLE 3
Example 4A method for preparing water-soluble polyester from a concentrate of wastewater from a tri-monomer production process
The procedure of example 1 was followed with the following modifications:
(1) esterification
Putting EG58 kg into an esterification kettle, starting stirring, slowly adding PTA110 kg, PEG10.2 kg, glycol adipate 6.6 kg and cobalt acetate 3.5 g, filling nitrogen into the esterification kettle to remove air in the kettle until the pressure (gauge pressure) in the esterification kettle is 0.04MPa, releasing pressure, starting heating, and heating to 240 ℃ within 80 minutes. The reaction temperature was controlled at 240 ℃ and the reaction was carried out at this temperature for 185 minutes. When the distilled water reaches 33.5Kg, the temperature of the rectifying column of the reaction kettle drops below 100 ℃ and continues to be in a descending trend, the esterification is finished.
(2) Charging of
The temperature of the esterification kettle is reduced to 225 ℃, 40.18 percent SIPE21 kg, 40 g ethylene glycol titanium, 65 g sodium acetate and 8 g trimethyl phosphate are added, the mixture is continuously stirred for 25 minutes, the materials are pressed into the polycondensation kettle by nitrogen (the tightness of the polycondensation kettle is checked before pressing the materials), and a feeding valve is closed.
(3) Prepolycondensation
And (3) starting to heat the polycondensation kettle, starting a vacuum pump, heating the polycondensation kettle to 235 ℃ within 20 minutes, gradually increasing the opening of a vacuum valve, and enabling the absolute pressure in the polycondensation kettle to reach 500Pa within 30 minutes. The temperature in the kettle is 235 ℃ and the absolute pressure in the kettle is 500Pa for 50 minutes.
(4) Post-condensation polymerization
After 50 minutes of low vacuum polycondensation, the vacuum system was switched and the vacuum was switched to the high vacuum system. And (3) heating the polycondensation kettle to make the absolute pressure in the polycondensation kettle reach 60Pa within 30 minutes, and heating the polycondensation kettle to 260 ℃ within 30 minutes. The reaction is continued at a kettle temperature of 260 ℃ and an absolute pressure in the kettle of 60 Pa. When the power of the motor is higher than that in normal operation by 30 percent, the stirring speed is reduced, and the viscosity of the materials in the polycondensation kettle is sampled and analyzed to be higher than 0.360dl/g, the stirring is continued for 20 minutes, and the reaction is finished.
Discharging under the protection of nitrogen, cooling and crushing.
The quality index analysis of the prepared water-soluble polyester is as follows 4:
TABLE 4
Example 5A method for preparing water-soluble polyester from a concentrate of wastewater from a tri-monomer production process
The procedure of example 1 was followed with the following modifications:
(1) esterification
Putting EG66 kg into an esterification kettle, starting stirring, slowly adding PTA120 kg, PEG10 kg, glycol adipate 8.5 kg and cobalt acetate 4 g, filling nitrogen into the esterification kettle to remove air in the kettle until the pressure (gauge pressure) in the esterification kettle is 0.03MPa, releasing pressure, starting heating, and heating to 230 ℃ within 70 minutes. The reaction temperature was controlled at 230 ℃ and the reaction was carried out at this temperature for 190 minutes. When the distilled water reaches 36.5Kg, the temperature of the rectifying column of the reaction kettle drops below 100 ℃ and continues to be in a descending trend, the esterification is finished.
(2) Charging of
The temperature of the kettle is reduced to 220 ℃, 40.18 percent SIPE21.5 kg, ethylene glycol titanium 40 g, sodium acetate 75 g and trimethyl phosphate 8.5 g are added, the mixture is continuously stirred for 30 minutes, the materials are pressed into the polycondensation kettle by nitrogen (the tightness of the polycondensation kettle is checked before pressing materials), and a feeding valve is closed.
(3) Prepolycondensation
And starting a vacuum pump, heating the polycondensation kettle to 230 ℃ within 25 minutes, gradually increasing the opening of a vacuum valve, and enabling the absolute pressure in the polycondensation kettle to reach 600Pa within 35 minutes. The reaction was maintained at a pot temperature of 230 ℃ and an absolute pressure in the pot of 600Pa for 55 minutes.
(4) Post-condensation polymerization
After 55 minutes of low vacuum polycondensation, the vacuum system was switched and the vacuum was switched to the high vacuum system. And (3) heating the polycondensation kettle to 50Pa in 35 minutes until the absolute pressure in the polycondensation kettle reaches 50Pa, and heating the polycondensation kettle to 260 ℃ in 30 minutes. The reaction was continued at a pot temperature of 260 ℃ and an absolute pressure in the pot of 50 Pa. When the power of the motor is higher than that in normal operation by 30 percent, the stirring speed is reduced, and the viscosity of the materials in the polycondensation kettle is sampled and analyzed to be higher than 0.360dl/g, the stirring is continued for 20 minutes, and the reaction is finished.
Discharging under the protection of nitrogen, cooling and crushing.
The quality index analysis of the prepared water-soluble polyester is shown in the following table 5:
TABLE 5
Example 6A method for preparing water-soluble polyester from a concentrate of wastewater from a tri-monomer production process
The procedure of example 1 was followed with the following modifications:
(1) esterification
Putting EG66 kg into an esterification kettle, starting stirring, slowly adding PTA120 kg, PEG12.5 kg, glycol adipate 7.2 kg and cobalt acetate 4.5 g, filling nitrogen into the esterification kettle to remove air in the kettle until the pressure (gauge pressure) in the esterification kettle is 0.05MPa, releasing pressure, starting heating, and heating to 240 ℃ in 90 minutes. The reaction temperature was controlled at 240 ℃ and the reaction was carried out at this temperature for 200 minutes. When the distilled water reaches 36.5Kg, the temperature of the rectifying column of the reaction kettle drops below 100 ℃ and continues to be in a descending trend, the esterification is finished.
(2) Charging of
The kettle temperature is reduced to 225 ℃, 40.18 percent SIPE22.5 kg, ethylene glycol titanium 45 g, sodium acetate 85 g and trimethyl phosphate 9 g are added, the mixture is continuously stirred for 30 minutes, the materials are pressed into the polycondensation kettle by nitrogen (the tightness of the polycondensation kettle is checked before pressing materials), and a feeding valve is closed.
(3) Prepolycondensation
And (3) starting to heat the polycondensation kettle, starting a vacuum pump, heating the polycondensation kettle to 230 ℃ within 20 minutes, gradually increasing the opening of a vacuum valve, and enabling the absolute pressure in the polycondensation kettle to reach 500Pa within 35 minutes. The temperature of the autoclave was 230 ℃ and the absolute pressure in the autoclave was 500Pa for 50 minutes.
(4) Post-condensation polymerization
After 50 minutes of low vacuum polycondensation, the vacuum system was switched and the vacuum was switched to the high vacuum system. The absolute pressure in the polycondensation kettle is 50Pa within 30 minutes, the polycondensation kettle is heated up to 255 ℃ within 30 minutes. The reaction was continued at a pot temperature of 255 ℃ and an absolute pressure in the pot of 50 Pa. When the power of the motor is higher than that in normal operation by 30 percent, the stirring speed is reduced, and the viscosity of the materials in the polycondensation kettle is sampled and analyzed to be higher than 0.360dl/g, the stirring is continued for 15 minutes, and the reaction is finished.
Discharging under the protection of nitrogen, cooling and crushing.
The quality index analysis of the prepared water-soluble polyester is as follows 6:
TABLE 6
The preparation method of the 40.18 percent SIPE solution comprises the following steps:
1. drying the concentrated material
And drying the tri-monomer production wastewater concentrated material until the moisture content is lower than 0.2% to obtain a dried concentrated material.
2. Dissolving and filtering
Adding 600 kg of ethylene glycol into a dissolving kettle, starting stirring, adding 400 kg of dried concentrated material into the kettle, introducing steam into a jacket of the dissolving kettle after the concentrated material is added, heating the kettle to 90 ℃ for 30 minutes, and stirring for 65 minutes at the temperature under heat preservation. Opening a discharge valve of the dissolution kettle, feeding materials to a centrifugal machine, centrifuging, and recovering sodium sulfate obtained by filtering cloth to obtain an industrial product meeting the national standard; the obtained filtrate is sucked into a synthesis kettle by vacuum to synthesize SIPP;
3. SIPE Synthesis
Sucking the filtrate obtained by centrifugation into a synthesis kettle in vacuum, starting stirring at the stirring speed of 80 rpm, adding 1500 g of calcium acetate and 720 g of dibutyltin oxide serving as catalysts, heating the synthesis kettle to 170 ℃ in 50 minutes, controlling the temperature of fraction at the top of the tower in stages, and controlling the temperature of fraction at the top of the tower in the first stageAt 64-67 deg.C, the fraction is mainly methanol, and the condensate at the temperature is put into a methanol receiving tank; when the temperature of the overhead fraction is observed to suddenly increase after a certain period of time and the temperature rises rapidly, the methyl ester group (-COOCH) in the system is indicated3) After the exchange with propylene glycol is basically finished, carboxylic acid groups (-COOH) in the system begin to perform esterification reaction with propylene glycol, water is generated as a product, the receiving tank is switched when the temperature of the overhead fraction is higher than 70 ℃, and the condensate is switched from the methanol receiving tank to the moisture receiving tank.
And after the switching is finished, adjusting the stirring speed to 130 r/min, raising the temperature of the synthesis kettle to 190 ℃ within 30 minutes, adding 360 g of catalyst cobalt acetate and 180 g of ether inhibitor sodium acetate, observing the change condition of the temperature of the overhead fraction, suddenly reducing the temperature of the overhead fraction after the temperature of the overhead fraction is stable for a period of time at 100 ℃, and simultaneously measuring the total amount of methanol in the methanol receiving tank and water in the water receiving tank to 37.9 kg, indicating that the esterification is about to finish, and continuing to react for 35 minutes. And cooling the obtained SIPE solution to 31 ℃. Sampling, and analyzing the purity of SIPE by liquid chromatography.
And (3) analysis results: the SIPE content in the solution is 40.18%, and the detection results of other indexes are shown in the following table 7.
TABLE 7
Unless otherwise specified, the proportions used in the present invention are mass proportions, and the percentages used are mass percentages.
Claims (1)
1. A method for synthesizing water-soluble polyester by a composite and concerted catalysis method is characterized in that: the method comprises esterification, feeding, pre-polycondensation and post-polycondensation;
performing esterification, namely adding ethylene glycol, terephthalic acid, polyethylene glycol, ethylene glycol adipate and a catalyst cobalt acetate;
the mass of the ethylene glycol is 50-55% of that of the terephthalic acid; the mass of the polyethylene glycol is 8.2-10.4% of that of the terephthalic acid; the mass of the adipic acid glycol ester is 5.7-7.1% of that of the terephthalic acid; the mass of the cobalt acetate is 0.002-0.0037 percent of that of the terephthalic acid;
the material is added, the temperature of the material obtained after esterification is reduced to 220-225 ℃, and SIPE solution, titanium glycol, sodium acetate and trimethyl phosphate are added;
the mass of the SIPE solution is 16.5-18.75% of that of the terephthalic acid; the mass of the ethylene glycol titanium is 0.025-0.038% of that of the terephthalic acid; the mass of the sodium acetate is 0.05-0.07% of that of the terephthalic acid; the mass of the trimethyl phosphate is 0.006-0.0075% of that of the terephthalic acid;
the pre-polycondensation is carried out at the reaction temperature of 230-235 ℃; the absolute pressure in the kettle is 500-600Pa, and the reaction is kept for 45-60 minutes;
the post-polycondensation is carried out at the reaction temperature of 245-260 ℃ and the absolute pressure in the kettle of 50-100 Pa;
the esterification is carried out at the reaction temperature of 230 ℃ and 240 ℃ for 150 minutes and 200 minutes;
after-polycondensation, when the power of the motor is observed to be 20% higher than that in normal operation, the stirring speed is reduced, and the viscosity of the materials in the polycondensation kettle is sampled and analyzed to be higher than 0.350dl/g, stirring is continued for 10-20 minutes, and the reaction is finished;
the SIPE solution with the content of 40.04-40.21%; the saponification value is 126.11-126.65 mgKOH/g, the acid value is 0.38-0.62 mgKOH/g, the iron content is 1.6-4.6ppm, the water content is 0.24-0.47%, and the sulfate radical content is 156.48-231.47 ppm.
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