CN109336791B - Method for producing m-phthalic acid diethylene glycol ester-5-sodium sulfonate by using three-monomer process wastewater concentrated material - Google Patents
Method for producing m-phthalic acid diethylene glycol ester-5-sodium sulfonate by using three-monomer process wastewater concentrated material Download PDFInfo
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Abstract
The invention provides a method for producing diethylene glycol isophthalate-5-sodium Sulfonate (SIPE) by using a three-monomer process wastewater concentrate, which is characterized by comprising the following steps of: the method comprises the steps of dissolving, filtering and SIPE synthesizing. The SIPE solution prepared by the invention has low sulfate radical content, wherein the sulfate radical content is 156.48-231.47 ppm; the SIPE solution prepared by the invention has good appearance, high purity and low impurity content; the appearance is yellowish transparent liquid, the purity is 94.33-95.1% (liquid chromatogram), and the DEG content is 0.12-0.28%. The reaction temperature of the invention is low, the reaction temperature of the first stage and the second stage is respectively 170-180 ℃ and 185-195 ℃, and the synthesis reaction time is 4.8-5.2 h.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and relates to a method for producing m-phthalic acid diethylene glycol ester-5-sodium sulfonate by using a three-monomer process wastewater concentrated material.
Background
Although the polyester fiber has the advantages of high modulus, good rigidity, good elasticity, high strength, water resistance, light resistance, good shape retention, difficult wrinkling and the like, because the polyester macromolecule lacks functional groups capable of being combined with direct dyes, acid dyes, basic dyes and the like, although the polyester fiber has ester groups capable of forming hydrogen bonds with disperse dyes, the crystallinity of the polyester fiber is high, the structure is compact, dye molecules are not easy to enter the fiber, and the dyeing is difficult and the color is monotonous. Therefore, a strongly acidic sulfonic acid group compound and polyester (PET for short) can be copolymerized, so that good cationic dyeable Copolyester (CDP) can be obtained. The melting point of the cation terylene prepared by the copolymerization of the isophthalic acid diethylene glycol ester-5-sodium sulfonate (SIPE for short in English) is lower than that of the common terylene, and the crystallinity of the cation terylene is lower than that of the common terylene, so that dye molecules are easy to permeate, the fiber is easy to dye, the color absorption rate is improved, and the moisture absorption is also improved. The cationic polyester not only ensures easy dyeing of the cations, but also can increase micropores of the fibers, improve the dyeing rate, air permeability and moisture absorption of the fibers, thereby further adapting to the simulated filamentation of the polyester fibers; the fabric is soft, breathable, comfortable, antistatic, anti-pilling and dyeable at normal temperature and normal pressure through silk simulation; a fabric woven from cationically modified fibers which, when dyed with a cationic dye, has the following characteristics: bright color tone and good deep dyeing property; the exhaustion rate is high; the fastness to sunlight and the fastness to smoke fading are good; when color matching and dyeing are carried out, the dye compatibility is good; in a high-temperature dye bath, the product is stable; the soiling property to other fibers including ordinary polyester fibers is small; the diffusion rate to the interior of the fiber is high, and the ring dyeing phenomenon is avoided; when the pH value in the dye bath changes, the stability of the dye is high. The fabric can be comparable to natural fabric in the aspects of wearing comfort, dyeing vividness and the like, is lower than natural real silk in price and can generate high added value. The apparent viscosity of the modified PET is reduced along with the increase of the shear rate, belongs to non-Newtonian fluid, but the rheological property of the non-Newtonian fluid is poor; the rheological property of the modified PET is improved by adding a fourth monomer polyethylene glycol (PEG); with the increase of the addition amount of the SIPE of the third monomer, the dye uptake of the modified PET fiber to the cationic dye is increased, and after the fourth monomer is added, the dye uptake and the final dye uptake are improved. Therefore, research on the synthesis process of the modifier SIPE increasingly draws high attention and attention of scientific researchers.
The prior SIPE in China and the similar research results thereof mainly comprise:
a method for preparing SIPE by ester exchange reaction at a certain temperature and under the condition of a catalyst by using dimethyl isophthalate-5-sodium Sulfonate (SIPM) and Ethylene Glycol (EG) as raw materials is provided by a paper synthesis research of dihydroxy ethyl isophthalate-5-sodium sulfonate published in the first period 26-29 of 2005 in the chemical world of Shanghai university, Zhang Jianqiu and the like;
chinese patent (publication No. CN 200710008698.1) discloses a method for preparing SIPE by directly esterifying isophthalic acid-5-Sulfonate (SIPA) and EG as raw materials, wherein the esterification rate is more than 99 percent, the acid value is less than 1(mgKOH/g), and the content of diethylene glycol (DEG) is less than 2.0 percent;
wangxihua published in polyester industry, 2006, 19-21, pp.04, thesis "optimization and quality control of SIPE solution preparation Process" adopts a method of synthesizing SIPE by ester exchange of dimethyl isophthalate-5-sodium sulfonate and ethylene glycol in the presence of a catalyst and an ether inhibitor;
jiangli, Suo sweet, leaf brocade, Sichuan university, published in "coating industry" 2012, 11 th year, a paper "Synthesis and research of novel sulfonic acid type waterborne polyurethane" proposes a process for synthesizing SIPE by using SIPM and ethylene glycol with zinc acetate as a catalyst;
marly reviewed several SIPE synthesis methods in a Master thesis (12 months in 2013) of Beijing clothing academy of academic, Peking, research on synthesizing cationic dyeable polyester by adding SIPA, and most SIPE is synthesized by taking SIPM as a starting material;
liu Yan Li, Shenfu, Zhu Wei, etc., available from Tung Kun group Ltd, published in synthetic fiber 2017, 03, discussing SIPE production conditions by ester exchange of SIPE and EG, and discussing and analyzing various index conditions of SIPE-EG solution produced under production conditions.
The synthesis of the SIPE in China mainly comprises two process routes, wherein firstly, dimethyl isophthalate-5-sodium sulfonate reacts with glycol in the presence of a catalyst; one is the reaction of 5-sodium sulfoisophthalate with ethylene glycol in the presence of a catalyst.
The subsequent utilization and treatment of the solid concentrate produced by the wastewater treatment of the existing tri-monomer production process are a great problem in the tri-monomer industry, and the solid concentrate has complex components, mainly contains sodium sulfate, tri-monomer homologues, water and the like.
The production of the modifier SIPE by using the three-monomer process wastewater concentrate is not reported at home and abroad, and the production of the SIPE by using the three-monomer process wastewater concentrate has the following technical problems to be solved urgently in the field:
(1) the concentrated solid material of the three-monomer wastewater has complex components and contains a certain amount of sodium sulfate, so that the prepared SIPE has high sulfate ion content, and the appearance and quality of the SIPE and the synthesized polyester are influenced by the high sulfate ion content; and the yarn breakage rate of the polyester finished product during spinning, the blockage of a precision filter during spinning and the cleaning and replacing period length can be further influenced.
(2) The components of the three-monomer wastewater concentrate are complex, esterification and ester exchange reactions occur simultaneously when the three-monomer wastewater concentrate reacts with ethylene glycol to prepare SIPE, and the reaction temperature and the reaction time have great influence on indexes such as product quality and purity. The reaction temperature is high, the reaction speed is high, but the reaction temperature is too high, so that the prepared SIPE solution has dark color and high DEG content of byproducts, and the internal quality of the product, such as appearance, purity, impurity content and the like, and the later application are influenced; if the reaction temperature is low, the reaction speed is slow, even the target product cannot be obtained, and sometimes the target product cannot be obtained even if the reaction time is long in the low-temperature reaction; if the reaction time is long at high temperature, more side reactions are caused, and the product quality is also affected.
The technical problem to be solved is how to reduce the reaction temperature and shorten the reaction time while ensuring that the product appearance meets the requirements, improving the product purity and reducing the impurity content.
(3) SIPE solution prepared by the prior art has poor stability, solid is easy to precipitate, and quality indexes are easy to change.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a method for producing m-phthalic acid diethylene glycol-5-sodium sulfonate by using a wastewater concentrate of a three-monomer process, which combines the molecular structure and content of a three-monomer homolog and the mechanism of reaction with ethylene glycol, and deeply researches the selection and the dosage of a catalyst, the quality requirement of reaction raw materials, the material ratio, the reaction temperature and temperature control, the determination of a reaction end point and the like to form a complete SIPE synthesis process, wherein the invention aims to:
(1) reducing the sulfate radical content of the SIPE product;
(2) the prepared SIPE has good appearance, high purity and low impurity content;
(3) the reaction temperature is reduced, and the reaction time is shortened;
(4) improving the stability of the SIPE solution.
In order to realize the purpose, the invention adopts the following technical scheme:
a method for producing m-phthalic acid diethylene glycol ester-5-sodium sulfonate by using a three-monomer process wastewater concentrated material comprises the steps of dissolving, filtering and SIPE (styrene-isoprene-ethylene-propylene-diene) synthesis.
Dissolving, filtering, adding ethylene glycol, adding the dried tri-monomer production wastewater concentrated material, heating to 85-95 ℃, keeping the temperature and stirring for 60-80 minutes at the temperature, and centrifuging; the obtained filtrate is used for synthesizing SIPE, and sodium sulfate obtained by filter cloth is recycled.
The weight ratio of the glycol to the dried tri-monomer production wastewater concentrate is 1.45-1.52: 1.
the dried tri-monomer production wastewater concentrated material has the water content of less than 0.2 percent, the content of dimethyl isophthalate-5-sodium sulfonate of 26.45 to 30.02 percent, the content of monomethyl isophthalate-5-sodium sulfonate of 7.35 to 9.94 percent and the content of isophthalic acid-5-sodium sulfonate of 22.64 to 25.77 percent.
The SIPE synthesis comprises a first-stage reaction; in the first-stage reaction, catalysts of calcium acetate and dibutyltin oxide are added, and the temperature of the synthesis kettle is raised to 170-180 ℃ within 50-60 minutes.
The mass of the calcium acetate is 0.25-0.5% of that of the ethylene glycol; the mass of the dibutyltin oxide is 0.08-0.18% of that of the ethylene glycol.
The SIPE synthesis comprises a second stage reaction; the second stage reaction comprises adding a catalyst; adding a catalyst, adjusting the stirring speed to be 115-125 r/min, heating the temperature of the synthesis kettle to be 188 ℃ at 180-25 min, and adding the catalyst cobalt acetate and the ether inhibitor sodium acetate.
The mass of the cobalt acetate is 0.055-0.075% of the mass of the glycol; the mass of the sodium acetate is 0.02-0.04% of that of the ethylene glycol.
The second stage reaction comprises determining a reaction end point; when the temperature of the overhead fraction is observed to suddenly drop after being stabilized at 100 ℃ for a period of time (generally 15-30 minutes), the total amount of the methanol amount in the methanol receiving tank and the water amount in the water receiving tank is measured to reach more than 95% of the theoretical calculated value, which indicates that the reaction is about to end, and the reaction is continued for 30-40 minutes.
The second stage reaction comprises temperature reduction; and cooling the obtained SIPE solution to below 35 ℃.
In the first-stage reaction, the temperature of the fraction at the top of the tower is controlled to be 64-67 ℃, the fraction is mainly methanol, and the condensate at the temperature is placed 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) Has been substantially transesterified with ethylene glycol, the carboxylic acid group (-COOH) in the system has begun to undergo esterification with ethylene glycolAnd when the product has water, switching the receiving tank when the temperature of the overhead fraction is higher than 70 ℃, and switching the condensate from the methanol receiving tank to the moisture receiving tank. And after the switching is finished, carrying out the second stage reaction.
And (3) recovering the sodium sulfate, wherein the weight ratio of the sodium sulfate obtained by methanol to the filter cloth is 1.1-1.3: 1, adding methanol into a dissolving kettle, starting stirring, adding sodium sulfate obtained by centrifugation, stirring for 30-40 minutes, and performing filter pressing. And drying the solid sodium sulfate to obtain the industrial sodium sulfate meeting the national standard (national standard GB/T6009-2014).
Sending the filtrate containing methanol and ethylene glycol to a distillation still, heating, intercepting the fraction (the main component is methanol) with the gas phase temperature of 64-66.5 ℃, and recycling; the main component of the tower bottom is glycol which is returned to the production system and used for dissolving the dried concentrated material.
The invention has the following beneficial effects:
(1) the SIPE solution prepared by the invention has low sulfate radical content, and the sulfate radical content is 156.48-231.47 ppm.
(2) The SIPE solution prepared by the invention has good appearance, high purity and low impurity content; the appearance is yellowish transparent liquid, the purity is 94.33-95.1% (liquid chromatogram), and the DEG content is 0.12-0.28%.
(3) The reaction temperature is low, and the reaction temperature in the first stage and the second stage is respectively 170-,
185 ℃ and 195 ℃, and the synthesis reaction time is 4.8-5.2 h.
(4) After the SIPE solution prepared by the invention is placed for one year, three indexes are analyzed, the purity in ethylene glycol is not lower than 39.6%, the saponification value is not lower than 124.7 mgKOH/g, the acid value is not higher than 0.8mgKOH/g, and the stability is good.
(5) The SIPE solution prepared by the invention has 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, and the water content is 0.24-0.47%; the yield was 74.92-77.5%.
Detailed Description
Definition of SIPE yield in examples: the obtained SIPE accounts for the percentage of the input dried concentrate with water content less than 0.2%.
Calculation of SIPE purity: and analyzing the product by liquid chromatography, deducting the area of the peak of the glycol solvent and the area of the peak of the solvent in the mobile phase, and dividing the area of the peak of the SIPE by the total area to obtain the purity of the SIPE.
Example 1 method for producing diethylene glycol isophthalate-5-sulfonate from concentrated wastewater from a three-monomer process
1. Dissolving and filtering
Adding 600 kg of ethylene glycol into a dissolving kettle, starting stirring, adding 400 kg of dried tri-monomer production wastewater 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 SIPE;
in the dried tri-monomer production wastewater concentrated material, the water content is lower than 0.2 percent, the content of dimethyl isophthalate-5-sodium sulfonate is 30.02 percent, the content of monomethyl isophthalate-5-sodium sulfonate is 7.35 percent, and the content of isophthalic acid-5-sodium sulfonate is 22.64 percent: the balance of sodium sulfate and a small amount of mechanical impurities.
2. Recovery treatment of sodium sulfate
Adding 250 kg of methanol into a dissolving kettle, starting stirring, adding 208 kg of sodium sulfate obtained by centrifugation, stirring for 35 minutes, and performing pressure filtration. And drying the solid sodium sulfate to obtain the industrial sodium sulfate meeting the national standard (national standard GB/T6009-2014).
Sending the filtrate containing methanol and ethylene glycol to a distillation still, heating, intercepting the fraction (the main component is methanol) with the gas phase temperature of 64-66.5 ℃, and recycling; the main component of the tower bottom is glycol which is returned to the production system and used for dissolving the dried concentrated material.
3. SIPE Synthesis
(1) First stage reaction
Vacuum sucking the filtrate into the synthesis kettle, and openingStirring at the stirring speed of 80 rpm, adding 1500 g of catalyst calcium acetate and 720 g of dibutyltin oxide, heating the synthesis kettle to 170 ℃ in 50 minutes, controlling the temperature of the overhead fraction in stages, controlling the temperature of the overhead fraction to 64-67 ℃ in the first stage, wherein the fraction is mainly methanol, and putting condensate at the temperature 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 glycol ester exchange is basically finished, carboxylic acid groups (-COOH) in the system begin to perform esterification reaction with 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.
(2) Second stage reaction
A. Adding a catalyst
After the switching is finished, the stirring speed is adjusted to 130 r/min, the temperature of the synthesis kettle is raised to 188 ℃ within 30 minutes, and 360 g of catalyst cobalt acetate and 180 g of ether inhibitor sodium acetate are added.
B. Determination of the end of the reaction
Note that a change in the temperature of the overhead fraction was observed, and when a sudden drop in the temperature of the overhead fraction after a period of stabilization at 100 ℃ was observed while the total amount of methanol in the methanol receiver tank and water in the water receiver tank was measured to reach 43.8 kg, it was indicated that esterification was about to be completed, and the reaction was continued for 35 minutes.
(3) Temperature reduction
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 1.
TABLE 1
The SIPE yield is: 77.45 percent; the time of SIPE synthesis reaction (from the time when the dried concentrated material is dissolved by using ethylene glycol and the filtrate of sodium sulfate is filtered out is added into the synthesis kettle to the time when the temperature of the ethylene glycol solution of SIPE is reduced) is 5 hours; the purity of SIPE was (analyzed by liquid chromatography): 94.88 percent.
Example 2 method for producing diethylene glycol isophthalate-5-sulfonate from concentrated wastewater from a three-monomer process
The process operating parameters were the same as in example 1, except that:
2. recovery treatment of sodium sulfate
Adding 245 kg of methanol into a dissolving kettle, starting stirring, adding 211 kg of sodium sulfate obtained by centrifugation, and performing the same operation;
3. SIPE Synthesis
The adding amount of the catalyst is changed into 3000 g of calcium acetate, 480 g of dibutyltin oxide and 330 g of cobalt acetate, the adding amount of the ether inhibitor is changed into 240 g of sodium acetate, and the rest operations are the same;
and (3) judging the reaction end point: when the total amount of methanol in the methanol receiver tank and water in the water receiver tank reached 43.9 kg, the esterification was about to end.
And (3) analysis results: the SIPE content in the solution is 40.16%, and the detection results of other indexes are shown in Table 2 below.
TABLE 2
The SIPE yield is: 77.19 percent; the time of SIPE synthesis reaction (from the time when the dried concentrated material is dissolved by using the ethylene glycol and the filtrate for filtering sodium sulfate is added into the synthesis kettle to the time when the temperature of the ethylene glycol solution of the SIPE is reduced to be finished) is 5.2 hours: the purity of SIPE was (analyzed by liquid chromatography): 94.59 percent.
Example 3 method for producing diethylene glycol isophthalate-5-sulfonate from concentrated wastewater from a three-monomer process
1. Dissolving and filtering
550 kg of ethylene glycol is added into a dissolving kettle, stirring is started, 370 kg of dried tri-monomer production wastewater concentrated material is added into the kettle, steam is introduced into a jacket of the dissolving kettle after the concentrated material is added, the kettle is heated to 90 ℃ within 25 minutes, and the kettle is kept at the temperature and stirred for 65 minutes. 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 SIPE;
the water content of the dried tri-monomer production wastewater concentrate of the batch is lower than 0.2 percent, the content of dimethyl isophthalate-5-sodium sulfonate is 28.33 percent, the content of monomethyl isophthalate-5-sodium sulfonate is 9.94 percent, and the content of isophthalic acid-5-sodium sulfonate is 23.05 percent: the balance of sodium sulfate and a small amount of mechanical impurities.
2. Recovery treatment of sodium sulfate
Adding 230 kg of methanol into a dissolving kettle, starting stirring, adding 192 kg of sodium sulfate obtained by centrifugation, stirring for 35 minutes, and performing pressure filtration. And drying the solid sodium sulfate to obtain the industrial sodium sulfate meeting the national standard (national standard GB/T6009-2014).
Sending the filtrate containing methanol and ethylene glycol to a distillation still, heating, intercepting the fraction (the main component is methanol) with the gas phase temperature of 64-66.5 ℃, and recycling; the main component of the tower bottom is glycol which is returned to the production system and used for dissolving the dried concentrated material.
3. SIPE Synthesis
(1) First stage reaction
Sucking the filtrate obtained by centrifugation into a synthesis kettle in vacuum, starting stirring at the stirring speed of 80 rpm, adding 1650 g of calcium acetate catalyst and 550 g of dibutyltin oxide catalyst, heating the synthesis kettle to 175 ℃ in 50 minutes, controlling the temperature of fraction at the top of the tower in stages, controlling the temperature of fraction at the top of the tower to 64-67 ℃ in the first stage, wherein the fraction is mainly methanol, and putting the condensate at the temperature 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 of glycol ester is basically completed, carboxylic acid group (-COOH) in the system begins to perform esterification reaction with glycol, water is generated as product, at this time, the receiving tank is switched, and when the temperature of overhead fraction is higher than 70 deg.C, the receiving tank is switchedAnd switching the condensate from the methanol receiving tank to the moisture receiving tank.
(2) Second stage reaction
A. Adding a catalyst
After the switching is finished, the stirring speed is adjusted to 130 r/min, the temperature of the synthesis kettle is raised to 185 ℃ within 20 minutes, and 385 g of catalyst cobalt acetate and 110 g of ether inhibitor sodium acetate are added.
B. Determination of the end of the reaction
Note that a change in the temperature of the overhead fraction was observed, and when a sudden drop in the temperature of the overhead fraction after a period of stabilization at 100 ℃ was observed while the total amount of methanol in the methanol receiver tank and water in the water receiver tank was measured to 38.6 kg, it was indicated that esterification was about to be completed, and the reaction was continued for 35 minutes.
(3) Temperature reduction
And cooling the obtained SIPE solution to 30 ℃, sampling, and analyzing the purity of the SIPE by adopting a liquid chromatography.
And (3) analysis results: the SIPE content in the solution is 40.04%, and the detection results of other indexes are shown in Table 3 below.
TABLE 3
The SIPE yield is: 75.55 percent; the time of SIPE synthesis reaction (from the time when the dried concentrated material is dissolved by using the ethylene glycol and the filtrate for filtering sodium sulfate is added into the synthesis kettle to the time when the temperature of the ethylene glycol solution of the SIPE is reduced to be finished) is 4.8 hours: the purity of SIPE was (analyzed by liquid chromatography): 94.33 percent.
Example 4 method for producing diethylene glycol isophthalate-5-sulfonate from concentrated wastewater from a three-monomer process
The process operating parameters were the same as in example 3, except that:
2. recovery treatment of sodium sulfate
Adding 230 kg of methanol into a dissolving kettle, starting stirring, adding 197 kg of sodium sulfate obtained by centrifugation, and performing the same operation;
3. SIPE Synthesis
The adding amount of the catalyst is changed into 2500 g of calcium acetate, 440 g of dibutyltin oxide and 360 g of cobalt acetate, the adding amount of the ether inhibitor is changed into 162 g of sodium acetate, and the rest operations are the same;
and (3) judging the reaction end point: the end of esterification was indicated when the total amount of methanol and water in the methanol receiver tank was measured to 38.7 kg.
And (3) analysis results: the SIPE content in the solution is 40.15%, and the detection results of other indexes are shown in Table 4 below.
TABLE 4
The SIPE yield is: 74.92 percent; the time of SIPE synthesis reaction (from the time when the dried concentrated material is dissolved by using the ethylene glycol and the filtrate for filtering sodium sulfate is added into the synthesis kettle to the time when the temperature of the ethylene glycol solution of the SIPE is reduced to be finished) is 5 hours: the purity of SIPE was (analyzed by liquid chromatography): 94.85 percent.
Example 5 method for producing diethylene glycol isophthalate-5-sulfonate from concentrated wastewater from a three-monomer process
1. Dissolving and filtering
Adding 500 kg of ethylene glycol into a dissolving kettle, starting stirring, adding 335 kg of dried tri-monomer production wastewater 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 SIPE; dissolving the dried concentrated material with ethylene glycol, and adding the filtrate into a synthesis kettle.
In the dried tri-monomer production wastewater concentrate of the batch, the water content is lower than 0.2 percent, the content of dimethyl isophthalate-5-sodium sulfonate is 26.45 percent, the content of monomethyl isophthalate-5-sodium sulfonate is 9.26 percent, and the content of isophthalic acid-5-sodium sulfonate is 25.77 percent: the balance being sodium sulfate, small amounts of mechanical impurities).
2. Recovery treatment of sodium sulfate
Adding 210 kg of methanol into a dissolving kettle, starting stirring, adding 175 kg of sodium sulfate obtained by centrifugation, stirring for 35 minutes, and performing pressure filtration. And drying the solid sodium sulfate to obtain the industrial sodium sulfate meeting the national standard (national standard GB/T6009-2014).
Sending the filtrate containing methanol and ethylene glycol to a distillation still, heating, intercepting the fraction (the main component is methanol) with the gas phase temperature of 64-66.5 ℃, and recycling; the main component of the tower bottom is glycol which is returned to the production system and used for dissolving the dried concentrated material.
3. SIPE Synthesis
(1) First stage reaction
Sucking the filtrate obtained by centrifugation into a synthesis kettle in vacuum, starting stirring at the stirring speed of 80 rpm, adding 2000 g of catalyst calcium acetate and 400 g of dibutyltin oxide, heating the synthesis kettle to 175 ℃ in 55 minutes, controlling the temperature of fraction at the top of the tower in stages, controlling the temperature of fraction at the top of the tower to 64-67 ℃ in the first stage, wherein the fraction is mainly methanol, and putting the condensate at the temperature 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 glycol ester exchange is basically finished, carboxylic acid groups (-COOH) in the system begin to perform esterification reaction with 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.
(2) Second stage reaction
A. Adding a catalyst
After the switching is finished, the stirring speed is adjusted to 130 r/min, the temperature of the synthesis kettle is raised to 182 ℃ within 25 minutes, and 375 g of cobalt acetate as a catalyst and 200 g of sodium acetate as an ether inhibitor are added.
B. Determination of the end of the reaction
Note that a change in the temperature of the overhead fraction was observed, and when a sudden drop in the temperature of the overhead fraction after a period of stabilization at 100 ℃ was observed while the total amount of methanol in the methanol receiver tank and water in the water receiver tank was measured to 34.5 kg, it was indicated that esterification was about to be completed, and the reaction was continued for 35 minutes.
(3) Temperature reduction
And cooling the obtained SIPE solution to 33 ℃, sampling, and analyzing the purity of the SIPE by adopting a liquid chromatography.
And (3) analysis results: the SIPE content in the solution is 40.21%, and the detection results of other indexes are shown in Table 5 below.
TABLE 5
| Water content is less than or equal to | 0.5 | 0.26 |
SIPE yield: 75.92 percent; the time of SIPE synthesis reaction (from the time when the dried concentrated material is dissolved by using the ethylene glycol and the sodium sulfate is filtered out of the filtrate is added into the synthesis kettle to the time when the temperature of the ethylene glycol solution of the SIPE is reduced to the end) is 4.9 hours: the purity of SIPE was (analyzed by liquid chromatography): 95.05 percent.
Example 6 method for producing diethylene glycol isophthalate-5-sulfonate from concentrated wastewater from a three-monomer process
The process operating parameters were the same as in example 5, except that:
2. recovery treatment of sodium sulfate
Adding 210 kg of methanol into a dissolving kettle, starting stirring, adding 168 kg of sodium sulfate obtained by centrifugation, and performing the same operation;
3. SIPE Synthesis
The adding amount of the catalyst is changed into 1500 g of calcium acetate, 900 g of dibutyltin oxide and 300 g of cobalt acetate, the adding amount of the ether inhibitor is changed into 150 g of sodium acetate, and the rest operations are the same;
and (3) judging the reaction end point: the end of esterification was indicated when the total amount of methanol and water in the methanol receiver tank was measured to 34.7 kg.
And (3) analysis results: the SIPE content in the solution is 40.12%, and the detection results of other indexes are shown in Table 6 below.
TABLE 6
The SIPE yield is: 76.12 percent; the time of SIPE synthesis reaction (from the time when the dried concentrated material is dissolved by using the ethylene glycol and the sodium sulfate is filtered out of the filtrate is added into the synthesis kettle to the time when the temperature of the ethylene glycol solution of the SIPE is reduced to the end) is 5.1 hours: the purity of SIPE was (analyzed by liquid chromatography): 94.87 percent.
The synthesis principle of the invention is as follows:
the three-monomer homologues in the concentrated material mainly comprise SIPM, sodium monomethyl isophthalate-5-sulfonate and SIPA. When reacting with ethylene glycol, SIPM and ethylene glycol produce ester exchange reaction to produce SIPE and methanol, SIPA and ethylene glycol produce esterification reaction to produce SIPE and water, and the molecular structure of the m-phthalic acid monomethyl ester-5-sodium sulfonate has a carboxyl group (-COOH), a monomethyl ester group (-COOCH)3) When the compound reacts with glycol, the carboxyl group generates water, the monomethyl ester group generates methanol, and SIPE is finally generated.
In particular ethylene glycol with sodium monomethyl isophthalate-5-sulphonate, the ethylene glycol progressively replaces the carboxyl group (-COOH) or a monomethyl group (-COOCH)3) One of the two generates a target product SIPE, and the generation of 1-carboxyl-3-monoethylene glycol ester-5-sodium sulfonate and 1-monomethyl ester-3-monoethylene glycol ester-5-sodium sulfonate cannot be avoided in the synthesis.
The generated SIPE generates self-polymerization reaction under certain conditions to generate products with different polymerization degrees, such as SIPE dimer, trimer and the like.
The selection of the process operation parameters and the influence on the SIPE synthesis and quality
1. Selection of catalysts
The three monomer homologues in the concentrate mainly comprise SIPM, monomethyl isophthalate-5-sodium sulfonate and SIPA, when they are reacted with glycol, they can simultaneously produce ester exchange reaction and esterification reaction, i.e. when the three monomer series organic substances of dimethyl isophthalate-5-sodium sulfonate, monomethyl isophthalate-5-sodium sulfonate and isophthalic acid-5-sodium sulfonate are reacted with glycol to prepare SIPE, the dimethyl isophthalate-5-sodium sulfonate and glycol produce ester exchange reaction to produce SIPE and methanol, the dimethyl isophthalate-5-sodium sulfonate and glycol produce esterification reaction to produce SIPE and water, and the monomethyl isophthalate-5-sodium sulfonate molecule simultaneously has carboxyl group (-COOH) and monomethyl ester group (-COOCH)3) When reacting with ethylene glycol, ester exchange and esterification reaction occur simultaneously, carboxyl group generates water, and monomethyl group generates methanol. The choice of catalyst is particularly important because of the different reaction temperatures of the transesterification and esterification reactions.
For an ester exchange catalyst, acetate of manganese, magnesium, calcium, cobalt and lithium is frequently used, the reaction activity of the catalyst and the influence on the quality of a final product are comprehensively considered, three components of two acetate of calcium acetate and cobalt acetate and dibutyltin oxide are selected as the catalyst, and the dibutyltin oxide and the two acetate act synergistically, so that the esterification reaction speed is accelerated, the esterification efficiency is effectively improved, and the yield and the purity of SIPE are improved.
2. Determination of reaction temperature and reaction time
The reaction aims at promoting the reaction of SIPM, sodium monomethyl isophthalate-5-sulfonate and SIPA in the trimonomer homologues and ethylene glycol to completely generate SIPE, simultaneously reducing the etherification of EG to generate DEG and reducing the polymerization of SIPE. In experiments, the reaction speed is higher when the reaction temperature is higher, but the reaction temperature is not high enough, so that the prepared SIPE solution has dark color and high DEG content of byproducts.
Because the product of the ester exchange reaction is methanol and the esterification product is water, the difference between the boiling points of the two products is large, the two products are difficult to completely separate when the reaction is carried out at the same reaction temperature, and the existence of moisture also influences the catalytic activity of the catalyst calcium acetate.
The invention controls the temperature by stages, adds the catalyst by two times, can fully utilize the heat emitted by the reaction, reduces the using amount of the heating medium and the heating time, and has obvious energy-saving effect; the reaction is stable, and side reactions such as excessive polymerization, oxidation, coking and the like of SIPE caused by local overheating are avoided;
in the first stage, the reaction is carried out at a lower temperature, and calcium acetate and dibutyltin oxide are added, so that the reaction speed of ester exchange is mainly accelerated; in the second stage, the temperature is increased, and simultaneously, the catalyst cobalt acetate is added to accelerate the reaction of the groups which are not subjected to the ester exchange reaction and promote the esterification reaction, so that the components with different molecular structures of the three monomers in the reaction system can react with the ethylene glycol more fully.
The reaction temperature of the two stages is lower than the operation temperature of the prior art, the generation amount of SIPE dimer and trimer is reduced, and the regularity of the molecular structure and the uniformity of block distribution are improved for the subsequent production of cation dyeable modified polyester;
3. selection of additives for inhibiting diethylene glycol (DEG), referred to as anti-ethering agents
Ester exchange and esterification reactions occur simultaneously in SIPE synthesis, and on one hand, the reaction of EG etherification to generate DEG inevitably occurs due to higher reaction temperature; on the one hand, due to sulfonic acid groups (-SO)3-) will react with PTA in the polycondensation reaction system to generate strong acid ions, which will catalyze EG to generate DEG. And the spinning performance of the prepared slices and the service performance of the prepared water-soluble polyester are seriously influenced by the excessive content of DEG in the SIPE or the product. For this purpose, an ether inhibitor must be added to reduce the formation of DEG. Sodium acetate CH is generally selected3COONa is an ether inhibitor, and the action mechanism of the ether inhibitor is as follows: sodium acetate and sodium sulfonate group (-SO)3Na) produces a homoionic effect of polar salts, whose equation for producing a homoionic effect is as follows:
side reaction-SO3Na + CH3COOH → -SO3H + CH3COONa
Inhibition of the reaction-SO3H + CH3COONa → -SO3Na + CH3COOH
By adding small amounts of CH3COONa reduces sulfonic acid groups (-SO)3-) generation.
4. Determination of the end-point of the reaction
Because three substances with different structures in the raw materials used for synthesis react with EG and simultaneously have ester exchange and esterification reactions, if the reaction end point is not controlled properly, the indexes of the final product SIPE, such as saponification value, DEG content and the like, can be influenced by the amount of distilled methanol and the amount of distilled water which are too much or too little. According to a plurality of experiments, the amount of distilled methanol and the amount of distilled water exceed the theoretical calculated value by more than 95 percent, which is reasonable.
Claims (2)
1. A method for producing m-phthalic acid diethylene glycol ester-5-sodium sulfonate by using a three-monomer process wastewater concentrate is characterized by comprising the following steps: the method comprises the steps of dissolving, filtering and SIPE synthesizing;
the SIPE synthesis comprises a first-stage reaction; in the first-stage reaction, catalysts of calcium acetate and dibutyltin oxide are added, and the temperature of the synthesis kettle is raised to 170-180 ℃ within 50-60 minutes;
the SIPE synthesis comprises a second stage reaction; the second stage reaction comprises adding a catalyst; adding a catalyst, adjusting the stirring speed to be 115-125 rpm, heating the temperature of the synthesis kettle to be 180-188 ℃ within 15-25 minutes, and adding a catalyst cobalt acetate and an ether inhibitor sodium acetate;
dissolving, filtering, adding ethylene glycol, adding the dried tri-monomer production wastewater concentrated material, heating to 85-95 ℃, keeping the temperature and stirring for 60-80 minutes at the temperature, and centrifuging; the obtained filtrate is used for synthesizing SIPE;
the weight ratio of the glycol to the dried tri-monomer production wastewater concentrate is 1.45-1.52: 1;
the dried tri-monomer production wastewater concentrated material has the water content of less than 0.2 percent, the content of dimethyl isophthalate-5-sodium sulfonate of 26.45 to 30.02 percent, the content of monomethyl isophthalate-5-sodium sulfonate of 7.35 to 9.94 percent and the content of isophthalic acid-5-sodium sulfonate of 22.64 to 25.77 percent;
the mass of the calcium acetate is 0.25-0.5% of that of the ethylene glycol; the mass of the dibutyltin oxide is 0.08-0.18% of that of the ethylene glycol;
the mass of the cobalt acetate is 0.055-0.075% of the mass of the glycol; the mass of the sodium acetate is 0.02-0.04% of that of the ethylene glycol.
2. The method for producing diethylene glycol isophthalate-5-sulfonate by using the tri-monomer process wastewater concentrate according to claim 1, wherein the method comprises the following steps: the second stage reaction comprises determining a reaction end point; and determining the reaction end point, when the temperature of the overhead fraction is observed to suddenly drop after being stabilized at 100 ℃ for a period of time, measuring that the total amount of the methanol quantity in the methanol receiving tank and the water quantity in the water receiving tank reaches more than 95% of a theoretical calculated value, indicating that the reaction is about to end, and continuing to react for 30-40 minutes.
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| CN109535041B (en) * | 2018-11-22 | 2021-08-10 | 青岛中科荣达新材料有限公司 | Method for producing polyester modifier SIPE (styrene-isoprene-styrene) by using composite catalyst |
| CN110252396B (en) * | 2019-06-27 | 2022-03-11 | 山东第一医科大学(山东省医学科学院) | Catalyst used in synthesis process of dimethyl isophthalate-5-sodium sulfonate, preparation method and application |
| CN110305044B (en) * | 2019-06-27 | 2021-09-28 | 山东第一医科大学(山东省医学科学院) | Method for producing dipropylene glycol isophthalate-5-sodium sulfonate by composite catalysis method with SIPA as raw material |
| CN110302793B (en) * | 2019-07-08 | 2022-04-15 | 山东第一医科大学(山东省医学科学院) | Catalyst for synthesizing dimethyl isophthalate-5-sodium sulfonate and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3936389A (en) * | 1973-06-14 | 1976-02-03 | Monsanto Company | Bis glycol ester of sodium sulfo isophthalic acid from its dimethyl ester |
| JPS58157761A (en) * | 1982-03-15 | 1983-09-19 | Teijin Ltd | Preparation of glycol solution of 5-metal sulfoisophthalic acid compound |
| JPH04169566A (en) * | 1990-11-01 | 1992-06-17 | Takemoto Oil & Fat Co Ltd | Production of alkylene glycol solution containing 5-sulfoisophthalic acid alkylene glycol ester metal salt |
| JP2000136178A (en) * | 1998-08-25 | 2000-05-16 | Sanyo Chem Ind Ltd | Production of glycol solution of 5-sulfoisophthalic acid diglycol ester metal salt |
| CN101265218A (en) * | 2007-03-12 | 2008-09-17 | 厦门翔鹭化纤股份有限公司 | Method for preparing SIPE from SIPA by direct esterification method |
| CN107557902A (en) * | 2017-09-07 | 2018-01-09 | 江苏恒科新材料有限公司 | A kind of preparation method of cation dyeable polyester POY silks |
-
2018
- 2018-11-16 CN CN201811368636.6A patent/CN109336791B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3936389A (en) * | 1973-06-14 | 1976-02-03 | Monsanto Company | Bis glycol ester of sodium sulfo isophthalic acid from its dimethyl ester |
| JPS58157761A (en) * | 1982-03-15 | 1983-09-19 | Teijin Ltd | Preparation of glycol solution of 5-metal sulfoisophthalic acid compound |
| JPH04169566A (en) * | 1990-11-01 | 1992-06-17 | Takemoto Oil & Fat Co Ltd | Production of alkylene glycol solution containing 5-sulfoisophthalic acid alkylene glycol ester metal salt |
| JP2000136178A (en) * | 1998-08-25 | 2000-05-16 | Sanyo Chem Ind Ltd | Production of glycol solution of 5-sulfoisophthalic acid diglycol ester metal salt |
| CN101265218A (en) * | 2007-03-12 | 2008-09-17 | 厦门翔鹭化纤股份有限公司 | Method for preparing SIPE from SIPA by direct esterification method |
| CN107557902A (en) * | 2017-09-07 | 2018-01-09 | 江苏恒科新材料有限公司 | A kind of preparation method of cation dyeable polyester POY silks |
Non-Patent Citations (4)
| Title |
|---|
| SIPE的合成研究;左志俊等;《合成技术及应用》;19990930(第03期);第5-9页 * |
| 间苯二甲酸二甲酯磺酸钠生产废水的综合利用;王建成等;《化工环保》;20011030(第05期);第279-281页 * |
| 间苯二甲酸双羟乙酯-5-磺酸钠(SIPE)制备工艺研究;杨崇岭等;《印染助剂》;20120920(第09期);第5-7页 * |
| 间苯二甲酸双羟乙酯-5-磺酸钠的合成研究;余喜理等;《化学世界》;20050125(第01期);第26-29页 * |
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