CN109517154B - Method for preparing isophthalic acid diethylene glycol ester-5-sodium sulfonate modified polyester - Google Patents
Method for preparing isophthalic acid diethylene glycol ester-5-sodium sulfonate modified polyester 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—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
- C08G63/78—Preparation processes
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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
- C08G63/82—Preparation processes characterised by the catalyst used
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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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
- D06P3/36—Material containing ester groups using dispersed dyestuffs
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Abstract
The application relates to a method for preparing a diethylene glycol isophthalate-5-sodium sulfonate modified polyester, which comprises S1, reacting dimethyl isophthalate-5-sodium sulfonate with excessive ethylene glycol under an inert atmosphere in the presence of a catalyst composition to obtain an ethylene glycol solution of diethylene glycol isophthalate-5-sodium sulfonate; and S2: reacting terephthalic acid, ethylene glycol and an ethylene glycol solution of phthalic acid diethylene glycol ester-5-sodium sulfonate to obtain isophthalic acid diethylene glycol ester-5-sodium sulfonate modified polyester; the catalyst composition comprises sodium acetate and calcium acetate, wherein the amount of the sodium acetate is 0.05-0.1% of the amount of the dimethyl isophthalate-5-sodium sulfonate, and the amount of the calcium acetate is 0.15-0.3% of the amount of the dimethyl isophthalate-5-sodium sulfonate. The m-phthalic acid diethylene glycol ester-5-sodium sulfonate modified polyester which has high dyeing rate and good color fastness and can be dyed by using the cationic dye can be prepared.
Description
Technical Field
The present application relates to the field of polyester technology. Specifically, the application relates to a method for preparing isophthalic acid diethylene glycol ester-5-sodium sulfonate modified polyester.
Background
The polyester fiber is a common chemical fiber fabric fiber, and is a synthetic fiber obtained by spinning polyester obtained by polycondensation of organic binary vinegar and dihydric alcohol. The common polyester fiber has the advantages of high breaking strength, high elastic modulus and the like, but because the polyester fiber has a compact structure and lacks groups for absorbing ionic dyes in molecules, the common polyester fiber is difficult to dye. In the case of using a cationic dye and a disperse dye, it is difficult to obtain good color yield and color fastness of the polyester fiber.
The isophthalic acid diethylene glycol ester-5-sodium sulfonate (also called 1, 3-phthalic acid diethylene glycol ester-5-sodium sulfonate, hereinafter abbreviated as SIPE) is a very important chemical raw material, can improve the dyeing property of polyester terylene, and is particularly widely applied in the synthetic process of normal pressure type cationic dye dyeable polyester and high temperature and high pressure type cationic dyeable polyester. Zhang Changhong, a paper "preparation and application of a polyester-modified third monomer solution" ("polyester industry", 2001, Vol.14, No. 1, 42-46) discloses the preparation of sodium diethylene glycol isophthalate-5-sulfonate by transesterification of sodium diethylene glycol isophthalate-5-sulfonate with ethylene glycol, and the subsequent synthesis of polyester using sodium diethylene glycol isophthalate-5-sulfonate as a third monomer. The process has the disadvantages that part of ethylene glycol is required to be added to cool the reaction system to about 230 ℃, and then the ethylene glycol used for cooling is removed by vacuum extraction, which not only increases the complexity of the process, but also causes difficulty in accurately determining the dosage proportion among the polycondensation raw materials of terephthalic acid, ethylene glycol and isophthalic acid diethylene glycol-5-sodium sulfonate.
Therefore, the method for preparing the isophthalic acid diethylene glycol ester-5-sodium sulfonate modified polyester with convenient operation and accurate quantification is still needed to be continuously developed in the field.
Disclosure of Invention
The application aims to provide a method for preparing m-phthalic acid diethylene glycol ester-5-sodium sulfonate modified polyester with high ester exchange rate and accurate quantification, thereby solving the technical problems in the prior art. The process of the present application comprises formulating a glycol solution of diethylene glycol isophthalate-5-sulfonate sodium and using it as a third monomer to prepare a diethylene glycol isophthalate-5-sulfonate sodium modified polyester.
Through repeated experiments, the application surprisingly discovers that the ester exchange rate of the sodium dimethyl isophthalate-5-sulfonate can be obviously improved and the content of diethylene glycol (DEG) in the obtained diethylene glycol isophthalate-5-sulfonate can be reduced by adjusting the type and the amount of the catalyst used in the exchange reaction of the sodium dimethyl isophthalate-5-sulfonate and the ethylene glycol ester.
In addition, the isophthalic acid diethylene glycol ester-5-sodium sulfonate modified polyester is prepared by one-time feeding, and the self-polymerization of ethylene glycol in the temperature rising process is effectively avoided by selecting the type and the using amount of a specific catalyst. And the diethylene glycol isophthalate-5-sodium sulfonate modified polyester which has high dyeing rate and good color fastness and can be dyed by cationic dye can be prepared by controlling the reaction temperature and the vacuum degree in the polycondensation stage.
In order to achieve the above object, the present application provides the following technical solutions.
In a first aspect, the present application provides a process for preparing a sodium diethylene glycol isophthalate-5-sulfonate modified polyester, the process comprising the steps of:
s1, preparing an ethylene glycol solution of isophthalic acid diethylene glycol ester-5-sodium sulfonate;
reacting dimethyl isophthalate-5-sodium sulfonate with excess ethylene glycol in the presence of a catalyst composition at a reaction temperature of less than or equal to 185 ℃ under an inert atmosphere to obtain an ethylene glycol solution of diethylene glycol phthalate-5-sodium sulfonate;
s2: preparing m-phthalic acid diethylene glycol ester-5-sodium sulfonate modified polyester;
reacting terephthalic acid, ethylene glycol, and the ethylene glycol solution of diethylene glycol phthalate-5-sodium sulfonate prepared by step S1 under vacuum conditions and at a temperature of 230 ℃ to 245 ℃ for a first predetermined period of time to obtain a first reaction mixture; then raising the reaction temperature to enable the first reaction mixture to react at the temperature of 265-270 ℃ for a second preset time period to obtain a second reaction mixture; then raising the reaction temperature, and continuously reacting the second reaction mixture at 275 +/-1 ℃ for a third preset time period to obtain the diethylene glycol isophthalate-5-sodium sulfonate modified polyester;
in step S1, the catalyst composition includes sodium acetate and calcium acetate, where the amount of sodium acetate is 0.05% to 0.1% of the amount of dimethyl isophthalate-5-sodium sulfonate, and the amount of calcium acetate is 0.15% to 0.3% of the amount of dimethyl isophthalate-5-sodium sulfonate.
In one embodiment of the first aspect, in step S1, the catalyst composition further comprises nickel acetate, and wherein the nickel acetate is present in an amount of 0.02% to 0.12% by mass based on the amount of sodium dimethyl isophthalate-5-sulfonate.
In one embodiment of the first aspect, in step S1, when adding the catalyst to the reaction mass, all of the calcium acetate and a first portion of the sodium acetate are added, and after the reaction has proceeded for a predetermined period of time, the remaining portion of the sodium acetate and the nickel acetate are added.
In one embodiment of the first aspect, in step S1, the ethylene glycol is used in a ratio greater than 2:1 relative to the sodium dimethyl isophthalate-5-sulfonate on a molar basis.
In one embodiment of the first aspect, in step S1, the reaction temperature is 130 ℃ to 185 ℃.
In one embodiment of the first aspect, in step S1, the ethylene glycol solution of sodium diethylene glycol phthalate-5-sulfonate has a concentration of 20% to 50% by weight.
In one embodiment of the first aspect, in step S1, the ethylene glycol solution of sodium diethylene glycol phthalate-5-sulfonate has a concentration of 36% to 40% by weight.
In one embodiment of the first aspect, in step S2, the first predetermined period of time is 4-12 hours; and/or, the second predetermined period of time is 2-5 hours; and/or, the third time period is 1-4 hours.
In one embodiment of the first aspect, in step S2, the degree of vacuum at which the first reaction mixture is prepared is greater than the degree of vacuum at which the second reaction mixture is prepared, and the degree of vacuum at which the second reaction mixture is prepared is greater than the degree of vacuum at which the third reactant is prepared.
Compared with the prior art, the method has the beneficial effects that the ester exchange rate of the dimethyl isophthalate-5-sodium sulfonate can be obviously improved and the DEG content in the obtained diethylene glycol isophthalate-5-sodium sulfonate can be reduced by adjusting the type and the dosage of the catalyst used in the exchange reaction of the dimethyl isophthalate-5-sodium sulfonate and the ethylene glycol ester. In addition, the temperature and the vacuum degree in the polycondensation process are regulated to prepare the diethylene glycol isophthalate-5-sodium sulfonate modified polyester which has high dyeing rate and good color fastness and can be dyed by cationic dye.
Detailed Description
The terms "comprising," "including," "having," and derivatives thereof do not exclude the presence of any other component, step or procedure, and are not intended to exclude the presence of other elements, steps or procedures not expressly disclosed herein. To the extent that any doubt is eliminated, all compositions herein containing, including, or having the term "comprise" may contain any additional additive, adjuvant, or compound, unless expressly stated otherwise. Rather, the term "consisting essentially of … …" excludes any other components, steps or processes from the scope of any of the terms hereinafter recited, except those necessary for performance. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. Unless explicitly stated otherwise, the term "or" refers to the listed individual members or any combination thereof.
Examples
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. The reagents and raw materials used are commercially available unless otherwise specified.
Preparing ethylene glycol solution of isophthalic acid diethylene glycol ester-5-sodium sulfonate
Example 1
Putting 500kg of dimethyl isophthalate and 1250kg of ethylene glycol into a reaction kettle, starting a stirrer, adding 0.25kg of sodium acetate and 0.75kg of calcium acetate, sealing a feeding port, introducing nitrogen for protection, starting a heater, and heating the materials to 185 ℃ from normal temperature within 2 hours. After about 4 to 6 hours of reaction, the reaction was stopped to obtain a reaction product containing diethylene glycol isophthalate. The reaction product was cooled to below 130 ℃ and characterized for its physicochemical properties, the results are given in table 1 below.
Example 2
Putting 500kg of dimethyl isophthalate and 1250kg of ethylene glycol into a reaction kettle, starting a stirrer, adding 0.5kg of sodium acetate and 1.5kg of calcium acetate, sealing a feeding port, introducing nitrogen for protection, starting a heater, and heating the materials to 185 ℃ from normal temperature within 2 hours. After about 4 to 6 hours of reaction, the reaction was stopped to obtain a reaction product containing diethylene glycol isophthalate. The reaction product was cooled to below 130 ℃ and characterized for its physicochemical properties, the results are given in table 1 below.
Example 3
Putting 500kg of dimethyl isophthalate and 1250kg of ethylene glycol into a reaction kettle, starting a stirrer, adding 0.25kg of sodium acetate, 0.75kg of calcium acetate and 0.6kg of nickel acetate, sealing a feeding port, introducing nitrogen for protection, starting a heater, and heating the materials to 185 ℃ from normal temperature within 2 hours. After about 4 to 6 hours of reaction, the reaction was stopped to obtain a reaction product containing diethylene glycol isophthalate. The reaction product was cooled to below 130 ℃ and characterized for its physicochemical properties, the results are given in table 1 below.
Example 4
Putting 500kg of dimethyl isophthalate and 1250kg of ethylene glycol into a reaction kettle, starting a stirrer, adding 0.15kg of sodium acetate and 0.75kg of calcium acetate, sealing a feeding port, introducing nitrogen for protection, starting a heater, and heating the materials to 185 ℃ from normal temperature within 2 hours. After about 2 hours of reaction, the reaction was stopped. Then 0.10kg of sodium acetate and 0.1kg of nickel acetate are added into the reaction kettle, and the reaction is continued for 3 to 4 hours to obtain a reaction product containing the isophthalic acid diethylene glycol ester. The reaction product was cooled to below 130 ℃ and characterized for its physicochemical properties, the results are given in table 1 below.
Table 1 physicochemical properties of SIPE according to examples 1 to 5.
Preparation of sodium isophthalate diethylene glycol-5-sulfonate modified polyester
Example 6
Weighing 60kg of Purified Terephthalic Acid (PTA), 40kg of ethylene glycol and 5kg of diethylene glycol isophthalate-5-sulfonate prepared according to example 1, adding all the raw materials into a polymerization reaction kettle, starting stirring, adjusting the vacuum degree to 0.1MPa, and reacting the raw materials at 230 ℃ for 4 hours to obtain a first reaction mixture; then adjusting the vacuum degree to 200Pa, raising the temperature to 265 ℃, and continuing to react for 2 hours to obtain a second reaction mixture; then the vacuum degree is adjusted to 20Pa, the temperature is increased to 275 ℃, and the reaction is continued for 2 hours to obtain the diethylene glycol isophthalate-5-sodium sulfonate modified polyester. After discharge at atmospheric pressure, cooling, pelletizing and drying, polyester chips according to example 6 were obtained.
The melting point of the slice is 155 ℃, the slice is subjected to melt spinning and woven into a fabric, and then the fabric is dyed by using disperse type cationic red SD-GRL under normal pressure and at 260 ℃, the dye-uptake is 94.5%, and the color fastness reaches 4 grades.
Example 7
Weighing 60kg of PTA, 40kg of ethylene glycol and 4kg of diethylene glycol isophthalate-5-sulfonate prepared according to example 4, adding all the raw materials into a polymerization reaction kettle, starting stirring, adjusting the vacuum degree to 0.1MPa, and reacting the raw materials at 230 ℃ for 4 hours to obtain a first reaction mixture; then adjusting the vacuum degree to 200Pa, raising the temperature to 265 ℃, and continuing to react for 2 hours to obtain a second reaction mixture; then the vacuum degree is adjusted to 20Pa, the temperature is increased to 275 ℃, and the reaction is continued for 2 hours to obtain the diethylene glycol isophthalate-5-sodium sulfonate modified polyester. After discharge at atmospheric pressure, cooling, pelletizing and drying, polyester chips according to example 7 were obtained.
The melting point of the slice is 151 ℃, the slice is subjected to melt spinning, and then the slice is dyed by using disperse cationic red SD-GRL under normal pressure and at 260 ℃, the dye-uptake is 95.6%, and the color fastness reaches 4 grades.
The embodiments described above are intended to facilitate the understanding and appreciation of the application by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art who have the benefit of this disclosure will appreciate that many modifications and variations are possible within the scope of the present application without departing from the scope and spirit of the present application.
Claims (3)
1. A process for preparing a diethylene glycol isophthalate-5-sulfonate-modified polyester, comprising the steps of:
s1, preparing an ethylene glycol solution of isophthalic acid diethylene glycol ester-5-sodium sulfonate;
reacting dimethyl isophthalate-5-sodium sulfonate with excess ethylene glycol in the presence of a catalyst composition at a reaction temperature of less than or equal to 185 ℃ under an inert atmosphere to obtain an ethylene glycol solution of diethylene glycol phthalate-5-sodium sulfonate;
s2: preparing m-phthalic acid diethylene glycol ester-5-sodium sulfonate modified polyester;
reacting terephthalic acid, ethylene glycol, and the ethylene glycol solution of diethylene glycol phthalate-5-sodium sulfonate prepared by step S1 under vacuum conditions and at a temperature of 230 ℃ to 245 ℃ for a first predetermined period of time to obtain a first reaction mixture; then raising the reaction temperature to enable the first reaction mixture to react at the temperature of 265-270 ℃ for a second preset time period to obtain a second reaction mixture; then raising the reaction temperature, and continuously reacting the second reaction mixture at 275 +/-1 ℃ for a third preset time period to obtain the diethylene glycol isophthalate-5-sodium sulfonate modified polyester;
wherein, step S1 includes the following steps:
putting 500kg of dimethyl isophthalate and 1250kg of ethylene glycol into a reaction kettle, starting a stirrer, adding 0.15kg of sodium acetate and 0.75kg of calcium acetate, sealing a feeding port, introducing nitrogen for protection, starting a heater, and heating the materials to 185 ℃ from normal temperature within 2 hours; after reacting for 2 hours, stopping the reaction; then 0.10kg of sodium acetate and 0.1kg of nickel acetate are added into the reaction kettle, and the reaction is continued for 3 to 4 hours to obtain a reaction product containing the isophthalic acid diethylene glycol ester.
2. The method for preparing a sodium diethylene glycol isophthalate-5-sulfonate-modified polyester according to claim 1, wherein in step S2, the first predetermined period of time is 4 to 12 hours; and/or, the second predetermined period of time is 2-5 hours; and/or the third predetermined period of time is 1-4 hours.
3. The method for preparing a sodium diethylene glycol isophthalate-5-sulfonate modified polyester according to claim 1, wherein, in step S2, the degree of vacuum at the time of preparing the first reaction mixture is greater than the degree of vacuum at the time of preparing the second reaction mixture, and the degree of vacuum at the time of preparing the second reaction mixture is greater than the degree of vacuum at the time of preparing the third reactant.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408554A (en) * | 2011-09-19 | 2012-04-11 | 江苏中鲈科技发展股份有限公司 | Preparation method for uvioresistant and cationic dyeable polyester chip |
| CN103866420A (en) * | 2012-12-14 | 2014-06-18 | 东丽纤维研究所（中国）有限公司 | Cationic dyeable polyester fiber and preparation method thereof |
| WO2015076540A1 (en) * | 2013-11-20 | 2015-05-28 | 도레이케미칼 주식회사 | Copolyester readily soluble in alkali, for preparing conjugate fiber, preparation method therefor, and conjugate fiber containing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408554A (en) * | 2011-09-19 | 2012-04-11 | 江苏中鲈科技发展股份有限公司 | Preparation method for uvioresistant and cationic dyeable polyester chip |
| CN103866420A (en) * | 2012-12-14 | 2014-06-18 | 东丽纤维研究所（中国）有限公司 | Cationic dyeable polyester fiber and preparation method thereof |
| WO2015076540A1 (en) * | 2013-11-20 | 2015-05-28 | 도레이케미칼 주식회사 | Copolyester readily soluble in alkali, for preparing conjugate fiber, preparation method therefor, and conjugate fiber containing same |
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