CN110964186A - Compound containing sulfonate group and preparation method and application thereof - Google Patents
Compound containing sulfonate group and preparation method and application thereof Download PDFInfo
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- CN110964186A CN110964186A CN201811156946.1A CN201811156946A CN110964186A CN 110964186 A CN110964186 A CN 110964186A CN 201811156946 A CN201811156946 A CN 201811156946A CN 110964186 A CN110964186 A CN 110964186A
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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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- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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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
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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
Abstract
The invention relates to a sulfonate group-containing compound for improving the dyeability of polyester fibers and a preparation method thereof, wherein the molecular chain of the sulfonate group-containing compound comprises an isophthalic acid-5-sulfonate unit, a terephthalic acid unit and a butanediol unit, and the compound also contains a tetrahydrofuran inhibitor. The compound containing sulfonate groups has good compatibility with polyester, the filtration pressure rise of subsequent polyester melt spinning is less, the replacement period of a filter screen in the spinning engineering is long, and the cost is low.
Description
Technical Field
The invention relates to a sulfonate group-containing compound containing an isophthalic acid-5-sulfonate structural unit, a terephthalic acid structural unit and a butanediol structural unit, and a preparation method and application thereof.
Background
The polyester has excellent physical and mechanical properties, but the polyester has poor dyeing effect because the molecular chain structure of the polyester is compact, the crystallinity and the orientation degree are higher, the polarity is smaller, the hydrophilicity is poor, and gaps which can properly contain dye molecules do not exist among long-chain molecules of the polyester.
Among the methods for improving the cationic dyeing effect of polyesters, the copolymerization of a third monomer, isophthalic acid-5-sulfonate, terephthalic acid-5-sulfonate or their esterified derivatives, in polyesters is most commonly used. For example, Japanese patent laid-open Nos. 2000-355831, 2003-301328 and Chinese patent CN204999829U all disclose that cationic dyeability is imparted to the final polyester by adding isophthalic acid-5-sulfonate or dimethyl isophthalate-5 sulfonate to the polymerization reaction of the polyester. However, the technical solutions disclosed in the above patents all have the influence of foreign matters formed due to poor compatibility of the isophthalic acid-5-sulfonate or dimethyl isophthalate-5 sulfonate monomer with the polymer on the filtration pressure of the post-polymerization.
Disclosure of Invention
The invention aims to provide a compound containing a sulfonate group and a preparation method thereof, wherein the compound can improve the dyeability of polyester cations. The compound containing sulfonate groups has good compatibility with polyester, the filtration pressure rise of subsequent polyester melt spinning is less, the replacement period of a filter screen in the spinning engineering is long, and the cost is low.
The technical solution of the invention is as follows:
a compound containing sulfonate groups comprises an isophthalic acid-5-sulfonate unit shown as a formula 1, a terephthalic acid unit shown as a formula 2 and a butanediol unit shown as a formula 3 in a molecular chain; the number average molecular weight of the compound is 600-2000 g/mol, and the compound contains a tetrahydrofuran inhibitor;
in the formula 1, X is sodium ion, potassium ion or lithium ion.
The content of the tetrahydrofuran inhibitor in the sulfonate group-containing compound is preferably 20 to 200ppm based on the total amount of the compound.
The molar ratio of the isophthalic acid-5-sulfonate unit to the terephthalic acid unit is preferably 1: 0.1 to 30.0; the molar ratio of the total amount of moles of isophthalic acid-5-sulfonate units and terephthalic acid units to the moles of butanediol units is preferably 1: 1.5 to 2.0.
The tetrahydrofuran inhibitor is preferably one or more of tetraethylammonium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, lithium hydroxide, magnesium acetate, potassium acetate, lithium acetate, potassium carbonate, calcium carbonate, magnesium carbonate and sodium hexametaphosphate.
The invention also discloses a preparation method of the compound containing the sulfonate group. Adding 5-sulfoisophthalic acid or an esterified product thereof, terephthalic acid or an esterified product thereof and butanediol into a reaction kettle, then adding a catalyst of tetrabutyl titanate or tetraisopropyl titanate and a tetrahydrofuran inhibitor, and reacting for 2-5 hours at 170-240 ℃ to obtain a sulfonate group-containing compound with the number average molecular weight of 600-2000 g/mol; the sulfonate is sodium sulfonate, potassium sulfonate or lithium sulfonate.
The molar ratio of the isophthalic acid-5-sulfonate or the esterified product thereof to the terephthalic acid or the esterified product thereof is preferably 1: 0.1 to 30.0. The molar ratio of the total amount of the isophthalic acid-5-sulfonate or the esterified product thereof and the terephthalic acid or the esterified product thereof to the butanediol is preferably 1: 1.5 to 2.0.
The addition amount of the tetrahydrofuran inhibitor is preferably 30-300 ppm of the total addition amount of butanediol; the tetrahydrofuran inhibitor is preferably one or more of tetraethylammonium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, lithium hydroxide, magnesium acetate, potassium acetate, lithium acetate, potassium carbonate, calcium carbonate, magnesium carbonate and sodium hexametaphosphate.
The sulfonate group-containing compound has good compatibility with polyester, can be added into polyester to improve the cationic dyeing property of the polyester, and the obtained polyester has little filtration pressure rise in subsequent processing such as spinning stage, long service life of components and low cost.
Detailed Description
In the general art, cationic dyes that impart dyeability to polyesters are copolymerized in polyesters isophthalic acid-5-sulfonate or esterified derivatives thereof. However, the isophthalic acid-5-sulfonate or the esterified derivative thereof has poor compatibility with polyester, and self-polymerization reaction is easy to occur in the polymerization process, so that the filtration pressure in the polyester preparation process and the subsequent processing process is increased, yarn breakage is easy to occur, and the strength of the prepared yarn is low.
In order to solve the problems, the invention provides a compound containing a sulfonate group, wherein a molecular chain of the compound containing the sulfonate group comprises three structural units, namely an isophthalic acid-5-sulfonate structural unit shown as a formula 1, a terephthalic acid structural unit shown as a formula 2 and a butanediol structural unit shown as a formula 3,
in the formula 1, X is sodium ion, potassium ion or lithium ion.
The terephthalic acid structural unit in the compound containing the sulfonate group can reduce the self-polymerization reaction of isophthalic acid-5-sulfonate or an esterified derivative thereof, and improve the compatibility of the compound containing the sulfonate group and polyester, so that the subsequent spinning filtration pressure of the cation dyeable polyester is improved. Meanwhile, the introduction of the benzene ring structure increases the steric hindrance in and among molecules of the sulfonate compound, thereby reducing the mutual attraction of sulfonate groups, effectively inhibiting the agglomeration of the sulfonate group-containing compound in the process of synthesizing the cationic dyeable polyester, reducing the generation of foreign matters in the polyester, and having no influence on the processability of the cationic dyeable polyester.
In the molar ratio of the isophthalic acid-5-sulfonate unit to the terephthalic acid unit, the molar weight of the isophthalic acid-5-sulfonate unit is 1, when the terephthalic acid unit is too much, a large amount of a compound containing a sulfonate group is required to be added when the compound is used as a dyeable third monomer, so that the cost is increased, and the copolyester is difficult to achieve the effect of cationic dyeability; when the terephthalic acid unit is too small, the isophthalic acid-5-sulfonate or the esterified derivative thereof is easily self-polymerized, and the cationic dyeable polyester obtained by using the sulfonate group-containing compound as the dyeable third monomer has high spinning filtration, low product yield and poor physical properties. The invention preferably has a molar ratio of the isophthalic acid-5-sulfonate unit to the terephthalic acid unit of 1: 0.1 to 30.0, more preferably 1: 0.5 to 20.0.
In the molar ratio of the total mole of the isophthalic acid-5-sulfonate unit and the terephthalic acid unit to the butanediol unit, the total mole of the isophthalic acid-5-sulfonate unit and the terephthalic acid unit is 1, when the butanediol unit is too low, the number average molecular weight of a generated substance containing sulfonate groups is too large, and when the butanediol unit is added into polyester, the substance containing sulfonate groups is not favorably dispersed, so that the coagulation is caused, foreign matters in the polyester are increased, and the spinning filtration pressure of the cation dyeable polyester is finally influenced. The molar ratio of the total amount of the isophthalic acid-5-sulfonate unit and the terephthalic acid unit to the butanediol unit is preferably 1: 1.3 to 2.0, more preferably 1: 1.5 to 2.0.
The number average molecular weight of the sulfonate group-containing compound is 600-2000 g/mol. If the number average molecular weight of the sulfonate group-containing compound is more than 2000g/mol, the sulfonate group-containing compound is caused to have too high a viscosity and to be easily coagulated, thereby decreasing its dispersibility in the polyester, increasing foreign matters in the polyester, and finally affecting the processability of the polyester. The number average molecular weight of the sulfonate group-containing substance is preferably 600 to 1500 g/mol.
The invention also discloses a preparation method of the compound containing the sulfonate group, which comprises the following specific steps: adding 5-sulfoisophthalic acid or an esterified product thereof, terephthalic acid or an esterified product thereof and butanediol into an esterification reaction kettle; starting a stirrer, adding a catalyst of tetrabutyl titanate or tetraisopropyl titanate, adding a tetrahydrofuran inhibitor of an alkaline compound, and reacting at 150-240 ℃ for 2-5 hours to reach an end point to obtain a compound containing a sulfonate group with the number average molecular weight of 600-2000 g/mol; the sulfonate is sodium sulfonate, potassium sulfonate or lithium sulfonate.
The isophthalic acid-5-sulfonate ester is small molecular weight sulfonate such as isophthalic acid-5-sulfonate, isophthalic acid dimethyl ester-5-sulfonate, isophthalic acid monomethyl ester-5 sulfonate, isophthalic acid monoethyl ester-5-sulfonate, isophthalic acid diethylene glycol ester-5-sulfonate, isophthalic acid dibutylene glycol-5-sulfonate and the like; the terephthalic acid ester is micromolecular aromatic dicarboxylic acid ester such as dimethyl terephthalate, diethyl terephthalate, monomethyl terephthalate, monoethyl terephthalate and the like.
The reaction temperature of the method is 150-240 ℃, when the temperature is lower than 150 ℃, the reaction is incomplete because of too low reaction temperature, and the obtained product contains a large amount of m-phthalic acid-5-sulfonate or an esterified substance thereof which do not participate in the reaction besides the sulfonate group-containing substance, so that when the obtained product is added into polyester, foreign matters in the polyester are increased, and the spinning filtration pressure of the cationic dyeable polyester is influenced; when the temperature is higher than 240 ℃, the formation of an isophthalic acid-5-sulfonate or an esterified product thereof is promoted, the compatibility of the copolymer with the polyester is low, and when the copolymer is added into the polyester, the amount of foreign matters in the polyester is increased, so that the processability of the polyester is affected.
When various raw materials are added, the molar ratio of the isophthalic acid-5-sulfonate or the esterified product thereof to terephthalic acid or the esterified product thereof is preferably 1: 0.1 to 30.0; the molar ratio of the total amount of the isophthalic acid-5-sulfonate or the esterified product thereof and the terephthalic acid or the esterified product thereof to the butanediol is preferably 1: 1.5 to 10.0.
In the molar ratio of the total mole amount of the isophthalic acid-5-sulfonate or the esterified product thereof and the terephthalic acid or the esterified product thereof to the butanediol, the total mole amount of the isophthalic acid-5-sulfonate or the esterified product thereof and the terephthalic acid or the esterified product thereof is 1, when the addition amount of the butanediol is too low, the reaction speed is low, the time is too long, the byproducts are more, the reaction rate is low, and the physical properties of the polyester are influenced when a compound containing a sulfonate group is used as a dyeable third monomer; if the amount of butanediol added is too large, bumping is likely to occur, and the amount of by-products in the reaction increases, which increases the treatment cost. The molar ratio of the total amount of the isophthalic acid-5-sulfonate unit and the terephthalic acid unit to the butanediol unit is preferably 1: 1.5 to 2.0.
The catalyst is tetrabutyl titanate or tetraisopropyl titanate, and if the addition amount of the catalyst is too low, the catalytic activity is insufficient, and the reaction speed is too low; if the amount of the compound is too large, the catalytic activity is too high, and side reactions such as thermal decomposition increase, which results in deterioration of the physical properties of the resulting sulfonate group-containing compound. In the present invention, the amount of the catalyst to be added is preferably 30 to 4500ppm, more preferably 300 to 3000ppm, based on the total amount of the isophthalic acid-5-sulfonate or the ester thereof and the terephthalic acid or the ester thereof.
Tetrahydrofuran is easily generated in the polymerization reaction process of butanediol, is volatile, toxic, inflammable and dangerous to explode, and the generation of a byproduct tetrahydrofuran can reduce the amount of the polymerized butanediol, so that the reaction rate of the butanediol is reduced. In the present invention, a tetrahydrofuran inhibitor is added to the reaction in order to inhibit the production of tetrahydrofuran. The tetrahydrofuran inhibitor is preferably selected from one or more of tetraethylammonium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, lithium hydroxide, magnesium acetate, potassium acetate, lithium acetate, calcium carbonate and sodium hexametaphosphate, and more preferably tetraethylammonium hydroxide. If the addition amount of the tetrahydrofuran inhibitor is too low, the effect of inhibiting the generation of tetrahydrofuran cannot be achieved; if the amount of the tetrahydrofuran inhibitor to be added is too high, the polymerization catalyst n-tetrabutyl titanate or tetraisopropyl titanate is easily hydrolyzed in an overbased environment due to the tetrahydrofuran inhibitor being a basic compound, thereby affecting the catalytic activity. In the present invention, the amount of the tetrahydrofuran inhibitor added is preferably 30 to 300ppm, more preferably 150 to 300ppm based on the total amount of butanediol added.
The compound containing sulfonate groups can be used as a cationic dyeable third monomer and applied to cationic dyeable polyester. The sulfonate group-containing compound can be added in the esterification reaction stage of the polyester or in the previous stage of the polycondensation reaction, and the addition amount of the sulfonate group-containing compound relative to the polyester can be changed within the range of 0.1-10 wt% according to the dyeing requirement and the type of the polyester.
Compared with the cation dyeable polyester prepared by directly adding the m-phthalic acid-5-sulfonate or the esterified monomer thereof, the cation dyeable polyester prepared from the compound containing the sulfonate group has better dyeing effect, and when the obtained polyester is prepared into fibers by a known melt spinning method, the melt spinning filter pressure rise is less, the filter screen replacement period is long, the cost is reduced, and meanwhile, the yarn prepared from the polyester has high strength and good hand feeling of fabrics.
The physical property parameters of the present invention are measured by the following methods.
(1) The content of each structural unit in the compound containing sulfonate group
By H1NMR Nuclear magnetic testing of the sulfonate group-containing compound, the molar ratio of the abovementioned units being determined by the ratio of the area of the characteristic peak of the hydrogen element on benzene in the terephthalic acid unit and the area of the peak of the characteristic peak of the hydrogen element on benzene in the isophthalic acid-5 sulfonate unit, and the area of the peak of the characteristic peak of the hydrogen element on the alkyl group in the linear diol.
(2) Tetrahydrofuran inhibitor content
After pressing 5g of the sample into a sheet, the intensity of the element was measured by a fluorescent X-ray analyzer, and the measured intensity was converted into a detection line prepared in advance for a sample having a known element content.
(3) Amount of tetrahydrofuran produced
Taking the generated compound effluent containing sulfonate groups, analyzing by liquid chromatography, and calculating the tetrahydrofuran content of each sample by an effluent area through a previously prepared calibration curve of the tetrahydrofuran content:
the device comprises the following steps: shimadzu SPD-COAVP
Column: YMC-Pack ODS-A model: AA/2S05-1546WT
Column temperature: 40 deg.C
Flow rate: 1.3mL/min
Injection amount: 0.05 mL.
(4) Differential filtration pressure Δ Pa
The test was performed using a filterability tester. The pore diameter of the filter screen is 5 μm, the test temperature is 290 ℃, the discharge rate is 10g/min, the initial pressure Pa1 is recorded 30 minutes after the start of feeding, the final pressure Pa2 is recorded 6 hours after the start of initial pressure, and the filter pressure rise value in 6 hours is Delta Pa-Pa 2-Pa 1. A smaller Δ Pa means that the amount of foreign matter in the cationic dyeable polyester is smaller and the spinning is more stable.
(5) Method for evaluating dyeing property
Drying the cationic dyeable polyester chip until the water content is below 100ppm, feeding the polyester chip into a screw through a stock bin to melt at the temperature of 260 ℃, controlling the discharge amount of the polyester chip by a metering pump, spinning primary fibers by a spinning assembly with the temperature controlled by a spinning manifold at 270 ℃, cooling, solidifying and forming the fibers under the condition of a cross-blow air speed of 25m/min, uniformly oiling the fibers by an oil feeding nozzle to cluster the fibers and reduce friction, wherein the oil feeding rate is 0.7%. The fiber after oil feeding and bundling passes through a spinning channel, is interlaced through a pre-interlacing device, enters a first roller (1 GR) at the speed of 2700m/min, passes through a main interlacing device, then enters a coiling machine for coiling after passing through a second roller (2 GR) at the winding speed of 2680m/min to obtain the pre-oriented fiber (POY), and the coiling speed of the coiling machine is 2690 m/min.
The obtained POY fiber is processed on a false twisting machine, false twisting is carried out under the conditions that the processing speed is 500m/min, the temperature of a first hot box is 170 ℃ and the extension ratio is 1.5, and the DTY yarn tube knitting is prepared. The obtained tubular knitted fabric was dyed by stirring the treatment liquid at 130 ℃ for 30min using a high temperature dyeing tester UR, seed, MINI-COLOR (manufactured by TEXAM technologies), and the chemical agents of the treatment liquid used were as follows:
dianix Blue E-Plus (disperse dye, manufactured by Desida) 5owf%,
NIKKA SUNSALT (leveling agent manufactured by Rihua chemical Co., Ltd.) 1g/l,
acetic acid (pH regulator) 0.5g/l,
after dyeing, a treatment liquid was prepared using the following agents at 80 ℃ for 20min, reduction washing was performed,
0.6g/l of sodium hydroxide,
sodium bisulfite 2 g/l.
Then, the tubular knitted fabric was washed with water and air-dried to be used as an evaluation sample. The sample was stacked into 8 layers and then measured for color with a spectrophotometer (Datacolor 650 manufactured by Datacolor Asia Pacific (H.K.) ltd.), denoted by L, which is the lightness of the color system, and the smaller the value, the better the dyeing property.
The technical solutions of the present invention are described in more detail below by way of specific embodiments, but the present invention is not limited to these embodiments.
Example 1
Sulfonate group-containing compound: adding m-phthalic acid-5 sodium sulfonate and terephthalic acid into an esterification kettle, wherein the molar ratio of the m-phthalic acid-5 sodium sulfonate to the terephthalic acid is 1: 0.1. Simultaneously adding 1, 4-butanediol, wherein the molar ratio of the total amount of the sodium sulfoisophthalate-5 and the terephthalic acid to the 1, 4-butanediol is 1: 1.3. The stirrer was started and 500ppm of tetrabutyl titanate was added. Then adding 200ppm of tetrahydrofuran inhibitor tetraethyl ammonium hydroxide, starting at room temperature for 150min, heating to 150 ℃ and reacting for 1 hr. And (4) after the time is up, stopping the reaction, cooling and spitting to obtain the compound containing the sulfonate group. The number average molecular weight of the sulfonate group-containing compound was 2000g/mol, where isophthalic acid-5-sodium sulfonate unit: terephthalic acid unit is 1: 0.1 (molar ratio); (5-sodium sulfoisophthalate unit + terephthalic acid unit) to 1, 4-butanediol unit: 1: 1.3 (molar ratio).
Cationic dyeable polyester: uniformly mixing terephthalic acid and 1, 4-butanediol, putting into a reaction kettle, adding a catalyst tetrabutyl titanate accounting for titanium element and accounting for 0.1wt% of an esterification reactant, and carrying out esterification reaction at 225 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding the prepared compound containing the sulfonate group and thermal stabilizer trimethyl phosphate, and carrying out polycondensation reaction at 250 ℃. And (3) after the polymer reaches the required viscosity, discharging and granulating to obtain the required cationic dyeable polyester. The copolymerized sulfonate group-containing substance in the cationic dyeable polyester accounts for 0.5wt% of the final cationic dyeable polyester in terms of sulfur. The cationic dyeable polyester is melt spun at 280 ℃ to obtain polyester fiber. Specific physical properties are shown in table 1.
Example 2
Sulfonate group-containing compound: adding dimethyl isophthalate-5 sodium sulfonate and terephthalic acid into an esterification kettle, wherein the molar ratio of the two is 1: 30. Simultaneously, 1, 4-butanediol, the molar ratio of the total amount of the sodium sulfoisophthalate-5 and the terephthalic acid to the 1, 4-butanediol is 1: 2.0. The stirrer was started and 500ppm of tetrabutyl titanate was added. Then adding 200ppm of tetrahydrofuran inhibitor tetraethyl ammonium hydroxide, starting 200min at room temperature, heating to 250 ℃ and reacting for 1 hr. And (4) after the time is up, stopping the reaction, cooling and spitting to obtain the compound containing the sulfonate group. The number average molecular weight of the sulfonate group-containing compound was 650g/mol, where isophthalic acid-5-sodium sulfonate unit: terephthalic acid unit is 1: 2.0 (molar ratio); (5-sodium sulfoisophthalate unit + terephthalic acid unit) and 1, 4-butanediol unit in a molar ratio of 1: 2.0.
Cationic dyeable polyester: uniformly mixing terephthalic acid, 1, 4-butanediol and the prepared compound containing the sulfonate group, putting the mixture into a reaction kettle, adding tetrabutyl titanate serving as a catalyst, wherein the tetrabutyl titanate is 0.1wt% of the esterification reactant relative to the titanium element, and carrying out esterification reaction at 225 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding a thermal stabilizer trimethyl phosphate, and carrying out polycondensation reaction at 250 ℃. And (3) after the polymer reaches the required viscosity, discharging and granulating to obtain the required cationic dyeable polyester. The copolymerized sulfonate group-containing material in the cationic dyeable polyester accounted for 0.5wt% of the final polyester, calculated as elemental sulfur. The cationic dyeable polyester is melt spun at 280 ℃ to obtain polyester fiber. Specific physical properties are shown in table 1.
Example 3
Sulfonate group-containing compound: the molar ratio of sodium dimethyl isophthalate-5 sulfonate to terephthalic acid was changed to 1: 15.0, and the amount of tetrahydrofuran inhibitor added was changed to 100 ppm. The compound containing a sulfonate group was prepared in the same manner as in example 1. The number average molecular weight of the sulfonate group-containing compound was 1800g/mol, wherein isophthalic acid-5-sodium sulfonate unit: terephthalic acid unit is 1: 15.0 (molar ratio); (5-sodium sulfoisophthalate unit + terephthalic acid unit) to 1, 4-butanediol unit: 1: 1.3 (molar ratio).
Cationic dyeable polyester: uniformly mixing terephthalic acid and 1, 4-butanediol, putting into a reaction kettle, adding a catalyst tetrabutyl titanate accounting for titanium element and accounting for 0.1wt% of an esterification reactant, and carrying out esterification reaction at 225 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding the prepared sulfonate group-containing substance and thermal stabilizer trimethyl phosphate, and carrying out polycondensation reaction at 250 ℃. And (3) after the polymer reaches the required viscosity, discharging and granulating to obtain the required cationic dyeable polyester. The copolymerized sulfonate group-containing material in the cationic dyeable polyester accounts for 5wt% of the final polyester in terms of sulfur. The cationic dyeable polyester is melt spun at 280 ℃ to obtain polyester fiber. Specific physical properties are shown in table 1.
Example 4
Sulfonate group-containing compound: the molar ratio of sodium dimethyl isophthalate-5 sulfonate to terephthalic acid was changed to 1: 20.0, and the amount of tetrahydrofuran inhibitor added was changed to 300 ppm. The compound containing a sulfonate group was prepared in the same manner as in example 1. The number average molecular weight of the sulfonate group-containing compound was 2000g/mol, where isophthalic acid-5-sodium sulfonate unit: terephthalic acid unit is 1: 20.0 (molar ratio); (5-sodium sulfoisophthalate unit + terephthalic acid unit) to 1, 4-butanediol unit: 1: 1.3 (molar ratio).
Cationic dyeable polyester: the preparation method is the same as example 1, and the specific physical properties are shown in Table 1.
Example 5
Sulfonate group-containing compound: adding dimethyl isophthalate-5 sodium sulfonate and dimethyl terephthalate into an esterification kettle, wherein the molar ratio of the two is 1: 10.0. Simultaneously, 1, 4-butanediol, the molar ratio of the total amount of sodium sulfoisophthalate-5 and dimethyl terephthalate to the 1, 4-butanediol is 1: 1.3. The stirrer was started and 700ppm tetraethyl titanate was added. Then adding 200ppm of tetrahydrofuran inhibitor potassium hydroxide, starting 160min at room temperature, heating to 180 ℃ and reacting for 3 hr. And (4) after the time is up, stopping the reaction, cooling and spitting to obtain the compound containing the sulfonate group. The number average molecular weight of the sulfonate group-containing compound was 2000g/mol, where isophthalic acid-5-sodium sulfonate unit: terephthalic acid unit is 1: 10.0 (molar ratio); (5-sodium sulfoisophthalate unit + terephthalic acid unit) to 1, 4-butanediol unit: 1: 1.3 (molar ratio).
Cationic dyeable polyester: uniformly mixing terephthalic acid and 1, 4-butanediol, putting into a reaction kettle, adding a catalyst tetrabutyl titanate accounting for titanium element and accounting for 0.1wt% of an esterification reactant, and carrying out esterification reaction at 225 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding the prepared sulfonate group-containing substance and thermal stabilizer trimethyl phosphate, and carrying out polycondensation reaction at 250 ℃. And (3) after the polymer reaches the required viscosity, discharging and granulating to obtain the required cationic dyeable polyester. The copolymerized sulfonate group-containing material in the cationic-dyeable polyester accounted for 2.0wt% of the final cationic-dyeable polyester in terms of elemental sulfur. The cationic dyeable polyester is melt spun at 280 ℃ to obtain polyester fiber. Specific physical properties are shown in table 1.
Example 6
Sulfonate group-containing compound: adding sodium sulfoisophthalate-5 and monoethyl terephthalate into an esterification kettle in a molar ratio of 1: 10.0. Simultaneously adding 1, 4-butanediol, the molar ratio of the total amount of the sodium sulfoisophthalate-5 and the monoethyl terephthalate to the 1, 4-butanediol is 1: 1.5. The stirrer was started and 700ppm tetraethyl titanate was added. Then adding 200ppm of tetrahydrofuran inhibitor tetraethyl ammonium hydroxide, starting 160min at room temperature, heating to 180 ℃ and reacting for 3 hr. And (4) after the time is up, stopping the reaction, cooling and spitting to obtain the compound containing the sulfonate group. The number average molecular weight of the sulfonate group-containing compound was 800g/mol, wherein the molar ratio of isophthalic acid-5-sodium sulfonate unit to terephthalic acid unit was 1: 10.0; (5-sodium sulfoisophthalate unit + terephthalic acid unit) to 1, 4-butanediol unit: 1: 1.5 (molar ratio).
Cationic dyeable polyester: the preparation method is the same as example 1, and the specific physical properties are shown in Table 2.
Example 7
Sulfonate group-containing compound: adding sodium sulfoisophthalate-5 and diethyl terephthalate into an esterification kettle, wherein the molar ratio of the sodium sulfoisophthalate to the diethyl terephthalate is 1: 10.0. Simultaneously adding 1, 4-butanediol, the molar ratio of the total amount of the sodium sulfoisophthalate-5 and the diethyl terephthalate to the 1, 4-butanediol is 1: 1.4. The stirrer was started and 700ppm tetraethyl titanate was added. Then adding 200ppm of tetrahydrofuran inhibitor tetraethyl ammonium hydroxide, starting 160min at room temperature, heating to 180 ℃ and reacting for 3 hr. And (4) after the time is up, stopping the reaction, cooling and spitting to obtain the compound containing the sulfonate group. The number average molecular weight of the sulfonate group-containing compound was 1200g/mol, where isophthalic acid-5-sodium sulfonate unit: terephthalic acid unit is 1: 10.0 (molar ratio); (5-sodium sulfoisophthalate unit + terephthalic acid unit) to 1, 4-butanediol unit: 1: 1.4 (molar ratio).
Cationic dyeable polyester: the preparation method is the same as example 1, and the specific physical properties are shown in Table 2.
Example 8
The sodium 5-sulfoisophthalate was replaced with lithium sodium 5-sulfoisophthalate, and the amount of lithium hydroxide added as a tetrahydrofuran inhibitor was 200 ppm. The other conditions were the same as in example 7. Specific physical properties are shown in table 2.
Example 9
The sodium 5-sulfoisophthalate is changed into potassium sodium 5-sulfoisophthalate, and the addition amount of the tetrahydrofuran inhibitor potassium acetate is 200 ppm. The other conditions were the same as in example 1. Specific physical properties are shown in table 2.
Example 10
Sulfonate group-containing compound: the molar ratio of the total amount of sodium sulfoisophthalate-5 and diethyl terephthalate and 1, 4-butanediol in example 7 was changed from 1: 1.4 to 1: 1.5, from 1: 10.0 to 1: 15.0. The amount of potassium carbonate added as a tetrahydrofuran inhibitor was 200 ppm. The compound containing a sulfonate group was prepared under the same conditions as in example 7. The number average molecular weight of the sulfonate group-containing compound was 1000g/mol, where isophthalic acid-5-sodium sulfonate unit: terephthalic acid unit is 1: 15.0 (molar ratio); (5-sodium sulfoisophthalate unit + terephthalic acid unit) to 1, 4-butanediol unit: 1: 1.5 (molar ratio).
Example 11
Sulfonate group-containing compound: adding m-phthalic acid-5 sodium sulfonate and terephthalic acid into an esterification kettle, wherein the molar ratio of the m-phthalic acid-5 sodium sulfonate to the terephthalic acid is 1: 0.2. Simultaneously adding 1, 4-butanediol, wherein the molar ratio of the total amount of the sodium sulfoisophthalate-5 and the terephthalic acid to the 1, 4-butanediol is 1: 1.5. The stirrer was started and 500ppm of tetrabutyl titanate was added. The tetrahydrofuran inhibitor tetraethylammonium hydroxide was added at 200 ppm. The temperature is raised to 150 ℃ for 1hr after 150min at room temperature. And (4) after the time is up, stopping the reaction, cooling and spitting to obtain the compound containing the sulfonate group. The number average molecular weight of the sulfonate group-containing compound was 1000g/mol, wherein isophthalic acid-5-sodium sulfonate unit: terephthalic acid unit was 1: 0.2 (molar ratio); (5-sodium sulfoisophthalate unit + terephthalic acid unit) to 1, 4-butanediol unit: 1: 1.5 (molar ratio).
Cationic dyeable polyester: uniformly mixing terephthalic acid and 1, 4-butanediol, putting into a reaction kettle, adding a catalyst tetrabutyl titanate accounting for titanium element and accounting for 0.1wt% of an esterification reactant, and carrying out esterification reaction at 225 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding the prepared sulfonate group-containing substance and thermal stabilizer trimethyl phosphate, and carrying out polycondensation reaction at 250 ℃. And (3) after the polymer reaches the required viscosity, discharging and granulating to obtain the required cationic dyeable polyester. The copolymerized sulfonate group-containing material in the cationic dyeable polyester accounted for 0.5wt% of the final polyester, calculated as elemental sulfur. The cationic dyeable polyester is melt spun at 280 ℃ to obtain polyester fiber. Specific physical properties are shown in table 2.
Example 12
Sulfonate group-containing compound: adding m-phthalic acid-5 sodium sulfonate and terephthalic acid into an esterification kettle, wherein the molar ratio of the m-phthalic acid-5 sodium sulfonate to the terephthalic acid is 1: 15.0. Simultaneously adding 1, 4-butanediol, wherein the molar ratio of the total amount of the sodium sulfoisophthalate-5 and the terephthalic acid to the 1, 4-butanediol is 1: 1.0. The stirrer was started and 500ppm of tetrabutyl titanate was added. 200ppm of tetraethylammonium hydroxide were added. The temperature is raised to 150 ℃ for 1hr after 150min at room temperature. And (4) after the time is up, stopping the reaction, cooling and spitting to obtain the compound containing the sulfonate group. The number average molecular weight of the sulfonate group-containing compound was 1000g/mol, where isophthalic acid-5-sodium sulfonate unit: terephthalic acid unit is 1: 15.0 (molar ratio); (5-sodium sulfoisophthalate unit + terephthalic acid unit) and 1, 4-butanediol unit in a molar ratio of 1: 1.0.
Cationic dyeable polyester: uniformly mixing terephthalic acid and 1, 4-butanediol, putting into a reaction kettle, adding a catalyst tetrabutyl titanate accounting for titanium element and accounting for 0.1wt% of an esterification reactant, and carrying out esterification reaction at 225 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding the prepared sulfonate group-containing substance and thermal stabilizer trimethyl phosphate, and carrying out polycondensation reaction at 250 ℃. And (3) after the polymer reaches the required viscosity, discharging and granulating to obtain the required cationic dyeable polyester. The copolymerized sulfonate group-containing material in the cationic dyeable polyester accounted for 0.5wt% of the final polyester, calculated as elemental sulfur. The cationic dyeable polyester is melt spun at 280 ℃ to obtain polyester fiber. Specific physical properties are shown in table 2.
The preparation method of the cationic dyeable polyester is the same as that of example 1, and the specific physical properties are shown in Table 2.
Comparative example 1
Uniformly mixing terephthalic acid and 1, 4-butanediol, putting into a reaction kettle, adding a catalyst tetrabutyl titanate accounting for titanium element and accounting for 0.1wt% of an esterification reactant, and carrying out esterification reaction at 225 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding a thermal stabilizer trimethyl phosphate, and carrying out polycondensation reaction at 250 ℃. And (4) after the polymer reaches the required viscosity, discharging and granulating to obtain the required copolyester. The copolymerized sulfonate group-containing material in the copolyester accounts for 0.5wt% of the final polyester in terms of sulfur element. The polyester is melt-spun at 280 ℃ to obtain the polyester fiber. Specific physical properties are shown in table 3.
Ordinary polybutylene terephthalate has poor dyeability.
Comparative example 2
Uniformly mixing terephthalic acid and 1, 4-butanediol, putting into a reaction kettle, adding a catalyst tetrabutyl titanate accounting for titanium element and accounting for 0.1wt% of an esterification reactant, and carrying out esterification reaction at 225 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding dibutylene glycol-5-sodium sulfonate isophthalate and trimethyl phosphate serving as a heat stabilizer, and carrying out polycondensation reaction at 250 ℃. And (4) after the polymer reaches the required viscosity, discharging and granulating to obtain the required copolyester. The copolymerized sulfonate group-containing material in the copolyester accounts for 0.5wt% of the final polyester in terms of sulfur element. The polyester is melt-spun at 280 ℃ to obtain the polyester fiber. Specific physical properties are shown in table 3.
Although the dyeability of the cationic dyeable polyester obtained by directly adding the butanediol isophthalate-5-sulfonic acid sodium salt monomer to the reaction of polybutylene terephthalate is improved, the filtration pressure during spinning is increased, and the spinnability of the polyester is poor.
Comparative example 3
Sulfonate group-containing compound: sodium m-phthalic acid-5 sulfonate and 1, 4-butanediol are put into an esterification kettle, and the molar ratio of the sodium m-phthalic acid-5 sulfonate to the 1, 4-butanediol is 1: 1.0. The stirrer was started and 500ppm of tetrabutyl titanate was added. 200ppm of tetraethylammonium hydroxide were added. The temperature is raised to 150 ℃ for 4hr after 150min at room temperature. And (4) after the time is up, stopping the reaction, cooling and spitting to obtain the compound containing the sulfonate group. The number average molecular weight of the sulfonate group-containing compound was 1000g/mol, wherein isophthalic acid-5-sodium sulfonate unit: 1, 4-butanediol unit was 1: 1.0 (molar ratio).
Cationic dyeable polyester: uniformly mixing terephthalic acid and 1, 4-butanediol, putting into a reaction kettle, adding a catalyst tetrabutyl titanate accounting for titanium element and accounting for 0.1wt% of an esterification reactant, and carrying out esterification reaction at 225 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding the prepared sulfonate group-containing substance and thermal stabilizer trimethyl phosphate, and carrying out polycondensation reaction at 250 ℃. And (3) after the polymer reaches the required viscosity, discharging and granulating to obtain the required cationic dyeable polyester. The copolymerized sulfonate group-containing material in the cationic dyeable polyester accounted for 0.5wt% of the final polyester, calculated as elemental sulfur. The cationic dyeable polyester is melt spun at 280 ℃ to obtain polyester fiber. Specific physical properties are shown in table 3.
Because the compound containing the sulfonate group does not contain an isophthalic acid unit, the compatibility of the substance containing the sulfonate group and the polyester is poor, the filtration pressure of the cation dyeable polyester prepared by the compound during spinning is increased, and the spinnability of the polyester is poor.
Comparative example 4
Sulfonate group-containing compound: adding m-phthalic acid-5 sodium sulfonate and terephthalic acid into an esterification kettle, wherein the molar ratio of the m-phthalic acid-5 sodium sulfonate to the terephthalic acid is 1: 15.0. Simultaneously adding 1, 4-butanediol, wherein the molar ratio of the total amount of the sodium sulfoisophthalate-5 and the terephthalic acid to the 1, 4-butanediol is 1: 1.0. The stirrer was started and 500ppm of tetrabutyl titanate was added. 200ppm of tetraethylammonium hydroxide were added. The temperature is raised to 150 ℃ for 4hr after 150min at room temperature. And (4) after the time is up, stopping the reaction, cooling and spitting to obtain the compound containing the sulfonate group. The number average molecular weight of the sulfonate group-containing compound was 3000g/mol, where isophthalic acid-5-sodium sulfonate unit: terephthalic acid unit is 1: 15.0 (molar ratio); (5-sodium sulfoisophthalate unit + terephthalic acid unit) and 1, 4-butanediol unit in a molar ratio of 1: 1.0.
Cationic dyeable polyester: uniformly mixing terephthalic acid and 1, 4-butanediol, putting into a reaction kettle, adding a catalyst tetrabutyl titanate accounting for titanium element and accounting for 0.1wt% of an esterification reactant, and carrying out esterification reaction at 225 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding the prepared sulfonate group-containing substance and thermal stabilizer trimethyl phosphate, and carrying out polycondensation reaction at 250 ℃. And (3) after the polymer reaches the required viscosity, discharging and granulating to obtain the required cationic dyeable polyester. The copolymerized sulfonate group-containing material in the cationic dyeable polyester accounted for 0.5wt% of the final polyester, calculated as elemental sulfur. The cationic dyeable polyester is melt spun at 280 ℃ to obtain polyester fiber. Specific physical properties are shown in table 3.
Since the data molecular weight of the sulfonate group-containing compound is greater than 2000g/mol, the spinnability of the final cationic dyeable polyester is poor, and the filtration pressure during spinning is obviously increased.
Comparative example 5
Sulfonate group-containing compound: adding sodium sulfoisophthalate-5 and diethyl terephthalate into an esterification kettle, wherein the molar ratio of the sodium sulfoisophthalate to the diethyl terephthalate is 1: 15.0. Simultaneously adding 1, 4-butanediol, the molar ratio of the total amount of the sodium sulfoisophthalate-5 and the diethyl terephthalate to the 1, 4-butanediol is 1: 1.4. The stirrer was started and 700ppm tetraethyl titanate was added. The temperature is increased to 180 ℃ for 3hr after 160min at room temperature. And (4) after the time is up, stopping the reaction, cooling and spitting to obtain the compound containing the sulfonate group. The number average molecular weight of the sulfonate group-containing compound was 1200g/mol, where isophthalic acid-5-sodium sulfonate unit: terephthalic acid unit is 1: 15.0 (molar ratio); (5-sodium sulfoisophthalate unit + terephthalic acid unit) to 1, 4-butanediol unit: 1: 1.4 (molar ratio).
Cationic dyeable polyester: uniformly mixing terephthalic acid and 1, 4-butanediol, putting into a reaction kettle, adding a catalyst tetrabutyl titanate accounting for titanium element and accounting for 0.1wt% of an esterification reactant, and carrying out esterification reaction at 225 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding the prepared sulfonate group-containing substance and thermal stabilizer trimethyl phosphate, and carrying out polycondensation reaction at 250 ℃. And (3) after the polymer reaches the required viscosity, discharging and granulating to obtain the required cationic dyeable polyester. The copolymerized sulfonate group-containing material in the cationic dyeable polyester accounted for 0.5wt% of the final polyester, calculated as elemental sulfur. The cationic dyeable polyester is melt spun at 280 ℃ to obtain polyester fiber. Specific physical properties are shown in table 3.
A tetrahydrofuran inhibitor is not added in the synthesis of the compound containing the sulfonate group, and the generation amount of tetrahydrofuran is large.
In tables 1 to 3, A represents an isophthalic acid-5-sulfonate unit, B represents a terephthalic acid unit, and BDO represents 1, 4-butanediol.
Claims (11)
1. A sulfonate group-containing compound characterized by: the molecular chain of the compound comprises an isophthalic acid-5-sulfonate unit shown as a formula 1, a terephthalic acid unit shown as a formula 2 and a butanediol unit shown as a formula 3; the number average molecular weight of the compound is 600-2000 g/mol, and the compound contains a tetrahydrofuran inhibitor;
in the formula 1, X is sodium ion, potassium ion or lithium ion.
2. The sulfonate group-containing compound according to claim 1, characterized in that: the content of the tetrahydrofuran inhibitor in the compound containing the sulfonate group is 20-200 ppm relative to the total amount of the compound.
3. The sulfonate group-containing compound according to claim 1 or 2, characterized in that: the mol ratio of the isophthalic acid-5-sulfonate unit to the terephthalic acid unit is 1: 0.1 to 30.0.
4. The sulfonate group-containing compound according to claim 1 or 2, characterized in that: the molar ratio of the total mole of the isophthalic acid-5-sulfonate unit and the terephthalic acid unit to the mole of the butanediol unit is 1: 1.5 to 2.0.
5. The sulfonate group-containing compound according to claim 1 or 2, characterized in that: the tetrahydrofuran inhibitor is one or more of tetraethyl ammonium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, lithium hydroxide, magnesium acetate, potassium acetate, lithium acetate, potassium carbonate, calcium carbonate, magnesium carbonate and sodium hexametaphosphate.
6. A method for preparing the sulfonate group-containing compound of claim 1, which comprises: adding 5-sulfoisophthalic acid or an esterified product thereof, terephthalic acid or an esterified product thereof and butanediol into a reaction kettle, then adding a catalyst of tetrabutyl titanate or tetraisopropyl titanate and a tetrahydrofuran inhibitor, and reacting for 2-5 hours at 150-240 ℃ to obtain a sulfonate group-containing compound with the number average molecular weight of 600-2000 g/mol; the sulfonate is sodium sulfonate, potassium sulfonate or lithium sulfonate.
7. The method for preparing a sulfonate group-containing compound according to claim 6, wherein: the mol ratio of the isophthalic acid-5-sulfonate or the esterified product thereof to the terephthalic acid or the esterified product thereof is 1: 0.1 to 30.0.
8. The method for producing the sulfonate group-containing compound according to claim 6 or 7, wherein: the mol ratio of the total amount of the isophthalic acid-5-sulfonate or the esterified product thereof and the terephthalic acid or the esterified product thereof to the butanediol is 1: 1.5 to 10.0.
9. The method for producing the sulfonate group-containing compound according to claim 6 or 7, wherein: the addition amount of the tetrahydrofuran inhibitor is 30-300 ppm of the total addition amount of butanediol.
10. The method for producing the sulfonate group-containing compound according to claim 6 or 7, wherein: the tetrahydrofuran inhibitor is one or more of tetraethyl ammonium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, lithium hydroxide, magnesium acetate, potassium acetate, lithium acetate, potassium carbonate, calcium carbonate, magnesium carbonate and sodium hexametaphosphate.
11. Use of a sulfonate group-containing compound of claim 1 in a polyester.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112029149A (en) * | 2020-09-16 | 2020-12-04 | 贺州学院 | Polyester water-soluble polymer modifier for calcium carbonate surface modification and preparation method thereof |
| CN114957627A (en) * | 2022-05-16 | 2022-08-30 | 万华化学集团股份有限公司 | Preparation method of polyester with low byproduct tetrahydrofuran |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112029149A (en) * | 2020-09-16 | 2020-12-04 | 贺州学院 | Polyester water-soluble polymer modifier for calcium carbonate surface modification and preparation method thereof |
| CN114957627A (en) * | 2022-05-16 | 2022-08-30 | 万华化学集团股份有限公司 | Preparation method of polyester with low byproduct tetrahydrofuran |
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