CN113801309A - Hydrolysis-resistant high-strength cation dyeable polyester composition and preparation method and application thereof - Google Patents
Hydrolysis-resistant high-strength cation dyeable polyester composition and preparation method and application thereof Download PDFInfo
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- CN113801309A CN113801309A CN202010533333.6A CN202010533333A CN113801309A CN 113801309 A CN113801309 A CN 113801309A CN 202010533333 A CN202010533333 A CN 202010533333A CN 113801309 A CN113801309 A CN 113801309A
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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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- 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
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
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Abstract
The application discloses a hydrolysis-resistant high-strength cation-dyeable polyester composition and a preparation method thereof. The cationic dyeable polyester composition mainly comprises an aromatic dicarboxylic acid structural unit and an aliphatic diol structural unit, wherein the cationic dyeable polyester composition comprises a compound shown in the formula 1 (A)
Description
Technical Field
The invention relates to a hydrolysis-resistant high-strength cationic dyeable polyester composition, in particular to a polyester composition containing a terminal blocked sulfonate group.
Background
Polyester resins are widely used in industrial fields such as clothing, industrial fibers, magnetic tapes, surface coating films, and tire meridian and mesh lines because of their excellent mechanical and chemical properties.
When used as a clothing fiber, in order to improve the dyeability of polyester, a copolymer modified cationic dyeable polyester is obtained by using an isophthalic acid component containing a sulfonate group, such as isophthalic acid-5-sodium sulfonate, as a comonomer. However, the sulfonate group is easy to physically crosslink in the polyester, so that the melt viscosity of the polyester is obviously increased under the condition of low Inherent Viscosity (IV), and the strength of the finally obtained yarn is low; meanwhile, the hydrolysis resistance of the polyester is poor due to the high content of the diethylene glycol as a byproduct and the carboxyl group at the end of the polyester, and the strength retention rate before and after yarn dyeing is poor, so that the application of the polyester in some fields with high strength requirements is limited.
Japanese patent laid-open No. 5-25708 discloses a modified polyester fiber, which is modified by using a component with blocked cation at the tail end, polyether and diol, the cation group in the obtained modified polyester is mainly connected at the tail end of a molecular chain, no physical crosslinking group is arranged in the middle of the molecular chain, the viscosity of the polyester is greatly reduced, the strength of the obtained cation polyester fiber is greatly improved compared with the prior polyester modified by the isophthalic acid component of sulfonate groups, and the spinning performance is not problematic. However, the terminal-blocked cationic component used in this patent causes a problem that the molecular weight of the polyester is not so large, and particularly, the polyester has a high terminal carboxyl group, poor hydrolysis resistance and low strength, and the strength retention ratio of the polyester before and after dyeing is low.
Disclosure of Invention
The invention aims to provide a hydrolysis-resistant high-strength cationic dyeable polyester composition and a preparation method thereof.
The technical solution of the invention is as follows:
the hydrolysis-resistant high-strength cationic dyeable polyester composition mainly comprises an aromatic dicarboxylic acid structural unit and an aliphatic diol structural unit. The polyester composition contains a sulfonate group shown in a formula 1, and the content of the group shown in the formula 1 accounts for 1000-5000 ppm, preferably 1000-3500 ppm of the total amount of the polyester composition in terms of sulfur element; the terminal carboxyl group COOH of the polyester composition is below 40 eq/t;
in the formula 1, Y is alkyl, phenyl or alkylbenzene with 2-20 carbon atoms, and Z is Li ion, Na ion or K ion.
The molar ratio of the alkali metal element to the sulfur element in the polyester composition is preferably greater than 1.00.
The polyester composition has a hydrolysis resistance index delta COOH of less than 80eq/t after being treated for 4 hours under saturated water vapor with the temperature of 155 ℃ and the humidity of 100 percent.
The invention also discloses a preparation method of the hydrolysis-resistant high-strength cationic dyeable polyester composition, which comprises the steps of firstly carrying out esterification or ester exchange reaction on aromatic dicarboxylic acid or esterified derivatives thereof and aliphatic diol to obtain an oligomer, then carrying out polymerization reaction on the oligomer, and finally carrying out solid-phase polymerization to obtain the polyester composition. Adding an alkali metal compound and a sulfonate compound shown as a formula 2 at any stage before the polymerization reaction is finished, wherein the alkali metal compound is one or more of sodium acetate, lithium acetate and potassium acetate; the addition amount of the sulfonate compound shown as the formula 2 is 1000-5000 ppm, preferably 1000-3500 ppm calculated by sulfur element relative to the total amount of the polyester composition,
in the formula 2, Y is alkyl, phenyl or alkylbenzene with 2-20 carbon atoms, and Z is Li ion, Na ion or K ion.
The amount of the alkali metal compound added is preferably 1000ppm or less based on the total amount of the polyester composition.
The sulfonate compound is preferably added 20 to 60min after the start of polymerization.
The reaction temperature of the solid-phase polymerization is preferably 200 to 240 ℃, the reaction pressure is preferably below 1000Pa, and the reaction time is preferably below 100 hours.
The polyester composition has good hydrolysis resistance, the contents of diethylene glycol and terminal carboxyl are low, the strength retention rate is good before and after dyeing, and the polyester composition can be applied to fibers.
Detailed Description
In the prior art, cationic dyeability is generally imparted to polyesters by copolymerizing in the polyester a cationic dyeable ingredient containing a sulfonate group, such as isophthalic acid-5-sulfonate or the like. However, since sulfonate groups are distributed in the middle of the molecular weight of the polyester, physical crosslinking of sulfonate groups in the polyester is likely to occur, resulting in an increase in the viscosity of the polyester and a decrease in the strength of the polyester. At the same time, the hydrolysis resistance of the polyester is also deteriorated.
In order to overcome the above problems, the cationic dyeable ingredient used in the present invention is a sulfonate compound represented by formula 2,
in the formula 2, Y is alkyl, phenyl or alkylbenzene with 2-20 carbon atoms, and Z is Li ion, Na ion or K ion.
The sulfonate compound shown as the formula 2 only contains one hydroxyl reaction group, the sulfonate compound is mainly connected to the tail end of a molecular chain in the polyester, and no physical crosslinking group is interacted between the molecular chains, so that the obtained polyester has high molecular weight and high strength.
Specific examples thereof include sodium 22-carboxybenzenesulfonate, potassium 2-carboxybenzenesulfonate, sodium 3-carboxybenzenesulfonate, lithium 3-carboxybenzenesulfonate, sodium 4-carboxybenzenesulfonate, methyl 2-sulfonate, methyl 3-sulfonate, methyl 4-sulfonate, ethyl 2-sulfonate, ethylene glycol 2-sulfonate, ethyl 3-sulfonate, ethylene glycol 4-sulfonate, and ethylene glycol 3-sulfonate, and sodium 3-sulfonate is preferably sodium 3-carboxybenzenesulfonate.
The polyester composition added with the cationic dyeable component of the sulfonate compound shown as the formula 2 contains a sulfonate group shown as the formula 1,
in the formula 1, Y is alkyl, phenyl or alkylbenzene with 2-20 carbon atoms, and Z is Li ion, Na ion or K ion.
The content of the sulfonate group shown in the formula 1 in the polyester composition accounts for 1000-5000 ppm of the total amount of the polyester composition in terms of sulfur element. When the content of the sulfonate group shown in the formula 1 in the polyester composition is lower than 1000ppm, the obtained product is difficult to achieve satisfactory color concentration in the subsequent dyeing process; when the content of the sulfonate group represented by the formula 1 in the polyester composition is more than 5000ppm, the growth of the polyester molecular chain is suppressed, and the polymerization is terminated without reaching the target viscosity, so that a polyester composition having good physical properties cannot be obtained. In view of both dyeing properties and physical properties of the polyester composition, the content of the sulfonate group represented by the formula 1 is preferably 1000 to 3500ppm in terms of sulfur in the polyester composition.
The molar ratio of the alkali metal element to the sulfur element in the polyester composition of the invention is greater than 1.00. The alkali metal element includes an alkali metal element in a sulfonate group shown in formula 1 and an alkali metal element in an alkali metal compound other than sulfonate.
The polyester composition of the present invention has a terminal carboxyl group COOH of 40 eq/ton or less, and preferably has a hydrolysis resistance index [ Delta ] COOH of 80 eq/ton or less after treatment for 4 hours with saturated water vapor at 155 ℃ and 100% humidity.
The invention also discloses a preparation method of the hydrolysis-resistant high-strength cationic dyeable polyester composition, which comprises the steps of firstly carrying out esterification or ester exchange reaction on aromatic dicarboxylic acid or an esterified derivative thereof and aliphatic diol to obtain an oligomer, then carrying out polymerization reaction on the oligomer, and finally carrying out solid-phase polymerization to obtain the polyester composition.
Adding an alkali metal compound and a sulfonate compound shown as a formula 2 at any stage before the polymerization reaction is finished,
in the formula 2, Y is alkyl, phenyl or alkylbenzene with 2-20 carbon atoms, and Z is Li ion, Na ion or K ion. Specific examples thereof include sodium 2-carboxylbenzenesulfonate, potassium 2-carboxylbenzenesulfonate, sodium 3-carboxylbenzenesulfonate, lithium 3-carboxylbenzenesulfonate, sodium 4-carboxylbenzenesulfonate, methyl 2-sulfonate, methyl 3-sulfonate, methyl 4-sulfonate, ethyl 2-sulfonate, ethylene glycol 2-sulfonate, ethyl 3-sulfonate, ethylene glycol 4-sulfonate, and ethylene glycol 3-sulfonate, among which sodium 3-carboxylbenzenesulfonate is preferable.
The addition amount of the sulfonate compound shown as the formula 2 is 1000-5000 ppm relative to the total amount of the polyester composition in terms of sulfur element. When the addition amount of the sulfonate compound shown as the formula 2 is less than 1000ppm, the obtained product is difficult to achieve satisfactory color concentration in the subsequent dyeing process; when the amount of the sulfonate compound represented by the formula 2 is more than 5000ppm, the increase of the molecular chain of the polyester is suppressed, causing a polymerization head phenomenon, and a polyester composition having good physical properties cannot be obtained. In view of both dyeability and physical properties of the polyester composition, the amount of the sulfonate compound represented by the formula 2 is preferably 1000 to 3500ppm in terms of sulfur in the polyester composition.
The sulfonate compound shown in the formula 2 can be added at any stage of esterification reaction, ester exchange reaction and polymerization reaction. When the polyester is added in the stage of esterification or transesterification, there is a risk that the polyester molecular chain segment is prematurely terminated and the polyester composition having a normal molecular weight range cannot be obtained, and the polyester composition contains a little more by-products than the conventional polyester and is also slightly inferior in dyeing stability and strength retention before and after dyeing. In order to obtain a polyester composition with high molecular weight and avoid the increase of byproducts in the polyester composition, the adding time of the sulfonate compound shown in the formula 2 is preferably in a polymerization reaction stage, enough time is left for the increase of the polyester molecular chain, and more preferably, the sulfonate compound is added 20min to 60min after the polymerization starts.
The sulfonate compound shown as the formula 2 is a powdery substance, so that when the sulfonate compound is added, the sulfonate compound shown as the formula 2 is dissolved in aliphatic diol to prepare aliphatic diol solution according to the conventional method in the field, and then the aliphatic diol solution is added. Specifically, according to the mass 1: 0.5-1: 10.0, at a temperature of 70-198 ℃ to form a homogeneous solution. The weight ratio of the sulfonate shown in the formula 2 to the aliphatic diol is preferably 1: 1.0-1: 2.0, the preferred dissolving temperature is 80-130 ℃. The aliphatic diol solution can be prepared by the above-mentioned method, but is not limited thereto.
Although the addition of the sulfonate compound as shown in formula 2 can impart cationic dyeability to the polyester composition without causing physical crosslinking between sulfonates, the strength of the polyester composition is maintained. However, the sulfonate compound represented by the formula 2 causes an increase in the content of terminal carboxyl groups of the polyester composition, affecting the heat resistance and hydrolysis resistance of the polyester composition.
In order to solve the above problems, the polyester product obtained by the polymerization reaction is subjected to solid-phase polymerization. The functional group terminal groups of the polyester macromolecules are mainly hydroxyethyl ester and terminal carboxyl, and in the solid-phase polymerization, the hydroxyethyl ester and the hydroxyethyl ester are subjected to ester exchange reaction and esterification reaction, so that the molecular weight of the polymer can be increased, and the terminal carboxyl of the polymer can be reduced. However, since the sulfonate compound of the present invention represented by formula 2 has only one reactive group, and after copolymerization with polyester, one end of the molecular chain of polyester is blocked, the reactive group at the end is reduced, which may decrease the reaction rate of solid phase polymerization. Therefore, the invention adds alkali metal compounds except sulfonate to adjust the reaction system of the polyester composition, improves the reactivity of the end group of the polyester molecular chain, improves the solid phase polymerization reaction speed, thereby reducing the content of the end carboxyl of the final polyester composition and improving the heat resistance and hydrolysis resistance of the polymer.
The timing of addition of the alkali metal compound may be any stage of esterification reaction, transesterification reaction or polymerization. The alkali metal compound can be one or more of sodium acetate, lithium acetate, potassium acetate and cesium acetate, wherein one or more of sodium acetate, lithium acetate and potassium acetate is preferred.
The amount of the alkali metal compound added is preferably 1000ppm or less based on the total amount of the polyester composition. If the amount of the alkali metal compound added is too large, the polyester side reaction rate increases, resulting in deterioration of heat resistance of the polyester composition.
The solid-phase polymerization method of the present invention is a method of polymerizing a polyester in a solid phase under an inert gas flow or in a vacuum at a temperature not higher than the melting point of the polyester composition. The conditions for the solid-phase polymerization are not particularly limited, and any reaction conditions generally used in the art may be employed. Specifically, the polyester product obtained by the polymerization reaction is subjected to pre-crystallization treatment, and then solid-phase polymerization is performed under the conditions that the reaction temperature is 200-240 ℃, the reaction pressure is less than 1000Pa, and the reaction time is less than 100 hours, so as to obtain the final polyester composition.
The aromatic dicarboxylic acid or esterified derivative thereof of the present invention may be terephthalic acid, isophthalic acid, naphthoic acid, dimethyl terephthalate, dimethyl isophthalate, dimethyl naphthalate, dimethyl phthalate, etc., and among them, terephthalic acid or dimethyl terephthalate is preferable. The aliphatic diol may be ethylene glycol, propylene glycol, butylene glycol, 1, 2-propylene glycol, pentylene glycol, neopentyl glycol, 1, 2-butylene glycol, etc., among which ethylene glycol, propylene glycol or butylene glycol is preferable.
The esterification reaction may be carried out in an esterification reaction tank in which an oligomer is present in advance, while continuously adding a slurry of an aliphatic diol and an aromatic dicarboxylic acid in a molar ratio of 1.05 to 1.50; in the esterification reaction tank in which the oligomer is present in advance, the aliphatic diol and the aromatic dicarboxylic acid may be added to the reaction mixture before the esterification reaction is started, and then the esterification reaction may be performed.
The ester exchange reaction can be controlled at a proper ester exchange reaction speed by adjusting the molar ratio of the aliphatic diol to the aromatic dicarboxylic acid esterification derivative to be within the range of 1.50-2.50. The catalyst used in this process may be any of various known catalysts, for example, oxides of metals such as cobalt, magnesium, manganese and titanium, or acetates thereof, and may be used in combination or singly.
The catalyst in the polymerization reaction may be any of various known polymerization catalysts. Such as antimony compounds, germanium compounds, titanium compounds, and the like. These catalysts may be used in combination or individually.
The esterification and polymerization reaction apparatus for producing the hydrolysis-resistant, high-strength cationic-dyeable polyester composition of the present invention can be any of various conventionally used reaction apparatuses.
The polyester group has good hydrolysis resistance, byproducts of diethylene glycol and terminal carboxyl are less, the strength retention rate before and after dyeing is good, and the polyester composition can be applied to fibers.
The measuring method and the evaluating method of each index of the invention are as follows:
(1) intrinsic Viscosity (IV)
0.8g of a polyester composition chip was dissolved in 10ml of an o-chlorophenol solution, and the intrinsic viscosity was measured at a water bath temperature of 25. + -. 0.2 ℃ by using an Ubbelohde viscometer.
(2) Carboxyl group Content (COOH)
The polyester chip was dissolved in a mixture of o-cresol and chloroform (70: 30 by weight), added with a bromothymol blue indicator, and then titrated with a 0.05N ethanol solution of potassium hydroxide, as measured by an optical titration method.
(3) Hydrolysis resistance index Δ COOH
Placing a certain amount of polyester granules in a sealed hydrolysis-resistant treatment system, treating for 4h under the saturated water vapor condition of 155 ℃ and 100% humidity, then measuring the terminal carboxyl of a treated sample, comparing the change of the terminal carboxyl of the polyester slices before and after treatment, and enabling the terminal carboxyl of the polyester slices after treatment to be delta COOH = the carboxyl of the slices before treatment.
(4) Analysis of Sulfur element content in polyester composition
And (4) carrying out quantitative analysis on the content of sulfur element in the polymer by an ICP element analyzer.
(5) Analysis of Sulfur element content in polyester composition
And quantitatively analyzing the content of the alkali element in the polymer by an ICP element analyzer.
(6) Evaluation of dyeing stability
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. Testing pre-dyed fibersThe fiber strength was S1, the fiber strength after dyeing was S2, and the strength retention was S2/S1. The stained sample was superposed in a light-tight state, and then subjected to CEI standard light sources D65 and 10 by a spectrophotometer (Datacolor 650 manufactured by Datacolor Asia Pacific (H.K.) Ltd.) under a CEI standard light sourceoColor measurements were performed under the angular conditions to yield L.
The advantages of the present invention will be described in detail below with reference to the examples and comparative examples. The present invention is not limited to the following examples.
Example 1
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding catalyst antimony trioxide, heat stabilizer trimethyl phosphate and lithium acetate, and carrying out polycondensation reaction at 290 ℃. Adding ethylene glycol solution of sulfonate shown as the formula 2 after the polymerization reaction is started for 30min, and discharging and granulating after the polymer reaches the required viscosity to obtain the required polyester composition.
After the polyester product obtained by polycondensation is subjected to pre-crystallization treatment, solid-phase polymerization is carried out under the conditions of the reaction temperature of 230 ℃, the reaction pressure of 50Pa and the reaction time of 30 hours to obtain solid-phase polymerization polyester, and the intrinsic viscosity IV of the polyester composition is 0.68 dl/g.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 80%, and the L value after dyeing is 25.
Example 2
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding catalyst antimony trioxide, heat stabilizer trimethyl phosphate and lithium acetate, and carrying out polycondensation reaction at 290 ℃. Adding ethylene glycol solution of sulfonate shown as the formula 2 after the polymerization reaction is started for 30min, and discharging and granulating after the polymer reaches the required viscosity to obtain the required polyester composition.
After the polyester product obtained by polycondensation is subjected to pre-crystallization treatment, solid-phase polymerization is carried out under the conditions of the reaction temperature of 230 ℃, the reaction pressure of 50Pa and the reaction time of 30 hours to obtain solid-phase polymerization polyester, and the intrinsic viscosity IV of the polyester composition is 0.67 dl/g.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 79%, and the L value after dyeing is 24.
Example 3
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding catalyst antimony trioxide, heat stabilizer trimethyl phosphate and lithium acetate, and carrying out polycondensation reaction at 290 ℃. Adding ethylene glycol solution of sulfonate shown as the formula 2 after the polymerization reaction is started for 30min, and discharging and granulating after the polymer reaches the required viscosity to obtain the required polyester composition.
After the polyester product obtained by polycondensation is subjected to pre-crystallization treatment, solid-phase polymerization is carried out under the conditions of the reaction temperature of 230 ℃, the reaction pressure of 50Pa and the reaction time of 20 hours to obtain solid-phase polymerization polyester, and the intrinsic viscosity IV of the polyester composition is 0.68 dl/g.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 82%, and the L value after dyeing is 24.
Example 4
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding catalyst antimony trioxide, heat stabilizer trimethyl phosphate and lithium acetate, and carrying out polycondensation reaction at 290 ℃. Adding ethylene glycol solution of sulfonate shown as the formula 2 after the polymerization reaction is started for 30min, and discharging and granulating after the polymer reaches the required viscosity to obtain the required polyester composition.
After the polyester product obtained by polycondensation is subjected to pre-crystallization treatment, solid-phase polymerization is carried out under the conditions of the reaction temperature of 230 ℃, the reaction pressure of 50Pa and the reaction time of 40 hours to obtain solid-phase polymerization polyester, and the intrinsic viscosity IV of the polyester composition is 0.65 dl/g.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 78%, and the L value after dyeing is 25.
Example 5
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding catalyst antimony trioxide, heat stabilizer trimethyl phosphate and lithium acetate, and carrying out polycondensation reaction at 290 ℃. Adding ethylene glycol solution of sulfonate shown as the formula 2 after the polymerization reaction is started for 30min, and discharging and granulating after the polymer reaches the required viscosity to obtain the required polyester composition.
After the polyester product obtained by polycondensation is subjected to pre-crystallization treatment, solid-phase polymerization is carried out under the conditions of the reaction temperature of 230 ℃, the reaction pressure of 50Pa and the reaction time of 20 hours to obtain solid-phase polymerization polyester, and the intrinsic viscosity IV of the polyester composition is 0.67 dl/g.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 77%, and the L value after dyeing is 24.
Example 6
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding catalyst antimony trioxide, heat stabilizer trimethyl phosphate and lithium acetate, and carrying out polycondensation reaction at 290 ℃. Adding ethylene glycol solution of sulfonate shown as the formula 2 after the polymerization reaction is started for 30min, and discharging and granulating after the polymer reaches the required viscosity to obtain the required polyester composition.
After the polyester product obtained by polycondensation is subjected to pre-crystallization treatment, solid-phase polymerization is carried out under the conditions of the reaction temperature of 230 ℃, the reaction pressure of 50Pa and the reaction time of 20 hours to obtain solid-phase polymerization polyester, and the intrinsic viscosity IV of the polyester composition is 0.64 dl/g.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 75%, and the L value after dyeing is 30.
Example 7
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding catalyst antimony trioxide, heat stabilizer trimethyl phosphate and lithium acetate, and carrying out polycondensation reaction at 290 ℃. Adding ethylene glycol solution of sulfonate shown as the formula 2 after the polymerization reaction is started for 30min, and discharging and granulating after the polymer reaches the required viscosity to obtain the required polyester composition.
After the polyester product obtained by polycondensation is subjected to pre-crystallization treatment, solid-phase polymerization is carried out under the conditions of the reaction temperature of 230 ℃, the reaction pressure of 50Pa and the reaction time of 30 hours to obtain solid-phase polymerization polyester, and the intrinsic viscosity IV of the polyester composition is 0.67 dl/g.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 80%, and the L value after dyeing is 23.
Example 8
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding catalyst antimony trioxide, heat stabilizer trimethyl phosphate and sodium acetate, and carrying out polycondensation reaction at 290 ℃. Adding ethylene glycol solution of sulfonate shown as the formula 2 after the polymerization reaction is started for 30min, and discharging and granulating after the polymer reaches the required viscosity to obtain the required polyester composition.
After the polyester product obtained by polycondensation is subjected to pre-crystallization treatment, solid-phase polymerization is carried out under the conditions of the reaction temperature of 230 ℃, the reaction pressure of 50Pa and the reaction time of 30 hours to obtain solid-phase polymerization polyester, and the intrinsic viscosity IV of the polyester composition is 0.64 dl/g.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 78%, and the L value after dyeing is 23.
Example 9
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding catalyst antimony trioxide, heat stabilizer trimethyl phosphate and potassium acetate, and carrying out polycondensation reaction at 290 ℃. Adding ethylene glycol solution of sulfonate shown as the formula 2 after the polymerization reaction is started for 30min, and discharging and granulating after the polymer reaches the required viscosity to obtain the required polyester composition.
After the polyester product obtained by polycondensation is subjected to pre-crystallization treatment, solid-phase polymerization is carried out under the conditions of the reaction temperature of 230 ℃, the reaction pressure of 50Pa and the reaction time of 30 hours to obtain solid-phase polymerization polyester, and the intrinsic viscosity IV of the polyester composition is 0.62 dl/g.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 75%, and the L value after dyeing is 23.
Example 10
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding catalyst antimony trioxide, heat stabilizer trimethyl phosphate and lithium acetate, and carrying out polycondensation reaction at 290 ℃. Adding ethylene glycol solution of sulfonate shown as the formula 2 after the polymerization reaction is started for 30min, and discharging and granulating after the polymer reaches the required viscosity to obtain the required polyester composition.
After the polyester product obtained by polycondensation is subjected to pre-crystallization treatment, solid-phase polymerization is carried out under the conditions of the reaction temperature of 230 ℃, the reaction pressure of 30Pa and the reaction time of 10 hours to obtain solid-phase polymerization polyester, and the intrinsic viscosity IV of the polyester composition is 0.64 dl/g.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 72%, and the L value after dyeing is 25.
Example 11
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding catalyst antimony trioxide, heat stabilizer trimethyl phosphate and lithium acetate, and carrying out polycondensation reaction at 290 ℃. Adding ethylene glycol solution of sulfonate shown as the formula 2 after the polymerization reaction is started for 30min, and discharging and granulating after the polymer reaches the required viscosity to obtain the required polyester composition.
After the polyester product obtained by polycondensation is subjected to pre-crystallization treatment, solid-phase polymerization is carried out under the conditions of the reaction temperature of 230 ℃, the reaction pressure of 30Pa and the reaction time of 30 hours to obtain solid-phase polymerization polyester, and the intrinsic viscosity IV of the polyester composition is 0.65 dl/g.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 74%, and the L value after dyeing is 23.
Example 12
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding catalyst antimony trioxide, heat stabilizer trimethyl phosphate and lithium acetate, and carrying out polycondensation reaction at 290 ℃. Adding ethylene glycol solution of sulfonate shown as the formula 2 after the polymerization reaction is started for 30min, and discharging and granulating after the polymer reaches the required viscosity to obtain the required polyester composition.
After the polyester product obtained by polycondensation is subjected to pre-crystallization treatment, solid-phase polymerization is carried out under the conditions of the reaction temperature of 230 ℃, the reaction pressure of 20Pa and the reaction time of 30 hours to obtain solid-phase polymerization polyester, and the intrinsic viscosity IV of the polyester composition is 0.62 dl/g.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 70%, and the L value after dyeing is 25.
Example 13
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding catalyst antimony trioxide, heat stabilizer trimethyl phosphate and lithium acetate, and carrying out polycondensation reaction at 290 ℃. And adding a glycol solution of sulfonate shown as a formula 2 after 10min from the beginning of the polymerization reaction, and spitting and granulating after the polymer reaches the required viscosity to obtain the required polyester composition.
After the polyester product obtained by polycondensation is subjected to pre-crystallization treatment, solid-phase polymerization is carried out under the conditions of the reaction temperature of 230 ℃, the reaction pressure of 30Pa and the reaction time of 30 hours to obtain solid-phase polymerization polyester, and the intrinsic viscosity IV of the polyester composition is 0.63 dl/g.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 71%, and the L value after dyeing is 25.
Example 14
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding catalyst antimony trioxide, heat stabilizer trimethyl phosphate and lithium acetate, and carrying out polycondensation reaction at 290 ℃. And adding a glycol solution of sulfonate shown as a formula 2 after 10min from the beginning of the polymerization reaction, and spitting and granulating after the polymer reaches the required viscosity to obtain the required polyester composition.
After the polyester product obtained by polycondensation is subjected to pre-crystallization treatment, solid-phase polymerization is carried out under the conditions of the reaction temperature of 230 ℃, the reaction pressure of 30Pa and the reaction time of 30 hours to obtain solid-phase polymerization polyester, and the intrinsic viscosity IV of the polyester composition is 0.63 dl/g.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 75%, and the L value after dyeing is 24.
Example 15
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding catalyst antimony trioxide, heat stabilizer trimethyl phosphate and lithium acetate, and carrying out polycondensation reaction at 290 ℃. And adding a glycol solution of sulfonate shown as a formula 2 after 10min from the beginning of the polymerization reaction, and spitting and granulating after the polymer reaches the required viscosity to obtain the required polyester composition.
After the polyester product obtained by polycondensation is subjected to pre-crystallization treatment, solid-phase polymerization is carried out under the conditions of the reaction temperature of 230 ℃, the reaction pressure of 30Pa and the reaction time of 30 hours to obtain solid-phase polymerization polyester, and the intrinsic viscosity IV of the polyester composition is 0.63 dl/g.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 68%, and the L value after dyeing is 26.
Example 16
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding catalyst antimony trioxide, heat stabilizer trimethyl phosphate and lithium acetate, and carrying out polycondensation reaction at 290 ℃. And adding a glycol solution of sulfonate shown as a formula 2 after 10min from the beginning of the polymerization reaction, and spitting and granulating after the polymer reaches the required viscosity to obtain the required polyester composition.
After the polyester product obtained by polycondensation is subjected to pre-crystallization treatment, solid-phase polymerization is carried out under the conditions of the reaction temperature of 230 ℃, the reaction pressure of 30Pa and the reaction time of 30 hours to obtain solid-phase polymerization polyester, and the intrinsic viscosity IV of the polyester composition is 0.63 dl/g.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 70%, and the L value after dyeing is 23.
Example 17
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding catalyst antimony trioxide, heat stabilizer trimethyl phosphate and lithium acetate, and carrying out polycondensation reaction at 290 ℃. And adding a solution of sulfonate shown as a formula 2 after 10min from the beginning of the polymerization reaction, and spitting and granulating after the polymer reaches the required viscosity to obtain the required polyester composition.
After the polyester product obtained by polycondensation is subjected to pre-crystallization treatment, solid-phase polymerization is carried out under the conditions of the reaction temperature of 230 ℃, the reaction pressure of 30Pa and the reaction time of 30 hours to obtain solid-phase polymerization polyester, and the intrinsic viscosity IV of the polyester composition is 0.60 dl/g.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 70%, and the L value after dyeing is 25.
Example 18
Uniformly mixing terephthalic acid (PTA), Ethylene Glycol (EG) and sulfonate shown as a formula 2, putting the mixture into a reaction kettle, and carrying out esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding catalyst antimony trioxide, heat stabilizer trimethyl phosphate and lithium acetate, and carrying out polycondensation reaction at 290 ℃. And (3) after the polymer reaches the required viscosity, discharging and granulating to obtain the required polyester composition.
After the polyester product obtained by polycondensation is subjected to pre-crystallization treatment, solid-phase polymerization is carried out under the conditions of the reaction temperature of 230 ℃, the reaction pressure of 30Pa and the reaction time of 30 hours to obtain solid-phase polymerization polyester, and the intrinsic viscosity IV of the polyester composition is 0.60 dl/g.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 68%, and the L value after dyeing is 25.
Comparative example 1
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding catalyst antimony trioxide, heat stabilizer trimethyl phosphate and lithium acetate, and carrying out polycondensation reaction at 290 ℃. Adding ethylene glycol solution of sulfonate shown as the formula 2 after the polymerization reaction is started for 30min, and discharging and granulating after the polymer reaches the required viscosity to obtain the required polyester composition.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 60%, and the L value after dyeing is 25.
Since no solid phase polymerization was carried out, the polyester composition had a low IV and a high COOH, and the strength retention before and after dyeing was poor.
Comparative example 2
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding a catalyst of antimony trioxide and a heat stabilizer of trimethyl phosphate, and carrying out polycondensation reaction at 290 ℃. Adding ethylene glycol solution of sulfonate shown as the formula 2 after the polymerization reaction is started for 30min, and discharging and granulating after the polymer reaches the required viscosity to obtain the required polyester composition.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 50%, and the L value after dyeing is 25.
Since no solid phase polymerization is carried out, and no alkali metal salt is added, the polyester composition has a low IV and a high COOH content, and the strength retention before and after dyeing is poor.
Comparative example 3
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding a catalyst of antimony trioxide and a heat stabilizer of trimethyl phosphate, and carrying out polycondensation reaction at 290 ℃. Adding ethylene glycol solution of sulfonate shown as the formula 2 after the polymerization reaction is started for 30min, and discharging and granulating after the polymer reaches the required viscosity to obtain the required polyester composition.
After the polyester product obtained by polycondensation is subjected to pre-crystallization treatment, solid-phase polymerization is carried out under the conditions of the reaction temperature of 230 ℃, the reaction pressure of 50Pa and the reaction time of 20 hours to obtain solid-phase polymerization polyester, and the intrinsic viscosity IV of the polyester composition is 0.56 dl/g.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 59%, and the L value after dyeing is 25.
Although solid-phase polymerization was carried out, the polyester composition had a low IV and a high COOH content because no alkali metal salt was added, and the strength retention before and after dyeing was poor.
Comparative example 4
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding catalyst antimony trioxide, heat stabilizer trimethyl phosphate and lithium acetate, and carrying out polycondensation reaction at 290 ℃. Adding m-phthalic acid-5-sodium sulfonate 30min after the polymerization reaction begins, and discharging and granulating after the polymer reaches the required viscosity to obtain the required polyester composition.
After the polyester product obtained by polycondensation is subjected to pre-crystallization treatment, solid-phase polymerization is carried out under the conditions of the reaction temperature of 230 ℃, the reaction pressure of 50Pa and the reaction time of 10 hours to obtain solid-phase polymerization polyester, and the intrinsic viscosity IV of the polyester composition is 0.59 dl/g.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 65%, and the L value after dyeing is 25.
Because the added sulfonate is sodium m-phthalic acid-5-sulfonate, the polyester composition has low IV, high COOH and poor strength retention rate before and after dyeing.
Comparative example 5
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding catalyst antimony trioxide, heat stabilizer trimethyl phosphate and lithium acetate, and carrying out polycondensation reaction at 290 ℃. Adding ethylene glycol solution of sulfonate shown as the formula 2 after the polymerization reaction is started for 30min, and discharging and granulating after the polymer reaches the required viscosity to obtain the required polyester composition.
After the polyester product obtained by polycondensation is subjected to pre-crystallization treatment, solid-phase polymerization is carried out under the conditions of the reaction temperature of 230 ℃, the reaction pressure of 50Pa and the reaction time of 20 hours to obtain solid-phase polymerization polyester, and the intrinsic viscosity IV of the polyester composition is 0.67 dl/g.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 80%, and the L value after dyeing is 45.
The amount of the sulfonate to be added is too low, the dyeability of the polyester composition is poor, and the L value is high.
Comparative example 6
Terephthalic Acid (PTA) and Ethylene Glycol (EG) are mixed evenly and then put into a reaction kettle for esterification reaction at 240 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding catalyst antimony trioxide, heat stabilizer trimethyl phosphate and lithium acetate, and carrying out polycondensation reaction at 290 ℃. Adding ethylene glycol solution of sulfonate shown as the formula 2 after the polymerization reaction is started for 30min, and discharging and granulating after the polymer reaches the required viscosity to obtain the required polyester composition.
After the polyester product obtained by polycondensation is subjected to pre-crystallization treatment, solid-phase polymerization is carried out under the conditions of the reaction temperature of 230 ℃, the reaction pressure of 50Pa and the reaction time of 20 hours to obtain solid-phase polymerization polyester, and the intrinsic viscosity IV of the polyester composition is 0.55 dl/g.
The polyester composition was spun to obtain drawn yarn, the drawn yarn was then doubled by 2 pieces to obtain a leg of a stocking at 22 gauge, and the leg of the stocking was dyed in a hot water bath of 130 ℃ with a dye (blue. TR) of 3% owf, acetic acid of 0.5ml/l, sodium acetate of 0.2g/l, and a bath ratio of 1:100 for 60 minutes. The strength of the fiber before dyeing is tested to be S1, the strength of the fiber after dyeing is S2, the strength retention rate is S2/S1 is 58%, and the L value after dyeing is 22.
The amount of the sulfonate to be added is too high, the IV of the polyester composition is low, COOH is high, and the strength retention before and after dyeing is poor.
Claims (11)
1. Hydrolysis-resistant high-strength cation-dyeable polyester composition mainly comprises aromatic dicarboxylic acid structural units and aliphatic diol structural units, and is characterized in that: the polyester composition contains a sulfonate group shown as a formula 1, and the content of the group shown as the formula 1 accounts for 1000-5000 ppm of the total amount of the polyester composition in terms of sulfur element; the terminal carboxyl group COOH of the polyester composition is below 40 eq/t;
in the formula 1, Y is alkyl, phenyl or alkylbenzene with 2-20 carbon atoms, and Z is Li ion, Na ion or K ion.
2. The hydrolysis-resistant high-strength cationic dyeable polyester composition as claimed in claim 1, wherein the molar ratio of the alkali metal element to the sulfur element in the polyester composition is greater than 1.00.
3. The hydrolysis-resistant high-strength cationic dyeable polyester composition according to claim 1 or 2, characterized in that: the content of the group shown in the formula 1 is 1000-3500 ppm of the total amount of the polyester composition calculated by sulfur element.
4. The hydrolysis-resistant high-strength cationic dyeable polyester composition according to claim 1 or 2, characterized in that: the polyester composition has a hydrolysis resistance index delta COOH of less than 80eq/t after being treated for 4 hours under saturated water vapor with the temperature of 155 ℃ and the humidity of 100 percent.
5. The method for preparing the hydrolysis-resistant high-strength cationic dyeable polyester composition as claimed in claim 1, wherein the polyester composition is prepared by esterification or ester exchange reaction of aromatic dicarboxylic acid or esterified derivative thereof and aliphatic diol, polymerization of the oligomer, and solid-phase polymerization, and is characterized in that: adding an alkali metal compound and a sulfonate compound shown as a formula 2 at any stage before the polymerization reaction is finished; the addition amount of the sulfonate compound shown as the formula 2 is 1000-5000 ppm relative to the total amount of the polyester composition in terms of sulfur element,
in the formula 2, Y is alkyl, phenyl or alkylbenzene with 2-20 carbon atoms, and Z is Li ion, Na ion or K ion.
6. The method for preparing the hydrolysis-resistant high-strength cationic dyeable polyester composition as claimed in claim 5, wherein the method comprises the following steps: the addition amount of the sulfonate shown in the formula 2 is 1000-3500 ppm relative to the total amount of the polyester composition in terms of sulfur element.
7. The process for preparing the hydrolysis-resistant high-strength cationic dyeable polyester composition according to claim 5 or 6, which comprises the steps of: the amount of the alkali metal compound added is 1000ppm or less based on the total amount of the polyester composition.
8. The process for preparing the hydrolysis-resistant high-strength cationic dyeable polyester composition according to claim 5 or 6, which comprises the steps of: the sulfonate compound is added 20min to 60min after the start of polymerization.
9. The process for preparing the hydrolysis-resistant high-strength cationic dyeable polyester composition according to claim 5 or 6, which comprises the steps of: the reaction temperature of the solid-phase polymerization is 200-240 ℃, the reaction pressure is below 1000Pa, and the reaction time is below 100 hours.
10. The process for preparing the hydrolysis-resistant high-strength cationic dyeable polyester composition according to claim 5 or 6, which comprises the steps of: the alkali metal compound is one or more of sodium acetate, lithium acetate and potassium acetate.
11. The use of the hydrolysis resistant high strength cationic dyeable polyester composition of claim 1 in fibers.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05331710A (en) * | 1992-05-26 | 1993-12-14 | Toyobo Co Ltd | Modified polyester fiber |
| US5637398A (en) * | 1990-11-26 | 1997-06-10 | Toyo Boseki Kabushiki Kaisha | Polyester fiber |
| CN103122059A (en) * | 2011-11-18 | 2013-05-29 | 东丽纤维研究所（中国）有限公司 | Cation dyeable flame-retardant polyester and preparation method thereof |
| CN104120504A (en) * | 2013-04-24 | 2014-10-29 | 东丽纤维研究所（中国）有限公司 | Hydrolysis resistant polyester fiber and preparation method thereof |
-
2020
- 2020-06-12 CN CN202010533333.6A patent/CN113801309A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5637398A (en) * | 1990-11-26 | 1997-06-10 | Toyo Boseki Kabushiki Kaisha | Polyester fiber |
| JPH05331710A (en) * | 1992-05-26 | 1993-12-14 | Toyobo Co Ltd | Modified polyester fiber |
| CN103122059A (en) * | 2011-11-18 | 2013-05-29 | 东丽纤维研究所（中国）有限公司 | Cation dyeable flame-retardant polyester and preparation method thereof |
| CN104120504A (en) * | 2013-04-24 | 2014-10-29 | 东丽纤维研究所（中国）有限公司 | Hydrolysis resistant polyester fiber and preparation method thereof |
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