WO2012027885A1

WO2012027885A1 - Preparation methods for copolyester and its fiber modified by aliphatic diol with side chains and isophthalic acid binary ester 5-sodium or potassium sulfonate

Info

Publication number: WO2012027885A1
Application number: PCT/CN2010/076487
Authority: WO
Inventors: 顾利霞; 谢宇江; 龚静华; 何正锋; 马敬红; 朱毅; 蔡再生; 徐冬
Original assignee: 东华大学; 上海联吉合纤有限公司
Priority date: 2010-08-31
Filing date: 2010-08-31
Publication date: 2012-03-08
Also published as: JP5751729B2; JP2013533905A

Abstract

Preparation methods for copolyester and its fiber modified by aliphatic diol with side chains and isophthalic acid binary ester 5-sodium or potassium sulfonate are disclosed. The copolyester is copolymerized by four kinds of monomers comprising terephthalic acid, ethylene glycol, isophthalic acid binary ester 5-sodium or potassium sulfonate and aliphaticdiol with side chains. The method comprises the following steps: synthesizing the copolyester by charging ethylene glycol and terephthalic acid into a first esterification kettle to carry out esterification; then, conveying the reaction materials into a second esterification kettle, charging isophthalic acid binary ester 5-sodium or potassium sulfonate for further esterification, wherein an aliphatic diol with side chains and ethylene glycol and terephthalic acid are charged into the first esterification kettle at the same time, or an aliphatic diol with side chains and isophthalic acid binary ester 5-sodium or potassium sulfonate are charged into the second esterification kettle to carry out esterification; then, conveying the reaction materials into a condensation kettle for condensation polymerization and obtaining copolyester product; during the copolymerization, the mole ratio of terephthalic acid, ethylene glycol, aliphatic diol with side chains and isophthalic acid binary ester 5-sodium or potassium sulfonate is 1:1.1-2.4:0.05-0.20:0.015-0.07. The copolyester can be polymerized continuously and spun into fiber directly.

Description

From aliphatic diols with side chains and isophthalic acid dibasic esters 5- or potassium sulfonate

Modified copolyester and preparation method thereof

The invention relates to the preparation of cationic dye-dyeable copolyester and fiber thereof, in particular to a modification of a fatty acid having a side chain and an isophthalic acid dibasic acid 5-sodium sulfonate or potassium. A novel copolyester and a method for preparing the same. Background technique

There are many methods for improving the dyeability of polyester fibers. The application of the modified monomers for copolymerization can be roughly divided into the following three types: (1) Cationic dye-dyeable monomers such as sodium (or potassium benzene sulfonate) (2) Disperse dye-dyeable monomers, such as isophthalic acid having a meta-structure; polyethylene glycol and sebacic acid having a flexible structure; (3) acid dye-dyeable monomers, such as Amino compound.

Cationic dye-dyeable polyester fiber, invented by DuPont in 1958, trade name DACRON T, referred to as CDP, industrialized in 1962. In the 1980s, Toray developed and developed the atmospheric pressure type cationic dye-dyeable polyester fiber, referred to as ECDP. High temperature and high pressure cationic dyeable copolyester fiber CDP, because dyeing must be carried out under high temperature and pressure conditions, natural fiber properties can be affected when blended with natural fibers such as fiber and cotton wool. The atmospheric pressure cationic dye is easy to dye polyester fiber ECDP. Due to the introduction of polyether in the macromolecule, the heat resistance of the fiber is poor, the spinning is unstable, and the spinnability and the properties of the fabric are affected. Since the 1990s, developed countries such as the United States and Japan and China have developed a number of new features of atmospheric pressure cationic dyes that are susceptible to dyeing by increasing the content of ethylene isophthalate-sodium 5-sulfonate (SIP). Polyester fiber HCDP, which has good dye uptake and color fastness, and its hygroscopicity increases with the increase of SIP content, but the interaction of ionic groups is enhanced due to the increase of SIP content in the polymerization stage. , resulting in a sharp increase in melt viscosity, making the polymerization difficult to carry out, it is very difficult to increase the molecular weight of the polymer, so the molecular weight of HCDP is generally low, and the high viscosity during melting also causes difficulty in product processing and deterioration of mechanical properties. Although the problem of blending with natural fiber is solved, the third monomer content is too high (three single content of 38 mol%), which leads to an increase in production cost, which further affects production. Summary of the invention

In view of the above problems in the prior art, the industry still needs to improve the dyeability and is easy to prepare, especially A method for preparing a modified copolyester produced industrially.

To this end, the present invention provides a novel copolyester modified with a side chain aliphatic diol and an isophthalic acid dibasic acid 5-sodium sulfonate or potassium and a fiber thereof.

A first aspect of the invention relates to a process for preparing a copolyester modified with a side chain aliphatic diol and an isophthalic acid dibasic acid 5-sodium sulfonate sodium or potassium. It is obtained by copolymerization of four kinds of monomers: terephthalic acid, ethylene glycol, isophthalic acid dibasic acid ester 5-sodium sulfonate or potassium, and an aliphatic diol containing a side chain.

The method includes the following steps:

Copolymerization of copolyester: Ethylene glycol and terephthalic acid are added to the first esterification tank for esterification; then, the reaction material is introduced into the second esterification tank to inject isophthalic acid dibasic acid 5-sodium sulfonate Or potassium, further esterified, wherein the aliphatic diol containing a side chain is injected into the first esterification kettle together with ethylene glycol and terephthalic acid, or an aliphatic diol having a side chain and an isophthalic acid The dibasic ester 5-sodium sulfonate or potassium is injected into the second esterification kettle to participate in the esterification reaction; then, the reaction material enters the polycondensation kettle for polycondensation to obtain a copolyester product; in the copolymerization, the reaction raw material is benzoic acid The molar ratio of formic acid, ethylene glycol, aliphatic diol with side chain and isophthalic acid dibasic acid 5-sodium sulfonate to potassium or potassium is 1: 1.1~2.4: 0.05-0.20: 0.015 0.07.

A second aspect of the invention relates to a process for preparing a copolyester fiber modified with a side chain aliphatic diol and an isophthalic acid dibasic acid 5-sodium sulfonate sodium or potassium, which method is continuous In the manner of polymerization and direct spinning, the copolyester is copolymerized from the following four monomers: terephthalic acid, ethylene glycol, isophthalic acid dibasic acid 5-sodium sulfonate Or potassium, and an aliphatic diol containing a side chain.

The method includes the following steps:

Copolymerization of copolyester: Ethylene glycol and terephthalic acid are added to the first esterification tank for esterification; then, the reaction material is introduced into the second esterification tank to inject isophthalic acid dibasic acid 5-sodium sulfonate Or potassium, further esterified, wherein the aliphatic diol containing a side chain is injected into the first esterification kettle together with ethylene glycol and terephthalic acid, or an aliphatic diol having a side chain and an isophthalic acid The dibasic ester 5-sodium sulfonate or potassium is injected into the second esterification kettle to participate in the esterification reaction; then, the reaction material enters the polycondensation kettle for polycondensation to obtain a copolyester product; in the copolymerization, the reaction raw material is benzoic acid The molar ratio of formic acid, ethylene glycol, aliphatic diol with side chain and isophthalic acid dibasic acid 5-sodium sulfonate to potassium or potassium is 1: 1.1~2.4: 0.05-0.20: 0.015 -0.07;

Spinning: The copolyester product obtained above is directly spun into a spinning device and spun into a filament or staple fiber of a copolyester.

In a preferred embodiment of the present invention, the isophthalic acid dibasic ester 5-sodium sulfonate or potassium is selected From: ethylene isophthalate-sodium 5-sulfonate, ethylene isophthalate-potassium 5-sulfonate, propylene glycol isophthalate-sodium 5-sulfonate, propylene glycol isophthalate Ester-5-sulfonic acid potassium, isobutylene isophthalate-sodium 5-sulfonate, pentylene isophthalate-sodium 5-sulfonate, or a combination thereof. More preferred is ethylene isophthalate-sodium 5-sulfonate.

In another preferred embodiment, the side chain-containing aliphatic diol is selected from the group consisting of: 2-methyl-1, 3-propanediol, 2-methyl-1,4-butanediol, 2, 3- Dimethyl-1,4-butanediol, 3-ethyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, 3,3-dimethyl-1, 5- Pentylene glycol, or 3-methyl-3-ethyl-1,5-pentanediol. More preferred is 2-methyl-1,3-propanediol.

In a further preferred embodiment, the side chain aliphatic diol is 2-methyl-1,3-propanediol, the isophthalic acid dibasic acid 5-sodium sulfonate or Potassium is ethylene isophthalate-sodium 5-sulfonate. The molar content of the ethylene isophthalate-5-sulfonate unit in the copolyester macromolecular chain is 1.5 mol% to 7 mol%, 2-methyl group relative to the molar content of the terephthalic acid unit. The molar content of the -1,3-propanediol unit is from 5 mol% to 20 mol% based on the molar content of the terephthalic acid unit.

In a further preferred embodiment of the method of the present invention, in the copolymerization step, a divalent or trivalent metal compound catalyst is added, selected from one of: a metal Zn, Sb, Mn, Ca or Co compound or Several kinds, the amount of which is 0.01% by weight to 0.08% by weight based on the weight of the terephthalic acid; and the addition of trimethyl phosphate or triphenyl phosphate as a heat stabilizer, the amount of which is 0.02% by weight relative to the weight of the terephthalic acid ~0.06 weight ⁰ / ₀ .

In the method of producing a fiber according to the present invention, the copolymerization and spinning step is preferably carried out sequentially on a large continuous polymerization-spinning apparatus. The large-scale continuous polymerization-spinning apparatus preferably includes: a first esterification tank, a second esterification tank, a polycondensation tank, and a spinning device.

In still another preferred embodiment of the method of the present invention, wherein the esterification reaction temperature in the first esterification kettle is from 240 ° C to 270 ° C, and the reaction time is from 2 to 4 hours; the reaction temperature in the second esterification kettle is 240 ° C - 270 ° C, time 1-3 hours; reaction temperature in the polycondensation kettle is 270 ° C -300 ° C, time 2-4 hours;

In a preferred embodiment of the method for producing a fiber of the present invention, in the spinning device, the spinning screw temperature is 270 ° C to 320 ° C, the spinning speed is 400 to 3200 m / min, and the drawing temperature is 70. °C~160°C, the draw ratio is 1~4 times.

In the process of the present invention, it is preferred that the copolyester product obtained in the polycondensation kettle has an intrinsic viscosity of 0.4 to 0.7 and a melting point of 200 to 240 °C.

In the method of the present invention, it is preferred that the filaments or staple fibers of the copolyester obtained are under atmospheric pressure boiling conditions, It can be dyed dark with a cationic dye or a disperse dye at 95-100 ° C under normal pressure, and its dye uptake rate is above 90%.

The copolyester fiber obtained by the method of the present invention can be dyed into a dark color by a cationic dye or a disperse dye under normal pressure boiling conditions, and has a bright color and a wide chromatogram. At the same time, due to the reduced crystallinity and glass transition temperature of the copolyester, the fiber has an ultra-soft hand, the fabric does not require alkali treatment, and the short fibers also have anti-pilling properties. More importantly, the method of the present invention is easy to implement, and the manufacturing process has no special requirements on the equipment, and can be implemented on the existing large-scale continuous polymerization-spinning equipment in the field, which is very easy to realize industrial production and is low in cost. detailed description

The present invention relates to a novel copolyester modified with a side chain aliphatic diol and an isophthalic acid dibasic acid 5-sodium sulfonate or potassium and a method for preparing the same.

The isophthalic acid dibasic acid 5-sodium sulfonate or potassium is preferably selected from the group consisting of: ethylene isophthalate-sodium 5-sulfonate, ethylene isophthalate 5-sulfonic acid Potassium, propylene glycol isophthalate-sodium 5-sulfonate, propylene glycol isophthalate-potassium 5-sulfonate, butylene glycol isophthalate-sodium 5-sulfonate, pentanediol isophthalate Ester-5-sodium sulfonate, or a combination thereof.

The side chain-containing aliphatic diol preferably contains 4 to 25 carbon atoms, and specific examples thereof include, but are not limited to, 2-methyl-1, 3-propanediol, 2-methyl-1, 4-butylene Glycol, 2, 3-dimethyl-1, 4-butanediol, 3-ethyl-1, 5-pentanediol, 2-methyl-1, 5-pentanediol, 3, 3-di Methyl-1, 5-pentanediol, 3-methyl-3-ethyl-1, 5-pentanediol, and the like.

The aliphatic diol having a side chain is most preferably 2-methyl-1, 3-propanediol, isophthalic acid dibasic acid 5-sodium sulfonate or potassium is most preferably ethylene isophthalate-5 - sodium sulfonate.

In the copolyester macromolecular chain obtained by the process of the present invention, isophthalic acid dibasic acid 5-sodium sulfonate or potassium such as sodium or isophthalate-5-sulfonate sodium or potassium monomer unit The molar content of the molar ratio of the terephthalic acid monomer unit is from 1.5 mol% to 7 mol%, and the molar content of the aliphatic diol having a side chain such as 2-methyl-1,3-propanediol monomer unit is relative to The molar content of the terephthalic acid monomer unit is

5 mol% to 20 mol%.

The catalyst and the heat stabilizer are added during the copolymerization. The specific kind of the catalyst and the heat stabilizer of the present invention is not particularly limited, and those known in the art can be employed. For example, a divalent or trivalent metal compound catalyst may be used, preferably one or more of the metal-containing Zn, Sb, Mn, Ca or Co compounds, in an amount of 0.01% to 0.08% by weight of the terephthalic acid (% by weight) And adding a heat stabilizer, preferably trimethyl phosphate Or triphenyl phosphate, the content of which is 0.02% to 0.06% by weight of terephthalic acid.

In a preferred embodiment of the method for preparing a copolyester of the present invention, the first esterification tank is esterified with ethylene glycol and terephthalic acid, and the reaction temperature is 240 ° C - 270 ° C for 2-4 hours; Then, entering the second esterification kettle, simultaneously injecting the aliphatic diol containing the side chain and the isophthalic acid dibasic ester 5-sodium sulfonate or potassium, and further esterifying, the reaction temperature is 240 ° C - 270 ° C , time 1-3 hours; then, into the polycondensation kettle, the reaction temperature is 270 ° C -300 ° C, time 2-4 hours, that is, a new copolyester melt; wherein the reaction raw materials terephthalic acid, ethylene glycol, The molar ratio of the aliphatic diol having a side chain and the isophthalic acid dibasic acid 5-sodium sulfonate or potassium is 1: 1.1 to 2.4: 0.05-0.2: 0.015 to 0.07.

An aliphatic diol having a side chain therein may also be added in the first esterification kettle. However, it is preferably added together with sodium or potassium isophthalic acid dibasic acid 5-sulfonate in the second esterification tank.

Generally, when a modified copolyester is prepared by using an isophthalic acid comonomer, if an isophthalic acid monomer is added in an esterification tank stage, since the reactivity of the isophthalic acid monomer is less than that of the p-benzoic acid monomer, Will cause agglomeration of isophthalic acid monomer, gp: In the macromolecular chain of the synthesized copolyester product, the m-benzoic acid monomer units aggregate together, resulting in non-uniform composition on the macromolecular chain, making the polyester impossible Smooth spinning is carried out in the subsequent spinning stage, and qualified fibers cannot be obtained. Further, since the isophthalic acid monomer has poor solubility in the glycol, it is not preferable to add it to the esterification tank together with the glycol. Therefore, it is common practice to first esterify an isophthalic acid monomer to an isophthalate ester, then add it to a polycondensation kettle, and copolycondensate with a p-benzoic acid ester such as ethylene terephthalate to form a copolyester. .

The inventors of the present invention have unexpectedly discovered through research that: in the method of the present invention, isophthalic acid dibasic acid 5-sodium sulfonate or potassium (preferably with a side chain-containing fat) is added to the second esterification kettle. The copolyester is added to the second esterification kettle together, and the prepared copolyester has excellent spinnability. The obtained modified copolyester can be smoothly spun to form an acceptable fiber having excellent properties.

Further, the modified copolyester obtained by the process of the present invention can not only be smoothly spun into an acceptable fiber, but also unexpectedly capable of forming fibers (including filaments or short fibers) in a continuous polymerization and direct spinning manner. This ensures that the process of the invention can be carried out on large continuous polymerization-spinning equipment and thus industrially produced.

In the prior art, not all copolyesters can be made into fibers by continuous polymerization and direct spinning, because the copolyesters introduce comonomer components during polymerization, which tends to result in non-uniform composition, and continuous Polymerization and direct spinning methods require higher uniformity of materials. Especially for a copolyester containing an isophthalic acid dibasic acid ester 5-sulfonate sodium or potassium unit and a fourth unit, even a copolyester prepared by adding a metabenzoate during the polycondensation stage, Both continuous polymerization and direct spinning must be applied. However, the process of the present invention comprises adding a meta-benzene dibasic acid ester to a sodium or potassium 5-sulfonate in a second esterification tank (preferably simultaneously adding a side chain) The aliphatic diol) was unexpectedly found to be suitable for continuous polymerization and direct spinning to obtain fibers having excellent properties.

Although the mechanism is not clear, it is presumed that when the toluene dibasic acid diester-sodium 5-sulfonate sodium or potassium monomer is added in the second esterification kettle, the isophthalic acid dibasic ester is 5 - the sodium or potassium sulfonate is dissolved in the diol, the unreacted ethylene glycol in the second esterification tank, and preferably the side chain-containing aliphatic diol added simultaneously, which facilitates the dissolution of the meta-benzene dibasic acid binary The ester 5-sulfonate sodium or potassium monomer promotes uniform dispersion in the reaction vessel and participates uniformly in the reaction, which helps to improve the composition uniformity of the copolyester product.

Synthesizing a side chain-chained aliphatic diol and an isophthalic acid dibasic ester-sodium 5-sulfonate-modified novel copolyester on a large continuous polymerization-spinning apparatus and directly spinning, the advantage is It can realize industrialized large-scale continuous production, and the obtained copolyester melt can directly spin short fibers or filaments, and the cost is greatly reduced, and the obtained copolyester has uniform quality and good spinnability.

The side chain aliphatic diol and the isophthalic acid dibasic ester 5-sodium sulfonate or potassium modified copolyester melt synthesized on a large continuous polymerization apparatus can be directly spun short fibers or long Silk, in the spinning step, the screw temperature in the spinning device is 270 to 320 ° C, the spinning speed is 400 to 3200 m/min, the drawing temperature is 70 to 160 ° C, and the draw ratio is 1 to 4 times. Modified new copolyester staple fibers or POY, FDY filaments can be obtained, and the elastic yarn DTY can be obtained by adding elastic.

The copolyester provided by the invention introduces a sulfonate group into its macromolecular chain and introduces a side chain alkane group, so that the copolyester staple fiber can be used for cationic dye under normal pressure boiling conditions. The disperse dye can be dyed dark, bright color, extensive chromatogram, anti-pilling, and at the same time, due to the volume effect of the side chain groups of the aliphatic diol with side chains, the crystallization properties of the copolyester are reduced. And the glass transition temperature makes the obtained fiber have a super soft hand and no itching.

In addition, the aliphatic diol with side chain and the isophthalic acid dibasic ester 5-sodium sulfonate or potassium modified copolyester fiber prepared by the invention have no special requirements for the manufacturing process. It is produced on imported or domestically produced ordinary equipment, and the cost is low, which makes it easy to realize industrial production. Example

The invention is further illustrated below in conjunction with specific embodiments. It is to be understood that the examples are merely illustrative of the invention and are not intended to limit the scope of the invention. In addition, it should be understood that various changes and modifications may be made by those skilled in the art in the scope of the invention. Example 1

Using a continuous polymerization apparatus, the first esterification tank is fed with 1 ton of terephthalic acid (PTA) and 600 kg of ethylene glycol (EG) for esterification, and a catalyst equivalent to 0.02% by weight of PTA is added. PTA weight 0.02% triphenyl phosphate, reaction temperature is 260 ° C, after esterification for 3 hours, the material enters the second esterification tank, while injecting 3,3-dimethyl-1, 5 equivalent to 7 mol% of PTA - pentanediol, and 1.5% by mole of PTA isophthalate-5-sulfonate (with EG as solvent), further esterification, reaction temperature 250 ° C, after 2 hours of reaction, the material enters The polycondensation kettle was heated at a reaction temperature of 275 ° C for 3 hours to obtain a copolyester melt. The intrinsic viscosity is 0.592 and the melting point is 228 °C. Example 2

Using a continuous polymerization apparatus, the first esterification tank was charged with 1 ton of PTA and 410 kg of EG for esterification, and a catalyst equivalent to 0.032% by weight of PTA and a triphenyl phosphate of 0.0125% by weight of PTA were added. The reaction temperature was After 260 ° C, after 3 hours of reaction, the material was introduced into the second esterification kettle while injecting a molar equivalent of 17 mol% of 3-methyl-3-ethyl-1,5-pentanediol and equivalent to PTA 1.8 mol%. A molar amount of sodium propylene isophthalate-5-sulfonate (with EG as solvent), further esterification, reaction temperature 252 ° C, after 3 hours of reaction, the material enters the polycondensation kettle, the reaction temperature is 275-286 ° C After the feed, a vacuum is applied. When the temperature rises to 286 ° C (about lh), the temperature is lowered and the reaction is carried out for 3 hours to obtain a copolyester melt. The copolyester has an intrinsic viscosity of 0.512 and a melting point of 216 °C. Example 3

Using a continuous polymerization apparatus, the first esterification tank was charged with 1 ton of PTA and 800 kg of EG for esterification, and a catalyst equivalent to 0.02% by weight of PTA and a triphenyl phosphate equivalent to 0.02% by weight of PTA were added. After the temperature was 260 ° C, after 3 hours of reaction, the material was introduced into the second esterification kettle while injecting 12 mol% of 3-ethyl-1,5-pentanediol equivalent to PTA and 3 mol% of PTA equivalent of PTA. Ethylene glycolate-5-sulfonate (with EG as solvent), further esterification, reaction temperature 250 ° C, after 3 hours of reaction, the material enters the polycondensation kettle, the reaction temperature is 270-280 ° C, and the reaction ends after 4 hours. A copolyester is obtained. The copolyester has an intrinsic viscosity of 0.498 and a melting point of 212 °C. Example 4 Continuous polymerization, mixed PTA and EG (molar ratio 1.18), added to the first esterification kettle, while adding a catalyst equivalent to 0.02% by weight of PTA, antimony trioxide and triphenyl phosphate equivalent to 0.02% by weight of PTA The reaction temperature was 263 ° C, and the esterification reaction time was 3.5 hours. Entering the second esterification kettle while injecting 10 mol% of 2-methyl-1,5-pentanediol equivalent to PTA and 1.5 mol% of PTA isophthalate-5-sulfonate equivalent to PTA (with EG For solvent), further esterification, reaction temperature 250 ° C, after 2 hours residence time, the reactants enter the pre-polycondensation kettle I, the reaction temperature is 270-275 ° C, the reaction time is 0.5 hours, and then enter the pre-polycondensation kettle II, the reaction The temperature was 270 to 275 ° C, the reaction time was 1.5 h, the final polycondensation reaction temperature was 280 to 285 ° C, the reaction time was 2 hours, and the copolyester melt intrinsic viscosity was 0.6. Direct spinning of short fibers, spinning screw temperature 290 ° C, spinning speed 1300 m / min, pre-stretching 1.013 times, first stretching ratio 2.9 times, second stretching ratio 1.1-1.14 times, stretching speed 190 m/min, stretching bath temperature 60 ° C, second drawing temperature 80 ° C, relaxation temperature of each zone 65 ° C / 65 ° C / 60 ° C / 60 ° C, the fiber fineness 1.4 dt, cut off The length is 38mm, the breaking strength is 3.98CN/dt, the elongation at break is 27.5 %, the dry heat shrinkage at 180 °C is 23.3%, and the defect is 0. The dyed fiber was dyed with a cationic red X-5 GL dye at 98 ° C under normal pressure at a rate of 93.7%. Further, the disperse dye was used to disperse red 3B, and the dye uptake rate at a normal pressure of 98 ° C was 90.7 %. Example 5

Continuous polymerization, mixed PTA and EG (molar ratio of 1.2), added to the first esterification kettle, while adding a catalyst equivalent to 0.02% by weight of PTA, antimony trioxide and triphenyl phosphate equivalent to 0.03% by weight of PTA The reaction temperature was 265 ° C and the esterification reaction time was 4 hours. Entering the second esterification kettle while injecting 10-dimethyl-1,4-butanediol equivalent to PTA 10 mol% and sodium isophthalate-5-sulfonate equivalent to PTA 2.0 mol% EG is a solvent), further esterification, reaction temperature 250 ° C, after a residence time of 2 hours, the reactants enter the pre-polycondensation kettle I, the reaction temperature is 270-275 ° C, the reaction time is 0.5 hours, and then enter the pre-polycondensation II, the reaction The temperature was 270 to 275 ° C, the reaction time was 1.5 h, and finally the final polycondensation was carried out at a reaction temperature of 280 to 285 ° C for a reaction time of 2 hours, and the obtained copolyester had an intrinsic viscosity viscosity of 0.53. Direct spinning of short fibers by melt, spinning speed 1300 m/min, pre-stretching 1.016 times, first draw ratio 2.95 times, second draw ratio 1.125 times, drawing speed 190 m/min, drawing bath temperature 60 ° C, the second drawing temperature is 80 ° C, the relaxation temperature of each zone is 80 ° C / 80 ° C / 75 ° C / 75 ° C, the obtained fiber has a fineness of 2.03 dt, a cut length of 51 mm, and a breaking strength of 2.79 CN/dt. The elongation at break is 42.5 %, the dry heat shrinkage at 180 °C is 23.8%, and the defect is 0.6. The dyed fiber was dyed with a cationic yellow X-8GL dye at a temperature of 95-100 ° C at a pressure of 95.2%. In addition, disperse dye red 3B is used, and the dye uptake rate at normal pressure of 98 ° C is 92.2 %. Example 6

Using continuous polymerization, mixed PTA and EG (molar ratio of 1.65), adding to the first esterification kettle, while adding a catalyst equivalent to 0.03% by weight of PTA, antimony trioxide and triphenyl phosphate equivalent to 0.04% by weight of PTA. The reaction temperature was 260 ° C, and the esterification reaction time was 3 hours. Entering the second esterification kettle while injecting 12 mol% of 2-methyl-1,3-propanediol equivalent to PTA and 2.5 wt% of ethylene isophthalate-5-sulfonate equivalent to PTA (with EG Solvent), further esterification, reaction temperature 253 ° C, residence time 1.5 hours, the reactants enter the pre-polycondensation kettle I, the reaction temperature is 268 ° C, the reaction time is 0.5 hours; then enter the pre-polycondensation kettle II, the reaction temperature is 268 °C, the reaction time was 1 hour; finally, the final polycondensation kettle was introduced, the reaction temperature was 268 ° C, and the reaction time was 2 hours, and the obtained copolyester intrinsic viscosity was 0.57. Direct spinning of short fibers by melt, spinning speed 870 m/min, pre-stretching 1.02 times, first stretching ratio 3 times, second stretching ratio 1.14 times, stretching speed 190 m/min, drawing bath temperature 65 ° C, the second draw 80 ° C, the relaxation temperature of each zone 65 ° C / 65 ° C / 60 ° C / 60 ° C, the fiber has a fineness of 3.01dt, a cut length of 38mm, a breaking strength of 3.28CN / dt, The elongation at break is 32.5 %, the dry heat shrinkage at 180 °C is 24%, and the defect is 4.5. The dyed fiber was dyed with a cationic pink X-FG dye at a normal pressure of 95 to 100 ° C and a dyeing rate of 96.5%. In addition, the disperse dye was used to disperse red 3B, and it was dyed under normal pressure at 98 ° C, and the dye uptake rate was 93.2 %. Example 7

Continuous polymerization, mixed PTA and EG (molar ratio of 1.2), added to the first esterification kettle, and simultaneously added a catalyst equivalent to 0.03% by weight of PTA, antimony trioxide and triphenyl phosphate equivalent to 0.03% by weight of PTA. The reaction temperature was 261 ° C, and the esterification reaction time was 3 hours. Entering the second esterification tank while injecting 2,3-dimethyl-1,4-butanediol equivalent to 12 mol% of PTA and sodium p-isophthalate-5-sulfonate equivalent to 3 mol% of PTA (with EG as solvent), further esterification, reaction temperature 250 ° C, after 2 hours residence time, the reactants enter pre-polycondensation kettle I, reaction temperature 270-275 ° C, reaction time is 0.5 hours; then, enter pre-polycondensation The kettle II has a reaction temperature of 270 to 275 ° C and a reaction time of 1.5 h. Finally, it enters a final polycondensation kettle at a reaction temperature of 280 to 285 ° C for a reaction time of 2 hours, and the obtained copolyester has an intrinsic viscosity of 0.56. . Direct spinning of hollow short fibers by melt, spinning speed 1100 m/min, pre-stretching 1.007 times, first draw ratio 2.95 times, second draw ratio 1.14 times, draw speed 128 m/min, drawing bath temperature 65 °C, relaxation temperature of each zone 70 °C / 80 °C / 80 °C / 80 °C / 75 °C / 70 °C / 60 °C, hollow short fiber fineness 2.47dt, cut length 64mm, breaking strength 3.3CN /dt, elongation at break 32.6%, dry heat shrinkage at 25% at 180 °C, and fiber openness at 18.43%. Spun The fiber was dyed with a cationic violet X-5BLH dye at a pressure of 95-100 ° C at a pressure of 96.2%. In addition, the disperse dye was used to disperse red 3B, and it was dyed at a normal pressure of 98 ° C, and the dyeing rate was 94. %.

Continuous polymerization, mixed PTA and EG (molar ratio 1.15), added to the first esterification kettle, while adding a catalyst equivalent to 0.02% by weight of PTA, antimony trioxide and triphenyl phosphate equivalent to 0.02% by weight of PTA The reaction temperature was 265 ° C and the esterification reaction time was 4 hours. Then, the second esterification kettle is introduced while injecting 12 mol% of 2-methyl-1,4-butanediol equivalent to PTA and sodium p-isophthalate-5-sulfonate equivalent to 2 mol% of PTA ( With EG as solvent, further esterification, reaction temperature 250 ° C, residence time 2 hours, the reactants enter pre-polycondensation tank I, reaction temperature 270-275 ° C, reaction time is 0.5 hours, and then enter pre-condensation kettle II , the reaction temperature is 270~275 ° C, the reaction time is 1.5 h, finally enters the final polycondensation kettle, the reaction temperature is 280~285 ° C, the reaction time is 2 hours, and the obtained copolyester melt is directly spun into a short cross shape. Fiber, spinning speed 1150 m / min, pre-stretching 1.05 times, first stretching ratio 2.8 times, second stretching ratio 1.14 times, stretching speed 128m / min, stretching bath temperature 65 ° C, relaxation temperature of each zone 70 ° C / 80 ° C / 8 (TC / 8 (rC / 75 ° C / 70 ° C / 60 ° C, the fiber obtained 2.27 dt, cut length 51mm, breaking strength 2.78CN / dt, elongation at break The rate is 34.2%, the dry heat shrinkage rate at 180 °C is 25.3%, the defect point is 4.5. The fiber hollowness is 18.5%, and the cationic X-GRRL dye is used in 95-1. The dyeing rate was 94.1% at 00 ° C under normal pressure. In addition, red 3B was dispersed by disperse dye, and dyed at normal pressure and 98 ° C, the dye uptake rate was 91.4%.

Continuous polymerization, mixed PTA and EG (molar ratio of 1.2), added to the first esterification kettle, while adding a catalyst equivalent to 0.02% by weight of PTA, antimony trioxide and triphenyl phosphate equivalent to 0.02% by weight of PTA The reaction temperature was 265 ° C, and the esterification reaction time was 3 hours. Entering the second esterification kettle while injecting 15 mol% of 3-dimethyl-1,4-butanediol equivalent to PTA and sodium p-isophthalate-5-sulfonate equivalent to PTA 2 mol% EG is a solvent), further esterification, reaction temperature 250 ° C, after a residence time of 2 hours, the reactants enter the pre-polycondensation kettle I, the reaction temperature is 270-275 ° C, the reaction time is 0.5 hours, and then, into the pre-polycondensation kettle II , the reaction temperature is 270~275 ° C, the reaction time is 1.5 h, finally, enter the final polycondensation kettle, the reaction temperature is 280~285 ° C, the reaction time is 20 hours, and the obtained copolyester melt is directly prepared by high speed spinning FDY : Spinning speed 3000m/min, 110dtex/72F, breaking strength 2.3cN/dtex, elongation at break 32%, boiling water shrinkage 16%. The obtained filament fiber is dyed at a constant pressure of 95-100 ° C using a cationic X-GRRL dye. 93.1%. In addition, the dyeing rate of the dyed red FX dye at 95-100 ° C under normal pressure was 91.3%. Example 10

Continuous polymerization, mixed PTA and EG (molar ratio 1.15), added to the first esterification kettle, while adding a catalyst equivalent to 0.02% by weight of PTA, antimony trioxide and triphenyl phosphate equivalent to 0.02% by weight of PTA The reaction temperature was 265 ° C, and the esterification reaction time was 3 hours. Entering the second esterification kettle while injecting 15 mol% of 2-methyl-1,3-propanediol equivalent to PTA and 2.5 wt% of ethylene isophthalate-5-sulfonate equivalent to PTA (with EG Solvent), further esterification, reaction temperature 250 ° C, residence time 2 hours, the reactants enter the pre-polycondensation kettle I, the reaction temperature is 270-275 ° C, the reaction time is 0.5 hours, and then, into the pre-polycondensation kettle II, the reaction The temperature was 270 to 275 ° C, the reaction time was 1.5 h, and finally, the final polycondensation kettle was introduced, the reaction temperature was 280 to 285 ° C, and the reaction time was 2 hours. Copolyester melt direct high speed spinning POY, spinning speed 2600m/min, 165dtex/144f, breaking strength 1.3cN/dtex, elongation at break 1155%, hot box temperature on DTY 137°C, lower heat box 120°C , speed 550m / min, draft ratio 1.75 times, fiber fineness 90 dtex / 72f, breaking strength 2.5cN / dtex, elongation at break 25%, boiling water shrinkage 8%. The obtained POY fiber was dyed with a cationic violet X-5BLH dye at 95-100 ° C under normal pressure at a pressure of 95.1%. In addition, the dye uptake rate of the dispersed AC-V dye at 95-100 ° C under normal pressure was 95.2. %.

Claims

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A method for preparing a copolyester modified with a side chain aliphatic diol and an isophthalic acid dibasic acid 5-sodium sulfonate or potassium, the copolyester comprising the following four The monomers are copolymerized: terephthalic acid, ethylene glycol, isophthalic acid dibasic ester 5-sodium or potassium 5-sulfonate, and an aliphatic diol containing a side chain;

The method includes the following steps:

2. A method for preparing a copolyester fiber modified with a side chain aliphatic diol and an isophthalic acid dibasic acid 5-sodium sulfonate or potassium, which comprises continuous polymerization and direct spinning In a manner, the copolyester is copolymerized by the following four monomers: terephthalic acid, ethylene glycol, isophthalic acid dibasic acid 5-sodium sulfonate sodium or potassium, and a side chain of an aliphatic diol;

The method includes the following steps:

3. Method according to claim 1 or 2, characterized in that:

The isophthalic acid dibasic acid 5-sodium sulfonate or potassium is selected from the group consisting of: ethylene isophthalate-sodium 5-sulfonate, ethylene isophthalate-potassium 5-sulfonate , propylene isophthalate-sodium 5-sulfonate, m-phenylene Propylene glycol formate 5-potassium sulfonate, butylene isophthalate 5-sodium sulfonate, pentylene isophthalate 5-sodium sulfonate, or a combination thereof.

4. Method according to claim 1 or 2, characterized in that it:

The side chain-containing aliphatic diol is selected from the group consisting of: 2-methyl-1, 3-propanediol, 2-methyl-1,4-butanediol, 2,3-dimethyl-1, 4- Butylene glycol, 3-ethyl-1, 5-pentanediol, 2-methyl-1, 5-pentanediol, 3,3-dimethyl-1, 5-pentanediol, or 3-methyl 3-ethyl-1,5-pentanediol.

5. Method according to claim 1 or 2, characterized in that it:

The side chain aliphatic diol is 2-methyl-1,3-propanediol, and the isophthalic acid dibasic acid 5-sodium sulfonate or potassium is isophthalic acid ethylene glycol. Ester-5-sodium sulfonate;

The molar content of the ethylene isophthalate-5-sulfonate unit in the copolyester macromolecular chain is 1.5 mol% to 7 mol%, 2-methyl group relative to the molar content of the terephthalic acid unit. The molar content of the -1,3-propanediol unit is from 5 mol% to 20 mol% based on the molar content of the terephthalic acid unit.

6. Method according to claim 1 or 2, characterized in that:

In the copolymerization step, a divalent or trivalent metal compound catalyst is added, which is selected from one or more of metal Zn, Sb, Mn, Ca or Co compounds, and the amount thereof is relative to the weight of terephthalic acid. 0.01% by weight to 0.08% by weight; and trimethyl phosphate or triphenyl phosphate is added as a heat stabilizer in an amount of from 0.02% by weight to 0.06% by weight based on the weight of the terephthalic acid.

7. The method of claim 2 wherein said copolymerizing and spinning steps are carried out sequentially on a large continuous polymerization-spinning apparatus.

8. The method according to claim 7, wherein said large continuous polymerization-spinning apparatus comprises: a first esterification tank, a second esterification tank, a polycondensation tank, and a spinning device.

The method according to any one of claims 1 to 2, wherein the esterification reaction temperature in the first esterification tank is from 240 ° C to 270 ° C, and the reaction time is from 2 to 4 hours; The reaction temperature in the autoclave is 240 ° C - 270 ° C, time 1-3 hours; the reaction temperature in the polycondensation kettle is 270 ° C -300 ° C, time 2-4 hours;

10. The method according to claim 2 or 8, wherein in the spinning device, the spinning screw temperature is 270 ° C ~ 320 ° C, the spinning speed is 400 ~ 3200 m / min, the drawing temperature is 70 ° C~160°C, the draw ratio is 1~4 times.

The method according to claim 1 or 2, wherein the copolyester product obtained in the polycondensation vessel has an intrinsic viscosity of 0.4 to 0.7 and a melting point of 200 to 240 °C.

12. The method according to claim 2, wherein: the obtained copolyester filament or staple fiber Under the conditions of atmospheric pressure boiling dyeing, it can be dyed dark with cationic dye or disperse dye at 95-100 ° C under normal pressure, and its dyeing rate is above 90%.