阅读说明：本技术 一种腈纶同浴染色型波斯纶用聚酯及其制备方法 (Polyester for acrylic fiber one-bath dyeing type Persian fiber and preparation method thereof ) 是由 吴福胜 许宏平 徐冬生 高峰 欧阳勇军 孟祥海 张龙 龚春生 金善强 葛琳 于 2020-08-07 设计创作，主要内容包括：本发明公开了一种腈纶同浴染色型波斯纶用聚酯及其制备方法,是采用直接酯化、缩聚法将PTA、EG、SIPE、CHDM、IPA进行共聚,成功制备出波斯纶用聚酯切片。本发明所得产品玻璃化转变温度高、二甘醇含量低、阳离子染色性能优异,上染速率和腈纶相似,提高了腈纶同浴染色的相容性,大大降低了产品染色能耗,缩短了染色时间。(The invention discloses a polyester for acrylic one-bath dyeing type Bosslon and a preparation method thereof. The product obtained by the invention has high glass transition temperature, low diethylene glycol content, excellent cationic dyeing performance and similar dyeing rate to acrylic fibers, improves the compatibility of acrylic fibers in one-bath dyeing, greatly reduces the dyeing energy consumption of the product and shortens the dyeing time.)

1. The polyester for the acrylic one-bath dyeing type Persian is characterized by comprising the following raw materials in parts by weight:

2. the polyester for acrylic one-bath dyeing type Persian fiber as claimed in claim 1, wherein: the aliphatic diol is polyethylene glycol PEG, and the molecular weight range of the aliphatic diol is 200-20000.

3. The polyester for acrylic one-bath dyeing type Persian fiber as claimed in claim 1, wherein: the heat stabilizer is TMP, TPP and H₃PO₄At least one of (1).

4. The polyester for acrylic one-bath dyed forscron according to claim 3, wherein: the heat stabilizer is a compound heat stabilizer formed by mixing TMP and TPP according to the mass ratio of 1: 3-5.

5. The polyester for acrylic one-bath dyeing type Persian fiber as claimed in claim 1, wherein: the catalyst is a complex catalyst consisting of an antimony catalyst and a titanium catalyst, the antimony catalyst is formed by combining at least two of antimony trioxide, antimony acetate and ethylene glycol antimony, and the titanium catalyst is formed by at least two of ethylene glycol titanium, tetrabutyl titanate and nano titanium dioxide.

6. The polyester for acrylic one-bath dyed forscron according to claim 5, wherein: the mass ratio of the titanium catalyst to the antimony catalyst is 1: 2-4.

7. The polyester for acrylic one-bath dyeing type Persian fiber as claimed in claim 1, wherein: the compound ether-proof agent is formed by combining at least two of sodium acetate, sodium chloride, acetic acid, citric acid and tartaric acid.

8. The polyester for acrylic one-bath dyeing type Persian fiber as claimed in claim 1, wherein: the SIPE is obtained by taking SIPA or SIPM as a precursor and performing esterification reaction with ethylene glycol.

9. The polyester for acrylic one-bath dyed forscron according to claim 8, wherein: the esterification reaction process comprises the following steps: adding SIPA or SIPM serving as a precursor into a reaction kettle, adding glycol, controlling the molar ratio of the glycol to the precursor to be 5-10: 1, controlling the temperature rise rate of 2 ℃/min to raise the internal temperature to 145 ℃, and adding a compound auxiliary agent into the kettle; after stirring evenly, continuing to raise the internal temperature to 175 ℃ at the heating rate of 1 ℃/min, preserving the temperature for 30min, then raising the internal temperature to 180 ℃ at the heating rate of 0.5 ℃/min, preserving the temperature, and reacting until the esterification rate is controlled to be 65-95 percent, thereby completing the esterification reaction and obtaining the SIPE.

10. A method for preparing polyester for the acrylic one-bath dyeing type Persian fiber according to any one of claims 1 to 9, which is characterized by comprising the following steps:

step 1, esterification

Adding CHDM and EG with specified amounts into a pulping kettle, controlling the temperature of the pulping kettle to be 50-130 ℃, uniformly stirring, sequentially adding PTA, IPA, a heat stabilizer, a catalyst and a compound ether inhibitor into the pulping kettle according to the proportion, uniformly stirring to form a stable suspension, wherein the molar ratio of alcohol to acid is controlled to be 1.1-1.3: 1; feeding the obtained suspension into an esterification kettle through a metering pump for esterification reaction, wherein the esterification temperature is controlled to be 240-260 ℃, the esterification pressure is normal pressure, the esterification reaction time is 3-3.5 hours, the esterification rate is controlled to be 80-85%, and BHET esterification liquid is formed after esterification is completed;

step 2, diester formation

Introducing the BHET esterified liquid prepared in the first esterification kettle into a second esterification kettle, adding normal-temperature ethylene glycol into the second esterification kettle for cooling, wherein the adding amount of the normal-temperature ethylene glycol accounts for 2-4% of the volume of the BHET esterified liquid, so that the temperature is reduced to 210-230 ℃, then sequentially adding a specified amount of SIPE and aliphatic diol, continuously heating to 230-240 ℃, and reacting for 90-120 min;

step 3, final polycondensation

Introducing the materials into a final polycondensation kettle, firstly carrying out normal pressure reaction for 10-30 min, and controlling the internal temperature at 245-255 ℃ in the normal pressure reaction stage; after the normal pressure reaction is finished, carrying out negative pressure reaction, wherein the initial pressure is 101kpa (G), slowly reducing the pressure to 1.8kpa (G), and controlling the time to be 45-60 min; continuously reducing the pressure in the kettle to 50pa (G), and controlling the time to be 30-50 min; maintaining the pressure in the kettle at 50pa (G) for polycondensation reaction, raising the temperature, controlling the final temperature of the reaction to be 265-280 ℃, and pressurizing, casting and granulating by using nitrogen after the reaction reaches the specified viscosity to obtain the finished product.

Technical Field

The invention relates to polyester for acrylic one-bath dyeing type Persian nylon and a preparation method thereof, belonging to the field of differential polyester manufacture.

Background

The Possian is based on common PET polyester and copolymerized with a third monomer SIPE and a fourth monomer aliphatic dibasic acid, the three monomers endow the product with hydrophilic and cationic dyeability, the four monomer aliphatic dibasic acid increases the flexibility of a molecular chain, the dye can be accelerated to diffuse into fibers during dyeing, and the spinning product is endowed with fluffy and crimping performance, so that the effect equal to that of acrylic fibers and wool is achieved, and the product is low in price, and the Possian product can be used for replacing or blending the acrylic fibers and the wool in certain fields. In order to increase the hydrophilic property and the cationic dyeing property of the Persian fiber product, a multi-component high-content modified monomer is required to be added, the addition amount of the modified monomer is more, the side reaction degree is intensified, and finally the condensed structure of the product is changed, so that the characteristics of low melting point, low glass transition temperature, high diethylene glycol content and the like are shown.

The dyeing process of the Poslon is divided into two processes of dye adsorption and dye diffusion, the cationic dye and the sulfonic acid groups on the three monomers are combined through ionic bonds during adsorption, and the dye adsorbed on the fibers gradually migrates to the inside of the fibers through the movement of molecular chain segments during diffusion, so that the transparent dyeing is formed. Anhui Uygur New materials GmbH is the largest polyester chip production base for Persian nations. Because the modified monomer content is high and the components are more in the production process, the glass transition temperature of the produced product is lower, generally between 53 and 57 ℃, and the diethylene glycol content is 4 to 6 percent. In addition, because the dyeing seat is a strong acid group cation, the dye is quickly combined with the trimonomer through ionic bonds during dyeing of the dye, and the dye is quickly diffused into the fiber at low temperature due to low glass transition temperature and high diethylene glycol content. The two different components are dyed by cationic dyes during the blending of the Boslon products and the acrylic fibers, and a one-bath dyeing method can be adopted for dyeing, so that the dyeing energy consumption is reduced and the dyeing efficiency is improved. Because the vitrification transition temperature of the acrylic fiber is high (the wet state at 80-85 ℃), most of dyeing groups are weak acidic groups, and therefore, when the dyeing temperature is lower than the vitrification transition temperature, the dye adsorbed on the fiber is less, the diffusion of the dye on the fiber is very slow, the dye can be rapidly diffused and adsorbed to the Bosslon component in the early stage during the one-bath dyeing, and the acrylic fiber component is not dyed basically, so the 'white residue' phenomenon often appears in the acrylic fiber component during the one-bath dyeing, and the appearance effect of the product is seriously influenced.

Chinese patent CN102942686A 'A flame-retardant polyester of Pollon and its preparation method' adopts aliphatic dibasic acid-adipic acid as the fourth modified monomer, and adds the fifth monomer flame retardant, giving the product cationic dyeable and flame-retardant double effects, but adipic acid is a flexible monomer, and can generate serious 'competitive dyeing' phenomenon when dyeing with acrylic fiber in one bath, therefore, the product and acrylic fiber blended fabric can only adopt two-step dyeing. Chinese patent CN110982052A 'titanium-based polyester for Pollon and its preparation method' uses high-efficiency titanium catalyst to prepare the Pollon polyester, the titanium catalyst has large positive reaction rate constant and large reverse reaction rate constant, especially the addition of three monomers of the Pollon product is high, the degradation reaction is more violent, the diglycol content in the product can be increased obviously, in addition, the Pollon also uses aliphatic dibasic acid as the fourth modified monomer, the one-bath dyeing property is poor when spinning the product and acrylic fiber blending.

Disclosure of Invention

The invention aims to prepare the polyester for the acrylic fiber one-bath dyeing type Persian fiber by innovating a formula and improving a process flow, so that the product has high glass transition temperature, low diethylene glycol content and excellent cationic dyeing performance, the half-dyeing time is similar to that of the weakly acidic group acrylic fiber, the compatibility of acrylic fiber one-bath dyeing is improved, the dyeing energy consumption of the product is greatly reduced, the dyeing time is shortened, and the polyester is widely applied to the field of high-performance differential chemical fibers.

The invention adopts the following technical scheme to achieve the aim of the invention

The polyester for the acrylic one-bath dyeing type Persian fiber comprises the following raw materials in parts by weight:

further, the aliphatic diol is polyethylene glycol (PEG), the molecular weight range of the aliphatic diol is 200-20000, the aliphatic diol is preferably 2000-8000, and the aliphatic diol is further preferably 3000-6000.

Further, the heat stabilizer is TMP, TPP and H₃PO₄At least one of the components is preferably a compound heat stabilizer formed by mixing TMP and TPP according to the mass ratio of 1: 3-5.

Further, the catalyst is a complex catalyst composed of an antimony catalyst and a titanium catalyst, wherein the antimony catalyst is composed of at least two of antimony trioxide, antimony acetate and ethylene glycol antimony, and the titanium catalyst is composed of at least two of ethylene glycol titanium, tetrabutyl titanate and nano titanium dioxide.

Furthermore, the mass ratio of the titanium catalyst to the antimony catalyst is 1: 2-4.

Further, the compound ether-proof agent is formed by combining at least two of sodium acetate, sodium chloride, acetic acid, citric acid and tartaric acid.

Furthermore, the SIPE is obtained by esterification reaction of SIPA (sodium 5-sulfoisophthalate) or SIPM (sodium dimethyl 5-sulfoisophthalate) serving as a precursor and ethylene glycol. In order to improve the product quality, the SIPM is preferably used as a precursor in the invention.

Furthermore, the content of sulfate in SIPE precursor SIPM or SIPA is controlled to be 20-500 ppm, preferably 100-300 ppm, and more preferably 150-250 ppm.

Further, the SIPE is obtained by carrying out pre-esterification reaction on a precursor SIPA or SIPM before being added into a reaction system, and the reaction process is as follows: adding SIPA or SIPM serving as a precursor into a reaction kettle, adding glycol, controlling the molar ratio of the glycol to the precursor to be 5-10: 1, controlling the temperature rise rate of 2 ℃/min to raise the internal temperature to 145 ℃, and adding a compound auxiliary agent into the kettle; after stirring uniformly, continuing to raise the internal temperature to 175 ℃ at the heating rate of 1 ℃/min, preserving the temperature for 30min, then raising the internal temperature to 180 ℃ at the heating rate of 0.5 ℃/min, preserving the temperature, and reacting until the esterification rate is controlled to be 65-95 percent, thereby completing the pre-esterification reaction and obtaining the SIPE. After the reaction is finished, the mass concentration control range of the prepared SIPE in the EG solution is 30-40%.

Furthermore, the compound auxiliary agent used in the SIPE preparation process is composed of at least two of calcium acetate, sodium acetate, cobalt acetate and magnesium acetate.

The invention relates to a preparation method of polyester for acrylic fiber one-bath dyeing type Persian fibers, which comprises the following steps:

step 1, esterification

Adding CHDM and EG with specified amounts into a pulping kettle, controlling the temperature of the pulping kettle to be 50-130 ℃, uniformly stirring, sequentially adding PTA, IPA, a heat stabilizer, a catalyst and a compound ether inhibitor into the pulping kettle according to the proportion, uniformly stirring to form a stable suspension, wherein the molar ratio of alcohol to acid is controlled to be 1.1-1.3: 1; feeding the obtained suspension into an esterification kettle through a metering pump for esterification reaction, wherein the esterification temperature is controlled to be 240-260 ℃, the esterification pressure is normal pressure, the esterification reaction time is 3-3.5 hours, the esterification rate is controlled to be 80-85%, and BHET esterification liquid is formed after esterification is completed;

step 2, diester formation

Introducing the BHET esterified liquid prepared in the first esterification kettle into a second esterification kettle, adding normal-temperature ethylene glycol into the second esterification kettle for cooling, wherein the adding amount of the normal-temperature ethylene glycol accounts for 2-4% of the volume of the BHET esterified liquid, so that the temperature is reduced to 210-230 ℃, then sequentially adding a specified amount of SIPE and aliphatic diol, continuously heating to 230-240 ℃, and reacting for 90-120 min;

step 3, final polycondensation

Introducing the materials into a final polycondensation kettle, firstly carrying out normal pressure reaction for 10-30 min, and controlling the internal temperature at 245-255 ℃ in the normal pressure reaction stage; after the normal pressure reaction is finished, carrying out negative pressure reaction, wherein the initial pressure is 101kpa (G), slowly reducing the pressure to 1.8Kpa (G), and controlling the time to be 45-60 min; continuously reducing the pressure in the kettle to 50pa (G), and controlling the time to be 30-50 min; maintaining the pressure in the kettle at 50pa (G) for polycondensation reaction, raising the temperature, controlling the final temperature of the reaction to be 265-280 ℃, and pressurizing, casting and granulating by using nitrogen after the reaction reaches the specified viscosity to obtain the finished product.

The invention has the beneficial effects that:

1. through formula improvement, aromatic dibasic acid CHDM and IPA are used for replacing aliphatic dibasic acid, the melting point is reduced, the glass transition temperature of the product is greatly increased, and the effect that the cationic dye quickly dyes on the Possian component at a low temperature stage to cause uneven integral dyeing in one-bath dyeing is relieved.

2. The optimized formula is improved by using high molecular weight PEG as a flexible modified monomer, and the addition amount is optimized, so that the effect equivalent to that of acrylic acid second monomer acrylate can be achieved, the diffusion rate of cationic dye is similar during one-bath dyeing, and the level dyeing effect is good.

3. The cation modified monomer adopts a precursor pre-configuration process, inhibits the self-polymerization reaction of the modified monomer to the maximum extent through a low-entropy configuration process and high-molar-ratio esterification, and is added into the body for uniform copolymerization reaction, so that the product quality is improved, and the phenomenon of partial dyeing depth difference of the product is reduced.

4. The SIPE is optimized and improved to prepare a precursor, the content of free sulfonate is preferably selected in a proper amount, the reaction rate is improved, meanwhile, the generation of a by-product diglycol is reduced, the melting point of a product is improved, and the competitive dyeing phenomenon of cationic dye to the Sprenol component is reduced during one-bath dyeing.

5. Antimony-based and titanium-based compound catalysts are adopted, double catalysis is achieved in a low-temperature stage and a high-temperature stage during polycondensation, positive reaction rates in different temperature stages are increased, side reaction degree is reduced, diethylene glycol content of a product is reduced, melting point and glass transition temperature of the product are increased, and acrylic fiber one-bath dyeing is matched.

6. The complex type ether inhibitor is selected, side reaction is inhibited in the reaction process, the dyeing retarding effect is achieved during dyeing, the competitive dyeing of the components of the Spanish nylon is reduced, and the one-bath dyeing effect is improved.

7. According to the invention, through a preferable formula system and a preferable process flow, the finally prepared polyester product for the acrylic one-bath dyeing type Bosmann has the intrinsic viscosity of 0.35-0.5 dl/g, the melting point of 195-225 ℃, the glass transition temperature of more than or equal to 60 ℃ and the content of diethylene glycol of less than or equal to 2.5 percent.

Detailed Description

The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.