Cationic dye dyeable polyester delustering agent as well as preparation method and application thereof

Abstract

The invention relates to the technical field of high-component materials, and discloses a cationic dye dyeable polyester matting agent, a preparation method and application thereof, the matting agent comprises the following raw materials: coated titanium dioxide and a modifier, the modifier comprises the following components in parts by mass: 2-15 parts of a stabilizer, 0.5-2 parts of a dispersant, 0.1-10 parts of a complexing agent and 1000 parts of a solvent, the coated titanium dioxide is prepared from the following raw materials in parts by mass: 100 parts of titanium dioxide, 0.1 to 3 parts of methacryloyloxyethyl trimethyl ammonium chloride, 0.001 to 0.3 part of initiator and 500 to 10000 parts of water; the matting agent has high compatibility with cationic polyester, and can slow down the influence of a third monomer and cations on titanium dioxide agglomeration; the delustering agent can be directly applied to in-situ polymerization of delustering cationic dye dyeable polyester, melt direct spinning of the delustering cationic dye dyeable polyester can be achieved, and the production efficiency of delustering cationic fibers is remarkably improved.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, in particular to a cationic dye-dyable polyester matting agent, a preparation method and application thereof. Background Art

[0002] Cationic dyeable polyester is a dye-modified polyester made by adding a third monomer, 5-sodium sulfoisophthalate, to polyethylene terephthalate during the synthesis process. The sulfonic acid group in the third monomer acts as an anionic dyeing site to chemically bond with the cationic dye, thereby improving dye absorption and achieving fabrics with vibrant color, high color absorption, and good deep dyeing properties. Furthermore, the introduction of a fourth monomer into the cationic dyeable polyester yields cationic dyeable polyester at normal pressure, capable of achieving excellent dyeing results even at low temperatures.

[0003] Adding titanium dioxide to cationic polyester can obtain highly glossy cationic polyester. Fibers made from highly glossy cationic polyester have high gloss, are dazzling, and have poor hiding power. Therefore, in order to soften the gloss of the fiber and enhance its hiding power, a matting agent is usually used in the prior art to prepare matte cationic polyester. However, currently, matte cationic dye-dyable polyester fibers are all made by blending highly glossy cationic polyester with fully matte cationic dye-dyable polyester masterbatch before spinning. Currently, it is not possible to directly prepare matte cationic dye-dyable polyester by in-situ polymerization by adding titanium dioxide and directly spin matte cationic dye-dyable polyester fibers. Publication No. JP7251260B2 points out that cationic dyeable polyester needs to be copolymerized with an isophthalic acid component having a sulfonic acid group represented by sodium 5-isophthalic acid sulfonate. Since the isophthalic acid component having a sulfonic acid group promotes the coagulation of titanium dioxide in the polymerization reaction, The accumulation of titanium dioxide causes the filtration pressure to decrease during spinning, which is not conducive to spinning compared to conventional matt polyester. Publication No. CN101891937B points out that the addition of titanium dioxide to polyester containing S components will cause serious self-polymerization of titanium dioxide due to its high acidity, resulting in serious end breakage during the spinning process. Therefore, it is currently impossible to directly use titanium dioxide slurry to in situ polymerize matt cationic dye-dyable polyester. The in situ synthesized matt cationic dye-dyable polyester can be used for direct spinning, and the spinning efficiency is higher. Therefore, it is of great significance to provide an in situ polymerized matt cationic dye-dyable polyester. Summary of the Invention

[0004] In order to overcome the problem in the prior art that titanium dioxide slurry cannot be directly used to in-situ polymerize matting cationic dye-dyeable polyester, the present invention provides a matting agent for cationic dye-dyeable polyester, a preparation method and an application thereof. The matting agent has high compatibility with cationic polyester, can also slow down the influence of a third monomer and cations on titanium dioxide agglomeration, and improve the stability, dispersion and uniformity of titanium dioxide in an in-situ polymerization reaction; the matting agent can be directly used in the in-situ polymerization of matting cationic dye-dyeable polyester, can realize melt direct spinning of the matting cationic dye-dyeable polyester, and significantly improve the production efficiency of matting cationic fibers.

[0005] The specific technical solutions of the present invention are: A cationic dye-dyable polyester matting agent comprises raw materials including coated titanium dioxide and a modifier. The modifier comprises, by weight, 2 to 15 parts of a stabilizer, 0.5 to 2 parts of a dispersant, 0.1 to 10 parts of a complexing agent, and 1,000 parts of a solvent. The raw materials of the coated titanium dioxide comprise, by weight, 100 parts of titanium dioxide, 0.1 to 3 parts of methacryloyloxyethyltrimethylammonium chloride, 0.001 to 0.3 parts of an initiator, and 500 to 10,000 parts of water.

[0006] Preferably, the solvent is one of an ethylene glycol aqueous solution, a 1,3-propylene glycol aqueous solution and a 1,4-butanediol aqueous solution.

[0007] Preferably, the complexing agent is one of poly(tert-butyl acrylate), poly(methacrylic acid-co-sulfobetaine), 1-vinyl-3-ethylimidazole bis(trifluoromethanesulfonyl)imide salt, 1-butyl-3-methylimidazole sulfonate, benzo-15-crown-5 and 15-crown-5.

[0008] Preferably, the stabilizer is one of sodium carboxymethyl cellulose, polyvinyl alcohol, hydroxy cellulose and pentaerythritol stearate.

[0009] Preferably, the dispersant is one of Triton X-100 and isomeric alcohol polyoxyethylene ether.

[0010] Preferably, the initiator is ammonium persulfate.

[0011] The present invention provides a matting agent for cationic dye-dyable polyester. The matting agent can be directly used in the in-situ polymerization of cationic polyester, does not generate large particle agglomerates during use, and has a slow pressure increase when the melt passes through a filter element. Direct melt spinning of the cationic dye-dyable polyester can be achieved, significantly shortening the processing process of matting cationic polyester fibers, reducing production energy consumption, and improving production efficiency.

[0012] The cationic dye flammable polyester matting agent consists of coated titanium dioxide and a modifier. The surface of the coated titanium dioxide is coated with a polymer. The coating is a polymer coating layer formed on the surface of the titanium dioxide by methacryloyloxyethyltrimethylammonium chloride under initiator conditions. The polymer coating layer can reduce the negative impact of ion compression on the double electric layer on the surface of the titanium dioxide, so that the titanium dioxide can be stably dispersed in the cationic polyester. The polymer coating layer can also enhance the compatibility of titanium dioxide and the cationic polyester, further weakening the influence of the third monomer on the agglomeration of titanium dioxide.

[0013] The modifier is composed of a dispersant, a stabilizer, a complexing agent and a solvent. The dispersant can improve the storage stability of titanium dioxide, the stabilizer can improve the stability of titanium dioxide in high-temperature polyester melt, the dispersant and the stabilizer can ensure the particle uniformity of titanium dioxide, the complexing agent can effectively alleviate the effect of cations on the agglomeration of titanium dioxide. In the melt environment, cations can be adsorbed to the surface of titanium dioxide through electrostatic action and compress the double electric layer on the surface of titanium dioxide, thereby causing titanium dioxide to agglomerate. The complexing agent can fix cations through complexation, thereby reducing the negative impact of cations on the dispersion of titanium dioxide.

[0014] The polymer can improve the compatibility of titanium dioxide and cationic polyester and reduce the influence of the third monomer on the agglomeration of titanium dioxide; the modifier contains a dispersant, a stabilizer and a complexing agent, and the complexing agent can produce a complexation with the cation to further slow down the influence of the cation on the agglomeration of titanium dioxide. A preparation method of the above-mentioned cationic dye-dyable polyester matting agent comprises the following steps: (1) titanium dioxide and methacryloyloxyethyl trimethyl ammonium chloride are polymerized in the presence of an initiator to prepare coated titanium dioxide; (2) Adding a stabilizer and a dispersant to a solvent and stirring until dissolved, then adding a complexing agent under heating and stirring conditions to prepare a modifier; (3) Dispersing the coated titanium dioxide in ethylene glycol, heating and stirring, and adjusting the pH to 9.5, then adding a modifier, continuing to stir, cooling, and grinding to prepare a cationic dye-dyable polyester matting agent.

[0015] Preferably, the polymerization reaction conditions in step (1) include: temperature 70-80° C., stirring speed 100-500 rpm; and heat preservation reaction time 6-8 h.

[0016] Preferably, the heating and stirring conditions in step (2) include: adding the complexing agent within 20 to 30 minutes at 30 to 60° C., continuously stirring for 2 to 3 hours, and then cooling to 20 to 30° C. for storage.

[0017] Preferably, the heating and stirring conditions in step (3) include: temperature 60-80° C., stirring speed 300-1000 rpm, and stirring time 2-6 h.

[0018] Preferably, the grinding time in step (3) is 1 to 4 hours.

[0019] The present invention also provides a method for preparing the above-mentioned cationic dye-dyable polyester matting agent. The method controls the polymer coating amount to 1-1.5% by the process, ensuring that the coating amount is neither too much nor too little. If the coating amount is too little, defects will appear on the titanium dioxide surface and it will not be completely coated, so that the titanium dioxide will still be affected by the third monomer. If the coating amount is too much, polymer agglomerates and long-chain gels will be formed, thereby forming impurity spots in the polymer melt and affecting the service life of the melt filter. In addition, excessive coating amount forms a thicker coating layer, which will mask the original surface characteristics of the titanium dioxide. Moreover, if the coating layer is too thick, it is more likely to agglomerate, which is not conducive to further dispersion. Therefore, it is necessary to control the coating amount of the polymer coating layer.

[0020] The invention discloses an application of the cationic dyeable polyester matting agent in the preparation of a cationic polyester having a matting property, comprising the following steps: esterifying terephthalic acid, ethylene glycol and a catalyst to prepare an esterified product; adding the cationic dyeable polyester matting agent and 5-sodium sulfoisophthalic acid to the esterified product to carry out a polymerization reaction to prepare a cationic polyester having a matting property.

[0021] Compared with the existing technology, this application has the following technical effects: (1) Encapsulated titanium dioxide is used in the cationic dye-dyeable polyester matting agent. The polymer coating layer on the surface of the encapsulated titanium dioxide can reduce the negative impact of ion compression on the double electric layer of the titanium dioxide surface, allowing it to be stably dispersed in the cationic polyester. At the same time, the introduction of the polymer coating layer can enhance the interaction between the titanium dioxide surface and the polyester main chain, improve the compatibility of titanium dioxide and cationic polyester, and further weaken the effect of the third monomer on the agglomeration of titanium dioxide; (2) The modifier in the cationic dye-dyable polyester matting agent contains a dispersant, a stabilizer and a complexing agent. The dispersant is beneficial to the storage stability of titanium dioxide, and the stabilizer is beneficial to improving the stability of titanium dioxide in high-temperature polyester melts. By combining the dispersant and the stabilizer, the uniformity of titanium dioxide particles can be maintained; the complexing agent can fix cations through complexation, thereby effectively alleviating the negative impact of cations on the dispersion stability of titanium dioxide; (3) The cationic dye-dyable polyester matting agent prepared by the present invention can be directly used for in-situ polymerization to prepare matting cationic dye-dyable polyester, and the polyester melt is directly used for melt direct spinning of matting cationic dye-dyable polyester fibers, which significantly shortens the processing process, reduces production energy consumption, and significantly improves production efficiency. DETAILED DESCRIPTION

[0022] The present invention will be further described below with reference to the embodiments.

[0023] Example 1: A method for preparing a cationic dye-dyable polyester matting agent comprises the following steps: (1) 100 parts of titanium dioxide were dispersed in 900 parts of water and ground for 0.5 h to form a uniform titanium dioxide suspension; the titanium dioxide suspension was transferred to a reaction vessel, nitrogen was introduced for 0.5 h to exclude oxygen, and the suspension was heated to 70°C, stirred at 200 rpm, and 0.5 parts of methacryloyloxyethyl trimethyl ammonium chloride monomer was added. After stirring until dissolved, 0.2 parts of initiator (ammonium persulfate) was added and the mixture was kept warm for 4 h. After the reaction, the suspension was washed three times with water by centrifugation and dried at 80°C to prepare coated titanium dioxide; (2) 100 parts of ethylene glycol were added to 100 parts of water and stirred to prepare a synthetic solvent. 10 parts of a dispersant (Triton X-100) and 1 part of a stabilizer (sodium carboxymethyl cellulose) were added to the solvent and stirred until dissolved. The solution was heated to 45°C and 5 parts of a complexing agent (benzo-15-crown-5) were added within 10 minutes. The solution was stirred continuously for 2 hours and then cooled to room temperature to prepare a modifier. (3) 100 parts of coated titanium dioxide were dispersed in 200 parts of ethylene glycol, heated and stirred at 80°C and 300 rpm, and the pH was adjusted to 9.5 with ammonia water. 10 parts of a modifier were added within 30 minutes, and the mixture was stirred continuously for 2 hours and then cooled to room temperature. The mixture was then ground with a grinder for 2 hours to prepare a cationic dyeable polyester matting agent.

[0024] An application of the cationic dye-dyable polyester matting agent in the preparation of semi-matt cationic polyester comprises the following steps: 830 parts of terephthalic acid, 387 parts of ethylene glycol and 200 ppm of ethylene glycol antimony catalyst were added to a polymerization kettle for beating. The polymerization kettle was closed for nitrogen replacement, and an esterification reaction was carried out at a temperature of 250° C. and a pressure of 3.5 bar. After separation in a process tower and cooling in a condenser, the esterification water was removed. 2.4 parts of a cationic dye-dyable polyester matting agent and 30 parts of 5-sodium sulfonate of isophthalic acid were added to the esterified product. The product was vacuumed and decompressed, and the polycondensation temperature was controlled at 278° C. After low vacuum pre-polycondensation and 50 Pa high vacuum polycondensation reaction, after reaching the expected stirring power, the melt was cast on a belt, cooled underwater, and pelletized to obtain semi-matt cationic polyester chips.

[0025] Example 2: A method for preparing a cationic dye-dyable polyester matting agent comprises the following steps: (1) 100 parts of titanium dioxide were dispersed in 500 parts of water and ground for 0.5 hours to form a uniform titanium dioxide suspension; the titanium dioxide suspension was transferred to a reaction vessel, nitrogen was introduced for 1 hour to exclude oxygen, the suspension was heated to 80°C, stirred at 500 rpm, and 0.5 parts of methacryloyloxyethyl trimethyl ammonium chloride monomer was added. After stirring until dissolved, 0.2 parts of initiator (ammonium persulfate) was added and kept warm for 4 hours. After the reaction was completed, the suspension was washed three times by centrifugation with water and dried at 60°C to prepare coated titanium dioxide; (2) 100 parts of ethylene glycol were added to 100 parts of water and stirred to prepare a synthetic solvent, 10 parts of dispersant (Triton X-100) and 1 part of stabilizer (hydroxy cellulose) were added to the solvent and stirred until dissolved, the solution was heated to 45°C, 5 parts of complexing agent (polytert-butyl acrylate) were added within 10 minutes, and the suspension was stirred continuously for 2 hours and then cooled to room temperature to prepare a modifier; (3) 100 parts of coated titanium dioxide were dispersed in 200 parts of ethylene glycol, heated and stirred at 80°C and 300 rpm, and the pH was adjusted to 9.5 with ammonia water. 10 parts of a modifier were added within 30 minutes, and the mixture was stirred continuously for 2 hours and then cooled to room temperature. The mixture was then ground with a grinder for 2 hours to prepare a cationic dyeable polyester matting agent.

[0026] An application of the above-mentioned cationic dye-dyable polyester matting agent in the preparation of semi-matt cationic polyester comprises the following steps: 830 parts of terephthalic acid, 387 parts of ethylene glycol and 200 ppm of ethylene glycol antimony catalyst were added to a polymerization kettle for beating. The polymerization kettle was closed for nitrogen replacement, and an esterification reaction was carried out at a temperature of 250° C. and a pressure of 3.5 bar. After separation in a process tower and cooling in a condenser, the esterification water was removed. 2.4 parts of a cationic dye-dyable polyester matting agent and 30 parts of 5-sodium sulfonate of isophthalic acid were added to the esterified product. The product was vacuumed and decompressed, and the polycondensation temperature was controlled at 278° C. After low vacuum pre-polycondensation and 50 Pa high vacuum polycondensation reaction, after reaching the expected stirring power, the melt was cast on a belt, cooled underwater, and pelletized to obtain semi-matt cationic polyester chips.

[0027] Example 3: A method for preparing a cationic dye-dyable polyester matting agent comprises the following steps: (1) 100 parts of titanium dioxide were dispersed in 10,000 parts of water and ground for 0.5 h to form a uniform titanium dioxide suspension; the titanium dioxide suspension was transferred to a reaction vessel, nitrogen was introduced for 0.5 h to exclude oxygen, and the suspension was heated to 70°C, stirred at 100 rpm, and 0.5 parts of methacryloyloxyethyl trimethyl ammonium chloride monomer was added. After stirring until dissolved, 0.2 parts of initiator (ammonium persulfate) was added and the mixture was kept warm for 4 h. After the reaction, the suspension was washed three times with water by centrifugation and dried at 80°C to prepare coated titanium dioxide; (2) 100 parts of ethylene glycol were added to 100 parts of water and stirred evenly to prepare a synthetic solvent. Then 10 parts of dispersant (isomeric alcohol polyoxyethylene ether) and 1 part of stabilizer (polyvinyl alcohol) were added to the solvent and stirred until dissolved. The solution was heated to 45°C and 5 parts of complexing agent (polymethacrylic acid-co-sulfobetaine) were added within 10 minutes. The mixture was stirred continuously for 2 hours and then cooled to room temperature to prepare a modifier. (3) 100 parts of coated titanium dioxide were dispersed in 200 parts of ethylene glycol, heated and stirred at 80°C and 300 rpm, and the pH was adjusted to 9.5 with ammonia water. 10 parts of modifier were added within 30 minutes, stirred continuously for 2 hours, and then cooled to room temperature. The mixture was then ground with a grinder for 2 hours to prepare a cationic dyeable polyester matting agent.

[0028] An application of the cationic dye-dyable polyester matting agent in the preparation of semi-matt cationic polyester comprises the following steps: 830 parts of terephthalic acid, 387 parts of ethylene glycol and 200 ppm of ethylene glycol antimony catalyst were added to a polymerization kettle for beating. The polymerization kettle was closed for nitrogen replacement, and an esterification reaction was carried out at a temperature of 250° C. and a pressure of 3.5 bar. After separation in a process tower and cooling in a condenser, the esterification water was removed. 2.4 parts of a cationic dye-dyable polyester matting agent and 30 parts of 5-sodium sulfonate of isophthalic acid were added to the esterified product. The product was vacuumed and decompressed, and the polycondensation temperature was controlled at 278° C. After low vacuum pre-polycondensation and 50 Pa high vacuum polycondensation reaction, after reaching the expected stirring power, the melt was cast on a belt, cooled underwater, and pelletized to obtain semi-matt cationic polyester chips.

[0029] Example 4: A method for preparing a cationic dye-dyable polyester matting agent comprises the following steps: (1) 100 parts of titanium dioxide were dispersed in 900 parts of water and ground for 0.5 h to form a uniform titanium dioxide suspension; the titanium dioxide suspension was transferred to a reaction vessel, nitrogen was introduced for 0.5 h to exclude oxygen, and the suspension was heated to 70°C, stirred at 200 rpm, and 0.5 parts of methacryloyloxyethyl trimethyl ammonium chloride monomer was added. After stirring until dissolved, 0.2 parts of initiator (ammonium persulfate) was added and the mixture was kept warm for 4 h. After the reaction, the suspension was washed three times with water by centrifugation and dried at 80°C to prepare coated titanium dioxide; (2) 100 parts of ethylene glycol were added to 100 parts of water and stirred to prepare a synthetic solvent. Then, 10 parts of a dispersant (Triton X-100) and 1 part of a stabilizer (pentaerythritol stearate) were added to the solvent and stirred until dissolved. The solution was heated to 45°C and 5 parts of a complexing agent (1-vinyl-3-ethylimidazole bis(trifluoromethanesulfonyl imide)) were added within 10 minutes. The solution was stirred continuously for 2 hours and then cooled to room temperature to prepare a modifier. (3) 100 parts of coated titanium dioxide were dispersed in 200 parts of ethylene glycol, heated and stirred at 80°C and 300 rpm, and the pH was adjusted to 9.5 with ammonia water. 10 parts of a modifier were added within 30 minutes, and the mixture was stirred continuously for 2 hours and then cooled to room temperature. The mixture was then ground with a grinder for 2 hours to prepare a cationic dyeable polyester matting agent.

[0030] An application of the above-mentioned cationic dye-dyable polyester matting agent in the preparation of semi-matt cationic polyester comprises the following steps: 830 parts of terephthalic acid, 387 parts of ethylene glycol and 200 ppm of ethylene glycol antimony catalyst were added to a polymerization kettle for beating. The polymerization kettle was closed for nitrogen replacement, and an esterification reaction was carried out at a temperature of 250° C. and a pressure of 3.5 bar. After separation in a process tower and cooling in a condenser, the esterification water was removed. 2.4 parts of a cationic dye-dyable polyester matting agent and 30 parts of 5-sodium sulfonate of isophthalic acid were added to the esterified product. The product was vacuumed and decompressed, and the polycondensation temperature was controlled at 278° C. After low vacuum pre-polycondensation and 50 Pa high vacuum polycondensation reaction, after reaching the expected stirring power, the melt was cast on a belt, cooled underwater, and pelletized to obtain semi-matt cationic polyester chips.

[0031] Example 5: A method for preparing a cationic dye-dyable polyester matting agent comprises the following steps: (1) 100 parts of titanium dioxide were dispersed in 900 parts of water and ground for 0.5 h to form a uniform titanium dioxide suspension; the titanium dioxide suspension was transferred to a reaction vessel, nitrogen was introduced for 0.5 h to exclude oxygen, and the suspension was heated to 70°C, stirred at 200 rpm, and 0.5 parts of methacryloyloxyethyl trimethyl ammonium chloride monomer was added. After stirring until dissolved, 0.2 parts of initiator (ammonium persulfate) was added and the mixture was kept warm for 4 h. After the reaction, the suspension was washed three times with water by centrifugation and dried at 80°C to prepare coated titanium dioxide; (2) 100 parts of ethylene glycol were added to 100 parts of water and stirred to prepare a synthetic solvent. Then, 10 parts of a dispersant (Triton X-100) and 1 part of a stabilizer (sodium carboxymethyl cellulose) were added to the solvent and stirred until dissolved. The solution was heated to 45°C and 5 parts of a complexing agent (1-butyl-3-methylimidazole sulfonate) were added within 10 minutes. The solution was stirred continuously for 2 hours and then cooled to room temperature to prepare a modifier. (3) 100 parts of coated titanium dioxide were dispersed in 200 parts of ethylene glycol, heated and stirred at 80°C and 300 rpm, and the pH was adjusted to 9.5 with ammonia water. 10 parts of a modifier were added within 30 minutes, and the mixture was stirred continuously for 2 hours and then cooled to room temperature. The mixture was then ground with a grinder for 2 hours to prepare a cationic dyeable polyester matting agent.

[0032] An application of the above-mentioned cationic dye-dyable polyester matting agent in the preparation of semi-matt cationic polyester comprises the following steps: 830 parts of terephthalic acid, 387 parts of ethylene glycol and 200 ppm of ethylene glycol antimony catalyst were added to a polymerization kettle for beating. The polymerization kettle was closed for nitrogen replacement, and an esterification reaction was carried out at a temperature of 250° C. and a pressure of 3.5 bar. After separation in a process tower and cooling in a condenser, the esterification water was removed. 2.4 parts of a cationic dye-dyable polyester matting agent and 30 parts of 5-sodium sulfonate of isophthalic acid were added to the esterified product. The product was vacuumed and decompressed, and the polycondensation temperature was controlled at 278° C. After low vacuum pre-polycondensation and 50 Pa high vacuum polycondensation reaction, after reaching the expected stirring power, the melt was cast on a belt, cooled underwater, and pelletized to obtain semi-matt cationic polyester chips.

[0033] Comparative Example 1: The difference between Comparative Example 1 and Example 1 is that titanium dioxide is directly used to carry out the in-situ polymerization reaction of the semi-matt cationic polyester; A method for preparing semi-dull cationic polyester fiber comprises the following steps: 830 parts of terephthalic acid, 387 parts of ethylene glycol and 200 ppm of ethylene glycol antimony catalyst were added to a polymerization kettle for beating. The polymerization kettle was closed for nitrogen replacement, and an esterification reaction was carried out at a temperature of 250° C. and a pressure of 3.5 bar. After separation in a process tower and cooling in a condenser, the esterification water was removed. 2.4 parts of titanium dioxide and 30 parts of 5-sodium sulfoisophthalate were added to the esterified product, and the pressure was reduced by vacuum. The condensation temperature was controlled at 278° C. After low vacuum pre-condensation and 50 Pa high vacuum polycondensation reaction, after reaching the expected stirring power, the melt was cast on a belt, cooled underwater, and pelletized to obtain semi-dull cationic polyester chips.

[0034] Comparative Example 2: The difference between Comparative Example 2 and Example 1 is that the titanium dioxide in the cationic dye-dyeable polyester matting agent is not coated; a method for preparing a cationic dye-dyeable polyester matting agent comprises the following steps: (1) 100 parts of ethylene glycol were added to 100 parts of water and stirred to prepare a synthetic solvent. 10 parts of a dispersant (Triton X-100) and 1 part of a stabilizer (sodium carboxymethyl cellulose) were added to the solvent and stirred until dissolved. The solution was heated to 45°C and 5 parts of a complexing agent (benzo-15-crown-5) were added within 10 minutes. The solution was stirred continuously for 2 hours and then cooled to room temperature to prepare a modifier. (2) 100 parts of titanium dioxide were dispersed in 200 parts of ethylene glycol, heated and stirred at 80°C and 300 rpm, and the pH was adjusted to 9.5 with ammonia water. 10 parts of a modifier were added within 30 minutes, and the mixture was stirred continuously for 2 hours and then cooled to room temperature. The mixture was then ground in a grinder for 2 hours to prepare a cationic dyeable polyester matting agent.

[0035] An application of the above-mentioned cationic dye-dyable polyester matting agent in the preparation of semi-matt cationic polyester comprises the following steps: 830 parts of terephthalic acid, 387 parts of ethylene glycol and 200 ppm of ethylene glycol antimony catalyst were added to a polymerization kettle for beating. The polymerization kettle was closed for nitrogen replacement, and an esterification reaction was carried out at a temperature of 250° C. and a pressure of 3.5 bar. After separation in a process tower and cooling in a condenser, the esterification water was removed. 2.4 parts of a cationic dye-dyable polyester matting agent and 30 parts of 5-sodium sulfonate of isophthalic acid were added to the esterified product. The product was vacuumed and decompressed, and the polycondensation temperature was controlled at 278° C. After low vacuum pre-polycondensation and 50 Pa high vacuum polycondensation reaction, after reaching the expected stirring power, the melt was cast on a belt, cooled underwater, and pelletized to obtain semi-matt cationic polyester chips.

[0036] Comparative Example 3: The difference between Comparative Example 2 and Example 1 is that no modifier is used in the cationic dye-dyeable polyester matting agent; A method for preparing a cationic dye-dyable polyester matting agent comprises the following steps: (1) 100 parts of titanium dioxide were dispersed in 900 parts of water and ground for 0.5 h to form a uniform titanium dioxide suspension; the titanium dioxide suspension was transferred to a reaction vessel, nitrogen was introduced for 0.5 h to exclude oxygen, and the suspension was heated to 70°C, stirred at 200 rpm, and 0.5 parts of methacryloyloxyethyl trimethyl ammonium chloride monomer was added. After stirring until dissolved, 0.2 parts of initiator (ammonium persulfate) was added and the mixture was kept warm for 4 h. After the reaction, the suspension was washed three times with water by centrifugation and dried at 80°C to prepare coated titanium dioxide; (2) 100 parts of coated titanium dioxide were dispersed in 200 parts of ethylene glycol, and then ground in a grinder for 2 hours to prepare a cationic dye-dyable polyester matting agent.

[0037] An application of the above-mentioned cationic dye-dyable polyester matting agent in the preparation of semi-matt cationic polyester comprises the following steps: 830 parts of terephthalic acid, 387 parts of ethylene glycol and 200 ppm of ethylene glycol antimony catalyst were added to a polymerization kettle for beating. The polymerization kettle was closed for nitrogen replacement, and an esterification reaction was carried out at a temperature of 250° C. and a pressure of 3.5 bar. After separation in a process tower and cooling in a condenser, the esterification water was removed. 2.4 parts of a cationic dye-dyable polyester matting agent and 30 parts of 5-sodium sulfonate of isophthalic acid were added to the esterified product. The product was vacuumed and decompressed, and the polycondensation temperature was controlled at 278° C. After low vacuum pre-polycondensation and 50 Pa high vacuum polycondensation reaction, after reaching the expected stirring power, the melt was cast on a belt, cooled underwater, and pelletized to obtain semi-matt cationic polyester chips.

[0038] Comparative Example 4: The difference between Comparative Example 4 and Example 1 is that no stabilizer is used in the cationic dye-dyeable polyester matting agent; A method for preparing a cationic dye-dyable polyester matting agent comprises the following steps: (1) 100 parts of titanium dioxide were dispersed in 900 parts of water and ground for 0.5 h to form a uniform titanium dioxide suspension; the titanium dioxide suspension was transferred to a reaction vessel, nitrogen was introduced for 0.5 h to exclude oxygen, and the suspension was heated to 70°C, stirred at 200 rpm, and 0.5 parts of methacryloyloxyethyl trimethyl ammonium chloride monomer was added. After stirring until dissolved, 0.2 parts of initiator (ammonium persulfate) was added and the mixture was kept warm for 4 h. After the reaction, the suspension was washed three times with water by centrifugation and dried at 80°C to prepare coated titanium dioxide; (2) 100 parts of ethylene glycol were added to 100 parts of water and stirred to prepare a synthetic solvent. 10 parts of a dispersant (Triton X-100) were then added to the solvent and stirred until dissolved. The solution was heated to 45°C and 5 parts of a complexing agent (benzo-15-crown-5) were added within 10 minutes. The solution was stirred continuously for 2 hours and then cooled to room temperature to prepare a modifier. (3) 100 parts of coated titanium dioxide were dispersed in 200 parts of ethylene glycol, heated and stirred at 80°C at 300 rpm, and the pH was adjusted to 9.5 with ammonia water. 10 parts of a modifier were added within 30 minutes, and the mixture was stirred continuously for 2 hours and then cooled to room temperature. The mixture was then ground in a grinder for 2 hours to prepare a cationic dyeable polyester matting agent.

[0039] An application of the cationic dye-dyable polyester matting agent in the preparation of semi-matt cationic polyester comprises the following steps: 830 parts of terephthalic acid, 387 parts of ethylene glycol and 200 ppm of ethylene glycol antimony catalyst were added to a polymerization kettle for beating. The polymerization kettle was closed for nitrogen replacement, and an esterification reaction was carried out at a temperature of 250° C. and a pressure of 3.5 bar. After separation in a process tower and cooling in a condenser, the esterification water was removed. 2.4 parts of a cationic dye-dyable polyester matting agent and 30 parts of 5-sodium sulfonate of isophthalic acid were added to the esterified product. The product was vacuumed and decompressed, and the polycondensation temperature was controlled at 278° C. After low vacuum pre-polycondensation and 50 Pa high vacuum polycondensation reaction, after reaching the expected stirring power, the melt was cast on a belt, cooled underwater, and pelletized to obtain semi-matt cationic polyester chips.

[0040] Comparative Example 5: The difference between Comparative Example 5 and Example 1 is that no complexing agent is used in the cationic dye-dyeable polyester matting agent; A method for preparing a cationic dye-dyable polyester matting agent comprises the following steps: (1) 100 parts of titanium dioxide were dispersed in 900 parts of water and ground for 0.5 h to form a uniform titanium dioxide suspension; the titanium dioxide suspension was transferred to a reaction vessel, nitrogen was introduced for 0.5 h to exclude oxygen, and the suspension was heated to 70°C, stirred at 200 rpm, and 0.5 parts of methacryloyloxyethyl trimethyl ammonium chloride monomer was added. After stirring until dissolved, 0.2 parts of initiator (ammonium persulfate) was added and the mixture was kept warm for 4 h. After the reaction, the suspension was washed three times with water by centrifugation and dried at 80°C to prepare coated titanium dioxide; (2) Add 100 parts of ethylene glycol to 100 parts of water and stir evenly to prepare a synthetic solvent, then add 10 parts of a dispersant (Triton X-100) and 1 part of a stabilizer (sodium carboxymethyl cellulose) to the solvent and stir until dissolved to prepare a modifier; (3) 100 parts of coated titanium dioxide were dispersed in 200 parts of ethylene glycol, heated and stirred at 80°C and 300 rpm, and the pH was adjusted to 9.5 with ammonia water. 10 parts of a modifier were added within 30 minutes, and the mixture was stirred continuously for 2 hours and then cooled to room temperature. The mixture was then ground with a grinder for 2 hours to prepare a cationic dyeable polyester matting agent.

[0041] An application of the above-mentioned cationic dye-dyable polyester matting agent in the preparation of semi-matt cationic polyester comprises the following steps: 830 parts of terephthalic acid, 387 parts of ethylene glycol and 200 ppm of ethylene glycol antimony catalyst were added to a polymerization kettle for beating. The polymerization kettle was closed for nitrogen replacement, and an esterification reaction was carried out at a temperature of 250° C. and a pressure of 3.5 bar. After separation in a process tower and cooling in a condenser, the esterification water was removed. 2.4 parts of a cationic dye-dyable polyester matting agent and 30 parts of 5-sodium sulfonate of isophthalic acid were added to the esterified product. The product was vacuumed and decompressed, and the polycondensation temperature was controlled at 278° C. After low vacuum pre-polycondensation and 50 Pa high vacuum polycondensation reaction, after reaching the expected stirring power, the melt was cast on a belt, cooled underwater, and pelletized to obtain semi-matt cationic polyester chips.

[0042] Comparative Example 6: The difference between Comparative Example 6 and Example 1 is that the amount of modifier used in the cationic dye-dyable polyester matting agent is too much; A method for preparing a cationic dye-dyable polyester matting agent comprises the following steps: (1) 100 parts of titanium dioxide were dispersed in 900 parts of water and ground for 0.5 h to form a uniform titanium dioxide suspension; the titanium dioxide suspension was transferred to a reaction vessel, nitrogen was introduced for 0.5 h to exclude oxygen, and the suspension was heated to 70°C, stirred at 200 rpm, and 0.5 parts of methacryloyloxyethyl trimethyl ammonium chloride monomer was added. After stirring until dissolved, 0.2 parts of initiator (ammonium persulfate) was added and the mixture was kept warm for 4 h. After the reaction, the suspension was washed three times with water by centrifugation and dried at 80°C to prepare coated titanium dioxide; (2) 100 parts of ethylene glycol were added to 100 parts of water and stirred to prepare a synthetic solvent. 10 parts of a dispersant (Triton X-100) and 1 part of a stabilizer (sodium carboxymethyl cellulose) were added to the solvent and stirred until dissolved. The solution was heated to 45°C and 5 parts of a complexing agent (benzo-15-crown-5) were added within 10 minutes. The solution was stirred continuously for 2 hours and then cooled to room temperature to prepare a modifier. (3) 100 parts of coated titanium dioxide were dispersed in 200 parts of ethylene glycol, heated and stirred at 80°C and 300 rpm, and the pH was adjusted to 9.5 with ammonia water. 50 parts of a modifier were added within 30 minutes, and the mixture was stirred continuously for 2 hours and then cooled to room temperature. The mixture was then ground in a grinder for 2 hours to prepare a cationic dyeable polyester matting agent.

[0043] An application of the cationic dye-dyable polyester matting agent in the preparation of semi-matt cationic polyester comprises the following steps: 830 parts of terephthalic acid, 387 parts of ethylene glycol and 200 ppm of ethylene glycol antimony catalyst were added to a polymerization kettle for beating. The polymerization kettle was closed for nitrogen replacement, and an esterification reaction was carried out at a temperature of 250° C. and a pressure of 3.5 bar. After separation in a process tower and cooling in a condenser, the esterification water was removed. 2.4 parts of a cationic dye-dyable polyester matting agent and 30 parts of 5-sodium sulfonate of isophthalic acid were added to the esterified product. The product was vacuumed and decompressed, and the polycondensation temperature was controlled at 278° C. After low vacuum pre-polycondensation and 50 Pa high vacuum polycondensation reaction, after reaching the expected stirring power, the melt was cast on a belt, cooled underwater, and pelletized to obtain semi-matt cationic polyester chips.

[0044] Comparative Example 7: The difference between Comparative Example 7 and Example 1 is that the amount of complexing agent used in the cationic dye-dyable polyester matting agent is too small; A method for preparing a cationic dye-dyable polyester matting agent comprises the following steps: (1) 100 parts of titanium dioxide were dispersed in 900 parts of water and ground for 0.5 h to form a uniform titanium dioxide suspension; the titanium dioxide suspension was transferred to a reaction vessel, nitrogen was introduced for 0.5 h to exclude oxygen, and the suspension was heated to 70°C, stirred at 200 rpm, and 0.5 parts of methacryloyloxyethyl trimethyl ammonium chloride monomer was added. After stirring until dissolved, 0.2 parts of initiator (ammonium persulfate) was added and the mixture was kept warm for 4 h. After the reaction, the suspension was washed three times with water by centrifugation and dried at 80°C to prepare coated titanium dioxide; (2) 100 parts of ethylene glycol were added to 100 parts of water and stirred to prepare a synthetic solvent. 10 parts of a dispersant (Triton X-100) and 1 part of a stabilizer (sodium carboxymethyl cellulose) were added to the solvent and stirred until dissolved. The solution was heated to 45°C and 1 part of a complexing agent (benzo-15-crown-5) was added within 10 minutes. The solution was stirred continuously for 2 hours and then cooled to room temperature to prepare a modifier. (3) 100 parts of coated titanium dioxide were dispersed in 200 parts of ethylene glycol, heated and stirred at 80°C and 300 rpm, and the pH was adjusted to 9.5 with ammonia water. 10 parts of a modifier were added within 30 minutes, and the mixture was stirred continuously for 2 hours and then cooled to room temperature. The mixture was then ground with a grinder for 2 hours to prepare a cationic dyeable polyester matting agent.

[0045] An application of the above-mentioned cationic dye-dyable polyester matting agent in the preparation of semi-matt cationic polyester comprises the following steps: 830 parts of terephthalic acid, 387 parts of ethylene glycol and 200 ppm of ethylene glycol antimony catalyst were added to a polymerization kettle for beating. The polymerization kettle was closed for nitrogen replacement, and an esterification reaction was carried out at a temperature of 250° C. and a pressure of 3.5 bar. After separation in a process tower and cooling in a condenser, the esterification water was removed. 2.4 parts of a cationic dye-dyable polyester matting agent and 30 parts of 5-sodium sulfonate of isophthalic acid were added to the esterified product. The product was vacuumed and decompressed, and the polycondensation temperature was controlled at 278° C. After low vacuum pre-polycondensation and 50 Pa high vacuum polycondensation reaction, after reaching the expected stirring power, the melt was cast on a belt, cooled underwater, and pelletized to obtain semi-matt cationic polyester chips.

[0046] Comparative Example 8: The difference between Comparative Example 8 and Example 1 is that the amount of complexing agent used in the cationic dye-dyable polyester matting agent is too much; A method for preparing a cationic dye-dyable polyester matting agent comprises the following steps: (1) 100 parts of titanium dioxide were dispersed in 900 parts of water and ground for 0.5 h to form a uniform titanium dioxide suspension; the titanium dioxide suspension was transferred to a reaction vessel, nitrogen was introduced for 0.5 h to exclude oxygen, and the suspension was heated to 70°C, stirred at 200 rpm, and 0.5 parts of methacryloyloxyethyl trimethyl ammonium chloride monomer was added. After stirring until dissolved, 0.2 parts of initiator (ammonium persulfate) was added and the mixture was kept warm for 4 h. After the reaction, the suspension was washed three times with water by centrifugation and dried at 80°C to prepare coated titanium dioxide; (2) 100 parts of ethylene glycol were added to 100 parts of water and stirred to prepare a synthetic solvent. 10 parts of a dispersant (Triton X-100) and 1 part of a stabilizer (sodium carboxymethyl cellulose) were added to the solvent and stirred until dissolved. The solution was heated to 45°C and 20 parts of a complexing agent (benzo-15-crown-5) were added within 10 minutes. The solution was stirred continuously for 2 hours and then cooled to room temperature to prepare a modifier. (3) 100 parts of coated titanium dioxide were dispersed in 200 parts of ethylene glycol, heated and stirred at 80°C and 300 rpm, and the pH was adjusted to 9.5 with ammonia water. 10 parts of a modifier were added within 30 minutes, and the mixture was stirred continuously for 2 hours and then cooled to room temperature. The mixture was then ground with a grinder for 2 hours to prepare a cationic dyeable polyester matting agent.

[0047] An application of the cationic dye-dyable polyester matting agent in the preparation of semi-matt cationic polyester comprises the following steps: 830 parts of terephthalic acid, 387 parts of ethylene glycol and 200 ppm of ethylene glycol antimony catalyst were added to a polymerization kettle for beating. The polymerization kettle was closed for nitrogen replacement, and an esterification reaction was carried out at a temperature of 250° C. and a pressure of 3.5 bar. After separation in a process tower and cooling in a condenser, the esterification water was removed. 2.4 parts of a cationic dye-dyable polyester matting agent and 30 parts of 5-sodium sulfonate of isophthalic acid were added to the esterified product. The product was vacuumed and decompressed, and the polycondensation temperature was controlled at 278° C. After low vacuum pre-polycondensation and 50 Pa high vacuum polycondensation reaction, after reaching the expected stirring power, the melt was cast on a belt, cooled underwater, and pelletized to obtain semi-matt cationic polyester chips.

[0048] Comparative Example 9: The difference between Comparative Example 9 and Example 1 is that the coating amount on the surface of the coated titanium dioxide is too small; A method for preparing a cationic dye-dyable polyester matting agent comprises the following steps: (1) 100 parts of titanium dioxide were dispersed in 900 parts of water and ground for 0.5 h to form a uniform titanium dioxide suspension; the titanium dioxide suspension was transferred to a reaction vessel, nitrogen was introduced for 0.5 h to exclude oxygen, and the suspension was heated to 70°C, stirred at 200 rpm, and 0.05 parts of methacryloyloxyethyl trimethyl ammonium chloride monomer was added. After stirring until dissolved, 0.2 parts of initiator (ammonium persulfate) was added and the mixture was kept warm for 4 h. After the reaction, the suspension was washed three times with water by centrifugation and dried at 80°C to prepare coated titanium dioxide; (2) 100 parts of ethylene glycol were added to 100 parts of water and stirred to prepare a synthetic solvent. 10 parts of a dispersant (Triton X-100) and 1 part of a stabilizer (sodium carboxymethyl cellulose) were added to the solvent and stirred until dissolved. The solution was heated to 45°C and 5 parts of a complexing agent (benzo-15-crown-5) were added within 10 minutes. The solution was stirred continuously for 2 hours and then cooled to room temperature to prepare a modifier. (3) 100 parts of coated titanium dioxide were dispersed in 200 parts of ethylene glycol, heated and stirred at 80°C and 300 rpm, and the pH was adjusted to 9.5 with ammonia water. 10 parts of a modifier were added within 30 minutes, and the mixture was stirred continuously for 2 hours and then cooled to room temperature. The mixture was then ground with a grinder for 2 hours to prepare a cationic dyeable polyester matting agent.

[0049] An application of the above-mentioned cationic dye-dyable polyester matting agent in the preparation of semi-matt cationic polyester comprises the following steps: 830 parts of terephthalic acid, 387 parts of ethylene glycol and 200 ppm of ethylene glycol antimony catalyst were added to a polymerization kettle for beating. The polymerization kettle was closed for nitrogen replacement, and an esterification reaction was carried out at a temperature of 250° C. and a pressure of 3.5 bar. After separation in a process tower and cooling in a condenser, the esterification water was removed. 2.4 parts of a cationic dye-dyable polyester matting agent and 30 parts of 5-sodium sulfonate of isophthalic acid were added to the esterified product. The product was vacuumed and decompressed, and the polycondensation temperature was controlled at 278° C. After low vacuum pre-polycondensation and 50 Pa high vacuum polycondensation reaction, after reaching the expected stirring power, the melt was cast on a belt, cooled underwater, and pelletized to obtain semi-matt cationic polyester chips.

[0050] Comparative Example 10: The difference between Comparative Example 10 and Example 1 is that the amount of coating on the surface of the coated titanium dioxide is too much; A method for preparing a cationic dye-dyable polyester matting agent comprises the following steps: (1) 100 parts of titanium dioxide were dispersed in 900 parts of water and ground for 0.5 h to form a uniform titanium dioxide suspension; the titanium dioxide suspension was transferred to a reaction vessel, nitrogen was introduced for 0.5 h to exclude oxygen, and the suspension was heated to 70°C, stirred at 200 rpm, and 5 parts of methacryloyloxyethyltrimethylammonium chloride monomer was added. After stirring until dissolved, 0.2 parts of initiator (ammonium persulfate) was added and the mixture was kept warm for 4 h. After the reaction, the suspension was washed three times with water by centrifugation and dried at 80°C to prepare coated titanium dioxide; (2) 100 parts of ethylene glycol were added to 100 parts of water and stirred to prepare a synthetic solvent. 10 parts of a dispersant (Triton X-100) and 1 part of a stabilizer (sodium carboxymethyl cellulose) were added to the solvent and stirred until dissolved. The solution was heated to 45°C and 5 parts of a complexing agent (benzo-15-crown-5) were added within 10 minutes. The solution was stirred continuously for 2 hours and then cooled to room temperature to prepare a modifier. (3) 100 parts of coated titanium dioxide were dispersed in 200 parts of ethylene glycol, heated and stirred at 80°C and 300 rpm, and the pH was adjusted to 9.5 with ammonia water. 10 parts of a modifier were added within 30 minutes, and the mixture was stirred continuously for 2 hours and then cooled to room temperature. The mixture was then ground with a grinder for 2 hours to prepare a cationic dyeable polyester matting agent.

[0051] An application of the above-mentioned cationic dye-dyable polyester matting agent in the preparation of semi-matt cationic polyester comprises the following steps: 830 parts of terephthalic acid, 387 parts of ethylene glycol and 200 ppm of ethylene glycol antimony catalyst were added to a polymerization kettle for beating. The polymerization kettle was closed for nitrogen replacement, and an esterification reaction was carried out at a temperature of 250° C. and a pressure of 3.5 bar. After separation in a process tower and cooling in a condenser, the esterification water was removed. 2.4 parts of a cationic dye-dyable polyester matting agent and 30 parts of 5-sodium sulfonate of isophthalic acid were added to the esterified product. The product was vacuumed and decompressed, and the polycondensation temperature was controlled at 278° C. After low vacuum pre-polycondensation and 50 Pa high vacuum polycondensation reaction, after reaching the expected stirring power, the melt was cast on a belt, cooled underwater, and pelletized to obtain semi-matt cationic polyester chips.

[0052] Comparative Example 11: The difference between Comparative Example 11 and Example 1 is that the cationic dye-dyeable polyester matting agent is not ground; A method for preparing a cationic dye-dyable polyester matting agent comprises the following steps: (1) 100 parts of titanium dioxide were dispersed in 900 parts of water and ground for 0.5 h to form a uniform titanium dioxide suspension; the titanium dioxide suspension was transferred to a reaction vessel, nitrogen was introduced for 0.5 h to exclude oxygen, and the suspension was heated to 70°C, stirred at 200 rpm, and 0.5 parts of methacryloyloxyethyl trimethyl ammonium chloride monomer was added. After stirring until dissolved, 0.2 parts of initiator (ammonium persulfate) was added and the mixture was kept warm for 4 h. After the reaction, the suspension was washed three times with water by centrifugation and dried at 80°C to prepare coated titanium dioxide; (2) 100 parts of ethylene glycol were added to 100 parts of water and stirred to prepare a synthetic solvent. 10 parts of a dispersant (Triton X-100) and 1 part of a stabilizer (sodium carboxymethyl cellulose) were added to the solvent and stirred until dissolved. The solution was heated to 45°C and 5 parts of a complexing agent (benzo-15-crown-5) were added within 10 minutes. The solution was stirred continuously for 2 hours and then cooled to room temperature to prepare a modifier. (3) 100 parts of coated titanium dioxide were dispersed in 200 parts of ethylene glycol, heated and stirred at 80°C and 300 rpm, and the pH was adjusted to 9.5 with ammonia water. 10 parts of a modifier were added within 30 minutes, and the mixture was stirred continuously for 2 hours and then cooled to room temperature to prepare a cationic dyeable polyester matting agent.

[0053] An application of the above-mentioned cationic dye-dyable polyester matting agent in the preparation of semi-matt cationic polyester comprises the following steps: 830 parts of terephthalic acid, 387 parts of ethylene glycol and 200 ppm of ethylene glycol antimony catalyst were added to a polymerization kettle for beating. The polymerization kettle was closed for nitrogen replacement, and an esterification reaction was carried out at a temperature of 250° C. and a pressure of 3.5 bar. After separation in a process tower and cooling in a condenser, the esterification water was removed. 2.4 parts of a cationic dye-dyable polyester matting agent and 30 parts of 5-sodium sulfonate of isophthalic acid were added to the esterified product. The product was vacuumed and decompressed, and the polycondensation temperature was controlled at 278° C. After low vacuum pre-polycondensation and 50 Pa high vacuum polycondensation reaction, after reaching the expected stirring power, the melt was cast on a belt, cooled underwater, and pelletized to obtain semi-matt cationic polyester chips.

[0054] Test Example 1: The melt filtration performance of the semi-matt cationic polyesters prepared in Examples 1 to 5 and Comparative Examples 1 to 11 was tested. The melt filtration performance test was conducted in accordance with the method disclosed in "FZ / T 51019-2021 Polyester Fiber Masterbatch". The melt was extruded through a 1400 mesh filter, and the difference between the maximum pressure before the head filter within a specific time and the initial pressure before the filter before the sample was added was tested; the pressure rise of the sample material in this section after being intercepted by the filter was characterized. The larger the DF value, the higher the pressure rise of the sample in this section, the more large particle agglomerates were trapped, and the worse the dispersion of titanium dioxide. The test results are shown in Table 1.

[0055] Table 1 Physical properties and melt filter press values ​​of semi-matt cationic polyester As shown in Table 1, Examples 1 to 5 are semi-matt cationic polyesters produced by in-situ polymerization using the cationic dyeable polyester matting agent provided by the present invention. While maintaining essentially the same intrinsic viscosity of the polyesters, other physical properties were compared. The melting point, carboxyl end groups, and diethylene glycol content of the polyesters produced in each Example and Comparative Example showed little difference. Agglomerated particles refer to the number of large impurities exceeding 10 μm in size in the sliced ​​thin film. There are significant differences between Examples 1 to 5 and Comparative Examples 1 to 11. No large particle agglomerates were observed in the semi-matt cationic polyester slices produced in Examples 1 to 5 using the preferred process, while relatively large agglomerates were observed in Comparative Examples 1 to 11. While these data generally correspond to the melt pressure (DF) values, the specific values ​​may not fully correspond to the DF values ​​due to the random nature of the slices. From the DF value results of Examples 1 to 5, it can be seen that under the preferred scheme and ratio of the present invention, by adjusting the ratio within a small range, semi-matt cationic polyester with a low melt pressure can be prepared, and its value is significantly lower than that of the conventional titanium dioxide in Comparative Example 1. Furthermore, by adjusting the coating scheme: no coating (Comparative Example 2), no modifier (Comparative Example 3), no stabilizer (Comparative Example 4), and no complexing agent (Comparative Example 5), the melt pressure of the product is significantly affected, demonstrating that the auxiliary materials in the scheme proposed by the present invention play an important role in the uniform dispersion of titanium dioxide in the cationic polyester. In addition, In addition to the scheme, each process and ratio also has a certain impact on the product performance: for example, the use of excessive modifier (Comparative Example 6), too little complexing agent (Comparative Example 7), excessive complexing agent (Comparative Example 8), too little coating (Comparative Example 9), too much coating (Comparative Example 10), and no grinding and dispersion (Comparative Example 11), although the melt pressure value is reduced relative to the lack of a certain auxiliary material, it is still higher than that of Examples 1-5, indicating that under the preferred ratio of the present invention, each additive can better play its role, avoid the influence of the three monomers in the cationic polyester on titanium dioxide, and can be more evenly dispersed.

[0056] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any way. Any simple modification, change and equivalent transformation made to the above embodiment based on the technical essence of the present invention still fall within the scope of protection of the technical solution of the present invention.

Claims

1. A cationic dye-dyable polyester matting agent, characterized in that: The raw materials include coated titanium dioxide and a modifier, wherein the modifier includes, by mass, 2 to 15 parts of a stabilizer, 0.5 to 2 parts of a dispersant, 0.1 to 10 parts of a complexing agent, and 1,000 parts of a solvent. The raw materials of the coated titanium dioxide include, by mass, 100 parts of titanium dioxide, 0.1 to 3 parts of methacryloyloxyethyltrimethylammonium chloride, 0.001 to 0.3 parts of an initiator, and 500 to 10,000 parts of water.

2. The cationic dyeable polyester matting agent according to claim 1, characterized in that: The solvent is one of an ethylene glycol aqueous solution, a 1,3-propylene glycol aqueous solution and a 1,4-butanediol aqueous solution.

3. The cationic dyeable polyester matting agent according to claim 1, characterized in that: The complexing agent is one of poly(tert-butyl acrylate), poly(methacrylic acid-co-sulfobetaine), 1-vinyl-3-ethylimidazolium bis(trifluoromethanesulfonyl)imide salt, 1-butyl-3-methylimidazolium sulfonate, benzo-15-crown-5 and 15-crown-5; the stabilizer is one of sodium carboxymethyl cellulose, polyvinyl alcohol, hydroxy cellulose and pentaerythritol stearate; and the dispersant is one of Triton X-100 and isomeric alcohol polyoxyethylene ether.

4. The cationic dyeable polyester matting agent according to claim 1, characterized in that: The initiator is ammonium persulfate.

5. A method for preparing a cationic dyeable polyester matting agent according to any one of claims 1 to 4, characterized in that: The following steps are involved: (1) Titanium dioxide and methacryloyloxyethyl trimethyl ammonium chloride are polymerized in the presence of an initiator to prepare coated titanium dioxide; (2) Add the stabilizer and dispersant to the solvent and stir until dissolved, then add the complexing agent under heating and stirring to prepare the modifier; (3) Disperse the coated titanium dioxide in ethylene glycol, heat and stir, and adjust the pH to 9-10. Then add the modifier, continue stirring, cool, and grind to make a cationic dye-dyable polyester matting agent.

6. The preparation method according to claim 1, wherein The conditions for the polymerization reaction in step (1) include: temperature 70-80°C, stirring speed 100-500 rpm; and insulation reaction time 6-8 h.

7. The preparation method according to claim 6, characterized in that: The heating and stirring conditions in step (2) include: adding the complexing agent within 20 to 30 minutes at 30 to 60°C, continuously stirring for 2 to 3 hours, and then cooling to 20 to 30°C for storage.

8. The preparation method according to claim 6, characterized in that: The heating and stirring conditions in step (3) include: temperature 60~100°C, stirring speed 300~1000 rpm, and stirring time 2~6 h.

9. The preparation method according to claim 6 or 8, characterized in that: The grinding time in step (3) is 1 to 4 h.

10. Use of the cationic dyeable polyester matting agent according to any one of claims 1 to 4 in the preparation of cationic polyester with matting properties, characterized in that: The following steps are involved: Terephthalic acid, ethylene glycol and a catalyst undergo esterification reaction to prepare an ester, and a cationic dye-dyeable polyester matting agent and sodium 5-sulfonisophthalic acid are added to the ester to carry out polymerization reaction to prepare a cationic polyester with matting properties.

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