CN111088546A - Method for preparing titanium-based polyester filament by multi-kettle melt direct spinning - Google Patents

Method for preparing titanium-based polyester filament by multi-kettle melt direct spinning Download PDF

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CN111088546A
CN111088546A CN201911407262.9A CN201911407262A CN111088546A CN 111088546 A CN111088546 A CN 111088546A CN 201911407262 A CN201911407262 A CN 201911407262A CN 111088546 A CN111088546 A CN 111088546A
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polyester
titanium
kettle
catalyst
esterification
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孙正清
孙小国
孙宾
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Shanghai Huiyi New Material Technology Co Ltd
Donghua University
National Dong Hwa University
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Shanghai Huiyi New Material Technology Co Ltd
Donghua University
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6886—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/785—Preparation processes characterised by the apparatus used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention relates to a method for preparing titanium-based polyester filament by direct spinning of four-kettle melt, which comprises the following steps: preparing a polyester melt by taking PTA, EG and a polyester titanium catalyst composite material system as raw materials and adopting a four-kettle polymerization process, and then performing melt direct spinning to prepare a titanium-based polyester filament; adding the PTA, EG and the polyester titanium catalyst composite material system into an esterification kettle 1 together; the polyester titanium catalyst composite material system mainly comprises a polyester prepolymer with the polymerization degree of 5-30 and a sheet-shaped titanium polyester catalyst dispersed in the polyester prepolymer. According to the method for preparing the polyester long fibers by the four-kettle melt direct spinning, the catalyst is wrapped by the polyester prepolymer with the polymerization degree of 5-30, so that agglomeration is effectively avoided; the adopted catalyst has excellent hydrolysis resistance and can be added in any stage of esterification and pre-polycondensation; the method for preparing the titanium-based polyester filament by direct spinning of the four-kettle melt has the advantages of simple process, low cost and good application prospect.

Description

Method for preparing titanium-based polyester filament by multi-kettle melt direct spinning
Technical Field
The invention belongs to the technical field of polyester fibers, and relates to a method for preparing titanium-based polyester filaments by multi-kettle melt direct spinning.
Background
The polyester filament is made of polyester. Terylene is an important variety in synthetic fibers and is the trade name of polyester fibers in China. Dacron has a wide range of applications and is used in a large number of articles of clothing and industry. The flame-retardant polyester has flame retardance and wide application range. Besides pure flame-retardant polyester, the polyester can be used for producing multifunctional series products with flame retardance, water resistance, oil repellency, static resistance and the like according to special requirements of users.
In the process of industrially synthesizing PET polyester, more than 95 percent of heavy metal antimony catalysts are adopted, the polyester at least contains 200-450 ppm, and the annual consumption of antimony catalysts exceeds one million tons, thereby bringing irreversible influence on resource consumption and environmental pollution in the world, particularly in China. The catalyst which can be used for replacing antimony catalyst has the advantages and disadvantages as follows: the aluminum catalyst has poor stability and low activity, and is not easy to dissolve in ethylene glycol; the germanium catalyst has proper catalytic activity, but has small storage amount and high price; the tin catalyst is toxic and has poor product color value; the titanium catalyst has high activity, safety, environmental protection and feasible cost, and the resin has high brightness, namely chromaticity L value, is most feasible and most concerned in the aspect of replacing antimony catalysts.
The titanium catalyst is applied to the direct esterification and continuous polycondensation PET process, has the advantages of environmental protection, safety and high efficiency, greatly reduces the temperature in the synthesis and spinning process, reduces the energy consumption, simultaneously ensures that the physical and mechanical properties of the fiber are excellent, improves the stability in the production process, and improves the material utilization rate.
Commercial titanium-based catalysts include two broad classes: 1) the compound/dispersion liquid of the catalyst and the glycol is in a liquid state, such as: the catalyst has poor long-term stability and dispersion performance, so that the catalyst can generate agglomeration and particle enlargement phenomena in the transportation and storage processes, can influence the catalytic activity due to hydrolysis, is easy to deteriorate, and can generate hydrolysis reaction to a greater extent at the high temperature of the synthesized polyester to destroy the catalytic activity of the catalyst; 2) the solid powder of the catalyst is introduced into a polyester synthesis system by preparing an ethylene glycol dispersion liquid during application, the catalytic activity of titanium element is generally regulated by introducing a certain proportion of Si element, and the particle size is designed to be micron-sized so as to inhibit the agglomeration of particles, but the catalyst still has the following defects: firstly, because the particle size of the solid catalyst is further increased undoubtedly when compounds of other elements such as Si element are introduced, the particle size of the catalyst is larger, and the dispersibility is not good; secondly, in order to improve the dispersion effect of the solid catalyst, methods such as surface modification and the like have complex process and higher cost; thirdly, it undergoes a large degree of hydrolysis reaction at the high temperature of the synthesis of polyester to destroy the catalytic activity of the catalyst.
In the prior art, the polyester synthesis is usually produced in a single kettle intermittent production mode, the esterification, polycondensation and cooling of the polyester synthesis are completed in one reaction kettle, one kettle is produced in each time through several processes of temperature rise, high-temperature vacuum and cooling, so that the operation process of each kettle is multiple, mistakes are easy to make, each process is difficult to stably control, the heating and cooling are repeatedly switched, and the energy consumption is high, so that the polyester production technology is gradually switched to a polymerization process of three kettles or more kettles.
When the traditional multi-kettle polymerization process is adopted for preparing polyester, a catalyst is generally added into a pre-polycondensation kettle after the esterification reaction of an esterification kettle 2 is finished, the main reason is that the catalyst is easy to hydrolyze under the action of high-temperature esterification reaction and water generated by the esterification reaction to reduce or even lose catalytic activity, however, the catalyst also has esterification catalytic action although mainly playing the role of polycondensation catalytic action, and the catalyst cannot play the role of esterification catalytic action and cannot fully play the role of the catalyst after the esterification reaction is finished;
therefore, it is very important to research a titanium catalyst which has good dispersibility and can be added in the esterification reaction stage, and then to prepare the polyester filament by the titanium catalyst.
Disclosure of Invention
The invention aims to overcome the defects of poor catalyst dispersibility and addition in the polycondensation stage in the prior art, and provides a method for preparing polyester long fibers by multi-kettle melt direct spinning. According to the invention, the catalyst is wrapped by the polyester prepolymer with the polymerization degree of 5-30, so that agglomeration is effectively avoided; the catalyst selected by the invention is a sheet titanium polyester catalyst, can be added before the esterification reaction, can also be added after the esterification reaction, can be added in the esterification kettle 1, can also be added in the esterification kettle 2, and can also be added in the pre-polycondensation kettle.
When the multi-kettle is a four-kettle, in order to achieve the purpose, the invention adopts the technical scheme that:
the method for preparing the titanium-based polyester filament by direct spinning of the four-kettle melt comprises the steps of firstly preparing the polyester melt by adopting a four-kettle polymerization process by taking PTA, EG and a polyester titanium catalyst composite material system as raw materials, and then performing direct spinning of the melt to prepare the titanium-based polyester filament; adding the PTA, EG and the polyester titanium catalyst composite material system into an esterification kettle 1 together; the polyester titanium catalyst composite material system mainly comprises a polyester prepolymer with the polymerization degree of 5-30 and a sheet-shaped titanium polyester catalyst dispersed in the polyester prepolymer.
When the traditional four-kettle polymerization process is adopted for preparing polyester, the catalyst is often easy to agglomerate before being added into a reaction kettle due to poor dispersion performance, so that the catalytic activity is influenced, and the catalyst is easy to deteriorate, in order to avoid agglomeration of the catalyst, the generally adopted method is to regulate the catalytic activity of titanium element by introducing a certain proportion of Si element, and the particle size is designed to be micron order, so as to inhibit agglomeration of particles, however, the methods have the following problems:
1) because the particle size of the solid catalyst is undoubtedly further increased when compounds of other elements such as Si element are introduced, the particle size of the catalyst is larger, and the dispersibility is poor; 2) in order to improve the dispersion effect of the solid catalyst, methods such as surface modification and the like have complex process and higher cost; 3) the catalyst can generate hydrolysis reaction to a large extent at high temperature for synthesizing polyester so as to destroy the catalytic activity of the catalyst;
the catalyst is wrapped by the polyester prepolymer with the polymerization degree of 5-30, so that agglomeration is effectively avoided, the problems are solved, the polyester prepolymer has a high melting point, and only melts at a high temperature to release the catalyst in the polyester synthesis process, so that the secondary agglomeration phenomenon in the transportation or storage process can be avoided, and meanwhile, the polyester prepolymer is an intermediate for preparing a polyester high polymer and has excellent intrinsic compatibility with an intermediate system for synthesizing the high polymer, so that the polyester prepolymer can show high dispersibility in the polyester synthesis process;
in addition, when the traditional four-kettle polymerization process is adopted for preparing polyester, the catalyst is generally added into the pre-polycondensation kettle after the esterification reaction of the esterification kettle 2 is finished, the main reason is that the catalyst is easy to hydrolyze under the action of high-temperature esterification reaction and water generated by the esterification reaction to reduce or even lose the catalytic activity, however, the catalyst also has the esterification catalytic action although mainly exerting the polycondensation catalytic action, and the catalyst cannot exert the esterification catalytic action and cannot fully exert the effectiveness of the catalyst after the esterification reaction is finished;
the catalyst can be added before the esterification reaction or after the esterification reaction, can be added into the esterification kettle 1 or the esterification kettle 2, or can be added into the pre-polycondensation kettle, can play the esterification catalysis and the polycondensation catalysis, and has the main reason that the catalyst is a sheet titanium polyester catalyst which has excellent hydrolysis resistance, can be used as a polyester prepolymer with the polymerization degree of 5-30 of a load substrate to avoid the agglomeration of the catalyst before the polyester prepolymer is added into a polymerization system, solves the problem of poor dispersibility, and can be melted in the esterification reaction process to release the catalyst so that the esterification catalysis can be generated.
The method for preparing the titanium-based polyester filament by the four-kettle melt direct spinning comprises the following specific steps:
(1) adding a PTA, EG and polyester titanium catalyst composite material system into an esterification kettle 1 to perform esterification reaction to obtain an esterification primary product, wherein the esterification reaction is performed under the nitrogen atmosphere, the pressure is 210-250 KPa, the temperature is 260-262 ℃, and the time is 190-200 min; the temperature of the esterification reaction in the esterification kettle 1 in the traditional process is generally 268-273 ℃, the temperature of the esterification reaction in the esterification kettle 1 is lower and is 260-263 ℃, and the main reason is that the high activity of the titanium catalyst can be fully exerted on the premise of better mass transfer condition, the esterification speed is higher, so the required esterification reaction temperature is relatively lower;
(2) conveying the primary esterification product to an esterification kettle 2 for esterification reaction to obtain an esterification oligomer, wherein the esterification reaction is carried out under the nitrogen atmosphere, the pressure is 90-110 KPa, the temperature is 263-265 ℃, and the time is 80-90 min;
(3) conveying the esterified oligomer to a pre-polycondensation kettle for pre-polycondensation reaction to obtain a pre-polycondensation product, wherein the pressure of the pre-polycondensation reaction is 10-2 KPa, the temperature is 265-270 ℃, and the time is 100-110 min;
(4) conveying the pre-polycondensation product to a final polycondensation kettle for final polycondensation to obtain a polyester melt, wherein the pressure of the final polycondensation reaction is 100-150 Pa, the temperature is 270-284 ℃, and the time is 180-200 min;
(5) and carrying out melt direct spinning on the polyester melt to obtain the titanium-based polyester filament.
In the method for preparing the titanium-based polyester filament by the direct spinning of the four-kettle melt, in the step (1), the molar ratio of PTA to EG is 1: 1.1-1.6, and the addition amount of the sheet-shaped titanium-based polyester catalyst contained in the polyester titanium-based catalyst composite material system in the esterification kettle 1 is 3-6 ppm of the theoretical mass of a polymerization product of PTA and EG; in the traditional process, the titanium catalyst is dispersed and not resistant to hydrolysis, and the addition amount is about 20ppm of the theoretical mass of the PTA and EG polymerization products, and the comparison shows that the addition amount of the catalyst is obviously reduced, the main reason is that the polyester titanium catalyst composite material is only melted at a higher temperature to release the titanium catalyst, so that the hydrolysis reaction of the titanium catalyst caused by water contained in the storage and transportation process can be reduced or even avoided, and meanwhile, the catalyst is a sheet titanium polyester catalyst, has excellent hydrolysis resistance and can avoid the hydrolysis reaction caused by water generated by the esterification reaction;
in the step (4), the intrinsic viscosity of the polyester melt is 0.64-0.68 dL/g, the chroma L value of the polyester resin obtained by sampling from the polyester melt is 86-90, and the b value is 3.8-7; the chromaticity L value of the polyester melt prepared by the traditional process is generally 78-84, and the b value is generally 1-5, compared with the traditional process, the chromaticity L value and the b value of the polyester melt are obviously improved, and the main reason is that the polyester prepolymer is an intermediate for preparing polyester chips, and has intrinsic good compatibility with an intermediate system of the synthesized polyester chips, so that the polyester prepolymer is prevented from being agglomerated, the high dispersibility and the high activity of a polyester catalyst are ensured, and more side reactions are inhibited;
in the step (5), the melt direct spinning process parameters are as follows: the spinning temperature is 282-285 ℃, and the technological parameters of melt direct spinning are as follows: the spinning speed is 1000-1200 m/min, the side blowing temperature is 30 +/-5 ℃, the side blowing air speed is 0.2-0.4 m/s, and the drafting multiplying power is 3.5-4.0.
According to the method for preparing the titanium-based polyester filament by direct spinning of the four-kettle melt, the polyester prepolymer also contains a stabilizer and a toner, and the mass contents of the sheet-shaped titanium-based polyester catalyst, the stabilizer and the toner in the polyester titanium-based catalyst composite material system are respectively 0.5-20 wt%, 5-15 wt% and 0.5-8 wt%; the stabilizer and the toner are not required to be added, and can be selected not to be added, the stabilizer is generally added after the esterification reaction and before the pre-polymerization reaction when the polyester is synthesized by adopting the traditional process, the titanium catalyst, the stabilizer and the toner are firstly introduced into the synthesis process of the prepolymer to prepare the polyester titanium catalyst composite material system, and then the polyester titanium catalyst composite material system is introduced into the polyester reaction system, and the stabilizer is not required to be added again, so that the operation convenience is improved.
The method for preparing the titanium-based polyester filament by direct spinning of the four-kettle melt has the structural general formula of Tix(ORO)y(OOC6C4H4COO)zH4Wherein R is C2～C4Z is more than or equal to 1, y + z is 2x +2, x is 4, the flaky titanium polyester catalyst is in a lamellar structure, and the thickness of the lamellar is 100-200 nm;
the preparation method of the sheet titanium polyester catalyst comprises the following steps: taking terephthalic acid or terephthalate, titanate and dihydric fatty alcohol as raw materials, carrying out reaction in stages under the conditions that the temperature is 150-280 ℃ and the pressure is 0.01-0.4 MPa, specifically comprising the steps of controlling the temperature to react for 0.5-2.0 h under the condition that the temperature is 150-250 ℃, then heating to 200-280 ℃ to continue the reaction, stopping the reaction when the degree of esterification or ester exchange reaches 70-90%, filtering while hot, and crushing and grinding the obtained solid product to prepare the sheet-shaped titanium polyester catalyst;
the terephthalic acid ester is dimethyl terephthalate, diethyl terephthalate, dihydroxyethyl terephthalate, dihydroxypropyl terephthalate or dihydroxybutyl terephthalate; the titanate is n-butyl titanate, tetraisopropyl titanate or ethyl titanate; the dihydric fatty alcohol is ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol;
the stabilizer is more than one of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, triphenyl phosphate, tripropyl octyl phosphate, phosphoric acid and phosphorous acid;
the toner is a bluing agent (e.g., Issman chemical OB-1, Claine solvent blue 45, Germany, Ciba Irganox1425, Ciba Irgamod 195, Germany) or a reddening agent (e.g., Poulva Oncolor Edgeglo, Clariant Red GFP, Germany).
The preparation method of the polyester titanium catalyst composite material system comprises the following steps: and melting and blending the solid polyester prepolymer with the polymerization degree of 5-30 with a sheet-shaped titanium polyester catalyst, a stabilizer and a toner, and cooling to obtain a solid polyester titanium catalyst composite material system, wherein the melting and blending temperature is 100-270 ℃, and the time is 1.5-6 hours.
The preparation method of the polyester titanium catalyst composite material system comprises the following steps: adding an additive or a dihydric alcohol dispersion liquid of the additive into a polyester prepolymer melt with the polymerization degree of 5-30, uniformly stirring and cooling to obtain a solid or slurry polyester titanium catalyst composite material system, wherein the additive is a sheet titanium polyester catalyst, a stabilizer and a toner, the sheet titanium polyester catalyst, the stabilizer and the toner can be directly added, can also be added after being dispersed in dihydric alcohol, can also be partially added directly, and can be partially added after being dispersed in the dihydric alcohol, the adding modes are all within the protection range of the invention, when the adding mode is adopted after being dispersed in the dihydric alcohol, when the mass ratio of the polyester prepolymer to the dihydric alcohol is more than 1, the final product is in a solid state; when the mass ratio of the polyester prepolymer to the dihydric alcohol is 0.5-1, the final product is in a slurry state; the mass concentration of the dihydric alcohol dispersion liquid of the additive is 30-70 wt%, and the dihydric alcohol is ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol.
The preparation method of the polyester titanium catalyst composite material system comprises the following steps: a, B and C are mixed evenly and then are processed by esterification, pre-polycondensation and cooling to obtain a solid or slurry polyester titanium catalyst composite material system, wherein A is dibasic acid or dibasic acid ester, B is dihydric alcohol, C is additive or dihydric alcohol dispersion liquid of the additive, and the additive is a sheet titanium polyester catalyst, a stabilizer and a toner; the sheet titanium polyester catalyst, the stabilizer and the toner can be added directly, or can be added after being dispersed in the dihydric alcohol, or can be added partially directly, or can be added after being dispersed in the dihydric alcohol, and the addition modes are all within the protection scope of the invention. In the polyester synthesis process in the prior art, a sheet-shaped titanium polyester catalyst, a stabilizer and a toner are added before esterification reaction, and the sheet-shaped titanium polyester catalyst, the stabilizer and the toner are subjected to system environment changes such as temperature, pressure and the like, and physical and chemical reactions possibly occur among each other or between the sheet-shaped titanium polyester catalyst, the stabilizer and the toner and reaction monomers for preparing polyester, so that the catalytic activity of the sheet-shaped titanium polyester catalyst, the stabilizer and the toner is changed. The invention firstly introduces the sheet titanium polyester catalyst, the stabilizer and the toner into the synthesis process of the prepolymer to prepare a polyester titanium catalyst composite material system, and then introduces the polyester titanium catalyst composite material system into a polyester reaction system, and as the synthesis process of the prepolymer is similar to the esterification and polycondensation reaction of polyester synthesis, the catalytic activity and the efficiency of the polyester titanium catalyst composite material system can be further improved when the polyester titanium catalyst composite material system is used as a polyester catalyst after the esterification and pre-polycondensation reaction of the prepolymer; the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 100-400 KPa, the temperature is 180-260 ℃, and the time is 2-2.5 h; the pressure of the pre-polycondensation reaction is 100-10 KPa, the temperature is 260-270 ℃, and the time is 10-30 min.
In the method for preparing the titanium-based polyester filament by the four-kettle melt direct spinning, when the molar ratio of the sum of the molar amounts of the dihydric alcohols in B and C to A is 1-2: 1, and the molar ratio of the sum of the molar amounts of the dihydric alcohols in B and C to A is 1-1.5, the final product is in a solid state, and when the molar ratio of the sum of the molar amounts of the dihydric alcohols in B and C to A is more than 1.5, the final product is in a slurry state; the B is the same as the dihydric alcohol in the dihydric alcohol dispersion liquid of the additive, the mass concentration of the dihydric alcohol dispersion liquid of the additive is 35-70 wt%, and the mass of the sheet titanium polyester catalyst accounts for 10-20% of the sum of the mass of the dihydric alcohol in the B and the dihydric alcohol in the C.
The method for preparing titanium-based polyester filament by four-kettle melt direct spinning, as described above, wherein the dibasic acid is terephthalic acid, isophthalic acid or sodium 5-sulfoisophthalic acid, the dibasic ester is dimethyl terephthalate, and the dihydric alcohol is ethylene glycol, 1, 3-propanediol or 1, 4-butanediol.
When the multi-kettle is five kettles, in order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the method for preparing the titanium-based polyester filament by the direct spinning of the five-kettle melt comprises the steps of firstly preparing the polyester melt by taking PTA, EG and a polyester titanium catalyst composite material system as raw materials and adopting a five-kettle polymerization process, and then performing the direct spinning of the melt to prepare the titanium-based polyester filament; adding the PTA, EG and the polyester titanium catalyst composite material system into an esterification kettle 1 together; the polyester titanium catalyst composite material system mainly comprises a polyester prepolymer with the polymerization degree of 5-30 and a sheet-shaped titanium polyester catalyst dispersed in the polyester prepolymer.
When the traditional five-kettle polymerization process is adopted for preparing polyester, the catalyst is often easy to agglomerate before being added into a reaction kettle due to poor dispersion performance, so that the catalytic activity is influenced, and the catalyst is easy to deteriorate, in order to avoid agglomeration of the catalyst, the generally adopted method is to regulate the catalytic activity of titanium element by introducing a certain proportion of Si element, and the particle size is designed to be micron order, so as to inhibit agglomeration of particles, however, the methods have the following problems:
1) because the particle size of the solid catalyst is undoubtedly further increased when compounds of other elements such as Si element are introduced, the particle size of the catalyst is larger, and the dispersibility is poor; 2) in order to improve the dispersion effect of the solid catalyst, methods such as surface modification and the like have complex process and higher cost;
the catalyst is wrapped by the polyester prepolymer with the polymerization degree of 5-30, so that agglomeration is effectively avoided, the problems are solved, the polyester prepolymer has a high melting point, and only melts at a high temperature to release the catalyst in the polyester synthesis process, so that the secondary agglomeration phenomenon in the transportation or storage process can be avoided, and meanwhile, the polyester prepolymer is an intermediate for preparing a polyester high polymer and has excellent intrinsic compatibility with an intermediate system for synthesizing the high polymer, so that the polyester prepolymer can show high dispersibility in the polyester synthesis process;
in addition, when the traditional five-kettle polymerization process is adopted for preparing polyester, the catalyst is generally added into the first pre-polycondensation kettle after the esterification reaction of the esterification kettle 2 is finished, the main reason is that the catalyst is easy to hydrolyze under the action of high-temperature esterification reaction and water generated by the esterification reaction to reduce or even lose the catalytic activity, however, the catalyst also has the esterification catalytic action although mainly exerting the polycondensation catalytic action, and the catalyst cannot exert the esterification catalytic action and cannot fully exert the effectiveness of the catalyst after the esterification reaction is finished;
the catalyst can be added before the esterification reaction or after the esterification reaction, can be added in the esterification kettle 1 or the esterification kettle 2, and can also be added in the first pre-polycondensation kettle and the second pre-polycondensation kettle, so that the esterification catalysis and the polycondensation catalysis can be performed, and the catalyst has excellent hydrolysis resistance, can be used as a polyester prepolymer with the polymerization degree of 5-30 of a load substrate, can avoid the agglomeration of the catalyst before the polyester prepolymer is added into a polymerization system, solves the problem of poor dispersibility, and can be melted in the esterification reaction process to release the catalyst, so that the esterification catalysis can be performed.
As a preferred technical scheme:
the method for preparing the titanium-based polyester filament by direct spinning of the five-kettle melt comprises the following specific steps:
(1) adding a PTA, EG and polyester titanium catalyst composite material system into an esterification kettle 1 to perform esterification reaction to obtain an esterification primary product, wherein the esterification reaction is performed under the nitrogen atmosphere, the pressure is 120-550 KPa, the temperature is 250-257 ℃, and the time is 200-210 min; the temperature of the esterification reaction in the esterification kettle 1 in the traditional process is generally 260-270 ℃, the temperature of the esterification reaction in the esterification kettle 1 is lower, and is 250-257 ℃, the main reason is that under the premise of better mass transfer condition, the high activity of the titanium catalyst can be fully exerted, the esterification speed is faster, and therefore, the required esterification reaction temperature is relatively lower;
(2) conveying the primary esterification product to an esterification kettle 2 for esterification reaction to obtain an esterification oligomer, wherein the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 100-150 KPa, the temperature is 257-63 ℃, and the time is 60-70 min;
(3) conveying the esterified oligomer to a first pre-polycondensation kettle for pre-polycondensation to obtain a pre-polycondensation initial product, wherein the pressure of the pre-polycondensation reaction is 13-9 KPa, the temperature is 263-270 ℃, and the time is 40-50 min;
(4) conveying the pre-polycondensation initial product to a second pre-polycondensation kettle for pre-polycondensation reaction to obtain a pre-polycondensation final product, wherein the pressure of the pre-polycondensation reaction is 200-300 Pa, the temperature is 270-275 ℃, and the termination condition is as follows: the inherent viscosity of the final product of the pre-polycondensation is 0.29-0.34 dL/g;
(5) conveying the final product of the pre-polycondensation into a final polycondensation kettle for final polycondensation to obtain a polyester melt, wherein the pressure of the final polycondensation is 100-150 ℃, the temperature is 275-284 ℃, and the time is 180-190 min;
(6) and carrying out melt direct spinning on the polyester melt to obtain the titanium-based polyester filament.
In the method for preparing the titanium-based polyester filament by the five-kettle melt direct spinning, in the step (1), the molar ratio of PTA to EG is 1: 1.1-1.6, and the addition amount of the sheet-shaped titanium-based polyester catalyst contained in the polyester titanium-based catalyst composite material system in the esterification kettle 1 is 3-5 ppm of the theoretical mass of a polymerization product of PTA and EG; in the traditional process, the titanium catalyst is dispersed and not resistant to hydrolysis, and the addition amount is about 20ppm of the theoretical mass of the PTA and EG polymerization products, and the comparison shows that the addition amount of the catalyst is obviously reduced, the main reason is that the polyester titanium catalyst composite material is only melted at a higher temperature to release the titanium catalyst, so that the hydrolysis reaction of the titanium catalyst caused by water contained in the storage and transportation process can be reduced or even avoided, and meanwhile, the catalyst is a sheet titanium polyester catalyst, has excellent hydrolysis resistance and can avoid the hydrolysis reaction caused by water generated by the esterification reaction;
in the step (5), the intrinsic viscosity of the polyester melt is 0.67-0.68 dL/g, the chroma L value of the polyester resin obtained by sampling from the polyester melt is 86-90, and the b value is 3.5-6; the chromaticity L value of the polyester melt prepared by the traditional process is generally 78-84, and the b value is generally 1-5, compared with the traditional process, the chromaticity L value of the polyester melt is obviously improved, and the main reason is that the polyester prepolymer is an intermediate for preparing polyester chips, and has intrinsic good compatibility with an intermediate system of the synthesized polyester chips, so that the polyester prepolymer is prevented from being agglomerated, the high dispersibility and the high activity of a polyester catalyst are ensured, and more side reactions are inhibited;
in the step (6), the melt direct spinning process parameters are as follows: the spinning temperature is 282-285 ℃, the spinning speed is 1000-1200 m/min, the side blowing temperature is 30 +/-5 ℃, the side blowing air speed is 0.2-0.4 m/s, and the drawing ratio is 3.5-4.0.
According to the method for preparing the titanium-based polyester filament by direct spinning of the five-kettle melt, the polyester prepolymer also contains a stabilizer and a toner, and the mass contents of the sheet-shaped titanium-based polyester catalyst, the stabilizer and the toner in the polyester titanium-based catalyst composite material system are respectively 0.5-20 wt%, 5-15 wt% and 0.5-8 wt%.
The method for preparing the titanium-based polyester filament by direct spinning of the five-kettle melt has the structural general formula of Tix(ORO)y(OOC6C4H4COO)zH4Wherein R is C2～C4Z is more than or equal to 1, y + z is 2x +2, x is 4, the flaky titanium polyester catalyst is in a lamellar structure, and the thickness of the lamellar is 100-200 nm;
the preparation method of the sheet titanium polyester catalyst comprises the following steps: taking terephthalic acid or terephthalate, titanate and dihydric fatty alcohol as raw materials, carrying out reaction in stages under the conditions that the temperature is 150-280 ℃ and the pressure is 0.01-0.4 MPa, specifically comprising the steps of controlling the temperature to react for 0.5-2.0 h under the condition that the temperature is 150-250 ℃, then heating to 200-280 ℃ to continue the reaction, stopping the reaction when the degree of esterification or ester exchange reaches 70-90%, filtering while hot, and crushing and grinding the obtained solid product to prepare the sheet-shaped titanium polyester catalyst;
the terephthalic acid ester is dimethyl terephthalate, diethyl terephthalate, dihydroxyethyl terephthalate, dihydroxypropyl terephthalate or dihydroxybutyl terephthalate; the titanate is n-butyl titanate, tetraisopropyl titanate or ethyl titanate; the dihydric fatty alcohol is ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol;
the stabilizer is more than one of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, triphenyl phosphate, tripropyl octyl phosphate, phosphoric acid and phosphorous acid;
the toner is a bluing agent (e.g., Issman chemical OB-1, Claine solvent blue 45, Germany, Ciba Irganox1425, Ciba Irgamod 195, Germany) or a reddening agent (e.g., Poulva Oncolor Edgeglo, Clariant Red GFP, Germany).
The preparation method of the polyester titanium catalyst composite material system comprises the following steps: and melting and blending the solid polyester prepolymer with the polymerization degree of 5-30 with a sheet-shaped titanium polyester catalyst, a stabilizer and a toner, and cooling to obtain a solid polyester titanium catalyst composite material system, wherein the melting and blending temperature is 100-270 ℃, and the time is 1.5-6 hours.
The preparation method of the polyester titanium catalyst composite material system comprises the following steps: adding an additive or a dihydric alcohol dispersion liquid of the additive into a polyester prepolymer melt with the polymerization degree of 5-30, uniformly stirring and cooling to obtain a solid or slurry polyester titanium catalyst composite material system, wherein the additive is a sheet titanium polyester catalyst, a stabilizer and a toner, the sheet titanium polyester catalyst, the stabilizer and the toner can be directly added, can also be added after being dispersed in dihydric alcohol, can also be partially added directly, and can be partially added after being dispersed in the dihydric alcohol, the adding modes are all within the protection range of the invention, when the adding mode is adopted after being dispersed in the dihydric alcohol, when the mass ratio of the polyester prepolymer to the dihydric alcohol is more than 1, the final product is in a solid state; when the mass ratio of the polyester prepolymer to the dihydric alcohol is 0.5-1, the final product is in a slurry state; the mass concentration of the dihydric alcohol dispersion liquid of the additive is 30-70 wt%, and the dihydric alcohol is ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol.
The preparation method of the polyester titanium catalyst composite material system comprises the following steps: a, B and C are mixed evenly and then are processed by esterification, pre-polycondensation and cooling to obtain a solid or slurry polyester titanium catalyst composite material system, wherein A is dibasic acid or dibasic acid ester, B is dihydric alcohol, C is additive or dihydric alcohol dispersion liquid of the additive, and the additive is a sheet titanium polyester catalyst, a stabilizer and a toner; the sheet titanium polyester catalyst, the stabilizer and the toner can be added directly, or can be added after being dispersed in the dihydric alcohol, or can be added partially directly, or can be added after being dispersed in the dihydric alcohol, and the addition modes are all within the protection scope of the invention. In the polyester synthesis process in the prior art, a sheet-shaped titanium polyester catalyst, a stabilizer and a toner are added before esterification reaction, and the sheet-shaped titanium polyester catalyst, the stabilizer and the toner are subjected to system environment changes such as temperature, pressure and the like, and physical and chemical reactions possibly occur among each other or between the sheet-shaped titanium polyester catalyst, the stabilizer and the toner and reaction monomers for preparing polyester, so that the catalytic activity of the sheet-shaped titanium polyester catalyst, the stabilizer and the toner is changed. The invention firstly introduces the sheet titanium polyester catalyst, the stabilizer and the toner into the synthesis process of the prepolymer to prepare a polyester titanium catalyst composite material system, and then introduces the polyester titanium catalyst composite material system into a polyester reaction system, and as the synthesis process of the prepolymer is similar to the esterification and polycondensation reaction of polyester synthesis, the catalytic activity and the efficiency of the polyester titanium catalyst composite material system can be further improved when the polyester titanium catalyst composite material system is used as a polyester catalyst after the esterification and pre-polycondensation reaction of the prepolymer; the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 100-400 KPa, the temperature is 180-260 ℃, and the time is 2-2.5 h; the pressure of the pre-polycondensation reaction is 100-10 KPa, the temperature is 260-270 ℃, and the time is 10-30 min.
In the method for preparing the titanium-based polyester filament by the five-kettle melt direct spinning, when the molar ratio of the sum of the molar amounts of the dihydric alcohols in B and C to A is 1-2: 1, and the molar ratio of the sum of the molar amounts of the dihydric alcohols in B and C to A is 1-1.5, the final product is in a solid state, and when the molar ratio of the sum of the molar amounts of the dihydric alcohols in B and C to A is more than 1.5, the final product is in a slurry state; the B is the same as the dihydric alcohol in the dihydric alcohol dispersion liquid of the additive, the mass concentration of the dihydric alcohol dispersion liquid of the additive is 35-70 wt%, and the mass of the sheet titanium polyester catalyst accounts for 10-20% of the sum of the mass of the dihydric alcohol in the B and the dihydric alcohol in the C.
The method for preparing titanium-based polyester filament by five-kettle melt direct spinning, wherein the dibasic acid is terephthalic acid, isophthalic acid or sodium 5-sulfoisophthalic acid, the dibasic ester is dimethyl terephthalate, and the dihydric alcohol is ethylene glycol, 1, 3-propanediol or 1, 4-butanediol.
Has the advantages that:
(1) according to the method for preparing the titanium-based polyester filament by direct spinning of the four-kettle melt, the catalyst is wrapped by the polyester prepolymer with the polymerization degree of 5-30, so that agglomeration is effectively avoided, and the catalyst has good dispersibility;
(2) according to the method for preparing the titanium-based polyester filament by the four-kettle melt direct spinning, the catalyst is a sheet-shaped titanium-based polyester catalyst which has excellent hydrolysis resistance, can be added before the esterification reaction, can also be added after the esterification reaction, can be added in the esterification kettle 1, can also be added in the esterification kettle 2, can also be added in the pre-polycondensation kettle, and can play roles of esterification catalysis and polycondensation catalysis at the same time;
(3) the invention relates to a method for preparing titanium-based polyester filament by four-kettle melt direct spinning, which is characterized in that a method for preparing polyester filament by four-kettle melt direct spinning is provided, a four-kettle continuous polyester synthesis device is provided, two ends of the four-kettle continuous polyester synthesis device are esterified, two ends of the four-kettle continuous polyester synthesis device are subjected to polycondensation, the time of materials in a reaction kettle is long, the reaction temperature and the pressure are lower, and the color phase of resin is better;
(4) the method for preparing the titanium-based polyester filament by direct spinning of the four-kettle melt has the advantages of simple process, low cost and good application prospect;
(5) according to the method for preparing the titanium-based polyester filament by direct spinning of the five-kettle melt, the catalyst is wrapped by the polyester prepolymer with the polymerization degree of 5-30, so that agglomeration is effectively avoided, and the catalyst has good dispersibility;
(6) according to the method for preparing the titanium-based polyester filament by the five-kettle melt direct spinning, the catalyst is a sheet-shaped titanium-based polyester catalyst which has excellent hydrolysis resistance, can be added before the esterification reaction, can also be added after the esterification reaction, can be added in the esterification kettle 1, can also be added in the esterification kettle 2, can also be added in the first pre-polycondensation kettle and the second pre-polycondensation kettle, and can play roles of esterification catalysis and polycondensation catalysis at the same time;
(7) according to the method for preparing the titanium-based polyester filament by direct spinning of the five-kettle melt, the five-kettle continuous polyester synthesis device is provided, and the five-kettle process flow enables the product to have good uniformity and good quality stability and is easy to control and operate;
(8) the method for preparing the titanium-based polyester filament by direct spinning of the five-kettle melt has the advantages of simple process, low cost and good application prospect.
Drawings
FIG. 1 is an infrared spectrum (FTIR spectrum) of a composite system of the polyester titanium based catalyst of example 7 of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of a sheet titanium polyester catalyst comprises the steps of mixing terephthalic acid, ethylene glycol and n-butyl titanate with a molar ratio of 1:1.5:0.01, reacting for 0.5h at 150 ℃ and under 0.01MPa, heating to 200 ℃, continuing to react until the esterification degree reaches 70%, terminating the reaction, filtering while hot, and crushing and grinding to obtain the sheet titanium polyester catalyst with the average particle size of 0.5 mu m.
Examples 2 to 6
A process for preparing the flaky Ti-series polyester catalyst includes such steps as mixing BT, CT and DT in mole ratio AT, reacting GT AT ET and FT, heating to HT, reacting until the esterification degree reaches IT, filtering, and pulverizing.
Figure BDA0002349004160000101
Example 7
A preparation method of a polyester titanium catalyst composite material system comprises the steps of firstly adding ethylene glycol dispersion liquid of a sheet-shaped titanium polyester catalyst with the mass concentration of 30 wt% into a polyester prepolymer (ethylene terephthalate prepolymer) melt with the polymerization degree of 5-8, and then uniformly stirring and cooling to obtain the polyester titanium catalyst composite material system, wherein the sheet-shaped titanium polyester catalyst is prepared from example 1, and the mass content of the sheet-shaped titanium polyester catalyst in the polyester titanium catalyst composite material system is 20 wt%.
0.1g of the polyester titanium catalyst composite system is dispersed in 30mL of water, after the mixture is heated and stirred for 3 hours at 70 ℃, the residual solid is washed by absolute ethyl alcohol and dried, and then the sample is subjected to FTIR characterization, as shown in figure 1, the crystal structure and characteristic groups of the sample of the polyester titanium catalyst composite system in the invention are not changed too much after the sample is treated by hot water, and the FTIR graph is also shown at 2924cm-1、2854cm-1Left and right CH2The vibration peak disappears, which indicates that the sample has better stability in water, and meanwhile, no stabilizer or toner is added in the above embodiment, so that the polyester titanium catalyst composite material system composed of the polyester prepolymer with the polymerization degree of 3-8 and the sheet titanium polyester catalyst has excellent stability.
Examples 8 to 12
A preparation method of a polyester titanium catalyst composite material system comprises the steps of firstly adding BN into a polyester prepolymer (ethylene terephthalate prepolymer) melt with the polymerization degree of AN, uniformly stirring and cooling to obtain the polyester titanium catalyst composite material system, wherein the BN contains additives, the additives comprise a titanium catalyst, a stabilizer and a toner, and the mass contents of the titanium catalyst, the stabilizer and the toner in the polyester titanium catalyst composite material system are CN, DN and EN.
Figure BDA0002349004160000111
Figure BDA0002349004160000121
Example 13
A preparation method of a polyester titanium catalyst composite material system comprises the steps of melting and blending a solid polyester prepolymer (ethylene terephthalate prepolymer) with the polymerization degree of 25-30, a sheet-shaped titanium polyester catalyst (catalyst), triisopropyl phosphate (stabilizer) and Germany Ciba Irganox1425 (toner) at the temperature of 150 ℃ for 2 hours, cooling and crushing to obtain the polyester titanium catalyst composite material system, wherein the sheet-shaped titanium polyester catalyst is prepared from example 2, and the mass contents of the sheet-shaped titanium polyester catalyst, the triisopropyl phosphate and the Germany Ciba Irganox1425 in the polyester titanium catalyst composite material system are respectively 18 wt%, 5 wt% and 4 wt%.
Examples 14 to 19
A preparation method of a polyester titanium catalyst composite material system comprises the steps of melting and blending a solid polyester prepolymer (ethylene terephthalate prepolymer) with polymerization degree of AS with a titanium catalyst, a stabilizer and a toner at the temperature of BS (styrene-butadiene-styrene) for CS, cooling and crushing to obtain the solid polyester titanium catalyst composite material system, wherein the mass contents of the titanium catalyst, the stabilizer and the toner in the polyester titanium catalyst composite material system are DS, ES and FS respectively.
Figure BDA0002349004160000122
Figure BDA0002349004160000131
Examples 20 to 24
A preparation method of a polyester titanium catalyst composite material system comprises the steps of uniformly mixing A, B and C, and then carrying out esterification reaction, pre-polycondensation reaction and cooling to obtain the polyester titanium catalyst composite material system, wherein A is dibasic acid (terephthalic acid, isophthalic acid or isophthalic acid-5-sodium sulfonate) or dibasic acid ester (dimethyl terephthalate), B is dihydric alcohol, C is an additive or a dihydric alcohol dispersion liquid of the additive, the additive is a titanium catalyst, a stabilizer and a toner, the molar ratio of the sum of the molar amounts of the dihydric alcohol in the B and the dihydric alcohol in the C to the molar amount of the dihydric alcohol in the A is 1-2: 1, B is the same as the dihydric alcohol in the glycol dispersion liquid of the additive (specifically ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol), the mass concentration of the dihydric alcohol dispersion liquid of the additive is 35-70 wt%, and the mass of the titanium catalyst accounts for 10-20% (D) of the sum of the mass of the dihydric alcohol in the B and the dihydric alcohol in the C, the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 100-400 KPa, the temperature is 180-260 ℃, the time is 2.0-2.5 h, the pressure of the pre-polycondensation reaction is 100-10 KPa, the temperature is 260-270 ℃, the time is 10-50 min, and the mass contents of the titanium catalyst, the stabilizer and the toner in the polyester titanium catalyst composite material system are respectively 0.5-20 wt% (E), 5-15 wt% (F) and 0.5-8 wt% (G).
Figure BDA0002349004160000132
Figure BDA0002349004160000141
Examples 25 to 42
The polyester titanium catalyst composite material system prepared in the example X is adopted to carry out four-kettle melt direct spinning to prepare the titanium-based polyester filament, and the specific steps are as follows:
(1) adding a PTA, EG and polyester titanium catalyst composite material system into an esterification kettle 1 to carry out esterification reaction to obtain an esterification primary product, wherein the esterification reaction is carried out under the nitrogen atmosphere, the pressure (P3) is 210-250 KPa, the temperature (T3) is 260-263 ℃, and the time (T3) is 190-200 min; wherein the molar ratio (molar ratio 2) of PTA to EG is 1: 1.1-1.6, and the addition amount of the sheet-shaped titanium polyester catalyst contained in the polyester titanium catalyst composite material system in the esterification kettle 1 is 3-6 ppm of the theoretical mass (titanium content) of the polymerization product of PTA and EG by the mass of titanium element;
(2) conveying the primary esterification product to an esterification kettle 2 for esterification reaction to obtain an esterification oligomer, wherein the esterification reaction is carried out in a nitrogen atmosphere, the pressure (P4) is 90-110 KPa, the temperature (T4) is 263-265 ℃, and the time (T4) is 80-90 min;
(3) conveying the esterified oligomer to a pre-polycondensation kettle for pre-polycondensation reaction to obtain a pre-polycondensation product, wherein the pressure (P5) of the pre-polycondensation reaction is 10-2 KPa, the temperature (T5) is 265-270 ℃, and the time (T5) is 100-110 min;
(4) conveying the pre-polycondensation product to a final polycondensation kettle for final polycondensation to obtain a polyester melt, wherein the pressure (P6) of the final polycondensation reaction is 100-150 Pa, the temperature (T6) is 270-284 ℃, and the time (T6) is 180-200 min; wherein the inherent viscosity of the polyester melt is 0.64-0.68 dL/g, the chroma L value of the polyester resin is 86-90, and the b value is 3.8-7;
(5) carrying out melt direct spinning on the polyester melt to obtain titanium-based polyester filaments; wherein the melt direct spinning process parameters are as follows: the spinning temperature (T7) is 282-285 ℃, the spinning speed (v1) is 1000-1200 m/min, the side blowing temperature (T8) is 30 +/-5 ℃, the side blowing wind speed (v2) is 0.2-0.4 m/s, and the drafting multiplying power (a) is 3.5-4.0;
the parameters for examples 25 to 42 are specifically shown in Table 1-2.
Example 43
The process for preparing titanium-based polyester filament by four-kettle melt direct spinning comprises the same steps as in example 25, except that the polyester titanium-based catalyst composite system and the addition amount thereof in the step (1) are added in the step (2), and the specific parameters are shown in Table 2.
Example 44
The process for preparing titanium-based polyester filament by four-kettle melt direct spinning comprises the same steps as in example 25, except that the polyester titanium-based catalyst composite system and the addition amount thereof in the step (1) are added in the step (3), and the specific parameters are shown in Table 2.
Table 1 parameters corresponding to examples 25 to 34
Figure BDA0002349004160000151
Figure BDA0002349004160000161
Table 2 parameters corresponding to examples 35 to 44
Figure BDA0002349004160000162
Figure BDA0002349004160000171
Examples 45 to 64
The polyester titanium catalyst composite material system prepared in the example Y is adopted to carry out five-kettle melt direct spinning to prepare the titanium-based polyester filament, and the specific steps are as follows:
(1) adding a PTA, EG and polyester titanium catalyst composite material system into an esterification kettle 1 to carry out esterification reaction to obtain an esterification primary product, wherein the esterification reaction is carried out under the nitrogen atmosphere, the pressure (P3) is 120-550 KPa, the temperature (T3) is 250-257 ℃, and the time (T3) is 200-210 min; wherein the molar ratio (molar ratio 2) of PTA to EG is 1: 1.1-1.6, and the addition amount of the sheet-shaped titanium polyester catalyst contained in the polyester titanium catalyst composite material system in the esterification kettle 1 is 3-5 ppm of the theoretical mass (titanium content) of the polymerization product of PTA and EG by the mass of titanium element;
(2) conveying the primary esterification product to an esterification kettle 2 for esterification reaction to obtain an esterification oligomer, wherein the esterification reaction is carried out in a nitrogen atmosphere, the pressure (P4) is 100-150 KPa, the temperature (T4) is 257-263 ℃, and the time (T4) is 60-70 min;
(3) conveying the esterified oligomer to a first pre-polycondensation kettle for pre-polycondensation to obtain a pre-polycondensation initial product, wherein the pressure (P5) of the pre-polycondensation reaction is 13-9 KPa, the temperature (T5) is 263-270 ℃, and the time (T5) is 40-50 min;
(4) conveying the pre-polycondensation initial product to a second pre-polycondensation kettle for pre-polycondensation reaction to obtain a pre-polycondensation final product, wherein the pressure (P6) of the pre-polycondensation reaction is 200-300 Pa, the temperature (T6) is 270-275 ℃, and the termination conditions are as follows: the inherent viscosity (viscosity 1) of the final product of the pre-polycondensation is 0.29-0.34 dL/g;
(5) conveying the final product of the pre-polycondensation into a final polycondensation kettle for final polycondensation to obtain a polyester melt, wherein the pressure (P7) of the final polycondensation is 100-150 Pa, the temperature (T7) is 275-284 ℃, and the time (T6) is 180-190 min; wherein the inherent viscosity (viscosity 2) of the polyester melt is 0.67-0.68 dL/g, the chroma L value of the polyester resin is 86-90, and the b value is 3.5-6;
(6) carrying out melt direct spinning on the polyester melt to obtain titanium-based polyester filaments; wherein the melt direct spinning process parameters are as follows: the spinning temperature (T8) is 282-285 ℃, the spinning speed (v1) is 1000-1200 m/min, the side blowing temperature (T9) is 30 +/-5 ℃, the side blowing wind speed (v2) is 0.2-0.4 m/s, and the drafting multiplying factor (a) is 3.5-4.0;
the parameters for examples 45-62 are specifically shown in the following tables 1-2.
Example 63
The five-kettle melt direct spinning process of preparing titanium-base polyester filament includes the same steps as in example 25 except that the polyester-titanium catalyst composite system in step (1) and its amount are added in step (2) and the specific parameters are shown in Table 2.
Example 64
The five-kettle melt direct spinning process of preparing titanium-base polyester filament includes the same steps as in example 25 except that the polyester-titanium catalyst composite system in step (1) and its amount are added in step (3), and the specific parameters are shown in Table 2.
Table 1 parameters corresponding to examples 45 to 54
Figure BDA0002349004160000181
TABLE 2 parameters corresponding to examples 55 to 64
Figure BDA0002349004160000182
Figure BDA0002349004160000191

Claims (10)

1. The method for preparing the titanium-based polyester filament by multi-kettle melt direct spinning is characterized by comprising the following steps: firstly, preparing a polyester melt by taking a PTA, EG and polyester titanium catalyst composite material system as raw materials and adopting a multi-kettle polymerization process, wherein the multi-kettle is a four-kettle or five-kettle, and then performing melt direct spinning to prepare a titanium-based polyester filament;
adding the PTA, EG and the polyester titanium catalyst composite material system into an esterification kettle 1 together;
the polyester titanium catalyst composite material system mainly comprises a polyester prepolymer with the polymerization degree of 5-30 and a sheet-shaped titanium polyester catalyst dispersed in the polyester prepolymer.
2. The method for preparing titanium-based polyester filament by multi-kettle melt direct spinning according to claim 1, wherein the multi-kettle is a four-kettle melt, and the multi-kettle melt direct spinning comprises the following specific steps:
(1) adding a PTA, EG and polyester titanium catalyst composite material system into an esterification kettle 1 to perform esterification reaction to obtain an esterification primary product, wherein the esterification reaction is performed in a nitrogen atmosphere, the pressure is 210-250 KPa, the temperature is 260-263 ℃, and the time is 190-200 min;
(2) conveying the primary esterification product to an esterification kettle 2 for esterification reaction to obtain an esterification oligomer, wherein the esterification reaction is carried out under the nitrogen atmosphere, the pressure is 90-110 KPa, the temperature is 263-265 ℃, and the time is 80-90 min;
(3) conveying the esterified oligomer to a pre-polycondensation kettle for pre-polycondensation reaction to obtain a pre-polycondensation product, wherein the pressure of the pre-polycondensation reaction is 10-2 KPa, the temperature is 265-270 ℃, and the time is 100-110;
(4) conveying the pre-polycondensation product to a final polycondensation kettle for final polycondensation to obtain a polyester melt, wherein the pressure of the final polycondensation reaction is 100-150 Pa, the temperature is 270-284 ℃, and the time is 180-200 min;
(5) carrying out melt direct spinning on the polyester melt to obtain titanium-based polyester filaments;
the multi-kettle is five kettles, and the multi-kettle melt direct spinning preparation method of the titanium-based polyester filament comprises the following specific steps:
(a) adding a PTA, EG and polyester titanium catalyst composite material system into an esterification kettle 1 to perform esterification reaction to obtain an esterification primary product, wherein the esterification reaction is performed under the nitrogen atmosphere, the pressure is 120-550 KPa, the temperature is 250-257 ℃, and the time is 200-210 min;
(b) conveying the primary esterification product to an esterification kettle 2 for esterification reaction to obtain an esterification oligomer, wherein the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 100-150 KPa, the temperature is 257-263 ℃, and the time is 60-70 min;
(c) conveying the esterified oligomer to a first pre-polycondensation kettle for pre-polycondensation to obtain a pre-polycondensation initial product, wherein the pressure of the pre-polycondensation reaction is 13-9 KPa, the temperature is 263-270 ℃, and the time is 40-50 min;
(d) conveying the pre-polycondensation initial product to a second pre-polycondensation kettle for pre-polycondensation reaction to obtain a pre-polycondensation final product, wherein the pressure of the pre-polycondensation reaction is 200-300 Pa, the temperature is 270-275 ℃, and the termination condition is as follows: the inherent viscosity of the final product of the pre-polycondensation is 0.29-0.34 dL/g;
(e) conveying the final product of the pre-polycondensation into a final polycondensation kettle for final polycondensation to obtain a polyester melt, wherein the pressure of the final polycondensation is 100-150 Pa, the temperature is 275-284 ℃, and the time is 180-190 min;
(f) and carrying out melt direct spinning on the polyester melt to obtain the titanium-based polyester filament.
3. The method for preparing the titanium-based polyester filament by the multi-kettle melt direct spinning according to claim 2, wherein in the step (1), the molar ratio of PTA to EG is 1: 1.1-1.6, and the addition amount of the sheet-shaped titanium-based polyester catalyst contained in the polyester-titanium-based catalyst composite material system in the esterification kettle 1 is 3-6 ppm of the theoretical mass of the polymerization product of PTA and EG based on the mass of titanium element;
in the step (4), the intrinsic viscosity of the polyester melt is 0.64-0.68 dL/g, the chroma L value of the polyester resin is 86-90, and the b value is 3.8-7;
in the step (5), the melt direct spinning process parameters are as follows: the spinning temperature is 282-285 ℃, and the technological parameters of melt direct spinning are as follows: the spinning speed is 1000-1200 m/min, the side blowing temperature is 30 +/-5 ℃, the side blowing air speed is 0.2-0.4 m/s, and the drafting multiplying power is 3.5-4.0;
in the step (a), the molar ratio of PTA to EG is 1: 1.1-1.6, and the addition amount of the sheet-shaped titanium polyester catalyst contained in the polyester titanium catalyst composite material system in the esterification kettle 1 is 3-5 ppm of the theoretical mass of the polymerization product of PTA and EG by the mass of titanium element;
in the step (e), the intrinsic viscosity of the polyester melt is 0.67-0.68 dL/g, the chroma L value of the polyester resin is 86-90, and the b value is 3.5-6;
in the step (f), the melt direct spinning process parameters are as follows: the spinning temperature is 282-285 ℃, the spinning speed is 1000-1200 m/min, the side blowing temperature is 30 +/-5 ℃, the side blowing air speed is 0.2-0.4 m/s, and the drawing ratio is 3.5-4.0.
4. The method for preparing the titanium-based polyester filament by the multi-kettle melt direct spinning as claimed in claim 1, wherein the polyester prepolymer further contains a stabilizer and a toner, and the mass contents of the sheet-shaped titanium-based polyester catalyst, the stabilizer and the toner in the polyester titanium-based catalyst composite material system are respectively 0.5-20 wt%, 5-15 wt% and 0.5-8 wt%.
5. The method for preparing titanium-based polyester filament by multi-kettle melt direct spinning according to claim 4, wherein the structural general formula of the sheet-shaped titanium-based polyester catalyst is Tix(ORO)y(OOC6C4H4COO)zH4Wherein R is C2～C4Z is more than or equal to 1, y + z is 2x +2, x is 4, and the flaky titanium polyester catalyst has a lamellar structure;
the stabilizer is more than one of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, triphenyl phosphate, tripropyl octyl phosphate, phosphoric acid and phosphorous acid;
the toner is a bluing agent or a reddening agent.
6. The method for preparing the titanium-based polyester filament by the multi-kettle melt direct spinning according to claim 5, wherein the preparation method of the polyester titanium catalyst composite material system comprises the following steps: and melting and blending the solid polyester prepolymer with the polymerization degree of 5-30 with a sheet-shaped titanium polyester catalyst, a stabilizer and a toner, and cooling to obtain the polyester titanium catalyst composite material system, wherein the melting and blending temperature is 100-270 ℃, and the time is 1.5-6 h.
7. The method for preparing the titanium-based polyester filament by the multi-kettle melt direct spinning according to claim 5, wherein the preparation method of the polyester titanium catalyst composite material system comprises the following steps: adding an additive or a dihydric alcohol dispersion liquid of the additive into a polyester prepolymer melt with the polymerization degree of 5-30, uniformly stirring and cooling to obtain a polyester titanium catalyst composite material system, wherein the additive is a sheet-shaped titanium polyester catalyst, a stabilizer and a toner, the mass concentration of the dihydric alcohol dispersion liquid of the additive is 30-70 wt%, and the dihydric alcohol is ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol.
8. The method for preparing the titanium-based polyester filament by the multi-kettle melt direct spinning according to claim 5, wherein the preparation method of the polyester titanium catalyst composite material system comprises the following steps: a, B and C are uniformly mixed and then subjected to esterification reaction, pre-polycondensation reaction and cooling to obtain a polyester titanium catalyst composite material system, wherein A is dibasic acid or dibasic acid ester, B is dihydric alcohol, C is an additive or a dihydric alcohol dispersion liquid of the additive, the additive is a sheet-shaped titanium polyester catalyst, a stabilizer and a toner, the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 100-400 KPa, the temperature is 180-260 ℃, and the time is 2-2.5 hours; the pressure of the pre-polycondensation reaction is 100-10 KPa, the temperature is 260-270 ℃, and the time is 10-30 min.
9. The method for preparing the titanium-based polyester filament by multi-kettle melt direct spinning according to claim 8, wherein the molar ratio of the sum of the molar amounts of the dihydric alcohols in B and C to A is 1-2: 1, B is the same as the dihydric alcohol in the dihydric alcohol dispersion liquid of the additive, the mass concentration of the dihydric alcohol dispersion liquid of the additive is 35-70 wt%, and the mass of the flaky titanium-based polyester catalyst accounts for 10-20% of the sum of the mass of the dihydric alcohols in B and C.
10. The process of claim 8, wherein the dibasic acid is terephthalic acid, isophthalic acid or sodium 5-sulfoisophthalate, the dibasic ester is dimethyl terephthalate, and the diol is ethylene glycol, 1, 3-propanediol or 1, 4-butanediol.
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