CN111040140A - Preparation method of antimony-based polyester composite material - Google Patents

Preparation method of antimony-based polyester composite material Download PDF

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CN111040140A
CN111040140A CN201911414066.4A CN201911414066A CN111040140A CN 111040140 A CN111040140 A CN 111040140A CN 201911414066 A CN201911414066 A CN 201911414066A CN 111040140 A CN111040140 A CN 111040140A
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polyester
antimony
particles
composite material
temperature
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CN111040140B (en
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詹伟东
孙宾
孙茂金
孙小国
柴晓东
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Zhejiang Dongtai New Material Co ltd
Donghua University
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Zhejiang Dongtai New Material Co ltd
Donghua University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—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
    • C08G63/78—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
    • C08G63/86—Germanium, antimony, or compounds thereof
    • C08G63/866—Antimony or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates

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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)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention relates to an antimony-based polyester composite materialThe preparation method of the material comprises the steps of mixing PTA, EG, ethylene glycol antimony and polyester in-situ polymerization modification nano composite materials, and then carrying out esterification reaction and polycondensation reaction to prepare antimony-based polyester composite resin, or further carrying out melt direct spinning to prepare antimony-based polyester composite fiber; the nano composite material for polyester in-situ polymerization modification mainly comprises a polyester prepolymer with the polymerization degree of 3-30 and functional particles dispersed in the polyester prepolymer, wherein the functional particles are SiO2Particles, TiO2Granules or BaSO4Particles; the method of the invention does not introduce dispersant, reduces the dosage of catalyst and has simple process; the antimony-based polyester composite fiber prepared from the antimony-based polyester composite melt prepared by the method has excellent performance, and a film prepared from the prepared resin has small separation strength and good antistatic effect.

Description

Preparation method of antimony-based polyester composite material
Technical Field
The invention belongs to the technical field of polyester composite materials, and relates to a preparation method of an antimony-based polyester composite material.
Background
Polyester (PET, PBT and the like) resins and products thereof (fibers, films, engineering plastics and the like) are high molecular products with the largest global production, the widest application and the fastest development speed, wherein most of the polyester is prepared by a melt direct spinning method. The melt direct spinning method has the advantages of high single-wire productivity, low cost and the like, but the product prepared by the method also has the defect of single variety, and in order to overcome the defect, the in-situ polymerization modification technology and the functional material online addition technology of the functional nano material of the polyester product need to be developed urgently.
The composite material obtained by compounding the inorganic substance and the polymer has the characteristics of organic and inorganic materials, generates a plurality of new excellent performances through the interaction between the inorganic substance and the polymer, and has very wide development prospect. Therefore, the micron-sized and nano-sized inorganic particle materials are applied to the modification of PET, and the processing performances of crystallization behavior, rheology and the like of the PET materials can be improved. Inorganic fine particles such as barium sulfate, titanium dioxide, silicon dioxide and the like exist in the melt of the polyester as small particles corresponding to the second phase in the crystallization process, the particles are in an insoluble state in a high temperature region, and in the process of cooling, the molecular chains of the polyester take the particles as centers, are adsorbed on the particles and are orderly arranged to form crystal nuclei. Researches find that the well-dispersed inorganic nanoparticles have a strong nucleating effect on PET, restrict the motion of polyester molecular chain segments, slow down the growth speed of spherulites and refine the polyester spherulites.
SiO2Can be used as additive to improve the performance of other organic or inorganic substances, such as SiO2Can be added into PET film to improve the roughness and antistatic property of surface. At present, antimony-based PET/SiO in the conventional sense2The in-situ synthesis method of the composite resin is to add reaction raw materials before esterification reaction to obtain PET/SiO2Composite resin, but the nano-functional material SiO used in the method2There are the following disadvantages: it will be agglomerated twice in the process of drying, storing, transporting, etc. and before being introduced into polyester synthesizing system, it is usually classified by twice grinding in polyester factory, while SiO without twice grinding is added directly2The ethylene glycol slurry of (a) may adversely affect the polymerization reaction and the properties of the product thereof due to the introduction of a dispersant. Further, in the case of using an antimony-based catalyst for the production of PET, SiO2The dispersant contained in (a) also causes a decrease in the activity of the antimony-based catalyst, and in order to ensure the catalytic effect, the amount of the catalyst used is often required to be increased significantly.
The titanium dioxide is added as the delustering agent to produce the delustering type polyester chip, and the fabric processed by the produced polyester fiber has soft and glossy handfeel and good dyeing performance, so the polyester fiber is widely applied to the fields of clothing, automobiles and the like. However, since the dispersing agent in the titanium dioxide has an influence on the activity of the antimony-based polyester catalyst, the catalytic activity is reduced after the titanium dioxide and the antimony-based catalyst are added into a reaction system; if the amount of the catalyst is not increased, the polyester with qualified viscosity can not be obtained in the same time; if no dispersing agent is used, because of TiO2The dispersibility of the high-performance high-pressure-resistant. To solve the above problems, TiO is often adopted in the existing market2The coating method includes high-pressure electrostatic method, precipitation method, spray drying method, etc., but still has the following disadvantages: TiO22Easy to agglomerate in organic matrix, poor dispersibility, easy to damage structure under high temperature condition, and unable to useAnd (4) carrying out melt processing.
BaSO prepared by the prior art4The modified antimony-based polyester has several problems: 1) because the aperture of the spinneret plate adopted in the fiber forming process is small and the winding and drafting speed is high, the BaSO in the polymerization system4The above requirements are satisfied by maintaining the nano-size, but BaSO is commercially available4The secondary agglomeration can occur in the processes of drying, storage, transportation and the like, so before the polyester synthesis system is introduced, the secondary grinding and grading of a polyester factory are often needed, but the secondary grinding and grading operation is more complicated, so that the direct addition of BaSO which does not need secondary grinding is mainly adopted4Due to BaSO in the ethylene glycol slurry4The particle size is uneven, agglomeration and caking are easy to occur, the dispersibility is poor, and the polyester can not be directly used for polyester modification, so that a dispersing agent needs to be added, but the introduction of the dispersing agent can inactivate a catalyst, and the dosage of the catalyst needs to be greatly increased in order to ensure sufficient catalytic action; 2) for BaSO4Coating method for BaSO4During modification, the stability, uniform dispersibility and reaction homogeneity of the nano functional material are poor, and BaSO is generated under high temperature4The structure is easily damaged and cannot be used for melt processing.
Therefore, the research on a method for avoiding the secondary agglomeration of functional particles and maintaining the high activity of the catalyst in the in-situ synthesis process of the antimony-based polyester composite material has very important significance.
Disclosure of Invention
The invention aims to overcome the defect that the functional particles (SiO) in the in-situ synthesis process of the antimony-based polyester composite material in the prior art2Particles, TiO2Granules or BaSO4Particles) possibly generates secondary agglomeration and introduces a dispersing agent to cause the catalytic activity of the catalyst to be poor, and provides the antimony-based polyester composite resin and the in-situ polymerization method and the application thereof.
When the functional particles are SiO2When in granulation:
the invention adopts polyester prepolymer to wrap SiO2Effectively solves the problems that the polyester prepolymer used as a carrier can only be melted at a higher temperature, thereby avoiding the situation thatSiO2Secondary agglomeration is carried out without introducing a dispersing agent; no dispersant is introduced to ensure the high activity of the catalyst, so that the dosage of the catalyst does not need to be greatly increased.
The technical scheme adopted by the invention is as follows:
mixing PTA, EG, ethylene glycol antimony and nano composite material for polyester in-situ polymerization modification, and then carrying out esterification reaction and polycondensation reaction to prepare the antimony-based polyester composite resin;
the nano composite material for polyester in-situ polymerization modification mainly comprises a polyester prepolymer with the polymerization degree of 3-30 and SiO dispersed in the polyester prepolymer2And (4) particle composition.
When the antimony-based polyester composite resin is prepared by adopting the traditional process, a dispersing agent is generally introduced, and the main reasons are as follows: SiO in polymerization systems2Can be uniformly dispersed in a polymer matrix only by keeping the nano size to achieve better modification effect, but the SiO sold in the market2The secondary agglomeration can occur in the processes of drying, storage, transportation and the like, so before the polyester synthesis system is introduced, the secondary grinding and grading of a polyester factory are often needed, but the secondary grinding and grading operation is more complicated, so that the direct addition of SiO which does not need secondary grinding is mainly adopted2Due to SiO in the ethylene glycol slurry2The particle size is uneven, agglomeration and caking are easy to occur, the dispersibility is poor, and the polyester can not be directly used for polyester modification, so that a dispersing agent needs to be added, but the introduction of the dispersing agent can inactivate a catalyst, and the dosage of the catalyst needs to be greatly increased in order to ensure sufficient catalytic action;
when the method is adopted to prepare the antimony-based polyester composite resin, no dispersant is introduced, so that the dosage of a catalyst does not need to be greatly increased, and the reason why no dispersant is introduced is that a polyester prepolymer with the polymerization degree of 3-30 is adopted to wrap SiO2The melting point of the polyester prepolymer is high, and the polyester prepolymer can only melt at high temperature to release functional materials in the polyester synthesis process, so that the secondary agglomeration phenomenon in the transportation or storage process can be avoided, meanwhile, the polyester prepolymer is an intermediate for preparing polyester high polymer,it has good compatibility with the intermediate system of high polymer synthesis, so it can show high dispersivity in the process of polyester synthesis.
As a preferred technical scheme:
the preparation method of the antimony-based polyester composite resin comprises the following specific steps:
(1) mixing PTA, EG, ethylene glycol antimony and polyester in-situ polymerization modification nano composite materials, and then carrying out esterification reaction to obtain an esterification product, wherein the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 100-400 KPa, the temperature is 235-245 ℃, and the time is 220-230 min;
(2) carrying out pre-polycondensation reaction on the esterification product to obtain a pre-polycondensation product, wherein the pressure of the pre-polycondensation reaction is 100-10 KPa, the temperature is 245-270 ℃, and the time is 170-180 min;
(3) and carrying out final polycondensation on the pre-polycondensation product to obtain the antimony-based polyester composite resin, wherein the pressure of the final polycondensation reaction is 150-200 Pa, the temperature is 270-284 ℃, and the time is 30-60 min.
According to the preparation method of the antimony-based polyester composite resin, in the step (1), the molar ratio of PTA to EG is 1: 1.1-1.6, the addition amount of ethylene glycol antimony in the esterification reaction process is 200-220 ppm of the theoretical mass of the polymerization products of PTA and EG, and in the traditional process, the addition amount of ethylene glycol antimony or other antimony catalysts is more than 330ppm of the theoretical mass of the polymerization products of PTA and EG, and the comparison shows that the addition amount of the catalyst is remarkably reduced, and the main reason is that the adverse effect of a dispersing agent on the catalyst is reduced by avoiding the use of the dispersing agent, so that the catalytic activity is ensured; SiO contained in nano composite material for polyester in-situ polymerization modification in esterification reaction process2The addition amount of the particles is 0.3-40 wt% of the theoretical mass of the PTA and EG polymerized products (when the nano composite material for polyester in-situ polymerization modification is master batch, the SiO contained in the nano composite material is2Large amount of added particles), in the conventional process, SiO2Because the stability, the uniform dispersibility, the reaction homogeneity and the addition amount are not good, the invention obviously reduces the SiO content2The main reason is that the invention adoptsThe polyester prepolymer with the polymerization degree of 3-30 is used as a carrier, the melting point is high, and the polyester prepolymer can be only melted at a high temperature to release functional materials in the polyester synthesis process, so that the secondary agglomeration phenomenon in the transportation or storage process can be avoided;
in the step (3), the intrinsic viscosity of the antimony-based polyester composite resin is 0.545-0.670 dL/g, the number of the coacervate particles is 1.0-3.0/mg, the size of the coacervate particles is 15-20 μm, the number of the coacervate particles of the antimony-based polyester composite resin prepared by the traditional process is generally 6.5/mg, and the comparison shows that the invention obviously reduces the number of the coacervate particles, and the main reason is that the nano composite material for polyester in-situ polymerization modification can only be melted at a higher temperature to release the functional material, so that the secondary agglomeration phenomenon in the storage and transportation process can be reduced or even avoided, and meanwhile, the polyester prepolymer is an intermediate for preparing the functional polyester product and has intrinsic good compatibility with an intermediate system synthesized by the functional polyester product, so that the high dispersibility of the polyester functional material is ensured, and the intrinsic viscosity of the polyester chip is further improved, the number of agglomerated particles is reduced; the filtration pressure value is 0.15-0.25 bar/g (the test standard is BS-EN13900-5:2005, SiO contained in the nano composite material for polyester in-situ polymerization modification in the esterification reaction process in the preparation process of the test sample2The addition amount of the particles is 8 wt% of the theoretical mass of the PTA and EG polymerization products, the filtration pressure value of a comparison sample is 0.50-0.70 bar/g under the same test condition, and the comparison sample is only different from the antimony-based polyester composite resin of the invention in the preparation of SiO adopted2The surface of the particle is not coated with the polyester prepolymer).
The preparation method of the antimony-based polyester composite resin comprises the step of preparing the SiO in the polyester in-situ polymerization modified nano composite material2The mass content of the particles is 10-40 wt%, and the SiO is2The particles are spherical or porous, the SiO is2The average particle diameter of the particles in the polyester prepolymer is less than700nm。
The preparation method of the antimony-based polyester composite resin comprises the following steps: mixing solid polyester prepolymer with polymerization degree of 3-30 and SiO2And (3) cooling the particles after melt blending to prepare the polyester in-situ polymerization modified nano composite material, wherein the melt blending temperature is 100-250 ℃, and the time is 1.5-3 h.
The preparation method of the antimony-based polyester composite resin comprises the following steps: adding SiO into a polyester prepolymer melt with the polymerization degree of 3-302Particles or SiO2After the dihydric alcohol dispersion of the particles is stirred evenly and cooled, the nano composite material SiO for in-situ polymerization modification of polyester is prepared2The particles can be directly added, or can be added after being dispersed in the dihydric alcohol, or can be partially directly added, or can be added after being dispersed in the dihydric alcohol, and the particles are all within the protection scope of the invention>At 1.5, the final product is in a solid state; when the mass ratio is between 0.5 and 1.5, the final product is in a slurry state; wherein, SiO2The mass concentration of the dihydric alcohol dispersion liquid of the particles is 30-70 wt%, and SiO2The dihydric alcohol in the dihydric alcohol dispersion liquid of the particles is the dihydric alcohol used for synthesizing the polyester prepolymer.
The preparation method of the antimony-based polyester composite resin comprises the following steps: a, B, C and a polyester catalyst are uniformly mixed and then subjected to esterification reaction, pre-polycondensation reaction and cooling to prepare the polyester in-situ polymerization modified nano composite material, wherein A is terephthalic acid, isophthalic acid-5-sodium sulfonate or dimethyl terephthalate, B is ethylene glycol, 1, 3-propanediol or 1, 4-butanediol, and C is SiO2Glycol dispersions of particles or SiO2Particles of B and SiO2The diol in the diol dispersion of the particles is the same when the molar ratio of the diol (including the diols in B and C) to A is the sameWhen the temperature is between 1 and 1.5, the final product is solid; when the molar ratio of the dihydric alcohol to the A is 1.5-2.0, the final product is slurry; the molar ratio of A to B is 1: 1.5-2, and SiO is2Particles account for 30 to 50 wt% of the sum of A, B and C, and SiO2The mass concentration of the glycol dispersion liquid of the particles is 60-70 wt%, the polyester catalyst is an antimony catalyst (ethylene glycol antimony, antimony trioxide), and the addition amount of the polyester catalyst is 170-300 ppm of the theoretical mass of a polymerization product of A and B in terms of the mass of antimony element; the esterification reaction is carried out in a nitrogen atmosphere, the temperature is 180-260 ℃, the time is 2-2.5 h, and the pressure is 100-400 KPa; the temperature of the pre-polycondensation reaction is 260-270 ℃, the time is 8-30 min, and the pressure is 100-10 KPa.
The invention also provides the antimony-based polyester composite resin prepared by the preparation method of the antimony-based polyester composite resin, which mainly comprises a PET matrix and ethylene glycol antimony and SiO dispersed in the PET matrix2And (4) particle composition.
The invention also provides the application of the antimony-based polyester composite resin, wherein the antimony-based polyester composite resin is prepared into a film, the thickness of the film is 90-110 mu m, the separation strength is 2.9-3.5N/15 mm, and the surface resistance is 1.6 ^ 10^ 8-3.2 ^ 10^8 omega.
When the functional particles are TiO2When in granulation:
the invention adopts polyester prepolymer with the polymerization degree of 3-30 to wrap the delustering agent (TiO)2Particles), reduced catalyst usage, improved TiO2Stability and dispersibility of the particles.
The scheme adopted by the invention is as follows:
the preparation method of the antimony-based polyester composite fiber comprises the steps of synthesizing an antimony-based extinction polyester melt by using PTA, EG, ethylene glycol antimony and a nano composite material for polyester in-situ polymerization modification as main raw materials, and then carrying out melt direct spinning to obtain the antimony-based polyester composite fiber;
the nano composite material for polyester in-situ polymerization modification mainly comprises a polyester prepolymer with the polymerization degree of 3-30 and TiO dispersed in the polyester prepolymer2And (4) particle composition.
When the traditional process is adopted to prepare the delustered polyester fiber, a dispersing agent is generally introduced, and the main reasons are as follows: the spinneret plate adopted in the fiber forming process has small aperture and high winding and drafting speed, the delustering agent (mostly adopting titanium dioxide) in a polymerization system can meet the requirements only by keeping small size and little agglomeration or no agglomeration, however, the commercial matting agents are subject to secondary agglomeration in the processes of drying, storage, transportation and the like, so that the matting agents are often subjected to secondary grinding classification in a polyester factory before being introduced into a polyester synthesis system, but the secondary grinding classification operation is more complicated, therefore, the method of directly adding the ethylene glycol slurry of the flatting agent without secondary grinding is mainly adopted, because the grain diameter of the flatting agent in the glycol slurry is uneven, the flatting agent is easy to agglomerate and agglomerate, the dispersibility is poor, and the flatting agent cannot be directly used for flatting polyester, a dispersing agent is required to be added, however, the introduction of the dispersant can deactivate the catalyst, and in order to ensure sufficient catalytic action, the dosage of the catalyst needs to be greatly increased;
the extinction polyester fiber prepared by the method can be free of dispersant, so that the dosage of a catalyst is not required to be greatly increased, the reason why the dispersant is not introduced is that the polyester prepolymer with the polymerization degree of 3-30 is adopted to wrap the extinction agent, the melting point of the polyester prepolymer is higher, and the polyester prepolymer can be melted only at higher temperature to release functional materials in the polyester synthesis process, so that the secondary agglomeration phenomenon in the transportation or storage process can be avoided.
As a preferred technical scheme:
the method for preparing the antimony-based full-dull polyester fiber by melt direct spinning comprises the following specific steps:
(1) mixing PTA, EG, ethylene glycol antimony and polyester in-situ polymerization modification nano composite materials, and then carrying out esterification reaction to obtain an esterification product, wherein the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 100-400 KPa, the temperature is 220-252 ℃, and the time is 140-160 min;
(2) carrying out pre-polycondensation reaction on the esterification product to obtain a pre-polycondensation product, wherein the pressure of the pre-polycondensation reaction is 100-10 KPa, the temperature is 252-270 ℃, and the time is 40-50 min;
(3) carrying out final polycondensation on the pre-polycondensation product to obtain an antimony-based extinction polyester melt, wherein the pressure of the final polycondensation reaction is 150-200 Pa, the temperature is 270-284 ℃, and the time is 40-50 min;
(4) and carrying out melt direct spinning on the antimony-based extinction polyester melt to obtain the antimony-based polyester composite fiber.
According to the preparation method of the antimony-based polyester composite fiber, in the step (1), the molar ratio of PTA to EG is 1: 1.1-1.8, the addition amount of ethylene glycol antimony in the esterification reaction process is 200-220 ppm of the theoretical mass of the polymerization products of PTA and EG, and in the traditional process, the addition amount of ethylene glycol antimony or other antimony catalysts is more than 330ppm of the theoretical mass of the polymerization products of PTA and EG, and the comparison shows that the addition amount of the catalyst is obviously reduced, and the main reason is that the adverse effect of a dispersing agent on the catalyst is reduced by avoiding the use of the dispersing agent, so that the catalytic efficiency is improved; TiO contained in nano composite material for polyester in-situ polymerization modification in esterification reaction process2The addition amount of the particles is 0.3-3.0 wt% of the theoretical mass of the polymerization product of PTA and EG, and when the nano composite material for polyester in-situ polymerization modification contains TiO2When the adding amount of the particles is 0.3 wt% of the theoretical mass of the polymerization product of PTA and EG, the obtained antimony-based semi-dull polyester fiber is obtained; TiO contained in nano composite material for modifying polyester in situ polymerization2When the addition amount of the particles is 0.6-3.0 wt% of the theoretical mass of the PTA and EG polymerization products, the obtained antimony-based full-dull polyester fiber is obtained; the addition of the flatting agent is far less than that of the prior art, the main reason is that the polyester prepolymer is adopted as a carrier, the melting point is higher, the polyester prepolymer can only melt at higher temperature in the polyester synthesis process to release functional materials, 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 polyester high polymer and has intrinsic good compatibility with an intermediate system for synthesizing the high polymer, so that the polyester prepolymer has good compatibility with the intermediate system for synthesizing the high polymer in polyesterHigh dispersity can be presented in the synthesis process;
in the step (3), the intrinsic viscosity of the antimony-based extinction polyester melt is 0.565-0.681 dL/g, the number of the aggregation particles is 1.0-3.0/mg, the size of the aggregation particles is 15-20 μm, and the number of the aggregation particles of the antimony-based extinction polyester melt prepared by the traditional process is generally 6.5/mg, and the comparison shows that the invention obviously reduces the number of the aggregation particles, mainly because the nano composite material for polyester in-situ polymerization modification can only be melted at a higher temperature to release a functional material, the secondary agglomeration phenomenon in the storage and transportation process can be reduced or even avoided, and simultaneously, because the polyester prepolymer is an intermediate for preparing the functional polyester product and has intrinsic good compatibility with an intermediate system synthesized by the functional polyester product, the high dispersibility of the polyester functional material is ensured, and the intrinsic viscosity of the polyester chip is further improved, the number of agglomerated particles is reduced; the filtration pressure value is 0.05-0.09 bar/g (the test standard is BS-EN13900-5:2005, TiO contained in the nano composite material for polyester in-situ polymerization modification in the esterification reaction process when preparing the test sample2The addition amount of the particles is 3 wt% of the theoretical mass of the PTA and EG polymerization products, the filtration pressure value of a comparison sample is 0.20-0.35 bar/g under the same test condition, and the comparison sample is only different from the antimony-based extinction polyester of the invention in TiO adopted in preparation2The surface of the particle is not coated with the polyester prepolymer);
in the step (4), the melt direct spinning process parameters are as follows: the spinning temperature is 282-285 ℃, and the modified TiO prepared by the traditional method2The structure of the nano-particles can be destroyed at the temperature of about 100 ℃, and the invention is realized by adopting the method in TiO2The polyester prepolymer is wrapped outside the nano particles to improve TiO2The structure stability of the nano particles enables the nano particles to be suitable for spinning processing, the spinning speed is 3500-4000 m/min, the side blowing temperature is 30 +/-5 ℃, the side blowing air speed is 0.3-0.5 m/s, and the drafting multiplying power is 3.5-4.0.
The preparation method of the antimony-based polyester composite fiber comprises the step of carrying out in-situ polymerization modification on the polyester to obtain the TiO nano composite material2The mass content of the particles is 10-40 wt%, and the TiO is2The particles being spherical or porous。
The preparation method of the antimony-based polyester composite fiber, the TiO2The average particle size of the particles in the polyester prepolymer is less than 700 nm.
The preparation method of the antimony-based polyester composite fiber comprises the following steps: mixing solid polyester prepolymer with polymerization degree of 3-30 and TiO2And (3) cooling the particles after melt blending to prepare the solid polyester in-situ polymerization modified nano composite material, wherein the melt blending temperature is 100-250 ℃, and the time is 1.5-3 h.
The preparation method of the antimony-based polyester composite fiber comprises the following steps: adding TiO into polyester prepolymer melt with polymerization degree of 3-302Particles or TiO2After the dihydric alcohol dispersion of the particles is stirred evenly and cooled, the solid or pulpous state nanometer composite material for in-situ polymerization modification of polyester, TiO is prepared2The particles can be directly added, or can be added after being dispersed in the dihydric alcohol, or can be partially directly added, or can be added after being dispersed in the dihydric alcohol, and the particles are all within the protection scope of the invention>At 1.5, the final product is in a solid state; when the mass ratio is between 0.5 and 1.5, the final product is in a slurry state; wherein, TiO2The mass concentration of the dihydric alcohol dispersion liquid of the particles is 30-70 wt%, and TiO2The dihydric alcohol in the dihydric alcohol dispersion liquid of the particles is the dihydric alcohol used for synthesizing the polyester prepolymer.
The preparation method of the antimony-based polyester composite fiber comprises the following steps: a, B and C are mixed evenly and then are processed through esterification, pre-polycondensation and cooling to prepare the solid or slurry polyester in-situ polymerization modified nano composite material, wherein A is terephthalic acid, isophthalic acid-5-sodium sulfonate or dimethyl terephthalate, B is ethylene glycol, 1, 3-propanediol or 1, 4-butanediol, C is TiO2Glycol dispersions of particles or TiO2Particles of B and TiO2The dihydric alcohols in the dihydric alcohol dispersion liquid of the particles are the same, and when the molar ratio of the dihydric alcohols (including the dihydric alcohols in B and C) to A is 1-1.5, the final product is solid; when the molar ratio of the dihydric alcohol to the A is 1.5-2.0, the final product is slurry; the molar ratio of A to B is 1: 1.5-2, and TiO2Particles accounting for 30 to 50 wt% of the sum of A, B and C, TiO2The mass concentration of the glycol dispersion liquid of the particles is 60-70 wt%, the polyester catalyst is an antimony catalyst (ethylene glycol antimony, antimony trioxide), and the addition amount of the polyester catalyst is 170-300 ppm of the theoretical mass of a polymerization product of A and B in terms of the mass of antimony element; the esterification reaction is carried out in a nitrogen atmosphere, the temperature is 180-260 ℃, the time is 2-2.5 h, and the pressure is 100-400 KPa; the temperature of the pre-polycondensation reaction is 260-270 ℃, the time is 8-30 min, and the pressure is 100-10 KPa.
The invention also provides the antimony-based polyester composite fiber prepared by the preparation method of any one of the antimony-based polyester composite fibers, which mainly comprises a polyester fiber matrix and ethylene glycol antimony and TiO dispersed in the polyester fiber matrix2And (4) particle composition.
As a preferred technical scheme:
the antimony-based polyester composite fiber has fineness of 3.2-4.0 dtex, breaking strength of 2.82-3.38 cN/dtex, and elongation at break of 13.2-27.4%, wherein TiO is2When the content of the particles is 0.6-2.0 wt%, the extinction PET fiber can achieve the full extinction effect.
When the functional particles are BaSO4When in granulation:
the invention adopts polyester prepolymer with polymerization degree of 3-30 to wrap BaSO4The using amount of the catalyst is reduced, and the BaSO is improved4Stability and dispersibility of (A).
The technical scheme adopted by the invention is as follows:
the preparation method of the antimony-based polyester composite fiber comprises the steps of synthesizing BaSO by taking PTA, EG, ethylene glycol antimony and nano composite material for polyester in-situ polymerization modification as main raw materials4Modified antimony-based polyester meltThen melt direct spinning is carried out to prepare the stibium-based polyester composite fiber;
the nano composite material for polyester in-situ polymerization modification mainly comprises a polyester prepolymer with the polymerization degree of 3-30 and BaSO dispersed in the polyester prepolymer4And (4) particle composition.
When the antimony-based polyester composite fiber is prepared by adopting the traditional process, a dispersing agent is generally introduced, and the main reasons are as follows: the spinneret plate adopted in the fiber forming process has small aperture, high winding and drafting speed and BaSO in a polymerization system4The above requirements are satisfied by maintaining the nano-size, but BaSO is commercially available4The secondary agglomeration can occur in the processes of drying, storage, transportation and the like, so before the polyester synthesis system is introduced, the secondary grinding and grading of a polyester factory are often needed, but the secondary grinding and grading operation is more complicated, so that the direct addition of BaSO which does not need secondary grinding is mainly adopted4Due to BaSO in the ethylene glycol slurry4The particle size is uneven, agglomeration and caking are easy to occur, the dispersibility is poor, and the polyester can not be directly used for polyester modification, so that a dispersing agent needs to be added, but the introduction of the dispersing agent can inactivate a catalyst, and the dosage of the catalyst needs to be greatly increased in order to ensure sufficient catalytic action;
when the method is adopted to prepare the antimony-based polyester composite fiber, no dispersant is introduced, so that the dosage of a catalyst does not need to be greatly increased, and the main reason for not introducing the dispersant is that a polyester prepolymer with the polymerization degree of 3-30 is adopted to wrap BaSO4The polyester prepolymer has high melting point, and only melts at high temperature to release functional materials in the polyester synthesis process, so that the secondary agglomeration phenomenon in the transportation or storage process can be avoided.
As a preferred technical scheme:
the preparation method of the antimony-based polyester composite fiber comprises the following specific steps:
(1) mixing PTA, EG, ethylene glycol antimony and polyester in-situ polymerization modification nano composite materials, and then carrying out esterification reaction to obtain an esterification product, wherein the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 100-400 KPa, the temperature is 220-252 ℃, and the time is 140-160 min;
(2) carrying out pre-polycondensation reaction on the esterification product to obtain a pre-polycondensation product, wherein the pressure of the pre-polycondensation reaction is 100-10 KPa, the temperature is 252-270 ℃, and the time is 40-50 min;
(3) carrying out final polycondensation on the pre-polycondensation product to obtain an antimony-based extinction polyester melt, wherein the pressure of the final polycondensation reaction is 150-200 Pa, the temperature is 270-284 ℃, and the time is 40-50 min;
(4) mixing BaSO4And carrying out melt direct spinning on the modified antimony-based polyester melt to obtain the antimony-based polyester composite fiber.
According to the preparation method of the antimony-based polyester composite fiber, in the step (1), the molar ratio of PTA to EG is 1: 1.1-1.8, the addition amount of ethylene glycol antimony in the esterification reaction process is 200-220 ppm of the theoretical mass of the polymerization products of PTA and EG, and in the traditional process, the addition amount of ethylene glycol antimony or other antimony catalysts is about 330ppm of the theoretical mass of the polymerization products of PTA and EG; BaSO contained in nano composite material for polyester in-situ polymerization modification in esterification reaction process4The addition of the particles is 0.3-0.8 wt% of the theoretical mass of the PTA and EG polymerization products, and in the traditional process, BaSO4As the stability, the uniform dispersibility and the reaction homogeneity are not good, the adding amount is 0.5-2.5 wt% of the theoretical mass of the PTA and EG polymerization products, and the comparison shows that the invention obviously reduces BaSO4The main reason for the addition amount of the functional material is that the polyester prepolymer with the polymerization degree of 3-30 is used as a carrier, the melting point of the functional material is high, and the functional material is only melted at a high temperature and released in the polyester synthesis process, so that the secondary agglomeration phenomenon of the functional material in the transportation or storage process can be avoided, and meanwhile, the polyester prepolymer isThe intermediate for preparing the polyester high polymer has intrinsic good compatibility with an intermediate system for synthesizing the high polymer, so that the intermediate can show high dispersity in the polyester synthesis process;
in step (3), BaSO4The intrinsic viscosity of the modified antimony-based polyester melt is 0.655-0.665 dL/g, the intrinsic viscosity of the common PET polyester is about 0.64dL/g, the viscosity of the common PET polyester is low, the post-spinning is difficult in head stretching, the filament winding is easy, the broken ends are more, and the tension change is large4The modified polyester effectively solves the problem; 1.0-3.0 agglomerated particles/mg, the size of the agglomerated particles is 15-20 μm, and BaSO is prepared by conventional method4The condensation particles of the modified antimony-based polyester melt are generally 6.5/mg, and the comparison shows that the quantity of the condensation particles is obviously reduced, the main reason is that the nano composite material for polyester in-situ polymerization modification is only melted at a higher temperature to release a functional material, so that the secondary agglomeration phenomenon in the storage and transportation process can be reduced or even avoided, and meanwhile, the polyester prepolymer is an intermediate for preparing a functional polyester product and has intrinsic good compatibility with an intermediate system synthesized by the functional polyester product, so that the high dispersibility of the polyester functional material is ensured, the intrinsic viscosity of a polyester chip is further improved, and the quantity of the condensation particles is reduced; t ismc(melt crystallization temperature) 213-217 ℃ and T of ordinary PETmcAt 206.85 ℃ C, TmcIs a function of the cooling rate, TmcThe higher the nucleation speed of the polymer, i.e. the higher the crystallization speed, the better the crystallization performance of the material, and the invention uses BaSO4The modified polyester obviously improves the crystallization property of the polyester; the filtration pressure value is 0.12-0.20 bar/g (the test standard is BS-EN13900-5:2005, BaSO contained in the nanocomposite for polyester in-situ polymerization modification in the esterification reaction process in the preparation process of the test sample4The addition of the particles is 8 wt% of the theoretical mass of the PTA and EG polymerization products, the filtration pressure value of a comparison sample is 0.36-0.65 bar/g under the same test condition, and the comparison sample and the BaSO of the invention4Modified antimony-based polyesters differ only in the BaSO employed in their preparation4Prepolymer of polyester not coated on particle surface)；
In the step (4), the melt direct spinning process parameters are as follows: the spinning temperature is 282-285 ℃, and the modified BaSO prepared by the traditional method4The structure of the nano particles can be destroyed at the temperature of about 100 ℃, and the invention adopts BaSO4The polyester prepolymer is wrapped outside the nano particles to improve BaSO4The structure stability of the nano particles enables the nano particles to be suitable for spinning processing, the spinning speed is 3500-4000 m/min, the side blowing temperature is 30 +/-5 ℃, the side blowing air speed is 0.3-0.5 m/s, and the drafting multiplying power is 3.5-4.0.
The preparation method of the antimony-based polyester composite fiber comprises the step of carrying out in-situ polymerization on BaSO in the polyester-modified nano composite material4The mass content of the particles is 10-40 wt%.
The preparation method of the antimony-based polyester composite fiber, the BaSO4The average particle size of the particles in the polyester prepolymer is less than 700 nm.
The preparation method of the antimony-based polyester composite fiber comprises the following steps: mixing solid polyester prepolymer with polymerization degree of 3-30 and BaSO4And (3) cooling the particles after melt blending to prepare the solid polyester in-situ polymerization modified nano composite material, wherein the melt blending temperature is 100-250 ℃, and the time is 1.5-3 h.
The preparation method of the antimony-based polyester composite fiber comprises the following steps: adding BaSO into a polyester prepolymer melt with the polymerization degree of 3-304Granules or BaSO4After the dihydric alcohol dispersion of the particles is stirred evenly and cooled, the solid or slurry-like nano composite material for in-situ polymerization modification of polyester, BaSO4The particles can be directly added, or can be added after being dispersed in the dihydric alcohol, or can be partially directly added, or can be added after being dispersed in the dihydric alcohol, and the particles are all within the protection scope of the invention>At 1.5, the final product is in a solid state; when the mass ratio is between 0.5 and 1.5, the mostThe final product is in a slurry state; wherein, BaSO4The mass concentration of the dihydric alcohol dispersion liquid of the particles is 30-70 wt%, and BaSO4The dihydric alcohol in the dihydric alcohol dispersion liquid of the particles is the dihydric alcohol used for synthesizing the polyester prepolymer.
The preparation method of the antimony-based polyester composite fiber comprises the following steps: a, B, C and a polyester catalyst are uniformly mixed and then subjected to esterification reaction, pre-polycondensation reaction and cooling to prepare the polyester in-situ polymerization modified nano composite material, wherein A is terephthalic acid, isophthalic acid-5-sodium sulfonate or dimethyl terephthalate, B is ethylene glycol, 1, 3-propanediol or 1, 4-butanediol, and C is BaSO4Glycol dispersions of particles or BaSO4Particles, B and BaSO4The dihydric alcohols in the dihydric alcohol dispersion liquid of the particles are the same, and when the molar ratio of the dihydric alcohols (including the dihydric alcohols in B and C) to A is 1-1.5, the final product is solid; when the molar ratio of the dihydric alcohol to the A is 1.5-2.0, the final product is slurry; the molar ratio of A to B is 1: 1.5-2, and BaSO4The particles account for 30 to 50 wt% of the sum of A, B and C, and BaSO4The mass concentration of the glycol dispersion liquid of the particles is 60-70 wt%, the polyester catalyst is an antimony catalyst (ethylene glycol antimony, antimony trioxide), and the addition amount of the polyester catalyst is 170-300 ppm of the theoretical mass of a polymerization product of A and B in terms of the mass of antimony element; the esterification reaction is carried out in a nitrogen atmosphere, the temperature is 180-260 ℃, the time is 2-2.5 h, and the pressure is 100-400 KPa; the temperature of the pre-polycondensation reaction is 260-270 ℃, the time is 8-30 min, and the pressure is 100-10 KPa.
The invention also provides the antimony-based polyester composite fiber prepared by the preparation method of the antimony-based polyester composite fiber, which mainly comprises a polyester fiber matrix and ethylene glycol antimony and BaSO dispersed in the polyester fiber matrix4And (4) particle composition.
As a preferred technical scheme:
the antimony-based polyester composite fiber mainly comprises a polyester fiber matrix and ethylene glycol antimony and BaSO dispersed therein4Particle groupForming; the diameter of the antimony-based polyester composite fiber is 1.5-2.5 mu m, the surface is smooth and has no protrusions, which indicates that BaSO4The particles are not agglomerated, and the breaking strength is 4.3-4.5 cN/dtex (the breaking strength of a comparison sample is 3.9-4.2 cN/dtex, and the comparison sample is different from the antimony-based polyester composite fiber of the invention only in BaSO adopted in preparation4The surface of the particle is not coated with the polyester prepolymer), the dynamic friction coefficient is 0.65-0.70 (the dynamic friction coefficient of a comparison sample is 0.69-0.72, and the comparison sample is only different from the antimony-based polyester composite fiber adopted in the preparation process in terms of BaSO4The surface of the particle is not coated with the polyester prepolymer), and the antimony-based polyester composite fiber is BaSO4The crystallization peak is narrow and high, the crystallization performance is better, the relative refractive index is about 1.48, and the theoretical maximum transmittance is about 92.5%.
Has the advantages that:
(1) the preparation method of the antimony-based polyester composite resin comprises the step of wrapping SiO with a polyester prepolymer with the polymerization degree of 3-302Effectively avoids agglomeration and improves SiO2Dispersion of (2);
(2) the preparation method of the antimony-based polyester composite resin does not introduce a dispersing agent, reduces adverse effects on a catalyst, ensures a catalytic effect, and further reduces the dosage of the catalyst;
(3) the preparation method of the antimony-based polyester composite resin has the advantages of simple process, low cost and good application prospect;
(4) the film prepared from the antimony-based polyester composite resin has small separation strength and good antistatic effect;
(5) according to the preparation method of the antimony-based polyester composite fiber, the polyester prepolymer with the polymerization degree of 3-30 is used for wrapping the delustering agent, the melting point of the polyester prepolymer is high, and the polyester prepolymer is only melted at a high temperature in the polyester synthesis process to release a functional material, so that the secondary agglomeration phenomenon in the transportation or storage process can be avoided, a dispersing agent is not introduced in the preparation of the delustering polyester fiber, the adverse effect of the dispersing agent on a catalyst is reduced, the catalytic efficiency is improved, and the using amount of the catalyst is remarkably reduced;
(6) according to the preparation method of the antimony-based polyester composite fiber, the polyester prepolymer with the polymerization degree of 3-30 is adopted to wrap the delustering agent, the polyester prepolymer is an intermediate for preparing the functional polyester product, and has intrinsic good compatibility with an intermediate system synthesized by the functional polyester product, so that the high dispersibility of the polyester functional material is ensured, and the number of agglomerated particles is reduced;
(7) the antimony-based polyester composite fiber of the invention is prepared by adding the antimony-based polyester composite fiber into TiO2The polyester prepolymer is wrapped outside the nano particles, so that the TiO content is improved2The structure stability of the nano particles enables the nano particles to adapt to spinning processing;
(8) the preparation method of the antimony-based polyester composite fiber comprises the step of wrapping BaSO by using a polyester prepolymer with the polymerization degree of 3-304The melting point of the polyester prepolymer is high, and the polyester prepolymer can only melt at the high temperature of the pre-polycondensation to release functional materials in the polyester synthesis process, so that BaSO can be avoided4Secondary agglomeration phenomenon;
(9) the preparation method of the antimony-based polyester composite fiber comprises the step of wrapping BaSO by using a polyester prepolymer with the polymerization degree of 3-304Thus BaSO4The dispersant can not be introduced, so that the adverse effect of the dispersant on the catalyst is reduced, and the use amount of the catalyst is reduced;
(10) the preparation method of the antimony-based polyester composite fiber adopts the polyester prepolymer as an intermediate for preparing the polyester high polymer, and the polyester prepolymer has intrinsic good compatibility with an intermediate system for synthesizing the high polymer, so that the polyester high polymer has BaSO in the polyester synthesis process4Can exhibit high dispersibility;
(11) the preparation method of the antimony-based polyester composite fiber is characterized in that BaSO4The outside of the nano-particles is wrapped with polyester prepolymer and BaSO4The structure stability of the nano particles is high, and the nano particles can adapt to spinning processing;
(12) the antimony-based polyester composite fiber has smooth and non-convex fiber surface, high breaking strength and excellent crystallization performance.
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 nano composite material for polyester in-situ polymerization modification comprises the steps of firstly adding SiO with the mass concentration of 30 wt% into a polyester prepolymer (ethylene terephthalate prepolymer) melt with the polymerization degree of 3-82The ethylene glycol dispersion liquid of the particles is stirred evenly and cooled to prepare the nano composite material SiO for in-situ polymerization modification of the polyester2The particles are spherical, the average diameter is 600nm, and SiO in the nano composite material for in-situ polymerization modification of polyester2The mass content of the particles was 20 wt%.
Examples 2 to 6
A process for preparing the nano-class composite material used for in-situ polymerizing and modifying polyester includes such steps as adding BN to the melt of polyester prepolymer (ethylene terephthalate prepolymer) with polymerization degree AN, stirring, and cooling2Particles or SiO2Glycol dispersion of particles, and SiO2The particles are porous, the average diameter is 680nm, and SiO in the nano composite material for in-situ polymerization modification of polyester2The mass content of the particles is CN; the specific parameters in each example are shown in the following table.
Examples AN BN(wt％) CN(wt％)
2 8～15 SiO with a mass concentration of 40 wt%2Glycol dispersions of particles 20
3 10～18 SiO with a mass concentration of 70 wt%2Glycol dispersions of particles 40
4 12～20 SiO with a mass concentration of 60 wt%2Glycol dispersions of particles 30
5 38～46 SiO2Granules 10
6 40～50 SiO2Granules 15
Example 7
A preparation method of a nano composite material for polyester in-situ polymerization modification comprises the step of mixing a solid polyester prepolymer (ethylene terephthalate prepolymer) with a polymerization degree of 3-8 with SiO2The particles are melted and blended for 2h at the temperature of 100 ℃ and then cooled to prepare the nano composite material for in-situ polymerization modification of polyester, wherein，SiO2The particles are spherical, the average diameter is 650nm, and the obtained SiO in the nano composite material for in-situ polymerization modification of polyester2The mass content of the particles is 18 wt% respectively.
Examples 8 to 12
A method for preparing nanometer composite material for polyester in-situ polymerization modification comprises mixing solid polyester prepolymer (ethylene terephthalate prepolymer) with polymerization degree of AS and SiO2The particles are melted and blended with CS at the temperature of BS, and then cooled and crushed to prepare the nano composite material for polyester in-situ polymerization modification, wherein SiO2The particles are spherical, the average diameter is 500nm, and SiO in the nano composite material for in-situ polymerization modification of polyester2The mass contents of the particles are DS respectively; the specific parameters in each example are shown in the following table.
Figure BDA0002350726710000121
Figure BDA0002350726710000131
Examples 13 to 18
A process for preparing the nano-class composite material used for in-situ polymerizing and modifying polyester includes such steps as mixing A, B, C with polyester catalyst, esterifying reaction, pre-polycondensing reaction and cooling, in which A is terephthalic acid, isophthalic acid, 5-sodium sulfoisophthalate or dimethyl terephthalate, B is ethanediol, 1, 3-propanediol or 1, 4-butanediol, and C is SiO2Glycol dispersions of particles or SiO2Particles of B and SiO2The dihydric alcohol in the dihydric alcohol dispersion liquid of the particles is the same; the molar ratio of A to B is 1: 1.5-2, and SiO is2The particles account for 30 to 50 wt% (D), SiO, of the sum of the masses of A, B and C2The mass concentration of the glycol dispersion liquid of the particles is 60-70 wt%, the polyester catalyst is an antimony catalyst, and the addition amount of the polyester catalyst is 170-300 ppm of the theoretical mass of the polymerization product of A and B in terms of the mass of antimony element; the esterification reaction is carried out in a nitrogen atmosphere at the temperature of 180-260 DEG C(the temperature is gradually increased), the time is 2-2.5 h, and the pressure is 100-400 KPa (the pressure is gradually increased); the temperature of the pre-polycondensation reaction is 260-270 ℃ (the temperature is gradually increased), the time is 8-30 min, and the pressure is 100-10 KPa (the pressure is gradually reduced); the specific parameters in each example are shown in the following table.
Figure BDA0002350726710000132
Figure BDA0002350726710000141
Examples 19 to 36
The preparation of the antimony-based polyester composite resin from the polyester in-situ polymerization modified nanocomposite prepared in the embodiment X comprises the following specific steps:
(1) mixing PTA, EG, ethylene glycol antimony and polyester in-situ polymerization modification nano composite materials, and then carrying out esterification reaction to obtain an esterification product, wherein the esterification reaction is carried out in a nitrogen atmosphere, the pressure (P3) is 100-400 KPa, the temperature (T3) is 235-245 ℃, and the time (T3) is 220-230 min; wherein the molar ratio (molar ratio 1) of PTA to EG is 1: 1.1-1.6, the addition amount (addition amount 1) of ethylene glycol antimony in the esterification reaction process is 200-220 ppm of the theoretical mass of the polymerization product of PTA and EG, and SiO contained in the nano composite material for polyester in-situ polymerization modification in the esterification reaction process2The addition amount of the particles (addition amount 2) is 0.3-40 wt% of the theoretical mass of the PTA and EG polymer product;
(2) carrying out pre-polycondensation reaction on the esterification product to obtain a pre-polycondensation product, wherein the pressure (P4) of the pre-polycondensation reaction is 100-10 KPa, the temperature (T4) is 245-270 ℃, and the time (T4) is 170-180 min;
(3) carrying out final polycondensation on the pre-polycondensation product to obtain antimony-based polyester composite resin, wherein the pressure (P5) of the final polycondensation reaction is 150-200 Pa, the temperature (T5) is 270-284 ℃, and the time (T5) is 30-60 min; wherein the antimony-based polyester composite resin has an intrinsic viscosity (viscosity) of 0.545 to 0.670dL/g, 1.0 to 3.0 agglomerated particles, a size of 15 to 20 μm, and a filtration pressure value of 0.15 to 0.25 bar/g;
the prepared antimony-based polyester composite resin is prepared into a film, the thickness of the film is 90-110 mu m, the separation strength is 2.9-3.5N/15 mm, and the surface resistance is 1.6 x 10^8～3.2*10^8Ω；
The parameters for examples 19 to 36 are specifically shown in the following tables 1 to 2.
Example 37
Antimony-based polyester composite resin and an in-situ polymerization method and application thereof have the same steps as those of example 25, except that the polyester titanium catalyst composite material system and the addition amount thereof in the step (1) are added in the step (2), and specific parameters are shown in Table 2.
Table 1 parameters corresponding to examples 19 to 27
Figure BDA0002350726710000151
TABLE 2 parameters corresponding to examples 28 to 37
Figure BDA0002350726710000161
Examples 38 to 55
The preparation method of the nano composite material for polyester in-situ polymerization modification is basically the same as the preparation process of the embodiment 1-18, and the difference is only that SiO is used2Replacement of the particles by TiO2The correspondence of the particles for each example is shown in the following table.
Figure BDA0002350726710000171
Examples 56 to 73
The preparation of the antimony-based polyester composite fiber by using the polyester in-situ polymerization modified nano composite material prepared in the embodiment X comprises the following specific steps:
(1) mixing PTA, EG, ethylene glycol antimony and polyester in-situ polymerization modification nano composite materials, and then carrying out esterification reaction to obtain an esterification product, wherein the esterification reaction is carried out in a nitrogen atmosphere, the pressure (P3) is 100-400 KPa, the temperature (T3) is 220-252 ℃, and the time (T3) is 140-160 min; wherein the molar ratio (molar ratio 1) of PTA to EG is 1: 1.1-1.8, the addition amount (addition amount 1) of ethylene glycol antimony in the esterification reaction process is 200-220 ppm of the theoretical mass of the polymerization products of PTA and EG, and the addition amount (addition amount 2) of TiO2 particles contained in the nano composite material for in-situ polymerization modification of polyester in the esterification reaction process is 0.3-3.0 wt% of the theoretical mass of the polymerization products of PTA and EG;
(2) carrying out pre-polycondensation reaction on the esterification product to obtain a pre-polycondensation product, wherein the pressure (P4) of the pre-polycondensation reaction is 100-10 KPa, the temperature (T4) is 252-270 ℃, and the time (T4) is 40-50 min;
(3) carrying out final polycondensation on the pre-polycondensation product to obtain an antimony-based extinction polyester melt, wherein the pressure (P5) of the final polycondensation reaction is 150-200 Pa, the temperature (T5) is 270-284 ℃, and the time (T5) is 40-50 min; wherein the intrinsic viscosity (viscosity) of the antimony-based extinction polyester melt is 0.565-0.681 dL/g, the number (N) of the condensed particles is 1.0-3.0/mg, the size of the condensed particles is 15-20 μm, and the filtration pressure value (P6) is 0.05-0.09 bar/g;
(4) carrying out melt direct spinning on the antimony-based extinction polyester melt to prepare antimony-based polyester composite fibers; wherein the melt direct spinning process parameters are as follows: the spinning temperature (T6) is 282-285 ℃, the spinning speed (v1) is 3500-4000 m/min, the side blowing temperature (T7) is 30 +/-5 ℃, the side blowing air speed (v2) is 0.3-0.5 m/s, and the drafting multiplying power (a) is 3.5-4.0;
the fineness (fineness) of the prepared antimony-based polyester composite fiber is 3.2-4.0 dtex, the breaking strength (strength) is 2.82-3.38 cN/dtex, and the elongation at break (elongation) is 13.2-27.4%.
The parameters corresponding to examples 56 to 73 are specifically shown in the following tables 3 to 4
Example 74
The preparation method of antimony-based polyester composite fiber and the product thereof have the same steps as the example 62, except that the polyester titanium catalyst composite material system in the step (1) and the addition amount thereof are added in the step (2), and the specific parameters are shown in the table 4
TABLE 3 parameters corresponding to examples 56-64
Figure BDA0002350726710000181
Figure BDA0002350726710000191
TABLE 4 parameters corresponding to examples 65 to 74
Figure BDA0002350726710000192
Figure BDA0002350726710000201
Example 75
A preparation method of a nano composite material for polyester in-situ polymerization modification comprises the steps of firstly adding BaSO with the mass concentration of 30 wt% into a polyester prepolymer (ethylene terephthalate prepolymer) melt with the polymerization degree of 3-84The ethylene glycol dispersion liquid of the particles is stirred evenly and cooled to prepare the nano composite material BaSO for the in-situ polymerization modification of the polyester4The particles are spherical, the average diameter is 600nm, and BaSO is contained in the nano composite material for in-situ polymerization modification of polyester4The mass content of the particles was 20 wt%.
Examples 76 to 80
A process for preparing the nano-class composite material used for in-situ polymerizing and modifying polyester includes such steps as adding BN to the melt of polyester prepolymer (glycol terephthalate prepolymer) with polymerization degree of AN, stirring, and cooling4Granules or BaSO4A glycol dispersion of particles, and BaSO4The particles are porous, the average diameter is 680nm, and BaSO in the nano composite material for in-situ polymerization modification of polyester4The mass content of the particles is CN.
Figure BDA0002350726710000202
Figure BDA0002350726710000211
Example 81
A preparation method of a nano composite material for polyester in-situ polymerization modification comprises the steps of mixing a solid polyester prepolymer (ethylene terephthalate prepolymer) with a polymerization degree of 3-8 and BaSO4The particles are melted and blended for 2h at the temperature of 100 ℃ and then cooled to prepare the nano composite material for polyester in-situ polymerization modification, wherein BaSO4The particles are spherical, the average diameter is 650nm, and BaSO in the obtained nano composite material for in-situ polymerization modification of polyester4The mass content of the particles is 18 wt% respectively.
Examples 82 to 86
A method for preparing nanometer composite material for polyester in-situ polymerization modification comprises mixing solid polyester prepolymer (ethylene terephthalate prepolymer) with polymerization degree of AS and BaSO4The particles are melted and blended with CS at the temperature of BS, and then cooled and crushed to prepare the nano composite material for polyester in-situ polymerization modification, wherein BaSO4The particles are spherical, the average diameter is 500nm, and BaSO is contained in the nano composite material for in-situ polymerization modification of polyester4The mass contents of the particles are respectively DS.
Examples AS BS(℃) CS(h) DS(wt％)
82 8～15 250 3 40
83 10～18 200 2.5 28
84 12～20 100 1.5 15
85 38～46 250 2.5 10
86 40～50 250 2 10
Examples 87 to 92
A process for preparing the nano-class composite material used for in-situ polymerizing and modifying polyester includes such steps as mixing A, B, C with polyester catalyst, esterifying reaction, pre-polycondensing reaction and cooling, in which A is terephthalic acid, isophthalic acid, 5-sodium sulfoisophthalate or dimethyl terephthalate, B is ethanediol, 1, 3-propanediol or 1, 4-butanediol, C isBaSO4Glycol dispersions of particles or BaSO4Particles of and BaSO4The particles are spherical and have an average diameter of 600 nm; b and BaSO4The dihydric alcohol in the dihydric alcohol dispersion liquid of the particles is the same; the molar ratio of A to B is 1: 1.5-2, and BaSO4The particles account for 30 to 50 wt% (D) of the sum of A, B and C, BaSO4The mass concentration of the glycol dispersion liquid of the particles is 60-70 wt%, the polyester catalyst is an antimony catalyst, and the addition amount of the polyester catalyst is 170-300 ppm of the theoretical mass of the polymerization product of A and B in terms of the mass of antimony element; (ii) a The esterification reaction is carried out in a nitrogen atmosphere, the temperature is 180-260 ℃ (the temperature is gradually increased), the time is 2-2.5 h, and the pressure is 100-400 KPa (the pressure is gradually increased); the temperature of the pre-polycondensation reaction is 260-270 ℃ (the temperature is gradually increased), the time is 8-30 min, and the pressure is 100-10 KPa (the pressure is gradually reduced).
Figure BDA0002350726710000221
Examples 93 to 110
The antimony-based polyester composite fiber is prepared by adopting the polyester in-situ polymerization modified nano composite material prepared in the embodiment X and a melt direct spinning method, and the method comprises the following specific steps:
(1) mixing PTA, EG, ethylene glycol antimony and polyester in-situ polymerization modification nano composite materials, and then carrying out esterification reaction to obtain an esterification product, wherein the esterification reaction is carried out in a nitrogen atmosphere, the pressure (P3) is 100-400 KPa, the temperature (T3) is 220-252 ℃, and the time (T3) is 140-160 min; wherein the molar ratio (molar ratio 1) of PTA to EG is 1: 1.1-1.8, the addition amount (addition amount 1) of ethylene glycol antimony in the esterification reaction process is 200-220 ppm of the theoretical mass of the polymerization products of PTA and EG, and the addition amount (addition amount 2) of BaSO4 particles contained in the nano composite material for in-situ polymerization modification of polyester in the esterification reaction process is 0.3-0.8 wt% of the theoretical mass of the polymerization products of PTA and EG;
(3) carrying out pre-polycondensation reaction on the esterification product to obtain a pre-polycondensation product, wherein the pressure (P4) of the pre-polycondensation reaction is 100-10 KPa, the temperature (T4) is 252-270 ℃, and the time (T4) is 40-50 min;
(4) carrying out final polycondensation on the pre-polycondensation product to obtain a BaSO4 modified antimony-based polyester melt, wherein the pressure (P5) of the final polycondensation reaction is 150-200 Pa, the temperature (T5) is 270-284 ℃, and the time (T5) is 40-50 min; wherein the inherent viscosity (viscosity) of the BaSO4 modified antimony-based polyester melt is 0.655-0.665 dL/g, the number of the condensed particles (N) is 1.0-3.0/m, the size of the condensed particles is 15-20 mu m, and the filtration pressure value (P6) is 0.12-0.20 bar/g;
(5) carrying out melt direct spinning on the BaSO4 modified antimony-based polyester melt to prepare antimony-based polyester composite fibers; wherein the melt direct spinning process parameters are as follows: the spinning temperature (T6) is 282-285 ℃, the spinning speed (v1) is 3500-4000 m/min, the side blowing temperature (T7) is 30 +/-5 ℃, the side blowing air speed (v2) is 0.3-0.5 m/s, and the drafting multiplying power (a) is 3.5-4.0;
the diameter (diameter) of the prepared antimony-based polyester composite fiber is 1.5-2.5 mu m, the breaking strength (strength) is 4.3-4.5 cN/dtex, and the dynamic friction coefficient (b) is 0.65-0.70;
the parameters for examples 93-110 are shown in tables 5-6 below
Example 111
The preparation method of antimony-based polyester composite fiber and the product thereof have the same steps as the example 25, except that the polyester titanium catalyst composite material system in the step (1) and the addition amount thereof are added in the step (2), and the specific parameters are shown in the table 6
TABLE 5 parameters corresponding to examples 93 to 101
Figure BDA0002350726710000231
Figure BDA0002350726710000241
Figure BDA0002350726710000251
TABLE 6 parameters corresponding to examples 102-111
Figure BDA0002350726710000252
Figure BDA0002350726710000261

Claims (7)

1. The preparation method of the antimony-based polyester composite material is characterized by comprising the following steps of: mixing PTA, EG, ethylene glycol antimony and polyester in-situ polymerization modification nano composite materials, and then carrying out esterification reaction and polycondensation reaction to obtain antimony-based polyester composite resin, or further carrying out melt direct spinning to obtain antimony-based polyester composite fibers;
the nano composite material for polyester in-situ polymerization modification mainly comprises a polyester prepolymer with the polymerization degree of 3-30 and functional particles dispersed in the polyester prepolymer, wherein the functional particles are SiO2Particles, TiO2Granules or BaSO4And (3) granules.
2. The preparation method of the antimony-based polyester composite material as claimed in claim 1, which is characterized by comprising the following specific steps:
(1) PTA, EG, ethylene glycol antimony and functional particles are SiO2Mixing the polyester in-situ polymerization modification nano composite materials of the particles, and then carrying out esterification reaction to obtain an esterification product, wherein the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 100-400 KPa, the temperature is 235-245 ℃, and the time is 220-230 min;
(2) carrying out pre-polycondensation reaction on the esterification product to obtain a pre-polycondensation product, wherein the pressure of the pre-polycondensation reaction is 100-10 KPa, the temperature is 245-270 ℃, and the time is 170-180 min;
(3) carrying out final polycondensation on the pre-polycondensation product to obtain antimony-based polyester composite resin, wherein the pressure of the final polycondensation reaction is 150-200 Pa, the temperature is 270-284 ℃, and the time is 30-60 min;
or, the specific steps are as follows:
(a) PTA, EG, ethylene glycol antimony and functional particles are TiO2Mixing the nano composite material for in-situ polymerization modification of polyester of particles, and then carrying out esterification reaction to obtain esterCarrying out esterification reaction on the product under the nitrogen atmosphere, wherein the pressure is 100-400 KPa, the temperature is 220-252 ℃, and the time is 140-160 min;
(b) carrying out pre-polycondensation reaction on the esterification product to obtain a pre-polycondensation product, wherein the pressure of the pre-polycondensation reaction is 100-10 KPa, the temperature is 252-270 ℃, and the time is 40-50 min;
(c) carrying out final polycondensation on the pre-polycondensation product to obtain an antimony-based extinction polyester melt, wherein the pressure of the final polycondensation reaction is 150-200 Pa, the temperature is 270-284 ℃, and the time is 40-50 min;
(d) carrying out melt direct spinning on the antimony-based extinction polyester melt to prepare antimony-based polyester composite fibers;
or, the specific steps are as follows:
(I) PTA, EG, ethylene glycol antimony and functional particles are BaSO4Mixing the polyester in-situ polymerization modification nano composite materials of the particles, and then carrying out esterification reaction to obtain an esterification product, wherein the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 100-400 KPa, the temperature is 220-252 ℃, and the time is 140-160 min;
(II) carrying out pre-polycondensation reaction on the esterification product to obtain a pre-polycondensation product, wherein the pressure of the pre-polycondensation reaction is 100-10 KPa, the temperature is 252-270 ℃, and the time is 40-50 min;
(III) carrying out final polycondensation on the pre-polycondensation product to obtain BaSO4Modifying the antimony-based polyester melt, wherein the pressure of final polycondensation reaction is 150-200 Pa, the temperature is 270-284 ℃, and the time is 40-50 min;
(IV) mixing BaSO4And carrying out melt direct spinning on the modified antimony-based polyester melt to obtain the antimony-based polyester composite fiber.
3. The preparation method of the antimony-based polyester composite material as claimed in claim 2, wherein in the step (1), the molar ratio of PTA to EG is 1: 1.1-1.6, the addition amount of ethylene glycol antimony in the esterification reaction process is 200-220 ppm of the theoretical mass of the polymerization product of PTA and EG based on the mass of antimony element, and SiO contained in the nanocomposite for in-situ polymerization modification of polyester in the esterification reaction process2The particles are added in an amount of 0.3 to E, based on the theoretical mass of the polymer product of PTA and EG40wt％；
In the step (3), the intrinsic viscosity of the antimony-based polyester composite resin is 0.545-0.670 dL/g, the number of the agglomerated particles is 1.0-3.0/mg, and the filtering pressure value is 0.15-0.25 bar/g;
in the step (a), the molar ratio of PTA to EG is 1: 1.1-1.8, the addition amount of ethylene glycol antimony in the esterification reaction process is 200-220 ppm of the theoretical mass of the polymerization products of PTA and EG, and TiO contained in the nano composite material for polyester in-situ polymerization modification in the esterification reaction process is calculated by the mass of antimony element2The addition amount of the particles is 0.3-3.0 wt% of the theoretical mass of the PTA and EG polymerization products;
in the step (c), the intrinsic viscosity of the antimony-based extinction polyester melt is 0.565-0.681 dL/g, the number of agglomerated particles is 1.0-3.0/mg, and the filtering pressure value is 0.05-0.09 bar/g;
in the step (d), the melt direct spinning process parameters are as follows: the spinning temperature is 282-285 ℃, the spinning speed is 3500-4000 m/min, the side blowing temperature is 3035 ℃, the side blowing air speed is 0.3-0.5 m/s, and the drafting multiplying power is 3.5-4.0;
in the step (I), the molar ratio of PTA to EG is 1: 1.1-1.8, the addition amount of ethylene glycol antimony in the esterification reaction process is 200-220 ppm of the theoretical mass of the polymerization products of PTA and EG, and BaSO contained in the nano composite material for polyester in-situ polymerization modification in the esterification reaction process4The addition amount of the particles is 0.3-0.8 wt% of the theoretical mass of the PTA and EG polymerization products;
in step (III), BaSO4The intrinsic viscosity of the modified antimony-based polyester melt is 0.655-0.665 dL/g, the number of condensed particles is 1.0-3.0/m, and the filtering pressure value is 0.12-0.20 bar/g;
in the step (IV), the melt direct spinning process parameters are as follows: the spinning temperature is 282-285 ℃, the spinning speed is 3500-4000 m/min, the side blowing temperature is 3035 ℃, the side blowing air speed is 0.3-0.5 m/s, and the drafting ratio is 3.5-4.0.
4. The preparation method of the antimony-based polyester composite material as claimed in claim 1, wherein the mass content of the functional particles in the nano composite material for polyester in-situ polymerization modification is 10-40 wt%, and the average particle size of the functional particles in the polyester prepolymer is less than 700 nm.
5. The preparation method of the antimony-based polyester composite material as claimed in claim 4, wherein the preparation method of the nanocomposite material for polyester in-situ polymerization modification comprises the following steps: and melting and blending the solid polyester prepolymer with the polymerization degree of 3-30 with the functional particles, and cooling to obtain the polyester in-situ polymerization modified nano composite material, wherein the temperature of melting and blending is 100-250 ℃, and the time is 1.5-3 h.
6. The preparation method of the antimony-based polyester composite material as claimed in claim 4, wherein the preparation method of the nanocomposite material for polyester in-situ polymerization modification comprises the following steps: adding functional particles or a dihydric alcohol dispersion liquid of the functional particles into a polyester prepolymer melt with the polymerization degree of 3-30, uniformly stirring and cooling to obtain the nano composite material for polyester in-situ polymerization modification, wherein the mass concentration of the dihydric alcohol dispersion liquid of the functional particles is 30-70 wt%, and the dihydric alcohol in the dihydric alcohol dispersion liquid of the functional particles and the dihydric alcohol used for synthesizing the polyester prepolymer.
7. The preparation method of the antimony-based polyester composite material as claimed in claim 4, wherein the preparation method of the nanocomposite material for polyester in-situ polymerization modification comprises the following steps: a, B, C and a polyester catalyst are uniformly mixed and then undergo esterification reaction, pre-polycondensation reaction and cooling to prepare the polyester in-situ polymerization modified nano composite material, wherein A is terephthalic acid, isophthalic acid-5-sodium sulfonate or dimethyl terephthalate, B is ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol, C is dihydric alcohol dispersion liquid or functional particles of the functional particles, and B is the same as the dihydric alcohol in the dihydric alcohol dispersion liquid of the functional particles; the molar ratio of A to B is 1: 1.5-2, the functional particles account for 30-50 wt% of the sum of A, B and C, the mass concentration of the dihydric alcohol dispersion liquid of the functional particles is 60-70 wt%, the polyester catalyst is an antimony catalyst, and the addition amount of the polyester catalyst is 170-300 ppm of the theoretical mass of a polymerization product of A and B in terms of the mass of antimony element; the esterification reaction is carried out in a nitrogen atmosphere, the temperature is 180-260 ℃, the time is 2-2.5 h, and the pressure is 100-400 KPa; the temperature of the pre-polycondensation reaction is 260-270 ℃, the time is 8-30 min, and the pressure is 100-10 KPa.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115558246A (en) * 2021-12-23 2023-01-03 上海涵点科技有限公司 High-dispersion inorganic powder auxiliary agent and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5478911A (en) * 1993-12-30 1995-12-26 Kolon Industries Inc. Process for the preparation of a polyester using an antimony-esterified trimellitate catalyst
CN101831151A (en) * 2010-04-21 2010-09-15 浙江恒逸石化股份有限公司 Antistatic polyethylene terephthalate fiber-grade polyester and preparation method thereof
CN103789868A (en) * 2014-01-26 2014-05-14 东华大学 Preparation method of functional polyester fiber
CN107936231A (en) * 2016-10-13 2018-04-20 中国石化仪征化纤有限责任公司 A kind of preparation method of new polyester master batch and its film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5478911A (en) * 1993-12-30 1995-12-26 Kolon Industries Inc. Process for the preparation of a polyester using an antimony-esterified trimellitate catalyst
CN101831151A (en) * 2010-04-21 2010-09-15 浙江恒逸石化股份有限公司 Antistatic polyethylene terephthalate fiber-grade polyester and preparation method thereof
CN103789868A (en) * 2014-01-26 2014-05-14 东华大学 Preparation method of functional polyester fiber
CN107936231A (en) * 2016-10-13 2018-04-20 中国石化仪征化纤有限责任公司 A kind of preparation method of new polyester master batch and its film

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115558246A (en) * 2021-12-23 2023-01-03 上海涵点科技有限公司 High-dispersion inorganic powder auxiliary agent and application thereof
CN115558246B (en) * 2021-12-23 2024-01-26 上海涵点科技有限公司 High-dispersion inorganic powder auxiliary agent and application thereof

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