CN114644752A - anti-UV (ultraviolet) regenerated polyester chip and preparation method and application thereof - Google Patents

anti-UV (ultraviolet) regenerated polyester chip and preparation method and application thereof Download PDF

Info

Publication number
CN114644752A
CN114644752A CN202210342327.1A CN202210342327A CN114644752A CN 114644752 A CN114644752 A CN 114644752A CN 202210342327 A CN202210342327 A CN 202210342327A CN 114644752 A CN114644752 A CN 114644752A
Authority
CN
China
Prior art keywords
preparation
dmt
reaction
ethylene glycol
refined
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210342327.1A
Other languages
Chinese (zh)
Inventor
张喜豹
朱福和
朱恩斌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujian Selon Technology Co ltd
Original Assignee
Fujian Selon Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujian Selon Technology Co ltd filed Critical Fujian Selon Technology Co ltd
Priority to CN202210342327.1A priority Critical patent/CN114644752A/en
Publication of CN114644752A publication Critical patent/CN114644752A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
    • C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
    • 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
    • D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Artificial Filaments (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention belongs to the technical field of chemical regeneration of waste polyester, and particularly relates to an anti-UV (ultraviolet) regenerated polyester chip and a preparation method and application thereof. The preparation method provided by the invention has the advantages that the recycled PET polyester is used as a raw material, the refined DMT is prepared through alcoholysis and ester exchange, the refined DMT is subjected to ester exchange reaction with ethylene glycol, cerium dioxide and titanium dioxide composite powder are added after the reaction is finished, blending polymerization is carried out, the regenerated polyester chip with excellent ultraviolet radiation resistance is prepared, the preparation method can be applied to preparation of fibers or fabrics, comprehensive utilization of solid and waste resources is realized, waste is changed into valuable, the preparation method is safe, non-toxic, green, clean and environment-friendly, and development and utilization of cerium dioxide in the chemical fiber field are developed and utilized.

Description

anti-UV (ultraviolet) regenerated polyester chip and preparation method and application thereof
Technical Field
The invention belongs to the technical field of chemical regeneration of waste polyester, and particularly relates to an anti-UV (ultraviolet) regenerated polyester chip and a preparation method and application thereof.
Background
Polyethylene terephthalate (PET, polyester for short) is a semicrystalline thermoplastic polymer material with excellent properties, has the characteristics of odorless, tasteless, non-toxic, light weight, high strength, good air tightness, high transparency and the like, is widely used in the fields of beverage bottles, fibers, films, sheet bases, electrical appliance insulating materials, chemical fibers, packaging, medicines, electronic machinery and the like, and is almost a polyester bottle in the product packaging of carbonated beverages, mineral water, edible oil and the like in the food field, and the application field of the polyester bottle is continuously expanded. Currently, worldwide polyester production is on the order of several million tons per year, while its consumption is still increasing at a rate of 11% per year. If the used waste polyester is directly discharged into the environment, the environment is polluted and resources are wasted. Therefore, the recycling of PET polyester has great significance for protecting the environment and relieving the world resource crisis, the recycling of waste polyester products can change waste into valuable, the pressure of the shortage of non-renewable resources such as petroleum and the like is relieved, and meanwhile, the recycling of PET polyester has great significance for protecting the ecological environment, the sustainable development of the polyester industry and the like.
Meanwhile, with the damage of human activities to the atmospheric ozone layer, ultraviolet radiation has become one of the great threats to human health, and the probability of human skin cancer is increased. Nowadays, the sales of ultraviolet-resistant cosmetics and daily necessities are increased rapidly, but the protection capability, the protection area and the action time are limited. Therefore, the textile with larger area and better protection effect is used for blocking the excessive damage of ultraviolet rays to human bodies, becomes a barrier for protecting the skin from the ultraviolet rays, and becomes an important direction.
At present, in the production of ultraviolet-proof textiles at home and abroad, an ultraviolet screening agent is generally used for dipping or coating on the surface of the textile to play a role in protection; or adding ultraviolet screening agent during polymerization or spinning. Among them, inorganic uv-screening agents have been increasingly regarded more attention than organic uv-screening agents because they have many superior properties in terms of chemical stability, thermal stability, safety, uv-screening effect, and the like. However, inorganic powder has poor compatibility with polymer matrix, is easy to agglomerate to block spinneret orifices, shortens the service life of a spinneret plate, has high processing difficulty and high cost, and is not suitable for natural fibers and fabrics thereof (such as various cotton, hemp, real silk, wool and other products), so the inorganic powder is not suitable for natural fibers and fabrics thereofFew applications have been reported. Patent CN200958152Y discloses a method for preparing an anti-ultraviolet towel, which uses towel yarn containing nano ZnO or TiO2The finishing agent is obtained by dipping treatment, and the method has simple process but poor durability. Patent CN101311398B discloses a nanometer durable uvioresistant textile, which uses nanometer metal oxide as uvioresistant agent, polyurethane, polyacrylate, etc. as film forming agent, treats the fiber, and finally forms a layer of film structure containing nanometer uvioresistant particles on the surface.
Therefore, how to combine the inorganic ultraviolet shielding agent and the waste PET to improve the ultraviolet protection performance of the textile is a goal that many fiber researchers and fabric manufacturers strive to pursue at present.
Disclosure of Invention
Therefore, the anti-UV regenerated polyester chip and the preparation method and the application thereof are needed to be provided, after chemical treatment is carried out on waste textile/bottle chip materials (recycled PET polyester), cerium dioxide and titanium dioxide composite powder are added for blending polymerization, the dispersibility of the composite powder in polymers is good, the agglomeration of the composite powder is avoided, and the prepared regenerated polyester chip has excellent anti-ultraviolet radiation performance and good spinnability.
In order to achieve the purpose, the invention adopts the main technical scheme that:
in a first aspect, the invention provides a preparation method of an anti-UV recycled polyester chip, which comprises the following steps:
s0, preparation of the composite additive: mixing cerium dioxide powder and titanium dioxide powder, and drying to obtain a composite additive for later use;
s1, alcoholysis: carrying out alcoholysis reaction on recycled PET (polyethylene terephthalate) polyester serving as a raw material under the action of dihydric alcohol and an alcoholysis catalyst to obtain crude BHET (BHET), and rectifying and purifying the crude BHET to obtain refined BHET;
s2, ester exchange: adding methanol into refined BHET, carrying out ester exchange reaction under the action of potassium carbonate catalyst to obtain crude DMT, and rectifying and purifying the crude DMT to obtain refined DMT;
s3, polymerization: and sequentially adding ethylene glycol, ethylene glycol antimony and the composite additive into the refined DMT for polymerization reaction to obtain a polymer melt, and casting and dicing the polymer melt to obtain the anti-UV regenerated polyester chip.
Wherein the polymerization reaction in step S3 is to prepare BHET from purified DMT by transesterification with ethylene glycol; after the ester exchange reaction is finished, ethylene glycol antimony and a composite additive are added, BHET is subjected to polycondensation to obtain a PET polymer melt, and the specific reaction process is as follows:
Figure BDA0003575278770000031
in a further embodiment of the present invention, in step S0, the cerium oxide powder and the titanium dioxide powder are mixed at a mass ratio of 1:2 to 3: 1. Wherein 1:2 to 3:1 can also be represented as 1 to 3:1 to 2.
As a further embodiment of the present invention, in step S3, the amount of the composite additive is 1% to 3% by mass of the purified DMT. By controlling the dosage of the composite additive, the UV resistant recycled polyester chips with different viscosities can be produced.
As a further embodiment of the present invention, in step S3, the molar ratio of the ethylene glycol to the purified DMT is 2: 1-4: 1.
in a further embodiment of the present invention, in step S3, the amount of ethylene glycol antimony added is 200 to 250ppm based on the total mass of the purified DMT. By adding 200-250 ppm of ethylene glycol antimony, the reaction speed can be accelerated, and the product color value is optimized; however, after the excessive ethylene glycol antimony is added, the reaction time is not shortened, but catalyst byproducts are increased, the rear-end treatment cost is increased, and the color value of the product is influenced.
As a further embodiment of the present invention, the reaction conditions of the polymerization reaction include:
the reaction temperature is 160-300 ℃, the reaction time is 2-3 h, the vacuum degree is 10-35 Pa, and the stirring speed is 0-200 r/min. Under the stirring condition, the composite additive (cerium dioxide powder and titanium dioxide powder) can be more uniformly dispersed in the polymer, and the agglomeration of the composite powder is avoided, so that the adhesion, ultraviolet resistance and washing resistance of cerium dioxide powder particles are improved.
As a further embodiment of the present invention, in step S1, the diol is selected from one or more of diethylene glycol, propylene glycol, and ethylene glycol.
As a further embodiment of the present invention, in step S1, the alcoholysis catalyst is selected from the group consisting of zinc oxide, tin chloride, and zinc acetate.
In a second aspect, the invention provides an anti-UV recycled polyester chip, which is prepared by the preparation method of the first aspect of the invention.
In a third aspect, the present invention provides the use of the UV resistant recycled polyester chip of the first aspect of the present invention in the preparation of a fiber or fabric.
Different from the prior art, the technical scheme takes the recycled PET as the raw material, and after DMT is prepared through alcoholysis and ester exchange, the cerium dioxide and titanium dioxide composite powder is added for blending polymerization to prepare the regenerated polyester chip with excellent ultraviolet radiation resistance.
Detailed Description
In order to explain technical contents, structural features, and objects and effects of the technical means in detail, the following detailed description is given with reference to specific embodiments.
In the description of this application, a numerical range denoted by "value a to value B" is intended to include the endpoint value A, B, and all integers and fractions within the range. For example, "1: 2-3: 1" means "1-3: 1-2" and includes, but is not limited to, 1:1, 1:2, 1.5:1, 1.5:2, 2:1, 2:2, 3:1, 3:2, etc.
In the present application, when an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or as a range defined by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed.
The term "prepared from …" as used herein is synonymous with "comprising". As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The indefinite articles "a" and "an" preceding an element or component of the present application do not limit the quantitative requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
Furthermore, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified. The experimental procedures in the following examples are conventional unless otherwise specified.
In the specific embodiment of the present application, the titanium dioxide powder is a nano titanium dioxide powder, and is commercially available.
In the embodiment of the application, the PET polyester is recycled by recycling waste PET polyester (including PET bottle flakes, PET fibers and PET textiles), granulating into a friction material with a particle size, and then melting, pressurizing and filtering the friction material by a screw extruder to be sent into an alcoholysis kettle for reaction.
In the specific embodiment of the application, recovered PET polyester is used as a raw material, alcoholysis is performed under the action of dihydric alcohol and an alcoholysis catalyst to prepare crude ethylene terephthalate (BHET), the crude BHET is rectified to prepare refined BHET, the refined BHET is reacted with methanol to prepare crude dimethyl terephthalate (DMT), and the crude DMT is rectified to prepare refined DMT. Then, in the polymerization reaction process, refined DMT, glycol and ethylene glycol antimony are subjected to ester exchange reaction, after the reaction is finished, composite additives (cerium dioxide powder and titanium dioxide powder) are added, then polymerization is carried out to generate polymer melt, and after casting and grain cutting, the anti-UV regenerated polyester chip is prepared. The specific steps for preparing refined DMT from recycled PET polyester are as follows:
s1, alcoholysis: the method comprises the steps of carrying out alcoholysis reaction on recycled PET polyester serving as a raw material under the action of dihydric alcohol and an alcoholysis catalyst to obtain crude BHET, and rectifying and purifying the crude BHET to obtain refined BHET. Wherein the dihydric alcohol is selected from one or more of diethylene glycol, propylene glycol and ethylene glycol; the alcoholysis catalyst is selected from zinc oxide, tin chloride or zinc acetate.
S2, ester exchange: methanol is added into the refined BHET, ester exchange reaction is carried out under the action of potassium carbonate catalyst to obtain crude DMT, and the crude DMT is rectified and purified to obtain the refined DMT.
The specific reaction conditions and steps of steps S1 and S2 may be set or adjusted according to the conventional methods in the art, and are not described in detail in the specific embodiments of the present application. The purified DMT thus obtained was used in the following specific examples to prepare UV resistant recycled polyester chips.
Example 1 preparation and application of anti-UV recycled polyester chip
Adding ethylene glycol into a polymerization kettle, starting a stirrer (the rotating speed is 30r/min), raising the reaction temperature to 160 ℃, removing water, then adding refined DMT into the polymerization kettle, raising the temperature to 210 ℃, and carrying out ester exchange reaction for 3h under the normal pressure state to generate BHET, wherein the molar ratio of the ethylene glycol to the refined DMT is 2: 1. after the ester exchange reaction is finished, adding 200ppm of ethylene glycol antimony, controlling the temperature at 230 ℃, adding a composite additive (comprising 1.8 wt% of cerium dioxide and 0.6 wt% of titanium dioxide in terms of the mass percentage of refined DMT), continuously heating to 250 ℃ after the addition is finished, switching to a polycondensation system, starting to vacuumize, carrying out the polycondensation reaction in a vacuum state, obtaining a polyester melt when the temperature reaches 285 ℃, keeping the vacuum degree at 10Pa, and reacting for 1.5h, and cooling and granulating to obtain the anti-UV regenerated polyester chip.
And spinning and weaving the regenerated polyester chips to respectively obtain polyester fibers (spun yarns) and functional polyester fabrics. The spinning equipment and the weaving equipment are conventional equipment in the field of textile, and working parameters of the spinning equipment and the weaving equipment can also be set according to a conventional method, which is not specifically discussed in the specific embodiment of the application.
Example 2 preparation and application of anti-UV recycled polyester chip
Adding ethylene glycol into a polymerization kettle, starting a stirrer (the rotating speed is 30r/min), raising the reaction temperature to 160 ℃, removing water, then adding refined DMT into the polymerization kettle, raising the temperature to 210 ℃, and carrying out ester exchange reaction for 3h under the normal pressure state to generate BHET, wherein the molar ratio of the ethylene glycol to the refined DMT is 3: 1. after the ester exchange reaction is finished, adding 210ppm of ethylene glycol antimony, controlling the temperature at 230 ℃, adding a composite additive (comprising 1.6 wt% of cerium dioxide and 0.8 wt% of titanium dioxide in terms of the mass percent of refined DMT), continuously heating to 250 ℃ after the addition is finished, switching to a polycondensation system, starting to vacuumize, carrying out the polycondensation reaction in a vacuum state, obtaining a polyester melt when the temperature reaches 292 ℃, the vacuum degree is 20Pa, and the reaction time is 2 hours, and cooling and granulating to obtain the anti-UV regenerated polyester chip. And spinning and weaving the regenerated polyester chips to respectively obtain polyester fibers (spun yarns) and functional polyester fabrics.
Example 3 preparation and application of anti-UV recycled polyester chip
Adding ethylene glycol into a polymerization kettle, starting a stirrer (the rotating speed is 30r/min), raising the reaction temperature to 160 ℃, removing water, then adding refined DMT into the polymerization kettle, raising the temperature to 210 ℃, and carrying out ester exchange reaction for 3h under the normal pressure state to generate BHET, wherein the molar ratio of the ethylene glycol to the refined DMT is 4: 1. after the ester exchange reaction is finished, adding 220ppm of ethylene glycol antimony, controlling the temperature at 230 ℃, adding a composite additive (comprising 1.4 wt% of cerium dioxide and 1.0 wt% of titanium dioxide in terms of the mass of refined DMT), continuously heating to 250 ℃ after the addition is finished, switching to a polycondensation system, starting vacuumizing, carrying out the polycondensation reaction in a vacuum state, obtaining a polyester melt under the vacuum degree of 25Pa when the temperature reaches 285 ℃, and carrying out cooling and granulation to obtain the anti-UV regenerated polyester chip. And spinning and weaving the regenerated polyester chips to respectively obtain polyester fibers (spun yarns) and functional polyester fabrics.
Example 4 preparation and application of anti-UV recycled polyester chip
Adding ethylene glycol into a polymerization kettle, starting a stirrer (the rotating speed is 30r/min), raising the reaction temperature to 160 ℃, removing water, then adding refined DMT into the polymerization kettle, raising the temperature to 210 ℃, and carrying out ester exchange reaction for 3h under the normal pressure state to generate BHET, wherein the molar ratio of the ethylene glycol to the refined DMT is 3.5: 1. after the ester exchange reaction is finished, 230ppm of ethylene glycol antimony is added, the temperature is controlled at 230 ℃, a composite additive (comprising 1.2 wt% of titanium dioxide and 1.2 wt% of cerium dioxide in terms of the mass percentage of refined DMT) is added, after the addition is finished, the temperature is continuously raised to 250 ℃, a polycondensation system is switched to start vacuumizing, the polycondensation reaction is carried out under the vacuum state, when the temperature reaches 290 ℃, the vacuum degree is 35Pa, the reaction time is 1.5h, the stirring speed is 30r/min, a polyester melt is obtained, and the anti-UV regeneration polyester chip is obtained through cooling and granulation. And spinning and weaving the regenerated polyester chips to respectively obtain polyester fibers (spun yarns) and functional polyester fabrics.
Example 5 preparation and application of anti-UV recycled polyester chip
Adding ethylene glycol into a polymerization kettle, starting a stirrer (the rotating speed is 30r/min), raising the reaction temperature to 160 ℃, removing water, then adding refined DMT into the polymerization kettle, raising the temperature to 210 ℃, and carrying out ester exchange reaction for 3h under the normal pressure state to generate BHET, wherein the molar ratio of the ethylene glycol to the refined DMT is 2.5: 1. after the ester exchange reaction is finished, adding 240ppm of ethylene glycol antimony, controlling the temperature at 230 ℃, adding a composite additive (comprising 1.0 wt% of cerium dioxide and 1.4 wt% of titanium dioxide in terms of the mass percentage of refined DMT), continuously heating to 250 ℃ after the addition is finished, switching to a polycondensation system, starting to vacuumize, carrying out the polycondensation reaction in a vacuum state, obtaining a polyester melt when the temperature reaches 288 ℃, keeping the vacuum degree at 20Pa, keeping the reaction time at 2h, and stirring at the rotating speed of 60r/min, cooling and granulating to obtain the anti-UV regenerated polyester chip. And spinning and weaving the regenerated polyester chips to respectively obtain polyester fibers (spun yarns) and functional polyester fabrics.
Example 6 preparation and application of anti-UV recycled polyester chip
Adding ethylene glycol into a polymerization kettle, starting a stirrer (the rotating speed is 180r/min), raising the reaction temperature to 160 ℃, removing water, then adding the refined DMT into the polymerization kettle, raising the temperature to 210 ℃, and carrying out ester exchange reaction for 3 hours under the normal pressure state to generate BHET, wherein the molar ratio of the ethylene glycol to the refined DMT is 3: 1. After the ester exchange reaction is finished, adding 250ppm of ethylene glycol antimony, controlling the temperature at 230 ℃, adding a composite additive (comprising 0.8 wt% of cerium dioxide and 1.6 wt% of titanium dioxide in terms of the mass percentage of refined DMT), continuously heating to 250 ℃ after the addition is finished, switching to a polycondensation system, starting to vacuumize, carrying out the polycondensation reaction in a vacuum state, obtaining a polyester melt when the temperature reaches 290 ℃, keeping the vacuum degree at 33Pa, keeping the reaction time at 3h, and stirring at the rotating speed of 100r/min, cooling and granulating to obtain the anti-UV regenerated polyester chip. And spinning and weaving the regenerated polyester chips to respectively obtain polyester fibers (spun yarns) and functional polyester fabrics.
Comparative example 1
The raw materials, the amounts and the preparation method of the comparative example are the same as those of example 1, except that the complex additive is not added.
Comparative example 2
The raw materials, amounts, and preparation methods of this comparative example were the same as in example 1, except that the composite additive was replaced with 2.4 wt% titanium dioxide (based on the mass of purified DMT).
Examples of the experiments
The polyester fibers and the polyester fabrics provided in examples 1 to 6 and comparative examples 1 to 2 were subjected to performance tests, and the test results are shown in table 1.
(1) Testing the breaking strength and the breaking elongation by adopting a GB/T14344-2008 chemical fiber filament tensile property test method;
(2) testing the viscosity by using a black viscometer according to the testing method in GB/T14189-2008;
(3) according to GB/T18830-2009-evaluation standards of ultraviolet resistance performance of textiles, 5 points are taken at different positions of each sample, the transmittance (UVA and UVB) of the sample to ultraviolet light with the wavelength of 200-400 nm and an ultraviolet resistance coefficient UPF are tested, and the average value is taken; washing with clean water with the same parameters for 100 times, comparing the ultraviolet transmittance (UVA, UVB) and ultraviolet protection coefficient (UPF) of each group after washing, taking 5 points at different positions for testing, and taking an average value.
Table 1:
Figure BDA0003575278770000091
it should be noted that, although the above embodiments have been described herein, the invention is not limited thereto. Therefore, based on the innovative concepts of the present invention, the technical solutions of the present invention can be directly or indirectly applied to other related technical fields by changing and modifying the embodiments described herein or by using the equivalent structure or equivalent flow chart of the content of the present invention, and are included in the scope of the patent protection of the present invention.

Claims (10)

1. The preparation method of the anti-UV recycled polyester chip is characterized by comprising the following steps:
s0, preparation of the composite additive: mixing cerium dioxide powder and titanium dioxide powder, and drying to obtain a composite additive for later use;
s1, alcoholysis: carrying out alcoholysis reaction on recycled PET (polyethylene terephthalate) polyester serving as a raw material under the action of dihydric alcohol and an alcoholysis catalyst to obtain crude BHET (BHET), and rectifying and purifying the crude BHET to obtain refined BHET;
s2, ester exchange: adding methanol into refined BHET, carrying out ester exchange reaction under the action of potassium carbonate catalyst to obtain crude DMT, and rectifying and purifying the crude DMT to obtain refined DMT;
s3, polymerization: and sequentially adding ethylene glycol, ethylene glycol antimony and the composite additive into the refined DMT for polymerization reaction to obtain a polymer melt, and casting and dicing the polymer melt to obtain the anti-UV regenerated polyester chip.
2. The production method according to claim 1, wherein in step S0, the mixing mass ratio of the cerium oxide powder to the titanium dioxide powder is 1:2 to 3: 1.
3. The method of claim 1, wherein the amount of the composite additive used in step S3 is 1 to 3% by mass of the purified DMT.
4. The method according to claim 1, wherein in step S3, the molar ratio of ethylene glycol to the purified DMT is 2: 1-4: 1.
5. the method according to claim 1, wherein the ethylene glycol antimony is added in an amount of 200 to 250ppm based on the total mass of the purified DMT in step S3.
6. The method of claim 1, wherein the polymerization reaction is carried out under reaction conditions comprising:
the reaction temperature is 160-300 ℃, the reaction time is 4.5-7 h, the vacuum degree is 10-35 Pa, and the stirring speed is 0-200 r/min.
7. The method according to claim 1, wherein in step S1, the diol is one or more selected from the group consisting of diethylene glycol, propylene glycol, and ethylene glycol.
8. The method of claim 1, wherein in step S1, the alcoholysis catalyst is selected from the group consisting of zinc oxide, tin chloride, and zinc acetate.
9. An anti-UV recycled polyester chip, which is prepared by the preparation method of any one of claims 1 to 8.
10. Use of the UV resistant recycled polyester chip of claim 9 for the preparation of fibers or fabrics.
CN202210342327.1A 2022-03-31 2022-03-31 anti-UV (ultraviolet) regenerated polyester chip and preparation method and application thereof Pending CN114644752A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210342327.1A CN114644752A (en) 2022-03-31 2022-03-31 anti-UV (ultraviolet) regenerated polyester chip and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210342327.1A CN114644752A (en) 2022-03-31 2022-03-31 anti-UV (ultraviolet) regenerated polyester chip and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN114644752A true CN114644752A (en) 2022-06-21

Family

ID=81996474

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210342327.1A Pending CN114644752A (en) 2022-03-31 2022-03-31 anti-UV (ultraviolet) regenerated polyester chip and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114644752A (en)

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1471110A1 (en) * 2003-04-23 2004-10-27 Nan Ya Plastics Corporation Polyester composition reducing ultraviolet light penetration and a polyester bottle manufactured from said polyester composition
CN101186746A (en) * 2006-11-15 2008-05-28 东丽纤维研究所（中国）有限公司 Ultraviolet light resistant polyester and preparation method thereof
CN101377024A (en) * 2007-08-28 2009-03-04 浙江恒逸集团有限公司 Anti-ultraviolet polyester fiber and producing method thereof
US20090099288A1 (en) * 2006-03-09 2009-04-16 Michael Berkei Stabilization of organic polymers against free radicals
CN101928445A (en) * 2009-06-23 2010-12-29 东丽纤维研究所（中国）有限公司 Uvioresistant polyester and application thereof
KR20120133549A (en) * 2011-05-31 2012-12-11 웅진케미칼 주식회사 Recycled polyester filament having infrared ray and ultraviolet ray shielding effect and low melting property
CN103451766A (en) * 2013-08-15 2013-12-18 苏州龙杰特种纤维股份有限公司 Polyester fiber containing anti-ultraviolet nanoparticles and production method thereof
CN107793560A (en) * 2017-09-18 2018-03-13 浙江理工大学 A kind of method that Waste Polyester alcoholysis method prepares regeneration high-contraction polyester
CN110818886A (en) * 2019-12-13 2020-02-21 中国科学院过程工程研究所 Method for preparing regenerated food-grade PET polyester from waste PET polyester
CN110951222A (en) * 2019-12-06 2020-04-03 江苏垶恒复合材料有限公司 High-impact-resistance regenerated PET material and preparation method thereof
CN111138641A (en) * 2018-11-02 2020-05-12 中国石油化工股份有限公司 Method for preparing bottle-grade slices by recycling waste polyester bottles
CN112011179A (en) * 2020-08-11 2020-12-01 成丹丹 Titanium dioxide-based ultraviolet-resistant nylon 66 resin and preparation method thereof
CN112646135A (en) * 2020-12-10 2021-04-13 北京服装学院 Method for continuously preparing spinnable colorless regenerated polyester from colored waste polyester textiles

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1471110A1 (en) * 2003-04-23 2004-10-27 Nan Ya Plastics Corporation Polyester composition reducing ultraviolet light penetration and a polyester bottle manufactured from said polyester composition
US20090099288A1 (en) * 2006-03-09 2009-04-16 Michael Berkei Stabilization of organic polymers against free radicals
CN101186746A (en) * 2006-11-15 2008-05-28 东丽纤维研究所（中国）有限公司 Ultraviolet light resistant polyester and preparation method thereof
CN101377024A (en) * 2007-08-28 2009-03-04 浙江恒逸集团有限公司 Anti-ultraviolet polyester fiber and producing method thereof
CN101928445A (en) * 2009-06-23 2010-12-29 东丽纤维研究所（中国）有限公司 Uvioresistant polyester and application thereof
KR20120133549A (en) * 2011-05-31 2012-12-11 웅진케미칼 주식회사 Recycled polyester filament having infrared ray and ultraviolet ray shielding effect and low melting property
CN103451766A (en) * 2013-08-15 2013-12-18 苏州龙杰特种纤维股份有限公司 Polyester fiber containing anti-ultraviolet nanoparticles and production method thereof
CN107793560A (en) * 2017-09-18 2018-03-13 浙江理工大学 A kind of method that Waste Polyester alcoholysis method prepares regeneration high-contraction polyester
CN111138641A (en) * 2018-11-02 2020-05-12 中国石油化工股份有限公司 Method for preparing bottle-grade slices by recycling waste polyester bottles
CN110951222A (en) * 2019-12-06 2020-04-03 江苏垶恒复合材料有限公司 High-impact-resistance regenerated PET material and preparation method thereof
CN110818886A (en) * 2019-12-13 2020-02-21 中国科学院过程工程研究所 Method for preparing regenerated food-grade PET polyester from waste PET polyester
CN112011179A (en) * 2020-08-11 2020-12-01 成丹丹 Titanium dioxide-based ultraviolet-resistant nylon 66 resin and preparation method thereof
CN112646135A (en) * 2020-12-10 2021-04-13 北京服装学院 Method for continuously preparing spinnable colorless regenerated polyester from colored waste polyester textiles

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
刘连利;赵志成;: "二氧化铈/氧化铝纳米复合粉体的制备及抗紫外线性能研究", 无机盐工业, no. 03, pages 17 - 19 *
张世明;罗春明;: "抗紫外线聚酯薄膜的研究", 绝缘材料, no. 05, pages 3 - 6 *
闫鹏飞;朱艳;: "纳米材料在抗紫外线功能纺织品中的应用研究进展", 山东化工, no. 11, pages 427 - 428 *

Similar Documents

Publication Publication Date Title
CN111088545B (en) Preparation method of cationic dye dyeable regenerated cotton-like polyester fiber
JP6963040B2 (en) Method for manufacturing graphene composite material
CA2420958C (en) Polyester polymerization catalyst and polyester produced by using the same and production method of polyester
JP2005320533A (en) Cationic dye-dyeable and flame-retardant polyester polymer and its manufacturing method
CN113512276B (en) Recycled polyester particles and preparation method thereof
CN110273197A (en) A kind of regeneration coloured silk yarn and preparation method thereof of discarded terylene textile fabric production
CN114524924A (en) Regenerated polyester and preparation method and application thereof
CN108179499B (en) Preparation process of regenerated polyester high-modulus low-shrinkage fiber
KR101197724B1 (en) Recycled polyester yarn using waste polyester and method thereof
CN114644752A (en) anti-UV (ultraviolet) regenerated polyester chip and preparation method and application thereof
CN115726057A (en) Regenerated low-melting-point polyester composite fiber with ultraviolet shielding function and preparation method thereof
CN115896976A (en) Regenerated low-melting-point polyester composite fiber with flame retardant function and preparation method thereof
CN114606591A (en) anti-UV (ultraviolet) regenerated polyester chip and preparation method and application thereof
KR20120033767A (en) Recycled polyester polymer and method for manufacturing the same, spun bond nonwoven fabric using the same
CN111321485A (en) Preparation method of regenerated polyester wool tops
KR20110118445A (en) Antibacterial fire retardancy recycled polyester filament for interior and method thereof
Bajaj et al. Reuse of polymer and fibre waste
CN110818943A (en) Method for preparing waste polyester particles containing micropores by gas foaming
CN114230858B (en) Ocean recovery fabric and preparation method thereof
CN111978526B (en) Preparation method of cation dyeable polyester master batch with high sulfonate content and high fluidity
CN111621004B (en) High-toughness biodegradable polyester and preparation method and application thereof
JP2005206760A (en) Method for producing polyester resin
CN114621565B (en) Processing technology for producing packing belt from nano modified PET bottle reclaimed materials
WO2024196205A1 (en) Manufacturing method of recycled polyester yarn, using waste textile
KR101240340B1 (en) Fire retardancy recycled polyester filament for interior and method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20220621

WD01 Invention patent application deemed withdrawn after publication