CN116656093A - Organic/inorganic composite ultraviolet-resistant extinction polyester master batch, preparation method and application thereof - Google Patents
Organic/inorganic composite ultraviolet-resistant extinction polyester master batch, preparation method and application thereof Download PDFInfo
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- CN116656093A CN116656093A CN202310367217.5A CN202310367217A CN116656093A CN 116656093 A CN116656093 A CN 116656093A CN 202310367217 A CN202310367217 A CN 202310367217A CN 116656093 A CN116656093 A CN 116656093A
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- 239000002131 composite material Substances 0.000 title claims abstract description 101
- 229920000728 polyester Polymers 0.000 title claims abstract description 99
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 61
- 230000008033 biological extinction Effects 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 56
- 239000002250 absorbent Substances 0.000 claims abstract description 34
- 230000002745 absorbent Effects 0.000 claims abstract description 33
- 239000007822 coupling agent Substances 0.000 claims abstract description 32
- 239000011159 matrix material Substances 0.000 claims abstract description 30
- 239000002086 nanomaterial Substances 0.000 claims abstract description 30
- 239000003999 initiator Substances 0.000 claims abstract description 29
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 25
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 25
- 239000004611 light stabiliser Substances 0.000 claims abstract description 25
- 239000002270 dispersing agent Substances 0.000 claims abstract description 23
- 239000011858 nanopowder Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000002244 precipitate Substances 0.000 claims description 22
- 239000004408 titanium dioxide Substances 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 14
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 14
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 14
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- -1 β-methoxyethoxy Chemical group 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 9
- VCYCUECVHJJFIQ-UHFFFAOYSA-N 2-[3-(benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 VCYCUECVHJJFIQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012965 benzophenone Substances 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- HZDPJHOWPIVWMR-UHFFFAOYSA-N benzyl n-(1-oxo-3-phenylpropan-2-yl)carbamate Chemical group C=1C=CC=CC=1COC(=O)NC(C=O)CC1=CC=CC=C1 HZDPJHOWPIVWMR-UHFFFAOYSA-N 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical class CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 7
- 230000006750 UV protection Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000009987 spinning Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000011812 mixed powder Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/132—Phenols containing keto groups, e.g. benzophenones
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
-
- 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
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The application relates to the technical field of high polymer materials, and discloses an organic/inorganic composite ultraviolet-resistant extinction polyester master batch, a preparation method and application thereof, wherein the master batch comprises the following components in parts by mass: 30-70 parts of polyester matrix, 30-65 parts of organic/inorganic composite anti-ultraviolet nano powder, 0.01-1.0 part of light stabilizer, 0.05-2.0 parts of antioxidant and 0.2-2.0 parts of dispersing agent; the organic/inorganic composite anti-ultraviolet nanometer material is an anti-ultraviolet material formed by compositing an inorganic anti-ultraviolet material and an organic ultraviolet absorbent through a coupling agent and an initiator, and the material is prepared from raw materials in a specific proportion, has multiple anti-ultraviolet effects, and can efficiently absorb ultraviolet rays; the preparation method has the advantages of simple process and low cost, and the organic/inorganic composite ultraviolet-resistant nano material has good dispersibility when being added into the polyester matrix, and the prepared organic/inorganic composite ultraviolet-resistant extinction polyester master batch has good mechanical property and high ultraviolet resistance when being applied to the fiber obtained in spinning.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to an organic/inorganic composite ultraviolet-resistant extinction polyester master batch, a preparation method and application thereof.
Background
In order to solve the above problems, many anti-ultraviolet materials have been developed in the prior art, which mainly include inorganic anti-ultraviolet materials and organic ultraviolet absorbers, wherein the inorganic anti-ultraviolet materials can reflect and refract ultraviolet rays, so as to weaken and even isolate the damage of ultraviolet rays to the materials, and chemical groups in the organic ultraviolet absorbers can absorb ultraviolet rays, so that the effect that the materials are not damaged by ultraviolet rays is achieved.
The synthetic fiber is made of organic polyester, and after the organic polyester fiber is irradiated by ultraviolet rays, chemical bonds among fiber molecules can be broken, so that the problems of ageing, breakage and the like of the fiber are caused. In the prior art, organic polyester is modified by an anti-ultraviolet material, so that the finally prepared synthetic fiber has anti-ultraviolet performance. The application discloses a nano titanium nitride ultraviolet-resistant polyester fiber, which is prepared by carrying out slice blending on inorganic nano titanium nitride ultraviolet-resistant master batch and polyester, so that the polyester fiber has ultraviolet-resistant performance. And as disclosed in publication No. CN102031580A, the method is to blend inorganic anti-ultraviolet master batch and organic anti-ultraviolet additive into polyester chips, so that the anti-ultraviolet performance of the polyester fiber is improved.
The inorganic anti-ultraviolet material and the organic anti-ultraviolet material adopted in the prior art are used independently, and the anti-ultraviolet mode is single; the damage of ultraviolet rays to the polyester material cannot be shielded efficiently. In addition, in actual production, when two materials are added independently, the two materials are difficult to disperse, and the problems of complex process and high cost exist.
Disclosure of Invention
In order to overcome the problems in the prior art, the application provides an organic/inorganic composite ultraviolet-resistant extinction polyester master batch, a preparation method and application thereof, wherein the master batch comprises organic/inorganic composite ultraviolet-resistant nano powder, the organic/inorganic composite ultraviolet-resistant nano powder is an ultraviolet-resistant material formed by compounding an inorganic ultraviolet-resistant material and an organic ultraviolet absorbent through a coupling agent and an initiator, and the material is prepared from raw materials in a specific proportion and has multiple ultraviolet-resistant effects; in addition, the material is added into polyester to have little influence on the mechanical properties of polyester fibers, and has simple process and low cost.
The specific technical scheme of the application is as follows:
the organic/inorganic composite ultraviolet-resistant extinction polyester master batch comprises the following components in parts by mass:
30-70 parts of polyester matrix;
30-65 parts of organic/inorganic composite ultraviolet-resistant nano material;
0.01 to 1.0 part of light stabilizer;
0.05 to 2.0 portions of antioxidant;
0.2 to 2.0 portions of dispersing agent.
The organic/inorganic composite uvioresistant nanomaterial comprises the following preparation steps:
the weight ratio is 90-98: 0.2 to 3.0:2.0 to 5.0:0.1 to 2.0 percent, inorganic anti-ultraviolet material, coupling agent, ultraviolet absorber and initiator are reacted to prepare the organic/inorganic composite anti-ultraviolet nano material.
Preferably, the inorganic anti-ultraviolet material is titanium dioxide, and the particle size of the titanium dioxide is 100-500 nm.
Preferably, the coupling agent is selected from one or more of vinyltrimethoxysilane (A-171), vinyltris (beta-methoxyethoxy) (A-172), gamma- (methacryloyloxy) propyltrimethoxysilane (A-174) and vinyltriethoxysilane (A-151).
Preferably, the ultraviolet absorber is selected from one or more of 2- (2 '-hydroxy-5' -methacryloyloxyethyl phenyl) -2H-benzotriazole, 2-hydroxy 4- (3-methacrylate-2-hydroxypropoxy) benzophenone and 2-hydroxy-4-methacrylate-based benzophenone.
Preferably, the initiator is selected from Azobisisobutyronitrile (AIBN) and/or Benzoyl Peroxide (BPO).
The application provides an organic/inorganic composite ultraviolet-resistant extinction polyester master batch, which comprises an organic/inorganic composite ultraviolet-resistant nano material, wherein the material is a special structural material prepared from an inorganic ultraviolet-resistant material, a coupling agent, an ultraviolet absorber and an initiator in a specific proportion; one end of the coupling agent contains double bonds, the other end of the coupling agent contains silane groups, the double bonds of the coupling agent can react with the ultraviolet absorbent with double bonds under the action of an initiator, and the silane groups of the coupling agent can carry out crosslinking reaction with hydroxyl groups on the surface of the inorganic ultraviolet-resistant material, so that the ultraviolet absorbent is modified on the surface of the inorganic ultraviolet-resistant absorbent and a special structure with the inorganic ultraviolet absorbent as a core and the ultraviolet-resistant absorbent as a shell is formed. In the using process of the organic/inorganic composite ultraviolet-resistant extinction polyester master batch, ultraviolet firstly needs to pass through a cross-linked net shell formed by an ultraviolet-resistant absorbent, one part of ultraviolet is absorbed by the ultraviolet absorbent, the other part of ultraviolet is irradiated onto an inorganic ultraviolet absorbent core through a gap of a net, the inorganic ultraviolet-resistant material core reflects the ultraviolet back into the ultraviolet-resistant absorbent cross-linked net shell through reflection and is absorbed by the ultraviolet absorbent, the ultraviolet can be efficiently absorbed through multiple ultraviolet-resistant actions, the ultraviolet is prevented from overflowing, and the damage of the ultraviolet to the polyester master batch can be extremely efficiently shielded.
Further, the reaction steps are as follows: the inorganic anti-ultraviolet material is placed in an organic solvent to be heated, stirred and dispersed in an ultrasonic way to prepare a mixture, the heating temperature is 40-80 ℃, then the coupling agent, the ultraviolet absorbent and the initiator are injected into the mixture to react for 2-6 hours, after the reaction is finished, the precipitate is removed by centrifugation, and then the precipitate is cleaned, dried and ground to prepare the organic/inorganic composite anti-ultraviolet nano material.
The preparation method of the organic/inorganic composite ultraviolet-resistant extinction polyester master batch comprises the following preparation steps:
and mixing the polyester matrix, the organic/inorganic composite ultraviolet-resistant nano material, the light stabilizer, the antioxidant and the dispersing agent, and extruding the mixture to prepare the organic/inorganic composite ultraviolet-resistant extinction polyester master batch.
Preferably, the polyester matrix is selected from one or more of polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT) and polybutylene terephthalate (PBT);
preferably, the light stabilizer is 2, 2-thiobis (4-tert-octylphenol) n-butylamine nickel salt (UV-1084);
preferably, the antioxidant is selected from pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1010) and/or tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168);
preferably, the dispersing agent is one or more selected from white oil, calcium stearate, low-density homo-wax, ethylene acrylic acid copolymer and maleic anhydride graft.
Further, the mixing conditions include: the mixing rotating speed is 1000-3000 r/min, and the mixing time is 20-40 min; the mixing conditions include: the mixing extrusion temperature is 210-250 ℃, and the mixing extrusion rotating speed is 300-600 r/min.
The application also provides a preparation method of the organic/inorganic composite ultraviolet-resistant extinction polyester master batch, which has simple preparation process and low cost. And the organic/inorganic composite ultraviolet-resistant nano material has good dispersibility when being added into a polyester matrix, and the prepared organic/inorganic composite ultraviolet-resistant extinction polyester master batch has good mechanical property and high ultraviolet resistance.
An organic/inorganic composite anti-ultraviolet extinction polyester master batch or an application of the preparation method of the organic/inorganic composite anti-ultraviolet extinction polyester master batch.
Compared with the prior art, the application has the following technical effects:
(1) The organic/inorganic composite ultraviolet resistant nanometer material is an ultraviolet resistant material formed by compositing an inorganic ultraviolet resistant material and an organic ultraviolet absorbent through a coupling agent and an initiator, is prepared from raw materials in a specific proportion, has multiple ultraviolet resistant effects, and can efficiently absorb ultraviolet rays;
(2) The preparation method provided by the application has the advantages of simple process and low cost, and the organic/inorganic composite ultraviolet-resistant nano material added into the polyester matrix has good dispersibility, and the prepared organic/inorganic composite ultraviolet-resistant extinction polyester master batch has good mechanical property and high ultraviolet resistance.
Detailed Description
The application is further described below with reference to examples.
Example 1:
the organic/inorganic composite ultraviolet-resistant extinction polyester master batch comprises the following components in parts by mass:
60 parts of polyester matrix, wherein the polyester matrix is PET (polyethylene terephthalate) slices;
35 parts of organic/inorganic composite anti-ultraviolet nano powder;
0.2 part of light stabilizer, wherein the light stabilizer is UV-1084;
0.3 part of antioxidant, wherein the antioxidant is antioxidant 1010;
2.0 parts of dispersing agent which is white oil;
the organic/inorganic composite uvioresistant nanomaterial comprises the following preparation steps:
dispersing inorganic anti-ultraviolet material in organic solvent, ultrasonic dispersing for 30min, heating and stirring at 60 ℃, and then adding coupling agent, organic ultraviolet absorbent and initiator respectively; after reacting for 4 hours, centrifugally taking out the precipitate, washing the precipitate with water and alcohol, drying the precipitate for 24 hours at 80 ℃ in a vacuum oven, and finally grinding to obtain the organic/inorganic composite ultraviolet-resistant nano material;
the mass ratio of the inorganic anti-ultraviolet material to the coupling agent to the organic ultraviolet absorbent to the initiator is 97:0.2:2.0:0.8;
the inorganic anti-ultraviolet material is titanium dioxide powder, and the particle size of the titanium dioxide powder is 200nm;
the organic solvent is ethanol;
the coupling agent is A-172;
the organic ultraviolet absorbent is 2- (2 '-hydroxy-5' -methacryloyloxyethyl phenyl) -2H-benzotriazole;
the initiator is AIBN;
the preparation method of the organic/inorganic composite ultraviolet-resistant extinction polyester master batch comprises the following preparation steps:
according to the formula proportion of the organic/inorganic composite ultraviolet-resistant extinction polyester master batch, adding the dried polyester matrix, the organic/inorganic composite ultraviolet-resistant nano powder, the light stabilizer, the antioxidant and the dispersing agent into a high-speed mixer for mixing, and conveying the obtained mixed powder into a double screw by a feeding system for dispersing, mixing, extruding and granulating to obtain the organic/inorganic composite ultraviolet-resistant extinction polyester master batch; the rotating speed of the high-speed mixer is 2000r/min, and the mixing time is 30min; the temperature of the twin-screw extruder was 220℃and the rotational speed was 500r/min.
Example 2:
the organic/inorganic composite ultraviolet-resistant extinction polyester master batch comprises the following components in parts by mass:
65 parts of polyester matrix, wherein the polyester matrix is a PET (polyethylene terephthalate) slice and a PBT slice, and the mass ratio of the PET slice to the PBT slice is 8:2; 30 parts of organic/inorganic composite anti-ultraviolet nano powder;
0.5 part of light stabilizer, wherein the light stabilizer is UV-1084;
0.5 part of antioxidant, wherein the antioxidant is antioxidant 1010 and antioxidant 168, and the mass ratio of the antioxidant 1010 to the antioxidant 168 is 1:1;
1.0 part of dispersing agent, wherein the dispersing agent is ethylene acrylic acid copolymer;
the organic/inorganic composite uvioresistant nanomaterial comprises the following preparation steps:
dispersing inorganic anti-ultraviolet material in organic solvent, ultrasonic dispersing for 30min, heating and stirring at 60 ℃, and then adding coupling agent, organic ultraviolet absorbent and initiator respectively; after reacting for 4 hours, centrifugally taking out the precipitate, washing the precipitate with water and alcohol, drying the precipitate for 24 hours at 80 ℃ in a vacuum oven, and finally grinding to obtain the organic/inorganic composite ultraviolet-resistant nano material;
the mass ratio of the inorganic anti-ultraviolet material to the coupling agent to the organic ultraviolet absorbent to the initiator is 95:2.0:2.0:1.0;
the inorganic anti-ultraviolet material is titanium dioxide powder, and the particle size of the titanium dioxide powder is 200nm;
the organic solvent is ethanol; the coupling agent is A-172;
the organic ultraviolet absorbent is 2-hydroxy 4- (3-methacrylate-2-hydroxy propoxy) benzophenone;
the initiator is AIBN;
the preparation method of the organic/inorganic composite ultraviolet-resistant extinction polyester master batch comprises the following preparation steps:
according to the formula proportion of the organic/inorganic composite ultraviolet-resistant extinction polyester master batch, adding the dried polyester matrix, the organic/inorganic composite ultraviolet-resistant nano powder, the light stabilizer, the antioxidant and the dispersing agent into a high-speed mixer for mixing, and conveying the obtained mixed powder into a double screw by a feeding system for dispersing, mixing, extruding and granulating to obtain the organic/inorganic composite ultraviolet-resistant extinction polyester master batch; the rotating speed of the high-speed mixer is 2500r/min, and the mixing time is 40min; the temperature of the twin-screw extruder was 215℃and the rotational speed was 400r/min.
Example 3:
the organic/inorganic composite ultraviolet-resistant extinction polyester master batch comprises the following components in parts by mass:
50 parts of a polyester matrix, wherein the polyester matrix is PTT slices;
40 parts of organic/inorganic composite anti-ultraviolet nano powder;
1.0 part of light stabilizer, wherein the light stabilizer is UV-1084;
1.0 part of antioxidant, wherein the antioxidant is antioxidant 1010 and antioxidant 168, and the mass ratio of the antioxidant 1010 to the antioxidant 168 is 1:2;
3.0 parts of a dispersing agent, wherein the dispersing agent is low-density homo-wax;
the organic/inorganic composite uvioresistant nanomaterial comprises the following preparation steps:
dispersing inorganic anti-ultraviolet material in organic solvent, ultrasonic dispersing for 30min, heating and stirring at 40 ℃, and then adding coupling agent, organic ultraviolet absorbent and initiator respectively; after reacting for 6 hours, centrifugally taking out the precipitate, washing the precipitate with water and alcohol, drying the precipitate for 24 hours at 80 ℃ in a vacuum oven, and finally grinding to obtain the organic/inorganic composite ultraviolet-resistant nano material;
the mass ratio of the inorganic anti-ultraviolet material to the coupling agent to the organic ultraviolet absorbent to the initiator is 95:2.0:2.0:1.0;
the inorganic anti-ultraviolet material is titanium dioxide powder, and the particle size of the titanium dioxide powder is 300nm;
the organic solvent is ethanol; the coupling agent is A-172;
the organic ultraviolet absorbent is 2- (2 '-hydroxy-5' -methacryloyloxyethyl phenyl) -2H-benzotriazole;
the initiator is BPO;
the preparation method of the organic/inorganic composite ultraviolet-resistant extinction polyester master batch comprises the following preparation steps:
according to the formula proportion of the organic/inorganic composite ultraviolet-resistant extinction polyester master batch, adding the dried polyester matrix, the organic/inorganic composite ultraviolet-resistant nano powder, the light stabilizer, the antioxidant and the dispersing agent into a high-speed mixer for mixing, and conveying the obtained mixed powder into a double screw by a feeding system for dispersing, mixing, extruding and granulating to obtain the organic/inorganic composite ultraviolet-resistant extinction polyester master batch; the rotating speed of the high-speed mixer is 2000r/min, and the mixing time is 30min; the temperature of the twin-screw extruder was 215℃and the rotational speed was 500r/min.
Example 4:
the organic/inorganic composite ultraviolet-resistant extinction polyester master batch comprises the following components in parts by mass:
50 parts of a polyester matrix, wherein the polyester matrix is PET (polyethylene terephthalate) slices;
40 parts of organic/inorganic composite anti-ultraviolet nano powder;
1.0 part of light stabilizer, wherein the light stabilizer is UV-1084;
1.0 part of antioxidant, wherein the antioxidant is antioxidant 1010 and antioxidant 168, and the mass ratio of the antioxidant 1010 to the antioxidant 168 is 1:2;
3.0 parts of dispersing agent, wherein the dispersing agent is low-density homo-wax and ethylene acrylic acid copolymer, and the mass ratio of the low-density homo-wax to the ethylene acrylic acid copolymer is 1:1;
the organic/inorganic composite uvioresistant nanomaterial comprises the following preparation steps:
dispersing inorganic anti-ultraviolet material in organic solvent, ultrasonic dispersing for 30min, heating and stirring at 60 ℃, and then adding coupling agent, organic ultraviolet absorbent and initiator respectively; after reacting for 4 hours, centrifugally taking out the precipitate, washing the precipitate with water and alcohol, drying the precipitate for 24 hours at 80 ℃ in a vacuum oven, and finally grinding to obtain the organic/inorganic composite ultraviolet-resistant nano material;
the mass ratio of the inorganic anti-ultraviolet material to the coupling agent to the organic ultraviolet absorbent to the initiator is 94:2.0:3.0:1.0;
the inorganic anti-ultraviolet material is titanium dioxide powder, and the particle size of the titanium dioxide powder is 300nm;
the organic solvent is ethanol;
the coupling agent is A-172;
the organic ultraviolet absorbent is 2-hydroxy-4-methyl acrylate benzophenone;
the initiator is AIBN;
the preparation method of the organic/inorganic composite ultraviolet-resistant extinction polyester master batch comprises the following preparation steps:
according to the formula proportion of the organic/inorganic composite ultraviolet-resistant extinction polyester master batch, adding the dried polyester matrix, the organic/inorganic composite ultraviolet-resistant nano powder, the light stabilizer, the antioxidant and the dispersing agent into a high-speed mixer for mixing, and conveying the obtained mixed powder into a double screw by a feeding system for dispersing, mixing, extruding and granulating to obtain the organic/inorganic composite ultraviolet-resistant extinction polyester master batch; the rotating speed of the high-speed mixer is 2000r/min, and the mixing time is 40min; the temperature of the twin-screw extruder was 220℃and the rotational speed was 400r/min.
Example 5:
the organic/inorganic composite ultraviolet-resistant extinction polyester master batch comprises the following components in parts by mass:
50 parts of a polyester matrix, wherein the polyester matrix is a PET (polyethylene terephthalate) slice and a PBT slice, and the mass ratio of the PET slice to the PBT slice is 8:2; 40 parts of organic/inorganic composite anti-ultraviolet nano powder;
1.0 part of light stabilizer, wherein the light stabilizer is UV-1084;
1.0 part of antioxidant, wherein the antioxidant is antioxidant 1010 and antioxidant 168, and the mass ratio of the antioxidant 1010 to the antioxidant 168 is 1:1;
3.0 parts of dispersing agent, wherein the dispersing agent is ethylene acrylic acid copolymer and maleic anhydride graft, and the mass ratio of the ethylene acrylic acid copolymer to the maleic anhydride graft is 2:1;
the organic/inorganic composite uvioresistant nanomaterial comprises the following preparation steps:
dispersing inorganic anti-ultraviolet material in organic solvent, ultrasonic dispersing for 30min, heating and stirring at 80 ℃, and then adding coupling agent, organic ultraviolet absorbent and initiator respectively; after reacting for 2 hours, centrifugally taking out the precipitate, washing the precipitate with water and alcohol, drying the precipitate for 24 hours at 80 ℃ in a vacuum oven, and finally grinding to obtain the organic/inorganic composite ultraviolet-resistant nano material;
the mass ratio of the inorganic anti-ultraviolet material to the coupling agent to the organic ultraviolet absorbent to the initiator is 96:1.0:2.5:0.5;
the inorganic anti-ultraviolet material is titanium dioxide powder, and the particle size of the titanium dioxide powder is 300nm;
the organic solvent is ethanol;
the coupling agent is A-151;
the organic ultraviolet absorbent is 2- (2 '-hydroxy-5' -methacryloyloxyethyl phenyl) -2H-benzotriazole;
the initiator is BPO;
the preparation method of the organic/inorganic composite ultraviolet-resistant extinction polyester master batch comprises the following preparation steps:
according to the formula proportion of the organic/inorganic composite ultraviolet-resistant extinction polyester master batch, adding the dried polyester matrix, the organic/inorganic composite ultraviolet-resistant nano powder, the light stabilizer, the antioxidant and the dispersing agent into a high-speed mixer for mixing, and conveying the obtained mixed powder into a double screw by a feeding system for dispersing, mixing, extruding and granulating to obtain the organic/inorganic composite ultraviolet-resistant extinction polyester master batch; the rotating speed of the high-speed mixer is 3000r/min, and the mixing time is 30min; the temperature of the twin-screw extruder was 215℃and the rotational speed was 400r/min.
Example 6:
the organic/inorganic composite ultraviolet-resistant extinction polyester master batch comprises the following components in parts by mass:
50 parts of a polyester matrix, wherein the polyester matrix is PTT slices;
45 parts of organic/inorganic composite anti-ultraviolet nano powder;
1.0 part of light stabilizer, wherein the light stabilizer is UV-1084;
0.5 part of antioxidant, wherein the antioxidant is antioxidant 1010 and antioxidant 168, and the mass ratio of the antioxidant 1010 to the antioxidant 168 is 1:1;
1.0 part of dispersing agent which is maleic anhydride graft;
the organic/inorganic composite uvioresistant nanomaterial comprises the following preparation steps:
dispersing inorganic anti-ultraviolet material in organic solvent, ultrasonic dispersing for 30min, heating and stirring at 80 ℃, and then adding coupling agent, organic ultraviolet absorbent and initiator respectively; after reacting for 2 hours, centrifugally taking out the precipitate, washing the precipitate with water and alcohol, drying the precipitate for 24 hours at 80 ℃ in a vacuum oven, and finally grinding to obtain the organic/inorganic composite ultraviolet-resistant nano material;
the mass ratio of the inorganic anti-ultraviolet material to the coupling agent to the organic ultraviolet absorbent to the initiator is 96:1.0:2.5:0.5;
the inorganic anti-ultraviolet material is titanium dioxide powder, and the particle size of the titanium dioxide powder is 200nm;
the organic solvent is ethanol;
the coupling agent is A-171;
the organic ultraviolet absorbent is 2- (2 '-hydroxy-5' -methacryloyloxyethyl phenyl) -2H-benzotriazole;
the initiator is BPO;
the preparation method of the organic/inorganic composite ultraviolet-resistant extinction polyester master batch comprises the following preparation steps:
according to the formula proportion of the organic/inorganic composite ultraviolet-resistant extinction polyester master batch, adding the dried polyester matrix, the organic/inorganic composite ultraviolet-resistant nano powder, the light stabilizer, the antioxidant and the dispersing agent into a high-speed mixer for mixing, and conveying the obtained mixed powder into a double screw by a feeding system for dispersing, mixing, extruding and granulating to obtain the organic/inorganic composite ultraviolet-resistant extinction polyester master batch; the rotating speed of the high-speed mixer is 2000r/min, and the mixing time is 40min; the temperature of the twin-screw extruder was 220℃and the rotational speed was 500r/min.
Comparative example 1: (inorganic anti-ultraviolet Material)
Compared with example 1, the master batch formula in comparative example 1 adopts inorganic nano titanium dioxide, does not adopt organic/inorganic composite anti-ultraviolet nano powder, and has the same other conditions as in example 1.
Comparative example 2: (organic ultraviolet absorber)
In comparison with example 1, the master batch formulation of comparative example 2 uses the organic ultraviolet absorber 2- (2 '-hydroxy-5' -methacryloyloxyethyl phenyl) -2H-benzotriazole, and does not use the organic/inorganic composite uvioresistant nano powder, and the other conditions are the same as in example 1.
Comparative example 3: (mixing inorganic UV-resistant material with organic UV absorber)
Compared with example 1, the master batch formula in comparative example 3 adopts inorganic nano titanium dioxide and an organic ultraviolet absorber 2- (2 '-hydroxy-5' -methacryloyloxyethyl phenyl) -2H-benzotriazole, does not adopt organic/inorganic composite ultraviolet resistant nano powder, and is respectively added with the inorganic nano titanium dioxide and the organic ultraviolet absorber in the preparation method, and the rest conditions are the same as those in example 1.
Test case
The anti-ultraviolet polyester master batches prepared in examples 1 to 6 and comparative examples 1 to 3 are applied to polyester fiber spinning, and comprise the following steps: and (3) drying the uvioresistant polyester master batch and the conventional PET slice for 20 hours at 120 ℃, uniformly mixing according to a mass ratio of 1:22, and spinning at a spinning temperature of 260-285 ℃ to obtain the uvioresistant polyester fiber, wherein the draft multiple is controlled to be 3.5-4.5.
The ultraviolet protection value (UPF) and mechanical property (breaking strength and breaking elongation) of the prepared ultraviolet resistant polyester fiber are tested, wherein the ultraviolet protection value test step is referred to GB/T18830-2009, the mechanical property test step is referred to GB/T1040.2-2022, and the test result is shown in Table 1;
TABLE 1 UPF value and mechanical characterization of UV resistant fibers
| UPF value | Breaking strength (cN/dtex) | Elongation at break (%) | |
| Example 1 | 59.46 | 4.09 | 20.45 |
| Example 2 | 58.48 | 3.96 | 21.06 |
| Example 3 | 58.66 | 3.66 | 24.56 |
| Example 4 | 58.47 | 3.73 | 23.52 |
| Example 5 | 59.28 | 3.82 | 22.19 |
| Example 6 | 58.84 | 3.68 | 24.28 |
| Comparative example 1 | 52.58 | 4.12 | 19.13 |
| Comparative example 2 | 46.34 | 3.73 | 31.45 |
| Comparative example 3 | 58.28 | 4.05 | 20.13 |
As shown in table 1, the UPF values of examples 1 to 6 are significantly higher than those of comparative examples 1 to 2, and the UPF value of example 1 is higher than that of comparative example 3, and as can be seen from the above results, the organic/inorganic composite uv-resistant nanomaterial provided by the present application can significantly improve the uv-resistant performance of polyester fibers, and the uv-resistant performance of the composite uv-resistant nanomaterial is higher than that of a simple combination of a single uv-resistant material and a single uv-resistant material; furthermore, as can be obtained from the mechanical property results of example 1 and comparative example 3, the mechanical property of the composite uv-resistant nanomaterial is higher than that of a simple combination of single uv-resistant materials, which results because the dispersion effect of the inorganic nanomaterial and the organic uv-absorbent added respectively in the polyester matrix is lower than that of the composite uv-resistant nanomaterial in the polyester matrix; as can be obtained from the UPF values of examples 1 to 6, the proportion of the masterbatch influences the anti-uv effect and the mechanical properties of the final product fibres.
The foregoing description is only a preferred embodiment of the present application, and is not intended to limit the present application, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present application still fall within the scope of the technical solution of the present application.
Claims (10)
1. The organic/inorganic composite ultraviolet-resistant extinction polyester master batch is characterized by comprising the following components in parts by mass:
30-70 parts of a polyester matrix;
30-65 parts of organic/inorganic composite anti-ultraviolet nano powder;
0.01-1.0 part of light stabilizer;
0.05-2.0 parts of an antioxidant;
0.2-2.0 parts of dispersing agent;
the organic/inorganic composite uvioresistant nanomaterial comprises the following preparation steps:
the weight ratio of the components is 90-98: 0.2 to 3.0:2.0 to 5.0: and (0.1-2.0 g), reacting the inorganic anti-ultraviolet material, the coupling agent, the ultraviolet absorber and the initiator to prepare the organic/inorganic composite anti-ultraviolet nano material.
2. The organic/inorganic composite ultraviolet-resistant extinction polyester master batch as claimed in claim 1, wherein the inorganic ultraviolet-resistant material is titanium dioxide, and the particle size of the titanium dioxide is 100-500 nm.
3. The organic/inorganic composite ultraviolet-resistant extinction polyester master batch as claimed in claim 1, wherein said coupling agent is selected from vinyl trimethoxy silane, vinyl tri [ ]β-methoxyethoxy),γOne or more of- (methacryloxy) propyl trimethoxy silane and vinyl triethoxy silane.
4. The organic/inorganic composite ultraviolet-resistant extinction polyester masterbatch as claimed in claim 1, wherein the ultraviolet absorber is selected from one or more of 2- (2 '-hydroxy-5' -methacryloyloxyethyl phenyl) -2H-benzotriazole, 2-hydroxy 4- (3-methacrylate-2-hydroxypropoxy) benzophenone and 2-hydroxy-4-methacrylate-based benzophenone.
5. An organic/inorganic composite uv-blocking polyester masterbatch according to claim 1 wherein said initiator is selected from azobisisobutyronitrile and/or benzoyl peroxide.
6. The organic/inorganic composite ultraviolet-resistant extinction polyester masterbatch according to claim 1 or 2 or 3 or 4 or 5, characterized in that the reaction steps are: and (3) placing the inorganic anti-ultraviolet material in an organic solvent, heating, stirring, ultrasonically dispersing to prepare a mixture, heating to 40-80 ℃, injecting a coupling agent, an ultraviolet absorbent and an initiator into the mixture for reaction for 2-6 hours, centrifuging to remove precipitate after the reaction is finished, and cleaning, drying and grinding the precipitate to prepare the organic/inorganic composite anti-ultraviolet nano material.
7. A method for preparing the organic/inorganic composite ultraviolet-resistant extinction polyester master batch as claimed in any one of claims 1 to 6, which is characterized by comprising the following preparation steps:
and mixing the polyester matrix, the organic/inorganic composite ultraviolet-resistant nano material, the light stabilizer, the antioxidant and the dispersing agent, and extruding the mixture to prepare the organic/inorganic composite ultraviolet-resistant extinction polyester master batch.
8. The method of claim 7, wherein the polyester matrix is selected from one or more of polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate;
the light stabilizer is 2, 2-thiobis (4-tert-octylphenol) n-butylamine nickel salt;
the antioxidant is selected from four [β- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol esters and/or tris (2, 4-di-tert-butylphenyl) phosphite;
the dispersing agent is one or more selected from white oil, calcium stearate, low-density homo-wax, ethylene acrylic acid copolymer and maleic anhydride graft.
9. The organic/inorganic composite uv-blocking polyester master batch according to claim 7, wherein the mixing conditions comprise: the mixing rotating speed is 1000-3000 r/min, and the mixing time is 20-40 min; the mixing conditions include: the mixing extrusion temperature is 210-250 ℃, and the mixing extrusion rotating speed is 300-600 r/min.
10. Use of the organic/inorganic composite anti-ultraviolet extinction polyester master batch as claimed in claims 1-6 or the organic/inorganic composite anti-ultraviolet extinction polyester master batch as claimed in claims 7-9.
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