CN112876760A - Light stabilizer controlled release type polymer composite material with light aging property prolonging function - Google Patents
Light stabilizer controlled release type polymer composite material with light aging property prolonging function Download PDFInfo
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- CN112876760A CN112876760A CN202110056427.3A CN202110056427A CN112876760A CN 112876760 A CN112876760 A CN 112876760A CN 202110056427 A CN202110056427 A CN 202110056427A CN 112876760 A CN112876760 A CN 112876760A
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- Prior art keywords
- light stabilizer
- light
- controlled release
- composite material
- polymer composite
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- 239000004611 light stabiliser Substances 0.000 title claims abstract description 109
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 229920000642 polymer Polymers 0.000 title claims abstract description 36
- 238000013270 controlled release Methods 0.000 title claims abstract description 33
- 230000003679 aging effect Effects 0.000 title claims abstract description 12
- 239000011256 inorganic filler Substances 0.000 claims abstract description 37
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 37
- 230000032683 aging Effects 0.000 claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 20
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 20
- 239000011159 matrix material Substances 0.000 claims abstract description 19
- 230000002035 prolonged effect Effects 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
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- 238000001179 sorption measurement Methods 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 150000001412 amines Chemical class 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 16
- 230000004048 modification Effects 0.000 claims description 15
- 238000012986 modification Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- -1 polyethylene Polymers 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 239000007822 coupling agent Substances 0.000 claims description 9
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 9
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- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
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- 239000004698 Polyethylene Substances 0.000 claims description 3
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- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 3
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- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
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- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 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 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
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- 239000004695 Polyether sulfone Substances 0.000 claims description 2
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- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
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- 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 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
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- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 2
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- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
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- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
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- 239000010456 wollastonite Substances 0.000 claims description 2
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- 230000000052 comparative effect Effects 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
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- 229910052759 nickel Inorganic materials 0.000 description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- SLFASZAYVJVNBZ-UHFFFAOYSA-N 2,4-diisocyanato-1-methylbenzene;toluene Chemical compound CC1=CC=CC=C1.CC1=CC=C(N=C=O)C=C1N=C=O SLFASZAYVJVNBZ-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
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- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
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- 239000002516 radical scavenger Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
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- 239000012974 tin catalyst Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- 150000003918 triazines Chemical class 0.000 description 1
Classifications
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention relates to a light stabilizer controlled release type polymer composite material with a prolonged light aging property, which is prepared by coating a light stabilizer on the surface of an inorganic filler through electrostatic action or physical adsorption and controlling the release of the light stabilizer in the use process, and specifically comprises the following raw materials in percentage by weight: 0.3-1.0 parts of light stabilizer; 0.3-0.5% of antioxidant; 4.0-8.7 of modified inorganic filler; 89.8-95.4 parts of matrix resin; according to the scheme, the light stabilizer is coated on the surface of the inorganic filler through electrostatic action or physical adsorption, and the light stabilizer is controlled to be released in the processes of production, storage, transportation and use, so that the light aging performance of the composite material is ensured, and the effective time of the light stabilizer is prolonged, so that the light aging performance of the composite material is prolonged, and the performance of the composite material is maintained for a longer time.
Description
Technical Field
The invention relates to a polymer composite material, in particular to a light stabilizer controlled release polymer composite material with a light aging performance prolonging function, and belongs to the technical field of composite materials.
Background
The plastic product has wide application in various aspects of daily life, brings convenience to life of people, simultaneously leads the use range and time of the plastic product to be limited due to the aging problem, and gradually reduces and deteriorates the performance, color and the like along with the lapse of time. Therefore, the light stability of the matrix resin is improved, and the light aging performance of the matrix resin is improved, which is very important for the development of composite materials.
Currently, the most common and effective treatment is the addition of light stabilizers to the composite. Light stabilizers can be classified into the following groups according to their mechanism of action: (1) light-shielding agent: this is a substance capable of shielding or reflecting ultraviolet rays so that light does not penetrate into the inside of the resin, thereby functioning to protect the resin. The light-shielding agent includes inorganic pigments such as carbon black and titanium oxide, and organic pigments such as phthalocyanine blue and phthalocyanine green, and among them, carbon black is most effective in shielding. (2) Ultraviolet absorber: the ultraviolet light absorbing material can effectively absorb ultraviolet rays with the wavelength of 290-410 nm, rarely absorbs visible light, and has good thermal stability and light stability. Mainly divided into the following according to the chemical structure: o-hydroxybenzophenones, benzotriazoles, salicylates, triazines, substituted acrylonitriles. Are commonly used with hindered light stabilizers, especially in polyolefins or coatings. (3) Quenching agent: can receive the energy absorbed by the chromophore in the plastic and emit the energy in the form of heat, fluorescence or phosphorescence, thereby protecting the polymer from ultraviolet light. It has good effect on stabilizing polymer and is widely used for films and fibers. Mainly some divalent organic nickel chelates. The organic nickel light stabilizer has good performance, but is basically forbidden or replaced by other nontoxic or low toxic quenchers at present due to the toxicity problem of heavy metal ions. (4) Radical scavenger: the light stabilizer can capture active free radicals generated in resin, so that the photooxidation process is inhibited, and the purpose of light stabilization is achieved. Mainly Hindered Amine Light Stabilizers (HALS). Is the most promising novel high-efficiency light stabilizer, and the annual average demand growth rate is 20-30% internationally. (5) Hydroperoxide decomposer: is one of hindered amine light stabilizers. The polymers can generate hydroperoxides during storage and processing, resulting in photooxidative degradation of the polymer, and hydroperoxide decomposers can decompose peroxides, generate stable nitrogen-oxygen radicals, and further trap free radicals, thereby inhibiting polymer degradation.
With the development of society, higher requirements are put on the service life of the composite material, and particularly, the market demand of the light aging performance of the composite material used outdoors is more and more difficult to meet. At present, the cost of the small molecular light stabilizer is low, but the defects of volatility, blooming, migration, extraction and the like exist in the using process, so that the actual light aging performance of the composite material is greatly reduced, and the service life is shortened. If the amount of the small molecular light stabilizer in the composite material is increased, the production cost is increased, and other properties of the composite material are influenced to a certain extent. Although the macromolecular light stabilizer has a better use effect, the macromolecular light stabilizer has higher cost and slow migration speed, and has certain influence on the cost and the anti-aging property of the composite material. Therefore, a new solution to solve the above technical problems is urgently needed.
Disclosure of Invention
The invention provides a light stabilizer controlled release type polymer composite material with prolonged light aging performance and a preparation method thereof aiming at the problems in the prior art.
In order to achieve the purpose, the technical scheme of the invention is that the light stabilizer controlled release type polymer composite material with the prolonged light aging performance is characterized in that an inorganic filler is used for coating the surface of the light stabilizer through electrostatic action or physical adsorption and controlling the release of the light stabilizer in the using process, and the light stabilizer controlled release type polymer composite material is prepared from the following raw materials in percentage by weight:
0.3-1.0 parts of light stabilizer;
0.3-0.5% of antioxidant;
4.0-8.7 of modified inorganic filler;
89.8-95.4 of matrix resin. According to the technical scheme, a light stabilizer is coated on the surface of an inorganic filler through electrostatic action or physical adsorption through surface modification, banburying and single-screw extrusion are carried out on the inorganic filler, an antioxidant and thermoplastic resin to prepare functional master batches, and then the functional master batches and matrix resin are subjected to double-screw extrusion to obtain the light stabilizer controlled release type high polymer composite material with the light aging performance prolonging function. The light stabilizer is controlled to release, so that the light aging performance of the composite material is ensured, and the effective time of the light stabilizer is prolonged, so that the light aging performance of the composite material is prolonged, the performance of the composite material is kept for a longer time, and the comprehensive performance of the small molecular light stabilizer used by controlled release can be comparable to that of the large molecular light stabilizer, so that the cost is obviously superior, and the requirements of industry on environmental protection are met.
Further, the light stabilizer is one or a combination of several of hindered amine light stabilizer 944, hindered amine light stabilizer 770, hindered amine light stabilizer 119, hindered amine light stabilizer 2020, hindered amine light stabilizer 783, hindered amine light stabilizer 791, hindered amine light stabilizer 610, hindered amine light stabilizer 611, hindered amine light stabilizer 114, ultraviolet absorber 531, ultraviolet absorber 326, ultraviolet absorber 329, and ultraviolet absorber 234. Wide applicability, and can satisfy various systems
Further, the antioxidant is one of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant DLTDP, antioxidant TNP and antioxidant MB. The light stability and the antioxidant are compounded to achieve the synergistic effect to further enhance the aging resistance of the composite material
Further, the inorganic filler is one of calcium carbonate, talcum powder, molecular sieve, montmorillonite, zeolite, wollastonite, titanium dioxide and mica powder.
Further, the matrix resin is one or a combination of several of polyethylene, polypropylene, polyvinyl chloride, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyimide, ABS, polyphenylene sulfide, polyether sulfone and polyether ether ketone. The formula system designed by the invention has universality in different plastics.
A preparation method of a light stabilizer controlled release type polymer composite material with a prolonged light aging property is characterized by comprising the following steps:
preparing raw materials according to the following weight percentage in the step (1):
0.3-1.0 parts of light stabilizer;
0.3-0.5% of antioxidant;
4.0-8.7 of modified inorganic filler;
89.8-95.4 parts of matrix resin;
step (2) modifying the inorganic filler;
coating the light stabilizer on the surface of the inorganic filler by heating and dry stirring;
step (4) banburying the modified inorganic filler coated by the light stabilizer in the step (3), the antioxidant and part of the matrix resin in the step (1) through an internal mixer, extruding by a single screw, and then performing bracing cooling, granulating and drying treatment to obtain functional master batches with the filling amount of 50-90%;
adding matrix resin and the functional master batch in the step (4) into a double-screw extruder from a main feeding port, and performing melt extrusion through the double-screw extruder (the reaction temperature is 160-390 ℃, and the screw rotating speed is 150-300 r/min);
and (6) bracing, cooling, granulating and drying to obtain the light stabilizer controlled release type polymer composite material with the light aging performance prolonging function.
Further, the modification treatment of the inorganic filler in the step (2) includes:
A. mechanical modification: crushing and rubbing; adding the massive inorganic filler into a pulverizer, and mechanically stirring to pulverize into micron-sized or even nano-sized inorganic powder;
B. surface covering modification by using a surfactant or a coupling agent: phosphate coupling agent, silane coupling agent, titanate coupling agent, aluminate coupling agent, stearic acid and stearate; the active functional groups at the two ends of the coupling agent can be effectively connected with the molecular ends of the inorganic filler and the stabilizing agent;
C. high energy surface modification: high energy discharge, plasma rays, ultraviolet rays; after the high-energy particle rays are irradiated, the change of the microscopic, mesoscopic and macroscopic forms of the inorganic filler and stabilizer system can be promoted;
D. local activity modification: graft modification; chemical grafting modification, compared with Van der Waals force and electrostatic adsorption, chemical bonding is more stable;
the treatment method is one or a combination of more of the modification methods.
Compared with the prior art, the invention has the advantages that 1) the technical scheme provides the preparation method of the light stabilizer controlled release type polymer composite material with the light aging performance prolonging function, the light stabilizer is coated on the surface of the modified inorganic filler through electrostatic action or physical adsorption, and the light stabilizer is controlled to release in the processes of production, storage, transportation and use, so that the light aging performance of the composite material is ensured, the effective time of the light stabilizer is prolonged, the light aging performance of the composite material is prolonged, and the performance of the composite material is kept for a longer time; 2) the invention can compare favorably with macromolecular light stabilizer by controlling the comprehensive performance of the micromolecular light stabilizer used for releasing, achieves the effect of continuously protecting materials by controlling the action, reduces the continuous migration loss of micromolecular light stability, has obvious advantages in cost, meets the requirement of industry on environmental protection, and can be industrially produced in large batch.
The specific implementation mode is as follows:
for the purpose of enhancing an understanding of the present invention, the following detailed description is given in conjunction with examples.
Example 1:
the light stabilizer controlled release type polymer composite material with the light aging property prolonged, provided by the embodiment of the invention, is prepared by coating a light stabilizer on the surface of an inorganic filler through electrostatic action or physical adsorption and controlling the release of the light stabilizer in the use process, and specifically comprises the following raw materials in percentage by weight:
0.3-1.0 parts of light stabilizer;
0.3-0.5% of antioxidant;
4.0-8.7 of modified inorganic filler;
89.8-95.4 parts of matrix resin;
the preparation method of the light stabilizer controlled release type polymer composite material with the light aging prolonging performance comprises the following steps:
preparing raw materials according to the following weight percentage in the step (1):
step (2) stirring and grinding calcium carbonate into superfine powder, grinding the calcium carbonate into zirconia balls with the medium of phi 5mm, grinding the zirconia balls to the concentration of 55 percent and the ball-to-material ratio of 4, finely grinding the zirconia balls to a certain time, and performing suction filtration and drying;
fully and uniformly mixing the light stabilizer and calcium carbonate in a heating stirrer to obtain the light stabilizer-coated modified inorganic filler;
step (4) banburying the modified inorganic filler coated by the light stabilizer in the step (3), the antioxidant and part of the matrix resin in the step (1) through an internal mixer, extruding by a single screw, and then performing bracing cooling, granulating and drying treatment to obtain functional master batch with the filling amount of 90%;
adding polyethylene and the functional master batch obtained in the step (4) into a double-screw extruder from a main feeding port, and performing melt extrusion through the double-screw extruder (the reaction temperature is 160-190 ℃, and the screw rotating speed is 150 r/min);
and (6) bracing, cooling, granulating and drying to obtain the light stabilizer controlled release type polymer composite material with the light aging performance prolonging function.
Example 2
The preparation method of the light stabilizer controlled release type polymer composite material with the light aging prolonging performance provided by the embodiment of the invention comprises the following steps:
preparing raw materials according to the following weight percentage in the step (1):
step (2) mixing vacuum-dried talcum powder with toluene with 4 times volume of the talcum powder, and removing O2General formula N2And (2) protecting, gradually dropwise adding a toluene diisocyanate toluene solution (1:1) mixed with an organic tin catalyst at the temperature of 30-45 ℃, reacting for 1h at the temperature of 55-60 ℃ after dropwise adding, dropwise adding a certain amount of propyl acrylate at the temperature of (70 +/-10 ℃), continuing reacting for 2h, and sampling to detect the NCO group content of reactants until the specified requirement is met. And continuously evaporating partial toluene and excessive propyl acrylate in vacuum, cooling to about 50 ℃, dropwise adding a methyl methacrylate mixed solution dissolved with AIBN, maintaining the temperature at 75-85 ℃ for reaction, polymerizing for 2.5h, then recovering unreacted monomers and solvents in vacuum, washing and drying to obtain the high-molecular talcum powder particles.
Dissolving a light stabilizer in a chloroform reagent, adding the talcum powder obtained in the step (2), fully and uniformly mixing, and evaporating to obtain a modified inorganic filler coated by the light stabilizer;
step (4) banburying the modified inorganic filler coated by the light stabilizer in the step (3), the antioxidant and part of the matrix resin in the step (1) through an internal mixer, extruding by a single screw, and then performing bracing cooling, granulating and drying treatment to obtain functional master batch with the filling amount of 80%;
adding polyvinyl chloride and the functional master batch in the step (4) into a double-screw extruder from a main feeding port, and performing melt extrusion through the double-screw extruder (the reaction temperature is 130-140 ℃, and the screw rotating speed is 150 r/min);
and (6) bracing, cooling, granulating and drying to obtain the light stabilizer controlled release type polymer composite material with the light aging performance prolonging function.
Example 3
The preparation method of the light stabilizer controlled release type polymer composite material with the light aging prolonging performance provided by the embodiment of the invention comprises the following steps:
preparing raw materials according to the following weight percentage in the step (1):
selecting SBA-15 for molecular screening, mechanically crushing to micron-sized particles (1-10 microns), and drying;
dissolving a light stabilizer in an ethanol reagent, adding the molecular sieve in the step (2), fully and uniformly mixing, and evaporating to obtain a modified inorganic filler coated by the light stabilizer;
step (4) banburying the modified inorganic filler coated by the light stabilizer in the step (3), the antioxidant and part of the matrix resin in the step (1) through an internal mixer, extruding by a single screw, and then performing bracing cooling, granulating and drying treatment to obtain functional master batch with the filling amount of 70%;
adding polypropylene and the functional master batch in the step (4) into a double-screw extruder from a main feeding port, and performing melt extrusion through the double-screw extruder (the reaction temperature is 160-210 ℃, and the screw rotating speed is 200 r/min);
and (6) bracing, cooling, granulating and drying to obtain the light stabilizer controlled release type polymer composite material with the light aging performance prolonging function.
Example 4
The preparation method of the light stabilizer controlled release type polymer composite material with the light aging prolonging performance provided by the embodiment of the invention comprises the following steps:
preparing raw materials according to the following weight percentage in the step (1):
step (2) adding a mixed solution of ethanol and water (the mass ratio is 4:1) into KH550, and stirring and hydrolyzing at 60 ℃ for 2 h. And adding titanium dioxide into a mixed solution of ethanol and water (volume ratio of 9:1), shearing and dispersing at the speed of 3000r/min, and stirring for 20 min. And (3) taking the hydrolyzed KH550 solution and titanium dioxide dispersion liquid, and stirring and reacting for 2 hours at room temperature. Vacuum distilling, washing with ethanol for 3 times, drying at 70 deg.C for 12 hr, taking out, and grinding to obtain modified titanium dioxide.
Dissolving a light stabilizer in an ethyl acetate reagent, adding the titanium dioxide obtained in the step (2), fully and uniformly mixing, and evaporating to obtain a modified inorganic filler coated by the light stabilizer;
step (4) banburying the modified inorganic filler coated by the light stabilizer in the step (3), the antioxidant and part of the matrix resin in the step (1) through an internal mixer, extruding by a single screw, and then performing bracing cooling, granulating and drying treatment to obtain functional master batch with the filling amount of 50%;
step (5) adding ABS and the functional master batch in the step (4) into a double-screw extruder from a main feeding port, and performing melt extrusion through the double-screw extruder (the reaction temperature is 200-240 ℃, and the screw rotating speed is 400 r/min);
and (6) bracing, cooling, granulating and drying to obtain the light stabilizer controlled release type polymer composite material with the light aging performance prolonging function.
Comparative examples
By adding the inorganic filler, the preparation step of the functional master batch is not carried out, and the other steps are repeated to prepare the composite material (a) with the same proportion as a reference.
By adding inorganic filler, the light stabilizer coating step is not carried out, and the other steps are repeated to prepare the composite material (b) with the same proportion as a contrast.
Application examples
Xenon arc lamp aging tests were performed on the light stabilizer controlled release polymer composite materials with extended light aging properties prepared in examples 1 to 4 and the light aging resistance properties of the composite materials prepared in the corresponding comparative examples, and the results are shown in the following table:
| sample (I) | Time/h of 70% of maximum residual tension |
| Example 1 | 434 |
| Comparative example 1a | 290 |
| Comparative example 1b | 195 |
| Sample (I) | Time of irradiation | Impact Strength/(kJ/m)2) |
| Example 2 | 0h | 3.31 |
| Comparative example 2a | 0h | 3.19 |
| Comparative example 2b | 0h | 3.07 |
| Sample (I) | Time of irradiation | Impact Strength/(kJ/m)2) |
| Example 2 | 1500h | 2.53 |
| Comparative example 2a | 1500h | 2.36 |
| Comparative example 2b | 1500h | 2.10 |
| Sample (I) | Time of irradiation | Impact Strength/(kJ/m)2) |
| Example 2 | 3000h | 1.21 |
| Comparative example 2a | 3000h | — |
| Comparative example 2b | 3000h | — |
| Sample (I) | YI (xenon lamp aging 1000h) |
| Example 4 | 15.8 |
| Comparative example 4a | 17.6 |
| Comparative example 4b | 17.2 |
It can be seen that the light stabilizer controlled release type polymer composite material prepared in embodiments 1-4 of the present invention has better light aging resistance, and the comprehensive performance of the small molecular light stabilizer used by controlled release can be compared favorably with that of the large molecular light stabilizer, which not only has an obvious advantage in cost, but also meets the requirements of industry environmental protection.
It should be noted that the above-mentioned embodiments are not intended to limit the scope of the present invention, and all equivalent modifications and substitutions based on the above-mentioned technical solutions are within the scope of the present invention as defined in the claims.
Claims (7)
1. A light stabilizer controlled release type polymer composite material with a prolonged light aging property is characterized in that an inorganic filler is used for coating a light stabilizer on the surface through electrostatic action or physical adsorption and controlling the release of the light stabilizer in the use process, and the light stabilizer controlled release type polymer composite material is prepared from the following raw materials in percentage by weight:
0.3-1.0 parts of light stabilizer;
0.3-0.5% of antioxidant;
4.0-8.7 of modified inorganic filler;
89.8-95.4 of matrix resin.
2. The light stabilizer controlled release polymer composite with extended light aging properties according to claim 1, wherein the light stabilizer is one or a combination of several of hindered amine light stabilizer 944, hindered amine light stabilizer 770, hindered amine light stabilizer 119, hindered amine light stabilizer 2020, hindered amine light stabilizer 783, hindered amine light stabilizer 791, hindered amine light stabilizer 610, hindered amine light stabilizer 611, hindered amine light stabilizer 114, ultraviolet absorber 531, ultraviolet absorber 326, ultraviolet absorber 329, and ultraviolet absorber 234.
3. The light stabilizer controlled release polymer composite with extended light aging properties of claim 2, wherein the antioxidant is one of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant DLTDP, antioxidant TNP and antioxidant MB.
4. The light stabilizer controlled release polymer composite with extended light aging properties of claim 3, wherein the inorganic filler is one of calcium carbonate, talc, molecular sieve, montmorillonite, zeolite, wollastonite, titanium dioxide, mica powder.
5. The light stabilizer controlled release polymer composite material with the prolonged light aging property as claimed in claim 3 or 4, wherein the matrix resin is one or more of polyethylene, polypropylene, polyvinyl chloride, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyimide, ABS, polyphenylene sulfide, polyether sulfone and polyether ether ketone.
6. A method for preparing a light stabilizer controlled release polymer composite having extended light aging properties using any one of claims 1 to 5, comprising the steps of:
preparing raw materials according to the following weight percentage in the step (1):
0.3 to 1.0% of a light stabilizer
0.3-0.5% of antioxidant
4.0-8.7 parts of modified inorganic filler
89.8-95.4 matrix resin
Step (2) modifying the inorganic filler;
coating the light stabilizer on the surface of the inorganic filler by heating and dry stirring;
step (4) banburying the modified inorganic filler coated by the light stabilizer in the step (3), the antioxidant and part of the matrix resin in the step (1) through an internal mixer, extruding by a single screw, and then performing bracing cooling, granulating and drying treatment to obtain functional master batches with the filling amount of 50-90%;
adding matrix resin and the functional master batch in the step (4) into a double-screw extruder from a main feeding port, and performing melt extrusion through the double-screw extruder (the reaction temperature is 160-390 ℃, and the screw rotating speed is 150-300 r/min);
and (6) bracing, cooling, granulating and drying to obtain the light stabilizer controlled release type polymer composite material with the light aging performance prolonging function.
7. The method for preparing a light stabilizer controlled release polymer composite with extended light aging performance as claimed in claim 6, wherein the modification treatment of the inorganic filler in the step (2) comprises:
A. mechanical modification: crushing and rubbing;
B. surface covering modification by using a surfactant or a coupling agent: phosphate coupling agent, silane coupling agent, titanate coupling agent, aluminate coupling agent, stearic acid and stearate;
C. high energy surface modification: high energy discharge, plasma rays, ultraviolet rays;
D. local activity modification: graft modification;
the treatment method is one or a combination of more of the modification methods.
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