CN114605754A - Preparation method of high-light-transmittance ultraviolet aging resistant polyvinyl chloride film - Google Patents
Preparation method of high-light-transmittance ultraviolet aging resistant polyvinyl chloride film Download PDFInfo
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- CN114605754A CN114605754A CN202210294619.2A CN202210294619A CN114605754A CN 114605754 A CN114605754 A CN 114605754A CN 202210294619 A CN202210294619 A CN 202210294619A CN 114605754 A CN114605754 A CN 114605754A
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- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 49
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 49
- 230000032683 aging Effects 0.000 title claims abstract description 26
- 238000002834 transmittance Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000463 material Substances 0.000 claims abstract description 34
- 239000011787 zinc oxide Substances 0.000 claims abstract description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 28
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 39
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- 239000011592 zinc chloride Substances 0.000 claims description 18
- 235000005074 zinc chloride Nutrition 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 230000004888 barrier function Effects 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000010445 mica Substances 0.000 claims description 6
- 229910052618 mica group Inorganic materials 0.000 claims description 6
- HCQVHZVGZCPSMA-UHFFFAOYSA-N [O-][O-].[Zn+2].[O-2].[O-2].[Ti+4] Chemical compound [O-][O-].[Zn+2].[O-2].[O-2].[Ti+4] HCQVHZVGZCPSMA-UHFFFAOYSA-N 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- IYVLHQRADFNKAU-UHFFFAOYSA-N oxygen(2-);titanium(4+);hydrate Chemical compound O.[O-2].[O-2].[Ti+4] IYVLHQRADFNKAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000004014 plasticizer Substances 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 230000000903 blocking effect Effects 0.000 claims description 4
- 238000003490 calendering Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 4
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 4
- 239000004611 light stabiliser Substances 0.000 claims description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- JTTXECQCCPZGII-UHFFFAOYSA-M sodium;ethane-1,2-diol;hydroxide Chemical compound [OH-].[Na+].OCCO JTTXECQCCPZGII-UHFFFAOYSA-M 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 240000007651 Rubus glaucus Species 0.000 claims description 3
- 235000011034 Rubus glaucus Nutrition 0.000 claims description 3
- 235000009122 Rubus idaeus Nutrition 0.000 claims description 3
- 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 group 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
- 238000005266 casting Methods 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 24
- 239000004408 titanium dioxide Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 7
- 230000005855 radiation Effects 0.000 abstract description 5
- JRFBNCLFYLUNCE-UHFFFAOYSA-N zinc;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Zn+2] JRFBNCLFYLUNCE-UHFFFAOYSA-N 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000003607 modifier Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000006096 absorbing agent Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000011358 absorbing material Substances 0.000 description 4
- 238000000703 high-speed centrifugation Methods 0.000 description 4
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000004383 yellowing Methods 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
- DMSSTTLDFWKBSX-UHFFFAOYSA-N 1h-1,2,3-benzotriazin-4-one Chemical class C1=CC=C2C(=O)N=NNC2=C1 DMSSTTLDFWKBSX-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical group CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
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- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- 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
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- 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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- 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
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Abstract
The invention relates to the field of polyvinyl chloride film materials, in particular to a preparation method of a high-light-transmittance ultraviolet aging resistant polyvinyl chloride film. According to the invention, zinc oxide is obtained by reacting and modifying in an ethylene glycol solvent, and then titanium dioxide grows in situ on the surface of the zinc oxide to obtain the titanium dioxide-zinc oxide composite material with a raspberry-like structure, the composite material can obviously improve the shielding effect on ultraviolet radiation, and a specific vinyl trimethoxy silane modifier is selected for modification, so that the modified titanium dioxide-zinc oxide better ensures that the film has better light transmittance, and the mechanical property of polyvinyl chloride is improved. The prepared high-transmittance ultraviolet aging resistant polyvinyl chloride film has excellent comprehensive performance and wide application prospect outdoors.
Description
Technical Field
The invention relates to the field of polyvinyl chloride film materials, in particular to a preparation method of a high-light-transmittance ultraviolet aging resistant polyvinyl chloride film.
Background
In recent years, with the development of the advertising industry, the advertising film is also developed rapidly, the advertising film needs to have certain light transmittance to ensure the advertisement viewing effect, but because outdoor advertisements are often exposed to the sun, the color of an advertisement picture and the aging radiation of the outdoor advertisement film per se need to be effectively prevented from being irradiated by ultraviolet rays, and the advertisement color is prolonged.
At present, the polyvinyl chloride film is widely applied to the field of advertisements due to the advantages of good flexibility, convenient installation, long service life and the like. When the outdoor high polymer material is used outdoors, the outdoor high polymer material can be exposed outdoors for a long time, and can be influenced by sunlight and irradiation of an internal lamp tube and various chemical components (such as temperature, moisture and the like) in the environment, the temperature and the humidity and the air, for example, in the aging degradation of a PVC film, the moisture also plays an important role, wherein, dust on the surface of the outdoor high polymer material can be washed away by rainfall, and part of additives can be taken away, so that the aging and the color change are accelerated, and the PVC oxidative degradation is accelerated under the humid condition. The outdoor environment has more complexity, and the color of the picture cloth and the color of the film are inevitably changed to a certain extent, so that the application of the picture cloth is limited.
In the prior art, in order to reduce the aging discoloration of the PVC film, different auxiliary agents such as an anti-aging agent, a plasticizer, a filler and the like are added. For example, ultraviolet absorbers are added to block ultraviolet rays and prevent the ultraviolet absorbers from damaging polyvinyl chloride molecular chains, and currently, ultraviolet absorbers containing organic components, such as o-hydroxybenzophenones, o-hydroxybenzotriazoles, hydroxybenzotriazines, benzosalicylates and the like, are mostly used, but most of the ultraviolet absorbers can turn yellow under ultraviolet radiation, so that the application of the ultraviolet absorbers in colorless or transparent products is limited, and organic ultraviolet absorber materials are harmful to the environment. The inorganic ultraviolet light shielding material is commonly used by carbon black, titanium dioxide and zinc dioxide, wherein the carbon black is difficult to be used in transparent products, while the titanium dioxide and the zinc dioxide can maintain the transparency of plastics and simultaneously endow ultraviolet light absorption capacity, but the ultraviolet light absorption capacity of the inorganic material is difficult to be further improved, and the application of the inorganic ultraviolet light absorption material in plastic products is influenced.
The application of the inorganic ultraviolet light absorbing material in polyvinyl chloride comprises the following steps: CN201410240114.3 an anti-ultraviolet aging PVC membrane material and its preparation method, it uses polyvinyl chloride, epoxidized soybean oil, titanium dioxide, colorant and antioxidant as raw materials to prepare, wherein use titanium dioxide as ultraviolet absorbent to prepare anti-ultraviolet aging PVC membrane material, can solve effectively in the prior art by the strong irradiation of ultraviolet ray to cause yellowing, it gives concrete performance, and has not studied the light transmittance of PVC membrane material. At present, the inorganic ultraviolet light absorbing material is adopted only by considering the compatibility with organic materials and the light protection effect. The effect on light transmission in transparent articles was not investigated. For outdoor films, it is also necessary to ensure excellent light transmittance and other effects, and further excellent overall properties are required. Therefore, how to ensure that the inorganic ultraviolet light absorbing material not only has high ultraviolet light prevention efficiency, but also can not influence the light transmittance of the polyvinyl chloride, and can also improve the mechanical property of the polyvinyl chloride is the technical problem to be solved by the invention.
Disclosure of Invention
Aiming at the problems of the inorganic ultraviolet light absorbing material in the PVC film in the outdoor environment in the background art, the ultraviolet shielding material prepared by the invention is applied to the PVC film, and has excellent ultraviolet light aging resistance, the PVC aging time is prolonged, and the PVC mechanical property is improved while the excellent light transmittance is ensured.
In order to achieve the purpose, the invention adopts the technical scheme that:
the high-light-transmission aging-resistant PVC film comprises the following raw materials in parts by weight: 80-100 parts of polyvinyl chloride, 10-30 parts of ethylene-vinyl acetate copolymer, 5-20 parts of plasticizer, 5-10 parts of ultraviolet barrier material, 3-10 parts of filler, 2-4 parts of antioxidant, 1-5 parts of polyethylene wax and 1-3 parts of stabilizer.
Further, the preferred plasticizer is epoxy fatty acid methyl ester (available from east China Industrial Co., Ltd., Qingzhou);
further, the filler can be the same as the ultraviolet barrier material or mica powder, preferably mica powder, and the mica powder and the ultraviolet barrier material can have good infrared radiation capability after being compounded, so that the light aging of the film is further reduced.
Further, the antioxidant is antioxidant 1010
Further, the stabilizer is a hindered amine light stabilizer UV-944.
Mixing the materials, feeding the mixture into an internal mixer for mixing and plasticizing, and obtaining the PVC film through conventional processes of tape casting, calendering by a calender, stretching and drawing, cooling and rolling.
Further, the mixing plasticizing temperature is 100-120 ℃, and the calendering temperature is 130-180 ℃.
The preparation method of the ultraviolet barrier material comprises the following steps:
(1) preparation of zinc oxide sol:
weighing zinc chloride, adding the zinc chloride into ethylene glycol, stirring to obtain a transparent zinc chloride solution, adding a sodium hydroxide ethylene glycol solution into the transparent zinc chloride solution, stirring for 30-60 min, placing the mixed solution into a reaction kettle, reacting at the temperature of 80-120 ℃ for 4-8 h, keeping the reaction at the stirring speed of 300-400 r/min, standing for 8-10 h after the reaction, adding absolute ethyl alcohol into the mixed solution, stirring, centrifuging, collecting precipitates, cleaning, and dispersing in the absolute ethyl alcohol again to obtain zinc oxide sol;
further, the molar ratio of zinc chloride to sodium hydroxide is 1: 1, the concentration of zinc chloride in ethylene glycol is 0.5-1.5 mol/L. The reaction time and the stirring speed are controlled so that the average particle size of the zinc oxide is preferably 50-150 nm.
(2) Under the condition of stirring, dripping a sodium hydroxide solution into a titanium tetrachloride solution until the pH value of the mixed solution is 6-7 to obtain a titanium dioxide hydrate precursor, adding the zinc oxide sol obtained in the step (1) into the precursor, stirring and mixing for 1-2 h, then putting into a hydrothermal kettle, carrying out hydrothermal reaction for 3-4 h at the stirring speed of 400-500 r/min and the temperature of 120-150 ℃, adding vinyl trimethoxy silane after the reaction, continuing stirring for 10-20 h, pouring out the reaction liquid in the reactor, carrying out high-speed centrifugation, collecting precipitates, washing, and freeze-drying to obtain a powdery solid, namely a titanium dioxide-zinc dioxide composite material serving as an ultraviolet barrier material;
furthermore, the addition amount of the vinyl trimethoxy silane is 0.1-0.3 time of the mass of the titanium tetrachloride.
The vinyl trimethoxy silane can play an organic modification role and improve the organic compatibility of the ultraviolet barrier material after being optimized through a large number of experiments, and most importantly, the vinyl trimethoxy silane can also be used as a raw material to modify polyvinyl chloride resin, so that the light transmittance and the mechanical property of the polyvinyl chloride resin can be improved after modification.
Further, the mass ratio of titanium tetrachloride to zinc oxide is 3-5: 1; wherein the particle size of the titanium dioxide is about 5-20 nm.
Titanium dioxide and zinc oxide are excellent ultraviolet aging resistant materials, are commonly used physical shielding type ultraviolet protective agents, but are poor in dispersibility when used in resin base materials, influence the transmission characteristics of films, are poor in stability after long-term use, and are difficult to further improve the ultraviolet shielding effect. According to the invention, the zinc oxide sol is synthesized in the glycol solvent, the glycol polycondensation plays a role in organic modification on the surface of the zinc oxide, the dispersibility of ZnO particles can be improved, the agglomeration is reduced, and the subsequent titanium dioxide can grow in situ and is combined on the surface of the titanium dioxide-zinc oxide composite material after the organic modification, so that the titanium dioxide-zinc oxide composite material is obtained, and the structure of the composite material is similar to a raspberry shape. Compared with the single zinc oxide and titanium dioxide, the ultraviolet radiation shielding effect and the heat-resistant stability can be obviously improved. Through subsequent organic modification, the dispersibility and compatibility of the ultraviolet-absorbing ultraviolet film are improved.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, firstly, the zinc oxide sol is obtained by reaction in an ethylene glycol solvent and modification, and then titanium dioxide grows in situ on the surface of the zinc oxide sol to obtain the titanium dioxide-zinc oxide composite material with a structure similar to a raspberry.
Drawings
Fig. 1 is an electron microscope image of the titanium dioxide-zinc dioxide ultraviolet blocking material prepared in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Preparation of zinc oxide sol:
weighing 136g of zinc chloride, adding the zinc chloride into 1L of ethylene glycol, stirring to obtain a transparent zinc chloride solution, adding 1L of sodium hydroxide ethylene glycol solution (with the concentration of 1mol/L), stirring for 50min, placing the mixed solution into a reaction kettle, reacting for 6h at the temperature of 100 ℃, stirring at the rotating speed of 350r/min, standing for 9h after reaction, adding absolute ethyl alcohol into the mixed solution, stirring, centrifuging, collecting precipitate, cleaning, and re-dispersing in the absolute ethyl alcohol to obtain zinc oxide sol (with the concentration of 150g/L), wherein the average particle size of the zinc oxide is 80 nm;
(2) under the stirring condition, 1.6L of titanium tetrachloride solution with the concentration of 1.5mol/L is dripped into 1.0mol/L of sodium hydroxide solution until the pH of the mixed solution is 6.5 to obtain a titanium dioxide hydrate precursor, 1L of zinc oxide sol obtained in the step (1) is added into the precursor, the mixture is stirred and mixed for 1h and then is put into a hydrothermal kettle, the hydrothermal reaction is carried out for 3h at 140 ℃ under the stirring rotation speed of 450r/min, 46g of vinyl trimethoxy silane is added after the reaction, the stirring is continued for 15h, the reaction liquid in the reactor is poured out after the stirring is finished, the high-speed centrifugation is carried out, the precipitate is collected, the washing is carried out, and the powdery solid obtained after the freeze drying is the ultraviolet barrier material;
the high-light-transmission aging-resistant PVC film comprises the following raw materials in parts by weight: 90 parts of polyvinyl chloride, 20 parts of ethylene-vinyl acetate copolymer, 15 parts of epoxy fatty acid methyl ester, 7 parts of ultraviolet barrier material, 8 parts of mica powder (3000 meshes), 10102 parts of antioxidant, 3 parts of polyethylene wax and 3 parts of hindered amine light stabilizer UV-944. Mixing the materials, feeding the mixture into an internal mixer, mixing and plasticizing the mixture for 15min at 120 ℃, then feeding the mixture into a calender for calendering at 150 ℃, and obtaining the PVC film through conventional processes of stretching, cooling and rolling.
Example 2
(1) Preparation of zinc oxide sol:
weighing 204g of zinc chloride, adding the zinc chloride into 1L of ethylene glycol, stirring to obtain a transparent zinc chloride solution, then adding 1L of a sodium hydroxide ethylene glycol solution (with the concentration of 1.5mol/L), stirring for 60min, placing the mixed solution into a reaction kettle, reacting for 4h at the temperature of 120 ℃, stirring at the rotating speed of 400r/min, standing for 10h after reaction, adding absolute ethyl alcohol into the mixed solution, stirring, centrifuging, collecting precipitate, cleaning, and dispersing in the absolute ethyl alcohol again to obtain zinc oxide sol (with the concentration of 120 g/L); the average grain diameter of the zinc oxide is 75 nm;
(2) under the condition of stirring, dripping 1.0mol/L sodium hydroxide solution into 1.6L titanium tetrachloride solution with the concentration of 1.5mol/L until the pH value of the mixed solution is 7 to obtain a titanium dioxide hydrate precursor, then adding 1L zinc oxide sol (with the concentration of 120g/L) obtained in the step (1) into the precursor, stirring and mixing for 1h, then putting into a hydrothermal kettle, carrying out hydrothermal reaction at 120 ℃ for 4h under the condition of the stirring rotation speed of 500r/min, adding 50g vinyl trimethoxy silane after the reaction, continuing stirring for 15h, pouring out the reaction liquid in the reactor after the stirring is finished, carrying out high-speed centrifugation, collecting precipitates, washing, and freeze-drying to obtain powdery solid, namely the ultraviolet barrier material;
the high-light-transmission aging-resistant PVC film comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride, 30 parts of ethylene-vinyl acetate copolymer, 15 parts of epoxy fatty acid methyl ester, 10 parts of ultraviolet barrier material, 5 parts of mica powder (3000 meshes), 10102 parts of antioxidant, 3 parts of polyethylene wax and 3 parts of hindered amine light stabilizer UV-944. And (2) mixing the materials, feeding the mixture into an internal mixer, mixing and plasticizing the mixture for 13min at 120 ℃, then feeding the mixture into a calender to calender the mixture at 170 ℃, and obtaining the PVC film through conventional processes of stretching, cooling and rolling.
Table 1 the effect of hydrothermal reaction time on PVC film performance in step (2) of example 1 was investigated.
| Reaction time | Ultraviolet transmittance,% of | Transmittance of visible light,% |
| 2h | 5.9 | 90.8 |
| 3h | 5.3 | 92.3 |
| 6h | 6.2 | 90.1 |
Table 2 the effect of step (2) agitation speed on PVC film performance under the conditions of example 1 was investigated.
| Stirring speed | Ultraviolet transmittance,% of | Transmittance of visible light,% |
| 300r/min | 5.7 | 91.5 |
| 450r/min | 5.3 | 92.3 |
| 600r/min | 5.8 | 90.6 |
Comparative example 1
Comparative example 1 compared with example 1, the ultraviolet blocking material was replaced with a mixed material of titanium dioxide and zinc dioxide (the mass ratio of titanium dioxide to zinc dioxide was 1.5: 1), and the other operations were the same as in example 1.
Comparative example 2
Comparative example 2 compared with example 1, vinyltrimethoxysilane was replaced with methyltrimethoxysilane, and the other operations were the same as in example 1.
Comparative example 3
Comparative example 3 the titanium dioxide-zinc dioxide composite was prepared by a different method than in example 1, and the other operations were the same as in example 1.
The preparation method of the ultraviolet blocking material in the comparative example 3 comprises the following steps:
(1) dispersing commercially available nano-grade zinc oxide in absolute ethyl alcohol to obtain zinc oxide dispersion liquid (the concentration is 150 g/L);
(2) under the condition of stirring, 1.6L of titanium tetrachloride solution with the concentration of 1.5mol/L is dripped with 1.0mol/L of sodium hydroxide solution until the pH value of the mixed solution is 6.5 to obtain a titanium dioxide hydrate precursor, 1L of zinc oxide dispersion liquid obtained in the step (1) is added into the precursor, the mixture is stirred and mixed for 1h and then is put into a hydrothermal kettle, the hydrothermal reaction is carried out for 3h at 140 ℃ under the condition that the stirring speed is 450r/min, 46g of vinyl trimethoxy silane is added after the reaction, the stirring is continued for 15h, the reaction liquid in the reactor is poured out after the stirring is finished, the high-speed centrifugation is carried out, precipitates are collected, and the powdery solid obtained after washing and freeze drying is the ultraviolet barrier material.
Table 3 shows the performance test of the PVC films prepared in the examples and comparative examples
The transmittance of the film (average thickness 0.8mm) at different wavelength bands was measured using a UV-visible spectrophotometer.
The yellowing index (delta YI) of ultraviolet light aging (30W ultraviolet lamp irradiation for 50 days) is determined according to the yellow index test method of GB-T2409-19801 plastic.
Claims (7)
1. A preparation method of a high-light-transmittance ultraviolet aging resistant polyvinyl chloride film is characterized by comprising the following steps: the polyvinyl chloride film comprises the following raw materials in parts by weight: 80-100 parts of polyvinyl chloride resin, 10-30 parts of ethylene-vinyl acetate copolymer, 5-20 parts of plasticizer, 5-10 parts of ultraviolet barrier material, 3-10 parts of filler, 2-4 parts of antioxidant, 1-5 parts of polyethylene wax and 1-3 parts of stabilizer, and preparing the materials into a polyvinyl chloride film;
wherein the ultraviolet blocking material is a titanium dioxide-zinc dioxide composite material with a raspberry structure.
2. The preparation method of the high-transmittance ultraviolet aging resistant polyvinyl chloride film according to claim 1, characterized in that: the preparation method of the ultraviolet barrier material comprises the following steps:
(1) preparation of zinc oxide sol:
weighing zinc chloride, adding the zinc chloride into ethylene glycol, stirring to obtain a transparent zinc chloride solution, adding a sodium hydroxide ethylene glycol solution into the transparent zinc chloride solution, stirring, placing the mixed solution into a reaction kettle, reacting at the temperature of 80-120 ℃ for 4-8 h under the condition that the stirring speed is 300-400 r/min, standing for 8-10 h after reaction, adding absolute ethyl alcohol into the mixed solution after standing, stirring, centrifuging, collecting precipitate, cleaning, and dispersing in the absolute ethyl alcohol again to obtain zinc oxide sol;
(2) under the condition of stirring, dripping a sodium hydroxide solution into a titanium tetrachloride solution until the pH value of the mixed solution is 6-7 to obtain a titanium dioxide hydrate precursor, adding the zinc oxide sol obtained in the step (1) into the precursor, stirring and mixing for 1-2 h, then putting into a hydrothermal kettle, carrying out hydrothermal reaction at the stirring speed of 400-500 r/min for 3-4 h at 120-150 ℃, adding vinyl trimethoxy silane after the reaction, continuing stirring for 10-20 h, pouring out the reaction liquid in the reactor, centrifuging at high speed, collecting precipitates, washing, and freeze-drying to obtain a powdery solid, namely the titanium dioxide-zinc dioxide composite material serving as an ultraviolet barrier material.
3. The preparation method of the high-transmittance ultraviolet aging resistant polyvinyl chloride film according to claim 2, characterized in that: the molar ratio of the zinc chloride to the sodium hydroxide in the step (1) is 1: 1, the concentration of zinc chloride in ethylene glycol is 0.5-1.5 mol/L; the average grain size of zinc oxide in the zinc oxide sol is 50-150 nm.
4. The preparation method of the high-transmittance ultraviolet aging resistant polyvinyl chloride film according to claim 2, characterized in that: the addition amount of the vinyl trimethoxy silane in the step (2) is 0.1-0.3 time of the mass of the titanium tetrachloride; the mass ratio of titanium tetrachloride to zinc oxide is 3-5: 1.
5. the preparation method of the high-transmittance ultraviolet aging resistant polyvinyl chloride film according to claim 1, characterized in that: the plasticizer is epoxy fatty acid methyl ester; the antioxidant is antioxidant 1010; the stabilizer is hindered amine light stabilizer UV-944.
6. The preparation method of the high-transmittance ultraviolet aging resistant polyvinyl chloride film according to claim 1, characterized in that: the filler is mica with the particle size of 3000 meshes.
7. The preparation method of the high-transmittance ultraviolet aging resistant polyvinyl chloride film according to claim 1, characterized in that: mixing the raw materials, mixing and plasticizing, casting, rolling to form a film, and obtaining the polyvinyl chloride film through the working procedures of traction, cooling and rolling; wherein the mixing plasticizing temperature is 100-120 ℃, and the calendering temperature is 130-180 ℃.
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| CN115401968A (en) * | 2022-09-14 | 2022-11-29 | 浙江达尔美塑胶有限公司 | Ultraviolet-resistant PVC (polyvinyl chloride) film and preparation process thereof |
| CN116478488A (en) * | 2023-06-25 | 2023-07-25 | 广州澳通电线电缆有限公司 | Anti-aging photovoltaic cable and preparation method thereof |
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