CN115093653A - Ultraviolet-proof PVC (polyvinyl chloride) film and preparation method thereof - Google Patents
Ultraviolet-proof PVC (polyvinyl chloride) film and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000004800 polyvinyl chloride Substances 0.000 title description 83
- 229920000915 polyvinyl chloride Polymers 0.000 title description 82
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- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 22
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- 239000011347 resin Substances 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000004014 plasticizer Substances 0.000 claims abstract description 14
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000003723 Smelting Methods 0.000 claims abstract description 6
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- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 claims description 9
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 9
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Classifications
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- 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
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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
- C08J2425/00—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 an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
-
- 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
- C08J2433/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/18—Homopolymers or copolymers of nitriles
- C08J2433/20—Homopolymers or copolymers of acrylonitrile
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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
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
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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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
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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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K9/00—Use of pretreated ingredients
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- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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Abstract
The invention discloses an ultraviolet-proof PVC film and a preparation method thereof, belonging to the technical field of polymer films, wherein the PVC film comprises the following raw materials in parts by weight: 50-60 parts of PVC resin, 15-24 parts of diisononyl phthalate, 1-1.2 parts of auxiliary plasticizer and modified TiO 2 1.5-1.8 parts of assistant and 8-10 parts of assistant; the invention also discloses a preparation method of the film, which comprises the steps of mixing and smelting the PVC resin, the plasticizer, the auxiliary plasticizer and the auxiliary agent, and then adding the modified TiO 2 Extruding, granulating and rolling to form the film. The invention is through to TiO 2 The modification is carried out, and the auxiliary agent is added into the membrane raw material, so that the ultraviolet resistance effect of the PVC membrane can be improved in various aspects such as chemically adsorbing ultraviolet rays, weakening the damage of ultraviolet rays to PVC chemical bonds, physically shielding ultraviolet rays and the like, and the toughness of the prepared PVC membrane is also obviously improved.
Description
Technical Field
The invention belongs to the technical field of polymer films, and particularly relates to an ultraviolet-proof PVC film and a preparation method thereof.
Background
Polyvinyl chloride (PVC) is one of the earliest industrialized and widely used general thermoplastic plastics, and has the advantages of light weight, high strength, insulation, flame retardance, corrosion resistance, excellent comprehensive performance, low price, wide raw material sources and the like. The PVC film is used for surface layer packaging of various panels, is also called as a decorative film and an adhesive film, and is applied to various industries such as building materials, packaging, medicines and the like. The building material industry accounts for 60% of the maximum proportion, the packaging industry is the second one, and other industries with small application range are also provided.
Ultraviolet rays can age plastic and other products, and can greatly reduce the effective service time of the PVC film, so that the PVC film needs to be subjected to ultraviolet resistance modification. Application number 201810306621.0 discloses anti UV and anti ultraviolet PVC membrane and preparation method thereof, including PVC membrane body, PVC membrane body includes basic unit, adhesive linkage, cold-resistant layer, heat preservation, fire-retardant layer, anti UV layer and anti ultraviolet layer, anti ultraviolet layer sets up the top on anti UV layer, cold-resistant layer sets up the top at the adhesive linkage, the adhesive linkage sets up the top at the basic unit, this anti UV and anti ultraviolet PVC membrane and preparation method thereof, the ultraviolet protection of being convenient for, the while is prepared simply, and work efficiency is high.
However, in the invention, the ultraviolet resistance of the PVC film is improved by adopting the multi-layer film compounding, and the PVC film body is not modified, so that the application of the PVC film is limited. In addition, TiO is mostly adopted in the prior art 2 、CeO 2 And the inorganic nanoparticles are used for carrying out the ultraviolet resistance modification of PVC, but the inorganic nanoparticles have poor compatibility with a PVC matrix, are easy to agglomerate, are difficult to exert a good ultraviolet resistance effect, and can influence the mechanical property of PVC. Therefore, new modification methods are required to achieve effective uv-protection modification of PVC films.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an ultraviolet-proof PVC film and a preparation method thereof.
The invention is through to TiO 2 Modifying to form TiO 2 The hybrid nano-particles with MgO and the epoxy groups grafted on the surface of the particles can improve TiO on the one hand 2 The anti-ultraviolet effect of the nano particle per se can be weakenedAgglomeration between the seeds; the invention adds auxiliary agent into membrane raw material, the molecular chain of the auxiliary agent contains-CN, benzene ring, -NH on the benzene ring 2 The auxiliary agent has the function of absorbing ultraviolet rays, and the auxiliary agent has good compatibility with the PVC matrix; firstly, melting PVC resin and an auxiliary agent to form a premix, and then adding modified TiO 2 To modify the TiO 2 Has good compatibility with the premix and promotes the modification of TiO 2 The ultraviolet resistance effect is stably exerted due to the uniform distribution in the film; the invention can improve the ultraviolet resistance effect of the PVC film from multiple aspects such as absorbing ultraviolet rays in a chemical sense, weakening the damage of ultraviolet rays to PVC chemical bonds, shielding ultraviolet rays in a physical aspect and the like, and the prepared PVC film is also obviously improved in toughness.
The purpose of the invention can be realized by the following technical scheme:
an ultraviolet-proof PVC film comprises the following raw materials in parts by weight: 50-60 parts of PVC resin, 15-24 parts of diisononyl phthalate, 1-1.2 parts of auxiliary plasticizer and modified TiO 2 1.5-1.8 parts of assistant and 8-10 parts of additive.
Further, the auxiliary plasticizer is epoxidized soybean oil; the epoxidized soybean oil has a plasticizing effect on PVC products, can improve the mechanical strength and weather resistance of the products, has a crosslinking and toughening effect on the PVC products, and has light and heat resistance, ageing resistance and other properties, but the epoxidized soybean oil has poor compatibility with PVC resin and is used as an auxiliary plasticizer; the diisononyl phthalate has good compatibility with PVC resin and can play a good toughening role, but the thermal stability is poor, so that the diisononyl phthalate is used as a main plasticizer, the epoxidized soybean oil is used as an auxiliary plasticizer, and the diisononyl phthalate and the epoxidized soybean oil act synergistically to effectively toughen the PVC film.
Further, modified TiO 2 Is prepared by the following steps:
s1, adding NaOH solution (with the concentration of 2.5mol/L) and MgSO 4 Solution (concentration 2.5mol/L), TiCl 3 Mixing the solution (with concentration of 2.5mol/L) at a certain proportion, adding into a high-pressure reaction kettle, performing hydrothermal reaction at 180 deg.C for 20-22h, cooling to room temperature, taking out, centrifuging at 7000r/min in a centrifuge6-7min, taking out the precipitate, washing with water and ethanol sequentially for three times, drying in a vacuum drying oven at 110 ℃ for 12h, grinding, calcining in a muffle furnace at a temperature of 5 ℃/min to 450 ℃ for 4h, and taking out to obtain the hybrid TiO 2 (ii) a NaOH solution, MgSO 4 Solution and TiCl 3 The volume ratio of the solution is 3:2: 2;
s2, dissolving a silane coupling agent KH560 in an ethanol aqueous solution (volume fraction of 50%), preparing a coupling agent solution with the mass fraction of 20%, and mixing the hybridized TiO 2 Mixing with coupling agent solution at a solid-to-liquid ratio of 1g:15mL, heating to 80 deg.C, stirring for 60min, filtering, and drying in a vacuum oven for 3-4h to obtain modified TiO 2 ；
Prepared by hydrothermal synthesis method and has MgO and TiO 2 The inorganic nano-particles are treated by a silane coupling agent KH560 on the surfaces of the inorganic nano-particles, so that the nano-particles can be prevented from agglomerating, and active groups, namely epoxy groups, are grafted on the surfaces of the inorganic nano-particles;
adding modified TiO into PVC film raw material 2 In which the nano TiO with high anti-ultraviolet aging property 2 Particles directly acting as an anti-aging agent when part of the UV light is transmitted through the TiO 2 When the PVC material is subjected to light-induced HCl elimination reaction, the PVC material reacts with part of MgO particles to form MgCl 2 And H 2 O, H inside the PVC film even though water molecules on the surface are easily evaporated 2 O and MgO can play a role in isolating air, no oxygen enters the PVC material, so that the PVC material is not easy to generate a second-stage photo-oxidation reaction in the photodegradation process, only a self-crosslinking reaction is generated, and the strength of the polymer can be improved by proper crosslinking, so that the PVC material is superior to the PVC material which is only singly used by TiO 2 And the hybridized MgO can improve the ultraviolet resistance effect to a certain extent.
Further, the auxiliary agent is prepared by the following steps:
adding 4-aminostyrene, acrylonitrile and an initiator BPO into a four-neck flask provided with a reflux condenser pipe, a thermometer and a stirrer, heating by using an electric heating sleeve, setting the reaction temperature to be 70 ℃ for carrying out polymerization reaction, controlling the reaction time to be 150-; the mol ratio of 4-aminostyrene to acrylonitrile is controlled to be 1:1, and the addition amount of the initiator BPO is 0.2 percent of the total mass of the 4-aminostyrene and the acrylonitrile;
under the action of an initiator, 4-aminostyrene and acrylonitrile undergo bulk polymerization to obtain an auxiliary agent, and the obtained auxiliary agent contains-CN, benzene ring and-NH on the benzene ring on the side chain of the molecule 2 The specific reaction equation is as follows:
the styrene component contained in the auxiliary agent molecules enables the auxiliary agent molecules to have good processing performance, and-CN on the auxiliary agent molecular chain and-Cl polar groups on the PVC molecular chain can interact, so that PVC and the auxiliary agent have good compatibility, and the auxiliary agent molecules are easily adhered to PVC resin during processing and melting to form the entanglement and pulling effects among the molecular chains, thereby being beneficial to breaking the multi-level particle structure of PVC and promoting the plasticization of PVC on one hand, and increasing the plasticizing torque on the other hand to achieve a certain toughening effect;
the electron of the benzene ring and the unsaturated bond contained in-CN in the auxiliary agent molecule is easy to generate pi → pi energy level transition under the irradiation of ultraviolet light, and the non-covalent electron of the nitrogen atom in-CN is also easy to generate n → pi energy level transition, so that the auxiliary agent has stronger absorption capacity to the ultraviolet light; the auxiliary agent is added into the PVC raw material, ultraviolet rays can be absorbed to a certain degree, the ultraviolet resistance of the PVC film is improved, then-CN of the auxiliary agent can form hydrogen bonds with PVC molecular chains, under the action of the ultraviolet rays, the hydrogen bonds can cause multi-proton transfer effect, molecules in an excited state are promoted to dissipate the excited energy in a harmless energy form, and therefore the damage of the ultraviolet rays to PVC chemical bonds is relieved; the addition of the auxiliary agent in the PVC raw material improves the anti-ultraviolet effect of the PVC film from two aspects of absorbing ultraviolet rays and weakening the damage of the ultraviolet rays to PVC chemical bonds.
A preparation method of an ultraviolet-proof PVC film comprises the following steps:
firstly, weighing PVC resin, diisononyl phthalate, an auxiliary plasticizer and an auxiliary agent according to the weight parts of the raw materials, mixing, putting the mixture into a high-speed blender, and stirring and smelting at the temperature of 130-140 ℃ for 12-15min to obtain a premix;
second, adding modified TiO into the premix 2 Continuously stirring at the temperature of 130 ℃ and 140 ℃ for 7-10min, and then sending into a double-screw extruder for extrusion granulation;
and thirdly, feeding the materials into a four-roller extruder, setting the heating temperature at 140-160 ℃, and calendering the materials into a film to obtain the ultraviolet-proof PVC film.
Further, the screw temperature of the twin-screw extruder is: the first zone temperature 138-.
Firstly, the auxiliary agent and PVC resin are smelted at high temperature, and then the modified TiO is added 2 Continuously mixing, the auxiliary agent and the PVC resin have good compatibility, the auxiliary agent and the PVC resin form a molecular chain winding effect to form a new matrix, and then the modified TiO is added 2 The auxiliary agent contains-NH in the molecule 2 Radical, modified TiO 2 Surface-grafted epoxy groups capable of reacting with-NH 2 Ring opening reaction is carried out to improve the modified TiO 2 Compatibility and interaction force with the matrix to modify the TiO 2 Uniformly distributed in the PVC film, and stably exerts the ultraviolet resistance from the physical layer.
The invention has the beneficial effects that:
in the process of toughening PVC resin, diisononyl phthalate is selected as a main plasticizer, epoxidized soybean oil is selected as an auxiliary plasticizer, and the diisononyl phthalate and the epoxidized soybean oil act synergistically to effectively toughen a PVC film; in addition, the toughness of the PVC film can be improved to a certain extent by adding the self-made auxiliary agent, so that the toughness of the PVC film is effectively improved;
the invention is through to TiO 2 Modified to form TiO 2 The hybrid nano particle with MgO and the epoxy group grafted on the surface of the hybrid nano particle can improve TiO on one hand 2 The ultraviolet resistance effect of the composition can be reducedAgglomeration between weak nanoparticles; the invention adds auxiliary agent into membrane raw material, the molecular chain of the auxiliary agent contains-CN, benzene ring, -NH on the benzene ring 2 The auxiliary agent has the function of absorbing ultraviolet rays, and the auxiliary agent has good compatibility with the PVC matrix; firstly, melting PVC resin and an auxiliary agent to form a premix, and then adding modified TiO 2 To modify TiO 2 Has good compatibility with the premix and promotes the modification of TiO 2 The ultraviolet resistance effect is stably exerted due to the uniform distribution in the film; the invention can improve the ultraviolet resistance effect of the PVC film in various aspects such as absorbing ultraviolet rays in a chemical sense, weakening the damage of ultraviolet rays to PVC chemical bonds, shielding ultraviolet rays in a physical aspect and the like.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to 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
Preparation of modified TiO 2 ：
S1, mixing 300mL of NaOH solution (concentration 2.5mol/L) and 200mL of MgSO 4 Solution (concentration 2.5mol/L) 200mL of TiCl 3 Mixing the solution (with the concentration of 2.5mol/L), adding the mixture into a high-pressure reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 20h, cooling to room temperature, taking out the mixture, centrifuging in a centrifuge at 7000r/min for 6min, taking out the precipitate, washing with water and ethanol successively for three times, drying in a vacuum drying oven at 110 ℃ for 12h, grinding, putting the product into a muffle furnace at the temperature of 5 ℃/min to 450 ℃, calcining for 4h, and taking out to obtain the hybrid TiO 2 ；
S2, dissolving a silane coupling agent KH560 in an ethanol aqueous solution (volume fraction is 50%), preparing a coupling agent solution with the mass fraction of 20%, and mixing 10g of prepared hybridized TiO 2 Mixing with 150mL of coupling agent solution, raising the temperature to 80 ℃, stirring for 60min, filtering, and drying in a vacuum oven for 3-4h to obtain the modifiedTiO 2 。
Example 2
Preparation of modified TiO 2 ：
S1, mixing 300mL of NaOH solution (concentration 2.5mol/L) and 200mL of MgSO 4 Solution (concentration 2.5mol/L) 200mL of TiCl 3 Mixing the solution (with the concentration of 2.5mol/L), adding the mixture into a high-pressure reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 22h, cooling to room temperature, taking out the mixture, centrifuging the mixture in a centrifuge at 7000r/min for 7min, taking out the precipitate, washing with water and ethanol sequentially for three times, putting the precipitate into a vacuum drying oven, drying the dried precipitate at 110 ℃ for 12h, grinding the dried precipitate, putting the ground precipitate into a muffle furnace, heating the ground precipitate to 450 ℃ at 5 ℃/min, calcining the calcined precipitate for 4h, and taking out the calcined precipitate to obtain the hybrid TiO 2 ；
S2, dissolving a silane coupling agent KH560 in an ethanol aqueous solution (volume fraction is 50%), preparing a coupling agent solution with the mass fraction of 20%, and mixing 10g of prepared hybridized TiO 2 Mixing with 150mL of coupling agent solution, raising the temperature to 80 ℃, stirring for 60min, filtering, and drying in a vacuum oven for 3-4h to obtain modified TiO 2 。
Example 3
Preparing an auxiliary agent:
1mol of 4-aminostyrene, 1mol of acrylonitrile and 0.344g of initiator BPO are added into a four-neck flask provided with a reflux condenser, a thermometer and a stirrer, heating is carried out by an electrothermal sleeve, the reaction temperature is set to be 70 ℃ for polymerization reaction, the reaction time is controlled to be 150min, after the reaction is finished, a polymerization product is cleaned by a small amount of 3% alcohol, and then drying treatment is carried out at 105 ℃ to obtain the auxiliary agent.
Example 4
Preparing an auxiliary agent:
1mol of 4-aminostyrene, 1mol of acrylonitrile and 0.344g of initiator BPO are added into a four-neck flask provided with a reflux condenser, a thermometer and a stirrer, heating is carried out by an electric heating sleeve, the reaction temperature is set to be 70 ℃, polymerization reaction is carried out, the reaction time is controlled to be 160min, after the reaction is finished, a small amount of 3% alcohol is used for cleaning a polymerization product, and drying treatment is carried out at 95 ℃ to obtain the auxiliary agent.
Example 5
Preparing an ultraviolet-proof PVC film:
firstly, weighing 50g of PVC resin, 15g of diisononyl phthalate, 1g of epoxidized soybean oil and 8g of the auxiliary agent prepared in the embodiment 3, mixing, putting the mixture into a high-speed blender, stirring and smelting at the temperature of 130-;
second, 1.5g of the modified TiO prepared in example 1 was added to the premix 2 Continuously stirring for 7min at the temperature of 130 ℃, and then feeding into a double-screw extruder for extrusion granulation;
and thirdly, feeding the materials into a four-roller extruder, setting the heating temperature at 140 ℃, and rolling the materials into a film to obtain the ultraviolet-proof PVC film.
The screw temperature of the twin-screw extruder was: the first zone temperature is 138 ℃, the second zone temperature is 135 ℃, the third zone temperature is 135 ℃, the fourth zone temperature is 132 ℃ and the fifth zone temperature is 130 ℃.
Example 6
Preparing an ultraviolet-proof PVC film:
firstly, weighing 55g of PVC resin, 20g of diisononyl phthalate, 1.1g of epoxidized soybean oil and 9g of the auxiliary agent prepared in the embodiment 3, mixing, putting the mixture into a high-speed blender, and stirring and smelting at the temperature of 135 ℃ for 14min to obtain a premix;
second, 1.7g of the modified TiO prepared in example 1 was added to the premix 2 Continuously stirring for 8min at the temperature of 135 ℃, and then feeding into a double-screw extruder for extrusion granulation;
and thirdly, feeding the materials into a four-roller extruder, setting the heating temperature at 150 ℃, and rolling the materials into a film to obtain the ultraviolet-proof PVC film.
The screw temperatures of the twin-screw extruder were: the first zone temperature was 150 ℃, the second zone temperature was 148 ℃, the third zone temperature was 145 ℃, the fourth zone temperature was 140 ℃ and the fifth zone temperature was 138 ℃.
Example 7
Preparing an ultraviolet-proof PVC film:
step one, weighing 60g of PVC resin, 24g of diisononyl phthalate, 1.2g of epoxidized soybean oil and 10g of the auxiliary agent prepared in the embodiment 3, mixing, putting the mixture into a high-speed blender, and stirring and smelting at the temperature of 140 ℃ for 15min to obtain a premix;
second, 1.8g of the modified TiO prepared in example 1 was added to the premix 2 Continuously stirring at 140 ℃ for 10min, and then feeding into a double-screw extruder for extrusion granulation;
and thirdly, feeding the materials into a four-roller extruder, setting the heating temperature at 160 ℃, and rolling the materials into a film to obtain the ultraviolet-proof PVC film.
The screw temperature of the twin-screw extruder was: the first zone temperature is 160 ℃, the second zone temperature is 160 ℃, the third zone temperature is 155 ℃, the fourth zone temperature is 150 ℃ and the fifth zone temperature is 148 ℃.
Comparative example 1
Modified TiO from example 5 2 Raw material is changed into common nano TiO 2 The other raw materials and the preparation process are not changed.
Comparative example 2
The auxiliary raw materials in example 5 are removed, and the rest raw materials and the preparation process are unchanged.
Comparative example 3
Modified TiO of example 5 2 And the auxiliary raw materials are removed, and the other raw materials and the preparation process are unchanged.
The following performance tests were carried out on the PVC films obtained in examples 5 to 7 and comparative examples 1 to 3:
and (3) testing tensile property: testing according to GB/T1040.3-2006, wherein the width of a sample is 25mm, the length of the sample is 150mm, the distance between clamps is 100mm, and the stretching speed is 300 mm/min;
ultraviolet resistance experiment: testing the change rate of tensile stress and elongation at break before and after 1008h aging according to a GB/T12527-2008 standard artificial weathering test method, wherein the higher the change rate is, the poorer the ultraviolet resistance effect is, and otherwise, the better the effect is;
the results obtained are shown in the following table:
as can be seen from the data in the table, the PVC films prepared in examples 5-7 have higher tensile stress and elongation at break, which indicates that the PVC films prepared by the invention have better mechanical properties; through ultraviolet aging tests, the change rates of the tensile strain and the elongation at break of the PVC films prepared in examples 5-7 are less than 20%, which shows that the PVC films prepared by the invention have high ultraviolet resistance; the data of the comparative example 1 and the comparative example 2 are combined, so that the modification and the auxiliary agent have a mutual synergistic and promoting effect, and the mechanical strength and the ultraviolet resistance of the PVC film can be improved to a certain extent by matching the modification and the auxiliary agent.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (8)
1. The ultraviolet-proof PVC film is characterized by comprising the following raw materials in parts by weight: 50-60 parts of PVC resin, 15-24 parts of diisononyl phthalate, 1-1.2 parts of auxiliary plasticizer and modified TiO 2 1.5-1.8 parts of assistant and 8-10 parts of additive;
wherein the auxiliary agent is prepared by the following steps:
adding 4-aminostyrene, acrylonitrile and an initiator BPO into a four-neck flask provided with a reflux condenser tube, a thermometer and a stirrer, heating by using an electric heating sleeve, setting the reaction temperature to be 70 ℃ for carrying out polymerization reaction, controlling the reaction time to be 150-160min, after the reaction is finished, cleaning a polymerization product by using a small amount of alcohol with the concentration of 3%, and then carrying out drying treatment at high temperature to obtain the auxiliary agent.
2. The UV-blocking PVC film according to claim 1, wherein the molar ratio of 4-aminostyrene to acrylonitrile is controlled to 1:1, and the initiator BPO is added in an amount of 0.2% of the total mass of 4-aminostyrene and acrylonitrile.
3. The UV-blocking PVC film according to claim 1, wherein said secondary plasticizer is epoxidized soybean oil.
4. The UV-blocking PVC film according to claim 1, wherein the modified TiO is selected from the group consisting of 2 Is prepared by the following steps:
s1, mixing NaOH solution and MgSO 4 Solution, TiCl 3 Mixing the solutions in proportion, adding the mixture into a high-pressure reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 20-22h, taking out the mixture after cooling to room temperature, centrifuging the mixture in a centrifuge at 7000r/min for 6-7min, taking out the precipitate, washing the precipitate with water and ethanol sequentially for three times, drying the precipitate in a vacuum drying oven at 110 ℃ for 12h, grinding the dried precipitate, putting the ground precipitate into a muffle furnace, heating the ground precipitate to 450 ℃ at 5 ℃/min, calcining the calcined precipitate for 4h, and obtaining the hybrid TiO 2 ；
S2, dissolving a silane coupling agent KH560 in an ethanol water solution to prepare a coupling agent solution with the mass fraction of 20%, and mixing hybridized TiO 2 Mixing with coupling agent solution at a solid-to-liquid ratio of 1g:15mL, heating to 80 deg.C, stirring for 60min, filtering, and drying in a vacuum oven for 3-4h to obtain modified TiO 2 。
5. The UV-blocking PVC film according to claim 4, wherein NaOH solution, MgSO, in step S1 4 Solution and TiCl 3 The concentration of the solution is 2.5mol/L, NaOH solution and MgSO 4 Solution and TiCl 3 The volume ratio of the solution was 3:2: 2.
6. The UV-blocking PVC film according to claim 4, wherein the volume fraction of the ethanol aqueous solution in step S2 is 50%.
7. The method for preparing the ultraviolet-proof PVC film according to claim 1, which comprises the following steps:
firstly, weighing PVC resin, diisononyl phthalate, an auxiliary plasticizer and an auxiliary agent according to the weight parts of the raw materials, mixing, putting the mixture into a high-speed blender, and stirring and smelting at the temperature of 130-140 ℃ for 12-15min to obtain a premix;
second, adding modified TiO into the premix 2 Continuously stirring at the temperature of 130 ℃ and 140 ℃ for 7-10min, and then sending into a double-screw extruder for extrusion granulation;
and thirdly, feeding the materials into a four-roller extruder, setting the heating temperature at 140-160 ℃, and calendering the materials into a film to obtain the ultraviolet-proof PVC film.
8. The method for preparing the ultraviolet-proof PVC film as claimed in claim 7, wherein the screw temperature of the twin-screw extruder is as follows: the first zone temperature 138-.
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