CN112574446B - PVC composite membrane with high visible light catalytic activity and preparation method thereof - Google Patents

PVC composite membrane with high visible light catalytic activity and preparation method thereof Download PDF

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CN112574446B
CN112574446B CN202011450696.XA CN202011450696A CN112574446B CN 112574446 B CN112574446 B CN 112574446B CN 202011450696 A CN202011450696 A CN 202011450696A CN 112574446 B CN112574446 B CN 112574446B
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CN112574446A (en
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黎银茵
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Xi'an Shangyouxing Ecological Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/246—All polymers belonging to those covered by groups B32B27/32 and B32B27/30
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/418—Refractive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/728—Hydrophilic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The invention discloses a PVC composite film with high visible light catalytic activity and a preparation method thereof. According to the invention, the composite film structure, components and the preparation process are arranged to form the first film layer and the second film layer with different refractive indexes, both the first film layer and the second film layer are made of thermoplastic resin and thermosetting resin, both the first film layer and the second film layer have hydrophilicity, and the photocatalysis effect of the component titanium dioxide can be fully exerted; the degradation of the composite membrane is promoted by the cooperation of materials, and the aesthetic degree of the composite membrane during degradation is improved while the high visible light catalytic activity is realized.

Description

PVC composite membrane with high visible light catalytic activity and preparation method thereof
Technical Field
The invention relates to the technical field of PVC composite membranes, in particular to a PVC composite membrane with high visible light catalytic activity and a preparation method thereof.
Background
The PVC is a polymer generated by polymerization reaction of vinyl chloride monomer, has stable physicochemical properties, low gas and water vapor permeability, fire resistance and heat resistance, and is widely applied in various industries due to the functional properties; the world film use amount of the polyvinyl chloride film is front, the polyvinyl chloride film is mostly applied to disposable products, the recycling value is low, if the polyvinyl chloride film is burnt and discarded after the polyvinyl chloride film is used, the environment can be polluted, the polyvinyl chloride film is degraded by heat, light, microorganisms and the like, the photocatalytic material titanium dioxide is utilized to promote the degradation of the polyvinyl chloride in the conventional practice, the photocatalytic activity of the titanium dioxide is only relied on, and the polyvinyl chloride is easy to yellow and lose luster when decomposed, so that the appearance of the polyvinyl chloride film is influenced. Therefore, a PVC composite membrane with high visible light catalytic activity and a preparation method thereof are provided.
Disclosure of Invention
The invention aims to provide a PVC composite film with high visible light catalytic activity and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the utility model provides a PVC complex film of high visible light catalytic activity, the complex film includes first rete and second rete, first rete is located the top of second rete, first rete is polylactic acid modified polyvinyl chloride rete, the second rete is furfural modified polyvinyl chloride rete.
Further, the first film layer comprises the following components in parts by weight: 100 parts of polyvinyl chloride, 10-15 parts of polylactic acid, 8-12 parts of methyl phenyl vinyl silicone rubber, 0.2-0.3 part of sulfur, 3-4 parts of acrylic acid, 1-3 parts of methacrylic acid, 2-4 parts of sodium vinylsulfonate, 1.0-1.5 parts of allyl alcohol, 2-6 parts of dimethyl carbonate and 2.8-9.0 parts of diethylene glycol.
Further, the second film layer comprises the following components in parts by weight: 100 parts of polyvinyl chloride, 11-43 parts of cellulose acetate, 5-43 parts of acrylate, 8-12 parts of titanium dioxide, 9-18 parts of urea, 14-29 parts of furfural and 0.6-1.2 parts of p-tert-butyl catechol.
Further, the refractive index of the first film layer is higher than that of the second film layer.
Further, the acrylate is one or more of methyl methacrylate, n-butyl methacrylate, isooctyl acrylate and isooctyl methacrylate.
Further, the titanium dioxide is anatase type nano titanium dioxide.
A preparation method of a PVC composite film with high visible light catalytic activity comprises the following steps:
(1) preparing a first film layer:
adding sulfur into methyl phenyl vinyl silicone rubber for mixing to prepare silicone rubber A; adding deionized water into acrylic acid, methacrylic acid and sodium vinylsulfonate to prepare a solution B; taking propylene alcohol, dimethyl carbonate and diethylene glycol to react, and then blending the propylene alcohol, the dimethyl carbonate and the solution B to react to prepare resin C; reacting polylactic acid with metal sodium, and then reacting with polyvinyl chloride to prepare modified polyvinyl chloride; adding silicon rubber A and resin C into modified polyvinyl chloride, and co-extruding to obtain a first film layer;
(2) preparing a second film layer:
respectively adding cellulose acetate and acrylic ester into polyvinyl chloride, blending, adding titanium dioxide and p-tert-butyl catechol, and blending to obtain modified polyvinyl chloride; reacting urea with furfural to prepare furfural resin; adding furfural resin into modified polyvinyl chloride for co-extrusion film making to obtain a second film layer;
(3) preparing a composite membrane: and compounding the first film layer and the second film layer to obtain the composite film.
Further, the step (1) comprises the steps of:
adding sulfur into methyl phenyl vinyl silicone rubber for mixing to prepare silicone rubber A;
adding deionized water into acrylic acid, methacrylic acid and sodium vinylsulfonate to prepare a solution B;
adding diethylene glycol and a catalyst into propylene alcohol and dimethyl carbonate, reacting at a constant temperature of 50-70 ℃ for 3-4 hours, adding N, N-dimethylacetamide into the product, fully mixing, adding the solution B, hydrogen peroxide and N, N' -methylene bisacrylamide, fully mixing, and reacting for 20-24 hours to obtain resin C;
adding polylactic acid into cyclohexanone to fully dissolve, adding metal sodium, heating to 140-150 ℃ in a nitrogen atmosphere, reacting for 8-9 h, slowly adding a product into a cyclohexane solution of polyvinyl chloride, and reacting for 4-8 h at 120-130 ℃ to obtain modified polyvinyl chloride;
adding the silicon rubber A and the resin C into the modified polyvinyl chloride, and co-extruding to obtain a first film layer.
Further, the step (2) comprises the following steps:
dissolving polyvinyl chloride in N, N-dimethylacetamide, adding cellulose acetate and disodium hydrogen phosphate aqueous solution, fully stirring, heating to 55-65 ℃, preserving heat, adding acrylate, slowly adding potassium persulfate, and reacting at constant temperature for 3-4 h; adding titanium dioxide and p-tert-butyl catechol into the reaction product, and blending to obtain modified polyvinyl chloride;
dissolving urea in deionized water, heating to 40-50 ℃, adding a sodium hydroxide aqueous solution to adjust the pH of the system to be alkaline, adding furfural with the weight of 80% of the components, stirring and reacting at a constant temperature for 40-50 min, adding sodium hydroxide again, stirring for 10-20 min, adding the remaining components, namely furfural, and reacting for 2-3 h to obtain furfural resin;
and adding furfural resin into the modified polyvinyl chloride, and co-extruding to prepare a second film layer.
Further, the step (3) comprises the following steps:
respectively coating potassium persulfate solution on the bottom of the first film layer and the top of the second film layer, then compounding the bottom of the first film layer and the top of the second film layer, and performing hot-pressing compounding at the temperature of 55-65 ℃ to obtain the composite film.
In the technical scheme, the polyvinyl chloride composite film structure is arranged, so that the refractive index of the upper layer of the prepared composite film is larger than that of the lower layer, the reflection of a film body to light after receiving light is reduced, the optical density of the prepared composite film is improved, and the prepared composite film is an active tamped substance foundation generated after the composite film is catalyzed by visible light;
when the first film layer is prepared, allyl diglycol carbonate is generated by allyl alcohol, dimethyl carbonate and diglycol under the action of a catalyst, has a high refractive index, and then is used as a reaction system of acrylic acid, methacrylic acid and sodium vinylsulfonate, so that the prepared polyacrylic acid molecular chain is inserted among the allyl diglycol carbonate molecules to form an interpenetrating network, and a resin C is formed, so that the mechanical property of the prepared first film layer can be ensured, and the hydrophilicity, the wear resistance and the optical property of the first film layer are improved; the polylactic acid is grafted with the polyvinyl chloride through the sodium metal to prepare the modified polyvinyl chloride, so that the biodegradability of the prepared first film layer can be improved; the methyl phenyl vinyl silicone rubber is sulfonated under the action of sulfur to prepare silicone rubber A, so that the mechanical property of the prepared first film layer is improved; the prepared resin C, the modified polyvinyl chloride and the silicon rubber A are blended to prepare the prepared first film layer, and the prepared first film layer has high refractive index, good wear resistance, mechanical strength and biodegradability;
when the second film layer is prepared, the acrylate is polymerized in the presence of polyvinyl chloride and cellulose acetate, the hydrophilicity of the prepared second film layer can be improved, the acrylate selects soft monomers of methyl methacrylate and n-butyl methacrylate, hard monomers of isooctyl acrylate and isooctyl methacrylate, the polymerization product has a better refractive index, the refractive index of the prepared second film layer is slightly smaller than that of the first film layer, the ratio of the soft monomers to the hard monomers is set to be (5:45) - (25:25), and the polymerization product has better surface tension; the furfural resin is prepared by polymerizing urea and furfural, is environment-friendly, and has better corrosion resistance and heat resistance; the two are blended to prepare a second film layer with better hydrophilicity;
the first film layer and the second film layer are both the mixture of thermoplastic resin and thermosetting resin, so that the first film layer and the second film layer are easier to separate during degradation, and the degradation difficulty of the composite film can be reduced; when the first film layer and the second film layer are compounded, a potassium persulfate solution is sprayed between the first film layer and the second film layer, and then hot-pressing compounding is carried out to initiate cross-linking compounding between the two film layers, so that the compounding strength of the prepared composite film is improved, and the prepared composite film has better transparency and glossiness;
when the prepared composite membrane is used, under the action of visible light, electrons in the titanium dioxide undergo transition to generate holes, the holes react with water to generate hydroxyl radicals, the prepared composite membrane has good hydrophilicity and can promote the reaction, the electrons react with oxygen to generate superoxide anions, and the prepared composite membrane has high oxygen content due to material combination, so that the reaction is promoted to move to the positive direction; polyvinyl chloride is decomposed under the action of illumination to generate HCl and generate double bonds, wherein the HCl promotes the decomposition of furfural resin to generate furfural, and can be used for inhibiting the polymerization of polyvinyl chloride decomposition product olefins in cooperation with sulfur and p-tert-butyl catechol in the first film layer, resisting oxidation, preventing the composite film from yellowing, keeping the glossiness of the composite film and improving the aesthetic degree of the composite film during degradation; due to the self-property of the furfural resin, the absorption of the composite film to visible light can be promoted, and the optical density of the composite film is improved, the photocatalytic effect of titanium dioxide is promoted, and the photocatalytic activity is improved by combining the refractive index difference between the first film layer and the second film layer; along with the extension of the illumination time, the furfural resin is decomposed to generate the conjugate resin with smaller molecular weight, the photoelectric effect is generated, the effect of titanium dioxide is enhanced, and the prepared composite membrane achieves high visible light catalytic activity.
Compared with the prior art, the invention has the following beneficial effects:
according to the PVC composite film with high visible light catalytic activity and the preparation method thereof, the first film layer and the second film layer with different refractive indexes are formed by setting the structure, components and preparation process of the composite film, and both the first film layer and the second film layer are made of thermoplastic resin and thermosetting resin, have hydrophilicity and can fully exert the photocatalytic effect of titanium dioxide; the degradation of the composite membrane is promoted by the cooperation of materials, and the aesthetic degree of the composite membrane during degradation is improved while the high visible light catalytic activity is realized.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be understood 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) Preparing a first film layer:
adding 8 parts of methyl phenyl vinyl silicone rubber into 0.2 part of sulfur for mixing to prepare silicone rubber A;
adding deionized water into 3 parts of acrylic acid, 1 part of methacrylic acid and 2 parts of sodium vinylsulfonate to prepare a solution B;
taking 1.0 part of propylene alcohol and 2 parts of dimethyl carbonate, adding 2.8 parts of diethylene glycol and a catalyst, placing at 50 ℃ for constant temperature reaction for 3 hours, taking a product, adding N, N-dimethylacetamide, fully mixing, adding the solution B, hydrogen peroxide and N, N' -methylene bisacrylamide, fully mixing, and reacting for 20 hours to obtain resin C;
adding 10 parts of polylactic acid into cyclohexanone to be fully dissolved, adding metal sodium, heating to 140 ℃ in a nitrogen atmosphere, reacting for 8 hours, slowly adding the product into a cyclohexane solution of 100 parts of polyvinyl chloride, and reacting for 4 hours at 120 ℃ to obtain modified polyvinyl chloride;
adding silicon rubber A and resin C into modified polyvinyl chloride, and co-extruding to obtain a first film layer;
(2) preparing a second film layer:
dissolving 100 parts of polyvinyl chloride in N, N-dimethylacetamide, adding 11 parts of cellulose acetate and disodium hydrogen phosphate aqueous solution, fully stirring, heating to 55 ℃, preserving heat, adding 5 parts of acrylate, slowly adding potassium persulfate, and reacting at constant temperature for 3 hours; adding 8 parts of titanium dioxide and 0.6 part of p-tert-butyl catechol into the reaction product, and blending to prepare modified polyvinyl chloride, wherein the acrylate is methyl methacrylate, n-butyl methacrylate, isooctyl acrylate and isooctyl methacrylate, and the mass ratio of the methyl methacrylate to the n-butyl methacrylate to the isooctyl acrylate to the isooctyl methacrylate is 5: 45;
dissolving 9 parts of urea in deionized water, heating to 40 ℃, adding a sodium hydroxide aqueous solution to adjust the pH of the system to be alkaline, adding furfural with the weight of 80% of the components, wherein the total weight of the furfural is 14 parts, stirring and reacting at constant temperature for 40min, adding sodium hydroxide again, stirring for 10min, adding the rest of the components, and reacting for 2h to obtain furfural resin;
taking modified polyvinyl chloride, adding furfural resin, and co-extruding to prepare a second film layer;
(3) preparing a composite membrane:
respectively coating potassium persulfate solution on the bottom of the first film layer and the top of the second film layer, then compounding the bottom of the first film layer and the top of the second film layer, and performing hot-press compounding at the temperature of 55 ℃ to obtain the composite film.
Example 2
(1) Preparing a first film layer:
taking 10 parts of methyl phenyl vinyl silicone rubber, adding 0.2 part of sulfur, and mixing to obtain silicone rubber A;
adding deionized water into 3.5 parts of acrylic acid, 2 parts of methacrylic acid and 3 parts of sodium vinylsulfonate to prepare a solution B;
taking 1.2 parts of propylene alcohol and 4 parts of dimethyl carbonate, adding 5.9 parts of diethylene glycol and a catalyst, placing at a constant temperature of 60 ℃ for reaction for 3.5 hours, taking a product, adding N, N-dimethylacetamide, fully mixing, adding the solution B, hydrogen peroxide and N, N' -methylene bisacrylamide, fully mixing, and reacting for 22 hours to obtain resin C;
adding 12 parts of polylactic acid into cyclohexanone to be fully dissolved, adding metal sodium, heating to 145 ℃ in a nitrogen atmosphere, reacting for 8.5 hours, slowly adding the product into a cyclohexane solution of 100 parts of polyvinyl chloride, and reacting for 6 hours at 125 ℃ to obtain modified polyvinyl chloride;
taking modified polyvinyl chloride, adding silicon rubber A and resin C, and co-extruding to obtain a first film layer;
(2) preparing a second film layer:
dissolving 100 parts of polyvinyl chloride in N, N-dimethylacetamide, adding 27 parts of cellulose acetate and disodium hydrogen phosphate aqueous solution, fully stirring, heating to 60 ℃, preserving heat, adding 24 parts of acrylate, slowly adding potassium persulfate, and reacting at constant temperature for 3.5 hours; adding 10 parts of titanium dioxide and 0.9 part of p-tert-butyl catechol into the reaction product, and blending to prepare modified polyvinyl chloride, wherein the acrylate is methyl methacrylate, n-butyl methacrylate, isooctyl acrylate and isooctyl methacrylate, and the mass ratio of the methyl methacrylate to the n-butyl methacrylate to the isooctyl acrylate to the isooctyl methacrylate is 15: 35;
dissolving 13 parts of urea in deionized water, heating to 45 ℃, adding a sodium hydroxide aqueous solution to adjust the pH of the system to be alkaline, adding furfural with the weight of 80% of the components, wherein the total weight of the furfural is 21 parts, stirring and reacting at constant temperature for 45min, adding sodium hydroxide again, stirring for 15min, adding the remaining components of furfural, and reacting for 2.5h to obtain furfural resin;
taking modified polyvinyl chloride, adding furfural resin, and co-extruding to prepare a second film layer;
(3) preparing a composite membrane:
respectively coating potassium persulfate solution on the bottom of the first film layer and the top of the second film layer, then compounding the bottom of the first film layer and the top of the second film layer, and performing hot-press compounding at the temperature of 60 ℃ to obtain the composite film.
Example 3
(1) Preparing a first film layer:
taking 12 parts of methyl phenyl vinyl silicone rubber, adding 0.3 part of sulfur, and mixing to obtain silicone rubber A;
adding deionized water into 4 parts of acrylic acid, 3 parts of methacrylic acid and 4 parts of sodium vinylsulfonate to prepare a solution B;
taking 1.5 parts of propylene alcohol and 6 parts of dimethyl carbonate, adding 9.0 parts of diethylene glycol and a catalyst, placing at 70 ℃ for constant-temperature reaction for 4 hours, taking a product, adding N, N-dimethylacetamide, fully mixing, adding the solution B, hydrogen peroxide and N, N' -methylene bisacrylamide, fully mixing, and reacting for 24 hours to obtain resin C;
taking 15 parts of polylactic acid, adding cyclohexanone to fully dissolve the polylactic acid, adding metal sodium, heating the polylactic acid to 150 ℃ in a nitrogen atmosphere, reacting for 9 hours, taking the product, slowly adding the product into a cyclohexane solution of 100 parts of polyvinyl chloride, and reacting for 8 hours at 130 ℃ to obtain modified polyvinyl chloride;
taking modified polyvinyl chloride, adding silicon rubber A and resin C, and co-extruding to obtain a first film layer;
(2) preparing a second film layer:
dissolving 100 parts of polyvinyl chloride in N, N-dimethylacetamide, adding 43 parts of cellulose acetate and disodium hydrogen phosphate aqueous solution, fully stirring, heating to 65 ℃ for heat preservation, adding 43 parts of acrylate, slowly adding potassium persulfate, and reacting at constant temperature for 4 hours; adding 12 parts of titanium dioxide and 1.2 parts of p-tert-butyl catechol into the reaction product, and blending to obtain modified polyvinyl chloride, wherein the acrylate is methyl methacrylate, n-butyl methacrylate, isooctyl acrylate and isooctyl methacrylate, and the mass ratio of the methyl methacrylate to the n-butyl methacrylate to the isooctyl acrylate to the isooctyl methacrylate is 20: 30;
dissolving 18 parts of urea in deionized water, heating to 50 ℃, adding a sodium hydroxide aqueous solution to adjust the pH of the system to be alkaline, adding furfural with the weight of 80% of the components, wherein the total weight of the furfural is 29 parts, stirring and reacting at a constant temperature for 50min, adding sodium hydroxide again, stirring for 20min, adding the rest of furfural, and reacting for 3h to obtain furfural resin;
adding furfural resin into modified polyvinyl chloride for co-extrusion film making to obtain a second film layer;
(3) preparing a composite membrane:
respectively coating potassium persulfate solution on the bottom of the first film layer and the top of the second film layer, then compounding the bottom of the first film layer and the top of the second film layer, and performing hot-press compounding at the temperature of 65 ℃ to obtain the composite film.
Comparative example 1
(1) Preparing a first film layer:
preparing a film from polyvinyl chloride to form a first film layer;
(2) preparing a second film layer:
dissolving 100 parts of polyvinyl chloride in N, N-dimethylacetamide, adding 27 parts of cellulose acetate and disodium hydrogen phosphate aqueous solution, fully stirring, heating to 60 ℃, preserving heat, adding 24 parts of acrylate, slowly adding potassium persulfate, and reacting at constant temperature for 3.5 hours; adding 10 parts of titanium dioxide and 0.9 part of p-tert-butyl catechol into the reaction product, and blending to obtain modified polyvinyl chloride, wherein the acrylate is methyl methacrylate, n-butyl methacrylate, isooctyl acrylate and isooctyl methacrylate, and the mass ratio of the methyl methacrylate to the n-butyl methacrylate to the isooctyl acrylate to the isooctyl methacrylate is 15: 35;
dissolving 13 parts of urea in deionized water, heating to 45 ℃, adding a sodium hydroxide aqueous solution to adjust the pH of the system to be alkaline, adding furfural with the weight of 80% of the components, wherein the total weight of furfural is 21 parts, stirring and reacting at constant temperature for 45min, adding sodium hydroxide again, stirring for 15min, adding the rest of furfural, and reacting for 2.5h to obtain furfural resin;
adding furfural resin into modified polyvinyl chloride for co-extrusion film making to obtain a second film layer;
(3) preparing a composite membrane:
respectively coating potassium persulfate solution on the bottom of the first film layer and the top of the second film layer, then compounding the bottom of the first film layer and the top of the second film layer, and performing hot-press compounding at the temperature of 60 ℃ to obtain the composite film.
Comparative example 2
(1) Preparing a first film layer:
taking 10 parts of methyl phenyl vinyl silicone rubber, adding 0.2 part of sulfur, and mixing to obtain silicone rubber A;
adding deionized water into 3.5 parts of acrylic acid, 2 parts of methacrylic acid and 3 parts of sodium vinylsulfonate to prepare a solution B;
taking 1.2 parts of propylene alcohol and 4 parts of dimethyl carbonate, adding 5.9 parts of diethylene glycol and a catalyst, placing at a constant temperature of 60 ℃ for reaction for 3.5 hours, taking a product, adding N, N-dimethylacetamide, fully mixing, adding the solution B, hydrogen peroxide and N, N' -methylene bisacrylamide, fully mixing, and reacting for 22 hours to obtain resin C;
taking 12 parts of polylactic acid, adding cyclohexanone to fully dissolve the polylactic acid, adding metal sodium, heating the polylactic acid to 145 ℃ in a nitrogen atmosphere, reacting for 8.5 hours, taking the product, slowly adding the product into a cyclohexane solution of 100 parts of polyvinyl chloride, and reacting for 6 hours at 125 ℃ to obtain modified polyvinyl chloride;
adding silicon rubber A and resin C into modified polyvinyl chloride, and co-extruding to obtain a first film layer;
(2) preparing a second film layer:
preparing a film from polyvinyl chloride, and adding silicon dioxide to prepare a second film layer;
(3) preparing a composite membrane:
respectively coating potassium persulfate solution on the bottom of the first film layer and the top of the second film layer, then compounding the bottom of the first film layer and the top of the second film layer, and performing hot-press compounding at the temperature of 60 ℃ to obtain the composite film.
Comparative example 3
(1) Preparing a first film layer:
taking 10 parts of methyl phenyl vinyl silicone rubber, adding 0.2 part of sulfur, and mixing to obtain silicone rubber A;
adding deionized water into 3.5 parts of acrylic acid, 2 parts of methacrylic acid and 3 parts of sodium vinylsulfonate to prepare a solution B;
taking 1.2 parts of propylene alcohol and 4 parts of dimethyl carbonate, adding 5.9 parts of diethylene glycol and a catalyst, placing at a constant temperature of 60 ℃ for reaction for 3.5 hours, taking a product, adding N, N-dimethylacetamide, fully mixing, adding the solution B, hydrogen peroxide and N, N' -methylene bisacrylamide, fully mixing, and reacting for 22 hours to obtain resin C;
adding 12 parts of polylactic acid into cyclohexanone to be fully dissolved, adding metal sodium, heating to 145 ℃ in a nitrogen atmosphere, reacting for 8.5 hours, slowly adding the product into a cyclohexane solution of 100 parts of polyvinyl chloride, and reacting for 6 hours at 125 ℃ to obtain modified polyvinyl chloride;
taking modified polyvinyl chloride, adding silicon rubber A and resin C, and co-extruding to obtain a first film layer;
(2) preparing a second film layer:
dissolving 100 parts of polyvinyl chloride in N, N-dimethylacetamide, adding 27 parts of cellulose acetate and disodium hydrogen phosphate aqueous solution, fully stirring, heating to 60 ℃, preserving heat, adding 24 parts of acrylate, slowly adding potassium persulfate, and reacting at constant temperature for 3.5 hours; adding 10 parts of titanium dioxide and 0.9 part of p-tert-butyl catechol into the reaction product, and blending to obtain modified polyvinyl chloride, wherein the acrylate is methyl methacrylate, n-butyl methacrylate, isooctyl acrylate and isooctyl methacrylate, and the mass ratio of the methyl methacrylate to the n-butyl methacrylate to the isooctyl acrylate to the isooctyl methacrylate is 15: 35;
dissolving 13 parts of urea in deionized water, heating to 45 ℃, adding a sodium hydroxide aqueous solution to adjust the pH of the system to be alkaline, adding furfural with the weight of 80% of the components, wherein the total weight of the furfural is 21 parts, stirring and reacting at constant temperature for 45min, adding sodium hydroxide again, stirring for 15min, adding the remaining components of furfural, and reacting for 2.5h to obtain furfural resin;
taking modified polyvinyl chloride, adding furfural resin, and co-extruding to prepare a second film layer;
(3) preparing a composite membrane:
and carrying out hot-pressing compounding on the first film layer and the second film layer to obtain the composite film.
Comparative example 4
(1) Preparing a first film layer:
adding deionized water into 3.5 parts of acrylic acid, 2 parts of methacrylic acid and 3 parts of sodium vinylsulfonate to prepare a solution B;
taking 1.2 parts of propylene alcohol and 4 parts of dimethyl carbonate, adding 5.9 parts of diethylene glycol and a catalyst, placing at a constant temperature of 60 ℃ for reaction for 3.5 hours, taking a product, adding N, N-dimethylacetamide, fully mixing, adding the solution B, hydrogen peroxide and N, N' -methylene bisacrylamide, fully mixing, and reacting for 22 hours to obtain resin C;
adding 12 parts of polylactic acid into cyclohexanone to be fully dissolved, adding metal sodium, heating to 145 ℃ in a nitrogen atmosphere, reacting for 8.5 hours, slowly adding the product into a cyclohexane solution of 100 parts of polyvinyl chloride, and reacting for 6 hours at 125 ℃ to obtain modified polyvinyl chloride;
taking modified polyvinyl chloride, adding 10 parts of methyl phenyl vinyl silicone rubber and resin C, and co-extruding to obtain a first film layer;
(2) preparing a second film layer:
dissolving 100 parts of polyvinyl chloride in N, N-dimethylacetamide, adding 27 parts of cellulose acetate and disodium hydrogen phosphate aqueous solution, fully stirring, heating to 60 ℃, preserving heat, adding 24 parts of acrylate, slowly adding potassium persulfate, and reacting at constant temperature for 3.5 hours; adding 10 parts of titanium dioxide and 0.9 part of p-tert-butyl catechol into the reaction product, and blending to obtain modified polyvinyl chloride, wherein the acrylate is methyl methacrylate, n-butyl methacrylate, isooctyl acrylate and isooctyl methacrylate, and the mass ratio of the methyl methacrylate to the n-butyl methacrylate to the isooctyl acrylate to the isooctyl methacrylate is 15: 35;
preparing a second film layer by taking the modified polyvinyl chloride and preparing a film;
(3) preparing a composite membrane:
respectively coating potassium persulfate solution on the bottom of the first film layer and the top of the second film layer, then compounding the bottom of the first film layer and the top of the second film layer, and performing hot-press compounding at the temperature of 60 ℃ to obtain the composite film.
Comparative example 6
(1) Preparing a first film layer:
taking 10 parts of methyl phenyl vinyl silicone rubber, adding 0.2 part of sulfur, and mixing to obtain silicone rubber A;
adding deionized water into 3.5 parts of acrylic acid, 2 parts of methacrylic acid and 3 parts of sodium vinylsulfonate to prepare a solution B;
taking 1.2 parts of propylene alcohol and 4 parts of dimethyl carbonate, adding 5.9 parts of diethylene glycol and a catalyst, placing at a constant temperature of 60 ℃ for reaction for 3.5 hours, taking a product, adding N, N-dimethylacetamide, fully mixing, adding the solution B, hydrogen peroxide and N, N' -methylene bisacrylamide, fully mixing, and reacting for 22 hours to obtain resin C;
adding 12 parts of polylactic acid into cyclohexanone to be fully dissolved, adding metal sodium, heating to 145 ℃ in a nitrogen atmosphere, reacting for 8.5 hours, slowly adding the product into a cyclohexane solution of 100 parts of polyvinyl chloride, and reacting for 6 hours at 125 ℃ to obtain modified polyvinyl chloride;
taking modified polyvinyl chloride, adding silicon rubber A and resin C, and co-extruding to obtain a first film layer;
(2) preparing a second film layer:
dissolving 100 parts of polyvinyl chloride in N, N-dimethylacetamide, adding 27 parts of cellulose acetate and disodium hydrogen phosphate aqueous solution, fully stirring, heating to 60 ℃, preserving heat, adding 24 parts of acrylate, slowly adding potassium persulfate, and reacting at constant temperature for 3.5 hours; adding 10 parts of titanium dioxide into the reaction product, and blending to prepare modified polyvinyl chloride, wherein the acrylate is methyl methacrylate, n-butyl methacrylate, isooctyl acrylate and isooctyl methacrylate, and the mass ratio of the methyl methacrylate to the n-butyl methacrylate to the isooctyl acrylate to the isooctyl methacrylate is 15: 35;
dissolving 13 parts of urea in deionized water, heating to 45 ℃, adding a sodium hydroxide aqueous solution to adjust the pH of the system to be alkaline, adding furfural with the weight of 80% of the components, wherein the total weight of the furfural is 21 parts, stirring and reacting at constant temperature for 45min, adding sodium hydroxide again, stirring for 15min, adding the remaining components of furfural, and reacting for 2.5h to obtain furfural resin;
adding furfural resin into modified polyvinyl chloride for co-extrusion film making to obtain a second film layer;
(3) preparing a composite membrane:
respectively coating potassium persulfate solution on the bottom of the first film layer and the top of the second film layer, then compounding the bottom of the first film layer and the top of the second film layer, and performing hot-press compounding at the temperature of 60 ℃ to obtain the composite film.
Comparative example 7
(1) Preparing a first film layer:
adding deionized water into 3.5 parts of acrylic acid, 2 parts of methacrylic acid and 3 parts of sodium vinylsulfonate to prepare a solution B;
taking 1.2 parts of propylene alcohol and 4 parts of dimethyl carbonate, adding 5.9 parts of diethylene glycol and a catalyst, placing at a constant temperature of 60 ℃ for reaction for 3.5 hours, taking a product, adding N, N-dimethylacetamide, fully mixing, adding the solution B, hydrogen peroxide and N, N' -methylene bisacrylamide, fully mixing, and reacting for 22 hours to obtain resin C;
adding 12 parts of polylactic acid into cyclohexanone to be fully dissolved, adding metal sodium, heating to 145 ℃ in a nitrogen atmosphere, reacting for 8.5 hours, slowly adding the product into a cyclohexane solution of 100 parts of polyvinyl chloride, and reacting for 6 hours at 125 ℃ to obtain modified polyvinyl chloride;
taking modified polyvinyl chloride, adding 10 parts of methyl phenyl vinyl silicone rubber and resin C, and co-extruding to obtain a first film layer;
(2) preparing a second film layer:
dissolving 100 parts of polyvinyl chloride in N, N-dimethylacetamide, adding 27 parts of cellulose acetate and disodium hydrogen phosphate aqueous solution, fully stirring, heating to 60 ℃, preserving heat, adding 24 parts of acrylate, slowly adding potassium persulfate, and reacting at constant temperature for 3.5 hours; adding 10 parts of titanium dioxide into the reaction product, and blending to prepare modified polyvinyl chloride, wherein the acrylate is methyl methacrylate, n-butyl methacrylate, isooctyl acrylate and isooctyl methacrylate, and the mass ratio of the methyl methacrylate to the n-butyl methacrylate to the isooctyl acrylate to the isooctyl methacrylate is 15: 35;
preparing a second film layer by taking the modified polyvinyl chloride and preparing a film;
(3) preparing a composite membrane:
respectively coating potassium persulfate solution on the bottom of the first film layer and the top of the second film layer, then compounding the bottom of the first film layer and the top of the second film layer, and performing hot-press compounding at the temperature of 60 ℃ to obtain the composite film.
Experiment of
Taking the composite films and the pure PVC films obtained in the examples 1-3 and the comparative examples 1-7 to prepare samples, respectively detecting the mechanical property and the degradation capability of the samples, and recording the detection results:
the higher the degradation degree of the composite membrane is, the larger the photocatalytic activity of the composite membrane is, the forward correlation is, and the photocatalytic activity of the composite membrane can be detected by using the degradation capability of the composite membrane;
degradation capability test: after visible light is irradiated for 250 hours at the temperature of 20 ℃, recording the weight loss and the color change of the sample, and taking the weight loss rate and the yellowing resistance grade before and after the experiment as technical indexes; (ii) a
Tensile Strength (MPa) Weight loss ratio (%) Grade of resistance to yellowing
Example 1 44.7 68.2 4-5
Example 2 45.5 68.6 4-5
Example 3 47.1 69.1 5
Comparative example 1 43.2 52.5 4
Comparative example 2 41.4 34.7 3-4
Comparative example 3 45.3 68.4 4-5
Comparative example 4 42.8 47.8 3-4
Comparative example 5 45.0 37.3 4
Comparative example 6 45.5 38.0 3-4
Comparative example 7 42.6 27.6 3
PVC 42.0 21.5 3
From the data in the table above, it is clear that the following conclusions can be drawn:
in comparison of the composite films obtained in examples 1 to 3 with the composite films obtained in comparative examples 1 to 7 and the pure PVC films, the detection results show that:
1. compared with a pure PVC (polyvinyl chloride) film, the tensile strength, the weight loss rate data and the yellowing resistance level of the composite film obtained in the embodiments 1-3 are obviously improved, which fully shows that the composite film prepared by the invention can improve the photocatalytic activity and the degradation capability while maintaining the mechanical property;
2. compared with the composite film obtained in the embodiment 2, the composite film obtained in the comparative examples 1-3 has the advantages that the tensile strength, the weight loss rate data and the yellowing resistance grade are all reduced, the reduction trends are different, and the improvement of the mechanical property, the photocatalytic activity and the degradation capability of the composite film can be promoted by arranging the first film layer, the second film layer and the composite process in the composite film.
3. Compared with the composite film obtained in the embodiment 2, the composite film obtained in the comparative examples 5-7 has the advantages that the first film layer in the comparative example 4 is not added with sulfur, the second film layer in the comparative example 5 is not added with furfural resin, the second film layer in the comparative example 6 is not added with p-tert-butyl catechol, and the composite film prepared in the comparative example 7 is not added with sulfur, furfural resin and p-tert-butyl catechol, so that the tensile strength change is not obvious, the weight loss rate data and the yellowing resistance grade are both obviously reduced, and the reduction trends are different, and the sulfur, furfural resin, p-tert-butyl catechol in the components of the prepared composite film and the combination action thereof have promotion effects on the improvement of the photocatalytic activity and the degradation capability of the composite film.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Furthermore, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (1)

1. A PVC composite film with high visible light catalytic activity is characterized in that: the composite membrane comprises a first membrane layer and a second membrane layer, wherein the first membrane layer is positioned above the second membrane layer, the first membrane layer is a polylactic acid modified polyvinyl chloride membrane layer, and the second membrane layer is a furfural modified polyvinyl chloride membrane layer;
the first film layer comprises the following components in parts by weight: 100 parts of polyvinyl chloride, 10-15 parts of polylactic acid, 8-12 parts of methyl phenyl vinyl silicone rubber, 0.2-0.3 part of sulfur, 3-4 parts of acrylic acid, 1-3 parts of methacrylic acid, 2-4 parts of sodium vinylsulfonate, 1.0-1.5 parts of allyl alcohol, 2-6 parts of dimethyl carbonate and 2.8-9.0 parts of diethylene glycol;
the second film layer comprises the following components in parts by weight: 100 parts of polyvinyl chloride, 11-43 parts of cellulose acetate, 5-43 parts of acrylate, 8-12 parts of titanium dioxide, 9-18 parts of urea, 14-29 parts of furfural and 0.6-1.2 parts of p-tert-butyl catechol;
the refractive index of the first film layer is higher than that of the second film layer;
the acrylate is one or more of methyl methacrylate, n-butyl methacrylate, isooctyl acrylate and isooctyl methacrylate;
the titanium dioxide is anatase type nano titanium dioxide;
the preparation method of the composite membrane comprises the following steps:
(1) preparing a first film layer:
adding sulfur into methyl phenyl vinyl silicone rubber for mixing to prepare silicone rubber A; adding deionized water into acrylic acid, methacrylic acid and sodium vinylsulfonate to prepare a solution B; taking propylene alcohol, dimethyl carbonate and diethylene glycol to react, and then blending and reacting with the solution B to obtain resin C; reacting polylactic acid with sodium metal, and reacting with polyvinyl chloride to obtain modified polyvinyl chloride; adding silicon rubber A and resin C into modified polyvinyl chloride, and co-extruding to obtain a first film layer;
(2) preparing a second film layer:
respectively adding cellulose acetate and acrylic ester into polyvinyl chloride, blending, adding titanium dioxide and p-tert-butyl catechol, and blending to obtain modified polyvinyl chloride; reacting urea with furfural to prepare furfural resin; adding furfural resin into modified polyvinyl chloride for co-extrusion film making to obtain a second film layer;
(3) preparing a composite membrane: compounding the first film layer and the second film layer to obtain a composite film;
the step (1) comprises the following steps:
adding sulfur into methyl phenyl vinyl silicone rubber for mixing to prepare silicone rubber A;
adding deionized water into acrylic acid, methacrylic acid and sodium vinylsulfonate to prepare a solution B;
adding diethylene glycol and a catalyst into propylene alcohol and dimethyl carbonate, reacting at a constant temperature of 50-70 ℃ for 3-4 hours, adding N, N-dimethylacetamide into the product, fully mixing, adding the solution B, hydrogen peroxide and N, N' -methylene bisacrylamide, fully mixing, and reacting for 20-24 hours to obtain resin C;
adding polylactic acid into cyclohexanone to fully dissolve, adding metal sodium, heating to 140-150 ℃ in a nitrogen atmosphere, reacting for 8-9 h, slowly adding a product into a cyclohexane solution of polyvinyl chloride, and reacting for 4-8 h at 120-130 ℃ to obtain modified polyvinyl chloride;
adding silicon rubber A and resin C into modified polyvinyl chloride, and co-extruding to obtain a first film layer;
the step (2) comprises the following steps:
dissolving polyvinyl chloride in N, N-dimethylacetamide, adding cellulose acetate and disodium hydrogen phosphate aqueous solution, fully stirring, heating to 55-65 ℃, preserving heat, adding acrylate, slowly adding potassium persulfate, and reacting at constant temperature for 3-4 h; adding titanium dioxide and p-tert-butyl catechol into the reaction product, and blending to obtain modified polyvinyl chloride;
dissolving urea in deionized water, heating to 40-50 ℃, adding a sodium hydroxide aqueous solution to adjust the pH of the system to be alkaline, adding furfural with the weight of 80% of the components, stirring and reacting at a constant temperature for 40-50 min, adding sodium hydroxide again, stirring for 10-20 min, adding the remaining components, furfural, and reacting for 2-3 h to obtain furfural resin;
adding furfural resin into modified polyvinyl chloride for co-extrusion film making to obtain a second film layer;
the step (3) comprises the following steps:
respectively coating potassium persulfate solution on the bottom of the first film layer and the top of the second film layer, then compounding the bottom of the first film layer and the top of the second film layer, and performing hot-pressing compounding at the temperature of 55-65 ℃ to obtain the composite film.
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