CN114683663B - Anti-aging TPU film and processing technology thereof - Google Patents

Anti-aging TPU film and processing technology thereof Download PDF

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CN114683663B
CN114683663B CN202210397855.7A CN202210397855A CN114683663B CN 114683663 B CN114683663 B CN 114683663B CN 202210397855 A CN202210397855 A CN 202210397855A CN 114683663 B CN114683663 B CN 114683663B
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film
stirring
cerium dioxide
zinc oxide
lignin
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CN114683663A (en
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肖�琳
林欲金
叶航
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Nantong Nakoda Polyurethane 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
    • C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
    • 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
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

The invention discloses an anti-aging TPU film and a processing technology thereof, wherein the anti-aging TPU film is prepared by taking components such as a thermoplastic polyurethane elastomer, organic silicon resin, a modified lignin-zinc oxide compound, modified cerium dioxide, color master batches, an antioxidant and the like as raw materials, and performing melt extrusion and blow molding to form a film to prepare a color-modified film; through preparation base film and outer membrane in this scheme, add the masterbatch of different colours in base film, the outer membrane during preparation, through the multilayer TPU stack of different colours in the actual operation, and every layer of TPU membrane can also set up different visual effects, colour difference or metallic effect, cloud and fog effect, scintillation effect or colorless effect, and the film that changes colour of consequently preparing can give its dynamic change's visual sense organ, and is more excellent pleasing to the eye. The process design of the scheme is reasonable, the prepared color-changed film has excellent mechanical properties, and the TPU color-changed film has color, excellent ultraviolet aging resistance, excellent high-temperature stability and higher practicability.

Description

Anti-aging TPU film and processing technology thereof
Technical Field
The invention relates to the technical field of TPU films, in particular to an anti-aging TPU film and a processing technology thereof.
Background
TPU (Thermoplastic polyurethanes), thermoplastic TPU elastomer, TPU film is a film prepared by special processes such as calendering, tape casting, film blowing, coating and the like on the basis of TPU granules; at present, the TPU film is widely applied, the TPU color changing film is a common one, various TPU color changing films are available in the market, and the TPU color changing films can be selectively purchased according to requirements and attached to articles of which the colors are required to be changed by people, so that the TPU color changing films meet the individual requirements of the people.
The TPU color changing film generally adds various color master batches into TPU plastics to realize the color change of the TPU, but the mechanical property, the ultraviolet aging resistance, the heat resistance and the like of the current TPU color changing film cannot meet the requirements of people, so that the practical application is inconvenient, and meanwhile, the current TPU color changing film has no dynamic sense because the colors of all parts are consistent, and the observed colors of all angles are consistent, so that a color product looks rigid.
Therefore, based on the above situation, we disclose an anti-aging TPU film and a processing technology thereof to solve the technical problem.
Disclosure of Invention
The invention aims to provide an anti-aging TPU film and a processing technology thereof, and aims to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a processing technology of an anti-aging TPU film comprises the following steps:
(1) Uniformly mixing the lignin-zinc oxide compound, sodium hydroxide and deionized water, adding a chloroacetic acid and sodium hydroxide mixed solution at the temperature of 60-65 ℃, carrying out heat preservation treatment for 1-2 hours, and collecting to obtain a material A; uniformly mixing the material A, thionyl chloride and pyridine, stirring and refluxing for 20-24h at 65 ℃, removing residual thionyl chloride, centrifugally washing, and drying in vacuum to obtain a material B;
mixing the material B, N and N-dimethylacetamide, adding 5-amino isophthalic acid and pyridine, stirring at 60-65 ℃ for 10-12h, centrifuging, washing, and vacuum drying to obtain a modified lignin-zinc oxide compound;
(2) Uniformly mixing carboxylated cerium dioxide and deionized water, adding 2- (4-aminophenyl) -5-aminobenzimidazole, performing ultrasonic dispersion in an ice bath, heating to 75-80 ℃, adding polyphosphoric acid, performing reflux reaction for 20-24 hours in a dark condition, performing suction filtration, washing, and performing freeze drying to obtain modified cerium dioxide;
(3) Taking a thermoplastic polyurethane elastomer, organic silicon resin, a modified lignin-zinc oxide compound, modified cerium dioxide, color master batches and an antioxidant, uniformly mixing, then carrying out melt extrusion, and carrying out blow molding to form a film, thus respectively preparing a base film and an outer layer film;
and taking a base film, coating polyurethane glue on the surface of the base film, drying, and heating and laminating the outer layer film and the surface of the base film coated with the polyurethane glue to obtain a finished product.
The optimized scheme comprises the following steps:
(1) Mixing the lignin-zinc oxide compound, sodium hydroxide and deionized water, stirring for 15-20min, adding chloroacetic acid and sodium hydroxide mixed solution at 60-65 ℃, carrying out heat preservation treatment for 1-2h, and collecting to obtain a material A; uniformly mixing the material A, thionyl chloride and pyridine, stirring and refluxing for 20-24 hours at 65 ℃, removing residual thionyl chloride, centrifuging, washing, and drying in vacuum to obtain a material B;
mixing B, N and N-dimethylacetamide, stirring for 15-20min, adding 5-amino isophthalic acid and pyridine, stirring for 10-12h at 60-65 ℃, centrifuging, washing, and vacuum drying to obtain a modified lignin-zinc oxide compound;
(2) Uniformly mixing carboxylated cerium dioxide and deionized water, performing ultrasonic dispersion for 20-30min, adding 2- (4-aminophenyl) -5-aminobenzimidazole, performing ultrasonic dispersion for 10-15min in an ice bath, heating to 75-80 ℃, adding polyphosphoric acid, performing reflux reaction for 20-24h in a dark condition, performing suction filtration, washing with hydrochloric acid and deionized water in sequence, and performing freeze drying to obtain modified cerium dioxide;
(3) Mixing and stirring a thermoplastic polyurethane elastomer, organic silicon resin, a modified lignin-zinc oxide compound, modified cerium dioxide, color master batches and an antioxidant for 20-30min, performing melt extrusion, and performing blow molding to form a film, so as to respectively prepare a base film and an outer layer film;
and taking a base film, coating polyurethane glue on the surface of the base film, drying, and heating and laminating the outer layer film and the surface of the base film coated with the polyurethane glue to obtain a finished product.
According to an optimized scheme, in the step (3), color master batches with different colors are added during preparation of the base film and the outer layer film.
According to an optimized scheme, in the step (3), the base film and the outer layer film are both prepared from the following raw materials: by mass, 80-100 parts of thermoplastic polyurethane elastomer, 10-20 parts of organic silicon resin, 3-8 parts of modified lignin-zinc oxide compound, 5-10 parts of modified cerium dioxide, 15-20 parts of color master batch and 0.5-1 part of antioxidant.
In a more preferable embodiment, the amount of the cerium dioxide is a, the amount of the silicone resin is b, and the amount of the thermoplastic polyurethane elastomer is c, so that the value of c/(a + b) is 4 to 5.
According to an optimized scheme, in the step (1), the preparation method of the lignin-zinc oxide compound comprises the following steps: mixing the quaternized modified lignin, sodium hydroxide and deionized water, stirring for 20-30min, adding a zinc acetate solution, uniformly stirring, heating to 80-85 ℃, carrying out heat preservation treatment for 4-5h, cooling, adjusting the pH value to 7.8, centrifuging, collecting, washing and drying to obtain the lignin-zinc oxide compound.
In a more optimized scheme, in the step (2), the preparation method of the carboxylated cerium dioxide comprises the following steps:
s1: taking vinyl trimethoxy silane, ethanol and deionized water, stirring for dissolving, performing ultrasonic dispersion for 5-10min, adjusting pH to 10, adding cerium dioxide, stirring for reacting for 2-3h at 60-65 ℃, washing and drying to obtain a material C;
s2: and taking the material C and concentrated sulfuric acid, stirring for 10-15min at 10-15 ℃, adding sodium nitrate and potassium permanganate, continuing to stir for 20-25min, reacting for 2h at 30-35 ℃, adding deionized water, stirring for reacting for 3-4h at 70-80 ℃, cooling, washing, and drying in vacuum to obtain the carboxylated cerium dioxide.
According to a more optimized scheme, the antioxidant is a docosanol ester and a ditetradecanol ester according to a mass ratio of 1:1 and mixing.
According to an optimized scheme, the color-changing film is prepared according to the processing technology of the anti-aging TPU film.
Compared with the prior art, the invention has the following beneficial effects:
the application discloses an anti-aging TPU film and a processing technology thereof, wherein components such as a thermoplastic polyurethane elastomer, organic silicon resin, a modified lignin-zinc oxide compound, modified cerium dioxide, color master batches, an antioxidant and the like are taken as raw materials during preparation, and the modified film is prepared by melt extrusion and blow molding; through preparation base film and outer membrane in this scheme, add the masterbatch of different colours in base film, the outer membrane during preparation, the purpose of this operation is in order to realize the dynamic change of changing the look membrane colour, through the multilayer TPU stack of different colours in the actual operation, and every layer of TPU membrane can also set up different visual effect, colour difference or metallic effect, cloud and fog effect, scintillation effect or colorless effect, the change look membrane of consequently preparation can give its dynamic change's visual sense organ, and is more excellent pleasing to the eye.
In the scheme, a modified lignin-zinc oxide compound is introduced, so that in order to improve the ultraviolet resistance of the color-changing film, the lignin-zinc oxide compound is introduced, and the lignin molecular structure contains cinnamyl alcohol, cinnamyl aldehyde, hydroxyl and other chromophoric groups and has excellent ultraviolet absorption performance, so that quaternized modified lignin is used as a raw material and is compounded with zinc oxide through electrostatic adsorption to prepare the lignin-zinc oxide compound; according to the composite scheme, on one hand, the excellent ultraviolet absorption performance of zinc oxide and quaternized modified lignin is kept, and on the other hand, the lignin-zinc oxide composite has excellent dispersing performance, so that agglomeration in the subsequent film preparation process can be avoided, and the performance of a color-modified film is ensured; in the compounding process, the mass ratio of the quaternized modified lignin to the sodium hydroxide is defined as 1: under the limitation of the parameters, the surface of the compound forms a rough and hydrophobic porous form, which is beneficial to the subsequent modification process of the lignin-zinc oxide compound, provides abundant reaction sites for the lignin-zinc oxide compound, and simultaneously improves the compatibility between the modified lignin-zinc oxide compound and other components.
On the basis of the lignin-zinc oxide compound, the lignin-zinc oxide compound is further modified, and during treatment, the lignin-zinc oxide compound is reacted with chloroacetic acid to introduce carboxyl groups, is subjected to acyl chlorination through thionyl chloride, and is grafted with 5-amino isophthalic acid, so that monocarboxylic acid on the surface of the lignin-zinc oxide compound is replaced by dicarboxylic acid, the dicarboxylic acid can be used as a bridge, the crosslinking between the lignin-zinc oxide compound and components can be improved, the connection between the lignin-zinc oxide compound and subsequent modified cerium dioxide can be improved, and the lignin-zinc oxide compound and the modified cerium dioxide can be uniformly dispersed through steric hindrance, so that the ultraviolet aging resistance and the mechanical property of the product are further improved.
On the basis, cerium dioxide is introduced, and is filled into the TPU color changing film, so that the cerium dioxide can be used as a filling material to reinforce and toughen the color changing film and improve the mechanical property of the color changing film, and the filling of the cerium dioxide can also improve the ultraviolet aging resistance and the thermal stability of the color changing film; according to the scheme, the ceric oxide is improved, carboxyl on the surface of the carboxylated ceric oxide is crosslinked and grafted with the 2- (4-aminophenyl) -5-aminobenzimidazole, and due to the existence of a benzo heterocyclic ring structure in the 2- (4-aminophenyl) -5-aminobenzimidazole, the rigidity of molecular chains of the color changing film can be improved, the acting force between the molecular chains is improved, and the heat resistance of the color changing film is improved.
In the scheme, due to the existence of dicarboxylic acid in the modified lignin-zinc oxide compound, the modified lignin-zinc oxide compound can be crosslinked with 2- (4-aminophenyl) -5-aminobenzimidazole surface amino, and simultaneously, the 2- (4-aminophenyl) -5-aminobenzimidazole surface amino can also participate in crosslinking grafting of a TPU membrane, so that the prepared color-changing membrane has excellent heat resistance and mechanical properties; and due to the existence of the modified lignin-zinc oxide compound and the modified cerium dioxide, no auxiliary agents such as a light stabilizer, a toughening agent and the like are required to be additionally added in the scheme.
When the components are set according to the scheme, the components are defined as 80-100 parts by mass of thermoplastic polyurethane elastomer, 10-20 parts by mass of organic silicon resin, 3-8 parts by mass of modified lignin-zinc oxide compound, 5-10 parts by mass of modified cerium dioxide, 15-20 parts by mass of color master batch and 0.5-1 part by mass of antioxidant, and in actual research and development, the modified cerium dioxide is treated by vinyl trimethoxy silane in a carboxylation process, so that the addition amount of the organic silicon resin is influenced due to the treatment step, and in order to ensure the ultraviolet resistance and the mechanical property of the product, the content of the components is further defined, wherein the content of the cerium dioxide is a, the amount of the organic silicon resin is b, the amount of the thermoplastic polyurethane elastomer is c, and the value of c/(a + b) is 4-5.
The scheme discloses a processing technology of an anti-aging TPU film, the technology is reasonable in design, the prepared color-changed film has excellent mechanical property, and the prepared color-changed TPU film has color, excellent ultraviolet aging resistance, excellent high-temperature stability and high practicability.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1:
a processing technology of an anti-aging TPU film comprises the following steps:
(1) Mixing the quaternized modified lignin, sodium hydroxide and deionized water, stirring for 20min, adding a zinc acetate solution, uniformly stirring, heating to 80 ℃, carrying out heat preservation treatment for 5h, cooling, adjusting the pH to 7.8, centrifuging, collecting, washing and drying to obtain the lignin-zinc oxide compound. The concentration of the zinc acetate solution is 20g/L, and the mass ratio of the quaternized modified lignin to the zinc acetate solution is 1:2; the mass ratio of the quaternized modified lignin to the sodium hydroxide is 1:2;
mixing lignin-zinc oxide compound, sodium hydroxide (pH of 10.5) and deionized water, stirring for 15min, adding mixed solution of chloroacetic acid and sodium hydroxide at 60 deg.C, keeping the temperature for 2h, and collecting to obtain material A; the mass ratio of the lignin-zinc oxide compound to chloroacetic acid is 2:1; uniformly mixing the material A, thionyl chloride and pyridine, stirring and refluxing for 20 hours at 65 ℃, removing residual thionyl chloride, centrifuging, washing, and drying in vacuum to obtain a material B; the dosage of the material A, the thionyl chloride and the pyridine is 2g, 50mL and 1mL;
mixing the material B, N and N-dimethylacetamide, stirring for 15min, adding 5-amino isophthalic acid and pyridine, stirring for 12h at 60 ℃, centrifuging, washing, and vacuum drying to obtain a modified lignin-zinc oxide compound; the mass ratio of the material B to the 5-amino isophthalic acid is 1:1;
(2) Taking vinyl trimethoxy silane, ethanol and deionized water, stirring for dissolving, performing ultrasonic dispersion for 5min, adjusting the pH value to 10, adding cerium dioxide, stirring for reacting for 3h at 60 ℃, washing and drying to obtain a material C; the volume ratio of ethanol to deionized water is 1:1, the mass ratio of vinyltrimethoxysilane to cerium dioxide is 2:1;
and taking the material C and concentrated sulfuric acid, stirring for 15min at 10 ℃, adding sodium nitrate and potassium permanganate, continuously stirring for 20min, reacting for 2h at 30 ℃, adding deionized water, stirring for reacting for 4h at 70 ℃, cooling, washing, and drying in vacuum to obtain the carboxylated cerium dioxide. The mass ratio of the material C to the sodium nitrate to the potassium permanganate is 1:5:3;
uniformly mixing carboxylated cerium dioxide and deionized water, performing ultrasonic dispersion for 20min, adding 2- (4-aminophenyl) -5-aminobenzimidazole, performing ultrasonic dispersion for 10min in an ice bath, heating to 75 ℃, adding polyphosphoric acid, performing reflux reaction for 24h under a dark condition, performing suction filtration, washing with hydrochloric acid and deionized water in sequence, and performing freeze drying to obtain modified cerium dioxide; carboxylated cerium dioxide, 2- (4-aminophenyl) -5-aminobenzimidazole in a molar ratio of 1:1;
(3) Mixing and stirring 80 parts of thermoplastic polyurethane elastomer, 10 parts of organic silicon resin, 3 parts of modified lignin-zinc oxide compound, 5 parts of modified cerium dioxide, 15 parts of color master batch and 0.5 part of antioxidant for 20min, carrying out melt extrusion, and carrying out blow molding to form a film so as to respectively prepare a base film and an outer film; the antioxidant is a docosanol ester and a ditetradecanol ester according to a mass ratio of 1:1 and mixing.
And taking a base film, coating polyurethane glue on the surface of the base film, drying, and heating and laminating the outer layer film and the surface of the base film coated with the polyurethane glue to obtain a finished product.
Example 2:
a processing technology of an anti-aging TPU film comprises the following steps:
(1) Mixing the quaternized modified lignin, sodium hydroxide and deionized water, stirring for 25min, adding a zinc acetate solution, uniformly stirring, heating to 82 ℃, carrying out heat preservation treatment for 4.5h, cooling, adjusting the pH to 7.8, centrifuging, collecting, washing and drying to obtain the lignin-zinc oxide compound. The concentration of the zinc acetate solution is 20g/L, and the mass ratio of the quaternized modified lignin to the zinc acetate solution is 1:2; the mass ratio of the quaternized modified lignin to the sodium hydroxide is 1:2;
mixing lignin-zinc oxide compound, sodium hydroxide (pH of 10.5) and deionized water, stirring for 18min, adding chloroacetic acid and sodium hydroxide mixed solution at 62 deg.C, keeping the temperature for 1.5h, and collecting to obtain material A; the mass ratio of the lignin-zinc oxide compound to chloroacetic acid is 2:1; uniformly mixing the material A, thionyl chloride and pyridine, stirring and refluxing for 22 hours at 65 ℃, removing residual thionyl chloride, centrifugally washing, and drying in vacuum to obtain a material B; the dosage of the material A, the thionyl chloride and the pyridine is 2g, 50mL and 1mL;
mixing the material B, N and N-dimethylacetamide, stirring for 18min, adding 5-amino isophthalic acid and pyridine, stirring for 11h at 62 ℃, centrifuging, washing, and vacuum drying to obtain a modified lignin-zinc oxide compound; the mass ratio of the material B to the 5-amino isophthalic acid is 1:1;
(2) Taking vinyl trimethoxy silane, ethanol and deionized water, stirring for dissolving, performing ultrasonic dispersion for 8min, adjusting the pH value to 10, adding cerium dioxide, stirring for reacting for 2.5h at 62 ℃, washing and drying to obtain a material C; the volume ratio of ethanol to deionized water is 1:1, the mass ratio of vinyltrimethoxysilane to cerium dioxide is 2:1;
and taking the material C and concentrated sulfuric acid, stirring for 13min at 12 ℃, adding sodium nitrate and potassium permanganate, continuously stirring for 22min, reacting for 2h at 34 ℃, adding deionized water, stirring for reacting for 3.5h at 75 ℃, cooling, washing, and drying in vacuum to obtain the carboxylated cerium dioxide. The mass ratio of the material C to the sodium nitrate to the potassium permanganate is 1:5:3;
uniformly mixing carboxylated cerium dioxide and deionized water, performing ultrasonic dispersion for 25min, adding 2- (4-aminophenyl) -5-aminobenzimidazole, performing ultrasonic dispersion for 12min in an ice bath, heating to 78 ℃, adding polyphosphoric acid, performing reflux reaction for 22h in a dark condition, performing suction filtration, washing with hydrochloric acid and deionized water in sequence, and performing freeze drying to obtain modified cerium dioxide; carboxylated cerium dioxide, 2- (4-aminophenyl) -5-aminobenzimidazole in a molar ratio of 1:1;
(3) Mixing and stirring 90 parts of thermoplastic polyurethane elastomer, 15 parts of organic silicon resin, 5 parts of modified lignin-zinc oxide compound, 8 parts of modified cerium dioxide, 18 parts of color master batch and 0.8 part of antioxidant for 25min, carrying out melt extrusion, and carrying out blow molding to form a film, thus respectively preparing a base film and an outer layer film; the antioxidant is a docosanol ester and a ditetradecanol ester according to a mass ratio of 1:1 and mixing.
And taking a base film, coating polyurethane glue on the surface of the base film, drying, and heating and laminating the outer layer film and the surface of the base film coated with the polyurethane glue to obtain a finished product.
Example 3:
a processing technology of an anti-aging TPU film comprises the following steps:
(1) Mixing the quaternized modified lignin, sodium hydroxide and deionized water, stirring for 30min, adding a zinc acetate solution, uniformly stirring, heating to 85 ℃, carrying out heat preservation treatment for 4h, cooling, adjusting the pH to 7.8, centrifuging, collecting, washing and drying to obtain the lignin-zinc oxide compound. The concentration of the zinc acetate solution is 20g/L, and the mass ratio of the quaternized modified lignin to the zinc acetate solution is 1:2; the mass ratio of the quaternized modified lignin to the sodium hydroxide is 1:2;
mixing lignin-zinc oxide compound, sodium hydroxide (pH of 10.5) and deionized water, stirring for 20min, adding mixed solution of chloroacetic acid and sodium hydroxide at 65 deg.C, keeping the temperature for 1h, and collecting to obtain material A; the mass ratio of the lignin-zinc oxide compound to chloroacetic acid is 2:1; uniformly mixing the material A, thionyl chloride and pyridine, stirring and refluxing for 24 hours at 65 ℃, removing residual thionyl chloride, centrifugally washing, and drying in vacuum to obtain a material B; the dosage of the material A, the thionyl chloride and the pyridine is 2g, 50mL and 1mL;
mixing the material B, N and N-dimethylacetamide, stirring for 20min, adding 5-amino isophthalic acid and pyridine, stirring for 12h at 60 ℃, centrifuging, washing, and vacuum drying to obtain a modified lignin-zinc oxide compound; the mass ratio of the material B to the 5-amino isophthalic acid is 1:1;
(2) Taking vinyl trimethoxy silane, ethanol and deionized water, stirring for dissolving, performing ultrasonic dispersion for 10min, adjusting the pH to 10, adding cerium dioxide, stirring for reacting for 2h at 65 ℃, washing and drying to obtain a material C; the volume ratio of ethanol to deionized water is 1:1, the mass ratio of vinyltrimethoxysilane to cerium dioxide is 2:1;
and taking the material C and concentrated sulfuric acid, stirring for 10min at 15 ℃, adding sodium nitrate and potassium permanganate, continuously stirring for 25min, reacting for 2h at 35 ℃, adding deionized water, stirring for reacting for 3h at 80 ℃, cooling, washing, and drying in vacuum to obtain the carboxylated cerium dioxide. The mass ratio of the material C to the sodium nitrate to the potassium permanganate is 1:5:3;
uniformly mixing carboxylated cerium dioxide and deionized water, performing ultrasonic dispersion for 30min, adding 2- (4-aminophenyl) -5-aminobenzimidazole, performing ultrasonic dispersion for 15min in an ice bath, heating to 80 ℃, adding polyphosphoric acid, performing reflux reaction for 20h under a dark condition, performing suction filtration, washing with hydrochloric acid and deionized water in sequence, and performing freeze drying to obtain modified cerium dioxide; carboxylated cerium dioxide, 2- (4-aminophenyl) -5-aminobenzimidazole in a molar ratio of 1:1;
(3) Taking 100 parts of thermoplastic polyurethane elastomer, 20 parts of organic silicon resin, 8 parts of modified lignin-zinc oxide compound, 10 parts of modified cerium dioxide, 20 parts of color master batch and 1 part of antioxidant, mixing and stirring for 30min, performing melt extrusion, and performing blow molding to form a film, thus respectively preparing a base film and an outer layer film; the antioxidant is a docosanol ester and a ditetradecanol ester according to a mass ratio of 1:1 and mixing.
And taking a base film, coating polyurethane glue on the surface of the base film, drying, and heating and laminating the outer layer film and the surface of the base film coated with the polyurethane glue to obtain a finished product.
Example 4:
a processing technology of an anti-aging TPU film comprises the following steps:
(1) Taking quaternized modified lignin, sodium hydroxide and deionized water, mixing, stirring for 25min, adding a zinc acetate solution, uniformly stirring, heating to 82 ℃, carrying out heat preservation treatment for 4.5h, cooling, adjusting the pH value to 7.8, carrying out centrifugal collection, washing and drying to obtain the lignin-zinc oxide compound. The concentration of the zinc acetate solution is 20g/L, and the mass ratio of the quaternized modified lignin to the zinc acetate solution is 1:2; the mass ratio of the quaternized modified lignin to the sodium hydroxide is 1:2;
mixing lignin-zinc oxide compound, sodium hydroxide (pH of 10.5) and deionized water, stirring for 18min, adding mixed solution of chloroacetic acid and sodium hydroxide at 62 deg.C, maintaining the temperature for 1.5h, and collecting to obtain material A; the mass ratio of the lignin-zinc oxide compound to chloroacetic acid is 2:1; uniformly mixing the material A, thionyl chloride and pyridine, stirring and refluxing for 22 hours at 65 ℃, removing residual thionyl chloride, centrifugally washing, and drying in vacuum to obtain a material B; the dosage of the material A, the thionyl chloride and the pyridine is 2g, 50mL and 1mL;
mixing the material B, N and N-dimethylacetamide, stirring for 18min, adding 5-amino isophthalic acid and pyridine, stirring for 11h at 62 ℃, centrifuging, washing, and vacuum drying to obtain a modified lignin-zinc oxide compound; the mass ratio of the material B to the 5-amino isophthalic acid is 1:1;
(2) Taking vinyl trimethoxy silane, ethanol and deionized water, stirring for dissolving, performing ultrasonic dispersion for 8min, adjusting the pH value to 10, adding cerium dioxide, stirring for reacting for 2.5h at 62 ℃, washing and drying to obtain a material C; the volume ratio of ethanol to deionized water is 1:1, the mass ratio of vinyltrimethoxysilane to cerium dioxide is 2:1;
and taking the material C and concentrated sulfuric acid, stirring for 13min at 12 ℃, adding sodium nitrate and potassium permanganate, continuously stirring for 22min, reacting for 2h at 34 ℃, adding deionized water, stirring for reacting for 3.5h at 75 ℃, cooling, washing, and drying in vacuum to obtain the carboxylated cerium dioxide. The mass ratio of the material C to the sodium nitrate to the potassium permanganate is 1:5:3;
uniformly mixing carboxylated cerium dioxide and deionized water, performing ultrasonic dispersion for 25min, adding 2- (4-aminophenyl) -5-aminobenzimidazole, performing ultrasonic dispersion for 12min in an ice bath, heating to 78 ℃, adding polyphosphoric acid, performing reflux reaction for 22h in a dark condition, performing suction filtration, washing with hydrochloric acid and deionized water in sequence, and performing freeze drying to obtain modified cerium dioxide; carboxylated cerium dioxide, 2- (4-aminophenyl) -5-aminobenzimidazole in a molar ratio of 1:1;
(3) Mixing and stirring 80 parts of thermoplastic polyurethane elastomer, 15 parts of organic silicon resin, 5 parts of modified lignin-zinc oxide compound, 5 parts of modified cerium dioxide, 18 parts of color master batch and 0.8 part of antioxidant for 25min, performing melt extrusion, and performing blow molding to form a film, thus respectively preparing a base film and an outer film; the antioxidant is a docosanol ester and a ditetradecanol ester according to a mass ratio of 1:1 and mixing.
And taking a base film, coating polyurethane glue on the surface of the base film, drying, and heating and laminating the outer layer film and the surface of the base film coated with the polyurethane glue to obtain a finished product.
The control test was carried out using example 4 as the experimental group, with the following specific comparative examples:
comparative example 1: based on example 4, only the carboxylated ceria was added, and no modification treatment was performed, and the remaining process and components were unchanged.
A processing technology of an anti-aging TPU film comprises the following steps:
(1) Mixing the quaternized modified lignin, sodium hydroxide and deionized water, stirring for 25min, adding a zinc acetate solution, uniformly stirring, heating to 82 ℃, carrying out heat preservation treatment for 4.5h, cooling, adjusting the pH to 7.8, centrifuging, collecting, washing and drying to obtain the lignin-zinc oxide compound. The concentration of the zinc acetate solution is 20g/L, and the mass ratio of the quaternized modified lignin to the zinc acetate solution is 1:2; the mass ratio of the quaternized modified lignin to the sodium hydroxide is 1:2;
mixing lignin-zinc oxide compound, sodium hydroxide (pH of 10.5) and deionized water, stirring for 18min, adding mixed solution of chloroacetic acid and sodium hydroxide at 62 deg.C, maintaining the temperature for 1.5h, and collecting to obtain material A; the mass ratio of the lignin-zinc oxide compound to chloroacetic acid is 2:1; uniformly mixing the material A, thionyl chloride and pyridine, stirring and refluxing for 22 hours at 65 ℃, removing residual thionyl chloride, centrifugally washing, and drying in vacuum to obtain a material B; the dosage of the material A, the thionyl chloride and the pyridine is 2g, 50mL and 1mL;
mixing the material B, N and N-dimethylacetamide, stirring for 18min, adding 5-amino isophthalic acid and pyridine, stirring for 11h at 62 ℃, centrifuging, washing, and vacuum drying to obtain a modified lignin-zinc oxide compound; the mass ratio of the material B to the 5-amino isophthalic acid is 1:1;
(2) Taking vinyl trimethoxy silane, ethanol and deionized water, stirring for dissolving, performing ultrasonic dispersion for 8min, adjusting the pH value to 10, adding cerium dioxide, stirring for reacting for 2.5h at 62 ℃, washing and drying to obtain a material C; the volume ratio of ethanol to deionized water is 1:1, the mass ratio of vinyltrimethoxysilane to cerium dioxide is 2:1;
and taking the material C and concentrated sulfuric acid, stirring for 13min at 12 ℃, adding sodium nitrate and potassium permanganate, continuously stirring for 22min, reacting for 2h at 34 ℃, adding deionized water, stirring for reacting for 3.5h at 75 ℃, cooling, washing, and drying in vacuum to obtain the carboxylated cerium dioxide. The mass ratio of the material C to the sodium nitrate to the potassium permanganate is 1:5:3;
(3) Mixing and stirring 80 parts of thermoplastic polyurethane elastomer, 15 parts of organic silicon resin, 5 parts of modified lignin-zinc oxide compound, 5 parts of carboxylated cerium dioxide, 18 parts of color master batch and 0.8 part of antioxidant for 25min, carrying out melt extrusion, and carrying out blow molding to form a film, thus respectively preparing a base film and an outer layer film; the antioxidant is a docosanol ester and a ditetradecanol ester according to the mass ratio of 1:1 and mixing.
And taking a base film, coating polyurethane glue on the surface of the base film, drying, and heating and laminating the outer layer film and the surface of the base film coated with the polyurethane glue to obtain a finished product.
Comparative example 2: based on example 4, only the lignin-zinc oxide complex is added, and the modification treatment is not carried out, and the rest processes and components are not changed.
A processing technology of an anti-aging TPU film comprises the following steps:
(1) Taking quaternized modified lignin, sodium hydroxide and deionized water, mixing, stirring for 25min, adding a zinc acetate solution, uniformly stirring, heating to 82 ℃, carrying out heat preservation treatment for 4.5h, cooling, adjusting the pH value to 7.8, carrying out centrifugal collection, washing and drying to obtain the lignin-zinc oxide compound. The concentration of the zinc acetate solution is 20g/L, and the mass ratio of the quaternized modified lignin to the zinc acetate solution is 1:2; the mass ratio of the quaternized modified lignin to the sodium hydroxide is 1:2;
(2) Taking vinyl trimethoxy silane, ethanol and deionized water, stirring for dissolving, performing ultrasonic dispersion for 8min, adjusting the pH value to 10, adding cerium dioxide, stirring for reacting for 2.5h at 62 ℃, washing and drying to obtain a material C; the volume ratio of ethanol to deionized water is 1:1, the mass ratio of vinyltrimethoxysilane to cerium dioxide is 2:1;
and taking the material C and concentrated sulfuric acid, stirring for 13min at 12 ℃, adding sodium nitrate and potassium permanganate, continuously stirring for 22min, reacting for 2h at 34 ℃, adding deionized water, stirring for reacting for 3.5h at 75 ℃, cooling, washing, and drying in vacuum to obtain the carboxylated cerium dioxide. The mass ratio of the material C to the sodium nitrate to the potassium permanganate is 1:5:3;
uniformly mixing carboxylated cerium dioxide and deionized water, performing ultrasonic dispersion for 25min, adding 2- (4-aminophenyl) -5-aminobenzimidazole, performing ultrasonic dispersion for 12min in an ice bath, heating to 78 ℃, adding polyphosphoric acid, performing reflux reaction for 22h in a dark condition, performing suction filtration, washing with hydrochloric acid and deionized water in sequence, and performing freeze drying to obtain modified cerium dioxide; carboxylated cerium dioxide, 2- (4-aminophenyl) -5-aminobenzimidazole in a molar ratio of 1:1;
(3) Mixing and stirring 80 parts of thermoplastic polyurethane elastomer, 15 parts of organic silicon resin, 5 parts of lignin-zinc oxide compound, 5 parts of modified cerium dioxide, 18 parts of color master batch and 0.8 part of antioxidant for 25min, carrying out melt extrusion, and carrying out blow molding to form a film, thus respectively preparing a base film and an outer layer film; the antioxidant is a docosanol ester and a ditetradecanol ester according to a mass ratio of 1:1 and mixing.
And taking a base film, coating polyurethane glue on the surface of the base film, drying, and heating and laminating the outer layer film and the surface of the base film coated with the polyurethane glue to obtain a finished product.
Comparative example 3: based on example 4, only lignin-zinc oxide complex and carboxylated cerium oxide were added, and no modification treatment was performed, and the remaining process and components were unchanged.
A processing technology of an anti-aging TPU film comprises the following steps:
(1) Mixing the quaternized modified lignin, sodium hydroxide and deionized water, stirring for 25min, adding a zinc acetate solution, uniformly stirring, heating to 82 ℃, carrying out heat preservation treatment for 4.5h, cooling, adjusting the pH to 7.8, centrifuging, collecting, washing and drying to obtain the lignin-zinc oxide compound. The concentration of the zinc acetate solution is 20g/L, and the mass ratio of the quaternized modified lignin to the zinc acetate solution is 1:2; the mass ratio of the quaternized modified lignin to the sodium hydroxide is 1:2;
(2) Taking vinyl trimethoxy silane, ethanol and deionized water, stirring for dissolving, performing ultrasonic dispersion for 8min, adjusting the pH value to 10, adding cerium dioxide, stirring for reacting for 2.5h at 62 ℃, washing and drying to obtain a material C; the volume ratio of ethanol to deionized water is 1:1, the mass ratio of vinyltrimethoxysilane to cerium dioxide is 2:1;
and taking the material C and concentrated sulfuric acid, stirring for 13min at 12 ℃, adding sodium nitrate and potassium permanganate, continuously stirring for 22min, reacting for 2h at 34 ℃, adding deionized water, stirring for reacting for 3.5h at 75 ℃, cooling, washing, and drying in vacuum to obtain the carboxylated cerium dioxide. The mass ratio of the material C to the sodium nitrate to the potassium permanganate is 1:5:3;
(3) Mixing and stirring 80 parts of thermoplastic polyurethane elastomer, 15 parts of organic silicon resin, 5 parts of lignin-zinc oxide compound, 5 parts of carboxylated cerium dioxide, 18 parts of color master batch and 0.8 part of antioxidant for 25min, carrying out melt extrusion, and carrying out blow molding to form a film, thus respectively preparing a base film and an outer layer film; the antioxidant is a docosanol ester and a ditetradecanol ester according to a mass ratio of 1:1 and mixing.
And taking a base film, coating polyurethane glue on the surface of the base film, drying, and heating and laminating the outer layer film and the surface of the base film coated with the polyurethane glue to obtain a finished product.
Detection experiment:
the sample color-changing films prepared in examples 1 to 4 were subjected to performance testing according to the following method, and the specific test results are shown in the following table one and table two:
1. thermal weight loss: heating to 250 ℃ and 300 ℃ at a heating rate of 10 ℃/min, and detecting the thermal weight loss of the sample color-changing film by a differential scanning calorimeter; wherein the thermal weight loss at 250 ℃ is A, and the thermal weight loss at 300 ℃ is B;
2. and (3) testing mechanical properties: and (3) carrying out mechanical property test according to the standard disclosed in GB/T13022-91.
Item Tensile strength MPa Elongation at break% Thermal weight loss A Thermal weight loss B
Example 1 54 312 2.6％ 28.3％
Example 2 55 315 2.5％ 27.6％
Example 3 53 310 2.8％ 30.4％
Example 4 57 324 2.1％ 25.3％
Watch 1
3. Anti-ultraviolet aging: taking the color-changed film sample, placing the color-changed film sample in an aging oven, and irradiating the color-changed film sample under the ultraviolet intensity of 500 mu W/cm 2 Sampling at fixed points of 50h, 100h, 150h and 200h under the condition that the relative humidity is 2%, testing the change of the chromatic aberration in the ultraviolet exposure process by a CR-10 type chromatic aberration meter, and recording corresponding data.
Figure BDA0003599647620000131
Figure BDA0003599647620000141
Watch 2
4. The sample films prepared in example 4 and comparative examples 1-3 were used for control detection, and the specific data are as follows:
item Tensile strength MPa Thermal weight loss A Thermal weight loss B 50h color difference 100h color difference 200h color difference
Example 4 57 2.1％ 25.3％ 0.3 0.4 0.8
Comparative example 1 49 5.4％ 38.7％ 0.4 0.7 1.2
Comparative example 2 52 4.1％ 33.5％ 0.6 0.9 1.5
Comparative example 3 45 8.2％ 46.1％ 0.7 1.1 1.7
Watch III
And (4) conclusion: the scheme discloses a processing technology of an anti-aging TPU film, the process design is reasonable, the prepared color-changed film has excellent mechanical properties, and the prepared TPU color-changed film has color, excellent anti-ultraviolet aging performance, excellent high-temperature stability and higher practicability.
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 modifications may be made to the embodiments described above, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. A processing technology of an anti-aging TPU film is characterized by comprising the following steps: the method comprises the following steps:
(1) Uniformly mixing the lignin-zinc oxide compound, sodium hydroxide and deionized water, adding a mixed solution of chloroacetic acid and sodium hydroxide at the temperature of 60-65 ℃, carrying out heat preservation treatment for 1-2 hours, and collecting to obtain a material A; uniformly mixing the material A, thionyl chloride and pyridine, stirring and refluxing for 20-24h at 65 ℃, removing residual thionyl chloride, centrifugally washing, and drying in vacuum to obtain a material B;
mixing B, N and N-dimethylacetamide, adding 5-amino isophthalic acid and pyridine, stirring at 60-65 ℃ for 10-12h, centrifuging, washing, and vacuum drying to obtain a modified lignin-zinc oxide compound;
(2) Uniformly mixing carboxylated cerium dioxide and deionized water, adding 2- (4-aminophenyl) -5-aminobenzimidazole, carrying out ultrasonic dispersion in an ice bath, heating to 75-80 ℃, adding polyphosphoric acid, carrying out reflux reaction for 20-24h in a dark condition, carrying out suction filtration, washing, and carrying out freeze drying to obtain modified cerium dioxide;
(3) Taking a thermoplastic polyurethane elastomer, organic silicon resin, a modified lignin-zinc oxide compound, modified cerium dioxide, color master batches and an antioxidant, uniformly mixing, then carrying out melt extrusion, and carrying out blow molding to form a film, thus respectively preparing a base film and an outer layer film;
and taking a base film, coating polyurethane glue on the surface of the base film, drying, and heating and laminating the outer layer film and the surface of the base film coated with the polyurethane glue to obtain a finished product.
2. The processing technology of the anti-aging TPU film as claimed in claim 1, is characterized in that: the method comprises the following steps:
(1) Mixing the lignin-zinc oxide compound, sodium hydroxide and deionized water, stirring for 15-20min, adding a mixed solution of chloroacetic acid and sodium hydroxide at 60-65 ℃, carrying out heat preservation treatment for 1-2h, and collecting to obtain a material A; uniformly mixing the material A, thionyl chloride and pyridine, stirring and refluxing for 20-24h at 65 ℃, removing residual thionyl chloride, centrifugally washing, and drying in vacuum to obtain a material B;
mixing B, N and N-dimethylacetamide, stirring for 15-20min, adding 5-amino isophthalic acid and pyridine, stirring for 10-12h at 60-65 ℃, centrifuging, washing, and vacuum drying to obtain a modified lignin-zinc oxide compound;
(2) Uniformly mixing carboxylated cerium dioxide and deionized water, performing ultrasonic dispersion for 20-30min, adding 2- (4-aminophenyl) -5-aminobenzimidazole, performing ultrasonic dispersion for 10-15min in ice bath, heating to 75-80 ℃, adding polyphosphoric acid, performing reflux reaction for 20-24h in a dark condition, performing suction filtration, washing with hydrochloric acid and deionized water in sequence, and performing freeze drying to obtain modified cerium dioxide;
(3) Mixing and stirring a thermoplastic polyurethane elastomer, an organic silicon resin, a modified lignin-zinc oxide compound, modified cerium dioxide, color master batches and an antioxidant for 20-30min, performing melt extrusion, and performing blow molding to form a film, so as to respectively prepare a base film and an outer layer film;
and taking a base film, coating polyurethane glue on the surface of the base film, drying, and heating and laminating the outer layer film and the surface of the base film coated with the polyurethane glue to obtain a finished product.
3. The processing technology of the anti-aging TPU film as claimed in claim 2, characterized in that: in the step (3), color master batches with different colors are added during preparation of the base film and the outer layer film.
4. The processing technology of the anti-aging TPU film as claimed in claim 2, characterized in that: in the step (3), the base film and the outer layer film are prepared from the following raw materials: by mass, 80-100 parts of thermoplastic polyurethane elastomer, 10-20 parts of organic silicon resin, 3-8 parts of modified lignin-zinc oxide compound, 5-10 parts of modified cerium dioxide, 15-20 parts of color master batch and 0.5-1 part of antioxidant.
5. The processing technology of the anti-aging TPU film of claim 4, characterized in that: the amount of the cerium dioxide is a, the amount of the organic silicon resin is b, the amount of the thermoplastic polyurethane elastomer is c, and the value of c/(a + b) is 4-5.
6. The processing technology of the anti-aging TPU film as claimed in claim 2, characterized in that: in the step (1), the preparation method of the lignin-zinc oxide compound comprises the following steps: mixing the quaternized modified lignin, sodium hydroxide and deionized water, stirring for 20-30min, adding a zinc acetate solution, uniformly stirring, heating to 80-85 ℃, carrying out heat preservation treatment for 4-5h, cooling, adjusting the pH value to 7.8, centrifuging, collecting, washing and drying to obtain the lignin-zinc oxide compound.
7. The processing technology of the anti-aging TPU film as claimed in claim 2, is characterized in that: in the step (2), the preparation method of the carboxylated cerium dioxide comprises the following steps:
s1: taking vinyl trimethoxy silane, ethanol and deionized water, stirring for dissolving, performing ultrasonic dispersion for 5-10min, adjusting pH to 10, adding cerium dioxide, stirring for reacting for 2-3h at 60-65 ℃, washing and drying to obtain a material C;
s2: and taking the material C and concentrated sulfuric acid, stirring for 10-15min at 10-15 ℃, adding sodium nitrate and potassium permanganate, continuing to stir for 20-25min, reacting for 2h at 30-35 ℃, adding deionized water, stirring for reacting for 3-4h at 70-80 ℃, cooling, washing, and drying in vacuum to obtain the carboxylated cerium dioxide.
8. The processing technology of the anti-aging TPU film of claim 4, characterized in that: the antioxidant is a docosanol ester and a ditetradecanol ester according to a mass ratio of 1:1 and mixing.
9. The film prepared by the processing technology of the anti-aging TPU film as claimed in any one of claims 1 to 8.
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