CN113696573A - Toughened home decoration base film and preparation method thereof - Google Patents
Toughened home decoration base film and preparation method thereof Download PDFInfo
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- B32—LAYERED PRODUCTS
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
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- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47B—TABLES; DESKS; OFFICE FURNITURE; CABINETS; DRAWERS; GENERAL DETAILS OF FURNITURE
- A47B95/00—Fittings for furniture
- A47B95/04—Keyplates; Ornaments or the like
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- 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
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
- C08G63/6954—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from polxycarboxylic acids and polyhydroxy compounds
- C08G63/6956—Dicarboxylic acids and dihydroxy compounds
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B32B2307/00—Properties of the layers or laminate
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- B32B2307/554—Wear resistance
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/762—Self-repairing, self-healing
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- B32B2451/00—Decorative or ornamental articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2479/00—Furniture
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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
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Abstract
The invention discloses a preparation method of a toughened home decoration base film, which comprises the following steps: s1: weighing a certain amount of monovinyl cage polysilsesquioxane, a compound (o-tetralone derivative) with a structural formula I and an initiator, dissolving in a solvent, introducing 1, 3-butadiene, and reacting to obtain a copolymerization product; s2: uniformly mixing the copolymerization product, the dihydric alcohol mixture, the dibenzoxazole fluorescent whitening powder and the modified nano filler, dropwise adding a mixed solution of terephthalic acid and an auxiliary agent for reaction, blending, extruding and granulating to obtain a high polymer slice with an interpenetrating/semi-interpenetrating network structure; s3: and (3) taking the high polymer slices as raw materials of the surface functional film layer and the PET slices as materials of the base film layer, and performing common film drawing by adopting a film drawing process to obtain the toughened home decoration base film. The home decoration film has the functions of toughening and brightening, has the functions of high temperature resistance, wear resistance and microcrack self-healing, and prolongs the service life of the home decoration film.
Description
Technical Field
The invention relates to the technical field of home decoration building materials, in particular to a toughened home decoration base film and a preparation method thereof.
Background
It is well known that home decoration and furniture construction involves the use of a large number of wood products, which are often painted on their surface with various types of paints currently on the market. The use of paint, both during the production of wooden furniture and during the use of the finished product, may present the risk of the emission of volatile VOC gases.
In order to meet the good pursuit of people for ideal home life and reduce the harm of harmful gas to the health of people; at present, the surface treatment is mainly carried out by replacing water paint, brushing diatom ooze or carrying out decorative film, so that the selection of wooden furniture or decorative materials is more environment-friendly, safer and healthier. Research on the performance of home films is receiving constant attention.
Disclosure of Invention
In view of the defects of the prior art, the invention provides the toughened home decoration base film and the preparation method thereof, which not only solve the problems of low toughness and low brightness of the existing home decoration film, but also have the functions of high temperature resistance, wear resistance and microcrack self-healing, and prolong the service life of the home decoration film.
In order to achieve the above purposes, the technical scheme adopted by the invention is as follows:
a method for preparing a toughened home decoration base film, comprising the following steps:
s1: weighing 90-120 parts by weight of monovinyl cage polysilsesquioxane, 30-50 parts by weight of compound monomer with structural formula I and 0.5-1.5 parts by weight of initiator, dissolving in 100 parts by weight of solvent, setting the reaction temperature to be 120-150 ℃, the reaction pressure to be 0.15-0.35 MPa, slowly introducing 20-50 parts of 1, 3-butadiene, reacting while stirring, and obtaining a copolymerization product after reacting for 60-180 min;
wherein R1 and R2 are each independently selected from H, methyl, ethyl, or methoxy; polyhedral oligomeric silsesquioxanes, also known as POSS, of the general formula (RSiO)3/2)nWherein R is a group to which eight apical Si atoms are attached. The copolymerization product is obtained by the polymerization reaction of a compound (o-tetralone derivative) with a structural formula I, 1, 3-butadiene and a monovinyl cage type polysilsesquioxane monomer, and the copolymerization product has an effective toughening effect and is analyzed, on one hand, the copolymerization product comes from the molecular structure characteristics of the copolymerization product, and on the other hand, the copolymerization product is brought by the unique cage type structure characteristics of the cage type polysilsesquioxane. In addition, the bonding force between the basement membrane layer and the surface functional membrane layer is further improved through the introduced o-oxonone structural unit, so that the basement membrane layer has the function of microcrack self-polymerization.
In the monovinyl cage-type polysilsesquioxane, a group connected with 1 vertex angle Si atom is vinyl, and groups connected with the other 7 vertex angle Si atoms are methyl. The preparation method comprises the following steps: hydrolyzing 28 parts of methyltrimethoxysilane in an aqueous solution of acetone with the mass concentration of 30% to prepare a cage-type polysilsesquioxane intermediate, adding 5 parts of triethylamine solution of vinyl trimethoxy silane with the mass concentration of 20% to perform a ring-closing reaction to obtain the monovinyl cage-type polysilsesquioxane.
S2: weighing 50-80 parts of the copolymerization product, 35-55 parts of a dihydric alcohol mixture, 1.5-3.5 parts of dibenzoxazole fluorescent whitening powder and 5-12 parts of modified nano filler, uniformly stirring and mixing, slowly dropwise adding a mixed solution of 18-25 parts of terephthalic acid and 1-2.5 parts of an auxiliary agent at 205-235 ℃, continuously reacting for 2-3 hours after dropwise adding, adding a double-screw extruder, blending, extruding and granulating to obtain a high polymer slice with an interpenetrating/semi-interpenetrating network structure formed by the copolymerization product and the modified PET resin; the extrusion temperature of the double-screw extruder is 280 ℃; the invention further utilizes the preparation process of the step S2 to obtain the high polymer slice with the interpenetrating/semi-interpenetrating network structure formed by the copolymerization product and the modified PET resin, and the high polymer structure physically enables the copolymerization product and the molecular structure chain segments of the modified PET resin to be mutually wound, thereby further improving the wear resistance and the heat resistance of the surface functional film layer and prolonging the service life of the home decoration film. The dibenzoxazole fluorescent whitening powder is added to play a role of a film layer brightening agent; the modified white nano-filler can cooperate with the dibenzoxazole fluorescent whitening powder to further brighten the film, and further improve the high temperature resistance and wear resistance of the surface functional film, so that the performance of the film is prevented from being reduced at high temperature.
S3: and (3) taking the high polymer slice as a raw material of a surface functional film layer, taking the high polymer slice and an unmodified PET slice as a material of a base film layer, and performing film drawing together by adopting a film drawing process to obtain the toughened brightness enhancement film for home decoration. When the slices are longitudinally stretched, the slices are preheated to 86 ℃, and are stretched by about 3 times along the extension direction of the slice plane at the temperature, so that the crystallinity of the slices can be improved to reach a higher temperature by orientation: the transverse stretching preheating temperature is 98 ℃, the stretching temperature is 110 ℃, the stretching ratio is 2.5, and the heat setting temperature is 230 ℃. The unmodified PET slice is a resin slice with the intrinsic viscosity of 0.65-0.75 dL/g, the melting point of 252-262 ℃ and the carboxyl end group content of less than or equal to 50 mol/t. The invention discloses a toughened brightness enhancement film for home decoration, which is prepared by compounding a high polymer slice with an interpenetrating/semi-interpenetrating network structure and an unmodified PET slice, thereby meeting the requirements of economy and performance modification of the film for home decoration.
Preferably, the compound of structural formula I is:
the preparation method of the compound of the structural formula I comprises the following steps: placing 81 parts by weight of 3-allyl-2-hydroxybenzaldehyde, 65 parts by weight of acetic anhydride and 3 parts by weight of anhydrous potassium acetate in a three-neck flask, heating to 150-160 ℃, evaporating acetic acid after the reaction starts, dropwise adding acetic anhydride with the same mass, naturally cooling to 80 ℃ after the reaction is finished, and washing with hot water and recrystallizing with methanol to obtain the compound with the structural formula I. The o-oxonone structural unit is introduced into the surface functional film layer, and the structural unit can perform crosslinking curing reaction under the illumination with the wavelength of more than 300nm to form a tightly crosslinked three-dimensional network structure, so that the stability of the whole surface functional film layer is further improved, the film layer is not easily damaged by external force, and the self-healing effect of microcracks can be realized under the condition that the surface functional film layer has microcracks and the illumination with the wavelength of more than 300 nm.
Preferably, the diol mixture consists of ethylene glycol and perfluoro cage polysilsesquioxane diol.
Preferably, the perfluoro-cage polysilsesquioxane diol is obtained by reacting vinyl perfluoro-cage polysilsesquioxane with an enediol. More preferably, the perfluoro cage polysilsesquioxane diol is prepared by the following method: hydrolyzing a certain weight part of perfluoro-trimethoxysilane in an aqueous solution of acetone with the mass concentration of 30-50% to prepare a cage-type polysilsesquioxane intermediate, adding a triethylamine solution of vinyl-trimethoxysilane with the mass concentration of 20-40%, wherein the molar ratio of the vinyl-trimethoxysilane to the cage-type polysilsesquioxane intermediate is 1: 1-1.1, performing a ring closing reaction to obtain vinyl perfluoro-cage polysilsesquioxane; and then adding the vinyl perfluoro-cage polysilsesquioxane and an initiator into a mixed solution compounded by the enediol and the ethanol, wherein the molar ratio of the vinyl perfluoro-cage polysilsesquioxane to the enediol is 1: 1-1.05, and reacting the vinyl perfluoro cage polysilsesquioxane with the alkene diol under the action of an initiator to obtain the perfluoro cage polysilsesquioxane diol. The initiator can be at least one of benzoyl peroxide, lauroyl peroxide, potassium persulfate and sodium persulfate, and the addition amount of the initiator accounts for 0.1-0.6% of the weight of the vinyl perfluoro cage polysilsesquioxane and the alkene glycol monomer. Polyhedral oligomeric silsesquioxanes, also known as POSS, of the general formula (RSiO)3/2)nWherein R is eight apex anglesSi atom to which a group is attached. In the invention, the intermediate of the cage type polysilsesquioxane, namely seven vertex angles are connected with perfluorinated groups, and the other vertex angle is not closed and is respectively three hydroxyl groups; further, the remaining vertex angle of the cage-type polysilsesquioxane contains an active functional group vinyl group through reaction with vinyl trimethoxy silane, and then the target product can be obtained through addition reaction with an olefin double bond carried by the alkene diol. By grafting the perfluoro group and the cage-type polysilsesquioxane group, the perfluoro group has strong stain resistance, and meanwhile, the cage-type polysilsesquioxane group has the spherical nanoparticle characteristic, so that the surface of the home decoration membrane has excellent self-cleaning, high temperature resistance, wear resistance and the like.
Preferably, the alkylene glycol is at least one of 3- (allyloxy) -1, 2-propanediol, 1, 4-butylene glycol, 3-butylene-1, 2-diol, or 1, 2-ethylene glycol.
Preferably, the modified nano filler is polyethylene glycol coated nano inorganic filler, and the modification method comprises the following steps: dissolving polyethylene glycol in water to obtain a polyethylene glycol aqueous solution, uniformly dispersing the nano inorganic filler in the polyethylene glycol aqueous solution, and evaporating water in the dispersion to dryness to obtain polyethylene glycol coated nano inorganic filler powder. The nano inorganic filler is at least one of white nano titanium oxide, nano silicon oxide, nano aluminum oxide or nano tin oxide.
Preferably, the initiator is at least one of ammonium persulfate, potassium persulfate and sodium persulfate.
Preferably, the auxiliary agent is at least one of an accelerator, a nucleating agent and a leveling agent.
The invention also provides a toughened home decoration base film which is prepared by the preparation method.
The invention has the beneficial effects that:
compared with the existing home decoration film, the toughened home decoration base film has the functions of toughening and brightening, has the functions of high temperature resistance, wear resistance and microcrack self-healing, and prolongs the service life of the home decoration film.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
Example 1
The preparation method of the toughened home decoration base film of the embodiment comprises the following steps:
s1: weighing 90 parts by weight of monovinyl cage-type polysilsesquioxane, 30 parts by weight of compound monomer with a structural formula I and 0.5 part by weight of ammonium persulfate, dissolving in 100 parts by weight of toluene, setting the reaction temperature to be 120 ℃, setting the reaction pressure to be 0.35MPa, slowly introducing 20 parts of 1, 3-butadiene, reacting while stirring, and obtaining a copolymerization product after reacting for 60 min;
s2: weighing 50 parts of the copolymerization product, 35 parts of a dihydric alcohol mixture, 1.5 parts of dibenzoxazole fluorescent whitening powder and 5 parts of modified nano filler, stirring and mixing uniformly, slowly dropwise adding a mixed solution of 18 parts of terephthalic acid, 1 part of accelerator zinc acetate and 1.5 parts of nucleating agent sodium perfluorobutyrate at 215 ℃, continuously reacting for 3 hours after the dropwise adding is finished, then adding a double-screw extruder, blending, extruding and granulating to obtain a copolymer slice with an interpenetrating/semi-interpenetrating network structure formed by the copolymerization product and the modified PET resin; the extrusion temperature of the double-screw extruder is 280 ℃; the diol mixture is prepared from the following components in a mass ratio of 2: 1, ethylene glycol and perfluoro-cage polysilsesquioxane diol;
s3: and (3) taking the high polymer slice as a raw material of a surface functional film layer, taking the high polymer slice and an unmodified PET slice as a material of a base film layer, and performing film drawing together by adopting a film drawing process to obtain the toughened brightness enhancement film for home decoration. When the slices are longitudinally stretched, the slices are preheated to 86 ℃, and are stretched by about 3 times along the extension direction of the slice plane at the temperature, so that the crystallinity of the slices can be improved to reach a higher temperature by orientation: the transverse stretching preheating temperature is 98 ℃, the stretching temperature is 110 ℃, the stretching ratio is 2.5, and the heat setting temperature is 230 ℃. The unmodified PET slice is a resin slice with the intrinsic viscosity of 0.7dL/g, the melting point of 258 ℃ and the carboxyl end group content of less than or equal to 50 mol/t.
The preparation method of the monovinyl cage-type polysilsesquioxane comprises the following steps: hydrolyzing 28 parts of methyltrimethoxysilane in an aqueous solution of acetone with the mass concentration of 30% to prepare a cage-type polysilsesquioxane intermediate, adding 5 parts of triethylamine solution of vinyl trimethoxy silane with the mass concentration of 20% to perform a ring-closing reaction to obtain the monovinyl cage-type polysilsesquioxane.
The preparation method of the compound of the structural formula I comprises the following steps: placing 81 parts by weight of 3-allyl-2-hydroxybenzaldehyde, 65 parts by weight of acetic anhydride and 3 parts by weight of anhydrous potassium acetate in a three-neck flask, heating to 150 ℃, evaporating acetic acid after the reaction starts, dropwise adding acetic anhydride with the same mass, naturally cooling to 80 ℃ after the reaction is finished, and washing with hot water and recrystallizing with methanol to obtain the compound with the structural formula I.
The perfluoro-cage polysilsesquioxane diol is prepared by the following method: hydrolyzing a certain weight part of perfluoro-trimethoxy silane in an aqueous solution of acetone with the mass concentration of 30% to prepare a cage-type polysilsesquioxane intermediate, adding a triethylamine solution of vinyl trimethoxy silane with the mass concentration of 25%, wherein the molar ratio of the vinyl trimethoxy silane to the cage-type polysilsesquioxane intermediate is 1: 105, performing a ring closing reaction to obtain vinyl perfluoro-cage polysilsesquioxane; and then adding the vinyl perfluoro-cage polysilsesquioxane and an initiator into a mixed solution compounded by 1, 4-butylene glycol and ethanol, wherein the molar ratio of the vinyl perfluoro-cage polysilsesquioxane to the alkylene glycol is 1: 1.02, under the action of an initiator, reacting vinyl perfluoro cage polysilsesquioxane with 1, 4-butylene glycol to obtain perfluoro cage polysilsesquioxane glycol. The initiator can be benzoyl peroxide, and the addition amount of the initiator accounts for 0.15 percent of the weight of the vinyl perfluoro cage polysilsesquioxane and the 1, 4-butylene glycol monomer.
The modified nano filler is polyethylene glycol coated nano titanium oxide, and the modification method comprises the following steps: dissolving polyethylene glycol in water to obtain a polyethylene glycol aqueous solution, uniformly dispersing nano titanium oxide in the polyethylene glycol aqueous solution, and evaporating water in the dispersion to dryness to obtain polyethylene glycol coated nano titanium oxide powder.
Example 2
The preparation method of the toughened home decoration base film of the embodiment comprises the following steps:
s1: weighing 100 parts by weight of monovinyl cage-type polysilsesquioxane, 40 parts by weight of compound monomer with a structural formula I and 1 part by weight of ammonium persulfate, dissolving in 100 parts by weight of toluene, setting the reaction temperature at 130 ℃ and the reaction pressure at 0.25MPa, slowly introducing 40 parts by weight of 1, 3-butadiene, reacting while stirring, and obtaining a copolymerization product after reacting for 120 min;
s2: weighing 70 parts of the copolymerization product, 45 parts of a dihydric alcohol mixture, 2.5 parts of dibenzoxazole fluorescent whitening powder and 8 parts of modified nano filler, stirring and mixing uniformly, slowly dropwise adding a mixed solution of 20 parts of terephthalic acid, 1.5 parts of an accelerator zinc acetate and 1 part of a nucleating agent sodium perfluorobutyrate at 235 ℃, continuously reacting for 3 hours after the dropwise adding is finished, then adding a double-screw extruder, and performing blending extrusion and granulation to obtain a copolymer slice with an interpenetrating/semi-interpenetrating network structure formed by the copolymerization product and the modified PET resin; the extrusion temperature of the double-screw extruder is 280 ℃; the diol mixture is prepared from the following components in a mass ratio of 2: 1, ethylene glycol and perfluoro-cage polysilsesquioxane diol;
s3: and (3) taking the high polymer slice as a raw material of a surface functional film layer, taking the high polymer slice and an unmodified PET slice as a material of a base film layer, and performing film drawing together by adopting a film drawing process to obtain the toughened brightness enhancement film for home decoration. When the slices are longitudinally stretched, the slices are preheated to 86 ℃, and are stretched by about 3 times along the extension direction of the slice plane at the temperature, so that the crystallinity of the slices can be improved to reach a higher temperature by orientation: the transverse stretching preheating temperature is 98 ℃, the stretching temperature is 110 ℃, the stretching ratio is 2.5, and the heat setting temperature is 230 ℃.
The monovinyl cage polysilsesquioxane, the compound of formula I, the perfluoro cage polysilsesquioxane diol, the modified nanofiller, and the PET chip of this example were the same as in example 1.
Example 3
The preparation method of the toughened brightness enhancement film for home decoration in the embodiment comprises the following steps:
s1: weighing 120 parts of monovinyl cage-type polysilsesquioxane, 50 parts of compound monomer with a structural formula I and 1.5 parts of ammonium persulfate according to parts by weight, dissolving in 100 parts of toluene, setting the reaction temperature to be 150 ℃, setting the reaction pressure to be 0.15MPa, slowly introducing 50 parts of 1, 3-butadiene, reacting while stirring, and obtaining a copolymerization product after reacting for 180 min;
s2: weighing 80 parts of the copolymerization product, 55 parts of a dihydric alcohol mixture, 3.5 parts of dibenzoxazole fluorescent whitening powder and 12 parts of modified nano filler, stirring and mixing uniformly, slowly dropwise adding a mixed solution of 25 parts of terephthalic acid, 1 part of accelerator zinc acetate and 1.5 parts of nucleating agent sodium perfluorobutyrate at 235 ℃, continuously reacting for 2 hours after the dropwise adding is finished, then adding a double-screw extruder, and performing blending extrusion and granulation to obtain a copolymer slice with an interpenetrating/semi-interpenetrating network structure formed by the copolymerization product and the modified PET resin; the extrusion temperature of the double-screw extruder is 280 ℃; the diol mixture is prepared from the following components in a mass ratio of 2: 1, ethylene glycol and perfluoro-cage polysilsesquioxane diol;
s3: and (3) taking the high polymer slice as a raw material of a surface functional film layer, taking the high polymer slice and an unmodified PET slice as a material of a base film layer, and performing film drawing together by adopting a film drawing process to obtain the toughened brightness enhancement film for home decoration. When the slices are longitudinally stretched, the slices are preheated to 86 ℃, and are stretched by about 3 times along the extension direction of the slice plane at the temperature, so that the crystallinity of the slices can be improved to reach a higher temperature by orientation: the transverse stretching preheating temperature is 98 ℃, the stretching temperature is 110 ℃, the stretching ratio is 2.5, and the heat setting temperature is 230 ℃.
The monovinyl cage polysilsesquioxane, the compound of formula I, the perfluoro cage polysilsesquioxane diol and the modified nanofiller of this example were the same as in example 1.
Comparative example 1
The procedure of the preparation method of the toughened base film for home decoration of the comparative example is substantially the same as that of the example 1, except that the monovinyl cage-type polysilsesquioxane is not added to the raw material of the copolymerization product of the step S1 in the preparation method of the toughened brightness enhancement film for home decoration of the comparative example.
Comparative example 2
The preparation method of the toughened home decoration base film of the comparative example is basically the same as that of the example 1, except that the compound of the structural formula I is not added in the raw material of the copolymerization product of the step S1 in the preparation method of the toughened brightness enhancement film for home decoration of the comparative example.
Comparative example 3
The preparation method of the toughened base film for home decoration of the comparative example is basically the same as that of the example 1, except that in the preparation method of the toughened brightness enhancement film for home decoration of the comparative example, in the step S2, the dihydric alcohol is only ethylene glycol and the perfluorinated cage-type polysilsesquioxane diol is not added in the raw material of the high polymer slice.
Comparative example 4
The preparation method of the toughened home decoration base film of the comparative example is basically the same as that of the example 1, except that in the preparation method of the toughened brightness enhancement film for home decoration of the comparative example, the modified nano filler is not added in the raw material of the high polymer slice of the step S2.
The toughened home decoration base films prepared in the examples 1 to 3 and the comparative examples 1 to 4 are subjected to performance tests, and the performance results are shown in tables 1 and 2:
brightening performance test: the toughened home decoration base film is attached to a wood board, the average brightness of the surface of the wood board is tested through a reflectivity tester, and the average brightness improvement rate of the surface of the wood board before and after film attachment is used as an investigation index of the brightening performance.
And (3) wear resistance test: according to GB/T1768-1979, after grinding 200 circles by a grinding wheel under a weight of 250g, the weight loss of the film layer is tested, so that the wear resistance of the film layer is judged.
Easy clean performance test: and (3) attaching the toughened home decoration base film to a wood board, then soaking the wood board in the red dragon fruit juice for 168 hours continuously, repeatedly cleaning the wood board with warm water at 25 ℃ for 3 times, and observing whether the fruit juice pigment residue exists on the surface of the home decoration film.
Testing self-healing performance: forming a microcrack shape on the surface of the film layer in a scribing way, observing the microcrack shape through a microscope to be visible, then placing the film layer under the illumination with the wavelength of 450nm to carry out self-healing operation, and observing the healing condition of the microcrack through the microscope again.
TABLE 1
TABLE 2
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed.
Claims (9)
1. The preparation method of the toughened home decoration base film is characterized by comprising the following steps of:
s1: weighing 90-120 parts by weight of monovinyl cage polysilsesquioxane, 30-50 parts by weight of compound monomer with structural formula I and 0.5-1.5 parts by weight of initiator, dissolving in 100 parts by weight of solvent, setting the reaction temperature to be 120-150 ℃, the reaction pressure to be 0.15-0.35 MPa, slowly introducing 20-50 parts of 1, 3-butadiene, reacting while stirring, and obtaining a copolymerization product after reacting for 60-180 min;
in the formula, R1And R2Each independently selected from H, methyl, ethyl or methoxy;
s2: weighing 50-80 parts of the copolymerization product, 35-55 parts of a dihydric alcohol mixture, 1.5-3.5 parts of dibenzoxazole fluorescent whitening powder and 5-12 parts of modified nano filler, uniformly stirring and mixing, slowly dropwise adding a mixed solution of 18-25 parts of terephthalic acid and 1-2.5 parts of an auxiliary agent at 205-235 ℃, continuously reacting for 2-3 hours after dropwise adding, adding a double-screw extruder, blending, extruding and granulating to obtain a high polymer slice with an interpenetrating/semi-interpenetrating network structure formed by the copolymerization product and the modified PET resin;
s3: and (3) taking the high polymer slice as a raw material of a surface functional film layer, taking the high polymer slice and an unmodified PET slice as a material of a base film layer, and performing film drawing together by adopting a film drawing process to obtain the toughened brightness enhancement film for home decoration.
2. The method of making a toughened home decoration base film according to claim 1 wherein the compound of formula I is:
3. the method of making a toughened home decoration base film according to claim 1 wherein the diol mixture is comprised of ethylene glycol and perfluoro cage polysilsesquioxane diol.
4. The method of making a toughened home decoration base film according to claim 1 wherein said perfluoro-cage polysilsesquioxane diol is obtained by reacting a vinyl perfluoro-cage polysilsesquioxane with an enediol.
5. The method of making a toughened home decoration base film according to claim 1 wherein the alkylene glycol is at least one of 3- (allyloxy) -1, 2-propanediol, 1, 4-butylene glycol, 3-butylene-1, 2-diol or 1, 2-ethylene glycol.
6. The preparation method of the toughened home decoration base film according to claim 1, wherein the modified nano filler is polyethylene glycol coated nano inorganic filler, and the modification method comprises the following steps: dissolving polyethylene glycol in water to obtain a polyethylene glycol aqueous solution, uniformly dispersing the nano inorganic filler in the polyethylene glycol aqueous solution, and evaporating water in the dispersion to dryness to obtain polyethylene glycol coated nano inorganic filler powder.
7. The method for preparing a toughened home decoration base film according to claim 1, wherein the initiator is at least one of ammonium persulfate, potassium persulfate and sodium persulfate.
8. The method for preparing a toughened home decoration base film according to claim 1, wherein the auxiliary agent is at least one of an accelerator, a nucleating agent and a leveling agent.
9. The toughened home decoration base film is characterized by being prepared by the preparation method of any one of claims 1 to 8.
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