CN112159542B - Decorative black and white film and preparation method thereof - Google Patents

Decorative black and white film and preparation method thereof Download PDF

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CN112159542B
CN112159542B CN202010875822.XA CN202010875822A CN112159542B CN 112159542 B CN112159542 B CN 112159542B CN 202010875822 A CN202010875822 A CN 202010875822A CN 112159542 B CN112159542 B CN 112159542B
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CN112159542A (en
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何建雄
杨博
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Suzhou Xionglin New Material Science & Technology Co ltd
Dongguan Xionglin New Materials Technology Co Ltd
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Dongguan Xionglin New Materials Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • 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
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
    • 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
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    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc

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Abstract

The invention provides a black and white film for decoration and a preparation method thereof, wherein the black and white film for decoration is formed by compounding a black film and a white film; the preparation raw materials of the black film comprise polyether polyol I, diisocyanate I, boric acid ester, a silane coupling agent I, carbon black and a chain extender I; the preparation raw materials of the white film comprise polyether polyol II, diisocyanate II, alkoxy aluminum, a silane coupling agent II, white filler and a chain extender II; wherein, the black film is attached to the base cloth to realize the shading effect; the white film can meet the aesthetic requirements of the window blind. The black and white film for decoration is prepared by a composite film blowing machine set, the two layers are compounded in the die head, the laminating process is omitted, the preparation process is convenient and quick, the shading rate of the obtained black and white film for decoration reaches 100 percent, the black and white film for decoration has excellent mechanical property and aging resistance, and the application requirement of the shading film in decorative materials such as shading curtains can be fully met.

Description

Decorative black and white film and preparation method thereof
Technical Field
The invention belongs to the technical field of polymer materials, and particularly relates to a black and white film for decoration and a preparation method thereof.
Background
The roller blind or the cloth curtain with the shading effect is an important decorative material, the conventional shading roller blind or the cloth curtain achieves the shading effect by coating shading coatings for many times, but the coating process can generate more waste gas and waste water to bring environmental protection pressure, and the coating process is complex, so that the production energy consumption is improved, and the cost is overlarge. Therefore, replacing the light-shielding coating with the light-shielding film is becoming the mainstream trend of the manufacturing process of the light-shielding curtain.
The base material of the light shielding film is a polymer film, including a polyolefin film or a polyurethane film. Among them, thermoplastic Polyurethane (TPU) is a high molecular compound which is generated by reacting polyol and isocyanate and has urethane as a repeating unit, has characteristics of adjustable hardness, wear resistance, solvent resistance, low temperature resistance, good adhesion with most materials, and the like, and has gained general attention in recent years. The thermoplastic polyurethane has aging resistance superior to that of rubber, and wear resistance and resilience superior to that of PVC, is an ideal polymer material with comprehensive properties, and is widely applied to tablecloths, bath curtains, furniture cloth, film-coated fabrics and interior materials.
CN110802898A discloses a production method of a full-shading curtain composite fabric, wherein the full-shading curtain composite fabric sequentially comprises a first base fabric layer, a first adhesive layer, a TPU black shading film, a second adhesive layer and a second base fabric layer; the preparation method comprises the following steps: and extruding and blow-molding to prepare the TPU black shading film, and then respectively hot-pressing and compounding a first base fabric layer and a second base fabric layer on two surfaces of the TPU black shading film. The full-shading curtain composite fabric has good shading, heat insulation and sound insulation effects.
CN109130425A discloses a three-layer integrated TPU light shielding film, which comprises a black TPU adhesive film layer and bonding layers positioned on the upper side and the lower side of the black TPU adhesive film layer; and the three layers of integrated TPU light shielding films are respectively subjected to mixing and melting, presetting, calendering and laminating to obtain a finished product. The black TPU layer and the bonding layer are integrally formed by the shading film, the bonding layer is made of polyurethane with cohesiveness, and therefore, the black TPU layer and the bonding layer are not needed to be bonded by glue, and only the cloth cover and the bonding layer are needed to be attached and then heated and pressed, so that the black TPU layer and the bonding layer have the characteristic of convenience in bonding and processing.
CN106346887A discloses a method for manufacturing multifunctional film cloth, wherein the multifunctional film cloth is seamless wall cloth or full-shading curtain cloth, and the specific manufacturing method comprises the following steps: and (3) compounding the surface cloth with a polyurethane TPU waterproof breathable film or a polyurethane TPU black full-shading waterproof film through PU or PUR glue, then curing, then compounding base cloth on the polyurethane TPU waterproof breathable film or the polyurethane TPU black full-shading waterproof film, finishing and packaging to obtain the multifunctional film pasting cloth.
The existing shading curtain has a sandwich-like structure, namely, a shading film is attached to base cloth, and then a layer of base cloth is compounded on the other surface of the shading film, so that the whole material is more attractive. However, the window shade with the structure needs at least two layers of base cloth, the production process and the raw material cost are increased, the resource waste is caused, and the obtained window shade is very thick and heavy, so that the use feeling of people is influenced.
Therefore, it is a research focus in the field to develop a light-shielding material with both light-shielding effect and aesthetic degree to meet the application requirements of decorative materials such as a light-shielding curtain.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a black and white film for decoration and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a black and white film for decoration, which is formed by compounding a black film and a white film; the black film is prepared from the following raw materials in parts by weight:
Figure BDA0002649570960000031
the white film is prepared from the following raw materials in parts by weight:
Figure BDA0002649570960000032
the black and white film for decoration is formed by compounding the black film and the white film, wherein the black film is attached to the base cloth to realize the shading effect; the white film can meet the aesthetic requirements of the window blind. The decorative black and white film is prepared by a composite film blowing machine set, the two layers are compounded in a die head, the laminating process is omitted, and the preparation process is convenient and quick. Moreover, the black film is prepared from boric acid ester, the white film is prepared from alkoxy aluminum, the alkoxy aluminum and the hydroxyl in polyether polyol can react with each other, and the hydroxyl and diisocyanate act together to form an interpenetrating cross-linked network in the film, so that the tensile strength and the tearing strength of the black and white decorative film are remarkably improved; meanwhile, metal aluminum atoms are embedded into the polymer chain segments through the crosslinking reaction of the alkoxy aluminum in the white film and the polyether polyol, so that the aging resistance of the black and white decorative film is improved, and the black and white decorative film has better ultraviolet oxidation resistance, weather resistance and service life.
The polyether polyol I is used in an amount of 30 to 50 parts by weight, for example, 31 parts by weight, 33 parts by weight, 35 parts by weight, 37 parts by weight, 39 parts by weight, 40 parts by weight, 41 parts by weight, 43 parts by weight, 45 parts by weight, 47 parts by weight or 49 parts by weight, and specific values therebetween are not exhaustive for the purpose of brevity and clarity.
The diisocyanate I is used in an amount of 10 to 20 parts by weight, for example 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight or 19 parts by weight, and the specific values therebetween are not exhaustive for the purpose of space and simplicity, and the specific values included in the ranges are not exhaustive.
The borate ester is used in an amount of 1 to 5 parts by weight, for example, 1.2 parts by weight, 1.5 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.2 parts by weight, 2.5 parts by weight, 2.8 parts by weight, 3 parts by weight, 3.2 parts by weight, 3.5 parts by weight, 3.8 parts by weight, 4 parts by weight, 4.2 parts by weight, 4.5 parts by weight, or 4.8 parts by weight, and specific point values therebetween are not limited to space and are not exhaustive, and specific point values included in the range are not intended to be exhaustive.
The silane coupling agent I is used in an amount of 2 to 5 parts by weight, for example, 2.2 parts by weight, 2.5 parts by weight, 2.8 parts by weight, 3 parts by weight, 3.2 parts by weight, 3.5 parts by weight, 3.8 parts by weight, 4 parts by weight, 4.2 parts by weight, 4.5 parts by weight or 4.8 parts by weight, and specific point values therebetween are not limited to space and for the sake of brevity, and the present invention is not exhaustive of the specific point values included in the range.
The carbon black is used in an amount of 15 to 30 parts by weight, for example 16 parts by weight, 18 parts by weight, 20 parts by weight, 21 parts by weight, 23 parts by weight, 25 parts by weight, 27 parts by weight or 29 parts by weight, and specific values therebetween are not exhaustive for the purpose of brevity and clarity, and the invention is not intended to be limited to the specific values included in the ranges set forth.
The chain extender I is used in an amount of 0.5 to 3 parts by weight, for example, 0.8 part by weight, 1 part by weight, 1.2 parts by weight, 1.5 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.2 parts by weight, 2.5 parts by weight or 2.8 parts by weight, and specific values therebetween are not exhaustive, and for the sake of brevity, the present invention is not intended to be limited to the specific values included in the ranges.
The amount of polyether polyol II used in the raw materials for preparing the white film is 30 to 50 parts by weight, for example, 31 parts by weight, 33 parts by weight, 35 parts by weight, 37 parts by weight, 39 parts by weight, 40 parts by weight, 41 parts by weight, 43 parts by weight, 45 parts by weight, 47 parts by weight or 49 parts by weight, and specific points therebetween are not exhaustive for the purpose of brevity and clarity.
The diisocyanate II is used in an amount of 10 to 20 parts by weight, for example 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight or 19 parts by weight, and specific values therebetween are not exhaustive for reasons of space and simplicity, and the invention is not intended to be exhaustive of the specific values included in the ranges.
The amount of the aluminum alkoxide is 0.5 to 3 parts by weight, for example, 0.8 parts by weight, 1 part by weight, 1.2 parts by weight, 1.5 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.2 parts by weight, 2.5 parts by weight, or 2.8 parts by weight, and specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the ranges for brevity.
The silane coupling agent II is used in an amount of 2 to 5 parts by weight, for example, 2.2 parts by weight, 2.5 parts by weight, 2.8 parts by weight, 3 parts by weight, 3.2 parts by weight, 3.5 parts by weight, 3.8 parts by weight, 4 parts by weight, 4.2 parts by weight, 4.5 parts by weight or 4.8 parts by weight, and specific points therebetween are not limited to space and for the sake of brevity, and the present invention is not exhaustive of the specific points included in the range.
The white filler is used in an amount of 1 to 15 parts by weight, for example, 2 parts by weight, 4 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, or 14 parts by weight, and specific values therebetween, which are not exhaustive for the purpose of brevity and clarity, are not intended to be exhaustive.
The chain extender II is used in an amount of 0.5 to 3 parts by weight, for example 0.8 parts by weight, 1 part by weight, 1.2 parts by weight, 1.5 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.2 parts by weight, 2.5 parts by weight or 2.8 parts by weight, and specific values therebetween are not exhaustive for the purpose of brevity and clarity.
In the present invention, the polyether polyol I and the polyether polyol II each independently include any one of polytetrahydrofuran diol, polypropylene glycol, tetrahydrofuran-propylene oxide copolymer diol, or trihydroxy polyether, or a combination of at least two thereof.
Preferably, the polyether polyols I, II each independently have a number average molecular weight of 700 to 7000g/mol, for example 800g/mol, 1000g/mol, 1200g/mol, 1500g/mol, 1800g/mol, 2000g/mol, 2200g/mol, 2500g/mol, 2800g/mol, 3000g/mol, 3500g/mol, 4000g/mol, 4500g/mol, 5000g/mol, 5500g/mol, 6000g/mol, 6500g/mol or 6800g/mol, and the specific values therebetween are limited in space and for the sake of brevity, the present invention is not exhaustive of the specific values included in the ranges.
In the present invention, the diisocyanate I and the diisocyanate II each independently include any one of 4,4 '-diphenylmethane diisocyanate, 2,4' -diphenylmethane diisocyanate, 2,2 '-diphenylmethane diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, or 4,4' -dicyclohexylmethane diisocyanate, or a combination of at least two thereof.
In the invention, the chain extender I and the chain extender II respectively and independently comprise any one or a combination of at least two of ethylene glycol, glycerol, trimethylolpropane, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,5-pentanediol or 1,4-cyclohexanediol.
In the invention, the silane coupling agent I and the silane coupling agent II respectively and independently comprise any one of KH-550, KH-560 or KH-570 or the combination of at least two of the same.
In the invention, the boric acid ester comprises any one of trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate or triphenyl borate or a combination of at least two of the boric acid esters.
In the present invention, the aluminum alkoxide includes any one or a combination of at least two of aluminum ethoxide, tri-n-propoxide, tri-isopropoxide, or tert-butoxyaluminum.
In the invention, the white filler comprises any one or the combination of at least two of titanium dioxide, talcum powder, calcium carbonate, barium sulfate, mica powder and white carbon black.
Preferably, the raw materials for preparing the white film further include 0.1 to 5 parts by weight of an inorganic light stabilizer, and the inorganic light stabilizer may be used in an amount of 0.3 part by weight, 0.5 part by weight, 0.8 part by weight, 1 part by weight, 1.2 parts by weight, 1.5 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.2 parts by weight, 2.5 parts by weight, 2.8 parts by weight, 3 parts by weight, 3.2 parts by weight, 3.5 parts by weight, 3.8 parts by weight, 4 parts by weight, 4.2 parts by weight, 4.5 parts by weight, or 4.8 parts by weight, and specific points therebetween are not exhaustive, and for brevity, the present invention does not list specific points included in the range.
Preferably, the inorganic light stabilizer comprises ZnO and/or CeO 2 。
Preferably, the inorganic light stabilizer is ZnO and CeO 2 The combination of (A), the ZnO and CeO 2 The mass ratio of (1) is (0.5-1.2), for example, 1.
As a preferable technical scheme of the invention, the raw materials for preparing the white film also comprise 0.1-5 parts by weight of inorganic light stabilizer, wherein the inorganic light stabilizer is ZnO and CeO 2 A combination of (1); the ultraviolet absorption bands of the two inorganic light stabilizers have good complementarity, and the two inorganic light stabilizers cooperate with each other to improve the aging resistance and yellowing resistance of the white film.
Preferably, the preparation raw materials of the black film comprise the following components in parts by weight:
Figure BDA0002649570960000071
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Figure BDA0002649570960000081
the white film is prepared from the following raw materials in parts by weight:
Figure BDA0002649570960000082
the inorganic light stabilizer is ZnO and CeO 2 Combinations of (a) and (b).
Preferably, the polyether polyol I and the polyether polyol II are the same polyether polyol.
Preferably, the chain extender I and the chain extender II are the same chain extender.
In another aspect, the present invention provides a method for preparing the black and white film for decoration, the method comprising the steps of:
(1) Reacting polyether polyol I, diisocyanate I, a silane coupling agent I, a chain extender I and carbon black in an extruder I of a composite film blowing unit, adding boric acid ester into a system after the reaction is finished, and mixing to obtain a black film pre-product; reacting polyether polyol II, diisocyanate II, a silane coupling agent II, a chain extender II and white filler in an extruder II of a composite film blowing unit, adding alkoxy aluminum into a system after the reaction is finished, and mixing to obtain a white film pre-product;
(2) And (2) respectively converging the black film pre-product and the white film pre-product obtained in the step (1) into an upper die head and a lower die head of the composite film blowing unit for compounding, and performing blowing molding, cooling and shaping and traction to obtain the black and white film for decoration.
The preparation method provided by the invention is carried out by a composite film blowing unit, the composite film blowing unit can realize the compounding of the white film and the black film in a die head, the process is simple, and the obtained black and white film for decoration has excellent mechanical strength. In the preparation process of the black film pre-product in the step (1), firstly reacting polyether polyol I, diisocyanate I, a silane coupling agent I, a chain extender I and carbon black to obtain a polyurethane prepolymer; introducing boric acid ester into the reaction system, performing crosslinking reaction with the residual hydroxyl in the system, and simultaneously reserving a part of active groups to react with the white film pre-product in the compounding process of the step (2); in a similar way, in the preparation process of the white film pre-product in the step (1), adding alkoxy aluminum for mixing reaction after the polyether polyol II, the diisocyanate II, the silane coupling agent II, the chain extender II and the white filler react, leaving part of unreacted active groups in the white film pre-product, and reacting with the black film pre-product in the compounding process in the step (2); the specific reaction process can form an interpenetrating cross-linked network in the film, further improves the mechanical strength of the black and white decorative film, and particularly plays an important role in improving the tear strength.
Preferably, the specific preparation method of the black film pre-product comprises the following steps: putting polyether polyol I, diisocyanate I, a silane coupling agent I and carbon black into an extruder I for prepolymerization reaction, then adding a chain extender I and an optional catalyst for chain extension reaction, then adding boric acid ester into a reaction system, and mixing to obtain the black film preproduct.
Preferably, the temperatures of the prepolymerization reaction and the chain extension reaction are each independently 70 to 120 ℃, such as 75 ℃,80 ℃,85 ℃,90 ℃, 95 ℃,100 ℃,105 ℃,110 ℃ or 115 ℃, and the specific values therebetween are limited in space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the ranges.
Preferably, the prepolymerization reaction time is 0.5 to 3 hours, such as 0.75h, 1h, 1.25h, 1.5h, 1.75h, 2h, 2.25h, 2.5h or 2.75h, and the specific values therebetween are not exhaustive for the sake of brevity and simplicity.
Preferably, the time of the chain extension reaction is 15 to 60min, such as 20min, 25min, 30min, 35min, 40min, 45min, 50min or 55min, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the ranges.
Preferably, the catalyst comprises an organotin catalyst, exemplary including but not limited to: dibutyltin dilaurate and/or stannous octoate.
Preferably, the temperature of the mixing is 100 to 130 ℃, such as 102 ℃,105 ℃, 108 ℃,110 ℃, 112 ℃,115 ℃, 118 ℃, 120 ℃, 122 ℃,125 ℃ or 128 ℃, and the specific values therebetween, are limited in space and for the sake of brevity, and the invention is not intended to be exhaustive of the specific values included in the ranges.
Preferably, the mixing time is 10-40 min, such as 12min, 15min, 18min, 20min, 22min, 25min, 28min, 30min, 32min, 35min or 38min, and the specific points between the above points, limited to space and for brevity, the present invention is not exhaustive of the specific points included in the ranges.
Preferably, the specific preparation method of the white film pre-product comprises the following steps: putting polyether polyol II, diisocyanate II, a silane coupling agent II, a white filler and an optional inorganic light stabilizer into an extruder II for prepolymerization reaction, then adding a chain extender II and an optional catalyst for chain extension reaction, then adding alkoxy aluminum into a reaction system, and mixing to obtain the white film preproduct.
Preferably, the temperatures of the prepolymerization reaction and the chain extension reaction are each independently 70 to 120 ℃, such as 75 ℃,80 ℃,85 ℃,90 ℃, 95 ℃,100 ℃,105 ℃,110 ℃ or 115 ℃, and the specific values therebetween are limited in space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the ranges.
Preferably, the prepolymerization reaction time is 0.5 to 3 hours, such as 0.75h, 1h, 1.25h, 1.5h, 1.75h, 2h, 2.25h, 2.5h or 2.75h, and the specific values therebetween are not exhaustive for the sake of brevity and simplicity.
Preferably, the time of the chain extension reaction is 15 to 60min, such as 20min, 25min, 30min, 35min, 40min, 45min, 50min or 55min, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the ranges.
Preferably, the temperature of the mixing is between 90 ℃ and 120 ℃, such as 92 ℃, 95 ℃, 98 ℃,100 ℃, 102 ℃,105 ℃, 108 ℃,110 ℃, 112 ℃,115 ℃ or 118 ℃, and specific values therebetween, are not exhaustive and are included for brevity and clarity.
Preferably, the mixing time is 10-40 min, such as 12min, 15min, 18min, 20min, 22min, 25min, 28min, 30min, 32min, 35min or 38min, and the specific points between the above points, limited to space and for brevity, the present invention is not exhaustive of the specific points included in the ranges.
In the invention, the reaction in the extruder I and the extruder II is carried out in a protective atmosphere.
Preferably, the pressure for blow molding is 0.4 to 0.8MPa, such as 0.42MPa, 0.45MPa, 0.48MPa, 0.5MPa, 0.52MPa, 0.55MPa, 0.58MPa, 0.6MPa, 0.62MPa, 0.65MPa, 0.68MPa, 0.7MPa, 0.72MPa, 0.75MPa or 0.78MPa, and specific values therebetween, limited to space and for the sake of brevity, the invention is not exhaustive of the specific values included in the ranges.
Preferably, the traction has a drive power of 0.8 to 1.5kW, such as 0.85kW, 0.9kW, 0.95kW, 1kW, 1.05kW, 1.1kW, 1.15kW, 1.2kW, 1.25kW, 1.3kW, 1.35kW, or 1.4kW, and the specific points between the above points are limited in space and for simplicity, and the invention is not exhaustive with the specific points included in the range.
Preferably, the speed of said traction is comprised between 2 and 25m/min, such as 3m/min, 5m/min, 8m/min, 10m/min, 12m/min, 15m/min, 18m/min, 20m/min, 21m/min, 23m/min or 24m/min, and the specific values between the above, limited to the space and for the sake of brevity, the present invention is not exhaustive of the specific values comprised in said range.
Compared with the prior art, the invention has the following beneficial effects:
the black and white film for decoration provided by the invention is formed by compounding the black film and the white film, the black film is attached to the base cloth, the shading effect is realized, and the white film can meet the aesthetic requirement of the shading curtain. The black and white film for decoration forms an interpenetrating cross-linked network in the film by screening and compounding the preparation raw materials, so that the mechanical strength of the black and white film is remarkably improved; meanwhile, metal aluminum atoms are embedded into the polymer chain segments of the white film, so that the aging resistance of the black and white decorative film is improved, and the black and white decorative film has better ultraviolet oxidation resistance, weather resistance and service life. The black and white film for decoration is prepared by a composite film blowing machine set, the process is simple, the generation of industrial three wastes is reduced, and the environment is protected. The black and white film for decoration has the shading rate of 100 percent, excellent mechanical property and aging resistance, tensile strength of 45.6-48.3 MPa, tear strength of 44.3-47.3 kN/m, elongation at break of 181-190 percent, tensile strength of 40-46.77 MPa after ultraviolet ozone aging treatment for 240 hours, yellowing resistance grade of not less than 4 grade, and can fully meet the application requirement of the shading film in decorative materials such as shading curtains and the like.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A black and white decorative film is composed of black and white films.
The preparation raw materials of the black film comprise:
Figure BDA0002649570960000121
Figure BDA0002649570960000131
/>
the white film is prepared from the following raw materials in parts by weight:
Figure BDA0002649570960000132
wherein the polytetrahydrofuran diol in the white film and the black film is the same polyether polyol, and the number average molecular weight is 4200g/mol; the silane coupling agent in the white film and the black film is KH-560; the inorganic light stabilizer is ZnO and CeO 2 A mass ratio of 1:1.
The preparation method comprises the following steps:
(1) Preparation of black film preproduct: dehydrating polytetrahydrofuran glycol in the black film preparation raw material in a melting section of an extruder I according to the formula amount, adding 4,4' -MDI, a silane coupling agent and carbon black, and carrying out prepolymerization reaction for 2h at 80 ℃; adding 1,4-butanediol for chain extension reaction for 40min; adding triethyl borate into the system after the chain extension reaction, and mixing for 35min at 110 ℃ to obtain the black film pre-product;
(2) Preparation of a white film pre-product: according to the formula amount, carrying out dehydration treatment on polytetrahydrofuran glycol in a white film preparation raw material in a melting section of an extruder II, then adding IPDI (isophorone diisocyanate), a silane coupling agent, titanium dioxide, talcum powder and an inorganic light stabilizer, and carrying out prepolymerization reaction for 2.5h at 85 ℃; adding 1,4-butanediol for chain extension reaction for 30min; adding aluminum ethoxide into the system after the chain extension reaction, and mixing for 30min at 100 ℃ to obtain the white film pre-product;
(3) Respectively converging the black film pre-product obtained in the step (1) and the white film pre-product obtained in the step (2) into an upper die head and a lower die head of a composite film blowing machine set for compounding, and performing blowing molding, cooling and shaping and traction to obtain the black and white film for decoration.
Example 2
A black and white decorative film is composed of black and white films.
The preparation raw materials of the black film comprise:
Figure BDA0002649570960000141
the white film is prepared from the following raw materials in parts by weight:
Figure BDA0002649570960000142
Figure BDA0002649570960000151
wherein the polytetrahydrofuran diol in the white film and the black film is the same polyether polyol, and the number average molecular weight is 4200g/mol; the silane coupling agent in the white film and the black film is KH-550; the inorganic light stabilizer is ZnO and CeO 2 The mass ratio of the components is 1.
The preparation method comprises the following steps:
(1) Preparation of black film preproduct: according to the formula amount, carrying out dehydration treatment on polytetrahydrofuran diol in a black film preparation raw material in a melting section of an extruder I, then adding XDI, a silane coupling agent and carbon black, and carrying out prepolymerization reaction for 1h at 100 ℃; adding 1,4-butanediol for chain extension reaction for 30min; adding trimethyl borate into the system after the chain extension reaction, and mixing for 15min at 125 ℃ to obtain a black film pre-product;
(2) Preparation of a white film pre-product: according to the formula amount, carrying out dehydration treatment on polytetrahydrofuran diol in a white film preparation raw material in a melting section of an extruder II, then adding HDI, a silane coupling agent, titanium dioxide and an inorganic light stabilizer, and carrying out prepolymerization reaction for 3h at 75 ℃; adding 1,4-butanediol for chain extension reaction for 60min; adding tri-n-propoxyaluminum into the system after the chain extension reaction, and mixing for 40min at 90 ℃ to obtain the white film pre-product;
(3) And (3) respectively converging the black film pre-product obtained in the step (1) and the white film pre-product obtained in the step (2) into an upper die head and a lower die head of a composite film blowing unit for compounding, and carrying out blowing molding, cooling and shaping and traction to obtain the black and white film for decoration.
Example 3
A black and white decorative film is composed of black and white films.
The preparation raw materials of the black film comprise:
Figure BDA0002649570960000152
Figure BDA0002649570960000161
the white film is prepared from the following raw materials in parts by weight:
Figure BDA0002649570960000162
wherein the polytetrahydrofuran diol in the white film and the black film is the same polyether polyol, and the number average molecular weight is 4200g/mol; the silane coupling agent in the white film and the black film is KH-570;the inorganic light stabilizer is ZnO and CeO 2 The mass ratio is 2:1.
The preparation method comprises the following steps:
(1) Preparation of black film preproduct: dehydrating polytetrahydrofuran glycol in the black film preparation raw material in a melting section of an extruder I according to the formula amount, then adding TDI, a silane coupling agent and carbon black, and carrying out prepolymerization reaction for 40min at 110 ℃; adding 1,4-butanediol for chain extension reaction for 20min; adding triisopropyl borate into the system after the chain extension reaction, and mixing for 40min at 105 ℃ to obtain the black film pre-product;
(2) Preparation of a white film pre-product: according to the formula amount, carrying out dehydration treatment on polytetrahydrofuran diol in a white film preparation raw material in a melting section of an extruder II, then adding HMDI, a silane coupling agent, titanium dioxide and an inorganic light stabilizer, and carrying out prepolymerization reaction at 115 ℃ for 40min; adding 1,4-butanediol for chain extension reaction for 25min; adding tert-butoxy aluminum into the system after the chain extension reaction, and mixing for 15min at 115 ℃ to obtain the white film pre-product;
(3) Respectively converging the black film pre-product obtained in the step (1) and the white film pre-product obtained in the step (2) into an upper die head and a lower die head of a composite film blowing machine set for compounding, and performing blowing molding, cooling and shaping and traction to obtain the black and white film for decoration.
Example 4
A black and white film for decoration is compounded by a black film and a white film, and the difference from the embodiment 1 is only that in the preparation raw materials of the white film, an inorganic light stabilizer is ZnO; other raw material components and preparation methods were the same as in example 1.
Example 5
A black and white decorative film is formed by compounding a black film and a white film, and the difference from the embodiment 1 is only that in the preparation raw material of the white film, an inorganic light stabilizer is CeO 2 (ii) a Other raw material components and preparation methods were the same as in example 1.
Example 6
A black and white film for decoration is compounded by a black film and a white film, and is only different from the black film and the white film in example 1 in that the raw materials for preparing the white film do not contain inorganic light stabilizer; other raw material components and preparation methods were the same as in example 1.
Comparative example 1
A black and white film for decoration is composed of a black film and a white film; it is different from example 1 only in that triethyl borate is not contained in the raw materials for the preparation of the black film; other raw material components and preparation methods were the same as in example 1.
Comparative example 2
A black and white film for decoration is composed of a black film and a white film; the difference from the example 1 is only that the raw materials for preparing the white film do not contain aluminum ethoxide; other raw material components and the preparation method were the same as in example 1.
Comparative example 3
A black and white film for decoration is composed of a black film and a white film; it differs from example 1 only in that the aluminum ethoxide in the white film was replaced with an equal amount of triethyl borate; other raw material components and preparation methods were the same as in example 1.
Comparative example 4
A black and white film for decoration is composed of a black film and a white film; the raw materials and the component ratios are the same as those of the example 1, and the difference is only that the preparation method comprises the following steps:
(1) Preparation of a black film: according to the formula amount, carrying out dehydration treatment on polytetrahydrofuran diol in the black film preparation raw material in a melting section of an extruder, then adding 4,4' -MDI, a silane coupling agent and carbon black, and carrying out prepolymerization reaction for 2h at 80 ℃; adding 1,4-butanediol for chain extension reaction for 40min; adding triethyl borate into the system after the chain extension reaction, mixing for 35min at 110 ℃, and obtaining the black film after blow molding, cooling and shaping and traction;
(2) Preparation of white film: according to the formula amount, carrying out dehydration treatment on polytetrahydrofuran glycol in a white film preparation raw material in a melting section of an extruder II, then adding IPDI (isophorone diisocyanate), a silane coupling agent, titanium dioxide, talcum powder and an inorganic light stabilizer, and carrying out prepolymerization reaction for 2.5h at 85 ℃; adding 1,4-butanediol for chain extension reaction for 30min; adding aluminum ethoxide into the system after the chain extension reaction, mixing for 30min at 100 ℃, and obtaining the white film after blow molding, cooling and shaping and traction;
(3) And (2) coating a PU hot melt adhesive (Nuobao YZ-001) on the surface of the black film obtained in the step (1), then covering the white film obtained in the step (2) on the surface of the hot melt adhesive, and curing at 100 ℃ to obtain the black and white film for decoration.
Comparative example 5
A black and white film for decoration is composed of a black film and a white film; the raw materials and the component ratios are the same as those of the example 1, and the difference is only that the preparation method comprises the following steps:
(1) Preparation of black film preproduct: dehydrating polytetrahydrofuran glycol in the raw materials for preparing the black film in a melting section of an extruder I according to the formula amount, adding 4,4' -MDI, a silane coupling agent, triethyl borate and carbon black, and carrying out prepolymerization reaction for 2h at 80 ℃; adding 1,4-butanediol to perform chain extension reaction for 40min to obtain the black film pre-product;
(2) Preparation of a white film pre-product: according to the formula amount, carrying out dehydration treatment on polytetrahydrofuran glycol in a white film preparation raw material in a melting section of an extruder II, then adding IPDI (isophorone diisocyanate), a silane coupling agent, aluminum ethoxide, titanium dioxide, talcum powder and an inorganic light stabilizer, and carrying out prepolymerization reaction for 2.5h at 85 ℃; adding 1,4-butanediol for chain extension reaction for 30min to obtain the white film pre-product;
(3) Respectively converging the black film pre-product obtained in the step (1) and the white film pre-product obtained in the step (2) into an upper die head and a lower die head of a composite film blowing machine set for compounding, and performing blowing molding, cooling and shaping and traction to obtain the black and white film for decoration.
And (3) performance testing:
(1) Tensile strength, elongation at break: testing is carried out according to the method specified in the national standard GB/T13022-1991;
(2) Light-shielding rate: mixing black and white film to be measured and pure color polyester fabric (gram weight 110 g/m) 2 ) Compounding, and testing the light shielding performance according to the light transmission box method recorded in AATCC-148-79;
(3) Tear strength: testing the right-angle tear strength according to the method specified in the national standard QB/T1130-1991;
(4) Aging resistance: will be provided withThe black and white film to be tested for decoration is placed in an ultraviolet ozone aging test box for testing, and the ultraviolet irradiation intensity is 350 mu W/cm 2 The ozone concentration is 20ppm, the temperature is 28 ℃, the tensile strength of the white film is tested after continuous irradiation for 240 hours, and the color difference of the white film before and after irradiation is carried out, so that the yellowing resistance of the white film is obtained; when the yellowing resistance grade is 5 grades, the color difference before and after irradiation is basically not generated.
The black and white decorative films provided in examples 1 to 6 and comparative examples 1 to 5 were tested according to the above-mentioned property test method, and the test data are shown in Table 1.
TABLE 1
Figure BDA0002649570960000201
As can be seen from the data in Table 1, the black and white film for decoration provided in the embodiments 1 to 6 of the present invention has a light shading rate of 100%, excellent mechanical properties and aging resistance, a tensile strength of 45.6 to 48.3MPa, an elongation at break of 181 to 190%, a tear strength of 44.3 to 47.3kN/m, a yellowing color difference of not less than 4 grade after being aged by ultraviolet and ozone for 240 hours, a tensile strength of 40MPa or more, even 46.77MPa, and a tensile strength retention rate of 95 to 97% after being aged, and the black and white film for decoration has excellent aging resistance.
Comparing examples 1 to 3 and examples 4 to 6 in parallel, it is understood that the inorganic light stabilizer in the white film greatly contributes to the improvement of the aging resistance, and that the aging resistance of the decorative black and white film can be optimized when the inorganic light stabilizer is a combination of zinc oxide and cerium oxide.
According to the invention, the introduction of the specific components of boric acid ester and aluminum alkoxide can form an interpenetrating cross-linked network in the film, so that the mechanical properties, especially the tear strength, of the black and white decorative film are obviously improved; if the raw materials for preparing the black film do not contain borate (comparative example 1) or the raw materials for preparing the white film do not contain aluminum alkoxide (comparative examples 2 and 3), the mechanical properties of the black and white film for decoration are reduced, the aging resistance is reduced, and the requirements for the strength and the service life of the shading material cannot be met.
The black and white film for decoration provided by the invention is prepared by a composite film blowing machine set, the process is simple, and the obtained black and white film for decoration has high mechanical strength; if the black and white films are separately blow-molded and then laminated (comparative example 4), the tear strength of the black and white decorative film is significantly reduced. Meanwhile, in the preparation process, boric acid ester and alkoxy aluminum which are specific components are respectively added in the reaction rear section, so that a part of unreacted active groups are left in the white film pre-product and the black film pre-product, the white film pre-product and the black film pre-product are further reacted in the compounding process, the bonding force between the black film and the white film is enhanced, and the decorative black and white film with high tearing strength is obtained; if the borate and the alkoxy aluminum are added in the initial reaction stage, the borate and the alkoxy aluminum completely react in the prepolymerization process and cannot react in the compounding process, so that the bonding force between the black film and the white film is weakened, and the tearing strength of the black and white film for decoration is reduced.
The applicant states that the invention is illustrated by the above examples, but the invention is not limited to the above examples, i.e. the invention must not be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (33)

1. The black and white film for decoration is characterized by being formed by compounding a black film and a white film; the black film is prepared from the following raw materials in parts by weight:
Figure FDA0004031672530000011
the white film is prepared from the following raw materials in parts by weight:
Figure FDA0004031672530000012
the black and white film for decoration is prepared by adopting the following method, and the method comprises the following steps:
(1) Reacting polyether polyol I, diisocyanate I, a silane coupling agent I, a chain extender I and carbon black in an extruder I of a composite film blowing unit, adding boric acid ester into a system after the reaction is finished, and mixing to obtain a black film pre-product; reacting polyether polyol II, diisocyanate II, a silane coupling agent II, a chain extender II and white filler in an extruder II of a composite film blowing unit, adding alkoxy aluminum into a system after the reaction is finished, and mixing to obtain a white film pre-product;
(2) And (2) respectively converging the black film pre-product and the white film pre-product obtained in the step (1) into an upper die head and a lower die head of the composite film blowing unit for compounding, and performing blowing molding, cooling and shaping and traction to obtain the black and white film for decoration.
2. The black and white decorative film of claim 1, wherein the polyether polyols I and II each independently comprise one or a combination of at least two of polytetrahydrofuran diol, polypropylene diol, tetrahydrofuran-propylene oxide copolymer diol, and trihydroxy polyether.
3. The black and white decorative film according to claim 1, wherein the polyether polyol I and the polyether polyol II have a number average molecular weight of 700 to 7000g/mol, respectively.
4. The black and white decorative film according to claim 1, wherein the diisocyanate I and the diisocyanate II each independently comprises any one or a combination of at least two of 4,4 '-diphenylmethane diisocyanate, 2,4' -diphenylmethane diisocyanate, 2,2 '-diphenylmethane diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, or 4,4' -dicyclohexylmethane diisocyanate.
5. The black and white decorative film according to claim 1, wherein the chain extender I and the chain extender II each independently comprise any one of ethylene glycol, glycerol, trimethylolpropane, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,5-pentanediol or 1,4-cyclohexanediol or a combination of at least two thereof.
6. The black and white decorative film according to claim 1, wherein the silane coupling agent I and the silane coupling agent II each independently comprises any one of KH-550, KH-560 or KH-570, or a combination of at least two thereof.
7. The decorative black and white film according to claim 1, wherein the borate comprises any one of trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate or triphenyl borate, or a combination of at least two thereof.
8. The decorative black and white film of claim 1, wherein the aluminum alkoxide comprises any one or a combination of at least two of aluminum ethoxide, tri-n-propoxide, tri-isopropoxide, or tert-butoxide.
9. The decorative black and white film according to claim 1, wherein the white filler comprises any one or a combination of at least two of titanium dioxide, talc, calcium carbonate, barium sulfate, mica powder and white carbon black.
10. The black and white decorative film according to claim 1, wherein the raw materials for preparing the white film further comprise 0.1 to 5 parts by weight of an inorganic light stabilizer.
11. The decorative film as claimed in claim 10, wherein the inorganic light stabilizer comprises ZnO and/or CeO 2 。
12. The decorative black and white film according to claim 10, wherein the inorganic light stabilizer is selected from the group consisting of ZnO and CeO 2 The combination of (A), the ZnO and CeO 2 The mass ratio of (1) to (1.5-1.2).
13. The black and white decorative film as claimed in claim 1, wherein the black film is prepared from the following raw materials in parts by weight:
Figure FDA0004031672530000031
the white film is prepared from the following raw materials in parts by weight:
Figure FDA0004031672530000032
/>
Figure FDA0004031672530000041
the inorganic light stabilizer is ZnO and CeO 2 Combinations of (a) and (b).
14. The black and white decorative film according to claim 1 or 13, wherein the polyether polyol I and the polyether polyol II are the same polyether polyol.
15. The black and white decorative film according to claim 1 or 13, wherein the chain extender I and the chain extender II are the same chain extender.
16. A method for preparing the black and white decorative film according to any one of claims 1 to 9, comprising the steps of:
(1) Reacting polyether polyol I, diisocyanate I, a silane coupling agent I, a chain extender I and carbon black in an extruder I of a composite film blowing unit, adding boric acid ester into a system after the reaction is finished, and mixing to obtain a black film pre-product; reacting polyether polyol II, diisocyanate II, a silane coupling agent II, a chain extender II and white filler in an extruder II of a composite film blowing unit, adding alkoxy aluminum into a system after the reaction is finished, and mixing to obtain a white film pre-product;
(2) And (2) respectively converging the black film pre-product and the white film pre-product obtained in the step (1) into an upper die head and a lower die head of the composite film blowing unit for compounding, and performing blowing molding, cooling and shaping and traction to obtain the black and white film for decoration.
17. The method for preparing the black film preproduct according to claim 16, wherein the black film preproduct is prepared by the following steps: putting polyether polyol I, diisocyanate I, a silane coupling agent I and carbon black into an extruder I for prepolymerization reaction, then adding a chain extender I and an optional catalyst for chain extension reaction, then adding boric acid ester into a reaction system, and mixing to obtain the black film preproduct.
18. The method according to claim 17, wherein the temperatures of the prepolymerization reaction and the chain extension reaction are each independently 70 to 120 ℃.
19. The method as claimed in claim 17, wherein the prepolymerization time is 0.5 to 3 hours.
20. The preparation method according to claim 17, wherein the time of the chain extension reaction is 15 to 60min.
21. The method of claim 17, wherein the catalyst comprises an organotin catalyst.
22. The method of claim 17, wherein the mixing temperature is 100 to 130 ℃.
23. The method of claim 17, wherein the mixing time is 10 to 40min.
24. The method for preparing the white film preproduct according to claim 16, wherein the specific method for preparing the white film preproduct is as follows: putting polyether polyol II, diisocyanate II, a silane coupling agent II, a white filler and an optional inorganic light stabilizer into an extruder II for prepolymerization reaction, then adding a chain extender II and an optional catalyst for chain extension reaction, then adding alkoxy aluminum into a reaction system, and mixing to obtain the white film preproduct.
25. The method according to claim 24, wherein the temperatures of the prepolymerization reaction and the chain extension reaction are each independently 70 to 120 ℃.
26. The method as claimed in claim 24, wherein the prepolymerization time is 0.5 to 3 hours.
27. The method according to claim 24, wherein the time for the chain extension reaction is 15 to 60min.
28. The method of claim 24, wherein the temperature of the mixing is 90 to 120 ℃.
29. The method of claim 24, wherein the mixing time is 10 to 40min.
30. The method according to claim 16, wherein the reaction in each of the extruders I and II is carried out in a protective atmosphere.
31. The method as claimed in claim 16, wherein the pressure of the blow molding is 0.4 to 0.8MPa.
32. The method according to claim 16, wherein the traction has a driving power of 0.8 to 1.5kW.
33. The method of claim 16, wherein the drawing speed is 2 to 25m/min.
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