CN110835463A - High-hydrophobic-angle TPU (thermoplastic polyurethane) film and preparation method thereof - Google Patents
High-hydrophobic-angle TPU (thermoplastic polyurethane) film and preparation method thereof Download PDFInfo
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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
- C08J5/18—Manufacture of films or sheets
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- 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
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
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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
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/16—Homopolymers or copolymers of vinylidene fluoride
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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
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08J2433/16—Homopolymers or copolymers of esters containing halogen atoms
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Abstract
The invention provides a TPU film with a high hydrophobic angle and a preparation method thereof, wherein the TPU film comprises the following raw materials in parts by weight: 30-50 parts of toluene diisocyanate, 20-40 parts of polyester polyol, 4-6 parts of hexafluorobutyl methacrylate, 1-2 parts of octadecyl acrylate, 5-10 parts of polyvinylidene fluoride, 3-8 parts of a chain extender and 1-3 parts of a catalyst; according to the TPU film provided by the invention, hexafluorobutyl methacrylate and octadecyl acrylate are matched for use, so that fluorine-containing groups are regularly arranged on a polymerization surface, a stable film is formed after reaction, and a formed coating has low surface and free energy; furthermore, by mixing polyvinylidene fluoride with good insulating property, water drops can roll off on the surface of the membrane more easily, and the hydrophobic angle of the membrane is improved by matching with the fluorine-containing group, can reach 121-124 degrees, is excellent in hydrophobic property and has a wide application prospect.
Description
Technical Field
The invention belongs to the field of high polymer materials, relates to a TPU film and a preparation method thereof, and particularly relates to a TPU film with a high hydrophobic angle and a preparation method thereof.
Background
TPU (thermoplastic polyurethanes), thermoplastic TPU elastomers, because of their good elasticity, good physical properties, and good mechanical strength, are widely used in processing methods such as injection, extrusion, calendering, and dissolution into solution resins, are plastic materials frequently used by plastic processing manufacturers, and their manufactured products cover the range of industrial applications and civil necessities.
The TPU film is prepared by special processes such as calendering, tape casting, film blowing, coating and the like on the basis of TPU granules. In recent years, new products are continuously developed, and new industrial opportunities with low cost and high added value are created for plastic processing manufacturers.
The hydrophobic property of the film is widely researched due to wide application in the aspects of self-cleaning, anti-freezing, oil-water separation and the like.
CN104108216A discloses a process method for improving light transmittance and hydrophobicity of a polyester film by modifying the polyester film with a star copolymer containing polysiloxane. Polystyrene is used as an initiator, atom transfer radical polymerization is carried out on the polystyrene and a methacrylic acid polysiloxane ester macromonomer to prepare star polystyrene-polydimethylsiloxane copolymer (PS-PDMS), and the obtained polymer is coated on the surface of a Polyester (PET) film in a spinning way to improve the anti-reflection, hydrophobicity and the like of the surface of the film. The antireflection film prepared by the method has stable performance and can meet the use requirements of electronic displays and other optical elements. However, the thin film provided by the method is only limited to the field of electronic devices.
CN102553813A discloses a sol-gel method for preparing micro-nano titanium dioxide and a hydrophobic film thereof on a metal surface, which comprises the following steps: (a) pretreating a metal substrate; (b) preparing micro-nano TiO on the surface of a pretreated metal substrate2A film; (c) micro-nano TiO on metal substrate surface2Preparing a heptadecafluorodecyl triisopropoxysilane-silicon dioxide hydrophobic film on the film. The method adopts titanium dioxide film as transition layer, and avoids direct silane coatingThe acidic sol corrodes the metal substrate when the film is hydrophobic, so that the wettability of the silane sol is improved, and the uniform and compact hydrophobic film is obtained. Meanwhile, the defects of cracks and the like are reduced by multiple coating, the corrosion resistance of the film is improved, the surface free energy of the film is reduced by hydrophobic treatment, and the deposition of dirt on the film is reduced. However, the film provided by the method has higher price and lower industrial economic benefit due to the adoption of the micro-nano technology.
CN104479140A discloses photolytic amphiphilic polyurethane and a preparation method thereof. The photo-degradable polyisocyanate is prepared by selecting a hydroxyl-terminated photoinitiator 2-hydroxy-2-methyl-p-hydroxyethyl ether phenyl acetone and polyisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate and the like, and then a hydrophilic chain and a hydrophobic chain are respectively connected to the isocyanate groups of the photo-degradable polyisocyanate, so that the photo-degradable amphiphilic polyurethane is finally obtained. The method has the advantages of low preparation process cost, few reaction steps, short preparation period, simple and convenient operation and easy control, thereby being more suitable for industrial production. But is an amphiphilic polyurethane and not a completely hydrophobic polyurethane.
Currently, a TPU film is a mature technology, and the research on the performance of the TPU film with hydrophobic property is less. Therefore, how to develop a TPU film with a high hydrophobic angle has important significance for the application of the TPU film in the fields of self-cleaning, anti-freezing and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a TPU film and a preparation method thereof, in particular to a TPU film with a high hydrophobic angle and a preparation method thereof, so as to solve the problems of small hydrophobic angle and poor hydrophobic property of the existing TPU film.
In order to achieve the purpose, the invention adopts the following technical scheme:
on one hand, the invention provides a TPU film, which comprises the following raw materials in parts by weight:
according to the TPU film provided by the invention, hexafluorobutyl methacrylate and octadecyl acrylate are matched for use, so that fluorine-containing groups are regularly arranged on a polymerization surface, a stable film is formed after reaction, and a formed coating has low surface free energy; furthermore, by mixing polyvinylidene fluoride with good insulating property, water drops can roll off on the surface of the membrane more easily, and the hydrophobic angle of the membrane is improved by matching with the fluorine-containing groups, can reach more than 120 degrees, and is excellent in hydrophobic property.
In the invention, the high hydrophobicity means that the hydrophobicity angle can reach more than 120 degrees.
The toluene diisocyanate of the present invention is 30 to 50 parts by weight, and may be, for example, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, or the like.
The hexafluorobutyl methacrylate of the present invention is 4 to 6 parts by weight, for example, 4 parts, 5 parts or 6 parts.
The weight part of the octadecyl acrylate is 1-2 parts, and can be 1 part or 2 parts, for example.
Stearyl acrylate is generally used as a resin crosslinking agent, a plastic, a rubber modifier, and the like. In the present invention, stearyl acrylate may facilitate the enhancement of the hydrophobic effect of hexafluorobutyl methacrylate.
The polyvinylidene fluoride of the present invention is 5 to 10 parts by weight, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts.
Polyvinylidene fluoride has many advantages such as elasticity, low weight, low thermal conductivity, high chemical resistance, and heat resistance. In the present invention, polyvinylidene fluoride and hexafluorobutyl methacrylate can exert the best hydrophobic property.
Preferably, the mass ratio of hexafluorobutyl methacrylate, stearyl acrylate and polyvinylidene fluoride is (2-3):1 (3-6), and may be, for example, 2:1:3, 2.5:1:4, 3:1:6, and the like.
In the invention, when the mass ratio of the hexafluorobutyl methacrylate, the octadecyl acrylate and the polyvinylidene fluoride is reasonably matched, the optimal hydrophobic effect can be achieved, and the maximum hydrophobic angle can reach 124 degrees.
The polyester polyol of the present invention is 20 to 40 parts by weight, and may be, for example, 20 parts, 22 parts, 25 parts, 30 parts, 33 parts, 35 parts, 38 parts, 40 parts, or the like.
Preferably, the polyester polyol comprises any one of or a combination of at least two of polyethylene glycol adipate diol, polyethylene glycol propylene adipate diol, or polyethylene glycol diethylene glycol adipate diol.
The polyester polyol of the present invention has a number average molecular weight of generally 500-5000, and may be, for example, 500, 600, 700, 800, 900, 1000, 1500, 2000, 2500, 3000, 4500, or 5000, and the like.
In the present invention, the number average molecular weight of the polyvinylidene fluoride is 25 to 50 ten thousand, for example 25, 28, 30, 33, 35, 38, 40, 43, 45, 48 or 50 ten thousand.
Preferably, the chain extender comprises any one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 4-cyclohexanediol or a combination of at least two thereof.
Preferably, the catalyst comprises any one of stannous octoate, dibutyltin dioctoate or dibutyltin diacetate or a combination of at least two of them.
In another aspect, the present invention provides a method for preparing the TPU film as described above, comprising the steps of:
(1) adding toluene diisocyanate and polyester polyol into a container, and dehydrating in vacuum under the stirring condition;
(2) adding a chain extender and a catalyst into the step (1) for mixing reaction;
(3) and (3) adding hexafluorobutyl methacrylate, octadecyl acrylate and polyvinylidene fluoride into the mixture after the reaction in the step (2), stirring and mixing, and then adding into a double-screw extruder for extrusion molding to obtain the TPU film.
The preparation method provided by the invention is simple, and the TPU film prepared by the method has good hydrophobic property and very good application prospect in the aspects of self-cleaning, anti-freezing, oil-water separation and the like.
Preferably, the temperature of the vacuum dehydration in the step (1) is 60 to 70 ℃, for example, 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃ or 70 ℃ and the like can be used.
Preferably, the vacuum dehydration time in step (1) is 1-3 hours, for example, 1 hour, 2 hours or 3 hours.
Preferably, the stirring rate in step (1) is 150-200r/min, such as 150r/min, 160r/min, 170r/min, 180r/min, 190r/min or 200 r/min.
Preferably, the temperature of the mixing reaction in the step (2) is 60 to 70 ℃, and may be, for example, 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃ or 70 ℃.
Preferably, the mixing reaction in step (2) is carried out for 2 to 3 hours, and may be carried out for 2 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours, 3 hours, or the like.
Preferably, the temperature of the stirring and mixing in the step (3) is 60 to 70 ℃, and may be, for example, 60 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃ or 70 ℃.
Preferably, the stirring and mixing time is 15-20h, for example, 15h, 16h, 17h, 18h, 19h or 20h, etc.
Preferably, the temperature of the feeding section of the twin-screw extruder in step (3) is 110-.
Compared with the prior art, the invention has the following beneficial effects:
according to the TPU film provided by the invention, hexafluorobutyl methacrylate and octadecyl acrylate are matched for use, so that fluorine-containing groups are regularly arranged on a polymerization surface, a stable film is formed after reaction, and a formed coating has low surface and free energy; furthermore, by mixing polyvinylidene fluoride with good insulating property, water drops can roll off on the surface of the membrane more easily, and the hydrophobic angle of the membrane is improved by matching with fluorine-containing groups, can reach 121-124 degrees, has good hydrophobic property, and is beneficial to the application in the aspects of self-cleaning, anti-freezing, oil-water separation 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
The preparation raw materials of the TPU film provided in this example include the following components in parts by weight:
the preparation method comprises the following steps:
(1) adding toluene diisocyanate and poly diethylene glycol adipate diol into a container, and dehydrating for 2 hours in vacuum at 65 ℃ under the stirring condition of 160 r/min;
(2) adding 1, 2-propylene glycol and dibutyltin dioctoate into the step (1), mixing and reacting for 18h at 65 ℃;
(3) adding hexafluorobutyl methacrylate, octadecyl acrylate and polyvinylidene fluoride into the mixture after the reaction in the step (2), stirring and mixing for 18h at 68 ℃, and then adding the mixture into a double-screw extruder to be extruded and molded to obtain the TPU film, wherein the temperature of a feeding section of the double-screw extruder is 115 ℃, the temperature of a mixing section is 150 ℃, the temperature of an extrusion section is 170 ℃, and the temperature of a machine head is 155 ℃.
Example 2
The preparation raw materials of the TPU film provided in this example include the following components in parts by weight:
the preparation method comprises the following steps:
(1) adding toluene diisocyanate and polyethylene glycol diethylene glycol adipate diol into a container, and dehydrating for 2 hours in vacuum at 65 ℃ under the stirring condition of 160 r/min;
(2) adding 1, 2-propylene glycol and stannous octoate into the step (1), mixing and reacting for 18h at 65 ℃;
(3) adding hexafluorobutyl methacrylate, octadecyl acrylate and polyvinylidene fluoride into the mixture after the reaction in the step (2), stirring and mixing for 18h at 68 ℃, and then adding the mixture into a double-screw extruder to be extruded and molded to obtain the TPU film, wherein the temperature of a feeding section of the double-screw extruder is 115 ℃, the temperature of a mixing section is 150 ℃, the temperature of an extrusion section is 170 ℃, and the temperature of a machine head is 155 ℃.
Example 3
The preparation raw materials of the TPU film provided in this example include the following components in parts by weight:
the preparation method comprises the following steps:
(1) toluene diisocyanate and poly (ethylene glycol adipate) propylene glycol are added into a container, and vacuum dehydration is carried out for 2 hours at 65 ℃ under the stirring condition of 160 r/min;
(2) adding ethylene glycol and dibutyltin diacetate into the step (1), mixing and reacting for 18h at 65 ℃;
(3) adding hexafluorobutyl methacrylate, octadecyl acrylate and polyvinylidene fluoride into the mixture after the reaction in the step (2), stirring and mixing for 18h at 68 ℃, and then adding the mixture into a double-screw extruder to be extruded and molded to obtain the TPU film, wherein the temperature of a feeding section of the double-screw extruder is 115 ℃, the temperature of a mixing section is 150 ℃, the temperature of an extrusion section is 170 ℃, and the temperature of a machine head is 155 ℃.
Example 4
The preparation raw materials of the TPU film provided in this example include the following components in parts by weight:
the preparation method comprises the following steps:
(1) adding toluene diisocyanate and poly diethylene glycol adipate diol into a container, and dehydrating for 2 hours in vacuum at 65 ℃ under the stirring condition of 160 r/min;
(2) adding 1, 4-cyclohexanediol and dibutyltin diacetate into the step (1), mixing and reacting for 18h at 65 ℃;
(3) adding hexafluorobutyl methacrylate, octadecyl acrylate and polyvinylidene fluoride into the mixture after the reaction in the step (2), stirring and mixing for 18h at 68 ℃, and then adding the mixture into a double-screw extruder to be extruded and molded to obtain the TPU film, wherein the temperature of a feeding section of the double-screw extruder is 115 ℃, the temperature of a mixing section is 150 ℃, the temperature of an extrusion section is 170 ℃, and the temperature of a machine head is 155 ℃.
Example 5
The preparation raw materials of the TPU film provided in this example include the following components in parts by weight:
the preparation method comprises the following steps:
(1) adding toluene diisocyanate and poly diethylene glycol adipate diol into a container, and dehydrating for 2 hours in vacuum at 65 ℃ under the stirring condition of 160 r/min;
(2) adding 1, 4-butanediol and dibutyltin diacetate into the step (1), mixing and reacting for 18h at 65 ℃;
(3) adding hexafluorobutyl methacrylate, octadecyl acrylate and polyvinylidene fluoride into the mixture after the reaction in the step (2), stirring and mixing for 18h at 68 ℃, and then adding the mixture into a double-screw extruder to be extruded and molded to obtain the TPU film, wherein the temperature of a feeding section of the double-screw extruder is 115 ℃, the temperature of a mixing section is 150 ℃, the temperature of an extrusion section is 170 ℃, and the temperature of a machine head is 155 ℃.
Comparative example 1
This comparative example differs from example 1 in that, in this comparative example, hexafluorobutyl methacrylate was not included, the weight part of octadecyl acrylate was 4 parts, and the weight part of polyvinylidene fluoride was 8 parts, and a TPU film was prepared.
Comparative example 2
This comparative example differs from example 1 in that the TPU film was prepared without including octadecyl acrylate, 5 parts by weight of hexafluorobutyl methacrylate, and 7 parts by weight of polyvinylidene fluoride.
Comparative example 3
This comparative example differs from example 1 in that, except for polyvinylidene fluoride, 7 parts by weight of hexafluorobutyl methacrylate and 5 parts by weight of stearyl acrylate, a TPU film was prepared.
Comparative example 4
This comparative example differs from example 1 in that the TPU film was prepared with 12 parts by weight of polyvinylidene fluoride, excluding hexafluorobutyl methacrylate and octadecyl acrylate.
The TPU films provided in examples 1-5 and comparative examples 1-4 above were tested for their hydrophobic angle using a contact angle tester, model VCA Optima/VCA 3000S, and the results are shown in Table 1 below:
TABLE 1
Sample (I) | Angle (°) |
Example 1 | 124 |
Example 2 | 122 |
Example 3 | 121 |
Example 4 | 118 |
Example 5 | 116 |
Comparative example 1 | 97 |
Comparative example 2 | 103 |
Comparative example 3 | 107 |
Comparative example 4 | 90 |
As can be seen from the data in Table 1, the TPU film provided by the invention has a high hydrophobic angle which reaches 116-124 degrees, and the hydrophobic angle can reach 121-124 degrees under a state with a good proportioning range.
In contrast, in comparative examples 1 to 4, when either one or both of hexafluorobutyl methacrylate, stearyl acrylate, and polyvinylidene fluoride were absent, the hydrophobic angle was greatly decreased, only about 100 °, and the performance was poor, which was not favorable for application.
The applicant states that the invention is illustrated by the above examples of the highly hydrophobic TPU film of the invention and the process for its preparation, but the invention is not limited to the above detailed process, i.e. it is not meant that the invention must rely on the above detailed process to be practiced. 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 (10)
2. the TPU film of claim 1, wherein the mass ratio of hexafluorobutyl methacrylate, stearyl acrylate and polyvinylidene fluoride is (2-3):1 (3-6).
3. The TPU film of claim 1 or 2 wherein the polyester polyol comprises any one or a combination of at least two of a polyethylene glycol adipate diol, a polyethylene glycol propylene adipate diol, or a polyethylene glycol adipate diol;
preferably, the number average molecular weight of the polyester polyol is 500-;
preferably, the polyvinylidene fluoride has a number average molecular weight of 25 to 50 ten thousand.
4. The TPU film of any of claims 1 to 3, wherein the chain extender comprises any one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 4-cyclohexanediol, or a combination of at least two thereof.
5. The TPU film of any of claims 1 to 4, wherein the catalyst comprises any one of stannous octoate, dibutyltin dioctoate or dibutyltin diacetate, or a combination of at least two thereof.
6. The method of making the TPU film of any of claims 1-5, comprising the steps of:
(1) adding toluene diisocyanate and polyester polyol into a container, and dehydrating in vacuum under the stirring condition;
(2) adding a chain extender and a catalyst into the step (1) for mixing reaction;
(3) and (3) adding hexafluorobutyl methacrylate, octadecyl acrylate and polyvinylidene fluoride into the mixture after the reaction in the step (2), stirring and mixing, and then adding into a double-screw extruder for extrusion molding to obtain the TPU film.
7. The method according to claim 6, wherein the temperature of the vacuum dehydration in the step (1) is 60 to 70 ℃;
preferably, the vacuum dehydration time in step (1) is 1-3 hours;
preferably, the stirring rate in step (1) is 150-.
8. The production method according to claim 6 or 7, wherein the temperature of the mixing reaction in the step (2) is 60 to 70 ℃;
preferably, the time for the mixing reaction in step (2) is 2 to 3 hours.
9. The production method according to any one of claims 6 to 8, wherein the temperature of the agitation and mixing in the step (3) is 60 to 70 ℃;
preferably, the stirring and mixing time is 15-20 h.
10. The method as claimed in any one of claims 6 to 9, wherein the temperature of the feeding section of the twin-screw extruder in step (3) is 110-.
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US20130337161A1 (en) * | 2011-02-21 | 2013-12-19 | Asahi Kasei Chemicals Corporation | Coating Material Containing Organic/Inorganic Composite, Organic/Inorganic Composite Film and Antireflection Member |
CN105189103A (en) * | 2012-10-18 | 2015-12-23 | 泰拉屏障膜公司 | Encapsulation barrier stack |
CN107429113A (en) * | 2015-03-31 | 2017-12-01 | 捷恩智株式会社 | Smears, epithelium, layered product, surface protection article |
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Publication number | Priority date | Publication date | Assignee | Title |
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US20130337161A1 (en) * | 2011-02-21 | 2013-12-19 | Asahi Kasei Chemicals Corporation | Coating Material Containing Organic/Inorganic Composite, Organic/Inorganic Composite Film and Antireflection Member |
CN105189103A (en) * | 2012-10-18 | 2015-12-23 | 泰拉屏障膜公司 | Encapsulation barrier stack |
CN107429113A (en) * | 2015-03-31 | 2017-12-01 | 捷恩智株式会社 | Smears, epithelium, layered product, surface protection article |
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