CN113337101B - High-barrier-property TPU (thermoplastic polyurethane) film for electronics and preparation method thereof - Google Patents

High-barrier-property TPU (thermoplastic polyurethane) film for electronics and preparation method thereof Download PDF

Info

Publication number
CN113337101B
CN113337101B CN202110557158.9A CN202110557158A CN113337101B CN 113337101 B CN113337101 B CN 113337101B CN 202110557158 A CN202110557158 A CN 202110557158A CN 113337101 B CN113337101 B CN 113337101B
Authority
CN
China
Prior art keywords
electronics
parts
tpu film
barrier
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110557158.9A
Other languages
Chinese (zh)
Other versions
CN113337101A (en
Inventor
何建雄
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongguan Xionglin New Materials Technology Co Ltd
Original Assignee
Dongguan Xionglin New Materials Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dongguan Xionglin New Materials Technology Co Ltd filed Critical Dongguan Xionglin New Materials Technology Co Ltd
Priority to CN202110557158.9A priority Critical patent/CN113337101B/en
Publication of CN113337101A publication Critical patent/CN113337101A/en
Application granted granted Critical
Publication of CN113337101B publication Critical patent/CN113337101B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04Polysiloxanes
    • C08J2483/07Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • C08K3/042Graphene or derivatives, e.g. graphene oxides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/05Alcohols; Metal alcoholates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/10Encapsulated ingredients

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a high-barrier TPU film for electronics and a preparation method thereof, wherein the high-barrier TPU film for electronics comprises the following components in parts by weight: 40-60 parts of hydroxyl-terminated TPU, 5-15 parts of ionol, 1-10 parts of graphene-hydrotalcite compound, 0.1-3 parts of cross-linking agent, 3-10 parts of vinyl polysiloxane and 1-8 parts of isocyanate curing agent. The TPU film provided by the invention has excellent water vapor and oxygen barrier properties, and also has the advantage of low dielectric loss, and can be applied to film capacitors or circuit boards.

Description

High-barrier-property TPU (thermoplastic polyurethane) film for electronics and preparation method thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a high-barrier TPU film for electronics and a preparation method thereof.
Background
With the advent of the information-oriented industry era, numerous countries around the world begin to develop the electronic information industry, and related electronic device products are more and more, and the presence of water vapor and oxygen can affect electronic products and reduce the use performance, so that the high-barrier packaging material is an indispensable product in the field. For the electronic industry, the water vapor transmission rate and the oxygen transmission rate of the barrier material are respectively lower than 10- 1 g/(m 2 X d) and 1cm 3 /(m 2 ×d)。
At present, a lot of researches on high-barrier materials exist, CN107903803A discloses a high-moisture-barrier polyurethane coating for a refrigerator and a preparation method thereof, the coating consists of two components A and B, the weight mixing ratio of the two components A and B is 1: isocyanates and polyether polyols. The formula of the component B comprises: fluorine-containing acrylic resin, polyether polyol, a chain extender, a catalyst, a pigment, a filler, a dispersing agent, a defoaming agent and an anti-settling agent. The polyurethane coating prepared by the invention can be used in the moisture-proof and steam-proof field of a polyurethane external thermal insulation system, and the water vapor transmission rate is 7.5 multiplied by 10 when the thickness of the coating reaches more than 1mm through tests -9 g/m 2 S.Pa. CN104015328A discloses a processing technology of a polyolefin high barrier film, the polyolefin high barrier film is processed by adopting a three-layer coextrusion casting technology, the polyolefin high barrier film comprises two surface layers and an intermediate layer, the intermediate layer comprises 7-8.5 parts of polyolefin and 1.5-3 parts of nano inorganic clay according to the mass part, the intermediate layer material is heated and extruded at 230-260 ℃ for multilayer superposition and then is pasted with the surface layersThe surface layer comprises 9 parts of polyolefin and 1 part of active organic silicon in parts by mass, the surface layer material is heated and extruded at 230-260 ℃ to be attached to the middle layer, and the thickness ratio of the middle layer to the surface layer is 4. The continuous multilayer inorganic nano barrier layer is formed under the conditions of heating, extruding and mixing the polyolefin and the nano inorganic clay, so that the barrier property of the polyolefin film is improved, the viscosity of the surface layer is changed by adding active organic silicon on the surface layer, the viscosity of the surface of the polyolefin film is reduced, and the polyolefin film is convenient to unwind. At present, the films have certain barrier property to water vapor and oxygen, but the barrier property still needs to be further improved, and for barrier materials in the electronic field, the films also need to have the characteristic of low dielectric loss.
Therefore, it is necessary to develop a thin film having high barrier properties against water vapor and oxygen and low dielectric loss.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a high-barrier TPU film for electrons and a preparation method thereof, wherein ionol is introduced into the TPU film, and the molecular structure contains double bonds and hydroxyl groups, so that the film can simultaneously react with an isocyanate curing agent, a cross-linking agent and vinyl polysiloxane in a system to form an interpenetrating network structure; after the ionol, the vinyl polysiloxane and the cross-linking agent react, the reaction product can be coated on the surface of the graphene-hydrotalcite, so that the agglomeration of a graphene-hydrotalcite compound is avoided, and the dispersion is uniform; meanwhile, the silicon-containing substance is combined with the graphene-hydrotalcite composite, so that the dielectric loss can be reduced, and the finally prepared TPU film can realize the effects of high barrier property and low dielectric loss.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a high-barrier TPU film for electronics, which is prepared from the following raw materials in parts by weight:
Figure BDA0003077703900000021
Figure BDA0003077703900000031
in the invention, the molecular structure of the ionol contains double bonds and hydroxyl, and can react with an isocyanate curing agent, a cross-linking agent and vinyl polysiloxane simultaneously to form an interpenetrating network structure. After the reaction between the ionol and the vinyl polysiloxane, the ionol can be coated on the surface of the graphene-hydrotalcite, so that the dispersibility is improved; meanwhile, the vinyl siloxane, the silicon-containing substance and the graphene-hydrotalcite compound are combined, so that the dielectric loss can be reduced, and the TPU film has the characteristic of low dielectric loss.
In the present invention, the hydroxyl-terminated TPU may be present in 42, 45, 48, 50, 52, 55, 58 or 59 parts by weight, and specific values therebetween are not exhaustive for the invention and are included in the recited range for reasons of brevity and clarity.
The parts by weight of ionol may be 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 12 parts, 13 parts or 14 parts, and specific values therebetween are not exhaustive of the invention for purposes of brevity and clarity.
The graphene-hydrotalcite composite may be present in 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, or 9 parts by weight, and specific values therebetween, which are included in the range not exhaustive for the invention, for reasons of brevity and clarity.
The crosslinking agent may be present in an amount of 0.5 parts, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, or 2.5 parts by weight, and specific values therebetween, not to be construed as limiting the disclosure and for the sake of brevity, and the invention is not intended to be exhaustive of the specific values included in the recited ranges.
The vinyl siloxane may be present in 4, 5, 6, 7, 8 or 9 parts by weight, and specific values therebetween, for reasons of space and clarity, and the invention is not intended to be exhaustive of the specific values included in the ranges.
The isocyanate-based curing agent may be present in 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 6 parts or 7 parts by weight, and specific values therebetween are not intended to be exhaustive, and for the sake of brevity, the invention is not intended to be limited to the specific values included in the ranges disclosed.
In the present invention, the hydroxyl-terminated TPU has a hydroxyl value of 30 to 110mg KOH/g, for example, 40mg KOH/g, 50mg KOH/g, 60mg KOH/g, 70mg KOH/g, 80mg KOH/g, 90mg KOH/g or 100mg KOH/g, and the specific values therebetween are not exhaustive, and for the sake of brevity and brevity, the present invention is not intended to be exhaustive.
Preferably, the hydroxyl-terminated TPU has a number average molecular weight of 800 to 5000g/mol, which may be, for example, 1000g/mol, 1500g/mol, 2000g/mol, 2500g/mol, 3000g/mol, 3500g/mol, 4000g/mol or 4500g/mol, and the particular values therebetween are not exhaustive and, for reasons of brevity, the invention is not intended to be limited to the particular values encompassed by the stated ranges.
In the present invention, the graphene-hydrotalcite composite is prepared by a method comprising: mixing and dispersing graphene oxide, hydrotalcite and a solvent to obtain a dispersion liquid; and carrying out reduction reaction on the dispersion liquid and ascorbic acid to obtain the graphene-hydrotalcite composite.
In the preparation process of the graphene-hydrotalcite composite, graphene is generated on hydrotalcite in situ, which is beneficial to improving the barrier property of the TPU film; the graphene oxide can generate hydroxyl and carboxyl after being reduced by ascorbic acid, and is beneficial to dispersion.
Preferably, the mass ratio of the graphene oxide to the hydrotalcite is (1 to 3) and may be, for example, 1.2.
Preferably, the solvent is water.
Preferably, the method of dispersion is ultrasonic dispersion.
Preferably, the mass ratio of the ascorbic acid to the graphene oxide is (2-10): 1, and for example, the ratio can be 3.
Preferably, the time of the reduction reaction is 4 to 24 hours, for example, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 23h, and specific values therebetween are limited for space and simplicity, and the invention is not exhaustive.
Preferably, the reduction reaction also comprises a drying step after the reduction reaction is completed.
Preferably, the method of drying is spray drying.
In the present invention, the crosslinking agent is an organic peroxide.
Preferably, the organic peroxide comprises any one of benzoyl peroxide, dicumyl peroxide, cyclohexanone peroxide or methyl isobutyl ketone peroxide or a combination of at least two thereof.
In the present invention, the viscosity of the vinyl polysiloxane is 500 to 10000 mPas, for example, 1000 mPas, 2000 mPas, 3000 mPas, 4000 mPas, 5000 mPas, 6000 mPas, 7000 mPas, 8000 mPas or 9000 mPas, and the specific values therebetween are not exhaustive, but the invention is not limited to the space and for the sake of brevity.
In the invention, the isocyanate curing agent comprises any one or combination of at least two of TDI trihydroxy adduct, TDI trimer, HDI biuret and HDI trimer.
In a second aspect, the present invention provides a method for preparing a high barrier TPU film for electronics, as described in the first aspect, comprising the steps of:
(1) Mixing and dispersing the graphene-hydrotalcite compound and ionol, mixing the graphene-hydrotalcite compound and vinyl polysiloxane, and uniformly dispersing to obtain a material A; mixing hydroxyl-terminated TPU with a solvent to obtain a material B;
(2) Uniformly mixing the material A and the material B obtained in the step (1), and adding a cross-linking agent and an isocyanate curing agent into the mixture to obtain slurry;
(3) And (3) casting the slurry obtained in the step (2) into a film to obtain the high-barrier TPU film for the electronics.
Preferably, the solvent in step (1) comprises any one of N, N-dimethylformamide, dimethyl sulfoxide or N, N-dimethylacetamide, or a combination of at least two thereof.
Preferably, the amount of the solvent used in step (1) is 2 to 10mL, for example, 3mL, 4mL, 5mL, 6mL, 7mL, 8mL or 9mL, based on 1g of the weight of the hydroxyl terminated TPU, and the specific values therebetween are not exhaustive, and are not included in the scope of the invention for reasons of space and brevity.
Preferably, the temperature for the cast film formation in the step (3) is 25 to 80 ℃, for example, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 60 ℃, 65 ℃, 70 ℃ or 75 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the time for casting the film in step (3) is 2-10 h, for example, 3h, 4h, 5h, 6h, 7h, 8h or 9h, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
In a third aspect, the present invention provides a use of the high barrier TPU film for electronics as described in the first aspect in a film capacitor or a circuit board.
Compared with the prior art, the invention has the following beneficial effects:
the invention introduces ionol into the TPU film to form an interpenetrating network structure; after reacting with vinyl polysiloxane, the ionol is coated on the surface of the graphene-hydrotalcite so as to be uniformly dispersed; meanwhile, the silicon-containing substance is combined with the graphene-hydrotalcite compound, so that the dielectric loss can be reduced, and the water vapor transmittance of the finally prepared TPU film is (0.23-0.71) multiplied by 10 -6 g/(m 2 X d) and oxygen transmission rate of (0.11 to 0.55) x 10 -6 cm 3 /(m 2 X d) simultaneouslyThe low dielectric loss is 0.0042 to 0.0089.
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.
The materials used in the following examples and comparative examples of the present invention include:
hydroxyl terminated TPU: purchased from Shanghai Plastic materials, inc., dongguan, JZ-PU640;
vinyl polysiloxane: the viscosity is 5000mPa & s, purchased from Guangdong Shenzhen Jipeng, model 203;
isocyanate curing agent: bayer N75.
Preparation example 1
A graphene-hydrotalcite composite is prepared by the following steps:
mixing graphene oxide and hydrotalcite according to the mass ratio of 2; and carrying out reduction reaction on the dispersion liquid and ascorbic acid for 24 hours, and then carrying out spray drying to obtain the graphene-hydrotalcite composite. The mass ratio of the ascorbic acid to the graphene oxide is 6.
Preparation example 2
A graphene-hydrotalcite composite is prepared by the following steps:
mixing graphene oxide and hydrotalcite according to the mass ratio of 1; and carrying out reduction reaction on the dispersion liquid and ascorbic acid for 24 hours, and then carrying out spray drying to obtain the graphene-hydrotalcite composite. The mass ratio of the ascorbic acid to the graphene oxide is 6.
Preparation example 3
A graphene-hydrotalcite composite is prepared by the following steps:
mixing graphene oxide and hydrotalcite with water according to the mass ratio of 5; and carrying out reduction reaction on the dispersion liquid and ascorbic acid for 24 hours, and then carrying out spray drying to obtain the graphene-hydrotalcite composite. The mass ratio of the ascorbic acid to the graphene oxide is 6.
Example 1
The embodiment provides a high-barrier TPU film for electronics, which is prepared from the following raw materials in parts by weight: 50 parts of hydroxyl-terminated TPU, 10 parts of ionol, 5 parts of graphene-hydrotalcite composite (preparation example 1), 1.5 parts of benzoyl peroxide, 6 parts of vinyl polysiloxane, 4 parts of N75 curing agent and 300ml of N, N-dimethylformamide.
The preparation method of the high-barrier TPU film for electronics specifically comprises the following steps:
(1) Mixing and dispersing the graphene-hydrotalcite compound and ionol, mixing the graphene-hydrotalcite compound and vinyl polysiloxane, and uniformly dispersing to obtain a material A; mixing hydroxyl-terminated TPU with N, N-dimethylformamide to obtain a material B;
(2) Uniformly mixing the material A and the material B obtained in the step (1), and adding benzoyl peroxide and an N75 curing agent into the mixture to obtain slurry;
(3) And (3) casting the slurry obtained in the step (2) at 60 ℃ to form a film for 6 hours, so as to obtain the high-barrier TPU film for electronics.
Example 2
The embodiment provides a high-barrier TPU film for electronics, which is prepared from the following raw materials in parts by weight: 40 parts of hydroxyl-terminated TPU, 5 parts of ionol, 1 part of graphene-hydrotalcite composite (preparation example 1), 0.1 part of benzoyl peroxide, 3 parts of vinyl polysiloxane, 1 part of N75 curing agent and 80ml of N, N-dimethylformamide.
The preparation method of the high-barrier TPU film for electronics specifically comprises the following steps:
(1) Mixing and dispersing the graphene-hydrotalcite compound and ionol, mixing the graphene-hydrotalcite compound and vinyl polysiloxane, and uniformly dispersing to obtain a material A; mixing hydroxyl-terminated TPU with N, N-dimethylformamide to obtain a material B;
(2) Uniformly mixing the material A and the material B obtained in the step (1), and adding benzoyl peroxide and an N75 curing agent into the mixture to obtain slurry;
(3) And (3) casting the slurry obtained in the step (2) into a film for 6h at the temperature of 25 ℃ to obtain the high-barrier TPU film for the electronics.
Example 3
The embodiment provides a high-barrier TPU film for electronics, which comprises the following raw materials in parts by weight: 60 parts of hydroxyl-terminated TPU, 15 parts of ionol, 10 parts of graphene-hydrotalcite composite (preparation example 1), 3 parts of benzoyl peroxide, 10 parts of vinyl polysiloxane, 8 parts of N75 curing agent and 600ml of N, N-dimethylformamide.
The preparation method of the high-barrier TPU film for electronics specifically comprises the following steps:
(1) Mixing and dispersing the graphene-hydrotalcite compound and ionol, mixing the graphene-hydrotalcite compound and vinyl polysiloxane, and uniformly dispersing to obtain a material A; mixing hydroxyl-terminated TPU with N, N-dimethylformamide to obtain a material B;
(2) Uniformly mixing the material A and the material B obtained in the step (1), and adding benzoyl peroxide and an N75 curing agent into the mixture to obtain slurry;
(3) And (3) casting the slurry obtained in the step (2) into a film for 10 hours at the temperature of 80 ℃ to obtain the high-barrier TPU film for electronics.
Example 4
The embodiment provides a high-barrier TPU film for electronics, which is different from the TPU film in embodiment 1 only in that the graphene-hydrotalcite composite in preparation example 2 is selected, and the other raw material components, contents, and preparation processes are the same as those in embodiment 1.
Example 5
This example provides a high-barrier TPU film for electronics, which is different from example 1 only in that the graphene-hydrotalcite composite of preparation example 3 is selected, and other raw material components, contents, and preparation processes are the same as those of example 1.
Comparative example 1
This comparative example provides a TPU film which is different from example 1 only in that no ionol is contained in the components, and the other raw material components, contents, and preparation processes are the same as those of example 1.
Comparative example 2
This comparative example provides a TPU film which differs from example 1 only in that the amount of ionol in the composition is 3 parts by weight, and the other raw material components, contents and preparation process are the same as those of example 1.
Comparative example 3
This comparative example provides a TPU film which is different from example 1 only in that the weight part of ionol in the composition is 20 parts, and other raw material components, contents and preparation processes are the same as example 1.
Comparative example 4
This comparative example provides a TPU film that differs from example 1 only in that the components do not contain vinyl polysiloxane and the other raw material components, contents and preparation process are the same as example 1.
Comparative example 5
This comparative example provides a TPU film which is different from example 1 only in that the weight part of vinyl polysiloxane in the composition is 2 parts, and the other raw material components, contents and preparation process are the same as example 1.
Comparative example 6
This comparative example provides a TPU film that differs from example 1 only in that the weight part of vinyl polysiloxane in the composition is 15 parts, and the other raw material components, contents and preparation process are the same as example 1.
Comparative example 7
This comparative example provides a TPU film which is different from example 1 only in that a graphene-hydrotalcite composite is not added, 3 parts of graphene and 2 parts of hydrotalcite are added, and other raw material components, contents, and preparation processes are the same as example 1.
And (3) performance testing:
1. testing the water vapor transmission rate: the TPU films provided in examples 1 to 5 and comparative examples 1 to 7 were subjected to a water vapor transmission rate test according to the test method GB/T21529 to 2008; the test results are shown in Table 1.
2. Oxygen transmission rate test: the TPU films provided in examples 1 to 5 and comparative examples 1 to 7 were subjected to an oxygen transmission rate test according to the test method GB/T19789-2005; the test results are shown in Table 1.
3. And (3) dielectric loss test: the TPU films provided in examples 1 to 5 and comparative examples 1 to 7 were tested for dielectric loss at 100Hz frequency at room temperature; the test results are shown in Table 1.
4. And (3) testing tensile property: the TPU films provided in examples 1 to 5 and comparative examples 1 to 7 were subjected to a tensile property test using a universal testing machine (Wallace Chuanghong, RS-8005 type), at a tensile rate of 50mm/min; the test results are shown in Table 1.
TABLE 1
Figure BDA0003077703900000111
Figure BDA0003077703900000121
According to the data in table 1, the hydroxyl-terminated TPU, ionol and vinyl polysiloxane are compounded to form a cross-linked interpenetrating network structure, and the cross-linked interpenetrating network structure is compounded with the graphene-hydrotalcite (examples 1 to 5), so that the water vapor transmittance of the TPU film is (0.23 to 0.71) × 10 -6 g/(m 2 X d) and oxygen transmission rate of (0.11 to 0.55) x 10 -6 cm 3 /(m 2 Xd), and has low dielectric loss of 0.0042-0.0089, excellent mechanical properties, mechanical strength of 19-24 MPa, and elongation at break of 640-702%.
As can be seen from the data in table 1, when the ratio of graphene to hydrotalcite in the graphene-hydrotalcite is too high or too low (examples 4 and 5), the barrier property against water vapor and oxygen of the TPU film is somewhat decreased, and the dielectric loss is also somewhat increased. When the content of the ionol is too high (comparative example 3), the water vapor and oxygen barrier properties of the TPU film are also reduced, and the dielectric loss is increased; when the content of the vinyl polysiloxane is too high, the water vapor and oxygen barrier properties of the TPU film are reduced, and the dielectric loss is increased; when the graphene and the hydrotalcite are not in the form of a composition and are respectively added into the TPU film, the water vapor and oxygen barrier properties of the TPU film are greatly reduced, and the dielectric properties are also reduced.
The applicant states that the present invention is illustrated by the above examples of the high barrier TPU film for electronics, but the present invention is not limited to the above examples, i.e., it is not meant that the present invention is necessarily implemented by the above examples. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (18)

1. The high-barrier TPU film for the electronics with the dielectric loss of 0.0042-0.0089 is characterized in that the preparation raw materials of the high-barrier TPU film for the electronics comprise the following components in parts by weight:
40 to 60 parts of hydroxyl-terminated TPU;
5 to 15 parts of ionol;
1 to 10 parts of graphene-hydrotalcite compound;
0.1 to 3 portions of cross-linking agent;
3 to 10 parts of vinyl polysiloxane;
1 to 8 parts of isocyanate curing agent;
the graphene-hydrotalcite composite is prepared by a method comprising: mixing and dispersing graphene oxide, hydrotalcite and a solvent to obtain a dispersion liquid; carrying out reduction reaction on the dispersion liquid and ascorbic acid to obtain the graphene-hydrotalcite compound;
the mass ratio of the graphene oxide to the hydrotalcite is (1 to 3) to 1;
the mass ratio of the ascorbic acid to the graphene oxide is (2-10) 1.
2. The high-barrier TPU film for electronics as claimed in claim 1, wherein the hydroxyl value of the hydroxyl-terminated TPU is from 30 to 110mg KOH/g.
3. The high-barrier TPU film for electronics according to claim 1, wherein the hydroxyl-terminated TPU has a number average molecular weight of from 800 to 5000 g/mol.
4. The high barrier TPU film for electronics as claimed in claim 1 wherein the solvent is water.
5. The high barrier TPU film for electronics as claimed in claim 1 wherein the method of dispersion is ultrasonic dispersion.
6. The high-barrier TPU film for electronics according to claim 1, wherein the reduction reaction time is from 4 to 24 hours.
7. The high barrier TPU film for electronics according to claim 1 further comprising a drying step after the reduction reaction is completed.
8. The high barrier TPU film for electronics of claim 7 wherein the drying process is spray drying.
9. The high barrier TPU film for electronics of claim 1 wherein the crosslinking agent is an organic peroxide.
10. The high barrier TPU film for electronics according to claim 9, wherein the organic peroxide comprises any one or a combination of at least two of benzoyl peroxide, dicumyl peroxide, cyclohexanone peroxide, or methyl isobutyl ketone peroxide.
11. The high-barrier TPU film for electronics as claimed in claim 1, wherein the viscosity of the vinylpolysiloxane is from 500 to 10000 mPas.
12. The high barrier TPU film for electronics of claim 1 wherein the isocyanate curing agent includes any one or a combination of at least two of TDI trihydroxy adduct, TDI trimer, HDI biuret, or HDI trimer.
13. A method for preparing the high-barrier TPU film for electronics according to any one of claims 1 to 12, comprising the following steps:
(1) Mixing and dispersing the graphene-hydrotalcite compound and ionol, mixing the graphene-hydrotalcite compound and vinyl polysiloxane, and uniformly dispersing to obtain a material A; mixing the hydroxyl-terminated TPU with a solvent to obtain a material B;
(2) Uniformly mixing the material A and the material B obtained in the step (1), and adding a cross-linking agent and an isocyanate curing agent into the mixture to obtain slurry;
(3) And (3) casting the slurry obtained in the step (2) into a film to obtain the high-barrier TPU film for electronics.
14. The method of claim 13, wherein the solvent of step (1) comprisesN,N-dimethylformamide, dimethyl sulfoxide orN,N-dimethylacetamide either alone or in combination of at least two.
15. The preparation method according to claim 13, wherein the solvent used in step (1) is 2 to 10mL, based on 1g of the hydroxyl terminated TPU.
16. The production method according to claim 13, wherein the temperature for casting the film in the step (3) is 25 to 80 ℃.
17. The method according to claim 13, wherein the casting time in step (3) is 2 to 10 hours.
18. Use of the high-barrier TPU film for electronics according to any one of claims 1 to 12 in film capacitors or circuit boards.
CN202110557158.9A 2021-05-21 2021-05-21 High-barrier-property TPU (thermoplastic polyurethane) film for electronics and preparation method thereof Active CN113337101B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110557158.9A CN113337101B (en) 2021-05-21 2021-05-21 High-barrier-property TPU (thermoplastic polyurethane) film for electronics and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110557158.9A CN113337101B (en) 2021-05-21 2021-05-21 High-barrier-property TPU (thermoplastic polyurethane) film for electronics and preparation method thereof

Publications (2)

Publication Number Publication Date
CN113337101A CN113337101A (en) 2021-09-03
CN113337101B true CN113337101B (en) 2023-01-10

Family

ID=77470574

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110557158.9A Active CN113337101B (en) 2021-05-21 2021-05-21 High-barrier-property TPU (thermoplastic polyurethane) film for electronics and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113337101B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116606541B (en) * 2023-05-15 2024-10-18 美瑞新材料股份有限公司 High-strength dirt-resistant TPU material and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110062797A (en) * 2016-11-28 2019-07-26 3M创新有限公司 Adhesive composition and the binder film obtained from it
CN106995643B (en) * 2017-05-23 2019-05-21 上海工程技术大学 A kind of water paint and preparation method thereof of containing graphene/zinc-aluminum gavite nano-complex
CN112175219B (en) * 2020-09-03 2023-02-03 苏州市雄林新材料科技有限公司 Low-permeability TPU (thermoplastic polyurethane) film for automobile headrest and preparation method thereof

Also Published As

Publication number Publication date
CN113337101A (en) 2021-09-03

Similar Documents

Publication Publication Date Title
CN1951968A (en) Fluorin-silicon modified core-shell structure polyurethane-acrylate emulsion preparation method
CN110951385B (en) Epoxy resin modified polyurethane waterproof coating and preparation method thereof
US11485857B2 (en) Amino silicone oil-modified elastomer material and preparation method thereof
CN113337101B (en) High-barrier-property TPU (thermoplastic polyurethane) film for electronics and preparation method thereof
CN114940885B (en) Heat-conducting bi-component polyurethane adhesive and preparation method and application thereof
CN111087651B (en) High-conductivity waterborne polyurethane/modified graphene composite emulsion and preparation method thereof
CN116438075A (en) Tetrafluoroethylene polymer composition, laminate and film
WO2022145333A1 (en) Aqueous dispersion and method for producing same
CN115516008A (en) Method for producing dispersion, paste, and kneaded powder
WO2022050253A1 (en) Powder dispersion and production method for composite
Chen et al. Synthesis and properties of novel UV–curable hyperbranched waterborne polyurethane/Fe 3 O 4 nanocomposite films with excellent magnetic properties
CN109486465B (en) Bi-component polyurethane adhesive and preparation method thereof
WO2022254960A1 (en) Low dielectric loss resin composition, method for producing same, molded body for high frequency devices, and high frequency device
KR20230129373A (en) Method for producing tetrafluoroethylene-based polymer composition, composition, metal-clad laminate, and stretched sheet
CN110358048B (en) Preparation method of waterborne polyurethane emulsion for temperature-resistant transfer coating
Yang et al. High microwave dielectric constant and improved thermal stability of functionalized Zn0. 15Nb0. 3Ti0. 55O2-filled polyolefin composites
CN111511792B (en) Thermally conductive polyurethane adhesive with excellent combination of mechanical properties
CN116410617A (en) Surface modified glass bead composite filler and preparation method and application thereof
CN114045146A (en) High-thermal-conductivity waterborne polyurethane composite material and preparation method thereof
CN115160826A (en) Functional nano ZnO and preparation method and application thereof
CN116348534A (en) Composition comprising tetrafluoroethylene polymer powder particles, process for producing the same, and process for producing dispersion from the composition
CN113999411A (en) Water-based polyurethane acrylate/silicon dioxide aerogel composite membrane and preparation method and application thereof
Liu et al. Preparation and Performance of Graphene Oxide Modified Polyurethane Thermal Conductive Insulating Adhesive
CN111944452B (en) Preparation method of functional graphene modified waterborne polyurethane single-component conductive adhesive
JP2022061412A (en) Production method of liquid composition and production method of laminate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant