CN117601541A - Colorful multilayer electroplating TPU film and preparation method and application thereof - Google Patents

Colorful multilayer electroplating TPU film and preparation method and application thereof Download PDF

Info

Publication number
CN117601541A
CN117601541A CN202311667544.9A CN202311667544A CN117601541A CN 117601541 A CN117601541 A CN 117601541A CN 202311667544 A CN202311667544 A CN 202311667544A CN 117601541 A CN117601541 A CN 117601541A
Authority
CN
China
Prior art keywords
tpu film
mixture
tpu
mixing
stirring
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.)
Pending
Application number
CN202311667544.9A
Other languages
Chinese (zh)
Inventor
陈芳荣
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 Quanfeng New Material Technology Co ltd
Original Assignee
Dongguan Quanfeng New Material 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 Quanfeng New Material Technology Co ltd filed Critical Dongguan Quanfeng New Material Technology Co ltd
Priority to CN202311667544.9A priority Critical patent/CN117601541A/en
Publication of CN117601541A publication Critical patent/CN117601541A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1207—Heat-activated adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1207—Heat-activated adhesive
    • B32B2037/1215—Hot-melt adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/404—Multi-coloured
    • 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
    • C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
    • C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • 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
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • 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
    • C08K3/041—Carbon nanotubes
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Abstract

The invention relates to a colorful multilayer electroplating TPU film, a preparation method and application thereof, and belongs to the technical field of TPU film materials. The invention relates to a colorful multilayer electroplating TPU film, which comprises a protective film, a toner layer, a polyurethane layer, a first hot melt adhesive layer, an electroplating metal layer, a second hot melt adhesive layer and a TPU film which are sequentially overlapped from top to bottom. In addition, the modified carbon nano tube and the waste ABS are subjected to melt mixing, and sorbic acid, calcium carbonate and a vulcanizing agent are added, so that the crosslinking density of the TPU film material is further increased. The synergistic effect of the modified components also obviously improves the compatibility of the waste ABS mixture and other components in the TPU system, thereby obviously improving the mechanical properties of the TPU film material. Meanwhile, the invention successfully realizes the effective recycling of the waste ABS material.

Description

Colorful multilayer electroplating TPU film and preparation method and application thereof
Technical Field
The invention belongs to the technical field of TPU film materials, and relates to a colorful multilayer electroplating TPU film, a preparation method and application thereof.
Background
ABS plastic is engineering plastic widely applied to the fields of electric and electronic product parts, automobile parts and the like. However, when these articles are scrapped, a large amount of waste ABS plastic is produced. Since ABS plastic is a thermoplastic, it is recyclable. However, the waste ABS plastic can be aged during service, so that the butadiene part of the rubber phase is oxidized in the light and heat environment, and the impact performance of the material is greatly reduced. Therefore, the direct recycling of waste ABS plastic is limited to a small extent.
The carbon nanotubes have excellent mechanical, thermal and electrical properties, and thus are widely used in the fields of nano devices, nano material templates, electronic materials and devices, composite material reinforcing agents, energy storage and conversion applications, catalytic and adsorption materials, biological and sensing materials, and the like. By compounding with the ABS plastic, the carbon nano tube can fully exert excellent mechanical, electrical and thermal properties, and simultaneously remarkably improve the mechanical property and the electric heat transmission property of the ABS plastic.
However, carbon nanotubes have a strong surface effect, and thus are extremely susceptible to agglomeration and entanglement, which may lead to a decrease in mechanical properties of the rubber material. In addition, the interaction between the ordinary carbon nanotubes and the polymer matrix is not strong, so that the carbon nanotubes may not be able to bear the load and be extracted from the matrix when the external force is applied.
Disclosure of Invention
The invention aims to provide a colorful multilayer electroplating TPU film, a preparation method and application thereof. In addition, the modified carbon nano tube and the waste ABS are subjected to melt mixing, and sorbic acid, calcium carbonate and a vulcanizing agent are added, so that the crosslinking density of the TPU film material is further increased. The synergistic effect of the modified components also obviously improves the compatibility of the waste ABS mixture and other components in the TPU system, thereby obviously improving the mechanical properties of the TPU film material. Meanwhile, the invention successfully realizes the effective recycling of the waste ABS material.
The aim of the invention can be achieved by the following technical scheme:
the utility model provides a colored multilayer electroplates TPU membrane, includes along from top to bottom superimposed protection film, toner layer, polyurethane layer, first hot melt adhesive layer, electroplate metal layer, second hot melt adhesive layer and TPU membrane in proper order, the preparation method of TPU membrane includes the following steps:
1) Placing waste ABS in an extruder for melting and mixing, adding modified carbon nano tubes for heating and melting blending, extruding and granulating, and drying to obtain a mixture A;
2) Stirring and mixing TPU, polyethylene, a dispersing agent, calcium carbonate, sorbic acid, a coupling agent and an antioxidant to obtain a mixture B;
3) And (3) carrying out melt blending, cooling, granulating and tape casting on the mixture A, the mixture B and the vulcanizing agent to obtain the TPU film.
As a preferable technical scheme of the invention, in the step 1), the mass ratio of the waste ABS to the modified carbon nano tube is 8-10:1, a step of; the conditions of melting and mixing are that mixing is carried out for 48-50 hours at the temperature of 135-150 ℃; the condition of heating, melting and blending is that the temperature is raised to 235-240 ℃ at a heating speed of 5-10 ℃/min, and then the melting and blending are carried out.
As a preferred technical scheme of the invention, in the step 2), the mass ratio of the TPU, the polyethylene, the dispersing agent, the calcium carbonate, the sorbic acid, the coupling agent and the antioxidant is 40-50:5-6:1-2:1.5-1.8:0.4-0.8:0.5-0.8:0.1-0.2.
As a preferable technical scheme of the invention, in the step 2), the dispersing agent is one or two of zinc stearate and magnesium stearate; the coupling agent is silane coupling agent KH-570; the antioxidant is one or more of 2,2 '-methylenebis- (4-methyl-6-tertiary butyl phenol), 1,3, 5-tris (3, 5-di-tertiary butyl-4-hydroxybenzyl) isocyanuric acid, N' -bis- (3, 5-di-tertiary butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine and pentaerythritol tetrakis [3- (3, 5-di-tertiary butyl-4-hydroxyphenyl) propionate ].
As a preferred embodiment of the present invention, in step 3), the vulcanizing agent is composed of DCP and triallyl isocyanurate in a mass ratio of 5:1, mixing; the mass ratio of the mixture A to the mixture B to the vulcanizing agent is 30-40:10:0.40-0.45; the condition of melt blending is that the melt blending is carried out in an extruder with the processing temperature of 210-220 ℃ and the injection pressure of 20-25 MPa.
As a preferred technical scheme of the invention, the preparation method of the modified carbon nano tube comprises the following steps:
s1, stirring and mixing a carbon nano tube and methacrylic acid to obtain a mixture;
s2, adding zinc oxide into the mixture, stirring uniformly, slowly dropwise adding methacrylic acid, stirring and mixing, and performing ionization reaction to obtain the modified carbon nanotube.
As a preferable technical scheme of the invention, in the step S1, the stirring and mixing conditions are that stirring is carried out for 5-10min at the temperature of 50-60 ℃ and the rotating speed of 1800-2000 r/min; the mass ratio of the carbon nano tube to the methacrylic acid is 10:0.9.
as a preferable technical scheme of the invention, in the step S2, the condition of uniform stirring is that stirring is carried out for 5-10min at the rotating speed of 2000-2500 r/min; the ionization reaction time is 30-45min; the mass ratio of the mixture to the zinc oxide to the methacrylic acid is 5:1.1-1.4:0.4.
a preparation method of a colorful multi-layer electroplating TPU film comprises the steps of sequentially laminating a protective film, a toner layer, a polyurethane layer, a first hot melt adhesive layer, an electroplated metal layer, a second hot melt adhesive layer and the TPU film from top to bottom to prepare the colorful multi-layer electroplating TPU film; the lamination includes, but is not limited to, using an adhesive, coating, electroplating, and the like.
As a preferred technical scheme of the invention, the colored multilayer electroplated TPU film is applied to cloth products and leather products.
As a preferable technical scheme of the invention, methacrylic acid is adopted to acidify and modify the carbon nano tube, then zinc oxide is added to carry out ionization reaction, and zinc methacrylate is generated on the surface of the carbon nano tube in situ, so that the modified carbon nano tube is prepared.
As a preferred embodiment of the present invention, the sources of materials for all examples and comparative examples in the present invention are as follows: the length-diameter ratio of the carbon nano tube is 800-1000, and the carbon nano tube is a multi-wall carbon nano tube and is purchased from Hebei Changchu energy-saving science and technology Co; pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] as antioxidant 1010 is purchased from Henan Tian Yi chemical products Co., ltd; vulcanizing agent: dicumyl peroxide and triallyl isocyanurate are all purchased from Qingdao Keno chemical Co., ltd; sorbic acid was purchased from Shanghai Seiyaka Biotechnology Co., ltd; zinc oxide was purchased from chun commercial limited, in the city of everstate; waste ABS was purchased from yangzhou Ningda noble metal limited.
The invention has the beneficial effects that:
the invention successfully improves the dispersibility of the carbon nano tube in a TPU system by carrying out in-situ modification treatment on the carbon nano tube. In addition, the modified carbon nano tube and the waste ABS are subjected to melt mixing, and sorbic acid, calcium carbonate and a vulcanizing agent are added, so that the crosslinking density of the TPU film material is further increased. The synergistic effect of the modified components also obviously improves the compatibility of the waste ABS mixture and other components in the TPU system, thereby obviously improving the mechanical properties of the TPU film material. Meanwhile, the invention successfully realizes the effective recycling of the waste ABS material.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description is given below with reference to the embodiments, structures, features and effects according to the present invention.
Example 1
The utility model provides a colored multilayer electroplates TPU membrane, includes along from top to bottom superimposed protection film, toner layer, polyurethane layer, first hot melt adhesive layer, electroplate metal layer, second hot melt adhesive layer and TPU membrane in proper order, the preparation method of TPU membrane includes the following steps:
1) Placing waste ABS in an extruder for melting and mixing, adding modified carbon nano tubes for heating and melting blending, extruding and granulating, and drying to obtain a mixture A; wherein, the mass ratio of the waste ABS to the modified carbon nano tube is 8:1, a step of; the condition of melting and mixing is that mixing is carried out for 48 hours at the temperature of 135 ℃; the heating, melting and blending conditions are that the temperature is raised to 235 ℃ at a heating speed of 5 ℃/min, and then the melting and blending are carried out;
2) Stirring and mixing TPU, polyethylene, magnesium stearate, calcium carbonate, sorbic acid, a silane coupling agent KH-570 and an antioxidant 1010 to obtain a mixture B; wherein the mass ratio of the TPU to the polyethylene to the magnesium stearate to the calcium carbonate to the sorbic acid to the silane coupling agent KH-570 to the antioxidant 1010 is 40:5:1:1.5:0.4:0.5:0.1;
3) Melt blending, cooling, granulating and tape casting the mixture A, the mixture B and the vulcanizing agent to obtain a TPU film; wherein the vulcanizing agent consists of DCP and triallyl isocyanurate according to the mass ratio of 5:1, mixing; the mass ratio of the mixture A to the mixture B to the vulcanizing agent is 30:10:0.40; the condition of melt blending is that the melt blending is carried out in an extruder with the processing temperature of 210 ℃ and the injection pressure of 20 MPa;
the preparation method of the modified carbon nano tube comprises the following steps:
s1, stirring and mixing a carbon nano tube and methacrylic acid to obtain a mixture; wherein the stirring and mixing conditions are that stirring is carried out for 5min at the temperature of 50 ℃ and the rotating speed of 1800 r/min; the mass ratio of the carbon nano tube to the methacrylic acid is 10:0.9;
s2, adding zinc oxide into the mixture, uniformly stirring, slowly dropwise adding methacrylic acid, stirring and mixing, and performing ionization reaction to obtain the modified carbon nanotube; wherein the stirring condition is that stirring is carried out for 5min at the rotating speed of 2000 r/min; the time of the ionization reaction is 30min; the mass ratio of the mixture to the zinc oxide to the methacrylic acid is 5:1.1:0.4.
example 2
The utility model provides a colored multilayer electroplates TPU membrane, includes along from top to bottom superimposed protection film, toner layer, polyurethane layer, first hot melt adhesive layer, electroplate metal layer, second hot melt adhesive layer and TPU membrane in proper order, the preparation method of TPU membrane includes the following steps:
1) Placing waste ABS in an extruder for melting and mixing, adding modified carbon nano tubes for heating and melting blending, extruding and granulating, and drying to obtain a mixture A; wherein, the mass ratio of the waste ABS to the modified carbon nano tube is 8.4:1, a step of; the condition of melting and mixing is mixing for 48.4 hours at the temperature of 138 ℃; the heating, melting and blending conditions are that the temperature is raised to 236 ℃ at a heating speed of 6 ℃/min, and then the melting and blending are carried out;
2) Stirring and mixing TPU, polyethylene, magnesium stearate, calcium carbonate, sorbic acid, a silane coupling agent KH-570 and an antioxidant 1010 to obtain a mixture B; wherein, the mass ratio of TPU, polyethylene, magnesium stearate, calcium carbonate, sorbic acid, silane coupling agent KH-570 and antioxidant 1010 is 42:5.2:1.2:1.56:0.5:0.56:0.12;
3) Melt blending, cooling, granulating and tape casting the mixture A, the mixture B and the vulcanizing agent to obtain a TPU film; wherein the vulcanizing agent consists of DCP and triallyl isocyanurate according to the mass ratio of 5:1, mixing; the mass ratio of the mixture A to the mixture B to the vulcanizing agent is 32:10:0.41; the condition of melt blending is that the melt blending is carried out in an extruder with the processing temperature of 212 ℃ and the injection pressure of 21 MPa;
the preparation method of the modified carbon nano tube comprises the following steps:
s1, stirring and mixing a carbon nano tube and methacrylic acid to obtain a mixture; wherein the stirring and mixing conditions are stirring for 6min at the temperature of 52 ℃ and the rotating speed of 1840 r/min; the mass ratio of the carbon nano tube to the methacrylic acid is 10:0.9;
s2, adding zinc oxide into the mixture, uniformly stirring, slowly dropwise adding methacrylic acid, stirring and mixing, and performing ionization reaction to obtain the modified carbon nanotube; wherein the stirring condition is stirring for 6min at 2100 r/min; the time of the ionization reaction is 33min; the mass ratio of the mixture to the zinc oxide to the methacrylic acid is 5:1.16:0.4.
example 3
The utility model provides a colored multilayer electroplates TPU membrane, includes along from top to bottom superimposed protection film, toner layer, polyurethane layer, first hot melt adhesive layer, electroplate metal layer, second hot melt adhesive layer and TPU membrane in proper order, the preparation method of TPU membrane includes the following steps:
1) Placing waste ABS in an extruder for melting and mixing, adding modified carbon nano tubes for heating and melting blending, extruding and granulating, and drying to obtain a mixture A; wherein, the mass ratio of the waste ABS to the modified carbon nano tube is 8.8:1, a step of; the condition of melting and mixing is that mixing is carried out for 48.8 hours at 141 ℃; the heating, melting and blending conditions are that the temperature is raised to 237 ℃ at a heating speed of 7 ℃/min, and then the melting and blending are carried out;
2) Stirring and mixing TPU, polyethylene, magnesium stearate, calcium carbonate, sorbic acid, a silane coupling agent KH-570 and an antioxidant 1010 to obtain a mixture B; wherein the mass ratio of the TPU, the polyethylene, the magnesium stearate, the calcium carbonate, the sorbic acid, the silane coupling agent KH-570 and the antioxidant 1010 is 44:5.4:1.4:1.62:0.56:0.62:0.14;
3) Melt blending, cooling, granulating and tape casting the mixture A, the mixture B and the vulcanizing agent to obtain a TPU film; wherein the vulcanizing agent consists of DCP and triallyl isocyanurate according to the mass ratio of 5:1, mixing; the mass ratio of the mixture A to the mixture B to the vulcanizing agent is 34:10:0.42; the condition of melt blending is that the melt blending is carried out in an extruder with the processing temperature of 214 ℃ and the injection pressure of 22 MPa;
the preparation method of the modified carbon nano tube comprises the following steps:
s1, stirring and mixing a carbon nano tube and methacrylic acid to obtain a mixture; wherein the stirring and mixing conditions are that stirring is carried out for 7min at the temperature of 54 ℃ and the rotating speed of 1880 r/min; the mass ratio of the carbon nano tube to the methacrylic acid is 10:0.9;
s2, adding zinc oxide into the mixture, uniformly stirring, slowly dropwise adding methacrylic acid, stirring and mixing, and performing ionization reaction to obtain the modified carbon nanotube; wherein the stirring condition is stirring for 7min at 2200 r/min; the time of the ionization reaction is 36min; the mass ratio of the mixture to the zinc oxide to the methacrylic acid is 5:1.22:0.4.
example 4
The utility model provides a colored multilayer electroplates TPU membrane, includes along from top to bottom superimposed protection film, toner layer, polyurethane layer, first hot melt adhesive layer, electroplate metal layer, second hot melt adhesive layer and TPU membrane in proper order, the preparation method of TPU membrane includes the following steps:
1) Placing waste ABS in an extruder for melting and mixing, adding modified carbon nano tubes for heating and melting blending, extruding and granulating, and drying to obtain a mixture A; wherein, the mass ratio of the waste ABS to the modified carbon nano tube is 9.2:1, a step of; the condition of the melting and mixing is that the mixing is carried out for 49.2 hours at the temperature of 144 ℃; the heating, melting and blending conditions are that the temperature is raised to 238 ℃ at a heating speed of 8 ℃/min, and then the melting and blending are carried out;
2) Stirring and mixing TPU, polyethylene, magnesium stearate, calcium carbonate, sorbic acid, a silane coupling agent KH-570 and an antioxidant 1010 to obtain a mixture B; wherein the mass ratio of the TPU to the polyethylene to the magnesium stearate to the calcium carbonate to the sorbic acid to the silane coupling agent KH-570 to the antioxidant 1010 is 46:5.6:1.6:1.68:0.64:0.68:0.16;
3) Melt blending, cooling, granulating and tape casting the mixture A, the mixture B and the vulcanizing agent to obtain a TPU film; wherein the vulcanizing agent consists of DCP and triallyl isocyanurate according to the mass ratio of 5:1, mixing; the mass ratio of the mixture A to the mixture B to the vulcanizing agent is 36:10:0.43; the condition of melt blending is that the melt blending is carried out in an extruder with the processing temperature of 216 ℃ and the injection pressure of 23 MPa;
the preparation method of the modified carbon nano tube comprises the following steps:
s1, stirring and mixing a carbon nano tube and methacrylic acid to obtain a mixture; wherein the stirring and mixing conditions are that stirring is carried out for 8min at the temperature of 56 ℃ and the rotating speed of 1920 r/min; the mass ratio of the carbon nano tube to the methacrylic acid is 10:0.9;
s2, adding zinc oxide into the mixture, uniformly stirring, slowly dropwise adding methacrylic acid, stirring and mixing, and performing ionization reaction to obtain the modified carbon nanotube; wherein the stirring condition is that stirring is carried out for 8min at the rotation speed of 2300 r/min; the time of the ionization reaction is 39min; the mass ratio of the mixture to the zinc oxide to the methacrylic acid is 5:1.28:0.4.
example 5
The utility model provides a colored multilayer electroplates TPU membrane, includes along from top to bottom superimposed protection film, toner layer, polyurethane layer, first hot melt adhesive layer, electroplate metal layer, second hot melt adhesive layer and TPU membrane in proper order, the preparation method of TPU membrane includes the following steps:
1) Placing waste ABS in an extruder for melting and mixing, adding modified carbon nano tubes for heating and melting blending, extruding and granulating, and drying to obtain a mixture A; wherein, the mass ratio of the waste ABS to the modified carbon nano tube is 9.6:1, a step of; the condition of melting and mixing is that mixing is carried out for 49.6 hours at 147 ℃; the heating, melting and blending conditions are that the temperature is raised to 239 ℃ at a heating speed of 9 ℃/min, and then the melting and blending are carried out;
2) Stirring and mixing TPU, polyethylene, magnesium stearate, calcium carbonate, sorbic acid, a silane coupling agent KH-570 and an antioxidant 1010 to obtain a mixture B; wherein, the mass ratio of TPU, polyethylene, magnesium stearate, calcium carbonate, sorbic acid, silane coupling agent KH-570 and antioxidant 1010 is 48:5.8:1.8:1.74:0.7:0.74:0.18;
3) Melt blending, cooling, granulating and tape casting the mixture A, the mixture B and the vulcanizing agent to obtain a TPU film; wherein the vulcanizing agent consists of DCP and triallyl isocyanurate according to the mass ratio of 5:1, mixing; the mass ratio of the mixture A to the mixture B to the vulcanizing agent is 38:10:0.44; the condition of melt blending is that the melt blending is carried out in an extruder with the processing temperature of 218 ℃ and the injection pressure of 24 MPa;
the preparation method of the modified carbon nano tube comprises the following steps:
s1, stirring and mixing a carbon nano tube and methacrylic acid to obtain a mixture; wherein the stirring and mixing conditions are that stirring is carried out for 9min at 58 ℃ and 1960 r/min; the mass ratio of the carbon nano tube to the methacrylic acid is 10:0.9;
s2, adding zinc oxide into the mixture, uniformly stirring, slowly dropwise adding methacrylic acid, stirring and mixing, and performing ionization reaction to obtain the modified carbon nanotube; wherein the stirring condition is that stirring is carried out for 9min at 2400 r/min; the time of the ionization reaction is 42min; the mass ratio of the mixture to the zinc oxide to the methacrylic acid is 5:1.34:0.4.
example 6
The utility model provides a colored multilayer electroplates TPU membrane, includes along from top to bottom superimposed protection film, toner layer, polyurethane layer, first hot melt adhesive layer, electroplate metal layer, second hot melt adhesive layer and TPU membrane in proper order, the preparation method of TPU membrane includes the following steps:
1) Placing waste ABS in an extruder for melting and mixing, adding modified carbon nano tubes for heating and melting blending, extruding and granulating, and drying to obtain a mixture A; wherein, the mass ratio of the waste ABS to the modified carbon nano tube is 10:1, a step of; the conditions of the melting and mixing are that the mixing is carried out for 50 hours at the temperature of 150 ℃; the heating, melting and blending conditions are that the temperature is raised to 240 ℃ at a heating speed of 10 ℃/min, and then the melting and blending are carried out;
2) Stirring and mixing TPU, polyethylene, magnesium stearate, calcium carbonate, sorbic acid, a silane coupling agent KH-570 and an antioxidant 1010 to obtain a mixture B; wherein the mass ratio of the TPU to the polyethylene to the magnesium stearate to the calcium carbonate to the sorbic acid to the silane coupling agent KH-570 to the antioxidant 1010 is 50:6:2:1.8:0.8:0.8:0.2;
3) Melt blending, cooling, granulating and tape casting the mixture A, the mixture B and the vulcanizing agent to obtain a TPU film; wherein the vulcanizing agent consists of DCP and triallyl isocyanurate according to the mass ratio of 5:1, mixing; the mass ratio of the mixture A to the mixture B to the vulcanizing agent is 40:10:0.45; the condition of melt blending is that the melt blending is carried out in an extruder with the processing temperature of 220 ℃ and the injection pressure of 25 MPa;
the preparation method of the modified carbon nano tube comprises the following steps:
s1, stirring and mixing a carbon nano tube and methacrylic acid to obtain a mixture; wherein the stirring and mixing conditions are that stirring is carried out for 10min at the temperature of 60 ℃ and the rotating speed of 2000 r/min; the mass ratio of the carbon nano tube to the methacrylic acid is 10:0.9;
s2, adding zinc oxide into the mixture, uniformly stirring, slowly dropwise adding methacrylic acid, stirring and mixing, and performing ionization reaction to obtain the modified carbon nanotube; wherein the stirring condition is stirring for 10min at 2500 r/min; the time of the ionization reaction is 45min; the mass ratio of the mixture to the zinc oxide to the methacrylic acid is 5:1.4:0.4.
comparative example 1
The difference compared to example 5 is that comparative example 1 does not modify the carbon nanotubes, and the remaining components, preparation steps and parameters are identical.
Comparative example 2
In comparison with example 5, comparative example 2 was a process in which zinc methacrylate was mixed with carbon nanotubes in a mass ratio of 4.7:10, and adopting the mixture to replace the modified carbon nano tube, and the rest components, the preparation steps and the parameters are consistent.
Comparative example 3
In comparison with example 5, the difference is that comparative example 3 does not use modified carbon nanotubes, and the remaining components, preparation steps and parameters are identical.
Comparative example 4
The difference compared to example 5 is in step 1);
step 1), adding modified carbon nanotubes into waste ABS for heating, melting, blending, extruding, granulating and drying to obtain a mixture A; wherein, the mass ratio of the waste ABS to the modified carbon nano tube is 9.6:1, a step of; the heating, melting and blending conditions are that the temperature is raised to 239 ℃ at a heating speed of 9 ℃/min, and then the melting and blending are carried out;
the other components, the preparation steps and the parameters are consistent.
Comparative example 5
The difference compared to example 5 is that no sorbic acid was added in comparative example 5 and the remaining components, preparation steps and parameters were identical.
Comparative example 6
The difference compared with example 5 is that the mass ratio of TPU, polyethylene, magnesium stearate, calcium carbonate, sorbic acid, silane coupling agent KH-570 and antioxidant 1010 in comparative example 6 is 48:5.8:1.8:1.74:1.0:0.74:0.18; that is, the amount of sorbic acid used in comparative example 6 was increased as compared with example 5, and the remaining components, preparation steps and parameters were consistent.
Comparative examples 7 to 8
The difference compared to example 5 is that the amounts of DCP and triallyl isocyanurate used in comparative examples 7-8 are shown in Table 1, with the remaining components, preparation steps and parameters being identical.
Table 1 (Unit: parts by weight)
DCP Triallyl isocyanurate
Example 5 5 1
Comparative example 7 6 0
Comparative example 8 0 6
Comparative example 9
The difference compared to example 5 is that in comparative example 9 no vulcanizing agent was added, and the remaining components, preparation steps and parameters were identical.
Mechanical property test:
the TPU films prepared in examples 1 to 6 and comparative examples 1 to 9 were cut into dumbbell-shaped strips with a cutter according to GB/T13022-1991, the width and thickness of the films were measured with a vernier caliper, the films were stretched at a speed of 300mm/min by a tensile tester, the tensile strength and elongation at break of the films were recorded, and the test results are shown in Table 2.
TABLE 2
From the test results in Table 2, it is understood that the tensile strength and elongation at break of the TPU films prepared in examples 1 to 6 of the present invention are significantly better than those of comparative examples 1 to 9 in examples 1 to 6 as compared with comparative examples 1 to 9.
From the analysis of examples 1 to 6 and comparative examples 1 to 3,5, it is seen that the tensile strength and elongation at break of the TPU film obtained in comparative examples 1 to 3,5 are both reduced because part of the rubber in the polyethylene and other systems is vulcanized with DCP vulcanizing agent and triallyl isocyanurate under high temperature conditions; in this process, the carboxyl group in sorbic acid and the metal ion in calcium carbonate create a bridging structure by forming a coordination bond. At the same time, the carbon-carbon double bond in sorbic acid forms free radical under the action of DCP, forms chemical cross-linking with other cross-linking matrix, and grafts onto TPU chain. In this way, the crosslinking density of the TPU system is effectively increased. In addition, sorbic acid enhances the dispersibility of the inorganic filler calcium carbonate in the TPU system. The calcium carbonate is modified by the sorbic acid, so that the calcium carbonate presents an intercalation-stripping structure in a TPU system, the contact area between the calcium carbonate and rubber is increased, the stress transmission is facilitated, and the TPU film material presents excellent mechanical properties. In addition, sorbic acid and zinc oxide in the ABS material generate zinc sorbate in the vulcanization stage. Under the initiation of vulcanizing agent DCP and triallyl isocyanurate, zinc sorbate undergoes self-polymerization reaction to generate zinc polysorbate, so that the TPU film material is further reinforced, and the tensile strength and the elongation at break of the TPU film material are obviously increased; on the other hand, methacrylic acid is adopted to acidify and modify the carbon nano tube, then zinc oxide is added to carry out ionization reaction, zinc methacrylate is generated on the surface of the carbon nano tube in situ, so that the dispersibility of the modified carbon nano tube in the waste ABS is obtained, the mechanical property of the waste ABS can be reinforced, when the zinc methacrylate is melt-blended with the waste ABS, free radicals are generated by the zinc methacrylate and are subjected to grafting reaction with hydroxyl groups in the waste ABS, and as the zinc methacrylate is generated on the carbon nano tube in situ, part of the decomposed free radicals are positioned in the carbon nano tube layer structure, and the free radicals can effectively enhance the combination between the carbon nano tube and the waste ABS, so that the reinforcing function of the modified carbon nano tube is realized.
As is evident from the analysis of examples 1-6 and comparative example 4, the tensile strength and elongation at break of the TPU film obtained in comparative example 4 are reduced, because the invention breaks a large number of carbon-carbon double bonds in the polybutadiene phase in the waste ABS by melting and mixing the waste ABS for a long time, generates carbonyl groups, hydroxyl groups and other oxidation groups, increases the compatibility of the waste ABS with other components of the TPU system, promotes the combination of the carboxyl groups of the waste ABS with zinc and calcium metal ions through forming coordination bonds, and further effectively increases the crosslinking density of the waste ABS with other components, such as sorbate and zinc methacrylate, and generates grafting reaction with hydroxyl groups in the waste ABS, and improves the compatibility between the waste ABS and the TPU by utilizing the ionic interaction between the metal ions and unsaturated carboxylate, thereby obtaining better tensile strength and elongation at break.
As can be seen from the analysis of examples 1-6 and comparative examples 5-6, an appropriate amount of sorbic acid can increase the mechanical properties of the TPU film material, and when the added sorbic acid is excessive, the sorbic acid can undergo self-polymerization reaction under the catalysis of DCP to form linear polysorbate, so that the crosslinking density of the crosslinked component of the TPU film is reduced, and the tensile strength and the elongation at break are reduced.
As is clear from the analysis of examples 1 to 6 and comparative examples 7 to 9, the present invention enhances the effect of the vulcanizing agent by synergistically acting the radical initiating ability of dicumyl peroxide and the crosslinking ability of triallyl isocyanurate during vulcanization to accelerate the decomposition and crosslinking reaction of the polymer.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.

Claims (9)

1. The colorful multilayer electroplating TPU film comprises a protective film, a toner layer, a polyurethane layer, a first hot melt adhesive layer, an electroplated metal layer, a second hot melt adhesive layer and a TPU film which are sequentially overlapped from top to bottom, and is characterized in that the preparation method of the TPU film comprises the following steps:
1) Placing waste ABS in an extruder for melting and mixing, adding modified carbon nano tubes for heating and melting blending, extruding and granulating, and drying to obtain a mixture A;
2) Stirring and mixing TPU, polyethylene, a dispersing agent, calcium carbonate, sorbic acid, a coupling agent and an antioxidant to obtain a mixture B;
3) And (3) carrying out melt blending, cooling, granulating and tape casting on the mixture A, the mixture B and the vulcanizing agent to obtain the TPU film.
2. A colored multilayer electroplated TPU film according to claim 1, wherein: in the step 1), the mass ratio of the waste ABS to the modified carbon nano tube is 8-10:1, a step of; the conditions of melting and mixing are that mixing is carried out for 48-50 hours at the temperature of 135-150 ℃; the condition of heating, melting and blending is that the temperature is raised to 235-240 ℃ at a heating speed of 5-10 ℃/min, and then the melting and blending are carried out.
3. A colored multilayer electroplated TPU film according to claim 1, wherein: in the step 2), the mass ratio of the TPU to the polyethylene to the dispersing agent to the calcium carbonate to the sorbic acid to the coupling agent to the antioxidant is 40-50:5-6:1-2:1.5-1.8:0.4-0.8:0.5-0.8:0.1-0.2.
4. A colored multilayer electroplated TPU film according to claim 1, wherein: in the step 2), the dispersing agent is one or two of zinc stearate and magnesium stearate; the coupling agent is silane coupling agent KH-570; the antioxidant is one or more of 2,2 '-methylenebis- (4-methyl-6-tertiary butyl phenol), 1,3, 5-tris (3, 5-di-tertiary butyl-4-hydroxybenzyl) isocyanuric acid, N' -bis- (3, 5-di-tertiary butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine and pentaerythritol tetrakis [3- (3, 5-di-tertiary butyl-4-hydroxyphenyl) propionate ].
5. A colored multilayer electroplated TPU film according to claim 1, wherein: in step 3), the vulcanizing agent consists of DCP and triallyl isocyanurate in a mass ratio of 5:1, mixing; the mass ratio of the mixture A to the mixture B to the vulcanizing agent is 30-40:10:0.40-0.45; the condition of melt blending is that the melt blending is carried out in an extruder with the processing temperature of 210-220 ℃ and the injection pressure of 20-25 MPa.
6. The colored multilayer electroplated TPU film according to claim 1, wherein said modified carbon nanotubes are prepared by a process comprising the steps of:
s1, stirring and mixing a carbon nano tube and methacrylic acid to obtain a mixture;
s2, adding zinc oxide into the mixture, stirring uniformly, slowly dropwise adding methacrylic acid, stirring and mixing, and performing ionization reaction to obtain the modified carbon nanotube.
7. A colored multilayer electroplated TPU film according to claim 6, wherein: in the step S1, stirring and mixing conditions are that stirring is carried out for 5-10min at the temperature of 50-60 ℃ and the rotating speed of 1800-2000 r/min; the mass ratio of the carbon nano tube to the methacrylic acid is 10:0.9.
8. a colored multilayer electroplated TPU film according to claim 6, wherein: in the step S2, stirring uniformly for 5-10min at the rotating speed of 2000-2500 r/min; the ionization reaction time is 30-45min; the mass ratio of the mixture to the zinc oxide to the methacrylic acid is 5:1.1-1.4:0.4.
9. use of a coloured multilayer electroplated TPU film according to any one of claims 1 to 8, characterized in that: the application of the colorful multi-layer plating TPU film in cloth products and leather products.
CN202311667544.9A 2023-12-07 2023-12-07 Colorful multilayer electroplating TPU film and preparation method and application thereof Pending CN117601541A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311667544.9A CN117601541A (en) 2023-12-07 2023-12-07 Colorful multilayer electroplating TPU film and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311667544.9A CN117601541A (en) 2023-12-07 2023-12-07 Colorful multilayer electroplating TPU film and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN117601541A true CN117601541A (en) 2024-02-27

Family

ID=89949744

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311667544.9A Pending CN117601541A (en) 2023-12-07 2023-12-07 Colorful multilayer electroplating TPU film and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN117601541A (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102585485A (en) * 2012-01-06 2012-07-18 华南理工大学 Starch/thermoplastic polyurethane (TPU) composite material with high mechanical property and preparation method thereof
CN108517123A (en) * 2018-04-17 2018-09-11 青岛泰歌新材料科技有限公司 A kind of modified composite material and preparation method using carbon nanotube and graphene
CN109320860A (en) * 2018-09-11 2019-02-12 东莞市雄林新材料科技股份有限公司 One kind having 3D three-dimensional sense TPU film and preparation method thereof
CN115926365A (en) * 2022-11-21 2023-04-07 宁波坚锋新材料有限公司 Modified regenerated ABS material and preparation method thereof
CN116574324A (en) * 2023-05-25 2023-08-11 三斯达（江苏）环保科技有限公司 Modified EVA (ethylene-vinyl acetate) child toy material and preparation method thereof
CN116948231A (en) * 2023-09-19 2023-10-27 南通通易航天科技股份有限公司 Heat-insulating polyurethane protective film and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102585485A (en) * 2012-01-06 2012-07-18 华南理工大学 Starch/thermoplastic polyurethane (TPU) composite material with high mechanical property and preparation method thereof
CN108517123A (en) * 2018-04-17 2018-09-11 青岛泰歌新材料科技有限公司 A kind of modified composite material and preparation method using carbon nanotube and graphene
CN109320860A (en) * 2018-09-11 2019-02-12 东莞市雄林新材料科技股份有限公司 One kind having 3D three-dimensional sense TPU film and preparation method thereof
CN115926365A (en) * 2022-11-21 2023-04-07 宁波坚锋新材料有限公司 Modified regenerated ABS material and preparation method thereof
CN116574324A (en) * 2023-05-25 2023-08-11 三斯达（江苏）环保科技有限公司 Modified EVA (ethylene-vinyl acetate) child toy material and preparation method thereof
CN116948231A (en) * 2023-09-19 2023-10-27 南通通易航天科技股份有限公司 Heat-insulating polyurethane protective film and preparation method thereof

Similar Documents

Publication Publication Date Title
EP1401654B1 (en) Multilayer polymeric article with intercrosslinked polymer layers and method of making same
EP0629653B1 (en) Process for producing composite articles from polyamides and elastomers
EP0344427A2 (en) Process for chemically binding a composition based on aliphatic polyamides with a composition based on carboxylic rubbers, and products prepared thereby
EP2107081B1 (en) Rubber composition
EP0315749B1 (en) Process for producing a chemical bond between moulding compositions based on the one hand on polyphenylene ethers and on the other hand on peroxidically vulcanized EP(D)M rubbers
CA1336420C (en) Process for radiation curing of epdm roof sheeting utilizing crosslinking promoters
WO2020011005A1 (en) Chlorine-containing rubber composition, and application thereof and preparation method therefor
EP0683195B1 (en) Process for preparing composite articles from polyesters and rubbers
CN110577743A (en) Dynamic vulcanized silicone rubber and preparation method thereof
EP0644225B1 (en) Process for manufacturing composite articles from polyesters and elastomers
CN117601541A (en) Colorful multilayer electroplating TPU film and preparation method and application thereof
US20230134305A1 (en) Process For Manufacturing A Conveyor Belt
CA3139602C (en) Polypropylene board and method for preparing same
CN115678121A (en) Natural rubber-based thermoplastic vulcanized rubber and preparation method thereof
EP0769515B1 (en) Process for the preparation of composite articles from polyesters and elastomers
CN115678135B (en) Rubber composition with vulcanization promoting effect
JPH04320411A (en) Vulcanizable rubber composition and vulcanized rubber product
JP2000073016A (en) Bonding of olefinic thermoplastic elastomer composition
JP2613627B2 (en) Method of bonding millable urethane elastomer to rubber and laminate thereof
JP3993785B2 (en) Unvulcanized rubber sheet for rubber-laminated laminate and method for producing rubber-laminated laminate
JP2965678B2 (en) Composite metal plate and its manufacturing method
CN115678154A (en) Wear-resistant anti-skidding EVA shoe sole and processing technology thereof
CN115044310A (en) Hot-melt foaming film suitable for aluminum-based composite board and preparation method and application thereof
JPH10113934A (en) Manufacture of rubber film composite body
CN116574362A (en) Calcium carbonate filling modified PBAT and preparation method thereof

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