CN113462053A - Flexible polymeric wear resistant sheet - Google Patents

Flexible polymeric wear resistant sheet Download PDF

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Publication number
CN113462053A
CN113462053A CN202110692295.3A CN202110692295A CN113462053A CN 113462053 A CN113462053 A CN 113462053A CN 202110692295 A CN202110692295 A CN 202110692295A CN 113462053 A CN113462053 A CN 113462053A
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polyolefin
layer
wear
parts
polyolefin layer
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CN113462053B (en
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李民
李庆北
蔡相成
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Shanghai HIUV Applied Materials Technology Co Ltd
Shanghai HIUV New Materials Co Ltd
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Shanghai HIUV Applied Materials Technology Co Ltd
Shanghai HIUV New Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—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
    • 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
    • B32B27/065—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 foam
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B32B5/20—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material foamed in situ
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • 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
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/025—Polyolefin
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—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
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—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
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • 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
    • C08J2423/08—Copolymers of ethene

Abstract

The present application provides a flexible polymeric wear resistant sheet comprising a wear resistant layer; the first polyolefin layer is laminated with the wear-resistant layer, and comprises 100 parts by weight of first polyolefin and 0-100 parts by weight of rubber elastomer, and the first polyolefin layer has a crosslinking degree of 1-95%; and a second polyolefin layer laminated on the side of the first polyolefin layer facing away from the wear-resistant layer, wherein the second polyolefin layer comprises 100 parts by mass of a second polyolefin and 0-100 parts by mass of a rubber elastomer and has a crosslinking degree of 1-95%, and the second polyolefin layer has a porous structure. According to the flexible polymer wear-resistant sheet provided by the application, the wear resistance and the softness of the material are improved through the structure of the wear-resistant layer, the first polyolefin layer and the second polyolefin layer; through setting up the second polyolefin layer into porous structure, promote the compliance of material, carry out the cross-linking to the material and obtain the sheet that wearability and compliance performance are all good.

Description

Flexible polymeric wear resistant sheet
Technical Field
The application belongs to the technical field of high molecular materials, and particularly relates to a flexible polymer wear-resistant sheet.
Background
At present, polyolefin composites are used in various fields of industry, agriculture and life, and all of them have high requirements for abrasion resistance of polyolefins.
However, the abrasion resistance of the polyolefin composite material conflicts with the flexibility of polyolefin to a certain extent, and most of polyolefin molecular chains have good flexibility but the abrasion resistance of the material is poor, so that the application range of the polyolefin composite material is limited. The prior art is mainly based on the modification of polypropylene and polyethylene composites, which have a basically satisfactory wear resistance, but have difficulties in having the desired flexibility. Therefore, improving the abrasion resistance of the polyolefin material while ensuring the flexibility of the material becomes an urgent technical problem in the art.
Disclosure of Invention
An object of the embodiments of the present application is to provide a flexible polymer wear-resistant sheet, so as to solve the technical problem that the wear-resistant performance and the flexibility of a polymer material in the prior art cannot be compatible.
To achieve the above objects, embodiments of the present application provide a flexible polymer wear resistant sheet comprising: a wear layer; the first polyolefin layer is laminated with the wear-resistant layer, and comprises 100 parts by weight of first polyolefin and 0-100 parts by weight of rubber elastomer, and the first polyolefin layer has a crosslinking degree of 1-95%; and a second polyolefin layer laminated with the side of the first polyolefin layer opposite to the wear-resistant layer, wherein the second polyolefin layer comprises 100 parts by mass of a second polyolefin and 0-100 parts by mass of a rubber elastomer and has a crosslinking degree of 1-95%, and the second polyolefin layer has a porous structure.
The flexible polymeric wear resistant sheet according to embodiments of the present application has a composite layer structure including a wear resistant layer, a first polyolefin layer, and a second polyolefin layer, and the first and second polyolefin layers have a prescribed degree of crosslinking, thereby ensuring excellent wear resistance of the sheet; in addition, the second polyolefin layer has a porous structure, so that the overall flexibility of the sheet can be ensured, and the sheet with excellent wear resistance and softness performance can be obtained.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise.
Fig. 1 is a schematic structural diagram of a flexible polymer wear-resistant sheet provided in an embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantageous effects of the present invention more clear, the present invention is described in detail with reference to specific embodiments below. It should be understood that the embodiments described in this specification are only for the purpose of explaining the present invention and are not intended to limit the present invention.
For the sake of brevity, only some numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form ranges not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and similarly any upper limit may be combined with any other upper limit to form a range not explicitly recited. Also, although not explicitly recited, each point or individual value between endpoints of a range is encompassed within the range. Thus, each point or individual value can form a range not explicitly recited as its own lower or upper limit in combination with any other point or individual value or in combination with other lower or upper limits.
In the description herein, it is to be noted that, unless otherwise specified, "above" and "below" are inclusive, and "one or more" of "plural" means two or more.
The above summary of the present invention is not intended to describe each disclosed embodiment or every implementation of the present invention. The following description more particularly exemplifies illustrative embodiments. At various points throughout this application, guidance is provided through a list of embodiments that can be used in various combinations. In various embodiments, the lists are provided as representative groups and should not be construed as exhaustive.
The present embodiments provide a flexible polymeric wear resistant sheet comprising: a wear layer, a first polyolefin layer, and a second polyolefin layer. The first polyolefin layer and the wear-resistant layer are laminated, and the first polyolefin layer and the wear-resistant layer comprise 100 parts by mass of first polyolefin and 0-100 parts by mass of rubber elastomer. The first polyolefin layer has a degree of crosslinking of 1% to 95%. The second polyolefin layer is laminated with the side of the first polyolefin layer, which faces away from the wear-resistant layer, comprises 100 parts by mass of the second polyolefin and 0-100 parts by mass of the rubber elastomer, and has a crosslinking degree of 1-95%. The second polyolefin layer has a porous structure. Fig. 1 shows a schematic structural view of a flexible polymeric wear resistant sheet according to an embodiment of the present application. As shown in fig. 1, in the polyolefin wear-resistant sheet, a first polyolefin layer 20 is laminated with a wear-resistant layer 10 and a second polyolefin layer 30, respectively, on opposite sides.
In the present application, the polymer wear-resistant sheet material has flexibility, which means that the sheet material can maintain the winding deformation without external force after being subjected to the winding deformation. The sheet material of the present application can be advantageously used in a variety of applications requiring a flexible sheet material. In some embodiments, the wear resistant sheet material herein may be provided in the form of a coil. The coiled material form can facilitate the transportation of products; subsequent users can cut sheets of various sizes and shapes from the roll as required, and the method is convenient to apply to various scenes.
The first polyolefin layer and the second polyolefin layer are both crosslinked layers having a certain degree of crosslinking. The crosslinked polyolefin allows the sheet to have improved abrasion resistance while maintaining flexibility. In some embodiments, the degree of crosslinking of the first polyolefin layer and the second polyolefin layer may be from 1% to 95%. Further, the degree of crosslinking of the first polyolefin layer and the second polyolefin layer may be 3% to 90%, 10% to 95%, 15% to 80%, 30% to 75%, 50% to 90%, 40% to 80%, 40% to 75%, or 60% to 80%. The first and second polyolefin layers having a suitable degree of crosslinking enable the wear resistant sheet material of the present application to have a higher flexibility and a better wear resistance.
The second polyolefin layer has a porous structure having an appropriate pore size, and the softness of the second polyolefin layer and the sheet as a whole can be effectively improved, and the weight thereof can be reduced. In some embodiments, the cellular structure is obtained by foaming by adding an appropriate amount of a foaming agent to the preparation stock of the second polyolefin layer. For example, the raw material for producing the second polyolefin layer contains 1 to 15 parts by mass of a blowing agent per 100 parts by mass of the second polyolefin.
In some embodiments, the first polyolefin layer has a degree of crosslinking of from 38.4% to 75.3%, preferably from 40.0% to 75.0%. The second polyolefin layer has a degree of crosslinking of 40.1% to 77.5%, preferably 40.0% to 75.0%. When the first polyolefin layer and the second polyolefin layer have the above crosslinking degree, respectively, a polyolefin material excellent in both abrasion resistance and softness performance can be obtained. Meanwhile, the leather hand feeling of the sheet can be obtained, and the application requirement can be better met.
In some embodiments, the first polyolefin is a radiation crosslinkable polyolefin, preferably polyethylene, a copolymer of ethylene-alpha olefin, or a combination of two or more thereof, and the first polyolefin layer is radiation crosslinked. According to an embodiment of the present application, the first polyolefin layer comprises a low melting point polyolefin material, and the low melting point polyolefin material is internally formed into a cross-linked network structure by, for example, a radiation cross-linking technique, so that the wear resistance is improved while the softness thereof is ensured. In addition, when the first polyolefin layer has a high degree of crosslinking, for example, when the degree of crosslinking is 38.4% to 75.3%, excellent temperature resistance can be further obtained.
In some embodiments, the second polyolefin is a radiation crosslinkable polyolefin, preferably polyethylene, a copolymer of ethylene-alpha olefin, or a combination of two or more thereof, and the second polyolefin layer is radiation crosslinked. According to the embodiment of the present application, the second polyolefin layer comprises a low melting point polyolefin material, and a cross-linked network structure is formed inside the low melting point polyolefin material by, for example, a radiation cross-linking technology, so that the wear resistance of the low melting point polyolefin material is improved while the softness of the low melting point polyolefin material is ensured. In addition, when the first polyolefin layer has a high degree of crosslinking, for example, when the degree of crosslinking is 40.1% to 77.5%, excellent temperature resistance can be further obtained. And predictable good resistance to aging and solvent.
In embodiments of the present application, radiation crosslinking may be achieved using high energy rays such as beta rays, alpha rays, gamma rays, X rays, neutron rays, high energy electron beams, and the like. The radiation dose may be selected according to the particular polyolefin material used and the desired degree of crosslinking.
The flexible polymer wear-resistant sheet according to the embodiment of the present application has a composite layer structure including a wear-resistant layer, a first polyolefin layer, and a second polyolefin layer, and the first and second polyolefin layers have a prescribed degree of crosslinking, thereby ensuring excellent wear resistance of the sheet; in addition, the second polyolefin layer has a porous structure, so that the overall flexibility of the sheet can be ensured, and the sheet with excellent wear resistance and softness performance can be obtained. In addition, the first polyolefin layer is disposed between the second polyolefin layer having a porous structure and the wear-resistant layer, the lamination strength between the wear-resistant layer and the lower polyolefin layer is ensured, and at least one sheet having a flat surface can be obtained.
In some embodiments, the first polyolefin and the second polyolefin are the same or different. The first polyolefin and the second polyolefin can adopt the same kind of polyolefin materials, and the performances of the first polyolefin layer and the second polyolefin layer are closer, so that the sheet material can have higher integrity. The first polyolefin and the second polyolefin can also adopt different types of polyolefin materials, the polyolefin materials with different melting points and flow properties are selected according to different use scenes and product requirements, the matching can be carried out according to different performance requirements of the product on the sheet, and the corresponding product performance standard can be achieved through compounding the two materials.
In some embodiments, the first polyolefin and/or the second polyolefin has a melt flow rate of 0.5 to 50g/10min, preferably 4 to 35g/10min at 190 ℃ and 2.16 Kg. The polyolefin with the melt flow rate in the range is selected, so that the film-forming performance and the stability of foam holes are better.
In some embodiments, the first polyolefin layer and/or the second polyolefin layer comprises 50 to 70 parts by mass of a rubber elastomer, and the addition of the rubber elastomer to the first polyolefin layer and/or the second polyolefin layer can improve the processability and wear resistance of the polyolefin layer.
Examples of the rubber elastomer include radiation-crosslinkable rubber elastomers such as Natural Rubber (NR), Ethylene Propylene Diene Monomer (EPDM), hydrogenated styrene butadiene block copolymer (SEBS), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), or a combination of two or more thereof. The radiation-crosslinkable rubber elastomer can form chemical bonds between polymer high-molecular long chains through radiation crosslinking, so that the physical and chemical properties of the polymer are improved. The radiation-crosslinkable rubber elastomer in the embodiment of the application can obtain good wear-resisting property of the sheet after radiation crosslinking, thereby being beneficial to obtaining the wear-resisting sheet which is simple to manufacture and low in production cost.
In some embodiments, the first polyolefin layer and/or the second polyolefin layer may comprise less than 100 parts of the rubber elastomer, based on 100 parts by weight of the polyolefin. In some embodiments, the first polyolefin layer and/or the second polyolefin layer may comprise 10 to 100 parts, 10 to 60 parts, 20 to 90 parts, 30 to 80 parts, 40 to 60 parts, 40 to 80 parts, or 50 to 70 parts of the rubber elastomer, based on 100 parts by weight of the polyolefin.
In some embodiments, the first polyolefin layer and/or the second polyolefin layer further comprises 20 to 80 parts by mass of a flame retardant, preferably 35 to 45 parts. The flame retardant is added into the first polyolefin layer and/or the second polyolefin layer, so that the flame retardant property of the wear-resistant sheet can be effectively improved. When the flame retardant is added in the amount of 35-45 parts, the Shore A hardness of the wear-resistant sheet can be kept within the range of 30-40.
In some embodiments, the flame retardant is an organic flame retardant. The organic flame retardant can obviously improve the flame retardant property of the material under the condition of less addition amount, and has less influence on the flexibility of the material. Examples of the organic flame retardant may include one or a mixture of more than one of a halogen-based flame retardant, an organic phosphorus-based flame retardant, and a nitrogen-based flame retardant.
In some embodiments, the first polyolefin and/or the second polyolefin may further comprise other auxiliaries and/or additives, such as one or more of a co-crosslinking agent, a filler, an antioxidant, or a colorant.
In some embodiments, the abrasion resistant layer is selected from a polyurethane layer, a polyacrylate layer, an alkyd layer, or a silicone layer. Preferably, the wear-resistant layer is a polyurethane layer or a silica gel layer.
The wear-resistant layer can play a role in protecting the first polyolefin and the second polyolefin, so that the wear resistance is further improved, and the performances such as temperature resistance, anti-sticking performance and the like can be improved. The wear layer may be made of wear resistant materials known in the art, such as a polyurethane layer, a polyacrylate layer, an alkyd layer, or a silicone layer.
In some embodiments, the wear layer has a thickness of 0.005 to 2.0mm, 0.01 to 1mm, 0.01 to 0.5mm, 0.01 to 0.1mm, or 0.02 to 0.05mm, etc. The wear-resistant layer has proper thickness, so that the wear-resistant sheet material is favorably high in flexibility and wear resistance.
In some embodiments, the polymeric wear resistant sheet further satisfies at least one of:
the total thickness of the polyolefin wear-resistant material is 0.205 mm-7.0 mm, preferably 0.4 mm-2.0 mm;
the thickness of the wear-resistant layer is 0.005 mm-2.0 mm, preferably 0.1 mm-0.5 mm;
the thickness of the first polyolefin layer is 0.1-1.0 mm, preferably 0.1-0.5 mm; the thickness of the second polyolefin layer is 0.1mm to 4.0mm, preferably 0.2mm to 2.0 mm.
The thickness of the first polyolefin layer may be determined according to actual requirements. In some embodiments, the first polyolefin layer has a thickness of 0.1mm to 1.0mm, 0.15mm to 1mm, 0.1mm to 0.5mm, 0.15mm to 0.5mm, or 0.5mm to 1.0mm, etc.
The thickness of the second polyolefin layer may be determined according to actual requirements. In some embodiments, the first polyolefin layer has a thickness of 0.1mm to 4.0mm, 0.2mm to 4.0mm, 0.1mm to 1mm, 0.2mm to 1.0mm, 0.2mm to 0.5mm, 0.5mm to 1.0mm, or 0.5mm to 4.0mm, and the like.
According to various embodiments of the present application, by selecting the kind of polyolefin, the degree of crosslinking of the polyolefin layer, the content of the rubber elastomer, the type and content of the flame retardant, the porous structure of the second polyolefin layer, the wear-resistant layer, and the thicknesses of the first and second polyolefin layers, a flexible polymeric wear-resistant sheet having excellent wear-resistant properties, good flame retardancy, and a leather hand can be provided. According to different application requirements, products suitable for different applications can be provided by a simpler and cost-effective process through matching different hardness, wear resistance, flame retardant property and the like.
Examples
The present disclosure is more particularly described in the following examples that are intended as illustrative only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the following examples are on a weight basis, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further treatment, and the equipment used in the examples is commercially available.
The polyolefins used in the following examples were selected from:
polyethylene: low density polyethylene, LDPE, designation LG chemical FB 3050;
ethylene-butene copolymer: LG chemical LC 875;
polyethylene-octene copolymer: brand dow chemical 8411.
The rubber elastomers used in the following examples were selected from:
EPDM, designation dow 3745P.
The blowing agents used in the following examples were selected from:
ADC foaming agent: memorial tablet L-C2 Weifang Yaxing
The flame retardants used in the following examples were selected from:
flame retardant: new Material Ltd of Shandong Taxing, No. HT-106
Preparation method
The preparation method of the flexible polymer wear-resistant sheet material comprises the following steps:
1. preparing related raw materials of a foaming layer and a modification layer;
2. fully mixing the raw materials of the foaming layer and the modified layer, respectively adding the mixture into an extruder, and extruding and casting the mixture into a required sheet;
3. extruding a sheet material in a high-temperature furnace for foaming, wherein the foaming temperature ranges from 100 ℃ to 230 ℃;
4. coating a wear-resistant layer on the foamed sheet, and performing other post-treatment processes;
5. and carrying out radiation crosslinking treatment on the coated wear-resistant layer sheet to obtain the flexible polymer wear-resistant sheet.
Test method
Degree of crosslinking
The measurements were carried out according to the xylene extraction method of GB/T29848-2018-5.5.3.
Shore A hardness
Shore A hardness of the test sheets according to JB6148-92 was measured with an LX-A type rubber durometer.
Flame retardant properties
The flame retardant properties of the sheets were tested according to GB 8410-2006.
Temperature resistance
A sample 3 piece of 900mm by 60mm was cut out in accordance with QJ/GAC1250.006-20134.15, placed in a constant temperature test chamber, subjected to 100 ℃ by 72 hours, and then visually inspected for discoloration, and the results were expressed in accordance with GB/T250-2008 scale.
Wear resistance
The abrasion resistance of the sheets was tested according to ASTM D1242-1995.
Example 1
Flexible polymeric wear resistant sheet of this example:
the total thickness is 0.205mm, the thickness of the wear-resistant layer is 0.005mm, the thickness of the first polyolefin layer is 0.1mm, and the thickness of the second polyolefin layer is 0.1 mm.
The wear-resistant layer is an acrylate coating.
The raw materials of the first polyolefin layer comprise 100 parts by mass of polyethylene and 20 parts by mass of flame retardant, and the crosslinking degree after radiation crosslinking is 4.3%. The raw materials of the second polyolefin layer comprise 100 parts of polyethylene, 4 parts of foaming agent and 20 parts of flame retardant by mass, and the crosslinking degree after radiation crosslinking is 3.0%.
The polyethylene in the first and second polyolefin layers was LDPE and had a melt flow rate of 50g/m2。
Example 2
Flexible polymeric wear resistant sheet of this example:
the total thickness is 0.355m, the thickness of the wear-resistant layer is 0.01mm, the thickness of the first polyolefin layer is 0.15mm, and the thickness of the second polyolefin layer is 0.2 mm.
The wear-resistant layer is an alkyd resin coating.
The raw materials of the first polyolefin layer comprise 100 parts of polyethylene-octene copolymer, 60 parts of rubber elastomer and 40 parts of flame retardant by mass, and the crosslinking degree after radiation crosslinking is 38.4%. Wherein the melt flow rate of the ethylene-octene copolymer is 0.5g/m2。
The raw materials of the second polyolefin layer comprise 100 parts by mass of polyethylene, 4 parts by mass of foaming agent and 20 parts by mass of flame retardant, and the crosslinking degree after radiation crosslinking is 40.1%.
Example 3
Flexible polymeric wear resistant sheet of this example:
the total thickness is 1.6m, the thickness of the wear-resistant layer is 0.1mm, the thickness of the first polyolefin layer is 0.5mm, and the thickness of the second polyolefin layer is 1.0 mm.
The wear-resistant layer is a polyurethane coating.
The first polyolefin layer comprises 100 parts by mass of ethylene-butylene copolymer, 60 parts by mass of rubber elastomer and 40 parts by mass of flame retardant, and the crosslinking degree after radiation crosslinking is 52.7%. Wherein the melt flow rate of the ethylene-butene copolymer is 5.0g/m2。
The second polyolefin layer comprises 100 parts of ethylene-butylene copolymer, 60 parts of rubber elastomer, 8 parts of foaming agent and 40 parts of flame retardant by mass, and the crosslinking degree after radiation crosslinking is 55.9%. Wherein the melt flow rate of the ethylene-butene copolymer is 5.0g/m2。
Example 4
Flexible polymeric wear resistant sheet of this example:
the total thickness is 1.5m, the thickness of the wear-resistant layer is 0.1mm, the thickness of the first polyolefin layer is 0.15mm, and the thickness of the second polyolefin layer is 0.5 mm.
The wear-resistant layer is a polyurethane coating.
The raw materials of the first polyolefin layer comprise 100 parts of ethylene-butylene copolymer, 100 parts of rubber elastomer and 80 parts of flame retardant by mass, and the crosslinking degree after radiation crosslinking is 89.2%. Wherein the melt flow rate of the ethylene-butene copolymer is 5.0g/m2。
The raw materials of the second polyolefin layer comprise 100 parts of ethylene-butylene copolymer, 100 parts of rubber elastomer, 8 parts of foaming agent and 80 parts of flame retardant by mass, and the crosslinking degree after radiation crosslinking is 95%. Wherein the melt flow rate of the ethylene-butene copolymer is 5.0g/m2。
Example 5
Flexible polymeric wear resistant sheet of this example:
the total thickness was 7.0m, the thickness of the wear layer was 2.0mm, the thickness of the first polyolefin layer was 1.0mm and the thickness of the second polyolefin layer was 4.0 mm.
The wear-resistant layer is a silica gel layer.
The raw materials of the first polyolefin layer comprise 100 parts of ethylene-butylene copolymer, 60 parts of rubber elastomer and 40 parts of flame retardant by mass, and the crosslinking degree after radiation crosslinking is 43.5%. Wherein the melt flow rate of the ethylene-butene copolymer is 5.0g/m2。
The raw materials of the second polyolefin layer comprise 100 parts of ethylene-butylene copolymer, 60 parts of rubber elastomer, 15 parts of foaming agent and 40 parts of flame retardant by mass, and the crosslinking degree after radiation crosslinking is 48.2%. Wherein the melt flow rate of the ethylene-butene copolymer is 5.0g/m2。
Example 6
Flexible polymeric wear resistant sheet of this example:
the total thickness is 1.6m, the thickness of the wear-resistant layer is 0.1mm, the thickness of the first polyolefin layer is 0.5mm, and the thickness of the second polyolefin layer is 1.0 mm.
The wear-resistant layer is a polyurethane coating.
The raw materials of the first polyolefin layer comprise 100 parts of ethylene-butylene copolymer, 60 parts of rubber elastomer and 40 parts of flame retardant by mass, and the crosslinking degree after radiation crosslinking is 75.3%. Wherein the melt flow rate of the ethylene-butene copolymer is 35.0g/m2。
The raw materials of the second polyolefin layer comprise 100 parts of ethylene-butylene copolymer, 60 parts of rubber elastomer, 8 parts of foaming agent and 40 parts of flame retardant by mass, and the crosslinking degree after radiation crosslinking is 77.5%.
Example 7
Flexible polymeric wear resistant sheet of this example:
the total thickness is 1.6m, the thickness of the wear-resistant layer is 0.1mm, the thickness of the first polyolefin layer is 0.5mm, and the thickness of the second polyolefin layer is 0.2 mm.
The wear-resistant layer is a polyurethane coating.
The raw materials of the first polyolefin layer comprise 100 parts by weight of ethylene-butylene copolymer and 60 parts by weight of rubber elastomer, and the crosslinking degree after radiation crosslinking is 43.1%. Wherein the melt flow rate of the ethylene-butene copolymer is 5.0g/m2。
The raw materials of the second polyolefin layer comprise 100 parts of ethylene-butylene copolymer, 60 parts of rubber elastomer, 8 parts of foaming agent and 40 parts of flame retardant by mass, and the crosslinking degree after radiation crosslinking is 57.8%. Wherein the melt flow rate of the ethylene-butene copolymer is 5.0g/m2。
Example 8
Flexible polymeric wear resistant sheet of this example:
the total thickness is 1.6m, the thickness of the wear-resistant layer is 0.1mm, the thickness of the first polyolefin layer is 0.5mm, and the thickness of the second polyolefin layer is 0.2 mm.
Wear-resistant layer polyurethane coating.
The raw materials of the first polyolefin layer comprise 50 parts by weight of polyethylene, 50 parts by weight of ethylene-butylene copolymer, 60 parts by weight of rubber elastomer and 40 parts by weight of flame retardant, and the crosslinking degree after radiation crosslinking is 24.5 percent, wherein the melt flow rate of the ethylene-butylene copolymer is 5.0g/m2。
The raw materials of the second polyolefin layer comprise 100 parts of ethylene-butylene copolymer, 60 parts of rubber elastomer, 8 parts of foaming agent and 40 parts of flame retardant by mass, and the crosslinking degree after radiation crosslinking is 29.9%. Wherein the polyethylene is selected from LDPE and has a melt flow rate of 50g/m2。
Example 9
Flexible polymeric wear resistant sheet of this example:
the total thickness is 1.6m, the thickness of the wear-resistant layer is 0.1mm, the thickness of the first polyolefin layer is 0.5mm, and the thickness of the second polyolefin layer is 1.0 mm.
Wear-resistant layer polyurethane coating.
The raw materials of the first polyolefin layer comprise 30 parts by mass of ethylene-octene, 70 parts by mass of ethylene-butene copolymer, 60 parts by mass of rubber elastomer and 40 parts by mass of flame retardant, and the crosslinking degree after radiation crosslinking is 49.6%. Wherein the melt flow rate of the ethylene-octene copolymer is 0.5g/m2。
The raw materials of the second polyolefin layer comprise 30 parts of ethylene-octene, 70 parts of ethylene-butene copolymer, 60 parts of rubber elastomer, 8 parts of foaming agent and 40 parts of flame retardant by weight, and the crosslinking degree of the second polyolefin layer is measured after radiation crosslinkingThe content was 54.7%. Wherein the melt flow rate of the ethylene-butene copolymer is 5.0g/m2。
Comparative example
Flexible polymeric wear resistant sheet of this example:
the total thickness is 1.6m, the thickness of the wear-resistant layer is 0.1mm, the thickness of the first polyolefin layer is 0.5mm, and the thickness of the second polyolefin layer is 1.0 mm.
The wear-resistant layer is a polyurethane coating.
The raw materials of the first polyolefin layer comprise 100 parts of ethylene-butylene copolymer, 60 parts of rubber elastomer and 40 parts of flame retardant by weight, and the first polyolefin layer is not subjected to radiation crosslinking. Wherein the melt flow rate of the ethylene-butene copolymer is 5.0g/m2。
The raw materials of the second polyolefin layer comprise 100 parts of ethylene-butylene copolymer, 60 parts of rubber elastomer, 8 parts of foaming agent and 40 parts of flame retardant by mass, and are not subjected to radiation crosslinking. Wherein the melt flow rate of the ethylene-butene copolymer is 5.0g/m2。
The properties of the sheets obtained in examples 1 to 9 and comparative example were measured, and the results are shown in Table 1.
TABLE 1 Performance data Table for each of the polymeric abrasion resistant sheets
Figure BDA0003126598870000131
As can be seen from the data of examples 1-9 and comparative examples, the wear-resistant sheet in the comparative example does not undergo radiation crosslinking treatment, and the wear resistance of the wear-resistant sheet cannot meet the requirements.
In the examples 1-2, the crosslinking degree is 3-40%, the crosslinking degree is low, but the wear resistance is still obviously superior to that of the comparative example.
In the embodiments 3-4 and 7-9, the high crosslinking degree is adopted, so that the obtained product has good wear resistance and the hardness meets the standard.
In examples 5 and 6, by adopting a proper crosslinking degree and matching with a wear-resistant layer with good wear resistance, a flame retardant with a proper proportion and raw materials with good fluidity, products with excellent wear resistance, hardness and flame retardant effect are obtained.
According to embodiments of the present application, radiation crosslinked flexible polymeric wear resistant sheets are low in odor while having good flexibility and flame retardancy as well as excellent wear resistance. And, after radiation crosslinking, the temperature resistance of the resulting sheet is improved. By adopting the radiation crosslinking process, the crosslinking degree is better controlled, the manufacturing process is simple, and the production cost is low.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (11)

1. A flexible, polymeric, abrasion resistant sheet comprising
A wear layer;
a first polyolefin layer laminated with the wear-resistant layer, wherein the first polyolefin layer comprises 100 parts by mass of a first polyolefin and 0-100 parts by mass of a rubber elastomer, and the first polyolefin layer has a crosslinking degree of 1-95%;
a second polyolefin layer laminated on a side of the first polyolefin layer facing away from the wear-resistant layer, the second polyolefin layer comprising 100 parts by mass of a second polyolefin and 0 to 100 parts by mass of a rubber elastomer and having a degree of crosslinking of 1% to 95%,
wherein the second polyolefin layer has a porous structure.
2. The flexible polymeric wear resistant sheet according to claim 1, wherein the first polyolefin layer has a degree of crosslinking of 40.0% to 75.0% and the second polyolefin layer has a degree of crosslinking of 40.0% to 75.0%.
3. The polymeric wear resistant sheet according to claim 2, wherein the first polyolefin is a radiation crosslinkable polyolefin, preferably polyethylene, a copolymer of ethylene-alpha olefin, or a combination of two or more thereof, and the first polyolefin layer is radiation crosslinked.
4. The polymeric wear resistant sheet according to claim 3, wherein the second polyolefin is a radiation crosslinkable polyolefin, preferably polyethylene, a copolymer of ethylene-alpha olefin, or a combination of two or more thereof, and the second polyolefin layer is radiation crosslinked.
5. The polymeric wear resistant sheet of claim 4 wherein the first polyolefin and the second polyolefin are the same or different.
6. The polymeric wear resistant sheet according to claim 5, wherein the first polyolefin and/or the second polyolefin has a melt flow rate of 0.5 to 50g/10min, preferably 4 to 35g/10min at 190 ℃ under 2.16 Kg.
7. The polymeric wear resistant sheet according to claim 2, wherein the first and/or second polyolefin layer comprises 10 to 60 parts by mass of a rubber elastomer, the rubber elastomer being a radiation crosslinkable rubber elastomer, preferably a natural rubber ethylene propylene diene monomer, a hydrogenated styrene butadiene block copolymer, a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, or a combination of two or more thereof.
8. The polymeric wear resistant sheet according to claim 7, wherein the first polyolefin layer and/or the second polyolefin layer further comprises 20 to 80 parts by weight of a flame retardant, preferably 35 to 45 parts.
9. The polymeric wear resistant sheet of claim 8 wherein the flame retardant comprises any one or more of a halogen based flame retardant, an organophosphorous based flame retardant, a nitrogen based flame retardant.
10. The polymeric wear resistant sheet of claim 8 wherein the wear resistant layer is selected from a polyurethane layer, a polyacrylate layer, an alkyd layer, or a silicone layer,
preferably, the wear-resistant layer is a polyurethane layer or a silica gel layer.
11. The polymeric wear resistant sheet according to any of claims 1-10, wherein the polymeric wear resistant sheet further satisfies at least one of:
the total thickness of the polyolefin wear-resistant material is 0.205 mm-7.0 mm, preferably 0.4 mm-2.0 mm;
the thickness of the wear-resistant layer is 0.005 mm-2.0 mm, preferably 0.1 mm-0.5 mm;
the thickness of the first polyolefin layer is 0.1-1.0 mm, preferably 0.1-0.5 mm;
the thickness of the second polyolefin layer is 0.1mm to 4.0mm, preferably 0.2mm to 2.0 mm.
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