WO2022233072A1 - 一种离子聚合物增强的木塑包覆型材 - Google Patents

一种离子聚合物增强的木塑包覆型材 Download PDF

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WO2022233072A1
WO2022233072A1 PCT/CN2021/096684 CN2021096684W WO2022233072A1 WO 2022233072 A1 WO2022233072 A1 WO 2022233072A1 CN 2021096684 W CN2021096684 W CN 2021096684W WO 2022233072 A1 WO2022233072 A1 WO 2022233072A1
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Prior art keywords
core material
resin
layer
ionomer
polyolefin resin
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PCT/CN2021/096684
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English (en)
French (fr)
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唐道远
黄东辉
张志勇
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安徽森泰木塑集团股份有限公司
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Publication of WO2022233072A1 publication Critical patent/WO2022233072A1/zh

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    • 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
    • B32B1/00—Layered products having a non-planar shape
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B15/082—Layered products comprising a layer of metal comprising metal 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 comprising vinyl resins; comprising acrylic resins
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B15/095—Layered products comprising a layer of metal comprising metal 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 comprising polyurethanes
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/30—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
    • B32B27/32—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
    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • B32B2307/51—Elastic
    • 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
    • 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
    • B32B2307/558—Impact strength, toughness
    • 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
    • B32B2307/584—Scratch resistance
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention relates to an ion polymer-reinforced wood-plastic cladding profile, belonging to the field of composite profile preparation.
  • Metal profiles are often used as building components. If they are used directly, there will be major defects. On the one hand, from the perspective of aesthetics, metal profiles will bring a stiff feeling, and surface reflection will also affect the vision. Corrosion is easy to occur, so some plastic materials, such as polyolefin, are often used to coat them to obtain metal composite profiles.
  • the polyolefin coating layer there are still some problems in the use of the polyolefin coating layer.
  • the disadvantages of materials such as polyethylene, polyvinyl chloride, and polypropylene commonly used in the prior art are that the surface strength is insufficient, and scratches and abrasions are prone to occur.
  • people have designed some different schemes, some of which propose to use sarin resin as the surface material to achieve the wear-resistant effect, for example: the patent application number CN201410048917.9 provides a polyolefin coating A co-extruded wood-plastic composite material, the wood-plastic composite material uses sodium-zinc ionized resin, high-density polyethylene and coupling agent as raw materials to prepare a wear-resistant coating layer.
  • the above-mentioned patented formula has a certain improvement effect on the wear resistance of the surface layer, but the content of sodium-zinc ionized resin in the surface layer accounts for more than 95%, and the polyethylene component is only 3% ⁇ 5%. It can be regarded as an ionized resin coating layer instead of a polyethylene coating layer, which leads to a substantial increase in cost and has a certain impact on economic benefits, and the application field of this solution is wood-plastic composite panels.
  • the metal base layer of metal composite profiles When used in metal composite sheets, due to the low Vicat softening point of ionized resin, usually not more than 80 °C, the metal base layer of metal composite profiles has extremely high thermal conductivity, especially when used outdoors, exposed to sunlight Long-term direct irradiation is likely to reach a temperature above the softening temperature of the ionized resin, which will greatly affect the physical properties of the surface layer.
  • the present invention provides an ion polymer reinforced profile.
  • the present invention uses polyolefin resin as matrix resin and ion polymer resin as modified material, and adopts extrusion process to produce the coating profile, so as to solve the problem of The problem of insufficient wear resistance of the cladding layer of the metal profile is improved, and the problem of compatibility between the cladding layer and the metal core material existing in the prior art is improved.
  • An ionomer-reinforced wood-plastic cladding profile comprising a metal core material and a cladding layer formed on the periphery of the metal core material, the cladding layer comprising polyolefin resin and ionomer resin, wherein the weight of the polyolefin resin is The fraction is not less than 60%, and the weight fraction of the ionomer resin is 20% to 30%.
  • the covering of the metal core material by the covering layer may be full covering or partial covering.
  • the profile is usually a strip with an overall structure in the form of a rectangular parallelepiped. According to actual needs, the four outer surfaces of the profile except for the end faces at both ends can be selectively coated.
  • the outer circumference of the metal core material is selected to be circumferentially clad.
  • the above-mentioned metal core material can be made of aluminum, iron, copper or contains various metal alloys, such as aluminum alloy, stainless steel, galvanized steel, etc. From the perspective of practical application and processing, the application of metal profiles in the construction field needs to be considered Due to the difficulty of construction and the influence of self-weight on the force of the structure, lighter materials are usually required. Since some profiles need to be processed to form a matching structure, the processing precision is high, and materials with strong plasticity are required. From several points of view, aluminum alloys are preferable as the metal core material.
  • the shape and structure of the metal core material also has a variety of options. When used as a profile, a cavity structure is usually provided in order to achieve light weight.
  • the cavity structure can be a closed cavity or an open type.
  • the closed cavity means that the surrounding sides of the profile form a closed shape, and the inside of the closed shape is closed.
  • a cavity is provided; an open cavity, that is, the surrounding sides of the profile cannot form a closed structure, and an opening is formed on one or more sides.
  • the two sides of the metal can also have a variety of different shapes, such as a planar structure without additional processing, a mating connection structure with both sides processed into protrusions or grooves, and a clip with grooves on both sides. connection structure, etc.
  • the metal core material is an aluminum core material with an oxide film on the surface.
  • the outer surface of the metal core material has a groove with a depth of 0.03-1.0 mm along the longitudinal direction.
  • the metal core material Before the metal core material is clad, it can preferably be subjected to surface treatment, and the surface treatment includes both chemical treatment and physical treatment.
  • Chemical treatment refers to the formation of an oxide film on the surface of the aluminum alloy.
  • the specific formation method is usually anodizing, that is, the aluminum alloy core material is connected to the anode of the power supply, the cathode of the power supply is connected to a conductor, and the aluminum alloy core material and the The conductor is placed in the electrolytic solution and energized.
  • the aluminum on the surface of the aluminum alloy receives oxygen atoms in the electrolytic solution and is oxidized to form aluminum oxide.
  • Some oxidizing substances in the cathode area accept electrons and are reduced. These oxidizing substances Taking hydrogen ions as an example, they are reduced to produce hydrogen gas.
  • the electrolyte can be phosphoric acid solution, sulfuric acid solution, oxalic acid solution and the like. Since the conductor connected to the cathode does not participate in the reaction, various materials can be selected. Preferably, in order to facilitate the reduction of hydrogen ions, an electrode material with a larger specific surface, such as a graphite electrode, can be used. After the surface oxidation, a relatively dense aluminum oxide film can be obtained on the surface of the aluminum alloy. At this time, the surface of the aluminum oxide film is microscopically uneven and has a hole structure.
  • the surface of the aluminum alloy oxide film needs to be sealed (usually treated with a sealing agent) after the formation of the oxide film to prevent the surface from corroding on the basis of the hole.
  • the isolation protection of the cladding layer does not need to be sealed, but the pore structure on the surface can increase the contact area between the intermediate layer and the aluminum alloy core material and form a microscopic mosaic structure, thereby increasing the interlayer and the aluminum alloy core.
  • the intermediate layer described in the present invention is usually an adhesive layer, and is an adhesive layer suitable for connecting metal substrates, such as made of polyurethane glue or grafted polyethylene with maleic anhydride with a lower glass transition temperature. Hot melt glue.
  • Physical treatment refers to the formation of grooves along the length direction on the outer surface of the aluminum alloy core material covered by the wood-plastic layer.
  • the longitudinal direction here is not limited to a straight line, and it may be a curved groove, as long as its general direction is along the longitudinal direction of the aluminum alloy core material, and a regular linear groove is preferably formed.
  • the grooves are designed to be lengthwise for two reasons. The first reason is that forming grooves along the length direction is less difficult to process than forming grooves in other directions, the total number of grooves to be formed is less, and the processing parts required are simpler; the other reason is that in this According to the design, the aluminum alloy core material moves into the mold along the direction of the groove and is coated.
  • the gas generated during the coating process can be discharged along the groove without generating pores on the coating layer. If the grooves are provided in the width direction, the gas cannot be discharged, and remains between the intermediate layer and the aluminum alloy core material to form voids.
  • the cross-section of the groove should be designed in a shape with a continuously decreasing groove width from the notch to the bottom of the groove, such as an inverted triangle, a circular arc, etc., so that the intermediate material can enter the groove.
  • the aluminum alloy core material is first subjected to physical treatment to form a groove, and then chemical treatment is performed to form an oxide film, so as to avoid damage to the oxide film during groove processing.
  • the formation of the grooves can be directly formed by the action of the die during extrusion of the aluminum alloy core material, or by secondary processing of the aluminum alloy core material.
  • the coating layer further includes a functional auxiliary agent, and the functional auxiliary agent includes an antioxidant, a light stabilizer and an ultraviolet absorber.
  • the composition of the cladding layer mainly includes polyolefin resin and ionomer resin. Since the cladding layer is used as a surface layer, some weather resistance enhancement treatments are required, such as the addition of antioxidants, light stabilizers, ultraviolet absorbers and other additives. Material.
  • the polyolefin resin here refers to the polymer chain, the part of the main chain is similar to the polyethylene structure, and the monomers constituting the main chain all have a carbon-carbon double bond structure, such as polyvinyl chloride, polypropylene, polyethylene propylene, polyvinyl alcohol, etc.
  • polyethylene is selected as the polyolefin resin
  • the ionomer resin is usually formed by copolymerizing ethylene and methacrylic acid, which has the best compatibility with polyethylene and can be mixed more uniformly during mixing.
  • the ion polymer resin is selected from one or more of ethylene-methacrylic acid polymer sodium salt and ethylene-methacrylic acid polymer zinc salt.
  • Ionic polymer resin refers to a resin with ionic properties, such as ethylene methacrylic acid polymer, ethylene acrylic acid polymer, acrylic acid- Sodium or zinc salts of polymers such as ethylene-methacrylic acid terpolymers.
  • the ionic polymer resin used in actual production is represented by sarin resin, which is a product obtained by introducing sodium or zinc ions into ethylene-methacrylic acid copolymer for cross-linking.
  • the ionic bond between the polymer chain of the copolymer or different regions of the same polymer chain can undergo strong cross-linking, thereby improving the physical properties of the ionomer resin, but this cross-linking effect is reversible.
  • the strong attraction between adjacent molecules is weakened, causing the material to melt and flow, so it has better melt processability.
  • this bond is re-established and the ionomer resin regains its physical strength.
  • the softening temperature of the polyolefin resin is not lower than 110°C.
  • the coating layer of the present invention is formed by using polyolefin resin with a weight ratio of not less than 60%, preferably 60% to 75% as the matrix material of the coating layer, and adding 20% to 30% of ionomer resin. Cladding body.
  • ionomer resin is usually applied in the form of film or layered sheet, such as cheese, fast food and pharmaceutical packaging, heat sealing layer for extrusion coating foil structure, etc.
  • ionomer resin is usually used as The main constituent material of its layered structure has a high weight ratio.
  • polyolefin resin is used as the main material, and ionic polymer resin is used as the modified material, so it has lower cost compared with the application method in which the ion polymer resin is used as the main material.
  • the cladding layer on the surface of the metal core material needs to reach a certain thickness, while the ionomer resin usually exists in the form of a thinner film during use.
  • the economic cost is not significantly increased On the premise of , it is more convenient to form a cladding layer structure with a certain thickness.
  • the Vicat softening point of ionomer resins is relatively low, for example, the softening point of sarin PC-2000 is 40 °C, the softening point of sarin 1605 is 64 °C, and the softening point of sarin 1601-2 is 74 °C, especially When used outdoors, due to the extremely strong thermal conductivity of the metal core material, the overall temperature of the profile is at risk of approaching or exceeding the softening point under strong direct sunlight in summer.
  • the cladding layer will suffer physical structural damage after being stressed, while polyolefin resin, taking polyethylene as an example, has a softening point of more than 100 °C, so using polyolefin resin as a base material can improve the ionic strength The problem of a decrease in physical strength of polymeric resins at higher temperatures.
  • polyolefin resin has an obvious defect when coating metal, that is, the adhesion between resin and metal is insufficient, especially polyolefin resin represented by polyethylene lacking polar side chain groups, directly The quality of the metal coating is far from the standard of use.
  • ion polymer resin has strong adhesion between the metal and some ion polymer resins in practical applications. It can also be used as a metal glue.
  • the addition of the ionomer resin greatly improves the bonding performance between the cladding layer and the metal core material, and improves the bonding strength between the cladding layer and the metal core material to the qualified standard. above.
  • Ionic polymer resins include a non-polar backbone and highly polar metal ion-containing side chains.
  • the non-polar main chain of the ionomer resin is combined with the polyolefin resin toward the inside, and the polar metal ion-containing groups are toward the outside to form a polar layer structure.
  • the oil stain is applied to the surface of the coating layer, the non-polar Due to the polarity incompatibility between the oily dirt and the coating surface, it is difficult to form adhesion.
  • the improvement of the wear resistance of the coating layer by the ionomer is also related to the above, because the main chain composition of the ionomer resin includes methacrylic acid, and polymethacrylic acid, which is often referred to as acrylic, is relatively Ethylene has higher density and hardness. Due to the interaction between the polyolefin resin and the ionomer resin, the ionomer resin will be oriented to a certain extent on the surface of the cladding layer, thereby forming a surface structure mainly composed of the ionomer resin, which has strong wear resistance. For polyolefin resins, it can protect the interior.
  • the occurrence of wear is essentially the interaction between the surface layers of the two objects, so the internal structure does not contribute much to the improvement of the surface wear resistance, so the internal ionomer resin is replaced with a polymer.
  • Olefin resin does not have a significant impact on wear resistance, but can greatly reduce production costs and obtain higher economic benefits.
  • the existing polyolefin polymer co-extrusion equipment can extrude the ion polymer resin, when the raw materials are polyolefin resin and ion polymer resin, it can be put into operation without additional modification of the equipment. It is easy to use, easy to produce and does not cause the cost of equipment to rise. However, it should be noted that since ionic polymers have a certain corrosion ability to metals, there are some requirements for the material of extrusion equipment. 4PH and other types of stainless steel.
  • the polyolefin resin is selected from high-density polyethylene.
  • the thickness of the coating layer is 0.5-5.0 mm.
  • the intermediate layer is a hot-melt adhesive layer or a self-adhesive composite polymer layer.
  • the self-adhesive composite polymer layer includes the following components in parts by weight: unsaturated carboxylic acid modified polyolefin resin 40-60, thermoplastic polyurethane elastomer 20-30, polyurethane Prepolymer 5 ⁇ 15, isocyanate 1 ⁇ 5, inorganic filler 5 ⁇ 10.
  • ion polymer resin is added to the coating layer of the composite profile, which improves the wear resistance and scratch resistance of the coating layer, and also improves the oil pollution resistance, so that the coating profile is more durable.
  • the present invention uses polyolefin resin as the main material, and ion polymer resin as the modified material to prepare the coating layer.
  • the ion polymer resin improves the wear resistance and oil stain resistance of the polyolefin resin, and enhances the The bonding ability of metal, polyolefin resin improves the physical strength of ionomer resin at high temperature, and the interaction between the two makes the cladding layer have excellent physical properties, and the bonding between the cladding layer and the metal core material is firm. .
  • the coating material of the present invention can be extruded by using the existing production equipment without additional investment in equipment improvement, the production process is simple, and the economic benefit is high.
  • a composite polymer layer with self-adhesion is arranged between the cladding layer and the metal core material, and the middle layer has good elasticity and impact resistance, so that good adhesion can be maintained in various environments. junction; thus further improving the stability of the product.
  • the metal core material in each comparative example and the example is uniformly selected as a square structure aluminum alloy core material with a specification of 200mm*200mm*2000mm, and the aluminum alloy core material has a square cross-section inside.
  • the closed cavity, the thickness of the aluminum alloy core material is 3mm.
  • Knurling treatment Use the knurling process to form a plurality of v-shaped grooves with a depth of 0.3mm on the outer surface of the core material along the length of the core material;
  • the pretreated aluminum alloy core material is introduced into the main channel of the co-extrusion die.
  • the intermediate layer material is melted and extruded through the extruder to the intermediate layer flow channel and wrapped around the metal core material.
  • the surface layer material is melted and extruded through the extruder to the surface layer flow channel and wrapped around the middle layer, and finally a three-layer structure including the core material is formed and then extruded from the die mouth.
  • the material of the intermediate layer is thermoplastic polyurethane hot melt adhesive.
  • the pretreated aluminum alloy core material is introduced into the main channel of the co-extrusion die.
  • the intermediate layer material is melted and extruded through the extruder to the intermediate layer flow channel and wrapped around the metal core material.
  • the surface layer material is melted and extruded through the extruder to the surface layer flow channel and wrapped around the middle layer, and finally a three-layer structure including the core material is formed and then extruded from the die mouth.
  • the material of the intermediate layer is thermoplastic polyurethane hot melt adhesive.
  • the pretreated aluminum alloy core material is introduced into the main channel of the co-extrusion die.
  • the intermediate layer material is melted and extruded through the extruder to the intermediate layer flow channel and wrapped around the metal core material.
  • the surface layer material is melted and extruded through the extruder to the surface layer flow channel and wrapped around the middle layer, and finally a three-layer structure including the core material is formed and then extruded from the die mouth.
  • the material of the middle layer is maleic acid graft modified polyethylene hot melt adhesive.
  • the pretreated aluminum alloy core material is introduced into the main channel of the co-extrusion die.
  • the intermediate layer material is melted and extruded through the extruder to the intermediate layer flow channel and wrapped around the metal core material.
  • the surface layer material is melted and extruded through the extruder to the surface layer flow channel and wrapped around the middle layer, and finally a three-layer structure including the core material is formed and then extruded from the die mouth.
  • the material of the intermediate layer is a self-adhesive composite polymer layer.
  • the composite polymer layer includes the following components in parts by weight: 40 parts of maleic anhydride grafted polyethylene, 20 parts of thermoplastic polyurethane elastomer, 10 parts of calcium carbonate, 10 parts of polyurethane prepolymer, and 5 parts of isocyanate.
  • the pretreated aluminum alloy core material is introduced into the main channel of the co-extrusion die.
  • the intermediate layer material is melted and extruded through the extruder to the intermediate layer flow channel and wrapped around the metal core material.
  • the surface layer material is melted and extruded through the extruder to the surface layer flow channel and wrapped around the middle layer, and finally a three-layer structure including the core material is formed and then extruded from the die mouth.
  • the material of the intermediate layer is a self-adhesive composite polymer layer.
  • the composite polymer layer includes the following components in parts by weight: 40 parts of maleic anhydride grafted polyethylene, 20 parts of thermoplastic polyurethane elastomer, 10 parts of calcium carbonate, and 10 parts of polyurethane prepolymer.
  • the pretreated aluminum alloy core material is introduced into the main channel of the co-extrusion die.
  • the intermediate layer material is melted and extruded through the extruder to the intermediate layer flow channel and wrapped around the metal core material.
  • the surface layer material is melted and extruded through the extruder to the surface layer flow channel and wrapped around the middle layer, and finally a three-layer structure including the core material is formed and then extruded from the die mouth.
  • the material of the intermediate layer is thermoplastic polyurethane hot melt adhesive.
  • 96 parts of ethylene-methacrylic acid sodium salt, 0.05 part of carbon black, 0.35 part of iron red, 0.6 part of antioxidant, 1.4 part of anti-ultraviolet absorber, and 1.6 part of lubricant are used as raw materials in a high-speed mixer, and the material is discharged after stirring for 15 minutes. , and put the mixture into the granulation for extrusion granulation to obtain the surface layer material.
  • the pretreated aluminum alloy core material is introduced into the main channel of the co-extrusion die.
  • the intermediate layer material is melted and extruded through the extruder to the intermediate layer flow channel and wrapped around the metal core material.
  • the surface layer material is melted and extruded through the extruder to the surface layer flow channel and wrapped around the middle layer, and finally a three-layer structure including the core material is formed and then extruded from the die mouth.
  • the material of the intermediate layer is thermoplastic polyurethane hot melt adhesive.
  • Scratch resistance test Use five metal finger-shaped scraping heads to scratch the surface of the material to form scratches, and visually compare the visibility of the scratches.
  • One top of the scraping rod is fixed with a highly polished scraping head made of tungsten carbide, and the other end of the scraping rod is fixed with a weight, so that the load forces are 5N, 10N, 15N and 20N respectively.
  • the scraping distance is set to 200mm
  • the scraping speed is set to 100mm/s.
  • the flat friction wheel test method is used to fix the sample on the rotating table.
  • the rotating table is provided with a rubber wheel with a fixed position. When the rotating table rotates, the rubber wheel will rub the sample.
  • the load was 1kg
  • the rotational speed was 72 rpm
  • the mass retention rate of the sample was analyzed after 5000 rpm to compare the wear resistance. The results are shown in Table II.
  • the data before and after the slash "/" in the table represent the data measured at room temperature and 60°C, respectively.
  • 1/2 represents the test result of scratch resistance at room temperature
  • the result measured at 60°C is a slight scratch.

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Abstract

本发明涉及一种离子聚合物增强的木塑包覆型材，属于复合板材制备领域。一种离子聚合物增强的木塑包覆型材，包括金属芯材和金属芯材外周的包覆层，包覆层包含聚烯烃树脂和离子聚合树脂，其中聚烯烃树脂的重量分数不低于60%，离子聚合树脂的重量分数为20%~30%。本发明以聚烯烃树脂作为主要材料，离子聚合树脂为改性材料进行包覆层的制备，离子聚合树脂提高了聚烯烃树脂的耐磨性能和防油污性能，并增强了聚烯烃树脂与金属的粘接能力，聚烯烃树脂提高了离子聚合树脂在高温下的物理强度，两者在相互作用下使包覆层具有优异的物理性能，且包覆层与金属芯材之间粘接牢固。

Description

一种离子聚合物增强的木塑包覆型材 技术领域
本发明涉及一种离子聚合物增强的木塑包覆型材，属于复合型材制备领域。
 背景技术
金属型材常作为建筑构件使用，若直接使用的话会存在较大的缺陷，一方面从美观度角度而言，金属型材会带来生硬感，且表面反光对视觉也会产生影响，另一方面金属容易发生腐蚀，因此常常采用一些塑制材料，如聚烯烃，对其进行包覆处理，得到金属复合型材。
然而，聚烯烃包覆层在使用过程中仍存在一些问题，现有的技术中常用的聚乙烯、聚氯乙烯、聚丙烯等材料的缺点在于表面强度不足，容易出现刮花、磨损等现象，为了解决这一问题，人们设计了一些不同的方案,其中一些方案提出将沙林树脂作为表层材料来实现耐磨效果，例如：申请号为CN201410048917.9的专利提供了一种聚聚烯烃包覆共挤木塑复合材料，该木塑复合材料以钠锌离子化树脂，高密度聚乙烯和偶联剂为原料来制备耐磨包覆层。上述专利配方对表层的耐磨性起到了一定的改进效果，但其表层中钠锌离子化树脂的含量占比达到了95%以上，聚乙烯成分仅有3%~5%，从整体而言可以看做是一种离子化树脂包覆层而非聚乙烯包覆层，这导致了成本的大幅提高，对经济效益产生一定的影响，且该方案应用领域为木塑复合板材。而在金属复合板材中进行应用时，由于离子化树脂的维卡软化点较低，通常不超过80℃，金属复合型材的金属基层具有极高的导热性能，特别是用在户外时，受到阳光长时间的直射很可能温度达到离子化树脂的软化温度以上，从而导致表层物理性能受到大幅影响。
 技术解决方案
本发明要解决上述技术问题，提供一种离子聚合物增强的型材，本发明以聚烯烃树脂为基质树脂，离子聚合树脂为改性材料，采用挤出工艺来生产来制备包覆型材，以解决金属型材包覆层耐磨性能不足的问题，同时改善了现有技术中存在的包覆层与金属芯材的配适性问题。
本发明解决上述问题的技术方案如下：
一种离子聚合物增强的木塑包覆型材，包括金属芯材和成型于金属芯材外周的包覆层，所述的包覆层包含聚烯烃树脂和离子聚合树脂，其中聚烯烃树脂的重量分数不低于60%，离子聚合树脂的重量分数为20%~30%。
需要说明的是，在本发明中，包覆层对金属芯材的包覆可以为全包覆，也可以为部分包覆。型材通常为整体结构呈长方体的条状物，根据实际需要可以对型材除了两端端面的四个外表面进行选择性包覆。优选地，选择对金属芯材外周进行周向包覆。
上述金属芯材可由铝、铁、铜或包含多种金属合金制成，例如铝合金、不锈钢、镀锌钢等，从实际应用和加工角度来看，金属型材在建筑领域的应用过程中需要考虑到施工难易程度以及自重对结构受力的影响，因此通常需要更加轻质的材料，而由于一些型材需要加工形成配合结构，因此对加工精密度要求较高，需要可塑性强的材料，综合以上几点来看铝合金作为金属芯材为优选。金属芯材的形状结构同样具有多种选择。当作为型材时，为了实现轻质化通常会设置空腔结构，空腔结构可以是封闭式空腔也可以是开放式，封闭式空腔即型材的四周侧面围成一个封闭形状，封闭形状内部设置空腔；开放式空腔即型材的四周侧面不能形成封闭结构，在一个或者多个侧面上形成开口。此外，金属的两个侧面也可以具有多种不同形状，如不进行额外加工的平面状结构、两侧分别加工成凸出或凹槽的配合连接结构、两侧均加工成凹槽的卡件连接结构等。
作为上述技术方案的优选，所述的金属芯材为铝制芯材，表面具有氧化膜。
作为上述技术方案的优选，所述的金属芯材贴合的外表面上具有沿长度方向深度为0.03~1.0mm的沟槽。
在金属芯材进行包覆之前，优选地可以对其进行表面处理，表面处理包括化学处理和物理处理两种。
化学处理指的是在铝合金表面形成一层氧化膜，具体的形成方法通常是阳极氧化法，即将铝合金芯材连通至电源的阳极，电源的阴极连接一导电体，将铝合金芯材和导电体置入电解溶液中并通电，此时铝合金表面层的铝接受电解液中的氧原子被氧化形成氧化铝，阴极区域一些具有氧化性的物质接受电子被还原，这些具有氧化性的物质以氢离子为例，被还原后产生氢气。为了实现上述过程，电解液中需要存在较多的氢离子，因此电解液可以是磷酸溶液、硫酸溶液、草酸溶液等。由于阴极连接的导电体不参与反应，因此可以选用多种材料，优选地为了便于氢离子的还原，可以采用比表面较大的电极材料，例如石墨电极。在进行表面氧化后，铝合金表层即可得到一层较为致密的氧化铝薄膜，此时的氧化铝薄膜表面微观上实际上凹凸不平且带有孔洞结构。在常规的工艺中，铝合金氧化膜形成后需要对其表面进行封孔处理（通常是利用封孔剂进行处理），防止其表面以孔洞为基点发生腐蚀，而在本发明中，因为将受到包覆层的隔离保护，并不需要进行封孔处理，反而其表面的孔隙结构可以增加中间层与铝合金芯材之间的接触面积以及形成微观上的嵌合结构，从而增大中间层与铝合金芯材之间的粘结力。本发明所述的中间层通常为胶黏剂层，且是适于连接金属基材的胶黏剂层，如用聚氨酯胶或用玻璃转化温度较低的马来酸酐接枝聚乙烯制成的热熔胶。
物理处理指的是在铝合金芯材受木塑层包覆的外表面上加工形成沿长度方向的沟槽，沟槽的作用是在宏观结构上与中间层形成嵌合结构，并提高中间层与铝合金芯材的接触面积，从而提高粘结强度。这里的沿长度方向并不限定于直线，也可以是曲线状的沟槽，只要其大致走向是沿着铝合金芯材的长度方向即可，优选地形成规整的直线状沟槽。之所以将沟槽设计成沿长度方向，存在两个原因。第一个原因是沿长度方向形成沟槽相较于沿其他方向形成沟槽加工难度更低，形成沟槽的总条数更少，需要的加工部件也更加简单；另一原因是，在该设计下铝合金芯材是沿着沟槽的走向移动进入模具内并被包覆的，包覆工艺处理时产生的气体可以顺着沟槽排出，不会在包覆层上生成气孔。若沿宽度方向设置沟槽，则气体无法排出，会残留在中间层与铝合金芯材之间形成空泡。沟槽的截面应当设计成从槽口至槽底，槽宽不断减小的形状，例如倒三角形、圆弧形等，以便于中间层物料进入槽内。优选地，铝合金芯材首先通过物理处理形成沟槽，再进行化学处理形成氧化膜，以免沟槽加工时对氧化膜造成破坏。沟槽的形成可以是铝合金芯材在挤出成型时通过模具的作用直接形成，也可以是对铝合金芯材进行二次加工处理。
作为上述技术方案的优选，所述包覆层还包括功能助剂，所述的功能助剂包括抗氧剂、光稳定剂和紫外线吸收剂。
包覆层的组成主要包括聚烯烃树脂和离子聚合树脂，由于包覆层是作为表层使用，因此需要进行一些耐候性增强处理，例如需要添加抗氧剂、光稳定剂、紫外线吸收剂等其他添加材料。这里的聚烯烃树脂指的是高分子链中，主链的部分与聚乙烯结构类似，构成主链的单体中均具有碳碳双键结构，例如聚氯乙烯、聚丙烯、聚乙丙烯、聚乙烯醇等。优选地，聚烯烃树脂选用聚乙烯，离子聚合树脂通常是由乙烯和甲基丙烯酸共聚形成，与聚乙烯的相容性最佳，在混料时可以更加均匀地混合。
作为上述技术方案的优选，所述的离子聚合树脂选自乙烯-甲基丙烯酸聚合物钠盐、乙烯-甲基丙烯酸聚合物锌盐中的一种或多种。离子聚合树脂指的是组成树脂的高分子链的侧链上的部分基团被金属离子取代，从而形成具有离子特性的一种树脂，例如乙烯甲基丙烯酸聚合物、乙烯丙烯酸聚合物、丙烯酸-乙烯-甲基丙烯酸三元共聚物等高分子的钠盐或锌盐。在实际生产中使用的离子聚合树脂以沙林树脂为代表，沙林树脂是向乙烯-甲基丙烯酸共聚物中引入钠或锌离子进行交联而成的产品，在不同的乙烯-甲基丙烯酸共聚物高分子链或同一个高分子链的不同区域之间离子键可以发生强烈的交联作用，从而提高离子聚合树脂的物理性能，但这种交联作用是可逆的，在受热时，相邻分子间强烈的吸引力减弱，导致材料融化并流动，因此具有较好的熔融加工性能，在冷却时，这种键合作用又重新建立，使离子聚合树脂恢复物理强度。作为上述技术方案的优选，所述的聚烯烃树脂的软化温度不低于110℃。
本发明的包覆层以重量占比为不低于60%，优选为60%~75%的聚烯烃树脂作为包覆层的基质材料，并添加有20%~30%的离子聚合树脂来形成包覆层主体。现有的工艺中，离子聚合树脂通常以薄膜或层状片材形式应用，例如作为奶酪、快餐食品以及药品的包装、用于挤出涂覆箔结构的热封层等，离子聚合树脂通常作为其层状结构的主体构成材料，具有较高的重量占比。本发明则是以聚烯烃树脂作为主体，离子聚合树脂为改性料，因此相较于以离子聚合树脂为主料的应用方法具有更低的成本。从另一角度，金属芯材表面的包覆层需要达到一定的厚度，而离子聚合树脂在使用过程中通常以较薄的膜形式存在，通过聚烯烃树脂的共混，在不明显增加经济成本的前提下，较为方便地形成具有一定厚度的包覆层结构。此外，离子聚合树脂的维卡软化点较低，例如沙林PC-2000的软化点为40℃、沙林1605的软化点为64℃、沙林1601-2的软化点为74℃，尤其是在户外使用时，由于金属芯材极强的导热能力，在夏天的强烈日光直射下，型材的整体温度有接近或超过软化点的风险，当以离子聚合树脂为基材时，一旦其软化程度达到较高水平，在受力后包覆层会发生物理性的结构破坏，而聚烯烃树脂，以聚乙烯为例，软化点达到了100℃以上，因此以聚烯烃树脂作为基材可以改善离子聚合树脂在较高温度下物理强度下降的问题。然而聚烯烃树脂在对金属进行包覆时具有一个明显的缺陷，即树脂与金属之间的粘接性能不足，尤其是以聚乙烯为代表的缺乏极性侧链基团的聚烯烃树脂，直接对金属进行包覆后的质量远远达不到使用标准，因此选用离子聚合树脂的另一优点在于，离子聚合树脂与金属之间具有较强的粘合性能，在实际应用中一些离子聚合树脂还可作为金属胶使用，在本发明中离子聚合树脂的添加极大地改善了包覆层与金属芯材之间的粘接性能，将包覆层与金属芯材的粘接强度提高到了合格标准以上。
除此之外，离子聚合树脂还具有一些其他性能，例如耐污性。离子聚合树脂包括非极性的主链和极性程度极高的含金属离子的侧链。离子聚合树脂的其非极性主链朝向内侧与聚烯烃树脂结合，极性的含金属离子的基团朝向外侧，形成一层极性层结构，当油污施加到包覆层表面时，非极性的油污与包覆层表面由于极性不相容性，难以形成附着。而离子聚合物使包覆层的耐磨性提高也与上述相关，因为组成离子聚合树脂的主链组成包括甲基丙烯酸，而聚甲基丙烯酸，也就是人们常说的亚力克，相较聚乙烯而言具有更高的密度和硬度。因为聚烯烃树脂和离子聚合树脂的相互作用，离子聚合树脂会一定程度上在包覆层的表面产生定向排布，从而形成主要由离子聚合树脂组成的表层结构，该表层结构的耐磨性能强于聚烯烃树脂，对内部可以起到保护作用。以物理角度来看，磨损的发生实质上是两个物体的表面层之间的相互作用，因此内部结构对表面耐磨能力的提高并没有过多贡献，因此将内部的离子聚合树脂替换为聚烯烃树脂并不会对耐磨性能造成明显影响，反而能大大降低生产成本，获得更高的经济效益。
在具体的生产过程中，因为现有的聚烯烃聚合物共挤设备就可以对离子聚合树脂进行挤出，因此当原料为聚烯烃树脂和离子聚合树脂时，无需对设备进行额外改进即可投入使用，生产方便且不会导致设备方面的成本上升。不过需要说明的是，由于离子聚合物对金属存在一定的腐蚀能力，因此对挤出设备的材质上有一些要求，例如构成挤出设备的钢材优选地应当选用316型、15-5PH、17-4PH等型号的不锈钢。
作为上述技术方案的优选，所述的聚烯烃树脂选用高密度聚乙烯。
作为上述技术方案的优选，所述的包覆层的厚度为0.5~5.0mm。
作为上述技术方案的优选，所述的包覆层和金属芯材之间还具有中间层，所述的中间层为热熔胶层或具有自粘性的复合高分子层。
作为上述技术方案的优选，所述的具有自粘性的复合高分子层包括以下重量份的组分：不饱和羧酸改性聚烯烃树脂40~60、热塑型聚氨酯弹性体20~30、聚氨酯预聚体5~15、异氰酸酯1~5、无机填料5~10。
 有益效果
与现有技术相比，本发明的有益效果为：
1、本发明在复合型材的包覆层中添加离子聚合树脂，提高了包覆层的耐磨、耐刮性能，同时也提高了防油污性能，使包覆型材更加经久耐用。
2、本发明以聚烯烃树脂作为主要材料，离子聚合树脂为改性材料进行包覆层的制备，离子聚合树脂提高了聚烯烃树脂的耐磨性能和防油污性能，并增强了聚烯烃树脂与金属的粘接能力，聚烯烃树脂提高了离子聚合树脂在高温下的物理强度，两者在相互作用下使包覆层具有优异的物理性能，且包覆层与金属芯材之间粘接牢固。
3、本发明的包覆层原料可以采用现有的生产设备来进行挤出，无需设备改进方面的额外投入，生产工艺简单，经济效益高。
4、本发明通过在包覆层和金属芯材之间设置具有自粘性的复合高分子层，中间层具有较好的弹性和抗冲击性能，使得在各种环境下均能保持较好的粘结性；从而进一步提升了产品的稳定性。
 本发明的实施方式
下面通过具体实施方式来对本发明的内容和有点进行进一步地说明。
为了便于比较各实施例与对比例的性能，在各对比例和实施例中的金属芯材统一选用规格为200mm*200mm*2000mm的方形结构铝合金芯材，铝合金芯材内部具有截面为方形的封闭式空腔，铝合金芯材的厚度为3mm。在对金属芯材包覆之前首先进行预处理，预处理过程包括：
（1）滚花处理：沿着芯材的长度方向使用滚花工艺在芯材的外表面上形成多条深度为0.3mm的v形沟槽；
（2）表面氧化处理：将（1）中带沟槽的芯材通过阳极氧化处理得到一层氧化铝膜（不进行封孔处理）。
实施例1
将76份聚乙烯、20份乙烯-甲基丙烯酸钠盐、炭黑0.05份、铁红0.35份、抗氧剂0.6份、抗紫外吸收剂1.4份、润滑剂1.6份作为原料在高速搅拌机中，搅拌15min后出料，并将混合料投入至造粒中进行挤出造粒，制得表层物料。
将经过预处理的铝合金芯材导入共挤模具的主通道内，在穿过通道的过程中，中间层物料通过挤出机熔融挤出至中间层流道并包覆在金属芯材的四周，随后表层物料通过挤出机熔融挤出至表层流道并包覆在中间层四周，最后形成包括芯材在内的三层结构后从模具口挤出。本实施例中，中间层物料为热塑性聚氨酯热熔胶。
实施例2
将71份聚乙烯、25份乙烯-甲基丙烯酸钠盐、炭黑0.05份、铁红0.35份、抗氧剂0.6份、抗紫外吸收剂1.4份、润滑剂1.6份作为原料在高速搅拌机中，搅拌15min后出料，并将混合料投入至造粒中进行挤出造粒，制得表层物料。
将经过预处理的铝合金芯材导入共挤模具的主通道内，在穿过通道的过程中，中间层物料通过挤出机熔融挤出至中间层流道并包覆在金属芯材的四周，随后表层物料通过挤出机熔融挤出至表层流道并包覆在中间层四周，最后形成包括芯材在内的三层结构后从模具口挤出。本实施例中，中间层物料为热塑性聚氨酯热熔胶。
实施例3
将66份聚乙烯、30份乙烯-甲基丙烯酸钠盐、炭黑0.05份、铁红0.35份、抗氧剂0.6份、抗紫外吸收剂1.4份、润滑剂1.6份作为原料在高速搅拌机中，搅拌15min后出料，并将混合料投入至造粒中进行挤出造粒，制得表层物料。
将经过预处理的铝合金芯材导入共挤模具的主通道内，在穿过通道的过程中，中间层物料通过挤出机熔融挤出至中间层流道并包覆在金属芯材的四周，随后表层物料通过挤出机熔融挤出至表层流道并包覆在中间层四周，最后形成包括芯材在内的三层结构后从模具口挤出。本实施例中，中间层物料为马来酸接枝改性聚乙烯热熔胶。
实施例4
将71份聚乙烯、25份乙烯-甲基丙烯酸锌盐、炭黑0.05份、铁红0.35份、抗氧剂0.6份、抗紫外吸收剂1.4份、润滑剂1.6份作为原料在高速搅拌机中，搅拌15min后出料，并将混合料投入至造粒中进行挤出造粒，制得表层物料。
将经过预处理的铝合金芯材导入共挤模具的主通道内，在穿过通道的过程中，中间层物料通过挤出机熔融挤出至中间层流道并包覆在金属芯材的四周，随后表层物料通过挤出机熔融挤出至表层流道并包覆在中间层四周，最后形成包括芯材在内的三层结构后从模具口挤出。本实施例中，中间层物料为具有自粘性的复合高分子层。
复合高分子层的包括以下重量份的组分：马来酸酐接枝聚乙烯40份、热塑性聚氨酯弹性体20份、碳酸钙10份、聚氨酯预聚体10份、异氰酸酯5份。
实施例5
将71份聚乙烯、15份乙烯-甲基丙烯酸钠盐、10份乙烯-甲基丙烯酸锌盐、炭黑0.05份、铁红0.35份、抗氧剂0.6份、抗紫外吸收剂1.4份、润滑剂1.6份作为原料在高速搅拌机中，搅拌15min后出料，并将混合料投入至造粒中进行挤出造粒，制得表层物料。
将经过预处理的铝合金芯材导入共挤模具的主通道内，在穿过通道的过程中，中间层物料通过挤出机熔融挤出至中间层流道并包覆在金属芯材的四周，随后表层物料通过挤出机熔融挤出至表层流道并包覆在中间层四周，最后形成包括芯材在内的三层结构后从模具口挤出。本实施例中，中间层物料为具有自粘性的复合高分子层。
复合高分子层的包括以下重量份的组分：马来酸酐接枝聚乙烯40份、热塑性聚氨酯弹性体20份、碳酸钙10份、聚氨酯预聚体10份。
对比例1
将聚乙烯96份、炭黑0.05份、铁红0.35份、抗氧剂0.6份、抗紫外吸收剂1.4份、润滑剂1.6份作为原料在高速搅拌机中，搅拌15min后出料，并将混合料投入至造粒中进行挤出造粒，制得表层物料。
将经过预处理的铝合金芯材导入共挤模具的主通道内，在穿过通道的过程中，中间层物料通过挤出机熔融挤出至中间层流道并包覆在金属芯材的四周，随后表层物料通过挤出机熔融挤出至表层流道并包覆在中间层四周，最后形成包括芯材在内的三层结构后从模具口挤出。
本对比例中，中间层物料为热塑性聚氨酯热熔胶。
对比例2
将乙烯-甲基丙烯酸钠盐96份、炭黑0.05份、铁红0.35份、抗氧剂0.6份、抗紫外吸收剂1.4份、润滑剂1.6份作为原料在高速搅拌机中，搅拌15min后出料，并将混合料投入至造粒中进行挤出造粒，制得表层物料。
将经过预处理的铝合金芯材导入共挤模具的主通道内，在穿过通道的过程中，中间层物料通过挤出机熔融挤出至中间层流道并包覆在金属芯材的四周，随后表层物料通过挤出机熔融挤出至表层流道并包覆在中间层四周，最后形成包括芯材在内的三层结构后从模具口挤出。
本对比例中，中间层物料为热塑性聚氨酯热熔胶。
上述实施例及对比例的性能测试：
耐刮性能测试：以五个金属手指状的刮擦头划过材料表面形成刮痕，目视比较划痕的可见度。实验前先将样品固定在试验台上，刮擦杆的一顶端固定碳化钨制材质的高度抛光刮擦头，刮擦杆另一端固定砝码，使负载力分别为5N、10N、15N和20N，刮擦距离设定为200mm，刮擦速度为100mm/s。测试完成后，在D65标准光源条件下，目测划痕，可通过改变样品与观察者的角度使划伤线以最清晰可见的角度呈现。评价时排除划痕起点和终点两端各10%的范围，即仅取中部80%的范围为有效评价区域。划痕分为五个等级，其中：1-无划痕，2-轻微划痕，3-中度划痕，4-明显划痕，5-严重划痕。上述实验分别在室温以及通过金属芯材的内部空腔将样品加热至60±2℃后进行测试，结果如表一所示。
耐磨性能测试：采用平板摩擦轮实验法，将样品固定旋转台上，旋转台上设有位置固定的橡胶轮，当旋转台转动时橡胶轮会对样品进行摩擦。具体地，测试时负重为1kg，转速为72转/min，在5000转后分析样品的质量保留率来比对耐磨性能。结果如表二所示。
表一
Figure dest_path_image002
表中的斜杠“/”前后的数据分别表示在室温和60℃温度下测得的数据，例如实施例4的10N这一栏的数据中，1/2代表在室温下耐刮性能测试结果为无刮痕，在60℃下测得的结果为轻微刮痕。从表中结果可看出，在常温下实施例1~5包覆层的耐刮性能均与对比例2中由离子聚合树脂制得的包覆层相当，且相较于对比例1的结果具有明显的优势，说明本发明在聚乙烯中添加离子聚合树脂，能显著提升产品的耐磨性能；在60℃下，对比例2出现了明显的耐刮性能下降，而实施例1~5中除了实施例4，均保持了较好的稳定性，因此本发明的包覆层相较于单独的离子聚合树脂包覆层具有更强的热稳定性。
表二
Figure dest_path_image003
通过表二我们可以看出，实施例1~5与对比例2的质量保留率差距细微，因此耐磨性能基本在同一水平，实施例1~5与对比例1的耐磨性能有显著差异，实施例1~5明显优于对比例1。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。

Claims (10)

  1. 一种离子聚合物增强的木塑包覆型材，包括金属芯材和成型于金属芯材外周的包覆层，其特征在于：所述的包覆层包含聚烯烃树脂和离子聚合树脂，其中聚烯烃树脂的重量分数不低于60%，离子聚合树脂的重量分数为20%~30%。
  2. 根据权利要求1所述的一种离子聚合物增强的木塑包覆型材，其特征在于：还包括功能助剂，所述的功能助剂包括抗氧剂、光稳定剂和紫外线吸收剂。
  3. 根据权利要求1所述的一种离子聚合物增强的木塑包覆型材，其特征在于：所述的离子聚合树脂选自乙烯-甲基丙烯酸聚合物钠盐、乙烯-甲基丙烯酸聚合物锌盐中的一种或多种。
  4. 根据权利要求3所述的一种离子聚合物增强的木塑包覆型材，其特征在于：所述的聚烯烃树脂的软化温度不低于110℃。
  5. 根据权利要求4所述的一种离子聚合物增强的木塑包覆型材，其特征在于：所述的聚烯烃树脂选用高密度聚乙烯。
  6. 根据权利要求1所述的一种离子聚合物增强的木塑包覆型材，其特征在于：所述的包覆层的厚度为0.5~5.0mm。
  7. 根据权利要求1所述的一种离子聚合物增强的木塑包覆型材，其特征在于：所述的金属芯材为铝制芯材，表面具有氧化膜。
  8. 根据权利要求7所述的一种离子聚合物增强的木塑包覆型材，其特征在于：所述的金属芯材贴合的外表面上具有沿长度方向深度为0.03~1.0mm的沟槽。
  9. 根据权利要求1所述的一种离子聚合物增强的木塑包覆型材，其特征在于：所述的包覆层和金属芯材之间还具有中间层，所述的中间层为热熔胶层或具有自粘性的复合高分子层。
  10. 根据权利要求1所述的一种离子聚合物增强的木塑包覆型材，其特征在于：所述的具有自粘性的复合高分子层包括以下重量份的组分：不饱和羧酸改性聚烯烃树脂40~60、热塑型聚氨酯弹性体20~30、聚氨酯预聚体5~15、异氰酸酯1~5、无机填料5~10。
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