WO2017215575A1 - 一种自增强异型材及其制备方法和应用 - Google Patents

一种自增强异型材及其制备方法和应用 Download PDF

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Publication number
WO2017215575A1
WO2017215575A1 PCT/CN2017/087969 CN2017087969W WO2017215575A1 WO 2017215575 A1 WO2017215575 A1 WO 2017215575A1 CN 2017087969 W CN2017087969 W CN 2017087969W WO 2017215575 A1 WO2017215575 A1 WO 2017215575A1
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Prior art keywords
styrene
reinforced
profile
self
copolymer
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PCT/CN2017/087969
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English (en)
French (fr)
Inventor
何超雄
陈平绪
叶南飚
肖鹏
李玉虎
官焕祥
魏金刚
刘建中
刘波
Original Assignee
金发科技股份有限公司
广东金发科技有限公司
天津金发新材料有限公司
四川金发科技发展有限公司
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Publication of WO2017215575A1 publication Critical patent/WO2017215575A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C08L51/003—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 macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • 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
    • B32B2307/70—Other properties
    • B32B2307/72—Density
    • 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
    • B32B2479/00—Furniture
    • 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 the technical field of plastic profiles, in particular to a self-reinforced profile material and a preparation method and application thereof.
  • the main board of the wardrobe, cabinet, and desk uses melamine board, MDF or particle board.
  • the main board needs to be sawed according to different sizes during the manufacturing process, so the sawed part is bare.
  • the core of the board seriously affects the appearance of the product, so it is necessary to wrap the bare core part of the edging material.
  • the quality of the edging is also an important criterion for measuring the quality of the wardrobe.
  • the edging material also plays an important role in the deformation of the cabinet, so the edging material of the wardrobe also requires a certain strength, rigidity and the like.
  • aluminum alloy edging strips in the wardrobe, desk and other aspects.
  • aluminum alloy has the advantages of light material, high strength, good sealing performance, good corrosion resistance and small deformation during installation.
  • the aluminum alloy edging material also has the following shortcomings: the production of aluminum alloy edging material High energy consumption, poor thermal insulation, poor sound insulation, high material density, single color, and complicated process during installation.
  • Another object of the present invention is to provide a process for the preparation of the above self-reinforced profile.
  • a self-reinforcing profile comprising a core layer and a skin layer disposed outside the core layer, the skin layer being a thermoplastic resin profile, the core layer being a reinforced styryl alloy composition material, the parts by weight of which are as follows:
  • the reinforced styryl alloy composition material is in parts by weight, and comprises the following components:
  • the self-reinforced profiled material is tested according to the GB/T 10297 standard, and the test equipment is a Xiangtan Xiangke DRX-II thermal conductivity tester with a thermal conductivity of 0.20-0.30 W/mK.
  • the self-reinforcing profile is tested according to the ISO 2813 standard.
  • the test equipment is WG60G of Weifu Optoelectronics, and the gloss of the angle tested by 60° is greater than 90°.
  • the thermoplastic resin profile is a polyvinyl chloride PVC profile, an acrylonitrile-styrene-acrylate copolymer ASA profile, an acrylonitrile-ethylene propylene diene monomer-styrene copolymer AES profile, acrylonitrile-butadiene-styrene Copolymer ABS profile, styrene-acrylonitrile copolymer AS profile or acrylonitrile-silicone rubber-styrene copolymer SAS profile.
  • the melt flow rate of the styrene-based copolymer at 220 ° C under a load of 10 kg is from 1 g/10 min to 80 g/10 min, preferably from 5 g/10 min to 20 g/10 min, more preferably from 10 g/10 min to 15 g/10 min.
  • the styrene-based copolymer is selected from the group consisting of styrene-acrylonitrile copolymer AS, styrene-butadiene-acrylonitrile copolymer ABS, methyl methacrylate-styrene-butadiene-acrylonitrile copolymer MABS, Acrylonitrile-styrene-acrylate copolymer ASA, acrylonitrile-ethylene propylene diene monomer-styrene copolymer AES, acrylonitrile-silicone rubber-styrene copolymer SAS, methyl methacrylate-styrene copolymer One or several of the MS.
  • the reinforcing agent is selected from one or more of glass fiber, carbon fiber, basalt fiber, talc powder, wollastonite, whisker, glass microbead, preferably glass fiber, and the glass fiber has a diameter of 6-20 ⁇ m.
  • the styrene-based alloy composition material of the present invention further comprises, by weight, 0.5-10 parts of a compatibilizing agent, 0.1-5.0 parts of a coupling agent, and 0.1-5.0 parts of a processing aid.
  • the compatibilizer is selected from the group consisting of styrene-butadiene-acrylonitrile-maleic anhydride copolymer, styrene-butadiene-acrylonitrile-glycidyl methacrylate copolymer, styrene-acrylonitrile-Malay One or more of an acid anhydride copolymer, a styrene-acrylonitrile-glycidyl methacrylate copolymer, an acrylate resin, a methyl methacrylate-styrene copolymer resin, a styrene-maleic anhydride copolymer ;
  • the coupling agent is selected from one or more of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a zirconate coupling agent; the processing aid includes a lubricant or an anti- One or several of the oxygen agents.
  • the lubricant is selected from the group consisting of a fatty acid salt, a fatty acid amide, pentaerythritol stearate, a solid paraffin, a liquid paraffin, a stearate, a silicone, an N, N'-ethylene bis stearic acid amide or Several.
  • the antioxidant is tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] quaternary tetraol and tris[2,4-di-tert-butylphenyl]phosphite a mixture of esters.
  • the method for preparing a self-reinforced profile according to the present invention comprises the following steps:
  • Co-extrusion preparation is carried out by using the main machine and the auxiliary machine vertically designed by the main machine.
  • the main machine is used for extruding and reinforced styrene-based alloy composition materials
  • the auxiliary machine is used for extruding thermoplastic resin profiles, main machine and auxiliary machine. Simultaneous extrusion, cooling and shaping after forming to obtain a self-reinforced profile.
  • the mixing temperature is 20-50 ° C, the rotation speed is 100-800 rpm, and the mixing time is 2-5 minutes; the temperature of each section of the twin-screw extruder is 200-240 ° C, double The screw extruder has a length to diameter ratio of 36-48 and a screw speed of 300-500 rpm.
  • the main machine is a single-screw extruder, and the temperature of each section of the single-screw extruder is 160-215 ° C;
  • the auxiliary machine is a twin-screw extruder, and the temperature of each section of the twin-screw extruder is 150-200 ° C.
  • the main machine is a single-screw extruder
  • the head temperature is 175-195 ° C
  • the temperature of the fuselage one zone is 160-165 ° C
  • the temperature of the fuselage two zone is 160-175 ° C
  • the temperature of the fuselage three zones is 175-185 ° C
  • the temperature of the four fuselage of the fuselage is 175-185 ° C
  • the screw speed is 18-22 rpm
  • the auxiliary machine is a twin-screw extruder
  • the head temperature is 175-195 ° C
  • the temperature of the fuselage area is 155 -165 ° C
  • the fuselage two zone temperature is 165-175 ° C
  • the fuselage three zone temperature is 175-185 ° C
  • the fuselage four zone temperature is 175-185 ° C
  • the screw speed is 18-22rpm.
  • the invention also provides the use of the above self-reinforced profile in a desk edging, a wardrobe edging or a cabinet edging.
  • the present invention has the following advantages:
  • the invention replaces the aluminum alloy edging material by using a self-reinforced profile prepared by co-extruding a thermoplastic resin profile and a reinforced styrene-based alloy composition material, wherein the skin layer is a thermoplastic resin profile, which provides an excellent appearance effect, and the core layer has high rigidity. Reinforced styrene-based alloy composition materials that provide the strength, rigidity, and the like properties required for the edging material.
  • the self-reinforced profile of the invention has excellent thermal insulation performance, low density and excellent appearance, and the co-extrusion process is simple, and can be applied to the wardrobe edging, the desk edging, the cabinet edging material, and has better. Application prospects.
  • the raw materials used are as follows:
  • AES profile AES HW500E, Kumho, South Korea;
  • ABS profile ABS AG10NP, Taihua
  • ASA styrene-acrylonitrile-acrylate copolymer ASA PW-997, Taiwan Chi Mei; melt flow rate 5g/10min;
  • PBT resin PBT 1200-211M, Changchun, Taiwan;
  • the raw materials of the styrene-based alloy composition are added to the high-mixing machine to be uniformly mixed according to the ratio of Table 1; the above mixed material is fed into the twin-screw extruder, wherein the reinforcing agent passes through the first exhaust gas.
  • the pore or side feed system is added, melt extrusion granulation, i.e., the styrene based alloy composition material is reinforced.
  • the mixing temperature is 20-50 ° C
  • the rotation speed is 100-800 rpm
  • the mixing time is 2-5 minutes
  • the temperature of each section of the twin-screw extruder is 200-240 ° C
  • the twin-screw extruder The aspect ratio is 36-48 and the screw speed is 300-500 rpm.
  • the obtained reinforced styryl alloy composition material was dried in a blast oven at 90 ° C for 4 hours, and then sampled by a Ningbo Haitian injection molding machine BS650-III, and the injection temperature was set to 230-240-240-250 ° C.
  • the properties of the physical property test results of the obtained reinforced styryl alloy composition materials are shown in Table 1.
  • the tensile strength was tested according to the ISO 527 standard.
  • the sample was a type I specimen and the test equipment was a tensile tester Z020 from Zwick, Germany.
  • the bending strength was tested according to the ISO 178 standard, the sample size was 4 mm ⁇ 10 mm ⁇ 80 mm, and the test equipment was the bending test machine Z005 of Zwick Roell, Germany.
  • the IZOD notched impact strength was tested in accordance with the ISO 180 standard, and the sample size was 4 mm ⁇ 10 mm ⁇ 80 mm, and the notch depth was 2 mm.
  • the test equipment is the impact tester HIT5.5P from Zwick Roell, Germany.
  • the density was tested according to the ISO 1183 standard, and the test equipment was a digital liquid density meter MD-300S of Japan ALFA MIRAGE.
  • the gloss was tested according to the ISO 2813 standard.
  • the test equipment was WG60G from Weifu Optoelectronics and the angle was tested at 60°.
  • the thermal conductivity is tested according to GB/T 10297 standard.
  • the test equipment is Xiangtan Xiangke DRX-II thermal conductivity tester.
  • the reinforced styrene-based alloy composition material of the present invention has excellent mechanical properties such as strength and rigidity as the core layer, and has a low density of only about half of the aluminum alloy material.
  • the main machine and the auxiliary machine vertically designed by the main machine are used for co-extrusion preparation.
  • the main machine is used for extruding and strengthening the styrene-based alloy composition material
  • the auxiliary machine is used for extruding the thermoplastic resin profile, and the main machine and the auxiliary machine are simultaneously Extrusion, cooling and shaping after forming to obtain self-reinforced profile;
  • the main machine is a single-screw extruder
  • the head temperature is 175-195 ° C
  • the temperature of the fuselage one zone is 160-165 ° C
  • the temperature of the fuselage two zone is 160-175 ° C
  • the temperature of the fuselage three zones is 175.
  • the temperature of the fuselage four zones is 175-185 ° C, the screw speed is 18-22 rpm; the auxiliary machine is a twin-screw extruder, the head temperature is 175-195 ° C, the temperature of the fuselage one zone is 155- At 165 ° C, the temperature in the second zone of the fuselage is 165-175 ° C, the temperature in the three zones of the fuselage is 175-185 ° C, the temperature in the four zones of the fuselage is 175-185 ° C, and the screw speed is 18-22 rpm.
  • the present invention utilizes a thermoplastic resin profile as a skin layer, and its glossiness is above 90°, which is significantly improved compared with the glossiness of the aluminum alloy (about 70°), and can provide an excellent appearance effect and high rigidity to enhance benzene.
  • the vinyl composition material serves as a core layer, which can provide the strength, rigidity and the like properties required for the edging material, and the self-reinforced profile obtained by co-extrusion has a thermal conductivity of 0.20-0.30 W/mK, which is significantly low.
  • the thermal conductivity of the aluminum alloy (about 200 W/mK) therefore, the self-reinforced profile of the present invention has a lower thermal conductivity and is more advantageous in terms of thermal insulation and appearance.
  • the profile prepared by the invention can replace the aluminum alloy edging material, and has good application prospects in the desk, the cabinet and the wardrobe edging.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明公开了一种自增强异型材及其制备方法和应用，包括芯层以及设置在芯层外的皮层，皮层为热塑性树脂型材，芯层为增强苯乙烯基合金组合物材料，增强苯乙烯基合金组合物材料100份，热塑性树脂型材5-100份。其制备方法是先制备增强苯乙烯基合金组合物材料，然后采用主机与该主机垂直设计的辅机进行共挤，主机用于挤出增强苯乙烯基合金组合物材料，辅机用于挤出热塑性树脂型材，主机、辅机同时挤出，成型后冷却定型得到自增强异型材。本发明的自增强异型材具有优异的保温隔热性能，较低的密度和优异的外观，且共挤工艺简单，可应用于衣柜、橱柜、办公桌包边材料，具有较好的应用前景。

Description

一种自增强异型材及其制备方法和应用 技术领域
本发明涉及塑料型材技术领域，具体涉及一种自增强异型材及其制备方法和应用。
背景技术
衣柜，橱柜，办公桌的主体板材使用三聚氰胺板，密度板或刨花板，但由于不同型号产品的尺寸不一样，在制作过程中都需要按照不同尺寸把主体板材锯开，那么锯开的部分就是裸露的板芯，严重影响产品的外观，所以就需要包边材料把裸露的板芯部分包住，包边的好坏也是衡量衣柜质量的一个重要标准。另外，包边材料还对柜体的变形起着重要的作用，所以衣柜的包边材料还需要一定的强度，刚性等要求。
目前，主要是采用铝合金包边条应用在衣柜，办公桌等方面。与钢材相比，铝合金具有材料轻，强度高，密闭性能好，耐腐蚀效果好，安装时变形小等优点，但是铝合金包边材料也存在以下不足之处：铝合金包边材料的生产能耗高，保温隔热、隔音效果差，材料密度大，颜色单一，而且在安装时，工艺复杂。
发明内容
为了克服上述现有技术的不足，本发明的目的在于提供一种自增强异型材，该自增强异型材具有优异的保温隔热性能，较低的密度和优异的外观等优点，可作为包边材料代替铝合金应用于衣柜、办公桌包边。
本发明的另一个目的是在于提供上述自增强异型材的制备方法。
本发明通过下述技术方案来实现：
一种自增强异型材，包括芯层以及设置在芯层外的皮层，所述皮层为热塑性树脂型材，所述芯层为增强苯乙烯基合金组合物材料，其重量份数如下：
增强苯乙烯基合金组合物材料  100份
热塑性树脂型材  5-100份；
其中，所述增强苯乙烯基合金组合物材料按重量份数计，包括如下组分：
苯乙烯基共聚物  22-55份；
PBT或PMMA  5-30份；
增强剂  30-65份。
所述自增强异型材的按GB/T 10297标准进行测试，测试设备为湘潭湘科DRX-Ⅱ导热系数测试仪，热导率为0.20-0.30W/mK。
所述自增强异型材按ISO 2813标准进行测试，测试设备为威福光电的WG60G，角度按60°进行测试的光泽度大于90°
所述热塑性树脂型材为聚氯乙烯PVC型材、丙烯腈-苯乙烯-丙烯酸酯共聚物ASA型材、丙烯腈-三元乙丙橡胶-苯乙烯共聚物AES型材、丙烯腈-丁二烯-苯乙烯共聚物ABS型材、苯乙烯-丙烯腈共聚物AS型材或丙烯腈-硅丙橡胶-苯乙烯共聚物SAS型材。
所述苯乙烯基共聚物在220℃，10kg载荷条件下的熔体流动速率为1g/10min-80g/10min，优选为5g/10min-20g/10min，更优选为10g/10min-15g/10min。
所述苯乙烯基共聚物选自苯乙烯-丙烯腈共聚物AS、苯乙烯-丁二烯-丙烯腈共聚物ABS、甲基丙烯酸甲酯-苯乙烯-丁二烯-丙烯腈共聚物MABS、丙烯腈-苯乙烯-丙烯酸酯共聚物ASA、丙烯腈-三元乙丙橡胶-苯乙烯共聚物AES、丙烯腈-硅丙橡胶-苯乙烯共聚物SAS、甲基丙烯酸甲酯-苯乙烯共聚物MS中的一种或几种。
所述增强剂选自玻璃纤维、碳纤维，玄武岩纤维、滑石粉、硅灰石、晶须、玻璃微珠中的一种或几种，优选玻璃纤维，所述玻璃纤维的直径为6-20μm。
本发明所述增强苯乙烯基合金组合物材料，按重量份数计，还包括相容剂0.5-10份、偶联剂0.1-5.0份、加工助剂0.1-5.0份。
所述相容剂选自苯乙烯-丁二烯-丙烯腈-马来酸酐共聚物、苯乙烯-丁二烯-丙烯腈-甲基丙烯酸缩水甘油酯共聚物、苯乙烯-丙烯腈-马来酸酐共聚物、苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯共聚物、丙烯酸酯树脂、甲基丙烯酸甲酯-苯乙烯共聚物树脂、苯乙烯-马来酸酐共聚物中的一种或几种；
所述偶联剂选自硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂、锆酸酯偶联剂中的一种或几种；所述加工助剂包括润滑剂或抗氧剂中的一种或几种。
所述润滑剂选自脂肪酸盐、脂肪酸酰胺、季戊四醇硬脂酸酯、固体石蜡、液体石蜡、硬脂酸盐、硅酮、N,N'-乙撑双硬脂酸酰胺中的一种或几种。
所述抗氧剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季茂四醇脂和三[2,4-二叔丁基苯基]亚磷酸酯的混合物。
本发明所述的自增强异型材的制备方法，包括以下步骤：
(1)增强苯乙烯基合金组合物材料的制备：除增强剂外，按配比将增强苯乙烯基合金组合物的各原料加入高混机中混合均匀；将上述混合物料送入双螺杆挤出机中，其中增强剂通过第一排气孔或侧喂系统加入，熔融挤出造粒，即得增强苯乙烯基合金组合物材料；
(2)共挤成型：采用主机与该主机垂直设计的辅机进行共挤制备，主机用于挤出增强苯乙烯基合金组合物材料，辅机用于挤出热塑性树脂型材，主机、辅机同时挤出，成型后冷却定型得到自增强异型材。
步骤(1)中，所述混合温度为20-50℃，转速为100-800转/分钟，混合时间为2-5分钟；所述双螺杆挤出机各段温度为200-240℃，双螺杆挤出机的长径比为36-48，螺杆转速为300-500转/分钟。
步骤(2)中，所述主机为单螺杆挤出机，单螺杆挤出机各段温度为160-215℃；所述辅机为双螺杆挤出机，双螺杆挤出机各段温度为150-200℃。
优选的，所述主机为单螺杆挤出机，机头温度为175-195℃，机身一区温度为160-165℃，机身二区温度为160-175℃，机身三区温度为175-185℃，机身四区温度为175-185℃，螺杆转速为18-22rpm；所述辅机为双螺杆挤出机，机头温度为175-195℃，机身一区温度为155-165℃，机身二区温度为165-175℃，机身三区温度为175-185℃，机身四区温度为175-185℃，螺杆转速为18-22rpm。
本发明还提供了上述自增强异型材在办公桌包边、衣柜包边或橱柜包边中的应用。
相对于现有技术，本发明具有如下优点：
本发明利用热塑性树脂型材和增强苯乙烯基合金组合物材料共挤制备的自增强异型材来代替铝合金包边材料，其中皮层为热塑性树脂型材，其提供优异的外观效果，芯层为高刚性增强苯乙烯基合金组合物材料，其提供包边材料所需要的强度，刚性等使用性能。本发明的自增强异型材具有优异的保温隔热性能，较低的密度和优异的外观，且共挤工艺简单，可应用于衣柜包边、办公桌包边、橱柜包边材料，具有较好的应用前景。
具体实施方式
为更好地理解本发明，下面通过实施例对本发明作进一步的说明，需要说明的是实施例并不构成对本发明保护范围的限制。
所用原材料如下：
PVC型材，PVC-EX23，金发科技自制；
ASA型材，ASA PW-997，台湾奇美；
AES型材，AES HW500E，韩国锦湖；
AS型材，SAN PN-137H，台湾奇美；
ABS型材，ABS AG10NP，台化；
SAS型材，DIALAC E259B，日本UMG；
AS苯乙烯-丙烯腈树脂，SAN PN-137H，台湾奇美，熔体流动速率12g/10min；
AS苯乙烯-丙烯腈树脂，SAN NF-5台化定制；熔体流动速率5g/10min；
AS苯乙烯-丙烯腈树脂，SAN NF2200，台化，熔体流动速率35g/10min；
ASA苯乙烯-丙烯腈-丙烯酸酯共聚物，ASA PW-997，台湾奇美；熔体流动速率5g/10min；
PBT树脂，PBT 1200-211M，台湾长春；
PMMA树脂，PMMA CM-205，台湾奇美；
玻璃纤维，ECS13-4.5-534A，桐乡巨石，直径为13μm。
马来酸酐苯乙烯共聚物，SMA-700，上海华雯公司；
偶联剂，KH560，沸点化工；
润滑剂，N,N'-亚乙基双硬脂酰胺，上海宁成；
抗氧剂，168和1010，瑞士汽巴精化公司。
增强苯乙烯基合金组合物材料的制备：
除增强剂外，按表1配比将增强苯乙烯基合金组合物的各原料加入高混机中混合均匀；将上述混合物料送入双螺杆挤出机中，其中增强剂通过第一排气孔或侧喂系统加入，熔融挤出造粒，即得增强苯乙烯基合金组合物材料。其中，所述混合温度为20-50℃，转速为100-800转/分钟，混合时间为2-5分钟；所述双螺杆挤出机各段温度为200-240℃，双螺杆挤出机的长径比为36-48，螺杆转速为300-500转/分钟。
将得到的增强苯乙烯基合金组合物材料在90℃的鼓风烘箱中干燥4小时后，用宁波海天注射成型机BS650-Ⅲ制样，注塑温度设定为230-240-240-250℃，所得增强苯乙烯基合金组合物材料的物性测试结果性能见表1。
拉伸强度按ISO 527标准进行测试，试样为Ⅰ型试样，测试设备为德国Zwick公司的拉伸试验机Z020。
弯曲强度按ISO 178标准进行测试，试样尺寸为4mm×10mm×80mm，测试设备为德国Zwick Roell公司的弯曲试验机Z005。
IZOD缺口冲击强度按照ISO 180标准进行测试，试样尺寸为4mm×10mm×80mm，缺口深度为2mm。测试设备为德国Zwick Roell公司的冲击试验机HIT5.5P。
密度按ISO 1183标准进行测试，测试设备为日本ALFA MIRAGE的数显液体密度计MD-300S。
光泽度按ISO 2813标准进行测试，测试设备为威福光电的WG60G，角度按60°进行测试。
热导率按GB/T 10297标准进行测试，测试设备为湘潭湘科DRX-Ⅱ导热系数测试仪。
表1增强苯乙烯基合金组合物各组分配比(重量份)及物性
Figure PCTCN2017087969-appb-000001
从表1可以看出，本发明的增强苯乙烯基合金组合物材料作为芯层，具有优异的强度、刚性等力学性能，且密度较低，只有铝合金材料的一半左右。
自增强异型材的制备：
采用主机与该主机垂直设计的辅机进行共挤制备，按表2配比，主机用于挤出增强苯乙烯基合金组合物材料，辅机用于挤出热塑性树脂型材，主机、辅机同时挤出，成型后冷却定型得到自增强异型材；
其中，所述主机为单螺杆挤出机，机头温度为175-195℃，机身一区温度为160-165℃，机身二区温度为160-175℃，机身三区温度为175-185℃，机身四区温度为175-185℃，螺杆转速为18-22rpm；所述辅机为双螺杆挤出机，机头温度为175-195℃，机身一区温度为155-165℃，机身二区温度为165-175℃，机身三区温度为175-185℃，机身四区温度为175-185℃，螺杆转速为18-22rpm。
表2自增强异型材的各组分配比及性能结果(重量份)
Figure PCTCN2017087969-appb-000002
由表2可以看出，本发明利用热塑性树脂型材作为皮层，其光泽度达到90°以上，较铝合金的光泽度(70°左右)有明显提高，可提供优异的外观效果，高刚性增强苯乙烯基组合物材料作为芯层，其可提供包边材料所需要的强度，刚性等使用性能，此外二者共挤制备得到的自增强异型材的导热率为0.20-0.30W/mK，显著低于铝合金的热导率(200W/mK左右)，因此，本发明的自增强型材具有更低的热导率，在保温隔热，外观效果方面更加具有优势。本发明制备的异型材可代替铝合金包边材料，在办公桌、橱柜、衣柜包边等具有较好的应用前景。

Claims (13)

  1. 一种自增强异型材，其特征在于，包括芯层以及设置在芯层外的皮层，所述皮层为热塑性树脂型材，所述芯层为增强苯乙烯基合金组合物材料，其重量份数如下：
    增强苯乙烯基组合物材料  100份
    热塑性树脂型材          5-100份；
    其中，所述增强苯乙烯基合金组合物材料按重量份数计，包括如下组分：
    苯乙烯基共聚物  20-55份；
    PBT或PMMA       5-30份；
    增强剂          30-65份。
  2. 根据权利要求1所述的自增强异型材，其特征在于，所述自增强异型材的按GB/T 10297标准进行测试，测试设备为湘潭湘科DRX-Ⅱ导热系数测试仪，热导率为0.20-0.30W/mK。
  3. 根据权利要求1所述的自增强异型材，其特征在于，所述自增强异型材按ISO 2813标准进行测试，测试设备为威福光电的WG60G，角度按60°进行测试的光泽度大于90°
    根据权利要求1所述的自增强异型材，其特征在于，所述热塑性树脂型材为聚氯乙烯PVC型材、丙烯腈-苯乙烯-丙烯酸酯共聚物ASA型材、丙烯腈-三元乙丙橡胶-苯乙烯共聚物AES型材、丙烯腈-丁二烯-苯乙烯共聚物ABS型材、苯乙烯-丙烯腈共聚物AS型材或丙烯腈-硅丙橡胶-苯乙烯共聚物SAS型材。
  4. 根据权利要求1所述的自增强异型材，其特征在于，所述苯乙烯基共聚物在220℃，10kg载荷条件下的熔体流动速率为1g/10min-80g/10min，优选为5g/10min-20g/10min，更优选为10g/10min-15g/10min。
  5. 根据权利要求5所述的自增强异型材，其特征在于，所述苯乙烯基共聚物选自苯乙烯-丙烯腈共聚物AS、丙烯腈-丁二烯-苯乙烯共聚物ABS、甲基丙烯酸甲酯-丙烯腈-丁二烯-苯乙烯共聚物MABS、丙烯腈-苯乙烯-丙烯酸酯共聚物ASA、丙烯腈-三元乙丙橡胶-苯乙烯共聚物AES、丙烯腈-硅丙橡胶-苯乙烯共聚物SAS、甲基丙烯酸甲酯-苯乙烯共聚物MS中的一种或几种。
  6. 根据权利要求1所述的自增强异型材，其特征在于，所述增强剂选自玻璃纤维、碳纤维、玄武岩纤维、滑石粉、硅灰石、晶须、玻璃微珠中的一种或几种，优选玻璃纤维。
  7. 根据权利要求6所述的自增强异型材，其特征在于，所述玻璃纤维的直径为6-20μm。
  8. 根据权利要求1所述的自增强异型材，其特征在于，按重量份数计，所述增强苯乙烯基合金组合物材料还包括相容剂0.5-10份、偶联剂0.1-5.0份、加工助剂0.1-5.0份。
  9. 根据权利要求8所述的自增强异型材，其特征在于，所述相容剂选自苯乙烯-丁二烯-丙烯 腈-马来酸酐共聚物、苯乙烯-丁二烯-丙烯腈-甲基丙烯酸缩水甘油酯共聚物、苯乙烯-丙烯腈-马来酸酐共聚物、苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯共聚物、丙烯酸酯树脂、甲基丙烯酸甲酯-苯乙烯共聚物、苯乙烯-马来酸酐共聚物中的一种或几种；所述偶联剂选自硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂、锆酸酯偶联剂中的一种或几种；所述加工助剂包括润滑剂或抗氧剂中的一种或几种。
  10. 根据权利要求1-9任一项所述的自增强异型材的制备方法，其特征在于，包括以下步骤：
    (1)增强苯乙烯基合金组合物的制备：除增强剂外，按配比将增强苯乙烯基合金组合物材料的各原料加入高混机中混合均匀；将上述混合物料送入双螺杆挤出机中，其中增强剂通过第一排气孔或侧喂系统加入，熔融挤出造粒，即得增强苯乙烯基合金组合物材料；
    (2)共挤成型：采用主机与该主机垂直设计的辅机进行共挤制备，主机用于挤出增强苯乙烯基合金组合物材料，辅机用于挤出热塑性树脂型材，主机、辅机同时挤出，成型后冷却定型得到自增强异型材。
  11. 根据权利要求10所述的增强异型材的制备方法，其特征在于，步骤(1)中，所述混合温度为20-50℃，转速为100-800转/分钟，混合时间为2-5分钟；所述双螺杆挤出机各段温度为200-240℃，双螺杆挤出机的长径比为36-48，螺杆转速为300-500转/分钟。
  12. 根据权利要求10所述的自增强异型材的制备方法，其特征在于，步骤(2)中，所述主机为单螺杆挤出机，单螺杆挤出机各段温度为160-215℃，所述辅机为双螺杆挤出机，双螺杆挤出机各段温度为150-200℃；优选的，所述主机为单螺杆挤出机，机头温度为175-195℃，机身一区温度为160-165℃，机身二区温度为160-175℃，机身三区温度为175-185℃，机身四区温度为175-185℃，螺杆转速为18-22rpm；所述辅机为双螺杆挤出机，机头温度为175-195℃，机身一区温度为155-165℃，机身二区温度为165-175℃，机身三区温度为175-185℃，机身四区温度为175-185℃，螺杆转速为18-22rpm。
  13. 权利要求1-9任一项所述的自增强异型材在办公桌包边、衣柜包边或橱柜包边中的应用。
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