WO2017215577A1 - 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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WO2017215577A1
WO2017215577A1 PCT/CN2017/087971 CN2017087971W WO2017215577A1 WO 2017215577 A1 WO2017215577 A1 WO 2017215577A1 CN 2017087971 W CN2017087971 W CN 2017087971W WO 2017215577 A1 WO2017215577 A1 WO 2017215577A1
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styrene
reinforced
self
temperature
based copolymer
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PCT/CN2017/087971
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English (en)
French (fr)
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李玉虎
陈平绪
叶南飚
肖鹏
官焕祥
魏金刚
陶四平
刘建中
何超雄
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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 WO2017215577A1 publication Critical patent/WO2017215577A1/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
    • 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
    • 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
    • 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
    • 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
    • C08L35/00—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 a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • 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
    • 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
    • C08L51/04—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 rubbers
    • 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
    • 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 the technical field of plastic profiles, in particular to a self-reinforced profile material and a preparation method and application thereof.
  • PVC profiles are widely used in building doors and windows, wood-plastic flooring, furniture panels, etc.
  • PVC materials themselves have low rigidity and poor resistance to deformation
  • steel linings are required when used as door and window materials.
  • the traditional metal steel lining can effectively improve the deformation resistance of PVC profiles
  • the steel lining has the disadvantages of high production energy consumption, poor corrosion resistance, thermal insulation, poor sound insulation, high material density and low welding angle strength.
  • the installer needs to fix the steel lining and the steel profile at the construction site, and the assembly process of the door and window installation is added. Based on this situation, related companies have introduced plastic-based materials to replace traditional steel.
  • the plastic itself has the advantages of good heat insulation, corrosion resistance and light weight.
  • the unmodified plastic rigidity is too far from the steel to meet the deformation resistance requirements of the profile.
  • glass fiber reinforced means can greatly increase the rigidity of the plastic, and provides a solution for this purpose, such as CN 102817529 B, CN 203066745 U, CN 202227876 U, CN 103075071 B and the like, a glass fiber reinforced PBT is disclosed. Any one of carbon fiber reinforced PBT and modified PBT is a reinforcing strip, and a self-reinforced profile material based on PVC material is used instead of the conventional steel lining reinforcing profile.
  • CN 103147664 B discloses a profiled co-extrusion die, which solves the problem of paste and compatibility of PVC by providing a heat insulation layer and an internal rib card groove inside the mold, although the above problems can be partially solved, but the mold cost greatly increase.
  • 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 profile and a reinforced liner disposed within a profile cavity, the profile being an ASA, SAS, ABS, AS, and/or AES profile, the reinforced liner being a reinforced styrene-based copolymer Composition material, the parts by weight such as under:
  • ASA ASA, SAS, ABS, AS and / or AES profiles 100 copies
  • the reinforcing styrene-based copolymer composition material is in parts by weight, and comprises the following components:
  • the adhesion of the ASA, SAS, ABS, AS, and/or AES profiles to the reinforced styrene-based copolymer composition material is 700-1000 N, and the adhesion test uses the following method: ASA, SAS, ABS, AS and / or AES profiles are injection molded into 2mm ⁇ 10mm ⁇ 100mm splines, then ASA, SAS, ABS, AS and / or AES splines are placed in a 4mm ⁇ 10mm ⁇ 100mm mold for overmolding reinforced styryl
  • the copolymer composition material was obtained as an adherend of ASA, SAS, ABS, AS and/or AES profiles and reinforced styrene-based copolymer composition materials, and finally the bond strength was tested by a Zwick tensile tester. .
  • the styrene-based copolymer composition material has an extrusion temperature interval of 160 to 215 °C.
  • the styrene-based copolymer resin has a melt flow rate of from 1 g/10 min to 80 g/10 min at 220 ° C under a load of 10 kg, which is more easily extruded, preferably from 5 g/10 min to 20 g/10 min, more preferably 10 g/ 10min-15g/10min.
  • 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 copolymer 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, One or more of stearate, silicone, N, N'-ethylene bis stearic acid amide.
  • 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:
  • each raw material of the styrene-based copolymer composition material is added to a high-mixer to be uniformly mixed according to the ratio; and the above mixture is fed into the double In a screw extruder, wherein the reinforcing agent is added through a first vent hole or a side feeding system, and melt extrusion granulation, that is, the styrene-based copolymer composition material is reinforced;
  • Co-extrusion preparation is carried out by using a main machine and a vertical machine designed vertically by the main machine.
  • the main machine is used for extruding ASA, SAS, ABS, AS and/or AES profiles
  • the auxiliary machine is used for extrusion-reinforced styrene-based
  • the copolymer composition material, the main machine and the auxiliary machine are simultaneously extruded, and the shape is cooled and shaped 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 twin-screw extruder, and the temperature of each section of the twin-screw extruder is 150-200 ° C;
  • the auxiliary machine is a single-screw extruder, and the temperature of each section of the single-screw extruder is 160-215 ° C.
  • the main machine is a twin-screw extruder
  • the head temperature is 175-195 ° C
  • the temperature of the fuselage one zone is 155-165 ° C
  • the temperature of the fuselage two zone is 165-175 ° 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 single screw extruder
  • the head temperature is 175-195 ° C
  • the temperature of the fuselage area is 160 -165 ° C
  • the fuselage two zone temperature is 160-175 ° 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 building doors and windows, wood-plastic flooring or furniture panels.
  • the present invention has the following advantages:
  • the reinforcing liner used in the present invention is a reinforced styrene-based copolymer composition material which is an amorphous material, and the profile is made of ASA, SAS, ABS, AS and/or AES profiles, due to the reinforcing lining material and profile.
  • the reinforced lining material used in the invention can be stably extruded in the temperature range of 160-215 ° C, has a wider processing window, and the lower molding temperature also greatly reduces energy consumption and is more environmentally friendly;
  • the reinforced lining material used in the present invention has higher melt strength and more excellent processing and molding properties, thereby greatly improving the stability of molding.
  • the reinforced lining material of the invention has lower density, and the self-reinforced co-extruded profile is lighter in weight, conforming to the light weight and low carbon environmental protection trend advocated by the state.
  • Figure 1 is a photograph of the adherence of the ASA, SAS, ABS, AS, and/or AES profiles to the reinforced liner during the adhesion test.
  • the raw materials used are as follows:
  • AES profile AES HW500E, Kumho, South Korea;
  • ABS profile ABS AG10NP, Taihua
  • ABS resin ABS AG10NP, Taiwan; melt flow rate 6g/10min;
  • PBT resin PBT 1200-211M, Changchun, Taiwan;
  • ASA styrene-acrylonitrile-acrylate copolymer ASA PW-997, Taiwan Chi Mei; melt flow rate 5g/10min;
  • the raw materials of the styrene-based copolymer composition material are added to the high-mixer to be uniformly mixed according to the ratio of Table 1; the above mixture is fed into a twin-screw extruder, wherein the reinforcing agent passes through the first A vent or side feed system is added, melt extrusion granulation, to enhance the styrene based copolymer composition material.
  • 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 styrene-based copolymer composition material was dried in a blast oven at 90 ° C for 4 hours, and then sampled by 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 styrene-based copolymer 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.
  • Adhesion test ASA, SAS, ABS, AS and/or AES resin are now injection molded into 2mm ⁇ 10mm ⁇ 100mm splines, then ASA, SAS, ABS, AS and / or AES splines are placed in 4mm ⁇
  • the lining material was overmolded in a 10 mm x 100 mm mold to obtain an adherend of the ASA, SAS, ABS, AS, and/or AES profiles and the reinforced liner material, as shown in FIG.
  • Zwick's tensile testing machine was used to test the bond strength to characterize the bond between the reinforced liner and the ASA, SAS, ABS, AS and/or AES profiles.
  • Table 1 reinforced lining each group distribution ratio (parts by weight) and physical properties
  • the reinforcing lining material of the present invention has more excellent mechanical properties in the case of the same glass fiber content, and in particular, the rigidity is better than that of the reinforced PBT material, and the advantage in plastic-forming steel is more obvious.
  • the reinforced lining material of the invention has lower density, and the prepared self-reinforced co-extruded profile has a lighter weight, which is in line with the nationally advocated lightweight and low carbon environmental protection trend.
  • the main machine is co-extruded with the auxiliary machine vertically designed by the main machine.
  • the main machine is used for extruding ASA, SAS, ABS, AS and/or AES profiles
  • the auxiliary machine is used for extruding the reinforcing lining material.
  • the main machine and the auxiliary machine are simultaneously extruded, and the shape is cooled and shaped to obtain a self-reinforced profile;
  • the main machine is a twin-screw extruder
  • the head temperature is 175-195 ° C
  • the temperature of the fuselage one zone is 155-165 ° C
  • the temperature of the fuselage two zone is 165-175 ° C
  • the temperature of the fuselage three zones is 175 -185 ° C
  • the temperature of the fuselage four zones is 175-185 ° C
  • the screw speed is 18-22 rpm
  • the auxiliary machine is a single screw extruder
  • the head temperature is 175-195 ° C
  • the temperature of the fuselage one zone is 160- At 165 ° C
  • the temperature in the second zone of the fuselage is 160-175 ° 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
  • the screw speed is 18-22 rpm.
  • the adhesion of the reinforced PBT material to the ASA, SAS, ABS, AS and/or AES profiles is only about 150 N, while the reinforced lining of the present invention is used with ASA, SAS, ABS, AS and / or AES profiles
  • the adhesion is increased to about 700-1000N, which is 5-6 times that of the reinforced PBT material, which shows that the reinforced liner of the present invention has better compatibility with ASA, SAS, ABS, AS or AES profiles, in the profile Peeling does not occur during transportation, installation and use.
  • the reinforced PBT material can be plasticized and stabilized in the temperature range of 220-250 ° C, the processing window is narrow and the processing temperature is high, and the reinforced lining of the invention is plasticized within a wide range of 160-215 ° C. It is very good and can be stably extruded, which shows that the reinforced liner of the present invention has a wider processing window, while the lower molding temperature also greatly reduces energy consumption and is more environmentally friendly.

Abstract

本发明公开了一种自增强异型材及其制备方法和应用，包括型材以及设置在型材型腔内的增强内衬，型材为ASA、SAS、ABS、AS和/或AES型材100份，增强内衬为增强苯乙烯基共聚物组合物材料5-120份，所述增强苯乙烯基共聚物组合物材料包括组分：苯乙烯基共聚物25-65份；增强剂30-65份。其制备方法是先制备增强苯乙烯基共聚物组合物材料，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ASA、SAS、ABS、AS和/或AES型材型材，辅机用于挤出增强苯乙烯基共聚物组合物材料，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可避免在运输，安装和使用过程中增强内衬与型材的剥离问题，且可低温成型，具有良好的生产稳定性和成型稳定性。

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
PVC异型材广泛应用在建筑门窗，木塑地板，家具板材等方面，然而PVC材料本身刚度较低，抗变形能力差，在用作门窗材料时需加装钢衬。传统的金属钢衬虽能有效提高PVC异型材的抗变形能力，但是钢衬存在生产能耗高，耐腐蚀效果差，保温隔热，隔音效果差，材料密度大，焊角强度低的缺点，而且在型材安装时，工艺复杂，需要安装人员在施工现场将钢衬和塑钢型材固定，增加了门窗安装的装配工序。基于此种情况，相关企业推出以塑代钢的材料，取代传统钢材。塑料本身有着良好的隔热，耐腐蚀，轻量化的优点，然而未改性的塑料刚度与钢材差距太大，不能满足异型材抗变形的要求。
采用玻纤增强的手段，能大幅提高塑料的刚度，为此提供了一种解决方案，如CN 102817529 B，CN 203066745 U，CN 202227876 U，CN 103075071 B等专利公开了一种以玻纤增强PBT，碳纤增强PBT，改性PBT中的任意一种为增强条，以PVC材料为基材的自增强型材，以替代常规的钢衬增强型材。但是在这些方案中，存在以下不足之处：(1)基材PVC与增强条PBT高温共挤容易造成PVC基材的分解发泡，碳化，从而产生型材变色，气味大；(2)增强条PBT与基材PVC的界面结合力差，在型材运输，安装和使用的过程中，由于碰撞和弯曲容易导致基材PVC和增强条PBT的剥离，这样就会大大降低增强条的增强作用，大大限制了其应用。CN 103147664 B公开了一种异型材共挤模头，通过在模具内部设置隔热层和内筋卡槽来解决PVC的糊料问题和相容性问题，虽然可以部分解决以上问题，但模具成本大大增加。
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，该自增强异型材可避免在运输，安装和使用过程中增强内衬与型材的剥离问题，且可低温成型，具有良好的生产稳定性和成型稳定性。
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，包括型材以及设置在型材型腔内的增强内衬，所述型材为ASA、SAS、ABS、AS和/或AES型材，所述增强内衬为增强苯乙烯基共聚物组合物材料，其重量份数如 下：
ASA、SAS、ABS、AS和/或AES型材  100份
增强苯乙烯基共聚物组合物材料  5份-120份
其中，所述增强苯乙烯基共聚物组合物材料按重量份数计，包括如下组分：
苯乙烯基共聚物  25-65份；
增强剂  30-65份；
所述ASA、SAS、ABS、AS和/或AES型材与增强苯乙烯基共聚物组合物材料的粘结力为700-1000N，所述粘结力测试采用如下方法：将ASA、SAS、ABS、AS和/或AES型材注塑成2mm×10mm×100mm的样条，然后再把ASA、SAS、ABS、AS和/或AES样条放置在4mm×10mm×100mm的模具中二次注塑增强苯乙烯基共聚物组合物材料，得到ASA、SAS、ABS、AS和/或AES型材与增强苯乙烯基共聚物组合物材料的粘附体，最后通过Zwick公司的拉伸试验机来测试粘结力的大小。
所述增强苯乙烯基共聚物组合物材料的挤出温度区间为160-215℃。
所述苯乙烯基共聚物树脂在220℃，10kg载荷条件下的熔体流动速率为1g/10min-80g/10min，为更易挤出成型，优选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共聚物组合物材料，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)增强苯乙烯基共聚物组合物材料的制备：除增强剂外，按配比将增强苯乙烯基共聚物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，即得增强苯乙烯基共聚物组合物材料；
(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ASA、SAS、ABS、AS和/或AES型材，辅机用于挤出增强苯乙烯基共聚物组合物材料，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，所述主机为双螺杆挤出机，双螺杆挤出机各段温度为150-200℃；所述辅机为单螺杆挤出机，单螺杆挤出机各段温度为160-215℃。
优选的，所述主机为双螺杆挤出机，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；所述辅机为单螺杆挤出机，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。
本发明还提供了上述自增强异型材在建筑门窗、木塑地板或家具板材中的应用。
相对于现有技术，本发明具有如下优点：
(1)本发明采用的增强内衬为增强苯乙烯基共聚物组合物材料，其为无定形材料，型材采用ASA、SAS、ABS、AS和/或AES型材，由于增强内衬材料与型材具有更好的相容性，避免了自增强异型材在运输，安装和使用的过程中出现增强内衬材料与型材的剥离问题，可广泛应用于建筑门窗、木塑地板或家具板材中；
(2)本发明采用的增强内衬材料能在160-215℃温度范围内稳定的挤出，具有更宽的加工窗口，同时较低的成型温度也会大大降低能耗，更加环保；
(3)本发明采用的增强内衬材料具有更高的熔体强度，具有更优异的加工成型性能，从而大大提高成型的稳定性。
(4)在提供同样刚性的条件下，本发明的增强内衬材料密度更低，自增强共挤型材重量更轻，符合国家提倡的轻量化，低碳环保趋势。
附图说明：
图1为粘结力测试时，ASA、SAS、ABS、AS和/或AES型材与增强内衬的粘附体照片。
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：
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；
ABS树脂，ABS AG10NP，台化；熔体流动速率6g/10min；
PBT树脂，PBT 1200-211M，台湾长春；
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；
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。
增强苯乙烯基共聚物组合物材料的制备：
除增强剂外，按表1配比将增强苯乙烯基共聚物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，即得增强苯乙烯基共聚物组合物材料。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共聚物组合物材料在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℃，所得增强苯乙烯基共聚物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。
粘结力测试：现将ASA、SAS、ABS、AS和/或AES树脂注塑成2mm×10mm×100mm的样条，然后再把ASA、SAS、ABS、AS和/或AES样条放置在4mm×10mm×100mm的模具中二次注塑增强内衬材料，得到ASA、SAS、ABS、AS和/或AES型材与增强内衬材料的粘附体，如图1所示。最后通过Zwick公司的拉伸试验机来测试粘结力的大小，从而表征增强内衬与ASA、SAS、ABS、AS和/或AES型材的粘结性能。
表1增强内衬各组分配比(重量份)及物性
Figure PCTCN2017087971-appb-000001
续表1：
Figure PCTCN2017087971-appb-000002
Figure PCTCN2017087971-appb-000003
从表1可以看出同样玻纤含量的情况下，本发明的增强内衬材料具有更加优异的力学性能，尤其是刚性更要优于增强PBT材料，在以塑代钢方面的优势更加明显。其次，在提供相同刚性的条件下，本发明的增强内衬材料密度更低，所制备的自增强共挤型材重量更轻，符合国家提倡的轻量化，低碳环保趋势。
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ASA、SAS、ABS、AS和/或AES型材，辅机用于挤出增强内衬材料，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；所述辅机为单螺杆挤出机，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。
表2自增强异型材的各组分配比及性能结果(重量份)
Figure PCTCN2017087971-appb-000004
续表2：
Figure PCTCN2017087971-appb-000005
从表2的数据可以看出，增强PBT材料与ASA、SAS、ABS、AS和/或AES型材的粘结力只有150N左右，而采用本发明的增强内衬，其与ASA、SAS、ABS、AS和/或AES型材的 粘结力提高到700-1000N左右，是增强PBT材料的5-6倍，这说明本发明的增强内衬与ASA、SAS、ABS、AS或AES型材具有更好的相容性，在型材的运输，安装和使用过程中不会出现剥离现象。其次，增强PBT材料在220-250℃的温度区间才可以塑化稳定挤出，加工窗口窄且加工温度高，而本发明的增强内衬在160-215℃较宽的范围之内塑化都很好，且可以稳定挤出，这说明本发明的增强内衬具有更宽的加工窗口，同时较低的成型温度也会大大降低能耗，更加环保。

Claims (13)

  1. 一种自增强异型材，其特征在于，包括型材以及设置在型材型腔内的增强内衬，所述型材为ASA、SAS、ABS、AS和/或AES型材，所述增强内衬为增强苯乙烯基共聚物组合物材料，其重量份数如下：
    ASA、SAS、ABS、AS和/或AES型材  100份
    增强苯乙烯基共聚物组合物材料   5份-120份
    其中，所述增强苯乙烯基共聚物组合物材料按重量份数计，包括如下组分：
    苯乙烯基共聚物  25-65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ASA、SAS、ABS、AS和/或AES型材与增强苯乙烯基共聚物组合物材料的粘结力为700-1000N，所述粘结力测试采用如下方法：将ASA、SAS、ABS、AS和/或AES型材注塑成2mm×10mm×100mm的样条，然后再把ASA、SAS、ABS、AS和/或AES样条放置在4mm×10mm×100mm的模具中二次注塑增强苯乙烯基共聚物组合物材料，得到ASA、SAS、ABS、AS和/或AES型材与增强苯乙烯基共聚物组合物材料的粘附体，最后通过Zwick公司的拉伸试验机来测试粘结力的大小。
  3. 根据权利要求1所述的自增强异型材，其特征在于，所述增强苯乙烯基共聚物组合物材料的挤出温度区间为160-215℃。
  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4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，所述增强苯乙烯基共聚物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)增强苯乙烯基共聚物组合物材料的制备：除增强剂外，按配比将增强苯乙烯基共聚物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，即得增强苯乙烯基共聚物组合物材料；
    (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ASA、SAS、ABS、AS和/或AES型材，辅机用于挤出增强苯乙烯基共聚物组合物材料，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，所述主机为双螺杆挤出机，双螺杆挤出机各段温度为150-200℃，所述辅机为单螺杆挤出机，单螺杆挤出机各段温度为160-215℃；优选的，所述主机为双螺杆挤出机，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；所述辅机为单螺杆挤出机，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。
  13. 权利要求1-9任一项所述的自增强异型材在建筑门窗、木塑地板或家具板材中的应用。
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