WO2020000588A1 - 热塑性弹性体材料 - Google Patents

热塑性弹性体材料 Download PDF

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WO2020000588A1
WO2020000588A1 PCT/CN2018/100002 CN2018100002W WO2020000588A1 WO 2020000588 A1 WO2020000588 A1 WO 2020000588A1 CN 2018100002 W CN2018100002 W CN 2018100002W WO 2020000588 A1 WO2020000588 A1 WO 2020000588A1
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parts
styrene
thermoplastic elastomer
elastomer material
material according
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PCT/CN2018/100002
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French (fr)
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邢胜俐
陆云
李明轩
李倩倩
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南通普力马弹性体技术有限公司
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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
    • C08L51/06—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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

Definitions

  • the invention relates to the technical field of polymer material modification, in particular to a thermoplastic elastomer material.
  • Polyamide is the most widely used engineering plastic among the five general-purpose engineering plastics.
  • the glass-reinforced polyamide has high mechanical strength and good dimensional stability. Its thermal deformation temperature can be as high as 250 ° C or more, and it can be used in It is used at 150 °C, so it is widely used in machinery, automobiles, electrical appliances, chemical equipment, aviation, metallurgy and other fields.
  • Thermoplastic elastomer (TPE) is a new type of elastomer material developed in recent years. It does not require vulcanization and uses a thermoplastic molding process to produce highly elastic products. Thermoplastic elastomers have a very wide range from 0A to 100A. Hardness range, hand-feeling and comfort. Compared with traditional PVC, it does not contain ester plasticizer, non-toxic, environmentally friendly and recyclable. Therefore, it can be widely used in automotive interior and exterior trim, medical industry, consumer goods and other fields. .
  • General-purpose plastic because it mainly provides mechanical properties, it has high rigidity, high hardness, and poor skin-friendly property. Toothbrushes, razors and other daily consumer products, tool handles, car interiors, medical sports equipment and other parts in direct contact with the human body, in order to make them have good skin affinity, softness and elasticity, usually on the surface of rigid plastic Vinyl chloride elastomer, vulcanized rubber, polyurethane elastomer, polyolefin elastomer, etc. However, polyamides and glass fiber-reinforced polyamides have difficulty in coating elastomers on their surfaces due to their own self-lubricating properties and extremely high heat distortion temperature.
  • the present invention provides a thermoplastic elastomer material for adhering polyamide and glass fiber reinforced polyamide.
  • thermoplastic elastomer material which is composed of the following parts by weight: 80 to 120 parts of styrenic thermoplastic elastomer, 20 to 200 parts of filling oil, 5 to 300 parts of graft-modified polar material, and adhesion copolymerization 5 to 180 parts, 5 to 180 parts of tackifier, 3 to 100 parts of reinforcement, 1 to 50 parts of polar surface treatment agent, 0 to 200 parts of inorganic filler, 1 to 5 parts of antioxidant, and lubrication 1 to 5 parts of agent.
  • the styrene-based thermoplastic elastomer is selected from the group consisting of styrene-butadiene-styrene block copolymer, styrene-ethylene / butene-styrene block copolymer, and styrene-ethylene / One or more of a propylene-styrene block copolymer and a styrene-ethylene-ethylene / propylene-styrene block copolymer.
  • the filling oil is selected from one or more of naphthenic oil and linear paraffin oil.
  • the graft-modified polymer is selected from the group consisting of polypropylene, polyamide, polyethylene, polyolefin-based elastomer, polystyrene-based elastomer, polyurethane-based elastomer, polyester-based elastomer, and poly One or more of the polar graft-modified polymers obtained by grafting an amide elastomer with maleic anhydride or an ester group, respectively.
  • the adhesion copolymer is selected from one or more of styrene and maleic anhydride copolymer, ethylene and acrylic acid copolymer, and styrene and butadiene diblock copolymer.
  • the adhesion tackifier is selected from one or more of epoxy resin, pure monomer resin, petroleum resin, and rosin resin.
  • the elastomer reinforcement is selected from one or more of polypropylene, polystyrene, polyethylene, and poly 2,6-dimethyl-1,4-phenylene ether (PPO). .
  • the polar surface-treating agent is selected from the group consisting of polyethylene wax, polypropylene wax, and fluoroplastic, which are obtained by grafting maleic anhydride or an ester group with a polar modification, And one or more of polyethylene wax, polypropylene wax and fluoroplastic.
  • the antioxidant is selected from one or more of a hindered phenol antioxidant, a hindered amine antioxidant, and a phosphite antioxidant.
  • the lubricant is selected from the group consisting of oleic acid amide, zinc stearate, erucamide, stearic acid, butyl stearate, calcium stearate, ethylene distearate, polyethylene wax And one or more of the silicone oils.
  • the inorganic filler is selected from one or more of calcium carbonate, talc, mica powder, kaolin, and barium sulfate.
  • the TPE material provided by the present invention makes the TPE material reinforced with polyamide and glass fiber by adding the graft-modified polar substance, the adhesion copolymer, the adhesion tackifier and the polar surface treatment agent.
  • the amide has excellent adhesion, and the TPE material has strong peeling strength when the polyamide and glass fiber reinforced polyamide are adhered.
  • the invention provides a thermoplastic elastomer (TPE) material, which is composed of the following components by weight: 80 to 120 parts of a styrene-based thermoplastic elastomer, 20 to 200 parts of a filling oil, and 5 to 60 of a graft-modified polar substance. 300 parts, 5 to 180 parts of adhesion copolymer, 5 to 180 parts of adhesion tackifier, 3 to 100 parts of reinforcement, 1 to 50 parts of polar surface treatment agent, 0 to 200 parts of inorganic filler, and antioxidant 1 ⁇ 5 parts, and lubricant 1-5 parts.
  • the TPE material provided by the invention has excellent adhesion strength with polyamide and glass fiber reinforced polyamide.
  • the styrene-based thermoplastic elastomer is selected from the group consisting of styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene / butene-styrene block copolymer (SEBS), and styrene-ethylene / One or more of propylene-styrene block copolymer (SEPS) and styrene-ethylene-ethylene / propylene-styrene block copolymer (SEEPS).
  • SBS styrene-butadiene-styrene block copolymer
  • SEBS styrene-ethylene / butene-styrene block copolymer
  • SEEPS propylene-styrene block copolymer
  • SEEPS propylene-styrene block copolymer
  • the filling oil is selected from one or more of naphthenic oil and linear paraffin oil.
  • the naphthenic oil is preferably a naphthenic oil.
  • the linear paraffin oil is preferably a paraffin oil.
  • the graft-modified polymer is selected from the group consisting of polypropylene, polyamide, polyethylene, polyolefin-based elastomer, polystyrene-based elastomer, polyurethane-based elastomer, polyester-based elastomer, and polyamide-based elastomer.
  • One or more of the polar graft-modified polymers obtained by grafting maleic anhydride or grafting ester groups.
  • the tack copolymer is selected from one or more of styrene and maleic anhydride copolymers, ethylene and acrylic acid copolymers, and styrene and butadiene diblock copolymers.
  • the adhesive copolymer has high polarity and has certain adhesion to polyamide and glass fiber reinforced polyamide.
  • the adhesive copolymer and the styrene thermoplastic elastomer have good compatibility, and the material obtained by mixing the adhesive copolymer and the styrene thermoplastic elastomer has good processability.
  • the tackifier is selected from one or more of epoxy resin, pure monomer resin, petroleum resin and rosin resin.
  • the adhesive tackifier is a low-molecular polymer, and the polyamide surface has self-lubricity.
  • the adhesive tackifier can make the surface of the material blended with the adhesive have a certain small-molecular viscosity, which is easy to make the TPE.
  • An adhesive layer is created between the material and the polyamide material or the glass fiber reinforced polyamide material.
  • the elastomer reinforcement is selected from one or more of polypropylene, polystyrene, polyethylene, and poly2,6-dimethyl-1,4-phenylene ether (PPO).
  • the polar surface treatment agent is selected from the group consisting of polyethylene wax, polypropylene wax, and fluoroplastic, which have polar modification obtained by grafting maleic anhydride or ester groups, and polyethylene wax and polypropylene.
  • the polar surface treatment agent is a small molecule polymer, which can migrate to the surface of the TPE material, and because of its high polarity, it can further enhance the adhesion to the polyamide material.
  • the inorganic filler is selected from one or more of calcium carbonate, talc, mica powder, kaolin, and barium sulfate.
  • the antioxidant is selected from one or more of a hindered phenol antioxidant, a hindered amine antioxidant, and a phosphite antioxidant.
  • the hindered phenol antioxidant is preferably antioxidant 1010, and the phosphite antioxidant is preferably antioxidant 168.
  • the lubricant is one selected from the group consisting of oleic acid amide, zinc stearate, erucamide, stearic acid, butyl stearate, calcium stearate, ethylene distearate, polyethylene wax, and silicone oil. Or several.
  • the present invention also provides a method for preparing the TPE material, which includes the following steps: adding a styrene-based thermoplastic elastomer and a filling oil to a high-speed mixer in proportion and stirring for 0 to 10 minutes, waiting for the styrene-based thermoplastic elasticity; After the filler oil is fully absorbed, the graft-modified polar substance, adhesion copolymer, adhesion tackifier, reinforcement, polar surface treatment agent, inorganic filler, antioxidant, and lubricant are added.
  • the TPE material is obtained by putting into a single screw extruder with an aspect ratio of 25: 1 to 30: 1, controlling the processing temperature to 180 to 260 ° C, and performing melting, extrusion, and pelletization.
  • the TPE material provided by the present invention has greater polarity and higher molding temperature, and can be adhered to the surface of polyamide and glass fiber reinforced polyamide through a secondary adhesion injection molding or two-color injection molding process.
  • the processing temperature is 180-270 ° C.
  • the TPE material consists of the following parts by weight: 80 parts of SEBS, 100 parts of naphthenic oil, 60 parts of SEBS grafted amino groups, 100 parts of polyolefin elastomer grafted maleic anhydride, and 20 parts of SEBS grafted maleic anhydride , 30 parts of styrene and maleic anhydride copolymer, 30 parts of styrene and butadiene diblock copolymer, 5 parts of petroleum resin, 10 parts of epoxy resin, 50 parts of pure monomer resin, 10 parts of polypropylene, polymer 5 parts of styrene, 10 parts of polypropylene wax grafted maleic anhydride, 5 parts of polyethylene wax grafted maleic anhydride, 50 parts of talc, 1010 parts of antioxidant, 1 part of antioxidant 168, polyethylene wax 3 Serving.
  • TPE material consists of the following components by weight: 35 parts SEPS, 50 parts SEBS, 60 parts naphthenic oil, 60 parts paraffin oil, 100 parts SEBS grafted amino groups, and 40 parts polyolefin elastomer grafted maleic anhydride , SEBS grafted maleic anhydride 30 parts, polypropylene grafted maleic anhydride 5 parts, styrene and maleic anhydride copolymer 70 parts, petroleum resin 60 parts, polypropylene 3 parts, polystyrene 20 parts, polyethylene wax 10 parts of grafted maleic anhydride, 45 parts of calcium carbonate, 2 parts of antioxidant 1010, 2 parts of antioxidant 168, 2 parts of erucamide.
  • TPE material is composed of the following components by weight: SBS 30 parts, SEPS 30 parts, SEBS 35 parts, naphthenic oil 50 parts, paraffin oil 50 parts, polyolefin elastomer grafted maleic anhydride 150 parts, SEBS grafted horses 60 parts of maleic anhydride, 60 parts of styrene and butadiene diblock copolymer, 10 parts of petroleum resin, 45 parts of pure monomer resin, 10 parts of polystyrene, 30 parts of polypropylene wax grafted maleic anhydride, polyethylene 1 part of wax grafted maleic anhydride, 65 parts of calcium carbonate, 2 parts of antioxidant 1010, 2 parts of antioxidant 168 parts, and 3 parts of oleic acid amide.
  • the TPE material is composed of the following components by weight: SBS 55 parts, SEPS 50 parts, paraffin oil 90 parts, polyolefin elastomer grafted maleic anhydride 100 parts, SEBS grafted maleic anhydride 100 parts, polypropylene grafted horses 5 parts of maleic anhydride, 80 parts of styrene and maleic anhydride copolymer, 45 parts of epoxy resin, 5 parts of pure monomer resin, 6 parts of polypropylene, 15 parts of polystyrene, 5 parts of polypropylene wax grafted with maleic anhydride , Polyethylene wax grafted with maleic anhydride 10 parts, calcium carbonate 55 parts, antioxidant 1010 2 parts, antioxidant 168 2 parts, erucamide 2 parts.
  • the TPE material consists of the following parts by weight: SBS 75 parts, SEBS 45 parts, naphthenic oil 20 parts, paraffin oil 100 parts, SEBS grafted amino groups 100 parts, polyolefin elastomer grafted maleic anhydride 150 parts , Polypropylene grafted maleic anhydride 5 parts, styrene and maleic anhydride copolymer 50 parts, styrene and butadiene diblock copolymer 5 parts, pure monomer resin 55 parts, polystyrene 15 parts, poly 5 parts of propylene wax grafted maleic anhydride, 15 parts of polyethylene wax grafted maleic anhydride, 1010 antioxidants, 1 part of polyethylene wax, 1 part of oleic acid amide, and 1 part of erucamide.
  • TPE material consists of the following components by weight: 120 parts of SEBS, 200 parts of paraffin oil, 300 parts of polyolefin elastomer grafted maleic anhydride, 100 parts of styrene and maleic anhydride copolymer, and styrene and butadiene bis 20 parts of block copolymer, 45 parts of petroleum resin, 35 parts of polypropylene, 20 parts of polypropylene wax grafted maleic anhydride, 100 parts of talc, 168 antioxidants, 5 parts, and 5 parts of erucamide.
  • the TPE material is composed of the following components by weight: 150 parts of SEBS, 100 parts of paraffin oil, 60 parts of polypropylene, 45 parts of calcium carbonate, 1010 parts of antioxidant, 1 part of antioxidant 168.
  • SBS is preferably YH792 produced by Sinopec Yueyang Baling Petrochemical Company
  • SEPS is preferably 4044 produced by Japan Kuraray Polymer Company
  • SEBS is preferably produced by Sinopec Yueyang Baling Petrochemical Company YH502
  • paraffin oil is preferably 220N produced by South Korea Ssangyong Company
  • naphthenic oil is preferably 4006 produced by Sinopec Karamay Petrochemical Company
  • SEBS grafted amino group is preferably MP10 produced by Asahi Kasei Japan
  • polyolefin elastomer grafted with maleic anhydride Preferably it is A2361 produced by Shenzhen Paste New Material Technology Co., Ltd.
  • the SEBS grafted maleic anhydride is preferably FG1901 produced by Kraton Performance Polymers, and the polypropylene grafted maleic anhydride is preferably Shanghai Risunsen CMG9801 produced by Technology Development Co., Ltd., preferably styrene and maleic anhydride copolymer is BMI-01 produced by Honghu Shuangma New Material Technology Co., Ltd., styrene and butadiene diblock copolymer is preferably produced by BASF, Germany 684D, epoxy resin is preferably CYDCN-200 produced by Guangzhou Desheng Chemical Co., Ltd., petroleum resin is preferably Kolon
  • the pure monomer resin SU-400 produced by the company is preferably R1100 produced by Eastman Chemical Co., Ltd.
  • the polypropylene is preferably PPH-T03 produced by Sinopec Zhenhai Refining and Chemicals Branch
  • the polystyrene is preferably produced by Taiwan Chi Mei Corporation PG33, poly
  • TPE materials obtained in Examples 1-6 and Comparative Examples were tested for adhesion properties of polyamide and glass fiber reinforced polyamide, respectively.
  • the TPE materials obtained in Examples 1 to 6 and the comparative example were respectively subjected to a two-color adhesion injection molding process, and were injection-molded on a polyamide or glass fiber reinforced polyamide sheet through an injection molding machine, and injection-molded and adhered to the polyamide or glass fiber.
  • the TPE material on the surface of the reinforced polyamide sheet is a sheet of 150 mm in length, 25 mm in width, and 2 mm in thickness; the TPE sheet is peeled by a peeling method such as hand tearing or blade cutting to a distance of about 25 mm, and one end of the tensile machine is clamped For the peeled TPE sheet, the other end of the tensile machine clamps the polyamide or glass fiber reinforced polyamide for a tensile test, and the peel strength is taken as the maximum force value during the tensile process. Test performance is shown in Table 1.
  • the TPE material provided by the present invention by adding the graft-modified polar material, the tack copolymer, the tack thickener and the polar surface treatment agent, makes the TPE material and polymer
  • the amide and the glass fiber reinforced polyamide have excellent adhesion, and the TPE material has strong peel strength when the polyamide and the glass fiber reinforced polyamide are adhered.

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

一种热塑性弹性体材料，其由以下重量份的组分组成：苯乙烯类热塑性弹性体80～120份，填充油20～200份，接枝改性极性物5～300份，粘覆共聚物5～180份，粘覆增粘剂5～180份，增强物3～100份，极性表面处理剂1～50份，无机填料0～200份，抗氧剂1～5份，以及润滑剂1～5份。所述热塑性弹性体材料用于粘覆聚酰胺和玻纤增强聚酰胺，其粘覆聚酰胺和玻纤增强聚酰胺剥离强度大。

Description

热塑性弹性体材料 技术领域
本发明涉及高分子材料改性技术领域，尤其涉及一种热塑性弹性体材料。
背景技术
聚酰胺是五大通用工程塑料中用途最广、品种最多、产量最大的工程塑料，经过玻纤增强的聚酰胺机械强度高，尺寸稳定性好，其热变形温度可以高达250℃以上，可以长期在150℃下使用，因此其广泛的应用于机械、汽车、电器、化工设备、航空、冶金等领域。热塑性弹性体(TPE)是近年来发展起来的一类新型弹性体材料，无需硫化采用热塑性成型的工艺，即可制取高弹性的产品，热塑性弹性体具有从邵氏0A至100A的极宽的硬度范围，手感亲肤舒适，与传统的PVC相比较，不含酯类增塑剂，无毒环保可回收再利用，因此其可以广泛的应用于汽车内外饰、医疗行业、日用消费品等领域。
通用塑料，由于其主要提供机械性能，因此其刚性大、硬度高、亲肤性差。牙刷、剃须刀等日用消费品，工具把手，汽车内饰，医疗体育器材等直接与人体接触的部分，为了使其具有良好的亲肤性、柔软弹性，通常在刚性塑料的表面包覆聚氯乙烯弹性体、硫化橡胶、聚氨酯弹性体、聚烯烃弹性体等。然而，聚酰胺和玻纤增强聚酰胺由于其自身的自润滑性和极高的热变形温度，导致难以在其表面进行弹性体的包覆。
发明内容
鉴于上述技术问题，本发明提供一种用于粘覆聚酰胺和玻纤增强聚酰胺的热塑性弹性体材料。
一种热塑性弹性体材料，其由以下重量份的组分组成：苯乙烯类热塑性弹性体80～120份，填充油20～200份，接枝改性极性物5～300份，粘覆共聚 物5～180份，粘覆增粘剂5～180份，增强物3～100份，极性表面处理剂1～50份，无机填料0～200份，抗氧剂1～5份，以及润滑剂1～5份。
作为一种优选方案，所述苯乙烯类热塑性弹性体选自苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯～乙烯/丁烯～苯乙烯嵌段共聚物、苯乙烯～乙烯/丙烯～苯乙烯嵌段共聚物以及苯乙烯～乙烯～乙烯/丙烯～苯乙烯嵌段共聚物中的一种或几种。
作为一种优选方案，所述填充油选自环烷烃油以及直链烷烃油中的一种或几种。
作为一种优选方案，所述接枝改性聚合物选自聚丙烯、聚酰胺、聚乙烯、聚烯烃类弹性体、聚苯乙烯类弹性体、聚氨酯类弹性体、聚酯类弹性体以及聚酰胺类弹性体分别接枝马来酸酐或者接枝酯类基团得到的具有极性的接枝改性聚合物中的一种或几种。
作为一种优选方案，所述粘覆共聚物选自苯乙烯和马来酸酐共聚物、乙烯和丙烯酸共聚物以及苯乙烯和丁二烯双嵌段共聚物中的一种或几种。
作为一种优选方案，所述的粘覆增粘剂选自环氧树脂、纯单体树脂、石油树脂以及松香树脂中的一种或几种。
作为一种优选方案，所述的弹性体增强物选自聚丙烯、聚苯乙烯、聚乙烯以及聚2,6-二甲基-1,4-苯醚(PPO)中的一种或几种。
作为一种优选方案，所述的极性表面处理剂选自聚乙烯蜡、聚丙烯蜡及氟塑料分别通过接枝马来酸酐或者枝接酯类基团获得的具有极性的改性物、以及聚乙烯蜡、聚丙烯蜡和氟塑料中的一种或几种。
作为一种优选方案，所述抗氧剂选自受阻酚类抗氧剂、受阻胺类抗氧剂以及亚磷酸酯类抗氧剂中的一种或几种。
作为一种优选方案，所述润滑剂选自油酸酰胺、硬脂酸锌、芥酸酰胺、硬脂酸、硬脂酸丁酯、硬脂酸钙、乙撑双硬脂酰胺、聚乙烯蜡以及硅油中的一种或几种。
作为一种优选方案，所述无机填料选自碳酸钙、滑石粉、云母粉、高岭土以及硫酸钡中的一种或几种。
本发明提供的的TPE材料，通过添加所述接枝改性极性物、粘覆共聚物、粘覆增粘剂以及极性表面处理剂，使得所述TPE材料与聚酰胺和玻纤增强聚酰胺具有优异的粘附性，所述TPE材料粘覆聚酰胺和玻纤增强聚酰胺剥离强度大。
具体实施方式
下面对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。在不冲突的情况下，下述的实施例及实施例中的特征可以相互组合。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。
本发明提供一种热塑性弹性体(TPE)材料，其由以下重量份的组分组成：苯乙烯类热塑性弹性体80～120份，填充油20～200份，接枝改性极性物5～300份，粘覆共聚物5～180份，粘覆增粘剂5～180份，增强物3～100份，极性表面处理剂1～50份，无机填料0～200份，抗氧剂1～5份，以及润滑剂1～5份。本发明提供的TPE材料与聚酰胺和玻纤增强聚酰胺均具有优异的粘覆粘接强度。
所述苯乙烯类热塑性弹性体选自苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、苯乙烯～乙烯/丁烯～苯乙烯嵌段共聚物(SEBS)、苯乙烯～乙烯/丙烯～苯乙烯嵌段共聚物(SEPS)以及苯乙烯～乙烯～乙烯/丙烯～苯乙烯嵌段共聚物(SEEPS)中的一种或几种。
所述填充油选自环烷烃油以及直链烷烃油中的一种或几种。所述环烷烃油优选为环烷油。所述直链烷烃油优选为石蜡油。
所述接枝改性聚合物选自聚丙烯、聚酰胺、聚乙烯、聚烯烃类弹性体、聚苯乙烯类弹性体、聚氨酯类弹性体、聚酯类弹性体以及聚酰胺类弹性体分别接枝马来酸酐或者接枝酯类基团得到的具有极性的接枝改性聚合物中的一种或几种。
所述粘覆共聚物选自苯乙烯和马来酸酐共聚物、乙烯和丙烯酸共聚物以 及苯乙烯和丁二烯双嵌段共聚物中的一种或几种。所述粘覆共聚物具有较高的极性，对聚酰胺和玻纤增强聚酰胺具有一定的粘附性。所述粘覆共聚物和所述苯乙烯热塑性弹性体具有很好的相容性，所述粘覆共聚物和所述苯乙烯热塑性弹性体混合后得到的材料具有良好的加工性能。
所述的粘覆增粘剂选自环氧树脂、纯单体树脂、石油树脂以及松香树脂中的一种或几种。所述粘覆增粘剂属于低分子聚合物，聚酰胺表面具有自润滑性，所述粘覆增粘剂可使与其共混后的材料表面具有一定的小分子粘性物，容易使所述TPE材料和所述聚酰胺材料或者和所述玻纤增强聚酰胺材料之间产生粘层。
所述的弹性体增强物选自聚丙烯、聚苯乙烯、聚乙烯以及聚2,6-二甲基-1,4-苯醚(PPO)中的一种或几种。
所述极性表面处理剂选自聚乙烯蜡、聚丙烯蜡及氟塑料分别通过接枝马来酸酐或者枝接酯类基团获得的具有极性的改性物、以及聚乙烯蜡、聚丙烯蜡和氟塑料中的一种或几种。所述极性表面处理剂是小分子聚合物，其可迁移至所述TPE材料的表面，且因其具有较高的极性，可进一步增强与聚酰胺材料的粘附性。
所述无机填料选自碳酸钙、滑石粉、云母粉、高岭土以及硫酸钡中的一种或几种。
所述抗氧剂选自受阻酚类抗氧剂、受阻胺类抗氧剂以及亚磷酸酯类抗氧剂中的一种或几种。所述受阻酚类抗氧剂优选为抗氧剂1010，所述亚磷酸酯类抗氧剂优选为抗氧剂168。
所述润滑剂选自油酸酰胺、硬脂酸锌、芥酸酰胺、硬脂酸、硬脂酸丁酯、硬脂酸钙、乙撑双硬脂酰胺、聚乙烯蜡以及硅油中的一种或几种。
本发明还提供一种上述TPE材料的制备方法，其包括以下步骤：将苯乙烯类热塑性弹性体和填充油按比例加入到高速混合机中搅拌0～10分钟，待所述苯乙烯类热塑性弹性体将所述填充油充分吸收后，加入所述接枝改性极性物、粘覆共聚物、粘覆增粘剂、增强物、极性表面处理剂、无机填料、 抗氧剂、润滑剂，再搅拌0～5分钟，搅拌混合得到预混物，高速混合机转速为180转/分钟；将充分混合的预混合物放入到长径比为36:1～48:1的双螺杆挤出机中或者放入到长径比为25:1～30:1的单螺杆挤出机中，控制加工温度为180～260℃，进行熔融、挤出、造粒得到所述TPE材料。
本发明提供的TPE材料具有较大的极性和较高的成型温度，可通过二次粘覆注塑或双色注塑成型工艺粘覆于聚酰胺和玻纤增强聚酰胺表面。所述TPE材料进行二次粘覆注塑或双色注塑加工时，其加工温度为180～270℃。
实施例1
TPE材料由以下重量份的组分组成：SEBS 80份，环烷油100份，SEBS接枝氨基基团60份，聚烯烃弹性体接枝马来酸酐100份，SEBS接枝马来酸酐20份，苯乙烯和马来酸酐共聚物30份，苯乙烯和丁二烯双嵌段共聚物30份，石油树脂5份，环氧树脂10份，纯单体树脂50份，聚丙烯10份，聚苯乙烯5份，聚丙烯蜡接枝马来酸酐10份，聚乙烯蜡接枝马来酸酐5份，滑石粉50份，抗氧剂1010 1份，抗氧剂168 1份，聚乙烯蜡3份。
实施例2
TPE材料由以下重量份的组分组成：SEPS 35份，SEBS 50份，环烷油60份，石蜡油60份，SEBS接枝氨基基团100份，聚烯烃弹性体接枝马来酸酐40份，SEBS接枝马来酸酐30份，聚丙烯接枝马来酸酐5份，苯乙烯和马来酸酐共聚物70份，石油树脂60份，聚丙烯3份，聚苯乙烯20份，聚乙烯蜡接枝马来酸酐10份，碳酸钙45份，抗氧剂1010 2份，抗氧剂168 2份，芥酸酰胺2份。
实施例3
TPE材料由以下重量份的组分组成：SBS 30份，SEPS 30份，SEBS 35份，环烷油50份，石蜡油50份，聚烯烃弹性体接枝马来酸酐150份，SEBS接枝马来酸酐60份，苯乙烯和丁二烯双嵌段共聚物60份，石油树脂10份，纯单体树脂45份，聚苯乙烯10份，聚丙烯蜡接枝马来酸酐30份，聚乙烯蜡接枝马来酸酐1份，碳酸钙65份，抗氧剂1010 2份，抗氧剂168 2 份，油酸酰胺3份。
实施例4
TPE材料由以下重量份的组分组成：SBS 55份，SEPS 50份，石蜡油90份，聚烯烃弹性体接枝马来酸酐100份，SEBS接枝马来酸酐100份，聚丙烯接枝马来酸酐5份，苯乙烯和马来酸酐共聚物80份，环氧树脂45份，纯单体树脂5份，聚丙烯6份，聚苯乙烯15份，聚丙烯蜡接枝马来酸酐5份，聚乙烯蜡接枝马来酸酐10份，碳酸钙55份，抗氧剂1010 2份，抗氧剂168 2份，芥酸酰胺2份。
实施例5
TPE材料由以下重量份的组分组成：SBS 75份，SEBS 45份，环烷油20份，石蜡油100份，SEBS接枝氨基基团100份，聚烯烃弹性体接枝马来酸酐150份，聚丙烯接枝马来酸酐5份，苯乙烯和马来酸酐共聚物50份，苯乙烯和丁二烯双嵌段共聚物5份，纯单体树脂55份，聚苯乙烯15份，聚丙烯蜡接枝马来酸酐5份，聚乙烯蜡接枝马来酸酐15份，抗氧剂1010 5份，聚乙烯蜡1份，油酸酰胺1份，芥酸酰胺1份。
实施例6
TPE材料由以下重量份的组分组成：SEBS 120份，石蜡油200份，聚烯烃弹性体接枝马来酸酐300份，苯乙烯和马来酸酐共聚物100份，苯乙烯和丁二烯双嵌段共聚物20份，石油树脂45份，聚丙烯35份，聚丙烯蜡接枝马来酸酐20份，滑石粉100份，抗氧剂168 5份，芥酸酰胺5份。
对比例
TPE材料由以下重量份的组分组成：SEBS 150份，石蜡油100份，聚丙烯60份，碳酸钙45份，抗氧剂1010 1份，抗氧剂168 1份。
其中，在实施例1-6和对比例中，SBS优选为中石化岳阳巴陵石化公司生产的YH792，SEPS优选为日本可乐丽聚合物公司生产的4044，SEBS优选为中石化岳阳巴陵石化公司生产的YH502，石蜡油优选为韩国双龙公司生产的220N，环烷油优选为中石化克拉玛依石化公司生产的4006，SEBS接 枝氨基基团优选为日本旭化成公司生产的MP10，聚烯烃弹性体接枝马来酸酐优选为深圳市帕斯特新材料科技有限公司生产的A2361，SEBS接枝马来酸酐优选为美国科腾高性能聚合物公司生产的FG1901，聚丙烯接枝马来酸酐优选为上海日之升新技术发展有限公司生产的CMG9801，苯乙烯和马来酸酐共聚物优选为洪湖市双马新材料科技有限公司生产的BMI-01，苯乙烯和丁二烯双嵌段共聚物优选为德国巴斯夫公司生产的684D，环氧树脂优选为广州德晟化工有限公司生产的CYDCN-200，石油树脂优选为韩国可隆聚合物公司生产的SU-400，纯单体树脂优选为伊士曼化工有限公司生产的R1100，聚丙烯优选为中石化镇海炼化分公司生产的PPH-T03，聚苯乙烯优选为台湾奇美公司生产的PG33，聚丙烯蜡接枝马来酸酐优选为科莱恩化工有限公司生产的Licocene PP MA 6452 TP，聚乙烯蜡接枝马来酸酐优选为山东利莱塑料助剂有限公司生产的B型，碳酸钙优选为上海诺成药业股份有限公司生产的PD60。
将实施例1-6以及对比例所得的TPE材料分别进行聚酰胺和玻纤增强聚酰胺的粘覆性能测试。具体地，将实施例1-6以及对比例所得的TPE材料分别采用双色粘附注塑工艺，通过注塑机注塑在聚酰胺或玻纤增强聚酰胺片材上，注塑粘附在聚酰胺或玻纤增强聚酰胺片材表面的TPE材料为长150mm，宽25mm，厚2mm的片材；将TPE片材采用手撕或刀片切割等剥离方法剥离出长度大约为25mm的距离，拉力机的一端夹紧被剥离的TPE片材，拉力机的另一端夹紧聚酰胺或玻纤增强聚酰胺进行拉伸测试，剥离强度取拉伸过程中的最大力值。测试性能参表1。
表1 各实施例得到的薄膜的测试性能列表
Figure PCTCN2018100002-appb-000001
Figure PCTCN2018100002-appb-000002
由上表可看出，本发明提供的TPE材料，通过添加所述接枝改性极性物、粘覆共聚物、粘覆增粘剂以及极性表面处理剂，使得所述TPE材料与聚酰胺和玻纤增强聚酰胺具有优异的粘附性，所述TPE材料粘覆聚酰胺和玻纤增强聚酰胺剥离强度大。
另外，本领域技术人员还可在本发明精神内做其它变化，当然，这些依据本发明精神所做的变化，都应包含在本发明所要求保护的范围内。

Claims (11)

  1. 一种热塑性弹性体材料，其特征在于，其由以下重量份的组分组成：苯乙烯类热塑性弹性体80～120份，填充油20～200份，接枝改性极性物5～300份，粘覆共聚物5～180份，粘覆增粘剂5～180份，增强物3～100份，极性表面处理剂1～50份，无机填料0～200份，抗氧剂1～5份，以及润滑剂1～5份。
  2. 如权利要求1所述的热塑性弹性体材料，其特征在于，所述苯乙烯类热塑性弹性体选自苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯～乙烯/丁烯～苯乙烯嵌段共聚物、苯乙烯～乙烯/丙烯～苯乙烯嵌段共聚物以及苯乙烯～乙烯～乙烯/丙烯～苯乙烯嵌段共聚物中的一种或几种。
  3. 如权利要求1所述的热塑性弹性体材料，其特征在于，所述填充油选自环烷烃油以及直链烷烃油中的一种或几种。
  4. 如权利要求1所述的热塑性弹性体材料，其特征在于，所述接枝改性聚合物选自聚丙烯、聚酰胺、聚乙烯、聚烯烃类弹性体、聚苯乙烯类弹性体、聚氨酯类弹性体、聚酯类弹性体以及聚酰胺类弹性体分别接枝马来酸酐或者接枝酯类基团得到的具有极性的接枝改性聚合物中的一种或几种。
  5. 如权利要求1所述的热塑性弹性体材料，其特征在于，所述粘覆共聚物选自苯乙烯和马来酸酐共聚物、乙烯和丙烯酸共聚物以及苯乙烯和丁二烯双嵌段共聚物中的一种或几种。
  6. 如权利要求1所述的热塑性弹性体材料，其特征在于，所述的粘覆增粘剂选自环氧树脂、纯单体树脂、石油树脂以及松香树脂中的一种或几种。
  7. 如权利要求1所述的热塑性弹性体材料，其特征在于，所述的弹性体增强物选自聚丙烯、聚苯乙烯、聚乙烯以及聚2,6-二甲基-1,4-苯醚中的一种或几种。
  8. 如权利要求1所述的热塑性弹性体材料，其特征在于，所述的极性表面处理剂选自聚乙烯蜡、聚丙烯蜡及氟塑料分别通过接枝马来酸酐或者枝接酯类基团获得的具有极性的改性物、以及聚乙烯蜡、聚丙烯蜡和氟塑料中的一种或几种。
  9. 如权利要求1所述的热塑性弹性体材料，其特征在于，所述抗氧剂选自受阻酚类抗氧剂、受阻胺类抗氧剂以及亚磷酸酯类抗氧剂中的一种或几种。
  10. 如权利要求1所述的热塑性弹性体材料，其特征在于，所述润滑剂选自油酸酰胺、硬脂酸锌、芥酸酰胺、硬脂酸、硬脂酸丁酯、硬脂酸钙、乙撑双硬脂酰胺、聚乙烯蜡以及硅油中的一种或几种。
  11. 如权利要求1所述的热塑性弹性体材料，其特征在于，所述无机填料选自碳酸钙、滑石粉、云母粉、高岭土以及硫酸钡中的一种或几种。
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