WO2015067178A1 - 一种金属/织物粘接胶及其制备、使用方法 - Google Patents

一种金属/织物粘接胶及其制备、使用方法 Download PDF

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WO2015067178A1
WO2015067178A1 PCT/CN2014/090367 CN2014090367W WO2015067178A1 WO 2015067178 A1 WO2015067178 A1 WO 2015067178A1 CN 2014090367 W CN2014090367 W CN 2014090367W WO 2015067178 A1 WO2015067178 A1 WO 2015067178A1
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metal
fabric
adhesive
coupling agent
silane coupling
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PCT/CN2014/090367
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English (en)
French (fr)
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戴李宗
毛杰
曾凡沛
陈凌南
陈志雄
曾碧榕
何两加
许一婷
罗伟昂
许厦生
王兆昌
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厦门大学
福建龙溪轴承(集团)股份有限公司
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Priority to US15/034,873 priority Critical patent/US20160298002A1/en
Publication of WO2015067178A1 publication Critical patent/WO2015067178A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • 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
    • B32B15/14—Layered products comprising a layer of metal next to a 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • 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
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/08—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different fibres
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • B32B2255/00—Coating on the layer surface
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0223—Vinyl resin fibres
    • B32B2262/023—Aromatic vinyl resin, e.g. styrenic (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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
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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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/14—Mixture of at least two fibres made of different materials
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
    • 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
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    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
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    • C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C08K2201/011—Nanostructured additives
    • 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
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring

Definitions

  • the present invention relates to an adhesive, and more particularly to an adhesive for bonding a fabric to a metal.
  • Non-structural bonding mainly refers to surface bonding, sealing and functional bonding.
  • Typical non-structural adhesives include adhesives for surface bonding, sealing and conductive adhesives; and structural bonding is to firmly fix structural units with adhesives. The bonding phenomenon together, the structural adhesive and its bonding points must be able to transmit structural stress, and the structural integrity and environmental applicability are not affected within the design range.
  • Li Zidong et al. (901 Fast Superglue and its preparation method, Chinese Patent, Publication No. CN 1074469A) discloses an adhesive modified styrene-butadiene adhesive for bonding natural
  • the peel strength of rubber/aluminum can reach 2.98kN/m, which is higher than that of general phenolic resin modified neoprene adhesive, but the process is troublesome.
  • Lu Guangqi adheresive bonding between metal and non-metal, and its preparation method, Chinese patent, publication number CN 1273261A
  • a metal was prepared by adding polar polymer chlorosulfonated polyethylene.
  • Non-metallic adhesive Although the adhesive has a low preparation cost, the process is complicated and the heat resistance and aging resistance are poor.
  • Feng Jicai et al. organic reactive gel and method of welding non-metal and metal materials, Chinese patent, CN 101402836A
  • this method can overcome the limitation of the inferiority of non-metallic materials, it needs to be welded at a high temperature in a vacuum furnace, which has high energy consumption and complicated process.
  • the object of the present invention is to provide an epoxy type metal/woven fabric with high fatigue resistance and uniform stress.
  • the adhesive solves the problem that the traditional fiber fabric is difficult to be bonded to the metal matrix, and overcomes the defects of ordinary epoxy resin, such as hard and brittle texture, low crack resistance and poor impact strength.
  • the interface between the metal substrate and the cushion fabric is very popular and applicable.
  • the invention provides a metal/fabric adhesive and a preparation and use method thereof.
  • the metal mainly includes steel, aluminum and alloys thereof.
  • the fabric mainly includes polyamide fibers, polyester fibers, polyvinyl alcohol fibers, polyacrylonitrile fibers, polyvinyl chloride fiber fabrics, and the like, and mixed fabrics thereof.
  • the formulation of the metal/fabric adhesive is as follows:
  • epoxy resin 80 to 120 parts of epoxy resin, 10 to 30 parts of reactive diluent, 0.5 to 5 parts of silane coupling agent, 0.5 to 5 parts of metal oxide nano powder, and 35 to 60 parts of curing agent.
  • the epoxy resin is a commercial epoxy resin, that is, a compound containing two or more epoxy groups in the molecule, such as epoxy E-44, E-51, E-55, E4-2, E3-1, E4-6, E-20, etc.
  • the reactive diluent is 1,6-hexanediol diacrylate, ⁇ -hydroxyethyl methacrylate, tolyl glycidyl ether, castor oil polyglycidyl ether, ethylene glycol diglycidyl ether, and the like.
  • the curing agent is an amine or an acid anhydride compound used in combination with an epoxy resin, an amine such as ethylenediamine, diethylenetriamine, m-phenylenediamine, etc.; an acid anhydride such as phthalic anhydride or benzophenone Formic anhydride, methylcyclohexene tetracarboxylic anhydride, and the like.
  • the metal oxide nanopowder is ZnO, Al 2 O 3 , BaO, Fe 3 O 4 or the like of 20 to 200 nm.
  • the preparation method of the metal/fabric adhesive is as follows: first, the metal oxide nano powder, the silane coupling agent and the curing agent are sequentially dissolved in the reactive diluent, and stirred for 0.5 to 1 hour to obtain a uniform emulsion; secondly, ultrasonic The epoxy resin was added to the emulsion in batches under shaking, and stirred for 0.5 to 2 hours until homogeneous.
  • the method for using the metal/fabric adhesive is as follows: first, the surface of the metal substrate is washed with acetone, washed with deionized water, dried in an oven, and then coated with the silane coupling agent for 0.5 to 1 hour; secondly, The fabric is immersed in a phosphoric acid/nitric acid mixed solution having a volume ratio of 1:9 to 4:6 at 40 to 60 ° C for 0.5 to 2 hours.
  • the phosphoric acid concentration is 1 to 3 mol/L; and the nitric acid concentration is 1 to 3 mol/L.
  • the metal/fabric adhesive of the invention has the following characteristics:
  • silane coupling agent and the metal nanopowder component are added to the adhesive to improve the bonding property between the adhesive and the metal substrate and improve the mechanical strength of the bonding layer, and the addition of the inorganic component also improves the heat resistance of the material.
  • the aluminum metal substrate was washed with acetone, washed with deionized water, and dried in an oven for 1 hour to remove impurities such as oxides on the metal surface.
  • the dried aluminum metal substrate is then wet-impregnated with the above-mentioned silane coupling agent to be dried on the surface for use.
  • the surface of the aramid fabric was rinsed with absolute ethanol to remove impurities and oven dried for 1 h. Then, it is immersed in the prepared phosphoric acid solution for 0.5 to 1 hour, and dried in an oven for use.
  • the treated aluminum metal substrate is brushed by using the adhesive of the invention, the treated aramid fabric is covered on the adhesive, baked in a blast oven at 50 ° C for 1 hour, and the pressure of 0.2 MPa is taken out and heated (program Curing, 2 hours) to 160 ° C for 2 hours. After the completion of the curing, the peel strength was measured by a tensile tester to be 0.82 N/mm.
  • the surface pretreatment method of metal and fabric is the same as in Example 1.
  • the treated aluminum metal substrate is brushed by using the adhesive of the invention, the treated aramid fabric is covered on the adhesive, baked in a blast oven at 50 ° C for 1 hour, and the pressure of 0.2 MPa is taken out and heated (program Curing, 2 hours) to 160 ° C for 2 hours. After the completion of the curing, the peel strength was measured by a tensile tester of 1.17 N/mm.
  • the surface pretreatment method of metal and fabric is the same as in Example 1.
  • the treated aluminum metal substrate is brushed by using the adhesive of the invention, the treated aramid fabric is covered on the adhesive, baked in a blast oven at 50 ° C for 1 hour, and the pressure of 0.2 MPa is taken out and heated (program Curing, 2 hours) to 160 ° C for 2 hours. After the completion of the curing, the peel strength was measured to 1.03 N/mm by a tensile tester.
  • the surface pretreatment method of metal and fabric is the same as in Example 1.
  • the treated aluminum metal substrate is brushed by using the adhesive of the invention, the treated aramid fabric is covered on the adhesive, baked in a blast oven at 50 ° C for 1 hour, and the pressure of 0.2 MPa is taken out and heated (program Curing, 2 hours) to 160 ° C for 2 hours. After the completion of the curing, the peel strength was measured by a tensile tester of 1.42 N/mm.
  • the invention provides an epoxy type metal/fabric adhesive with high fatigue resistance and uniform stress, which solves the problem that the traditional fiber fabric and the metal matrix are difficult to be bonded, and overcomes the hard brittleness and crack resistance of the common epoxy resin. Low, low impact strength and other shortcomings.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

一种金属/织物粘接胶及其制备、使用方法，涉及一种胶粘剂及其制备、使用方法。其配方为：环氧树脂80～120g，活性稀释剂10～30g，硅烷偶联剂0.5～5g，金属氧化物纳米粉0.5～5g，固化剂35～60g。使用时，通过硅烷偶联剂、磷酸/硝酸混合溶液分别对金属、织物进行表面处理引入活性基团，增强界面粘接力。本发明在提高金属/织物界面粘接的同时，解决了传统环氧型粘接胶质地硬脆、耐开裂性能低、抗冲击强度差等缺点，且操作简单，易于推广。

Description

一种金属/织物粘接胶及其制备、使用方法 技术领域
本发明涉及一种胶粘剂，尤其是一种用于织物与金属粘接的胶粘剂。
技术背景
金属粘接是新兴的金属与金属和金属与非金属的固体界面相连接的技术，其根本是通过借助胶粘剂在固体表面上所产生的粘合力，将两种材料牢固地连接在一起。粘接的主要形式有两种：非结构型和结构型。非结构粘接主要是指表面粘涂、密封和功能性粘接，典型的非结构胶包括表面粘接用胶粘剂、密封和导电胶粘剂等；而结构型粘接是将结构单元用胶粘剂牢固地固定在一起的粘接现象，结构胶粘剂及其粘接点必须能传递结构应力，在设计范围内不影响其结构的完整性及对环境的适用性。
近年来，由金属与非金属材料复合而成的功能材料逐渐在航天、军工等领域得到越来越重要的应用。但是，由于金属材料与非金属材料自身的性质和胶粘剂难以反应形成稳定的粘接层，进而影响复合材料的粘接强度。长久以来，剥离强度低、耐冲击强度弱、抗疲劳寿命短等因素限制金属粘接的应用，因而寻找一种简单易行的粘接金属与非金属材料的方法成为焦点。
在金属与非金属材料胶粘领域，李子东等(901快速强力胶及其制备方法，中国专利，公开号CN 1074469A)公开了一种增强剂改性丁苯胶的胶粘剂，用来粘合天然橡胶/铝的剥离强度可达2.98kN/m,高于一般酚醛树脂改性氯丁橡胶胶粘剂，但该工艺较为麻烦。吕广镛(金属与非金属间粘合的胶粘剂及其制备方法，中国专利，公开号CN 1273261A)以丁苯胶为主要聚合物，通过加入极性聚合物氯磺化聚乙烯制备了一种金属/非金属胶粘剂。这种胶粘剂虽然制备成本较低，但是工艺较为复杂且耐热性及耐老化性较差。冯吉才等(有机活性胶状物及胶焊非金属与金属材料的方法，中国专利，CN 101402836A)以有机胶状物为过渡层，再通过钎料焊接金属/非金属界面。这种方法虽然能克服非金属材料难焊性的限制，但是使用时需在真空炉中高温进行焊接，能耗高，工艺复杂。
发明内容
本发明的目的在于提供一种抗疲劳强度高、承受应力均匀的环氧型金属/织 物胶粘剂，解决了传统纤维织物与金属基体难粘接的问题，同时克服了普通环氧树脂质地硬脆、耐开裂性能低、抗冲击强度差等缺点。在粘接金属/非金属界面，尤其是自润滑关节轴承中金属基体与衬垫织物界面极具推广与应用价值。
本发明提供了一种金属/织物粘接胶及其制备、使用方法。
所述金属主要包括钢材、铝材及其合金。
所述织物主要包括聚酰胺纤维、聚酯纤维、聚乙烯醇纤维、聚丙烯腈纤维、聚氯乙烯纤维织物等及其混合织物。
所述金属/织物粘接胶的配方如下：
环氧树脂80～120份，活性稀释剂10～30份，硅烷偶联剂0.5～5份，金属氧化物纳米粉0.5～5份，固化剂35～60份。
所述环氧树脂即商品环氧树脂，即分子中含有两个或多个环氧基团的化合物，如环氧E-44、E-51、E-55、E4-2、E3-1、E4-6、E-20等。
所述活性稀释剂为1,6-己二醇二丙烯酸酯、甲基丙烯酸-β-羟乙酯、甲苯缩水甘油醚、蓖麻油多缩水甘油醚，乙二醇二缩水甘油醚等。
所述硅烷偶联剂采用通式为Y(CH2)nSiX3的硅烷偶联剂，其中，n＝0～3；X为氯基、甲氧基、乙氧基、甲氧基乙氧基、乙酰氧基等，Y为氨基或环氧基。
所述固化剂为与环氧树脂配合使用的胺类或酸酐类化合物等，胺类如乙二胺、二乙烯三胺、间苯二胺等；酸酐类如邻苯二甲酸酐、均苯四甲酸酐、甲基环己烯四羧酸酐等。
所述金属氧化物纳米粉为20～200nm的ZnO、Al2O3、BaO、Fe3O4等。
所述金属/织物粘接胶的制备方法为：首先，金属氧化物纳米粉、硅烷偶联剂、固化剂、先后依次溶于活性稀释剂中，搅拌0.5～1小时得到均匀乳液；其次，超声振荡下往乳液中分批逐量加入环氧树脂，搅拌0.5～2小时至均匀。
所述金属/织物粘接胶的使用方法为：首先，金属基板表面用丙酮清洗冲刷干净、去离子水洗涤、烘箱干燥后，涂覆所述硅烷偶联剂静置0.5～1小时；其次，将织物置于体积比为1:9～4:6的磷酸/硝酸混合溶液中40～60℃下浸泡0.5～2小时。所述磷酸浓度为1～3mol/L；所述硝酸浓度为1～3mol/L。
本发明所述金属/织物粘接胶具有如下特点：
(1)对金属和织物表面进行了预处理使其带上官能基团参与胶粘剂的固化 反应，从而使粘接强度大幅提高，剥离强度显著增加。
(2)胶粘剂中加入了硅烷偶联剂和金属纳米粉组分，提高胶粘剂和金属基底的结合性且提高了粘接层的力学强度，无机组分的加入也提高了材料的耐热性。
(3)活性稀释剂组分的加入降低了环氧树脂的脆性，提高了粘接层的抗冲击强度。
附图表说明
图1～图4分别为实施例1～实施例4的剥离强度图。
具体实施方式
下面通过实施例对本发明做进一步说明。
实施例1
先将铝制金属基板用丙酮清洗冲刷干净、去离子水洗涤、烘箱干燥1h以除去金属表面氧化物等杂质。再将干燥的铝制金属基板用上述的硅烷偶联剂润湿浸渍待表面干燥后备用。用无水乙醇冲洗芳纶织物表面以除去杂质、烘箱干燥1h。再用配制的磷酸溶液浸渍处理0.5～1h，烘箱干燥后备用。
1gAl2O3纳米粉、10ml乙二醇二缩水甘油醚、0.5gγ-缩水甘油醚氧丙基三甲氧基硅烷偶联剂、40g4,4’—二氨基二苯砜先后溶于35ml丙酮中，搅拌一小时后在超声振荡下分10次共添加90g环氧树脂E51，继续搅拌1小时即得到自润滑涂层。使用本发明胶粘剂对处理过的铝制金属基板进行刷涂，将处理过的芳纶织物覆盖于胶粘剂上，置于鼓风烘箱中50℃烘1小时，取出施加0.2MPa的压力并升温(程序升温，2小时内)至160℃固化2小时。固化完成后，用拉伸试验机测得剥离强度0.82N/mm。
实施例2
金属与织物的表面预处理方法同实施例1。
1gAl2O3纳米粉、15ml乙二醇二缩水甘油醚、1gγ-缩水甘油醚氧丙基三甲氧基硅烷偶联剂、50g4,4’—二氨基二苯砜先后溶于35ml丙酮中，搅拌一小时后在超声振荡下分10次共添加100g环氧树脂E51，继续搅拌1小时即得到自润滑涂层。使用本发明胶粘剂对处理过的铝制金属基板进行刷涂，将处理过的芳纶织物覆盖于胶粘剂上，置于鼓风烘箱中50℃烘1小时，取出施加0.2MPa的压力并 升温(程序升温，2小时内)至160℃固化2小时。固化完成后，用拉伸试验机测得剥离强度1.17N/mm。
实施例3
金属与织物的表面预处理方法同实施例1。
0.5gAl2O3纳米粉、10ml乙二醇二缩水甘油醚、1gγ-缩水甘油醚氧丙基三甲氧基硅烷偶联剂、60g4,4’—二氨基二苯砜先后溶于35ml丙酮中，搅拌一小时后在超声振荡下分10次共添加120g环氧树脂E51，继续搅拌1小时即得到自润滑涂层。使用本发明胶粘剂对处理过的铝制金属基板进行刷涂，将处理过的芳纶织物覆盖于胶粘剂上，置于鼓风烘箱中50℃烘1小时，取出施加0.2MPa的压力并升温(程序升温，2小时内)至160℃固化2小时。固化完成后，用拉伸试验机测得剥离强度1.03N/mm。
实施例4
金属与织物的表面预处理方法同实施例1。
1gAl2O3纳米粉、20ml乙二醇二缩水甘油醚、0.5gγ-缩水甘油醚氧丙基三甲氧基硅烷偶联剂、55g4,4’—二氨基二苯砜先后溶于35ml丙酮中，搅拌一小时后在超声振荡下分10次共添加100g环氧树脂E51，继续搅拌1小时即得到自润滑涂层。使用本发明胶粘剂对处理过的铝制金属基板进行刷涂，将处理过的芳纶织物覆盖于胶粘剂上，置于鼓风烘箱中50℃烘1小时，取出施加0.2MPa的压力并升温(程序升温，2小时内)至160℃固化2小时。固化完成后，用拉伸试验机测得剥离强度1.42N/mm。
工业实用性
本发明提供一种抗疲劳强度高、承受应力均匀的环氧型金属/织物胶粘剂，解决了传统纤维织物与金属基体难粘接的问题，同时克服了普通环氧树脂质地硬脆、耐开裂性能低、抗冲击强度差等缺点。

Claims (7)

  1. 一种金属/织物粘接胶，所述金属主要包括钢材、铝材及其合金，
    所述织物主要包括聚酰胺纤维、聚酯纤维、聚乙烯醇纤维、聚丙烯腈纤维、聚氯乙烯纤维织物及其混合织物；所述金属/织物粘接胶的配方如下：
    环氧树脂80～120g，活性稀释剂10～30g，硅烷偶联剂0.5～5g，金属氧化物纳米粉0.5～5g，固化剂35～60g；
    金属/织物粘接胶的使用方法，首先，将金属基板表面用丙酮清洗冲刷干净、去离子水洗涤、烘箱干燥后，涂覆硅烷偶联剂静置0.5～1小时；其次，将织物置于体积比为1:9～4:6的磷酸/硝酸混合溶液中40～60℃下浸泡0.5～2小时；所述磷酸浓度为1～3mol/L；所述硝酸浓度为1～3mol/L；使用所述胶粘剂对处理过的铝制金属基板进行刷涂，将处理过的织物覆盖于胶粘剂上，经烘干、加压固化完成。
  2. 根据权利要求1所述的一种金属/织物粘接胶，其特征在于所述环氧树脂为商品环氧树脂，即分子中含有两个或多个环氧基团的化合物，包括环氧E-44、E-51、E-55、E4-2、E3-1、E4-6、E-20。
  3. 根据权利要求2所述的一种金属/织物粘接胶，其特征在于所述活性稀释剂为1,6-己二醇二丙烯酸酯、甲基丙烯酸-β-羟乙酯、甲苯缩水甘油醚、蓖麻油多缩水甘油醚，乙二醇二缩水甘油醚。
  4. 根据权利要求3所述的一种金属/织物粘接胶，其特征在于所述硅烷偶联剂采用通式为Y(CH2)nSiX3的硅烷偶联剂，其中，n＝0～3；X为氯基、甲氧基、乙氧基、甲氧基乙氧基、乙酰氧基，Y为氨基或环氧基。
  5. 根据权利要求4所述的一种金属/织物粘接胶，其特征在于所述固化剂为与环氧树脂配合使用的胺类或酸酐类化合物，包括乙二胺、二乙烯三胺、间苯二胺；酸酐类包括邻苯二甲酸酐、均苯四甲酸酐、甲基环己烯四羧酸酐。
  6. 根据权利要求5所述的一种金属/织物粘接胶，其特征在于所述金属氧化物纳米粉为20～200nm的ZnO、Al2O3、BaO、Fe3O4。
  7. 根据权利要求1至6所述的一种金属/织物粘接胶的制备方法，其特征在于：金属氧化物纳米粉、硅烷偶联剂、固化剂、先后依次溶于活性稀释剂中，搅拌0.5～1小时得到均匀乳液；其次，超声振荡下往乳液中分批逐量加入环氧树脂，搅拌0.5～2小时至均匀。
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US10843854B2 (en) 2015-10-13 2020-11-24 Pultrusion Technique Inc. Techniques for making and using holding straps with hook-and-strap attachment

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