A metal binder, a method of preparation, a method of bonding

Abstract

The present application relates to a kind of metal binder, preparation method, bonding method, the raw material of metal binder includes thermoplastic resin, carbon fiber, thermoplastic elastomer sulfur-based resin, in parts by weight, in the raw material described in: thermoplastic resin: 100 parts;Carbon fiber: 10-30 parts;Thermoplastic elastomer sulfur-based resin: 3-15 parts;Wherein, the raw material of thermoplastic elastomer sulfur-based resin includes: thermoplastic elastomer: 100 parts;Metal compound: 30-80 parts;Sulfur-containing modifier: 20-40 parts.The metal binder provided by the present application, solvent is not used in the preparation process, the binder has no irritating smell, meets the environmental protection requirement;Metal binder is rich in a variety of polar groups, and there is stronger interaction between metal surface, not easy to fall off with metal layer in long-term use process;The hardness, toughness of metal binder is better, and temperature resistance, acid and alkali resistance is excellent.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of metal binder preparation, and particularly relates to a metal binder, a preparation method and a binding method. BACKGROUND

[0002] With the development of society and the improvement of the level of science and technology, people have higher and higher requirements for material strength. Most products adopt metal materials such as aluminum alloy, stainless steel, zinc alloy, etc. Metal materials have the advantages of high strength, thin thickness, fast heat dissipation and good texture. In order to realize the rapid and effective connection of metal and other materials, the main methods are: 1. Screw holes or buckles and other structures are bonded. This method is easy to increase weight and requires processes such as hole opening, which destroys the integrity of the material; 2. Welding. This method is complex to clamp and fix, and when the metal shell is thin, it will affect the appearance of the product and subsequent processing; 3. Binder bonding.

[0003] The third method of binder bonding is light in quality and convenient in construction, so many studies are devoted to binder bonding metal surfaces. For example, patent US2003 / 0135197 discloses a method for connecting metal and polymer surfaces for medical devices by using a coupling agent. The coupling agent contains at least two sets of functional groups with binding affinity to organic and inorganic compounds, respectively. The preferred coupling agent has a first functional group that forms a covalent bond with the polymeric material, and a second functional group that forms an ionic bond with the metal such as stainless steel. The coupling agent can be used with or without heat activation. However, this method still needs to use a third-party adhesive, and the performance is limited.

[0004] For example, in patent CN201711166435.3, by compounding ternary chlorovinyl resin and fluororesin in the resin, the adhesion to metal is improved, and the tensile shear strength of the polymer resin and the metal can be increased by nearly 70%. However, the ternary chlorovinyl resin used in this method has poor heat resistance, and part of it will decompose during processing, increasing the processing difficulty and causing unstable product performance and reducing the service life. SUMMARY

[0005] The purpose of the present application is to provide a metal binder with the advantages of good processing performance, stable product performance after bonding, and strong adhesion to metal.

[0006] The present application also provides a preparation method of the above-mentioned metal binder.

[0007] The present application also provides a binding method of the above-mentioned metal binder and metal.

[0008] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is:

[0009] A metal binder, raw materials of which include a thermoplastic resin, carbon fiber, a thermoplastic elastomer sulfur-based resin, in parts by weight, the raw materials include:

[0010] Thermoplastic resin: 100 parts;

[0011] Carbon fiber: 10-30 parts;

[0012] Thermoplastic elastomer sulfur-based resin: 3-15 parts;

[0013] The raw materials of the thermoplastic elastomer sulfur-based resin include:

[0014] Thermoplastic elastomer: 100 parts;

[0015] Metal compound: 30-80 parts;

[0016] Sulfur-containing modifier: 20-40 parts.

[0017] In some embodiments of the present application, the thermoplastic resin is one or more combinations selected from polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyamide, polyformaldehyde, polycarbonate, polyphenylene ether, polysulfone, rubber, polyester, and polyphenyl sulfonic acid resin. The thermoplastic resin has the property of softening when heated and hardening when cooled, and no chemical reaction occurs during heating, and this property is maintained regardless of the number of times heating and cooling are repeated.

[0018] According to some specific aspects of the present application, the thermoplastic resin is a polyphenyl sulfonic acid resin, which contains sulfur elements and benzene ring functional groups in its molecular structure, and has better mechanical properties and good adhesion to metals.

[0019] According to some specific aspects of the present application, the polyphenyl sulfonic acid resin includes, but is not limited to, one or more combinations selected from polystyrene sulfonic acid resin, polyphenylene sulfide resin, polyphenylene sulfone resin, polyether sulfone resin, and polyaryl sulfone resin.

[0020] According to some specific aspects of the present application, the polyphenyl sulfonic acid resin is preferably one or more combinations of polyphenylene sulfide resin and polyphenylene sulfone resin, which can achieve better mechanical properties.

[0021] According to some specific aspects of the present application, the thermoplastic resin has a melt index of 10-50 g / 10 min at 235°C and 2.16 kg, and has preferable processing performance and physical and mechanical properties. The melt index (MI) is the weight of the melt of a thermoplastic plastic passing through a standard capillary in ten minutes at a certain temperature and pressure, expressed in (g / 10 min). The larger the MI value, the lower the viscosity and average molecular weight of the raw material, the better the processing performance and flowability; on the contrary, the smaller the MI value, the greater the viscosity and average molecular weight of the raw material, the worse the processing performance and flowability, but the higher the physical and mechanical properties.

[0022] In some embodiments of the present application, the carbon fiber is mainly composed of carbon elements, has the characteristics of high temperature resistance, friction resistance, heat conduction and corrosion resistance, and can be processed into various fabrics in the form of fibers. The carbon fiber is one or a combination of more than one selected from the group consisting of powder carbon fiber, carbon fiber short fiber, carbon fiber long fiber, carbon fiber bundle, carbon fiber cloth, and carbon fiber felt.

[0023] According to some specific aspects of the present application, in order to facilitate and uniformity of processing, the carbon fiber is preferably powder carbon fiber.

[0024] According to some specific aspects of the present application, the fiber length of the powder carbon fiber is in the micron level, and can be a mixture of powder carbon fibers with different fiber lengths within 1-1000 microns.

[0025] According to some specific aspects of the present application, in order to facilitate mixing uniformity and better mechanical properties, the amount of powder carbon fibers with different fiber lengths is different, based on 100 parts by weight of the amount of carbon fiber.

[0026] Further preferably, the carbon fiber comprises powder carbon fiber with a fiber length of 30 μm and powder carbon fiber with a fiber length of 130 μm, wherein the weight percentage of the powder carbon fiber with a fiber length of 30 μm is 40-95%, and the weight percentage of the powder carbon fiber with a fiber length of 130 μm is 5-60%. Alternatively, the carbon fiber comprises powder carbon fiber with a fiber length of 30 μm and powder carbon fiber with a fiber length of 130 μm, wherein the weight percentage of the powder carbon fiber with a fiber length of 30 μm is 60-95%, and the weight percentage of the powder carbon fiber with a fiber length of 130 μm is 5-40%.

[0027] In some embodiments of the present application, the thermoplastic elastomer includes, but is not limited to, a combination of one or more selected from styrene-based (SBS, SIS, SEBS, SEPS), olefin-based (TPO, TPV), diene-based (TPB, TPI), chlorovinyl-based (TPVC, TCPE), urethane-based (TPU), polyester-based (TPEE), polyamide-based (TPAE), organic fluorine-based (TPF), organosilicon-based, and ethylene-based. The thermoplastic elastomer is a type of elastomer that has the elasticity of rubber at room temperature and can be molded into a plastic at high temperature. The structural feature of the thermoplastic elastomer is that the different resin segments and rubber segments are composed of chemical bonds, the resin segments form physical crosslinking points by interchain forces, and the rubber segments are highly elastic segments that contribute to elasticity; the physical crosslinking of the plastic segments reversibly changes with temperature, showing the plastic processing characteristics of the thermoplastic elastomer.

[0028] According to some specific aspects of the present application, the thermoplastic elastomer includes a thermoplastic polyamide elastomer, which is a block copolymer including hard segments and soft segments, wherein the soft segments are aliphatic polyester or polyether soft segments, and the hard segments are polyamide hard segments; the soft segments and the hard segments induce the formation of hard segment and soft segment microzones and produce a microphase separation structure due to thermodynamic incompatibility; the crystalline microzones formed by the hard segments and hydrogen bonds act as physical crosslinking points, and the flexible soft segments are distributed in the amorphous region, giving the product good elasticity.

[0029] According to some specific aspects of the present application, the soft segment is preferably a polyether block, which has good toughness and mechanical properties.

[0030] In some embodiments of the present application, the metal compound includes one or more of S and N elements, which have strong metal adsorption properties.

[0031] According to some specific aspects of the present application, the metal compound is a combination of one or more selected from sodium sulfide, potassium sulfide, zinc sulfide, magnesium sulfide, ferrous sulfide, manganese sulfide, lead sulfide, cadmium sulfide, antimony sulfide, stannous sulfide, silver sulfide, copper sulfide, mercury sulfide, calcium sulfide, strontium sulfide, barium sulfide, manganese nitride, tungsten nitride, zirconium nitride, aluminum nitride, lithium nitride, and magnesium nitride.

[0032] According to some specific aspects of the present application, the metal compound is preferably one or more of cadmium sulfide and zirconium nitride.

[0033] According to some specific aspects of the present application, the amount of the metal compound is 30-80 parts. A smaller amount and a smaller content of S element weaken the affinity and are not conducive to metal adhesion; if the amount is larger, the thermoplastic elastomer is prone to rapid degradation, reducing the service life.

[0034] According to some specific aspects of the present application, the metal compound is used in an amount of 40-70 parts.

[0035] In some embodiments of the present application, the sulfur-containing modifier is a combination of one or more selected from thiourea, disodium lauryl sulfosuccinate, dimethyl sulfoxide, fatty alcohol polyoxyethylene ether (3) sulfosuccinate disodium MES, sodium dodecyl sulfate, and 1-dodecyl mercaptan, which can further bond the metal.

[0036] According to some specific aspects of the present application, the sulfur-containing modifier is a combination of one or more selected from thiourea and sodium dodecyl sulfate, which facilitates processing and has good thermal stability.

[0037] The present application provides another technical solution:

[0038] A preparation method of the metal binder, comprising:

[0039] The thermoplastic elastomer and the sulfur-containing modifier are heated to 200-300°C and stirred, then the metal compound is added, and the temperature is lowered to obtain a thermoplastic elastomer sulfur-based resin; then the thermoplastic resin is heated to melt, and finally the thermoplastic resin, the thermoplastic elastomer sulfur-based resin, and the carbon fiber are mixed to obtain the metal binder.

[0040] The present application provides another technical solution:

[0041] A preparation method of the metal binder, comprising:

[0042] The metal binder is cut and bonded with the metal through a hot riveting device, and the hot riveting temperature is 150-300°C, and the metal product bonded by the metal binder is placed at room temperature.

[0043] According to some specific aspects of the present application, the metal product bonded by the metal binder is placed at room temperature for 24 hours after bonding.

[0044] Due to the use of the above technical solutions, the present application has the following advantages compared with the prior art:

[0045] The metal binder preparation process of the present application does not use solvent, the binder has no irritating odor, and meets the environmental protection requirements; the metal binder is rich in various polar groups, has a strong interaction with the metal surface, and is not easy to fall off from the metal layer during long-term use; the hardness and toughness of the metal binder are better. DETAILED DESCRIPTION

[0046] The present application will be further described below in conjunction with the illustrated embodiments.

[0047] Examples 1-15 and Comparative Examples 1-5 are provided, and the raw materials used in each of the examples and comparative examples are as follows:

[0048]

Thermoplastic Resin

[0049] A1: Polyphenylene sulfide resin, BR-111BL polyphenylene sulfide resin produced by Chevron Phillips, USA, with a melt index of 35.2 g / 10 min.

[0050] A2: Polyphenylene sulfone resin, Paryls F1350 polyphenylene sulfone resin produced by Guangdong Youjuxian Advanced New Materials Co., Ltd., with a melt index of 18.7 g / 10 min.

[0051]

Carbon Fiber

[0052] B1: Powdered carbon fiber, MLD-30 carbon fiber powder produced by Toray Industries, Inc., Japan, with a fiber length of 30 μm.

[0053] B2: Powdered carbon fiber, MLD-300 carbon fiber powder produced by Toray Industries, Inc., Japan, with a fiber length of 130 μm.

[0054] The carbon fibers (M1-M3) were prepared by weighing the ingredients according to the formulations shown in Table 1 and physically mixing them uniformly. See Table 1.

[0055] Table 1 Formulations of Carbon Fibers (M1-M3)

[0056] Carbon fibers Carbon fibers B1 Parts by weight Carbon fibers B2 Parts by weight M1 B1 80 B2 20 M2 B1 95 B2 5 M3 B1 60 B2 40

[0057]

Thermoplastic Polyamide Elastomer

[0058] C1: Polyether-block polyamide elastomer, PEBAX-4033 polyether-block polyamide elastomer produced by Arkema.

[0059] C2: Polyolefin elastomer, POE6102 polyolefin elastomer produced by Exxon.

[0060]

Metal Compound

[0061] D1: Cadmium sulfide, C305399 cadmium sulfide produced by Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0062] D2: Zirconium nitride, Z119196 zirconium nitride produced by Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0063]

Sulfur-containing Modifier

[0064] E1: Thiourea, T400612 thiourea produced by Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0065] E2: Sodium dodecyl sulfate, S348686 sodium dodecyl sulfate produced by Shanghai Aladdin Biochem Technology Co., Ltd.

[0066] Thermoplastic elastomer sulfur-based resin (N1, N3-N10) was prepared according to the formulation in Table 2. A certain amount of thermoplastic elastomer and sulfur-containing modifier were weighed and heated to 270°C, stirred for 1 h, and mixed uniformly. Then a certain amount of metal compound was weighed and added, and the mixture was stirred for 2 h to obtain the thermoplastic elastomer sulfur-based resin. See Table 2.

[0067] Thermoplastic elastomer sulfur-based resin (N2) was prepared according to the formulation in Table 2. A certain amount of thermoplastic elastomer and sulfur-containing modifier were weighed and heated to 180°C, stirred for 1 h, and mixed uniformly. Then a certain amount of metal compound was weighed and added, and the mixture was stirred for 2 h to obtain the thermoplastic elastomer sulfur-based resin. See Table 2.

[0068] Table 2 Formulation of thermoplastic elastomer sulfur-based resin (N1-N10)

[0069]

[0070]

[0071] The raw material formulation of Examples 1-15 and Comparative Examples 1-5 is shown in Table 3.

[0072] Table 3 Raw material formulation of Examples 1-15 and Comparative Examples 1-5

[0073]

[0074] Examples 1-15, Comparative Examples 1, 2, 4, and 5 were prepared according to the formulation shown in Table 3. The process was as follows: a certain amount of thermoplastic resin was weighed and heated to melt, then thermoplastic elastomer sulfur-based resin and carbon fiber were added, stirred uniformly for 2 h, and cooled to obtain a metal adhesive. Next, the metal adhesive was used to bond the metal layer by the following method: the bonding surface of the metal (copper sheet) was cleaned and dried, then the metal adhesive sample was cut to match the size of the bonding surface of the metal, and the metal adhesive sample and copper sheet were bonded by a hot riveting device at a temperature of 280°C with a bonding area of 2.5 mm x 2.5 mm. The bonded metal product was placed at room temperature for 24 h.

[0075] Comparative Example 3: According to the formulation shown in Table 3, the preparation process is as follows: weigh a certain amount of thermoplastic resin, heat to melt, then add thermoplastic elastomer resin and carbon fiber, stir uniformly for 2 h, and cool to obtain a metal adhesive. Next, the metal adhesive is used to bond the metal layer by the following method: the bonding surface of the metal (copper sheet) is cleaned and dried, then the metal adhesive sample is cut to match the size of the metal bonding surface, and the metal adhesive sample and copper sheet are bonded by a hot riveting device at a temperature of 280°C, with a bonding area of 2.5 mm x 2.5 mm. After 24 h at room temperature, a metal product bonded by the metal adhesive is obtained.

[0076] The metal adhesives of Examples 1-15 and Comparative Examples 1-5 were injection molded into corresponding samples according to ISO test standards, and the following tests were performed. Unless otherwise specified, each test was performed at 25°C, and the main indicators are as follows:

[0077] 1. Tensile strength: tested according to GB / T 1040.1-2018;

[0078] 2. Elongation at break: tested according to GB / T 1040-1992;

[0079] 3. Metal bonding strength: a pressure of 10 N / min was applied to the copper sheet surface of the prepared metal product until the bonding layer failed, and the failure force was recorded. The greater the force, the higher the bonding strength.

[0080] Table 4: Performance test data of metal adhesives of Examples 1-15 and Comparative Examples 1-5

[0081]

[0082]

[0083] As shown in Tables 3 and 4, the metal adhesives prepared in the examples have better mechanical properties; the metal adhesives prepared in the examples have a stronger interaction force between the metal and the metal, and the bonding force is better.

[0084] In Example 7, the thermoplastic elastomer and sulfur-containing modifier were heated to 180°C; in Example 8, the thermoplastic elastomer and sulfur-containing modifier were heated to 270°C, and the tensile strength, elongation at break, and metal bonding strength of the metal adhesive of Example 8 were higher than those of the metal adhesive of Example 7.

[0085] The above examples are only for illustrating the technical concept and characteristics of the present application, and the purpose is to enable those skilled in the art to understand the content of the present application and to implement it, and cannot limit the protection scope of the present application. Any equivalent changes or modifications made in accordance with the spirit and essence of the present application should be covered within the protection scope of the present application.

Claims

1. A metal binder, characterized in that, The raw materials of the metal binder include a thermoplastic resin, carbon fibers, a thermoplastic elastomer sulfur-based resin, and the raw materials are in parts by weight: The thermoplastic resin: 100 parts; The carbon fibers: 10-30 parts; The thermoplastic elastomer sulfur-based resin: 3-15 parts; The raw materials of the thermoplastic elastomer sulfur-based resin include: The thermoplastic elastomer: 100 parts; The metal compound: 30-80 parts; The sulfur-containing modifier: 20-40 parts; The thermoplastic resin is one or a combination of more than one selected from polyphenylene sulfide resin and polyphenylene sulfone resin; The thermoplastic elastomer is one or a combination of more than one selected from polyether block polyamide elastomer and polyolefin elastomer; The sulfur-containing modifier is one or a combination of more than one selected from thiourea and sodium dodecyl sulfate; The metal compound is one or a combination of more than one selected from sodium sulfide, potassium sulfide, zinc sulfide, magnesium sulfide, ferrous sulfide, manganese sulfide, lead sulfide, cadmium sulfide, antimony sulfide, stannous sulfide, silver sulfide, copper sulfide, mercury sulfide, calcium sulfide, strontium sulfide, barium sulfide, manganese nitride, tungsten nitride, zirconium nitride, aluminum nitride, lithium nitride, magnesium nitride.

2. The metal bond of claim 1, wherein, The carbon fibers are one or a combination of more than one selected from powder carbon fibers, carbon fiber short fibers, carbon fiber long fibers, carbon fiber bundle wires, carbon fiber cloth, and carbon fiber felt.

3. A method of producing the metal binder as claimed in any one of claims 1 to 2, characterized in that, The method includes: The thermoplastic elastomer and the sulfur-containing modifier are heated and stirred, and then the metal compound is added to obtain the thermoplastic elastomer sulfur-based resin; The thermoplastic resin is then heated to melt, and finally the thermoplastic resin, the thermoplastic elastomer sulfur-based resin, and the carbon fibers are mixed to obtain the metal binder.

4. A method of bonding metal to metal binder, characterized by, The metal binder is the metal binder according to any one of claims 1-2, and the method includes: bonding the metal binder with a metal at a temperature of 150-300°C, and then placing the metal at room temperature to obtain a metal bonded by the metal binder.

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