WO2021243798A1 - 一种橡胶粘合剂及其制备方法 - Google Patents

一种橡胶粘合剂及其制备方法 Download PDF

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Publication number
WO2021243798A1
WO2021243798A1 PCT/CN2020/100648 CN2020100648W WO2021243798A1 WO 2021243798 A1 WO2021243798 A1 WO 2021243798A1 CN 2020100648 W CN2020100648 W CN 2020100648W WO 2021243798 A1 WO2021243798 A1 WO 2021243798A1
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Prior art keywords
filler
rubber
mixture
temperature
mass ratio
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PCT/CN2020/100648
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English (en)
French (fr)
Inventor
赵会岩
张志胜
赵海林
闫玉良
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山东汇达橡胶有限公司
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Publication of WO2021243798A1 publication Critical patent/WO2021243798A1/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
    • C09J115/00—Adhesives based on rubber derivatives
    • C09J115/02—Rubber derivatives containing halogen
    • 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
    • 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
    • C09J11/08—Macromolecular additives
    • 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
    • C09J111/00—Adhesives based on homopolymers or copolymers of chloroprene
    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

Definitions

  • the invention relates to the technical field of adhesives, in particular to a rubber adhesive and a preparation method thereof.
  • Rubber adhesive is a kind of adhesive made of synthetic rubber or natural rubber such as neoprene, nitrile, butyl silicone rubber, polysulfide, etc. as the main material. It has excellent elasticity, and is especially suitable for bonding soft materials or materials with very different thermal expansion coefficients, such as rubber and rubber, rubber and metal, plastic, leather, wood and other materials.
  • One of the shortcomings in the prior art is that the thermodynamic properties of the rubber adhesive are not ideal and are not resistant to high temperatures.
  • the present invention aims to solve at least one of the above technical problems.
  • the first object of the present invention is to provide a method for preparing a rubber adhesive.
  • the second object of the present invention is to provide a rubber adhesive.
  • an embodiment of the present invention provides a method for preparing a rubber adhesive, which includes the following steps:
  • Step S100 Use graphene filler, inorganic filler, fiber filler, organic filler and rubber main material to prepare the first mixture;
  • the obtained first mixture is uniformly mixed with 1,6-hexanediol diacrylate and dibutyltin dilaurate under a temperature condition of 20°C to 30°C to obtain a second mixture;
  • Step S300 The second mixture obtained in step S200 is cured under a temperature condition of 60° C. to 80° C. for 12 to 18 hours to obtain a rubber adhesive.
  • the graphene filler is used to improve the thermodynamic stability of the rubber adhesive.
  • Graphene is a nanomaterial with excellent thermodynamic properties and toughness.
  • the addition of graphene filler can increase the thermal decomposition temperature of the rubber adhesive.
  • Inorganic fillers and fiber fillers are used to further improve the thermodynamic stability and mechanical properties of rubber adhesives.
  • graphene fillers, inorganic fillers, fiber fillers, organic fillers and rubber main materials are used to prepare the first mixture.
  • the first mixture is subjected to the action of 1,6-hexanediol diacrylate and dibutyltin dilaurate. Curing at a temperature higher than room temperature.
  • the rubber adhesive obtained by this embodiment has good thermodynamic stability and mechanical properties.
  • the inorganic filler is composed of silicon oxide, aluminum oxide, yttrium oxide, and lithium oxide.
  • the inorganic powder mixture composed of silicon oxide, aluminum oxide, yttrium oxide and lithium oxide has excellent mechanical and thermodynamic properties.
  • step S100 the fiber filler is obtained by spinning using an aramid fiber spinning solution under the action of a high-voltage electric field.
  • the fiber filler obtained by spinning aramid fiber spinning solution under the action of high-voltage electric field has the advantages of high strength, high modulus, high temperature resistance, acid and alkali resistance.
  • the organic filler includes liquid hydroxy-terminated nitrile rubber.
  • Liquid hydroxy-terminated nitrile rubber can not only ensure the uniform dispersion of graphene fillers, inorganic fillers, and fiber fillers, but also improve the toughness of rubber adhesives.
  • the main rubber material includes chlorinated rubber.
  • Chlorinated rubber is a rubber chlorinated derivative obtained by chlorination modification of natural rubber. Adhesives formulated with it can be widely used in aircraft manufacturing, automobile manufacturing, construction, light industry, rubber product processing and many other fields.
  • step S100 specifically includes:
  • Step S110 The silicon oxide, aluminum oxide, yttrium oxide and lithium oxide are uniformly mixed and then heated to 1400°C to 1600°C and kept for 2 hours. After cooling, they are ground and crushed to obtain an inorganic filler;
  • Step S120 Spinning with an aramid fiber spinning solution under the action of a DC high-voltage electric field to obtain a fiber filler
  • Step S130 Mix the liquid hydroxy-terminated nitrile rubber, isophorone diisocyanate and 3-dimethylamino-1-propanol uniformly at a temperature of 20°C to 30°C, and under nitrogen protection and 50°C to 55°C React at a temperature of °C for 20h to 24h to obtain an organic filler;
  • Step S140 Use chlorinated natural rubber, chloroprene rubber and ethyl acetate to stir at a temperature of 20°C to 30°C for 2h to 3h to obtain a main rubber material;
  • Step S150 The graphene filler, inorganic filler, fiber filler and organic filler are uniformly mixed in the diphenol-based propane epoxy resin to obtain a filler mixture;
  • Step S160 Add the filler mixture obtained in step S150 to the rubber main material obtained in step S140, and stir at a temperature of 40°C to 50°C for 4h to 5h to obtain a first mixture.
  • step S110 silicon oxide, aluminum oxide, yttrium oxide, and lithium oxide are uniformly mixed and then sintered at a high temperature.
  • the silicon oxide, aluminum oxide and yttrium oxide form yttrium aluminum under the action of lithium oxide as a nucleating agent.
  • the garnet crystal phase of the inorganic ceramic structure, and then the sintered product is ground and pulverized to obtain a fine powdery inorganic filler.
  • the inorganic filler with the yttrium aluminum garnet crystal phase not only has excellent mechanical properties, but also can greatly improve the thermodynamic stability of the rubber adhesive.
  • the main rubber material of this embodiment includes chlorinated natural rubber and chloroprene rubber, while the organic filler of this embodiment includes liquid hydroxy-terminated nitrile rubber.
  • the molecular structure of chlorinated natural rubber is different from that of neoprene.
  • the side chain of chloroprene rubber is a carbon-chlorine group with less steric hindrance, while the side chain of chlorinated natural rubber is a six-membered cyclic group.
  • the addition of an organic filler including nitrile rubber can improve the toughness of the main rubber material including chlorinated natural rubber and neoprene.
  • step S150 this embodiment adds graphene fillers, inorganic fillers, fiber fillers, and organic fillers to the diphenol-based propane epoxy resin and mixes them so as to improve the composition of graphene fillers, inorganic fillers, fiber fillers, and organic fillers in the main rubber. The uniformity of dispersion in the material.
  • step S120 specifically includes:
  • Step S122. Press N,N-dimethylformamide: N,N-dimethylacetamide: N-methylpyrrolidone: lithium chloride (15-30): (20-30): (40-50 ): (5-10) the mass ratio of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and lithium chloride under the temperature conditions of 90°C to 95°C Mix well to obtain solvent;
  • Step S125 Dissolve the poly(p-phenylene terephthalamide) obtained in step S124 in tetrahydrofuran and mix them uniformly at a temperature of 40°C to 60°C to prepare an aramid fiber spinning solution;
  • Step S126 The aramid fiber spinning solution obtained in step S125 is loaded into an electrostatic spinning device, and the aramid fiber spinning solution is sprayed to form a fiber filler under the action of a direct current high voltage electric field of 60kV to 70kV.
  • step S121 o-chloro-p-phenylenediamine is a chlorine-containing monomer, and 2,5-diaminobenzenesulfonic acid is an ammonia-containing monomer.
  • a chlorine-containing monomer and an ammonia-containing monomer By introducing a chlorine-containing monomer and an ammonia-containing monomer, the phase change in step S121 can be avoided.
  • the emergence of the problem prevents the molecules from being closely arranged, increases the free volume, and weakens the hydrogen bond between the molecules. Therefore, the crystallinity of the polyparaphenylene terephthalamide obtained later is reduced and the solubility is improved.
  • the positive and negative ions are grafted onto the molecular chain of poly(p-phenylene terephthalamide) with sulfonic acid groups.
  • the fluidity of the poly(p-phenylene terephthalamide) is improved, and the properties of the fiber filler are uniform and stable.
  • the solubility of the polymerized product in the solvent will continue to decrease. Therefore, in order to ensure the continued progress of the reaction and the viscosity of the polymerized product, lithium chloride is added to the solvent as an auxiliary additive in this embodiment.
  • the complexation between lithium chloride and polar solvent ensures the continuous progress of the reaction, and the complex product between lithium chloride and N-methylpyrrolidone can further interact with the amine group hydrogen on the molecular chain of the polymer product. It acts to further weaken the hydrogen bonds between molecular chains and increase the molecular weight of poly(p-phenylene terephthalamide).
  • the embodiment of the present invention uses an ammonium bicarbonate aqueous solution to adjust the pH value, and successively uses an ethylenediaminetetraacetic acid aqueous solution and deionized water for multiple repeated washings.
  • the aqueous solution of ammonium bicarbonate can neutralize the small-molecule hydrochloric acid that is continuously generated in the reaction. Since lithium chloride is used as an auxiliary additive of the solvent in the embodiment of the present invention, after the reaction is completed, the lithium ions adsorbed on the surface of the polyparaphenylene terephthalamide are difficult to be completely cleaned and removed. The remaining lithium ions will react with the solvent of the spinning solution in the subsequent electrospinning process and affect the performance of the fiber filler.
  • the embodiment of the present invention uses an ethylenediaminetetraacetic acid aqueous solution to clean the polymerization product, so that the lithium ions adsorbed on the surface of the poly(paraphenylene terephthalamide) and the ethylenediaminetetraacetic acid For complexation, the complex product of lithium ion and ethylenediaminetetraacetic acid can be easily washed with water.
  • Electrospinning is a process in which polymer solutions or polymer melts form fibers under the action of a high-voltage electrostatic field. The main principle is to make charged polymer solutions or melts flow, split and deform in the electrostatic field, and then undergo The solvent evaporates or the melt cools and solidifies, and finally the fiber filler is obtained.
  • graphene filler is prepared by the following steps:
  • Graphene has a sheet-layer structure with a large specific surface area and strong adsorption capacity. The interaction between the sheets and the sheets causes the graphene to agglomerate during use. Therefore, in this embodiment, the silicon-carbon coating is obtained through the above steps.
  • silicon carbide particles are uniformly dispersed in chitosan as a carbon source, and then subjected to high-temperature carbonization composite treatment with graphene.
  • the silicon-carbon element is bonded and coated on the surface of the graphene particles to improve the graphene On the basis of thermal stability, agglomeration between graphenes is avoided.
  • an embodiment of the present invention provides a rubber adhesive, and the rubber adhesive is obtained by the method for preparing the rubber adhesive according to any embodiment of the present invention.
  • the rubber adhesive of this embodiment is obtained by the method of preparing the rubber adhesive of any embodiment of the present invention, so it has all the beneficial effects of the method of preparing the rubber adhesive of any embodiment of the present invention. This will not be repeated here.
  • the embodiment of the present invention provides a method for preparing a rubber adhesive, including the following steps:
  • Step S100 Use graphene filler, inorganic filler, fiber filler, organic filler and rubber main material to prepare the first mixture;
  • the obtained first mixture is uniformly mixed with 1,6-hexanediol diacrylate and dibutyltin dilaurate under a temperature condition of 20°C to 30°C to obtain a second mixture;
  • Step S300 The second mixture obtained in step S200 is cured under a temperature condition of 60° C. to 80° C. for 12 to 18 hours to obtain a rubber adhesive.
  • the graphene filler is used to improve the thermodynamic stability of the rubber adhesive.
  • Graphene is a nanomaterial with excellent thermodynamic properties and toughness.
  • the addition of graphene filler can increase the thermal decomposition temperature of the rubber adhesive.
  • Inorganic fillers and fiber fillers are used to further improve the thermodynamic stability and mechanical properties of rubber adhesives.
  • graphene fillers, inorganic fillers, fiber fillers, organic fillers and rubber main materials are used to prepare the first mixture.
  • the first mixture is subjected to the action of 1,6-hexanediol diacrylate and dibutyltin dilaurate. Curing at a temperature higher than room temperature.
  • the rubber adhesive obtained by this embodiment has good thermodynamic stability and mechanical properties.
  • the inorganic filler is composed of silicon oxide, aluminum oxide, yttrium oxide, and lithium oxide.
  • the inorganic powder mixture composed of silicon oxide, aluminum oxide, yttrium oxide and lithium oxide has excellent mechanical and thermodynamic properties.
  • the fiber filler is obtained by spinning using an aramid fiber spinning solution under the action of a high-voltage electric field.
  • the fiber filler obtained by spinning aramid fiber spinning solution under the action of high-voltage electric field has the advantages of high strength, high modulus, high temperature resistance, acid and alkali resistance.
  • the organic filler in step S100, includes liquid hydroxy-terminated nitrile rubber.
  • Liquid hydroxy-terminated nitrile rubber can not only ensure the uniform dispersion of graphene fillers, inorganic fillers, and fiber fillers, but also improve the toughness of rubber adhesives.
  • the main rubber material includes chlorinated rubber.
  • Chlorinated rubber is a rubber chlorinated derivative obtained by chlorination modification of natural rubber. Adhesives formulated with it can be widely used in aircraft manufacturing, automobile manufacturing, construction, light industry, rubber product processing and many other fields.
  • step S100 specifically includes:
  • Step S110 The silicon oxide, aluminum oxide, yttrium oxide and lithium oxide are uniformly mixed and then heated to 1400°C to 1600°C and kept for 2 hours. After cooling, they are ground and crushed to obtain an inorganic filler;
  • Step S120 Spinning with an aramid fiber spinning solution under the action of a DC high-voltage electric field to obtain a fiber filler
  • Step S130 Mix the liquid hydroxy-terminated nitrile rubber, isophorone diisocyanate and 3-dimethylamino-1-propanol uniformly at a temperature of 20°C to 30°C, and under nitrogen protection and 50°C to 55°C React at a temperature of °C for 20h to 24h to obtain an organic filler;
  • Step S140 Use chlorinated natural rubber, chloroprene rubber and ethyl acetate to stir at a temperature of 20°C to 30°C for 2h to 3h to obtain a main rubber material;
  • Step S150 The graphene filler, inorganic filler, fiber filler and organic filler are uniformly mixed in the diphenol-based propane epoxy resin to obtain a filler mixture;
  • Step S160 Add the filler mixture obtained in step S150 to the rubber main material obtained in step S140, and stir at a temperature of 40°C to 50°C for 4h to 5h to obtain a first mixture.
  • step S110 silicon oxide, aluminum oxide, yttrium oxide, and lithium oxide are uniformly mixed and then sintered at a high temperature.
  • the silicon oxide, aluminum oxide and yttrium oxide form yttrium aluminum under the action of lithium oxide as a nucleating agent.
  • the garnet crystal phase of the inorganic ceramic structure, and then the sintered product is ground and pulverized to obtain a fine powdery inorganic filler.
  • the inorganic filler with the yttrium aluminum garnet crystal phase not only has excellent mechanical properties, but also can greatly improve the thermodynamic stability of the rubber adhesive.
  • the main rubber material of this embodiment includes chlorinated natural rubber and chloroprene rubber, while the organic filler of this embodiment includes liquid hydroxy-terminated nitrile rubber.
  • the molecular structure of chlorinated natural rubber is different from that of neoprene.
  • the side chain of chloroprene rubber is a carbon-chlorine group with less steric hindrance, while the side chain of chlorinated natural rubber is a six-membered cyclic group.
  • the addition of an organic filler including nitrile rubber can improve the toughness of the main rubber material including chlorinated natural rubber and neoprene.
  • step S150 this embodiment adds graphene fillers, inorganic fillers, fiber fillers, and organic fillers to the diphenol-based propane epoxy resin and mixes them so as to improve the composition of graphene fillers, inorganic fillers, fiber fillers, and organic fillers in the main rubber. The uniformity of dispersion in the material.
  • step S120 specifically includes:
  • Step S122. Press N,N-dimethylformamide: N,N-dimethylacetamide: N-methylpyrrolidone: lithium chloride (15-30): (20-30): (40-50 ): (5-10) the mass ratio of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and lithium chloride under the temperature conditions of 90°C to 95°C Mix well to obtain solvent;
  • Step S125 Dissolve the poly(p-phenylene terephthalamide) obtained in step S124 in tetrahydrofuran and mix them uniformly at a temperature of 40°C to 60°C to prepare an aramid fiber spinning solution;
  • Step S126 The aramid fiber spinning solution obtained in step S125 is loaded into an electrostatic spinning device, and the aramid fiber spinning solution is sprayed to form a fiber filler under the action of a direct current high voltage electric field of 60kV to 70kV.
  • step S121 o-chloro-p-phenylenediamine is a chlorine-containing monomer, and 2,5-diaminobenzenesulfonic acid is an ammonia-containing monomer.
  • a chlorine-containing monomer and an ammonia-containing monomer By introducing a chlorine-containing monomer and an ammonia-containing monomer, the phase change in step S121 can be avoided.
  • the emergence of the problem prevents the molecules from being closely arranged, increases the free volume, and weakens the hydrogen bond between the molecules. Therefore, the crystallinity of the polyparaphenylene terephthalamide obtained later is reduced and the solubility is improved.
  • the positive and negative ions are grafted onto the molecular chain of poly(p-phenylene terephthalamide) with sulfonic acid groups.
  • the fluidity of the poly(p-phenylene terephthalamide) is improved, and the properties of the fiber filler are uniform and stable.
  • the solubility of the polymerized product in the solvent will continue to decrease. Therefore, in order to ensure the continued progress of the reaction and the viscosity of the polymerized product, lithium chloride is added to the solvent as an auxiliary additive in this embodiment.
  • the complexation between lithium chloride and polar solvent ensures the continuous progress of the reaction, and the complex product between lithium chloride and N-methylpyrrolidone can further interact with the amine group hydrogen on the molecular chain of the polymer product. It acts to further weaken the hydrogen bonds between molecular chains and increase the molecular weight of poly(p-phenylene terephthalamide).
  • the embodiment of the present invention uses an ammonium bicarbonate aqueous solution to adjust the pH value, and successively uses an ethylenediaminetetraacetic acid aqueous solution and deionized water for multiple repeated washings.
  • the aqueous solution of ammonium bicarbonate can neutralize the small-molecule hydrochloric acid that is continuously generated in the reaction. Since lithium chloride is used as an auxiliary additive of the solvent in the embodiment of the present invention, after the reaction is completed, the lithium ions adsorbed on the surface of the polyparaphenylene terephthalamide are difficult to be completely cleaned and removed. The remaining lithium ions will react with the solvent of the spinning solution in the subsequent electrospinning process and affect the performance of the fiber filler.
  • the embodiment of the present invention uses an ethylenediaminetetraacetic acid aqueous solution to clean the polymerization product, so that the lithium ions adsorbed on the surface of the poly(paraphenylene terephthalamide) and the ethylenediaminetetraacetic acid For complexation, the complex product of lithium ion and ethylenediaminetetraacetic acid can be easily washed with water.
  • Electrospinning is a process in which polymer solutions or polymer melts form fibers under the action of a high-voltage electrostatic field. The main principle is to make charged polymer solutions or melts flow, split and deform in the electrostatic field, and then undergo The solvent evaporates or the melt cools and solidifies, and finally the fiber filler is obtained.
  • the graphene filler is prepared by the following steps:
  • Graphene has a sheet-layer structure with a large specific surface area and strong adsorption capacity. The interaction between the sheets and the sheets causes the graphene to agglomerate during use. Therefore, in this embodiment, the silicon-carbon coating is obtained through the above steps.
  • silicon carbide particles are uniformly dispersed in chitosan as a carbon source, and then subjected to high-temperature carbonization composite treatment with graphene.
  • the silicon-carbon element is bonded and coated on the surface of the graphene particles to improve the graphene On the basis of thermal stability, agglomeration between graphenes is avoided.
  • This embodiment provides a method for preparing a rubber adhesive, which includes the following steps:
  • Step S9 Load the aramid fiber spinning solution obtained in step S8 into an electrostatic spinning device, and spray the aramid fiber spinning solution to form a fiber filler under the action of a 60kV DC high-voltage electric field;
  • Step S15 curing the second mixture obtained in step S14 under a temperature condition of 60° C. for 12 hours to obtain a rubber adhesive.
  • This embodiment provides a method for preparing a rubber adhesive, which includes the following steps:
  • Step S9 Load the aramid fiber spinning solution obtained in step S8 into an electrostatic spinning device, and spray the aramid fiber spinning solution to form a fiber filler under the action of a 70kV DC high-voltage electric field;
  • Step S15 The second mixture obtained in step S14 is cured at a temperature of 80° C. for 18 hours to obtain a rubber adhesive.
  • Example 1 and Example 2 According to the standard GB/T 3738-2004, the shear strength of the samples obtained in Example 1 and Example 2 were tested. At room temperature, clamp the sample on the chuck of the CSS-44100 electronic universal testing machine, and place the sample so that its longitudinal direction is consistent with the axis of the chuck of the testing machine. Load evenly at a speed of (50 ⁇ 1)mm/min until it breaks. The shear strengths of the samples obtained in Example 1 and Example 2 were 5.0 MPa and 5.1 MPa, respectively.
  • Example 1 and Example 2 put the samples obtained in Example 1 and Example 2 into an electric thermostatic oven at (100 ⁇ 2)°C, take them out after baking for 7 days, and obtain the shear of the samples obtained in Example 1 and Example 2 after baking.
  • the strength is 4.8MPa and 4.7MPa respectively.
  • the description of the terms “one embodiment”, “some embodiments”, “specific embodiments”, etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or examples are included in the present invention In at least one embodiment or example.
  • the schematic representations of the above-mentioned terms do not necessarily refer to the same embodiment or example.
  • the described specific features, structures, materials or characteristics can be combined in any one or more embodiments or examples in a suitable manner.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Artificial Filaments (AREA)

Abstract

一种橡胶粘合剂，其制备方法包括以下步骤：步骤S100.采用石墨烯填料、无机填料、纤维填料、有机填料和橡胶主料制备第一混合物；步骤S200.按第一混合物∶1,6-己二醇二丙烯酸酯：二月桂酸二丁基锡＝(92-96)∶(2-4)∶(2-4)的质量百分比在20℃至30℃的温度条件下混合均匀，获得第二混合物；步骤S300.将第二混合物在60℃至80℃的温度条件下固化12h至18h，获得橡胶粘合剂。所述橡胶粘合剂具有优异的耐高温性能和力学性能。

Description

一种橡胶粘合剂及其制备方法 技术领域
本发明涉及粘合剂的技术领域，特别涉及一种橡胶粘合剂及其制备方法。
背景技术
橡胶胶粘剂是一类以氯丁、丁腈、丁基硅橡胶、聚硫等合成橡胶或天然橡胶为主体材料配制成的胶粘剂。其具有优良的弹性，尤其适于粘接柔软的或热膨胀系数相差悬殊的材料，例如橡胶与橡胶、橡胶与金属、塑料、皮革、木材等材料之间的粘接。现有技术中的其中一项不足是，橡胶胶粘剂的热力学性能不够理想，且不耐高温。
发明内容
本发明旨在解决上述技术问题的至少之一。
为此，本发明的第一目的在于提供一种橡胶粘合剂的制备方法。
本发明的第二目的在于提供一种橡胶粘合剂。
为实现本发明的第一目的，本发明的实施例提供了一种橡胶粘合剂的制备方法，包括以下步骤：
步骤S100.采用石墨烯填料、无机填料、纤维填料、有机填料和橡胶主料制备第一混合物；
步骤S200.按第一混合物∶1,6-己二醇二丙烯酸酯：二月桂酸二丁基锡＝(92-96)∶(2-4)∶(2-4)的质量百分比，将通过步骤S100获得的第一混合物与1,6-己二醇二丙烯酸酯和二月桂酸二丁基锡在20℃至30℃的温度条件下混合均匀，获得第二混合物；
步骤S300.将通过步骤S200获得的第二混合物在60℃至80℃的温度条件下固化12h至18h，获得橡胶粘合剂。
本实施例中，石墨烯填料用于提高橡胶粘合剂的热力学稳定性。石墨烯是一种纳米材料，其具有优良的热力学性能和韧性。石墨烯填料的加入可提高橡胶粘合剂的热分解温度。无机填料和纤维填料用于进一步提高橡胶粘合剂的热力学稳定性和力学性能。本实施例采用石墨烯填料、无机填料、纤维填料、有机填料和橡胶主料制备第一混合物，将第一混合物在1,6-己二醇二丙烯酸酯和二月桂酸二丁基锡的作用下以高于室温的温度条件进行固化。通过本实施例获得的橡胶粘合剂具有良好的热力学稳定性和力学性能。
进一步的，在步骤S100中，无机填料由氧化硅、氧化铝、氧化钇和氧化锂组成。
氧化硅、氧化铝、氧化钇和氧化锂组成的无机粉体混合物具有优异的机械性能和热力学性能。
进一步的，在步骤S100中，纤维填料采用芳纶纤维纺丝液在高压电场作用下通过纺丝获得。
采用芳纶纤维纺丝液在高压电场作用下通过纺丝获得的纤维填料具有强度高、模量高、耐高温、耐酸耐碱的优点。
进一步的，在步骤S100中，有机填料包括液体端羟基丁腈橡胶。
液体端羟基丁腈橡胶不仅能够保证石墨烯填料、无机填料、纤维填料的分散均匀程度，亦能够提高橡胶粘合剂的韧性。
进一步的，在步骤S100中，橡胶主料包括氯化橡胶。
氯化橡胶是由天然橡胶经过氯化改性得到的橡胶氯化衍生物，采用其配成的胶粘剂可广泛应用于飞机制造、汽车制造、建筑、轻工、橡胶制品加工等诸多领域。
进一步的，步骤S100具体包括：
步骤S110.将氧化硅、氧化铝、氧化钇和氧化锂混合均匀后升温至1400℃至1600℃并保温2小时，冷却后研磨粉碎获得无机填料；
步骤S120.采用芳纶纤维纺丝液在直流高压电场作用下进行纺丝，获得纤维填料；
步骤S130.将液体端羟基丁腈橡胶、异佛尔酮二异氰酸酯和3-二甲基氨基-1-丙醇在20℃至30℃的温度条件下混合均匀，在氮气保护和50℃至55℃的温度条件下反应20h至24h，获得有机填料；
步骤S140.采用氯化天然橡胶、氯丁橡胶和乙酸乙酯在20℃至30℃的温度条件下搅拌2h至3h，获得橡胶主料；
步骤S150.将石墨烯填料、无机填料、纤维填料和有机填料在二酚基丙烷型环氧树脂中混合均匀，获得填料混合物；
步骤S160.将通过步骤S150获得的填料混合物加入通过步骤S140获得的橡胶主料，在40℃至50℃的温度条件下搅拌4h至5h，获得第一混合物。
在步骤S110中，本实施例将氧化硅、氧化铝、氧化钇和氧化锂混合均匀后在高温下烧结，氧化硅、氧化铝和氧化钇在作为成核剂的氧化锂的作用下形成钇铝石榴石晶相的无机陶瓷结构，进而将烧结产物进行研磨粉碎，获得细小的粉末状的无机填料。相比于将无机氧化物粉体直接加入橡胶粘合剂的相关技术，具有钇 铝石榴石晶相的无机填料不仅力学性能优异，并且能够极大地提高橡胶粘合剂的热力学稳定性。本实施例的橡胶主料包括氯化天然橡胶和氯丁橡胶，而本实施例的有机填料包括液体端羟基丁腈橡胶。氯化天然橡胶与氯丁橡胶分子结构不同，氯丁橡胶的侧链是空间位阻较小的碳氯基团，而氯化天然橡胶的侧链是六元环状基团。在步骤S130中，包括丁腈橡胶的有机填料的加入能够提高包括氯化天然橡胶和氯丁橡胶的橡胶主料的韧性。在步骤S150中，本实施例将石墨烯填料、无机填料、纤维填料与有机填料加入二酚基丙烷型环氧树脂中混合，以提高石墨烯填料、无机填料、纤维填料以及有机填料在橡胶主料之中的分散均匀程度。
进一步的，在步骤S110中，氧化硅、氧化铝、氧化钇和氧化锂的质量比为氧化硅∶氧化铝∶氧化钇∶氧化锂＝(44-46)∶(26-28)∶(19-22)∶(6-10)；和/或在步骤S120中，聚对苯二甲酰对苯二胺和四氢呋喃的质量比为聚对苯二甲酰对苯二胺∶四氢呋喃＝(10-15)∶(85-90)；和/或在步骤S130中，液体端羟基丁腈橡胶、异佛尔酮二异氰酸酯和3-二甲基氨基-1-丙醇的质量比为液体端羟基丁腈橡胶∶异佛尔酮二异氰酸酯∶3-二甲基氨基-1-丙醇＝(60-75)∶(15-25)∶(10-15)；和/或在步骤S140中，氯化天然橡胶、氯丁橡胶和乙酸乙酯的质量比为氯化天然橡胶∶氯丁橡胶∶乙酸乙酯＝(20-30)∶(20-30)∶(40-60)；和/或在步骤S150中，石墨烯填料、无机填料、纤维填料、有机填料和二酚基丙烷型环氧树脂的质量比为石墨烯填料∶无机填料∶纤维填料∶有机填料∶二酚基丙烷型环氧树脂＝(5-10)∶(5-10)∶(5-10)∶(5-10)∶(60-80)；和/或在步骤S160中，填料混合物和橡胶主料的质量比为填料混合物∶橡胶主料＝(30-40)∶(60-70)。
进一步的，步骤S120具体包括：
步骤S121.按对苯二胺：邻氯对苯二胺：2,5-二氨基苯磺酸＝(35-40)：(35-40)：(20-30)的质量比将对苯二胺、邻氯对苯二胺和2,5-二氨基苯磺酸混合均匀，获得单体混合物；
步骤S122.按N,N-二甲基甲酰胺：N,N-二甲基乙酰胺：N-甲基吡咯烷酮：氯化锂＝(15-30)：(20-30)：(40-50)：(5-10)的质量比将N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮和氯化锂在90℃至95℃的温度条件下混合均匀，获得溶剂；
步骤S123.按单体混合物：溶剂＝(20-30)：(70-80)的质量比，将通过步骤S121获得的单体混合物和通过步骤S122获得的溶剂在氮气保护和30℃至35℃的温度条件下混合并搅拌至单体混合物完全溶解，获得单体溶液；
步骤S124.按单体溶液：对苯二甲酰氯＝(40-50)：(50-60)的质量比，将通过步骤S123获得的单体溶液和对苯二甲酰氯在0℃至4℃的温度条件下反应20min至30min后，采用5wt％至8wt％的碳酸氢铵水溶液调节pH值为7至8，依次采用0.06wt％-0.08wt％的乙二胺四乙酸水溶液和去离子水进行洗涤后干燥，获得聚对苯二甲酰对苯二胺；
步骤S125.将通过步骤S124获得的聚对苯二甲酰对苯二胺溶于四氢呋喃，在40℃至60℃的温度条件下混合均匀，配制芳纶纤维纺丝液；
步骤S126.将通过步骤S125获得的芳纶纤维纺丝液装入静电纺丝装置，在60kV至70kV的直流高压电场作用下，将芳纶纤维纺丝液喷射形成纤维填料。
在步骤S121中邻氯对苯二胺为含氯单体，2,5-二氨基苯磺酸为含氨单体，通过引入含氯单体和含氨单体，可避免步骤S121中相变问题的出现，使得分子不能紧密排列，增加了自由体积，减弱了分子间的氢键作用，因此使得后续获得的聚对苯二甲酰对苯二胺的结晶性下降，溶解性提高。此外，由于采用了含有苯磺酸基团的单体原料参与聚合反应，聚合反应结束后，正负离子接枝在聚对苯二甲酰对苯二胺带有磺酸基团的分子链上，从而提高了聚对苯二甲酰对苯二胺的流动性，保证纤维填料的性质均一稳定。由于随着聚合反应的不断进行，聚合产物在溶剂中的溶解性会不断降低，因此，为了保证反应的持续进行和保证聚合产物的粘度，本实施例向溶剂中加入氯化锂作为辅助添加剂，通过氯化锂与极性溶剂之间的络合作用保证反应的持续进行，并且，氯化锂与N-甲基吡咯烷酮之间的络合产物能进一步地和聚合产物分子链上的胺基氢进行作用，进一步弱化分子链间的氢键，提高了聚对苯二甲酰对苯二胺的分子量。在获得聚合产物后，本发明实施例采用碳酸氢铵水溶液进行pH值调节，依次采用乙二胺四乙酸水溶液和去离子水进行多次反复洗涤。其中碳酸氢铵水溶液可中和反应中不断生成的小分子盐酸。由于本发明实施例中采用了氯化锂作为溶剂的辅助添加剂，而反应完成后，吸附在聚对苯二甲酰对苯二胺表面的锂离子很难被完全清洗和除去。残留的锂离子会在后续的静电纺丝工艺中与纺丝液的溶剂发生反应，影响纤维填料性能。因此，为了完全除去残留的锂离子，本发明实施例采用乙二胺四乙酸水溶液对聚合产物进行清洗，使得吸附在聚对苯二甲酰对苯二胺表面的锂离子与乙二胺四乙酸进行络合，锂离子与乙二胺四乙酸的络合产物能够容易地被水清洗。静电纺丝是聚合物溶液或聚合物熔体在高压静电场的作用下形成纤维的过程，其主要原理 是使带电荷的高分子溶液或熔体在静电场中流动、分裂和变形，然后经溶剂蒸发或熔体冷却而固化，最后得到纤维填料。
进一步的，石墨烯填料通过以下步骤制备：
步骤S410.将碳化硅与壳聚糖按碳化硅：壳聚糖＝(40-50)：(50-60)的质量比混合均匀，在180℃至200℃的温度条件下保温2小时，冷却后获得硅碳混合物；
步骤S420.将通过步骤S410获得的硅碳混合物与石墨烯按硅碳混合物：石墨烯＝(5-15)：(85-95)的质量比混合均匀，在620℃至660℃的温度条件下保温2小时，冷却后获得石墨烯填料。
石墨烯具有片层结构，其比表面积大，吸附能力强，片层和片层之间的相互作用力导致石墨烯在使用时会出现团聚现象，因此本实施例通过上述步骤获得硅碳包覆的石墨烯，首先使碳化硅颗粒均匀分散在作为碳源的壳聚糖中，再与石墨烯进行高温碳化复合处理，将硅碳元素在石墨烯颗粒的表面粘结包覆，在提高石墨烯热稳定性的基础上，避免石墨烯之间的团聚。
为实现本发明的第二目的，本发明的实施例提供了一种橡胶粘合剂，橡胶粘合剂采用如本发明任一实施例的橡胶粘合剂的制备方法获得。
本实施例的橡胶粘合剂采用如本发明任一实施例的橡胶粘合剂的制备方法获得，因此其具有如本发明任一实施例的橡胶粘合剂的制备方法的全部有益效果，在此不再赘述。
本发明的附加方面和优点将在下面的描述部分中变得明显，或通过本发明的实践了解到。
具体实施方式
为了能够更清楚地理解本发明的上述目的、特征和优点，下面结合具体实施方式对本发明进行进一步的详细描述。需要说明的是，在不冲突的情况下，本申请的实施例及实施例中的特征可以相互组合。
在下面的描述中阐述了很多具体细节以便于充分理解本发明，但是，本发明还可以采用其他不同于在此描述的其他方式来实施，因此，本发明的保护范围并不受下面公开的具体实施例的限制。
本发明的实施例提供了一种橡胶粘合剂的制备方法，包括以下步骤：
步骤S100.采用石墨烯填料、无机填料、纤维填料、有机填料和橡胶主料制备第一混合物；
步骤S200.按第一混合物∶1,6-己二醇二丙烯酸酯：二月桂酸二丁基锡＝(92-96)∶(2-4)∶(2-4)的质量百分比，将通过步骤S100获得的第一混合物与1,6-己二醇二丙烯酸酯和二月桂酸 二丁基锡在20℃至30℃的温度条件下混合均匀，获得第二混合物；
步骤S300.将通过步骤S200获得的第二混合物在60℃至80℃的温度条件下固化12h至18h，获得橡胶粘合剂。
本实施例中，石墨烯填料用于提高橡胶粘合剂的热力学稳定性。石墨烯是一种纳米材料，其具有优良的热力学性能和韧性。石墨烯填料的加入可提高橡胶粘合剂的热分解温度。无机填料和纤维填料用于进一步提高橡胶粘合剂的热力学稳定性和力学性能。本实施例采用石墨烯填料、无机填料、纤维填料、有机填料和橡胶主料制备第一混合物，将第一混合物在1,6-己二醇二丙烯酸酯和二月桂酸二丁基锡的作用下以高于室温的温度条件进行固化。通过本实施例获得的橡胶粘合剂具有良好的热力学稳定性和力学性能。
在本发明的部分实施方式中，在步骤S100中，无机填料由氧化硅、氧化铝、氧化钇和氧化锂组成。
氧化硅、氧化铝、氧化钇和氧化锂组成的无机粉体混合物具有优异的机械性能和热力学性能。
在本发明的部分实施方式中，在步骤S100中，纤维填料采用芳纶纤维纺丝液在高压电场作用下通过纺丝获得。
采用芳纶纤维纺丝液在高压电场作用下通过纺丝获得的纤维填料具有强度高、模量高、耐高温、耐酸耐碱的优点。
在本发明的部分实施方式中，在步骤S100中，有机填料包括液体端羟基丁腈橡胶。
液体端羟基丁腈橡胶不仅能够保证石墨烯填料、无机填料、纤维填料的分散均匀程度，亦能够提高橡胶粘合剂的韧性。
在本发明的部分实施方式中，在步骤S100中，橡胶主料包括氯化橡胶。
氯化橡胶是由天然橡胶经过氯化改性得到的橡胶氯化衍生物，采用其配成的胶粘剂可广泛应用于飞机制造、汽车制造、建筑、轻工、橡胶制品加工等诸多领域。
在本发明的部分实施方式中，步骤S100具体包括：
步骤S110.将氧化硅、氧化铝、氧化钇和氧化锂混合均匀后升温至1400℃至1600℃并保温2小时，冷却后研磨粉碎获得无机填料；
步骤S120.采用芳纶纤维纺丝液在直流高压电场作用下进行纺丝，获得纤维填料；
步骤S130.将液体端羟基丁腈橡胶、异佛尔酮二异氰酸酯和3-二甲基氨基-1-丙醇在20℃至30℃的温度条件下混合均匀，在氮气保护和50℃至55℃的温度条件下反应20h至24h，获得有机填 料；
步骤S140.采用氯化天然橡胶、氯丁橡胶和乙酸乙酯在20℃至30℃的温度条件下搅拌2h至3h，获得橡胶主料；
步骤S150.将石墨烯填料、无机填料、纤维填料和有机填料在二酚基丙烷型环氧树脂中混合均匀，获得填料混合物；
步骤S160.将通过步骤S150获得的填料混合物加入通过步骤S140获得的橡胶主料，在40℃至50℃的温度条件下搅拌4h至5h，获得第一混合物。
在步骤S110中，本实施例将氧化硅、氧化铝、氧化钇和氧化锂混合均匀后在高温下烧结，氧化硅、氧化铝和氧化钇在作为成核剂的氧化锂的作用下形成钇铝石榴石晶相的无机陶瓷结构，进而将烧结产物进行研磨粉碎，获得细小的粉末状的无机填料。相比于将无机氧化物粉体直接加入橡胶粘合剂的相关技术，具有钇铝石榴石晶相的无机填料不仅力学性能优异，并且能够极大地提高橡胶粘合剂的热力学稳定性。本实施例的橡胶主料包括氯化天然橡胶和氯丁橡胶，而本实施例的有机填料包括液体端羟基丁腈橡胶。氯化天然橡胶与氯丁橡胶分子结构不同，氯丁橡胶的侧链是空间位阻较小的碳氯基团，而氯化天然橡胶的侧链是六元环状基团。在步骤S130中，包括丁腈橡胶的有机填料的加入能够提高包括氯化天然橡胶和氯丁橡胶的橡胶主料的韧性。在步骤S150中，本实施例将石墨烯填料、无机填料、纤维填料与有机填料加入二酚基丙烷型环氧树脂中混合，以提高石墨烯填料、无机填料、纤维填料以及有机填料在橡胶主料之中的分散均匀程度。
在本发明的部分实施方式中，在步骤S110中，氧化硅、氧化铝、氧化钇和氧化锂的质量比为氧化硅∶氧化铝∶氧化钇∶氧化锂＝(44-46)∶(26-28)∶(19-22)∶(6-10)。在步骤S120中，聚对苯二甲酰对苯二胺和四氢呋喃的质量比为聚对苯二甲酰对苯二胺∶四氢呋喃＝(10-15)∶(85-90)。在步骤S130中，液体端羟基丁腈橡胶、异佛尔酮二异氰酸酯和3-二甲基氨基-1-丙醇的质量比为液体端羟基丁腈橡胶∶异佛尔酮二异氰酸酯∶3-二甲基氨基-1-丙醇＝(60-75)∶(15-25)∶(10-15)。在步骤S140中，氯化天然橡胶、氯丁橡胶和乙酸乙酯的质量比为氯化天然橡胶∶氯丁橡胶∶乙酸乙酯＝(20-30)∶(20-30)∶(40-60)。在步骤S150中，石墨烯填料、无机填料、纤维填料、有机填料和二酚基丙烷型环氧树脂的质量比为石墨烯填料∶无机填料∶纤维填料∶有机填料∶二酚基丙烷型环氧树脂＝(5-10)∶(5-10)∶(5-10)∶(5-10)∶(60-80)。在步骤S160中，填料混合物和橡胶主料的质量比为填料混合物∶橡胶主料＝(30-40)∶(60-70)。
在本发明的部分实施方式中，步骤S120具体包括：
步骤S121.按对苯二胺：邻氯对苯二胺：2,5-二氨基苯磺酸＝(35-40)：(35-40)：(20-30)的质量比将对苯二胺、邻氯对苯二胺和2,5-二氨基苯磺酸混合均匀，获得单体混合物；
步骤S122.按N,N-二甲基甲酰胺：N,N-二甲基乙酰胺：N-甲基吡咯烷酮：氯化锂＝(15-30)：(20-30)：(40-50)：(5-10)的质量比将N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮和氯化锂在90℃至95℃的温度条件下混合均匀，获得溶剂；
步骤S123.按单体混合物：溶剂＝(20-30)：(70-80)的质量比，将通过步骤S121获得的单体混合物和通过步骤S122获得的溶剂在氮气保护和30℃至35℃的温度条件下混合并搅拌至单体混合物完全溶解，获得单体溶液；
步骤S124.按单体溶液：对苯二甲酰氯＝(40-50)：(50-60)的质量比，将通过步骤S123获得的单体溶液和对苯二甲酰氯在0℃至4℃的温度条件下反应20min至30min后，采用5wt％至8wt％的碳酸氢铵水溶液调节pH值为7至8，依次采用0.06wt％-0.08wt％的乙二胺四乙酸水溶液和去离子水进行洗涤后干燥，获得聚对苯二甲酰对苯二胺；
步骤S125.将通过步骤S124获得的聚对苯二甲酰对苯二胺溶于四氢呋喃，在40℃至60℃的温度条件下混合均匀，配制芳纶纤维纺丝液；
步骤S126.将通过步骤S125获得的芳纶纤维纺丝液装入静电纺丝装置，在60kV至70kV的直流高压电场作用下，将芳纶纤维纺丝液喷射形成纤维填料。
在步骤S121中邻氯对苯二胺为含氯单体，2,5-二氨基苯磺酸为含氨单体，通过引入含氯单体和含氨单体，可避免步骤S121中相变问题的出现，使得分子不能紧密排列，增加了自由体积，减弱了分子间的氢键作用，因此使得后续获得的聚对苯二甲酰对苯二胺的结晶性下降，溶解性提高。此外，由于采用了含有苯磺酸基团的单体原料参与聚合反应，聚合反应结束后，正负离子接枝在聚对苯二甲酰对苯二胺带有磺酸基团的分子链上，从而提高了聚对苯二甲酰对苯二胺的流动性，保证纤维填料的性质均一稳定。由于随着聚合反应的不断进行，聚合产物在溶剂中的溶解性会不断降低，因此，为了保证反应的持续进行和保证聚合产物的粘度，本实施例向溶剂中加入氯化锂作为辅助添加剂，通过氯化锂与极性溶剂之间的络合作用保证反应的持续进行，并且，氯化锂与N-甲基吡咯烷酮之间的络合产物能进一步地和聚合产物分子链上的胺基氢进行作用，进一步弱化分子链间的氢键，提高了聚对苯二 甲酰对苯二胺的分子量。在获得聚合产物后，本发明实施例采用碳酸氢铵水溶液进行pH值调节，依次采用乙二胺四乙酸水溶液和去离子水进行多次反复洗涤。其中碳酸氢铵水溶液可中和反应中不断生成的小分子盐酸。由于本发明实施例中采用了氯化锂作为溶剂的辅助添加剂，而反应完成后，吸附在聚对苯二甲酰对苯二胺表面的锂离子很难被完全清洗和除去。残留的锂离子会在后续的静电纺丝工艺中与纺丝液的溶剂发生反应，影响纤维填料性能。因此，为了完全除去残留的锂离子，本发明实施例采用乙二胺四乙酸水溶液对聚合产物进行清洗，使得吸附在聚对苯二甲酰对苯二胺表面的锂离子与乙二胺四乙酸进行络合，锂离子与乙二胺四乙酸的络合产物能够容易地被水清洗。静电纺丝是聚合物溶液或聚合物熔体在高压静电场的作用下形成纤维的过程，其主要原理是使带电荷的高分子溶液或熔体在静电场中流动、分裂和变形，然后经溶剂蒸发或熔体冷却而固化，最后得到纤维填料。
在本发明的部分实施方式中，石墨烯填料通过以下步骤制备：
步骤S410.将碳化硅与壳聚糖按碳化硅：壳聚糖＝(40-50)：(50-60)的质量比混合均匀，在180℃至200℃的温度条件下保温2小时，冷却后获得硅碳混合物；
步骤S420.将通过步骤S410获得的硅碳混合物与石墨烯按硅碳混合物：石墨烯＝(5-15)：(85-95)的质量比混合均匀，在620℃至660℃的温度条件下保温2小时，冷却后获得石墨烯填料。
石墨烯具有片层结构，其比表面积大，吸附能力强，片层和片层之间的相互作用力导致石墨烯在使用时会出现团聚现象，因此本实施例通过上述步骤获得硅碳包覆的石墨烯，首先使碳化硅颗粒均匀分散在作为碳源的壳聚糖中，再与石墨烯进行高温碳化复合处理，将硅碳元素在石墨烯颗粒的表面粘结包覆，在提高石墨烯热稳定性的基础上，避免石墨烯之间的团聚。
实施例1
本实施例提供了一种橡胶粘合剂的制备方法，其包括以下步骤：
步骤S1.将碳化硅与壳聚糖按碳化硅：壳聚糖＝40：60的质量比混合均匀，在180℃的温度条件下保温2小时，冷却后获得硅碳混合物；
步骤S2.将通过步骤S1获得的硅碳混合物与石墨烯按硅碳混合物：石墨烯＝5：95的质量比混合均匀，在620℃的温度条件下保温2小时，冷却后获得石墨烯填料；
步骤S3.按氧化硅∶氧化铝∶氧化钇∶氧化锂＝44∶28∶22∶10的质量比，将氧化硅、氧化铝、氧化钇和氧化锂混合均匀 后升温至1400℃并保温2小时，冷却后研磨粉碎获得无机填料；
步骤S4.按对苯二胺：邻氯对苯二胺：2,5-二氨基苯磺酸＝35：40：30的质量比将对苯二胺、邻氯对苯二胺和2,5-二氨基苯磺酸混合均匀，获得单体混合物；
步骤S5.按N,N-二甲基甲酰胺：N,N-二甲基乙酰胺：N-甲基吡咯烷酮：氯化锂＝15：30：50：5的质量比将N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮和氯化锂在90℃的温度条件下混合均匀，获得溶剂；
步骤S6.按单体混合物：溶剂＝20：80的质量比，将通过步骤S4获得的单体混合物和通过步骤S5获得的溶剂在氮气保护和30℃的温度条件下混合并搅拌至单体混合物完全溶解，获得单体溶液；
步骤S7.按单体溶液：对苯二甲酰氯＝40：60的质量比，将通过步骤S6获得的单体溶液和对苯二甲酰氯在0℃的温度条件下反应20min后，采用5wt％的碳酸氢铵水溶液调节pH值为7，依次采用0.06wt％的乙二胺四乙酸水溶液和去离子水进行洗涤后干燥，获得聚对苯二甲酰对苯二胺；
步骤S8.按聚对苯二甲酰对苯二胺∶四氢呋喃＝10∶90的质量比，将通过步骤S7获得的聚对苯二甲酰对苯二胺溶于四氢呋喃，在40℃的温度条件下混合均匀，配制芳纶纤维纺丝液；
步骤S9.将通过步骤S8获得的芳纶纤维纺丝液装入静电纺丝装置，在60kV的直流高压电场作用下，将芳纶纤维纺丝液喷射形成纤维填料；
步骤S10.按液体端羟基丁腈橡胶∶异佛尔酮二异氰酸酯∶3-二甲基氨基-1-丙醇＝60∶25∶15的质量比，将液体端羟基丁腈橡胶、异佛尔酮二异氰酸酯和3-二甲基氨基-1-丙醇在20℃的温度条件下混合均匀，在氮气保护和50℃的温度条件下反应20h，获得有机填料；
步骤S11.按氯化天然橡胶∶氯丁橡胶∶乙酸乙酯＝20∶20∶60的质量比，采用氯化天然橡胶、氯丁橡胶和乙酸乙酯在20℃的温度条件下搅拌2h，获得橡胶主料；
步骤S12.按石墨烯填料∶无机填料∶纤维填料∶有机填料∶二酚基丙烷型环氧树脂＝5∶5∶5∶5∶80的质量比，将通过步骤S2获得的石墨烯填料、通过步骤S3获得的无机填料、通过步骤S9获得的纤维填料和通过步骤S10获得的有机填料在二酚基丙烷型环氧树脂中混合均匀，获得填料混合物；
步骤S13.按填料混合物∶橡胶主料＝30∶70的质量比，将通过步骤S12获得的填料混合物加入通过步骤S11获得的橡胶主料， 在40℃的温度条件下搅拌4h，获得第一混合物；
步骤S14.按第一混合物∶1,6-己二醇二丙烯酸酯：二月桂酸二丁基锡＝92∶4∶4的质量百分比，将通过步骤S13获得的第一混合物与1,6-己二醇二丙烯酸酯和二月桂酸二丁基锡在20℃的温度条件下混合均匀，获得第二混合物；
步骤S15.将通过步骤S14获得的第二混合物在60℃的温度条件下固化12h，获得橡胶粘合剂。
实施例2
本实施例提供了一种橡胶粘合剂的制备方法，其包括以下步骤：
步骤S1.将碳化硅与壳聚糖按碳化硅：壳聚糖＝50：50的质量比混合均匀，在200℃的温度条件下保温2小时，冷却后获得硅碳混合物；
步骤S2.将通过步骤S1获得的硅碳混合物与石墨烯按硅碳混合物：石墨烯＝15：85的质量比混合均匀，在660℃的温度条件下保温2小时，冷却后获得石墨烯填料；
步骤S3.按氧化硅∶氧化铝∶氧化钇∶氧化锂＝46∶26∶22∶6的质量比，将氧化硅、氧化铝、氧化钇和氧化锂混合均匀后升温至1600℃并保温2小时，冷却后研磨粉碎获得无机填料；
步骤S4.按对苯二胺：邻氯对苯二胺：2,5-二氨基苯磺酸＝40：40：20的质量比将对苯二胺、邻氯对苯二胺和2,5-二氨基苯磺酸混合均匀，获得单体混合物；
步骤S5.按N,N-二甲基甲酰胺：N,N-二甲基乙酰胺：N-甲基吡咯烷酮：氯化锂＝30：25：40：5的质量比将N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮和氯化锂在95℃的温度条件下混合均匀，获得溶剂；
步骤S6.按单体混合物：溶剂＝30：70的质量比，将通过步骤S4获得的单体混合物和通过步骤S5获得的溶剂在氮气保护和35℃的温度条件下混合并搅拌至单体混合物完全溶解，获得单体溶液；
步骤S7.按单体溶液：对苯二甲酰氯＝50：50的质量比，将通过步骤S6获得的单体溶液和对苯二甲酰氯在4℃的温度条件下反应30min后，采用8wt％的碳酸氢铵水溶液调节pH值为8，依次采用0.08wt％的乙二胺四乙酸水溶液和去离子水进行洗涤后干燥，获得聚对苯二甲酰对苯二胺；
步骤S8.按聚对苯二甲酰对苯二胺∶四氢呋喃＝15∶85的质量比，将通过步骤S7获得的聚对苯二甲酰对苯二胺溶于四氢呋喃，在60℃的温度条件下混合均匀，配制芳纶纤维纺丝液；
步骤S9.将通过步骤S8获得的芳纶纤维纺丝液装入静电纺丝装置，在70kV的直流高压电场作用下，将芳纶纤维纺丝液喷射形成纤维填料；
步骤S10.按液体端羟基丁腈橡胶∶异佛尔酮二异氰酸酯∶3-二甲基氨基-1-丙醇＝75∶15∶10的质量比，将液体端羟基丁腈橡胶、异佛尔酮二异氰酸酯和3-二甲基氨基-1-丙醇在30℃的温度条件下混合均匀，在氮气保护和55℃的温度条件下反应24h，获得有机填料；
步骤S11.按氯化天然橡胶∶氯丁橡胶∶乙酸乙酯＝30∶30∶40的质量比，采用氯化天然橡胶、氯丁橡胶和乙酸乙酯在30℃的温度条件下搅拌3h，获得橡胶主料；
步骤S12.按石墨烯填料∶无机填料∶纤维填料∶有机填料∶二酚基丙烷型环氧树脂＝10∶10∶10∶10∶60的质量比，将通过步骤S2获得的石墨烯填料、通过步骤S3获得的无机填料、通过步骤S9获得的纤维填料和通过步骤S10获得的有机填料在二酚基丙烷型环氧树脂中混合均匀，获得填料混合物；
步骤S13.按填料混合物∶橡胶主料＝40∶60的质量比，将通过步骤S12获得的填料混合物加入通过步骤S11获得的橡胶主料，在50℃的温度条件下搅拌5h，获得第一混合物；
步骤S14.按第一混合物∶1,6-己二醇二丙烯酸酯：二月桂酸二丁基锡＝96∶2∶2的质量百分比，将通过步骤S13获得的第一混合物与1,6-己二醇二丙烯酸酯和二月桂酸二丁基锡在30℃的温度条件下混合均匀，获得第二混合物；
步骤S15.将通过步骤S14获得的第二混合物在80℃的温度条件下固化18h，获得橡胶粘合剂。
性能测试
按照标准GB/T 3738-2004对采用实施例1和实施例2获得的样品的剪切强度进行测试。在室温下，将样品夹在CSS-44100电子万能试验机夹头上，样品放置时使其纵向与试验机夹头的轴线一致。以(50±1)mm/min的速度均匀加荷，直到破坏。获得采用实施例1和实施例2获得的样品的剪切强度分别为5.0MPa和5.1MPa。
将采用实施例1和实施例2获得的样品放入(100±2)℃电热恒温烘箱中，烘烤7天后取出，获得采用实施例1和实施例2获得的样品在烘烤后的剪切强度分别为4.8MPa和4.7MPa。
在本发明中，术语“第一”、“第二”、“第三”仅用于描述的目的，而不能理解为指示或暗示相对重要性；术语“多个”则指两个或两个以上，除非另有明确的限定。
在本说明书的描述中，术语“一个实施例”、“一些实施例”、“具体实施例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施例或实例。而且，描述的具体特征、结构、材料或特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
以上仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种橡胶粘合剂的制备方法，其特征在于，包括以下步骤：
    步骤S100.采用石墨烯填料、无机填料、纤维填料、有机填料和橡胶主料制备第一混合物；
    步骤S200.按第一混合物∶1,6-己二醇二丙烯酸酯：二月桂酸二丁基锡＝(92-96)∶(2-4)∶(2-4)的质量百分比，将通过步骤S100获得的所述第一混合物与1,6-己二醇二丙烯酸酯和二月桂酸二丁基锡在20℃至30℃的温度条件下混合均匀，获得第二混合物；
    步骤S300.将通过步骤S200获得的所述第二混合物在60℃至80℃的温度条件下固化12h至18h，获得所述橡胶粘合剂。
  2. 根据权利要求1所述的橡胶粘合剂的制备方法，其特征在于，
    在所述步骤S100中，所述无机填料由氧化硅、氧化铝、氧化钇和氧化锂组成。
  3. 根据权利要求1所述的橡胶粘合剂的制备方法，其特征在于，
    在所述步骤S100中，所述纤维填料采用芳纶纤维纺丝液在高压电场作用下通过纺丝获得。
  4. 根据权利要求1所述的橡胶粘合剂的制备方法，其特征在于，
    在所述步骤S100中，所述有机填料包括液体端羟基丁腈橡胶。
  5. 根据权利要求1所述的橡胶粘合剂的制备方法，其特征在于，
    在所述步骤S100中，所述橡胶主料包括氯化橡胶。
  6. 根据权利要求1至5中任一项所述的橡胶粘合剂的制备方法，其特征在于，所述步骤S100具体包括：
    步骤S110.将氧化硅、氧化铝、氧化钇和氧化锂混合均匀后升温至1400℃至1600℃并保温2小时，冷却后研磨粉碎获得所述无机填料；
    步骤S120.采用芳纶纤维纺丝液在直流高压电场作用下进行纺丝，获得所述纤维填料；
    步骤S130.将液体端羟基丁腈橡胶、异佛尔酮二异氰酸酯和3-二甲基氨基-1-丙醇在20℃至30℃的温度条件下混合均匀，在氮气保护和50℃至55℃的温度条件下反应20h至24h，获得所述有机填料；
    步骤S140.采用氯化天然橡胶、氯丁橡胶和乙酸乙酯在20℃至30℃的温度条件下搅拌2h至3h，获得所述橡胶主料；
    步骤S150.将所述石墨烯填料、所述无机填料、所述纤维填料和所述有机填料在二酚基丙烷型环氧树脂中混合均匀，获得填料混合物；
    步骤S160.将通过所述步骤S150获得的所述填料混合物加入通过所述步骤S140获得的所述橡胶主料，在40℃至50℃的温度条件下搅拌4h至5h，获得所述第一混合物。
  7. 根据权利要求6所述的橡胶粘合剂的制备方法，其特征在于，
    在所述步骤S110中，所述氧化硅、所述氧化铝、所述氧化钇和所述氧化锂的质量比为氧化硅∶氧化铝∶氧化钇∶氧化锂＝(44-46)∶(26-28)∶(19-22)∶(6-10)；和/或
    在所述步骤S120中，所述芳纶纤维纺丝液包括聚对苯二甲酰对苯二胺和四氢呋喃，所述聚对苯二甲酰对苯二胺和所述四氢呋喃的质量比为聚对苯二甲酰对苯二胺∶四氢呋喃＝(10-15)∶(85-90)；和/或
    在所述步骤S130中，所述液体端羟基丁腈橡胶、所述异佛尔酮二异氰酸酯和所述3-二甲基氨基-1-丙醇的质量比为液体端羟基丁腈橡胶∶异佛尔酮二异氰酸酯∶3-二甲基氨基-1-丙醇＝(60-75)∶(15-25)∶(10-15)；和/或
    在所述步骤S140中，所述氯化天然橡胶、所述氯丁橡胶和所述乙酸乙酯的质量比为氯化天然橡胶∶氯丁橡胶∶乙酸乙酯＝(20-30)∶(20-30)∶(40-60)；和/或
    在所述步骤S150中，所述石墨烯填料、所述无机填料、所述纤维填料、所述有机填料和所述二酚基丙烷型环氧树脂的质量比为石墨烯填料∶无机填料∶纤维填料∶有机填料∶二酚基丙烷型环氧树脂＝(5-10)∶(5-10)∶(5-10)∶(5-10)∶(60-80)；和/或
    在所述步骤S160中，所述填料混合物和所述橡胶主料的质量比为填料混合物∶橡胶主料＝(30-40)∶(60-70)。
  8. 根据权利要求7所述的橡胶粘合剂的制备方法，其特征在于，所述步骤S120具体包括：
    步骤S121.按对苯二胺：邻氯对苯二胺：2,5-二氨基苯磺酸＝(35-40)：(35-40)：(20-30)的质量比将对苯二胺、邻氯对苯二胺和2,5-二氨基苯磺酸混合均匀，获得单体混合物；
    步骤S122.按N,N-二甲基甲酰胺：N,N-二甲基乙酰胺：N-甲基吡咯烷酮：氯化锂＝(15-30)：(20-30)：(40-50)：(5-10) 的质量比将N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮和氯化锂在90℃至95℃的温度条件下混合均匀，获得溶剂；
    步骤S123.按单体混合物：溶剂＝(20-30)：(70-80)的质量比，将通过步骤S121获得的所述单体混合物和通过步骤S122获得的所述溶剂在氮气保护和30℃至35℃的温度条件下混合并搅拌至所述单体混合物完全溶解，获得单体溶液；
    步骤S124.按单体溶液：对苯二甲酰氯＝(40-50)：(50-60)的质量比，将通过步骤S123获得的所述单体溶液和对苯二甲酰氯在0℃至4℃的温度条件下反应20min至30min后，采用5wt％至8wt％的碳酸氢铵水溶液调节pH值为7至8，依次采用0.06wt％-0.08wt％的乙二胺四乙酸水溶液和去离子水进行洗涤后干燥，获得聚对苯二甲酰对苯二胺；
    步骤S125.将通过步骤S124获得的所述聚对苯二甲酰对苯二胺溶于四氢呋喃，在40℃至60℃的温度条件下混合均匀，配制所述芳纶纤维纺丝液；
    步骤S126.将通过步骤S125获得的所述芳纶纤维纺丝液装入静电纺丝装置，在60kV至70kV的直流高压电场作用下，将所述芳纶纤维纺丝液喷射形成所述纤维填料。
  9. 根据权利要求7所述的橡胶粘合剂的制备方法，其特征在于，所述石墨烯填料通过以下步骤制备：
    步骤S410.将碳化硅与壳聚糖按碳化硅：壳聚糖＝(40-50)：(50-60)的质量比混合均匀，在180℃至200℃的温度条件下保温2小时，冷却后获得硅碳混合物；
    步骤S420.将通过步骤S410获得的所述硅碳混合物与石墨烯按硅碳混合物：石墨烯＝(5-15)：(85-95)的质量比混合均匀，在620℃至660℃的温度条件下保温2小时，冷却后获得所述石墨烯填料。
  10. 一种橡胶粘合剂，其特征在于，
    所述橡胶粘合剂采用如权利要求1至9中任一项所述的橡胶粘合剂的制备方法获得。
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