Wear-resistant high-activity metal rubber heat vulcanization adhesive and preparation method thereof

Abstract

The invention relates to an anti-wear high-activity metal rubber heat vulcanization adhesive and a preparation method thereof, and relates to the technical field of adhesive preparation, and the adhesive comprises film-forming resin, a nitroso compound, a special high-activity vulcanizing agent, a special reactive coupling agent, a reinforcing filler, an acid acceptor and a solvent. The anti-wear high-activity metal rubber heat vulcanization adhesive provided by the invention has excellent bonding strength on various rubber products which are difficult to bond, such as natural rubber products containing reclaimed rubber, low-compression permanent deformation rubber products, high-hardness rubber products, low-hardness rubber products, rubber products with high oil filling content and the like.

Description

Technical Field

[0001] This invention relates to the field of adhesive preparation technology, and in particular to a wear-resistant, highly active metal-rubber heat-cured adhesive and its preparation method. Background Technology

[0002] Metal-rubber heat-cured adhesives are bonding agents used to bond metal substrates with significantly different elastic moduli to rubber products. Utilizing the elasticity of rubber and the rigidity of metal, they achieve both metal support and reinforcement of rubber, as well as rubber protection and corrosion resistance of metal, and are currently widely used in construction, automotive, and military industries. However, some difficult-to-bond rubber products present challenges to the bonding process due to their low surface energy, strong chemical inertness, high non-polarity, and incompatible vulcanization systems.

[0003] For difficult-to-bond rubber products, highly active adhesives must be used. In existing technologies, one way to improve adhesive activity is to increase the amount of vulcanizing agent. For example, Chinese invention patent CN85102008A discloses a composition consisting of at least one 2,3-dihalo-1,3-butadiene polymer, at least one aryl nitrite compound, at least one inorganic or organic acid salt, and at least one maleic anhydride compound. Chinese invention patent CN1060182C discloses a halogenated functional monomer adhesive promoter and adhesive composition. Polymers modified with certain halogenated functional monomer materials significantly improve the adhesion between the elastomer and adhesive interface by improving the bonding performance and eliminating the need for a large amount of additional adhesive components, such as nitrosamines or carbamates, thus significantly increasing the adhesion between the elastic matrix and the metal surface. As can be seen from the above patents, a large amount of maleimide and nitrosamine compounds contributes to improving the activity of the adhesive. Because of the high content of powdery substances (nitroso compounds, vulcanizing agents, fillers, etc.) in this highly active adhesive system, they cannot be completely encapsulated by a small amount of resin, causing the effective substances to be exposed on the adhesive surface, resulting in a powdery appearance and consequently poor wear resistance of the adhesive during use.

[0004] From a practical production perspective, during the transportation and movement of the substrates to be bonded after applying adhesive, contact and friction are unavoidable. This causes wear on the adhesive surface, affecting the bonding effect. During the bonding process, especially with difficult-to-bond rubber types, it is crucial to carefully protect the adhesive surface to prevent the effective substances floating on the adhesive surface from falling off, significantly reducing production efficiency and product yield. Therefore, inventing a wear-resistant, highly active metal-rubber heat-curing adhesive is the focus of this application. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides a method for preparing and using a wear-resistant, highly active metal-rubber heat-cured adhesive. According to existing technology, the addition of maleimide polymers effectively improves adhesion because maleimide can chemically react with unsaturated diene rubbers to form chemical cross-linking bonds. The reaction mechanism is as follows: Inspired by the above, this invention synthesizes a highly active vulcanizing agent by designing a chemical structural formula that simultaneously introduces maleimide groups and polysulfide bonds into a single molecule. Both the maleimide groups and polysulfide bonds in this special vulcanizing agent can react with the active α-H groups on the rubber molecular chain to form CC and SC bonds. Experimental results show that the two chemical reactions synergistically improve the adhesive strength. Furthermore, the applicant discovered that only a small amount of this highly active vulcanizing agent powder is needed to achieve satisfactory bonding results, avoiding the powdering phenomenon caused by excessive vulcanizing agent. In addition, the special reactive coupling agent used in this invention also contains maleimide groups. The alkoxy groups in the coupling agent hydrolyze and form chemical bonds with the substrate, thereby improving wear resistance. The maleimide groups in the coupling agent can also form chemical bonds with rubber, improving the adhesive strength. The synergistic effect of these two special substances gives the adhesive both wear resistance and high activity, solving the problem of poor surface wear resistance after applying adhesive to the substrate in actual production.

[0006] The wear-resistant, highly active metal-rubber heat-curing adhesive provided by this invention exhibits excellent bonding strength to various difficult-to-bond rubber products, including natural rubber products containing reclaimed rubber, low compression set rubber products, high-hardness rubber products, low-hardness rubber products, and rubber products with high oil content.

[0007] In a first aspect, the present invention provides an anti-wear, highly active metal-rubber hot-curing adhesive, wherein, by mass parts, the adhesive comprises 10-50 parts of film-forming resin, 5-15 parts of nitroso compound, 5-20 parts of special highly active curing agent, 2-10 parts of reinforcing filler, 5-15 parts of special reactive coupling agent, 3-8 parts of acid scavenger, and 200-500 parts of solvent; The film-forming resin is any one or more of polyvinyl chloride, chlorosulfonated polyethylene, chlorinated polyethylene, high-chlorinated polyethylene, chlorinated polypropylene, chlorinated polybutadiene, chlorinated ethylene-propylene copolymer, brominated natural rubber, epoxidized natural rubber, hydrochlorinated natural rubber, and cyclized natural rubber; the nitroso compound is any one of p-nitrosobenzene, m-nitrosobenzene, o-nitrosobenzene, p-nitrosophenol, and 3-methyl-1,4-nitrosobenzene; the acid scavenger is any one of magnesium oxide, zinc oxide, calcium oxide, titanium dioxide, calcium hydroxide, and magnesium hydroxide; the reinforcing filler is carbon black; and the solvent is any one or more of xylene, trichloroethylene, tetrachloroethylene, methyl isobutyl ketone, and toluene.

[0008] In the above technical solution, the film-forming resin, as the matrix of the adhesive, can provide the adhesive itself with mechanical strength and resist peeling and shear stress. It can also encapsulate and fix vulcanizing agents, fillers, and other substances within the film, preventing them from powdering and detaching. The selected chlorinated, brominated, or cyclized polymers have high polarity, enabling them to physically adsorb and interact with metal surfaces. Simultaneously, their molecular chains can participate in cross-linking reactions during the vulcanization process.

[0009] The nitrosyl group (-N=O) in nitrosyl compounds is highly reactive. Under heating conditions, it can react with oxides on the surface of metals (such as iron and copper) to form stable nitrosyl-metal oxide complexes, which firmly adhere to the metal surface. This enhances the adhesion strength between the adhesive and the metal, preventing peeling off at the interface.

[0010] The molecular structure of this special high-activity vulcanizing agent contains both maleimide groups and polysulfide bonds (-Sx-). At the vulcanization temperature, the maleimide groups can form CC bonds with double bonds or α-H on the rubber molecular chain, while the polysulfide bonds can form SC bonds. This dual crosslinking mechanism produces a strong synergistic effect, enhancing adhesive strength. Due to its high activity, a small amount is required to achieve good results, thus avoiding the powdering problem caused by the large amount of vulcanizing agent used in traditional techniques.

[0011] The special reactive coupling agent has an alkoxysilane at one end of its molecule, which forms a Si-OM covalent bond with the metal surface after hydrolysis, and a maleimide group at the other end, which can form a C-C bond with rubber. This chemical bonding more firmly locks the adhesive film onto the metal surface, enhancing the coating's scratch resistance and abrasion resistance. Combined with a special highly reactive vulcanizing agent, it further strengthens the interfacial crosslinking density with rubber.

[0012] Carbon black is used as a reinforcing filler to improve the abrasion resistance of the adhesive coating. It also helps adjust the viscosity of the adhesive, ensuring suitable leveling properties during application. Preferably, any one of N220, N330, N550, or N770 carbon black can be used.

[0013] Acid absorbers may decompose into acidic substances such as HCl during vulcanization or material aging (especially with chlorine-containing resins). These acids corrode metal interfaces, break the chemical bonds formed by nitrosamines, and lead to adhesive failure. Acid absorbers can neutralize these acidic substances in a timely manner, protecting the adhesive interface and extending the service life of bonded components in high-temperature environments.

[0014] The solvent dissolves or uniformly disperses the solid resin and other components, forming a homogeneous solution that gives the adhesive a suitable application viscosity for brushing, spraying, or dipping. It also helps the adhesive fully wet the metal surface, ensuring good contact.

[0015] Optionally, the film-forming resin is any one or more of polyvinyl chloride, highly chlorinated polyethylene, chlorosulfonated polyethylene, and hydrochlorinated natural rubber.

[0016] Optionally, the reaction formula of the special highly active vulcanizing agent is as follows: Ⅰ In the above general chemical structural formula I, R1 and R2 are organic groups, including aliphatic hydrocarbon and / or aromatic hydrocarbon groups. In -Sx, x takes the values ​​1-7, preferably 2-4.

[0017] Optionally, the specific preparation steps of the special highly active vulcanizing agent are shown in the following reaction equation: 1 2 Ⅰ Using an amino-containing reactant as shown in chemical structural formula 1 and maleic anhydride as shown in chemical structural formula 2 as raw materials, the amino-containing reactant and the maleic anhydride are dissolved in reaction solvent A, the molar ratio of the amino-containing reactant to the maleic anhydride is 1:2-4, and the reaction is carried out at a temperature of 40-80 °C for 2-10 h to obtain a special high-activity vulcanizing agent as shown in general chemical structural formula I.

[0018] In the above technical solution, the -NH2 group in the amino-containing reactant nucleophilically attacks the carbonyl carbon in the maleic anhydride molecule. One amino group reacts with one maleic anhydride molecule, opening the anhydride ring and generating an amide acid. Since the amino-containing reactant used is a diamine (with one -NH2 group at each end of the molecule), it can react with two maleic anhydride molecules, generating a linear intermediate with amide acid structures at both ends. Under heating conditions, this amide acid intermediate undergoes intramolecular dehydration cyclization. The carboxyl group (-COOH) in the amide acid structure undergoes a condensation reaction with the adjacent amide group (-NH-C(O)-), removing one molecule of water to form a stable five-membered ring.

[0019] Optionally, the amino-containing reactant is 4,4'-dithiodiphenylamine, 4,4'-tetrathiodiphenylamine, 4,4'-dithiodi(2-methylaniline), 4,4'-tetrathiodi(2-methylaniline), 4,4'-dithiodi(2-ethylaniline), 4,4'-tetrathiodi(2-ethylaniline), more preferably, any one of 4,4'-dithiodiphenylamine and 4,4'-tetrathiodiphenylamine; the reaction solvent A is any one or more of xylene, 1,4-dioxane, tetrahydrofuran, tetrachloroethylene, trichloroethylene, chloroform, dimethyl sulfoxide, and methanol.

[0020] Optionally, the reaction formula of the special reactive coupling agent is as follows: II In the above general formula II, R1-R4 are organic groups, including aliphatic hydrocarbon and / or aromatic hydrocarbon groups.

[0021] Optionally, the specific preparation steps of the special reactive coupling agent are shown in the following reaction equation: Using an amino-containing silane coupling agent as shown in chemical structural formula 3 and maleic anhydride as shown in chemical structural formula 4 as raw materials, the amino-containing silane coupling agent and the maleic anhydride are dissolved in reaction solvent B, the molar ratio of the amino-containing silane coupling agent to the maleic anhydride is 1:1-2, and the reaction is carried out at a temperature of 50-70℃ for 10-20 hours to obtain a special reactive coupling agent as shown in general chemical structural formula II.

[0022] In the above technical solution, the -NH2 group at the end of the aminosilane coupling agent molecule acts as a nucleophile, attacking the carbonyl carbon in the maleic anhydride molecule. The reaction opens the anhydride ring, generating an amide acid intermediate. This intermediate contains both a carboxyl group (-COOH) and an amide bond (-NH-C(O)-). Under heating conditions, the generated amide acid intermediate undergoes intramolecular dehydration cyclization. The carboxyl group (-COOH) in the intermediate molecule undergoes a condensation reaction with the adjacent amide group (-NH-C(O)-), removing one molecule of water to form a stable maleimide ring containing a double bond.

[0023] Optionally, the amino-containing silane coupling agent is any one of amino-containing triethoxysilane coupling agent, amino-containing diethoxymethylsilane coupling agent, amino-containing dimethylethoxysilane coupling agent, amino-containing trimethoxysilane coupling agent, amino-containing dimethoxyethoxysilane coupling agent, and amino-containing dimethoxymethylsilane coupling agent; the reaction solvent B is any one or more of xylene, 1,4-dioxane, tetrahydrofuran, tetrachloroethylene, trichloroethylene, chloroform, dimethyl sulfoxide, and ethanol.

[0024] Secondly, the present invention provides a method for preparing a wear-resistant, highly active metal rubber hot-curing adhesive. The preparation method includes the following steps: mixing the film-forming resin, nitrosamine compound, carbon black and acid scavenger, making 3-4 triangular bags, and then discharging the mixture through a thin tube to obtain a compound; then adding the compound, a special highly active vulcanizing agent, a special reactive coupling agent and solvent into a grinding container with zirconia bead dispersion medium, and mixing and grinding for 3-5 hours to obtain the adhesive.

[0025] In the above technical solution, the zirconium oxide particle size of the dispersion medium used is 2-10 mm. The grinding time is not less than 3 hours, which can fully ensure that the fineness of the adhesive of this invention is less than 15 μm.

[0026] Thirdly, the present invention provides the application of the adhesive prepared by the above-mentioned method of preparing a wear-resistant high-activity metal rubber hot vulcanizing adhesive in the construction industry, automotive industry, sporting goods manufacturing industry and military industry.

[0027] In summary, the present invention has at least one of the following beneficial technical effects: 1. The hot vulcanizing adhesive provided by this invention incorporates a special high-activity vulcanizing agent and a reactive coupling agent. The two work synergistically to give the adhesive both wear resistance and high activity, solving the problem of the contradiction between high activity and wear resistance in metal-rubber adhesives. This makes it more operable in the actual production process of rubber bonding, greatly improving production efficiency and product quality.

[0028] 2. The wear-resistant, highly active metal-rubber heat-curing adhesive provided by this invention has excellent bonding strength for difficult-to-bond rubber products such as natural rubber products containing reclaimed rubber, low compression set rubber products, high hardness rubber products, low hardness rubber products, and rubber products with high oil content, further expanding its application range. Attached Figure Description

[0029] Figure 1The 1H NMR spectrum of the special highly active vulcanizing agent 1,1'-(tetrathionidinediylbis(4,1-phenylene))bis(1H-pyrrole-2,5-dione) in Example 6 of the present invention; Figure 2 The infrared spectrum of the special highly active vulcanizing agent 1,1'-(tetrathionidinediylbis(4,1-phenylene))bis(1H-pyrrole-2,5-dione) in Example 6 of the present invention; Figure 3 The 1H NMR spectrum of the special reactive coupling agent 1-(3-(triethoxysilyl)propyl)-1H-pyrrole-2,5-dione in Example 6 of the present invention; Figure 4 The infrared spectrum of the special reactive coupling agent 1-(3-(triethoxysilyl)propyl)-1H-pyrrole-2,5-dione in Example 6 of the present invention is shown. Detailed Implementation

[0030] The present invention will be further described in detail below with reference to the embodiments.

[0031] All materials used in the following examples are available for purchase on the market.

[0032] Example 1 This embodiment provides a wear-resistant, highly active metal-rubber heat-curing adhesive, comprising the following components by weight: The special high-activity vulcanizing agent is 1,1'-(tetrathionidinediylbis(4,1-phenylene))bis(1H-pyrrole-2,5-dione), and its structural formula is as follows: ; The special reactive coupling agent is a maleimide-containing triethoxysilane coupling agent 1-(3-(triethoxysilyl)propyl)-1H-pyrrole-2,5-dione, with the following structural formula: ; The preparation method is as follows: S1. Preparation of a special high-activity vulcanizing agent: 4,4'-tetrathiodiphenylamine and maleic anhydride are dissolved in tetrahydrofuran, wherein the molar ratio of 4,4'-tetrathiodiphenylamine and maleic anhydride is 1:2, and the mixture is reacted at 40 °C for 10 h to obtain 1,1'-(tetrathionidinediylbis(4,1-phenylene))bis(1H-pyrrole-2,5-dione).

[0033] S2. Preparation of special reactive coupling agent: An amino-containing triethoxysilane coupling agent and the maleic anhydride are dissolved in tetrachloroethylene, wherein the molar ratio of the amino-containing triethoxysilane coupling agent and the maleic anhydride is 1:1. The mixture is reacted at 50 °C for 20 h to obtain 1-(3-(triethoxysilyl)propyl)-1H-pyrrole-2,5-dione.

[0034] S3. Polyvinyl chloride, hydrochlorinated natural rubber, p-nitrosobenzene, carbon black N330 and magnesium oxide are mixed and kneaded into three triangular bags, and then discharged through a thin tube to obtain the mixed rubber.

[0035] S4. Add the above-mentioned compound rubber, special high-activity vulcanizing agent, special reactive coupling agent and mixed solvent of tetrachloroethylene and toluene into a grinding container with zirconia bead dispersion medium, mix and grind for 3 hours to obtain the adhesive #1.

[0036] Example 2 This embodiment provides a wear-resistant, highly active metal-rubber heat-curing adhesive, comprising the following components by weight: The special high-activity vulcanizing agent is 1,1'-(tetrathionidinediylbis(4,1-phenylene))bis(1H-pyrrole-2,5-dione), and its structural formula is as follows: ; The special reactive coupling agent is a maleimide-containing triethoxysilane coupling agent 1-(3-(triethoxysilyl)propyl)-1H-pyrrole-2,5-dione, with the following structural formula: ; The preparation method is as follows: S1. Preparation of a special high-activity vulcanizing agent: 4,4'-tetrathiodi(2-methylaniline) and maleic anhydride are dissolved in dimethyl sulfoxide, wherein the molar ratio of 4,4'-tetrathiodi(2-methylaniline) and maleic anhydride is 1:4. The mixture is reacted at 80 °C for 2 h to obtain 1,1'-(tetrathionidinediylbis(4,1-phenylene))bis(1H-pyrrole-2,5-dione).

[0037] S2. Preparation of special reactive coupling agent: An amino-containing triethoxysilane coupling agent and the maleic anhydride are dissolved in xylene, wherein the molar ratio of the amino-containing triethoxysilane coupling agent and the maleic anhydride is 1:2. The mixture is reacted at 70 °C for 10 h to obtain 1-(3-(triethoxysilyl)propyl)-1H-pyrrole-2,5-dione.

[0038] S3. Chlorinated ethylene-propylene copolymer, epoxidized natural rubber, o-nitrosobenzene, carbon black N770 and calcium oxide are mixed and kneaded into four triangular bags, and then discharged through a thin tube to obtain the mixed rubber.

[0039] S4. Add the above-mentioned compound rubber, special high-activity vulcanizing agent, special reactive coupling agent and methyl isobutyl ketone solvent to a grinding container with zirconia bead dispersion medium, mix and grind for 5 hours to obtain the adhesive #2.

[0040] Example 3 This embodiment provides a wear-resistant, highly active metal-rubber heat-curing adhesive, comprising the following components by weight: The special high-activity vulcanizing agent is 1,1'-(tetrathionidinediylbis(4,1-phenylene))bis(1H-pyrrole-2,5-dione), and its structural formula is as follows: ; The special reactive coupling agent is a maleimide-containing triethoxysilane coupling agent 1-(3-(triethoxysilyl)propyl)-1H-pyrrole-2,5-dione, with the following structural formula: ; The preparation method is as follows: S1. Preparation of a special high-activity vulcanizing agent: 4,4'-tetrathiodi(2-ethylaniline) and maleic anhydride are dissolved in chloroform, with a molar ratio of 1:3 between the two. The mixture is reacted at 60 °C for 5 h to obtain 1,1'-(tetrathionidinediylbis(4,1-phenylene))bis(1H-pyrrole-2,5-dione).

[0041] S2. Preparation of special reactive coupling agent: An amino-containing triethoxysilane coupling agent and maleic anhydride are dissolved in tetrachloroethylene, wherein the molar ratio of the amino-containing triethoxysilane coupling agent and the maleic anhydride is 1:1.5. The mixture is reacted at 60 °C for 15 h to obtain 1-(3-(triethoxysilyl)propyl)-1H-pyrrole-2,5-dione.

[0042] S3. Chlorinated polybutadiene, cyclized natural rubber, 3-methyl-1,4-dinitrosobenzene, carbon black N770 and titanium dioxide are mixed and compounded. After being wrapped in three triangular bags, the mixture is discharged through a thin tube to obtain the compound rubber.

[0043] S4. Add the above-mentioned compound rubber, special high-activity vulcanizing agent, special reactive coupling agent and trichloroethylene solvent to a grinding container with zirconia bead dispersion medium, mix and grind for 4 hours to obtain the adhesive #3.

[0044] Example 4 This embodiment provides a wear-resistant, highly active metal-rubber heat-curing adhesive, which comprises the following components by weight: The special high-activity vulcanizing agent is 1,1'-(tetrathionidinediylbis(4,1-phenylene))bis(1H-pyrrole-2,5-dione), and its structural formula is as follows: ; The special reactive coupling agent is a maleimide-containing triethoxysilane coupling agent 1-(3-(triethoxysilyl)propyl)-1H-pyrrole-2,5-dione, with the following structural formula: ; The preparation method is as follows: S1. Preparation of a special high-activity vulcanizing agent: 4,4'-tetrathiodiphenylamine and maleic anhydride are dissolved in tetrahydrofuran, wherein the molar ratio of 4,4'-tetrathiodiphenylamine and maleic anhydride is 1:2.2. The mixture is reacted at 60 °C for 5 h to obtain 1,1'-(tetrathionidinediylbis(4,1-phenylene))bis(1H-pyrrole-2,5-dione).

[0045] S2. Preparation of special reactive coupling agent: An amino-containing triethoxysilane coupling agent and maleic anhydride are dissolved in ethanol, wherein the molar ratio of the amino-containing triethoxysilane coupling agent and the maleic anhydride is 1:1.1. The mixture is reacted at 60°C for 15 h to obtain 1-(3-(triethoxysilyl)propyl)-1H-pyrrole-2,5-dione.

[0046] S3. Chlorosulfonated polyethylene, high-chlorinated polyethylene, m-nitrosobenzene, carbon black N220 and zinc oxide are mixed and kneaded three times in triangular bundles, and then discharged through a thin tube to obtain the compound rubber.

[0047] S4. Add the above-mentioned compound rubber, special high-activity vulcanizing agent, special reactive coupling agent and mixed solvent of xylene and trichloroethylene into a grinding container with zirconia bead dispersion medium, mix and grind for 5 hours to obtain the adhesive #4.

[0048] Example 5 This embodiment provides a wear-resistant, highly active metal-rubber heat-curing adhesive, which comprises the following components by weight: Wherein: the chlorosulfonated polyethylene; the highly chlorinated polyethylene; the nitroso compound is m-dinitrobenzene; the special highly active vulcanizing agent is 1,1'-(tetrathionidinediylbis(4,1-phenylene))bis(1H-pyrrole-2,5-dione), whose structural formula is as follows: ; The special reactive coupling agent is a maleimide-containing triethoxysilane coupling agent 1-(3-(triethoxysilyl)propyl)-1H-pyrrole-2,5-dione, with the following structural formula: ; The preparation method is as follows: S1. Preparation of a special high-activity vulcanizing agent: 4,4'-tetrathiodiphenylamine and maleic anhydride are dissolved in dimethyl sulfoxide, wherein the molar ratio of 4,4'-tetrathiodiphenylamine and maleic anhydride is 1:2.2. The mixture is reacted at 60 °C for 5 h to obtain 1,1'-(tetrathionidinediylbis(4,1-phenylene))bis(1H-pyrrole-2,5-dione).

[0049] S2. Preparation of special reactive coupling agent: An amino-containing triethoxysilane coupling agent and maleic anhydride are dissolved in tetrahydrofuran, wherein the molar ratio of the amino-containing triethoxysilane coupling agent and the maleic anhydride is 1:1.1. The mixture is reacted at 60 °C for 15 h to obtain 1-(3-(triethoxysilyl)propyl)-1H-pyrrole-2,5-dione.

[0050] S3. Chlorosulfonated polyethylene, high-chlorinated polyethylene, m-nitrosobenzene, carbon black N220 and zinc oxide are mixed and kneaded three times in triangular bundles, and then discharged through a thin tube to obtain the compound rubber.

[0051] S4. Add the above-mentioned compound rubber, special high-activity vulcanizing agent, special reactive coupling agent and mixed solvent of xylene and trichloroethylene into a grinding container with zirconia bead dispersion medium, mix and grind for 5 hours to obtain the adhesive #5.

[0052] Example 6 This embodiment provides a wear-resistant, highly active metal-rubber heat-curing adhesive, comprising the following components by weight: The special high-activity vulcanizing agent is 1,1'-(tetrathionidinediylbis(4,1-phenylene))bis(1H-pyrrole-2,5-dione), and its structural formula is as follows: ; The special reactive coupling agent is a maleimide-containing triethoxysilane coupling agent 1-(3-(triethoxysilyl)propyl)-1H-pyrrole-2,5-dione, with the following structural formula: ; The preparation method is as follows: S1. Preparation of a special high-activity vulcanizing agent: 4,4'-tetrathiodiphenylamine and maleic anhydride are dissolved in dimethyl sulfoxide, wherein the molar ratio of 4,4'-tetrathiodiphenylamine and maleic anhydride is 1:2.2. The mixture is reacted at 60 °C for 5 h to obtain 1,1'-(tetrathionidinediylbis(4,1-phenylene))bis(1H-pyrrole-2,5-dione).

[0053] S2. Preparation of special reactive coupling agent: An amino-containing triethoxysilane coupling agent and maleic anhydride are dissolved in tetrahydrofuran, wherein the molar ratio of the amino-containing triethoxysilane coupling agent and the maleic anhydride is 1:1.1. The mixture is reacted at 60 °C for 15 h to obtain 1-(3-(triethoxysilyl)propyl)-1H-pyrrole-2,5-dione.

[0054] S3. Chlorosulfonated polyethylene, high-chlorinated polyethylene, m-nitrosobenzene, carbon black N220 and zinc oxide are mixed and kneaded three times in triangular bundles, and then discharged through a thin tube to obtain the compound rubber.

[0055] S4. Add the above-mentioned compound rubber, special high-activity vulcanizing agent, special reactive coupling agent and mixed solvent of xylene and trichloroethylene into a grinding container with zirconia bead dispersion medium, mix and grind for 5 hours to obtain the adhesive #6.

[0056] Comparative Example 1 This embodiment provides a wear-resistant, highly active metal-rubber heat-curing adhesive, which comprises the following components by weight: The preparation method is as follows: S1. Chlorosulfonated polyethylene, high-chlorinated polyethylene, m-nitrosobenzene, carbon black N220 and zinc oxide are mixed and compounded. After being wrapped in three triangular bags, the mixture is discharged through a thin tube to obtain the compound rubber.

[0057] S4. Add the above-mentioned compound rubber, xylene and trichloroethylene mixed solvent to a grinding container with zirconia bead dispersion medium, mix and grind for 5 hours to obtain the adhesive D1.

[0058] Comparative Example 2 This embodiment provides a wear-resistant, highly active metal-rubber heat-curing adhesive, which comprises the following components by weight: The special high-activity vulcanizing agent is 1,1'-(tetrathionidinediylbis(4,1-phenylene))bis(1H-pyrrole-2,5-dione), and its structural formula is as follows: ; The preparation method is as follows: S1. Preparation of a special high-activity vulcanizing agent: 4,4'-tetrathiodiphenylamine and maleic anhydride are dissolved in dimethyl sulfoxide, wherein the molar ratio of 4,4'-tetrathiodiphenylamine and maleic anhydride is 1:2.2. The mixture is reacted at 60 °C for 5 h to obtain 1,1'-(tetrathionidinediylbis(4,1-phenylene))bis(1H-pyrrole-2,5-dione).

[0059] S2. Chlorosulfonated polyethylene, high-chlorinated polyethylene, m-nitrosobenzene, carbon black N220 and zinc oxide are mixed and kneaded three times in triangular bundles, and then discharged through a thin tube to obtain the compound rubber.

[0060] S3. Add the above-mentioned compound rubber, special high-activity vulcanizing agent, xylene and trichloroethylene mixed solvent to a grinding container with zirconia bead dispersion medium, mix and grind for 5 hours to obtain the adhesive D2.

[0061] Comparative Example 3 This embodiment provides a wear-resistant, highly active metal-rubber heat-curing adhesive, which comprises the following components by weight: The special reactive coupling agent is a maleimide-containing triethoxysilane coupling agent 1-(3-(triethoxysilyl)propyl)-1H-pyrrole-2,5-dione, with the following structural formula: ; The preparation method is as follows: S1. Preparation of special reactive coupling agent: An amino-containing triethoxysilane coupling agent and maleic anhydride are dissolved in tetrahydrofuran, wherein the molar ratio of the amino-containing triethoxysilane coupling agent and the maleic anhydride is 1:1.1. The mixture is reacted at 60 °C for 15 h to obtain 1-(3-(triethoxysilyl)propyl)-1H-pyrrole-2,5-dione.

[0062] S2. Chlorosulfonated polyethylene, high-chlorinated polyethylene, m-nitrosobenzene, carbon black N220 and zinc oxide are mixed and kneaded three times in triangular bundles, and then discharged through a thin tube to obtain the compound rubber.

[0063] S3. Add the above-mentioned compound rubber, special reactive coupling agent and mixed solvent of xylene and trichloroethylene into a grinding container with zirconia bead dispersion medium, mix and grind for 5 hours to obtain the adhesive D3.

[0064] Performance Testing: The abrasion resistance of the adhesive was verified by reciprocating friction on the adhesive-coated test pieces using an abrasion tester manufactured by Changzhou Second Textile Machinery Co., Ltd. Subsequently, it was co-vulcanized and bonded with the raw rubber compound under vulcanization conditions of 145℃ / 25min / 10MPa. Finally, the adhesive was tested according to GB / T7760-2003 "Determination of Adhesion Strength between Vulcanized Rubber or Thermoplastic Elastomer and Rigid Sheet Material - 90° Peel Method", and the peel strength and rubber retention percentage were measured. The adhesive bonding strength test results are shown in Table 1.

[0065] Table 1 As can be seen from the peel strength and rubber retention percentage in the test data obtained from Examples 1-6 in Table 1, the wear-resistant high-activity metal rubber hot vulcanized adhesive of this application has good wear resistance.

[0066] Figure 1 The above is the 1H NMR spectrum of the special highly active vulcanizing agent 1,1'-(tetrathionidinediylbis(4,1-phenylene))bis(1H-pyrrole-2,5-dione) in Example 6 of the present invention. Figure 1 It can be seen that 1H NMR (600 MHz, DMSO) δ 7.49 (m,2H, Ar-H), 7.36-7.31 (m, 2H, Ar-H), 7.18 (s, 2H, -CH=CH-). Figure 2 The infrared spectrum of the special highly active vulcanizing agent 1,1'-(tetrathionidinediylbis(4,1-phenylene))bis(1H-pyrrole-2,5-dione) in Example 6 of the present invention is shown below. Figure 2 It can be seen that the peak at 3092 cm1 is the absorption peak of the stretching vibration of the aromatic ring CH; the peak at 845 cm1 is the absorption peak of the stretching vibration of SS; the peak at 1705 cm1 is the absorption peak of the stretching vibration of C=O; and the peak at 1595 cm1 is the absorption peak of the stretching vibration of C=C.

[0067] Figure 3 The above is the 1H NMR spectrum of the special reactive coupling agent 1-(3-(triethoxysilyl)propyl)-1H-pyrrole-2,5-dione in Example 6 of the present invention. Figure 3It can be seen that the 1H NMR (600 MHz, DMSO) δ 7.00 (s, 2H, -CH=CH-), 3.75 (q, 6H, -OCH2CH3), 3.60 (t, 2H, -CH2), 1.80-1.70 (m, 2H, -CH2), 1.15 (t, 9H, -OCH2CH3), 0.70-0.64 (m, 2H, -SiCH2). Figure 4 The image shows the infrared spectrum of the special reactive coupling agent 1-(3-(triethoxysilyl)propyl)-1H-pyrrole-2,5-dione used in Example 6 of this invention. Figure 4 It can be seen that the peak at 2987-2873 cm1 is the stretching vibration absorption peak of alkyl CH; the peak at 1717 cm1 is the stretching vibration absorption peak of C=O; and the peak at 1584 cm1 is the stretching vibration absorption peak of C=C.

[0068] As can be seen from Comparative Examples 1-3, the special high-activity vulcanizing agent and the special reactive coupling agent of this application play an important role in the adhesive of this application. The special high-activity vulcanizing agent and the special reactive coupling agent work synergistically to make the adhesive have both wear resistance and high activity, which solves the problem of the contradiction between high activity and wear resistance in metal rubber adhesives. This makes it more operable in the actual production process of rubber bonding, and greatly improves production efficiency and product quality.

[0069] The above are all preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Therefore, all equivalent changes made in accordance with the structure, shape and principle of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A wear-resistant, highly active metal-rubber heat-curing adhesive, characterized in that, The adhesive comprises, by weight, 10-50 parts film-forming resin, 5-15 parts nitroso compound, 5-20 parts special high-activity vulcanizing agent, 2-10 parts reinforcing filler, 5-15 parts special reactive coupling agent, 3-8 parts acid scavenger, and 200-500 parts solvent. The film-forming resin is any one or more of polyvinyl chloride, chlorosulfonated polyethylene, chlorinated polyethylene, high-chlorinated polyethylene, chlorinated polypropylene, chlorinated polybutadiene, chlorinated ethylene-propylene copolymer, brominated natural rubber, epoxidized natural rubber, hydrochlorinated natural rubber, and cyclized natural rubber; the nitroso compound is any one of p-nitrosobenzene, m-nitrosobenzene, o-nitrosobenzene, p-nitrosophenol, and 3-methyl-1,4-nitrosobenzene; the acid scavenger is any one of magnesium oxide, zinc oxide, calcium oxide, titanium dioxide, calcium hydroxide, and magnesium hydroxide; the reinforcing filler is carbon black; and the solvent is any one or more of xylene, trichloroethylene, tetrachloroethylene, methyl isobutyl ketone, and toluene.

2. The wear-resistant, highly active metal-rubber heat-curing adhesive according to claim 1, characterized in that, The film-forming resin is any one or more of polyvinyl chloride, high-chlorinated polyethylene, chlorosulfonated polyethylene, and hydrochlorinated natural rubber.

3. The wear-resistant, highly active metal-rubber heat-curing adhesive according to claim 1, characterized in that, The reaction formula of the special high-activity vulcanizing agent is shown in the figure below: Ⅰ In the above general chemical structural formula I, R1 and R2 are organic groups, including aliphatic hydrocarbon and / or aromatic hydrocarbon groups. In -Sx, x takes the values ​​1-7, preferably 2-4.

4. The wear-resistant, highly active metal-rubber heat-curing adhesive according to claim 3, characterized in that, The specific preparation steps of the special high-activity vulcanizing agent are shown in the following reaction equation: 1 2 I Using an amino-containing reactant as shown in chemical structural formula 1 and maleic anhydride as shown in chemical structural formula 2 as raw materials, the amino-containing reactant and the maleic anhydride are dissolved in reaction solvent A, the molar ratio of the amino-containing reactant to the maleic anhydride is 1:2-4, and the reaction is carried out at a temperature of 40-80 °C for 2-10 h to obtain a special high-activity vulcanizing agent as shown in general chemical structural formula I.

5. The wear-resistant, highly active metal-rubber heat-curing adhesive according to claim 4, characterized in that, The amino-containing reactant is 4,4'-dithiodiphenylamine, 4,4'-tetrathiodiphenylamine, 4,4'-dithiodi(2-methylaniline), 4,4'-tetrathiodi(2-methylaniline), 4,4'-dithiodi(2-ethylaniline), 4,4'-tetrathiodi(2-ethylaniline), more preferably, any one of 4,4'-dithiodiphenylamine and 4,4'-tetrathiodiphenylamine; the reaction solvent A is any one or more of xylene, 1,4-dioxane, tetrahydrofuran, tetrachloroethylene, trichloroethylene, chloroform, dimethyl sulfoxide, and methanol.

6. The wear-resistant, highly active metal-rubber heat-curing adhesive according to claim 1, characterized in that, The reaction formula of the special reactive coupling agent is shown in the figure below: Ⅱ In the above general formula II, R1-R4 are organic groups, including aliphatic hydrocarbon and / or aromatic hydrocarbon groups.

7. The wear-resistant, highly active metal-rubber heat-curing adhesive according to claim 6, characterized in that, The specific preparation steps of the special reactive coupling agent are shown in the following reaction equation: Using an amino-containing silane coupling agent as shown in chemical structural formula 3 and maleic anhydride as shown in chemical structural formula 4 as raw materials, the amino-containing silane coupling agent and the maleic anhydride are dissolved in reaction solvent B, the molar ratio of the amino-containing silane coupling agent to the maleic anhydride is 1:1-2, and the reaction is carried out at a temperature of 50-70℃ for 10-20 hours to obtain a special reactive coupling agent as shown in general chemical structural formula II.

8. The wear-resistant, highly active metal-rubber heat-curing adhesive according to claim 7, characterized in that, The amino-containing silane coupling agent is any one of the following: amino-containing triethoxysilane coupling agent, amino-containing diethoxymethylsilane coupling agent, amino-containing dimethylethoxysilane coupling agent, amino-containing trimethoxysilane coupling agent, amino-containing dimethoxyethoxysilane coupling agent, and amino-containing dimethoxymethylsilane coupling agent; the reaction solvent B is any one or more of xylene, 1,4-dioxane, tetrahydrofuran, tetrachloroethylene, trichloroethylene, chloroform, dimethyl sulfoxide, and ethanol.

9. A method for preparing an anti-wear, highly active metal-rubber heat-curing adhesive as described in any one of claims 1-8, characterized in that, The preparation method includes the following steps: The film-forming resin, nitroso compound, carbon black and acid scavenger are mixed and kneaded 3-4 times in a triangular bag, and then the mixture is discharged through a thin tube to obtain a compound. The compound, a special high-activity vulcanizing agent, a special reactive coupling agent and solvent are then added to a grinding container with zirconia bead dispersion medium and mixed and ground for 3-5 hours to obtain the adhesive.

10. An adhesive used in the construction, automotive, sporting goods manufacturing, and military industries, characterized in that... The adhesive is prepared using the anti-wear highly active metal rubber hot vulcanizing adhesive as described in any one of claims 1-8, or the preparation method of the anti-wear highly active metal rubber hot vulcanizing adhesive as described in claim 9.

Images