High-performance adhesive rubber suitable for cord fabric fibers as well as preparation method and application of high-performance adhesive rubber

Abstract

The invention relates to the technical field of rubber industrial manufacturing, in particular to high-performance adhesive rubber suitable for cord fabric fibers and a preparation method and application of the high-performance adhesive rubber. According to the invention, the non-phenolic aldehyde environment-friendly bonding resin, the bio-based phenol and the bio-based aldehyde are used together, and a rubber system, an activation system, a sulfur promoting system and a reinforcing filling system are optimized, so that the novel bonding rubber is provided. The high-performance adhesive rubber provided by the invention not only remarkably reduces the release of toxic substances in the processing and using processes, but also has excellent dynamic and static adhesive properties, mechanical properties and rubber self-adhesive properties, and is suitable for the adhesion of various fibers of cord fabrics for the rubber industry.

Description

Technical Field

[0001] The present invention relates to the technical field of rubber industrial manufacturing, and more particularly to a high-performance adhesive rubber suitable for cord fabric fibers, and a preparation method and application thereof. Background Art

[0002] Fiber / rubber composites combine the high elasticity of the rubber matrix with the high strength of the fiber skeleton material, and can synergistically resist large deformations and structural damage caused by stress. They are widely used in high-load or pressure-resistant fields such as aircraft / automobile tires, automotive hoses, and large rubber conveyor belts for mining / metallurgy / ports. However, the high crystallinity and chemical inertness of the fiber, as well as the differences in polarity and modulus with rubber, lead to insufficient fiber-rubber interfacial adhesion, which seriously affects the service life and safety performance of fiber / rubber composites. Therefore, improving the interfacial adhesion strength between fiber and rubber is the core challenge to improving the overall performance of fiber / rubber composites.

[0003] In the rubber industry, the current industry mainly focuses on improving the interface performance from two aspects: surface modification of tire cord fibers and optimization of adhesive rubber components:

[0004] 1. Fiber surface modification: In industry, fibers are usually impregnated and modified before being compounded with rubber. Traditionally, a resorcinol-formaldehyde-latex (RFL) impregnation system is used. However, because resorcinol and formaldehyde are carcinogens and pose significant risks to humans and the environment, environmentally friendly non-RFL systems have gradually been developed. These systems primarily use epoxy resins, isocyanates, or acrylic resins to construct an impregnation system with a non-RF resin network. The chemical bonding between the fiber and the rubber is enhanced by forming an intermediate transition layer (e.g., JP2021578203A, CN112160169A).

[0005] 2. Optimization of adhesive rubber components: Petroleum-based phenolic resins (such as adhesives A / RS, SL3020, etc.) are often added to the adhesive rubber for cord fabric fibers to improve the interfacial adhesion between the fiber and rubber. Petroleum-based phenolic adhesive resins form a phenolic network at high temperatures that can combine with the active groups on the fiber surface (phenolic resin, epoxy groups, etc.), and the hydroxyl and hydroxymethyl groups in the phenolic resin can react to form a methylene quinone intermediate, which reacts with the active methylene of the rubber molecular chain, thereby significantly improving the interfacial effect of the fiber / rubber composite material. However, these petroleum phenolic resins still release a large amount of formaldehyde and resorcinol during processing, and are highly brittle and have poor impact resistance after curing. They are prone to fatigue fracture under dynamic stress, affecting the dynamic fatigue performance and durability of the fiber / rubber composite material.

[0006] To reduce the toxicity and defects of currently used petroleum-based phenolic resins, various phenolic adhesive resins have been developed through modification. For example, CN109160986A provides a modified meta-cresol-phenol-formaldehyde resin, a preparation method, and a rubber composition thereof. The resin is prepared from raw materials including cresol, a modifier, phenol, and at least one aldehyde. The modified meta-cresol-phenol-formaldehyde resin has significantly reduced free phenol and free alkylphenol contents and exhibits comparable adhesive properties to traditional petroleum-based resorcinol-formaldehyde adhesive resins. CN112300349A discloses a high-ortho-phenolic adhesive resin and a preparation method. Using phenol as a raw material, zinc oxide, zinc hydroxide, or an organic zinc acid catalyst, and meta-cresol or resorcinol as a modification agent, the resulting high-ortho-phenolic resin can be used as an adhesive resin in rubber compositions to provide excellent interfacial adhesion and enhance the overall performance of the rubber.

[0007] However, the above modification technology is still limited to petroleum-based phenolic resin systems. Although it partially alleviates the toxicity and performance defects, it does not fundamentally solve the following problems: (1) Formaldehyde / resorcinol is still released during the processing, which poses a prominent environmental risk; (2) The resin is brittle after curing, which easily causes interfacial crack propagation, resulting in insufficient dynamic fatigue performance of the composite material; (3) Over-reliance on petroleum-based raw materials is inconsistent with the trend of green manufacturing. Therefore, it is urgent to develop a new adhesive resin system that is environmentally friendly, has excellent dynamic and static bonding properties, and can replace petroleum-based phenolic resins. It can be used in the bonding rubber of tire cord fibers to break through the technical bottleneck of fiber / rubber composite materials in the existing rubber industry. Summary of the Invention

[0008] In order to solve the technical problems that petroleum-based phenolic resin systems as rubber adhesive resins release large amounts of resorcinol and formaldehyde during processing and use, which are harmful to the human body and the environment, and that the petroleum-based phenolic adhesive resins are highly brittle after curing, resulting in insufficient dynamic fatigue performance of the adhesive rubber, the present invention provides a high-performance adhesive rubber suitable for cord fabric fibers for the rubber industry, as well as its preparation method and application.

[0009] The present invention provides a novel adhesive rubber by combining a non-phenolic, environmentally friendly adhesive resin with bio-based phenol and bio-based aldehyde, and optimizing the rubber system, activation system, sulfur-promoting system, and reinforcing filler system. This adhesive rubber not only significantly reduces the release of toxic substances during processing and use, but also exhibits excellent dynamic and static adhesion properties (high H extraction force, high peel force, and long fatigue life), mechanical properties, and rubber self-adhesion. It is suitable for bonding various cord fabric fibers used in the rubber industry, such as polyester fibers, nylon fibers, aramid fibers, and ultra-high molecular weight polyethylene fibers.

[0010] One of the objects of the present invention is to provide a high-performance adhesive rubber suitable for use in tire cord fabrics for the rubber industry.

[0011] The high-performance adhesive rubber is prepared from raw materials comprising the following components; the components and their weight parts are as follows:

[0012] 100 parts by weight of base rubber;

[0013] 2-15 parts by weight, preferably 6-12 parts by weight, of an activator;

[0014] 10-50 parts by weight of reinforcing filler, preferably 21-43 parts by weight;

[0015] 1-5 parts by weight, preferably 1-3.5 parts by weight, of a vulcanizing agent;

[0016] 0.1-5 parts by weight, preferably 0.5-2 parts by weight, of a vulcanization accelerator;

[0017] 0.5-20 parts by weight, preferably 3-7 parts by weight, of an environmentally friendly adhesive resin;

[0018] 0.2-3 parts by weight of bio-based phenol, preferably 0.2-1 parts by weight;

[0019] 0.4-6 parts by weight of bio-based aldehyde, preferably 0.4-3 parts by weight.

[0020] The rubber industry cord fabric fiber can be any existing cord fabric fiber. Specifically, the cord fabric fiber can be selected from polyester fiber, nylon fiber, aramid fiber, ultra-high molecular weight polyethylene fiber, etc.

[0021] The rubber can be any natural rubber or / and synthetic rubber currently used in the rubber industry. Preferably, the base rubber is natural rubber, or a mixture of natural rubber, styrene-butadiene rubber, and / or butadiene rubber. When the base rubber is a mixture of natural rubber, styrene-butadiene rubber, and / or butadiene rubber, the base rubber comprises 70-95 parts by weight, preferably 75-95 parts by weight, and more preferably 80-90 parts by weight, of natural rubber per 100 parts by weight of the base rubber, with the balance being styrene-butadiene rubber and / or butadiene rubber.

[0022] The activator can be selected from any one or more activators currently used in the rubber industry. As a preferred embodiment, the activator is selected from one or more of zinc oxide and stearic acid.

[0023] The reinforcing filler can be selected from any one or more existing reinforcing fillers in the rubber industry. As a preferred embodiment, the reinforcing filler is selected from one or more of carbon black, white carbon black, carbon nanotubes, nano-aramid fibers, and graphene oxide.

[0024] The vulcanizing agent can be selected from any one or more existing vulcanizing agents in the rubber industry. As a preferred embodiment, the vulcanizing agent is selected from one or more of ordinary sulfur and insoluble sulfur.

[0025] The vulcanization accelerator can be selected from any one or more existing vulcanization accelerators in the rubber industry. As a preferred embodiment, the vulcanization accelerator is selected from one or more of accelerator M, accelerator CZ, accelerator NS, and accelerator NOBS.

[0026] The environmentally friendly adhesive resin is selected from one or more of functionalized unsaturated olefin resins, isocyanate resins, acrylic resins, epoxy resins, and polyurethane resins.

[0027] Among them, the functionalized unsaturated olefin resin includes carboxylated polybutadiene resin, epoxidized polybutadiene resin, maleic anhydride polybutadiene resin, etc.; the isocyanate resin includes blocked isocyanate resin, etc.; the acrylic resin includes polyacrylic acid resin, polyacrylate-acrylic acid copolymer resin, acrylic acid-isocyanate copolymer resin, acrylate-acrylic acid copolymer resin, etc.; the epoxy resin includes epoxy silane resin, butyl glycidyl ether, epoxy acrylic resin, etc.; the polyurethane resin includes polyester polyurethane resin, aliphatic polyurethane resin, etc.

[0028] As a preferred solution, the environmentally friendly adhesive resin is selected from at least one of maleic anhydride polybutadiene resin, blocked isocyanate resin, polyacrylic resin, butyl glycidyl ether, and polyester polyurethane resin.

[0029] As a preferred embodiment, the bio-based phenol is selected from one or more of tannic acid, eugenol, and tea polyphenols.

[0030] As a preferred embodiment, the bio-based aldehyde is selected from one or more of vanillin, syringaldehyde, phenylacetaldehyde, and cinnamaldehyde.

[0031] Specifically, when the bio-based phenol is tannic acid, the bio-based aldehyde may be syringaldehyde or phenylacetaldehyde; when the bio-based phenol is eugenol, the bio-based aldehyde may be vanillin; when the bio-based phenol is tea polyphenol, the bio-based aldehyde may be syringaldehyde or cinnamaldehyde.

[0032] The present invention is the first to add an environmentally friendly adhesive resin together with bio-based phenol and bio-based aldehyde to an adhesive rubber. Experiments have shown that compared with petroleum-based phenolic adhesive rubbers, the high-performance adhesive rubber to which environmentally friendly adhesive resin, bio-based phenol and bio-based aldehyde are added simultaneously and bonded to rubber industrial tire cord fiber cords (regardless of whether it is an RFL impregnation system or a non-RFL impregnation system treated rubber industrial tire cord fiber) has significantly improved interfacial properties, improved dynamic and static adhesive properties (high H extraction force, high peeling force, long fatigue life), and better mechanical properties. It can be seen that the use of environmentally friendly adhesive resin in combination with bio-based phenol and bio-based aldehyde in the present invention plays a strong role in improving adhesive properties, and is an adhesive resin with excellent adhesive properties. Moreover, compared with petroleum-based phenolic adhesive resins, the performance of environmentally friendly adhesive resins in combination with bio-based phenol and bio-based aldehyde is significantly improved; specifically, the H extraction force, peeling force, dynamic fatigue life, and rubber mechanical properties are significantly improved.

[0033] Rubber self-adhesion is crucial in the rubber industry's processing and molding processes. The higher the self-adhesion, the more securely each layer of rubber material adheres during molding, ensuring the structural integrity and ultimate performance of the finished product. Compared to adhesive rubbers made with environmentally friendly non-phenolic resins alone, the high-performance adhesive rubbers prepared by combining environmentally friendly adhesive resins with bio-based phenols and bio-based aldehydes exhibit significantly improved self-adhesion and superior tire-forming properties.

[0034] As a preferred solution, the weight ratio of the environmentally friendly adhesive resin to the total amount of the bio-based phenol and the bio-based aldehyde is (0.5-7):1.

[0035] The preparation method of the high-performance adhesive rubber can adopt the existing preparation method of adhesive rubber.

[0036] A second object of the present invention is to provide a method for preparing the high-performance adhesive rubber described in the first object of the invention.

[0037] The preparation method includes one-stage banburying and two-stage banburying;

[0038] One-stage internal mixing: the base rubber, activator and reinforcing filler are internally mixed at 50-80°C and 40-70r / min for 8-15 minutes, and then cooled to obtain a mixed rubber sheet.

[0039] Second stage mixing: mixing the first stage mixed rubber sheet with a vulcanization accelerator, a vulcanizing agent, an environmentally friendly adhesive resin, a bio-based phenol, and a bio-based aldehyde adhesive resin at 30-80°C and 40-70r / min for 4-7 minutes, and then cooling to obtain an adhesive rubber.

[0040] As a specific solution, a preparation method of the high-performance adhesive rubber includes a first-stage mixing and a second-stage mixing;

[0041] First stage internal mixing: set the temperature to 50-80℃ and the speed to 40-70r / min

[0042] Step 1) adding the base rubber into an internal mixer and mixing for 2.5 minutes;

[0043] Step 2) adding the activator into an internal mixer and mixing for 1.5 min;

[0044] Step 3) adding 1 / 3 of the reinforcing filler into an internal mixer and mixing for 1.5 minutes;

[0045] Step 4) adding 1 / 3 of the reinforcing filler into an internal mixer and mixing for 1.0 min;

[0046] Step 5) adding the remaining reinforcing filler into an internal mixer and mixing for 2.0 min;

[0047] Step 6) adding the mixed rubber to an open mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0048] Second stage internal mixing: set the temperature to 30-80℃ and the speed to 40-70r / min

[0049] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0050] Step 2) adding a vulcanization accelerator, an environmentally friendly adhesive resin, a bio-based phenol, and a bio-based aldehyde into an internal mixer and mixing for 2.0 minutes;

[0051] Step 3) adding the vulcanizing agent into an internal mixer and mixing for 2.0 min;

[0052] Step 4) adding the mixed rubber into an open mill with the cooling water of the open mill kept on, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the high-performance adhesive rubber.

[0053] The high-performance adhesive rubber provided by this invention is particularly suitable for high-speed, high-load applications such as automotive and aircraft tires, hoses, and conveyor belts. Its excellent dynamic and static bonding properties and environmentally friendly properties provide an efficient and sustainable solution for bonding cord fabric fibers used in the rubber industry.

[0054] The third object of the present invention is the use of the high-performance adhesive rubber described in the first object of the invention or the high-performance adhesive rubber prepared by the preparation method described in the second object of the invention in the rubber industry.

[0055] Compared with the prior art, the present invention has the following beneficial effects:

[0056] Environmental protection: Environmentally friendly adhesive resins, bio-based phenols and bio-based aldehydes do not release formaldehyde and resorcinol during processing, significantly reducing harm to humans and the environment.

[0057] High Performance: Compared to petroleum-based phenolic adhesive rubbers, the adhesive rubber provided by this invention significantly improves H extraction force, peel force, dynamic fatigue life, and rubber mechanical properties. Compared to adhesive rubbers using only non-phenolic environmentally friendly adhesive resins, the adhesive rubber provided by this invention significantly improves self-adhesion and offers better molding and processing performance.

[0058] Wide applicability: Suitable for a variety of fibers treated with traditional RFL impregnation systems and new non-RFL impregnation systems, such as nylon fibers, polyester fibers, aramid fibers, and ultra-high molecular weight polyethylene fibers. Suitable for high-speed and high-load automobile and aircraft tires, hoses, conveyor belts, and other fields.

[0059] Simple process: The preparation process is simple and easy to industrialize. DETAILED DESCRIPTION

[0060] The present invention will be described in detail below with reference to specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and are not to be construed as limiting the scope of protection of the present invention. Non-essential improvements and adjustments made by those skilled in the art to the present invention based on the contents of the present invention still fall within the scope of protection of the present invention.

[0061] The raw materials used in the following examples and comparative examples can all be obtained commercially, among which:

[0062] Natural rubber, brand: Smoked sheet No. 1, purchased from Shanghai Cunsi Industrial Co., Ltd.

[0063] Styrene butadiene rubber, brand: 1500E, purchased from China National Petroleum Corporation

[0064] Zinc oxide, purchased from Guangzhou Luchang Chemical Co., Ltd.

[0065] Stearic acid, purchased from Hangzhou Wangjiang Oil Chemical Co., Ltd.

[0066] Accelerator M, purchased from Shanghai Jiacheng Chemical Co., Ltd.

[0067] Accelerator CZ, purchased from Hebi Ruida Chemical Technology Co., Ltd.

[0068] Accelerator NS, purchased from Hebi Yuanhao Chemical Co., Ltd.

[0069] Accelerator NOBS, purchased from Jiangsu Runfeng Synthetic Technology Co., Ltd.

[0070] Carbon black N330, purchased from Shanxi Sanqiang New Energy Technology Co., Ltd.

[0071] Carbon black N550, purchased from Shanxi Sanqiang New Energy Technology Co., Ltd.

[0072] White carbon black, purchased from Shandong Kasong New Materials Co., Ltd.

[0073] Carbon nanotubes were purchased from Shandong Tanfeng New Materials Technology Co., Ltd.

[0074] Nano-aramid fiber, purchased from Jiangxi Shuobang New Material Technology Co., Ltd.

[0075] Graphene oxide was purchased from Zancheng Technology Co., Ltd.

[0076] Ordinary sulfur, purchased from Shanghai Ruiba New Material Technology Co., Ltd.

[0077] Insoluble sulfur IS-7020, purchased from Guangdong Fengzheng New Materials Co., Ltd.

[0078] Insoluble sulfur IS-60, purchased from Guangdong Fengzheng New Materials Co., Ltd.

[0079] Insoluble sulfur IS-90, purchased from Guangdong Fengzheng New Materials Co., Ltd.

[0080] Maleic anhydride polybutadiene resin, brand Ricobond 1731HS, purchased from Shanghai Sendi Chemical Co., Ltd.

[0081] Blocked isocyanate resin, CAS 2556-36-7, purchased from Jiangsu Runfeng Synthetic Technology Co., Ltd.

[0082] Polyacrylic acid resin, brand P756765, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0083] Butyl glycidyl ether, brand B829911, was purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0084] Polyester polyurethane resin, brand Bayhydrol UH XP 2592, purchased from Shanghai Yuanhe Chemical Co., Ltd.

[0085] Eugenol was purchased from Beijing Bailingwei Technology Co., Ltd.

[0086] Tannic acid, purchased from Beijing Bailingwei Technology Co., Ltd.

[0087] Tea polyphenols were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0088] Vanillin was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0089] Clove aldehyde was purchased from Beijing Bailingwei Technology Co., Ltd.

[0090] Phenylacetaldehyde was purchased from Beijing Bailingwei Technology Co., Ltd.

[0091] Cinnamaldehyde was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0092] Adhesive A was purchased from Changzhou Xince Polymer Materials Co., Ltd.

[0093] Adhesive RS, purchased from Changzhou Xince Polymer Materials Co., Ltd.

[0094] Phenolic resin SL3020, purchased from Huaqi (China) Chemical Co., Ltd.

[0095] Phenolic resin SL3022, purchased from Huaqi (China) Chemical Co., Ltd.

[0096] Adhesive RA-65 was purchased from Hubei Xingyan New Material Technology Co., Ltd.

[0097] Example 1

[0098] A formula for an adhesive rubber comprising a non-phenolic environmentally friendly adhesive resin, bio-based phenol, and bio-based aldehyde suitable for use in rubber industrial cord fabric fibers is as follows:

[0099]

[0100]

[0101] The preparation method comprises:

[0102] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0103] Step 1) adding natural rubber into an internal mixer and mixing for 2.5 minutes;

[0104] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 minutes;

[0105] Step 3) 1 / 3 of carbon black N330 and white carbon black were added to an internal mixer and mixed for 1.5 min;

[0106] Step 4) adding 1 / 3 of carbon black N330 and white carbon black into an internal mixer and mixing for 1.0 min;

[0107] Step 5) The remaining carbon black N330 and white carbon black were added to an internal mixer and mixed for 2.0 min;

[0108] Step 6) adding the mixed rubber to an open mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0109] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0110] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0111] Step 2) adding accelerator M, polyacrylic acid resin, tea polyphenols and cinnamaldehyde into an internal mixer and mixing for 2.0 min;

[0112] Step 3) adding ordinary sulfur into an internal mixer and mixing for 2.0 min;

[0113] Step 4) adding the mixed rubber into an open mill with the cooling water of the open mill kept on, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the high-performance adhesive rubber.

[0114] Example 2

[0115] A formula for an adhesive rubber comprising a non-phenolic environmentally friendly adhesive resin, bio-based phenol, and bio-based aldehyde suitable for use in rubber industrial cord fabric fibers is as follows:

[0116] Components parts by weight natural rubber 100 zinc oxide 4 stearic acid 2 Accelerator NS 0.8 Carbon black N330 35 Maleic anhydride polybutadiene resin 3 Tannic acid 1 Phenylacetaldehyde 1.5 Insoluble sulfur IS-7020 2.8

[0117] The preparation method comprises:

[0118] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0119] Step 1) adding natural rubber into an internal mixer and mixing for 2.5 minutes;

[0120] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 minutes;

[0121] Step 3) adding 1 / 3 of the carbon black N330 into an internal mixer and mixing for 1.5 min;

[0122] Step 4) adding 1 / 3 of the carbon black N330 into an internal mixer and mixing for 1.0 min;

[0123] Step 5) adding the remaining carbon black N330 into an internal mixer and mixing for 2.0 min;

[0124] Step 6) adding the mixed rubber to an open mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0125] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0126] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0127] Step 2) adding accelerator NS, maleic anhydride polybutadiene resin, tannic acid and phenylacetaldehyde into an internal mixer and mixing for 2.0 min;

[0128] Step 3) adding insoluble sulfur IS-7020 into an internal mixer and mixing for 2.0 min;

[0129] Step 4) adding the mixed rubber into an open mill with the cooling water of the open mill kept on, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the high-performance adhesive rubber.

[0130] Example 3

[0131] A formula for an adhesive rubber comprising a non-phenolic environmentally friendly adhesive resin, bio-based phenol, and bio-based aldehyde suitable for use in rubber industrial cord fabric fibers is as follows:

[0132] Components parts by weight natural rubber 100 zinc oxide 10 stearic acid 2 Accelerator CZ 1.5 Carbon black N330 30 Silica 5 carbon nanotubes 5 Blocked isocyanate resin 3 Eugenol 0.24 Vanillin 0.5 Insoluble sulfur IS-7020 2.8

[0133] The preparation method comprises:

[0134] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0135] Step 1) adding natural rubber into an internal mixer and mixing for 2.5 minutes;

[0136] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 minutes;

[0137] Step 3) adding 1 / 3 of carbon black N330, white carbon black, and carbon nanotubes into an internal mixer and mixing for 1.5 minutes;

[0138] Step 4) adding 1 / 3 of carbon black N330, white carbon black, and carbon nanotubes into an internal mixer and mixing for 1.0 min;

[0139] Step 5) adding the remaining carbon black N330, white carbon black, and carbon nanotubes into an internal mixer and mixing for 2.0 min;

[0140] Step 6) adding the mixed rubber to an open mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0141] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0142] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0143] Step 2) adding accelerator CZ, blocked isocyanate resin, eugenol and vanillin into an internal mixer and mixing for 2.0 min;

[0144] Step 3) adding insoluble sulfur IS-7020 into an internal mixer and mixing for 2.0 min;

[0145] Step 4) adding the mixed rubber into an open mill with the cooling water of the open mill kept on, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the high-performance adhesive rubber.

[0146] Example 4

[0147] A formula for an adhesive rubber comprising a non-phenolic environmentally friendly adhesive resin, bio-based phenol, and bio-based aldehyde suitable for use in rubber industrial cord fabric fibers is as follows:

[0148] Components parts by weight natural rubber 90 Styrene-butadiene rubber 10 zinc oxide 8 stearic acid 2 Accelerator NOBS 1.2 Carbon black N330 30 Nano-aramid fiber 5 Butyl glycidyl ether 5 Tannic acid 1 Clove aldehyde 3 Insoluble sulfur IS-60 3.2

[0149] The preparation method comprises:

[0150] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0151] Step 1) adding natural rubber and styrene-butadiene rubber into an internal mixer and mixing for 2.5 minutes;

[0152] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 minutes;

[0153] Step 3) adding 1 / 3 of the carbon black N330 and nano-aramid fiber into an internal mixer and mixing for 1.5 minutes;

[0154] Step 4) adding 1 / 3 of the carbon black N330 and nano-aramid fiber into an internal mixer and mixing for 1.0 min;

[0155] Step 5) adding the remaining carbon black N330 and nano-aramid fiber into an internal mixer and mixing for 2.0 min;

[0156] Step 6) adding the mixed rubber to an open mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0157] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0158] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0159] Step 2) adding accelerator NOBS, butyl glycidyl ether, tannic acid and syringaldehyde into an internal mixer and mixing for 2.0 min;

[0160] Step 3) adding insoluble sulfur IS-60 into an internal mixer and mixing for 2.0 min;

[0161] Step 4) adding the mixed rubber into an open mill with the cooling water of the open mill kept on, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the high-performance adhesive rubber.

[0162] Example 5

[0163] A formula for an adhesive rubber comprising a non-phenolic environmentally friendly adhesive resin, bio-based phenol, and bio-based aldehyde suitable for use in rubber industrial cord fabric fibers is as follows:

[0164] Components parts by weight natural rubber 90 Styrene-butadiene rubber 10 zinc oxide 10 stearic acid 2 Accelerator M 1 Carbon black N330 30 Silica 5 Polyacrylic resin 2 Tannic acid 1 Phenylacetaldehyde 1.5 Ordinary sulfur 2.5

[0165] The preparation method comprises:

[0166] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0167] Step 1) adding natural rubber and styrene-butadiene rubber into an internal mixer and mixing for 2.5 minutes;

[0168] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 minutes;

[0169] Step 3) 1 / 3 of carbon black N330 and white carbon black were added to an internal mixer and mixed for 1.5 min;

[0170] Step 4) adding 1 / 3 of carbon black N330 and white carbon black into an internal mixer and mixing for 1.0 min;

[0171] Step 5) The remaining carbon black N330 and white carbon black were added to an internal mixer and mixed for 2.0 min;

[0172] Step 6) adding the mixed rubber to an open mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0173] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0174] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0175] Step 2) adding accelerator M, polyacrylic acid resin, tannic acid and phenylacetaldehyde into an internal mixer and mixing for 2.0 min;

[0176] Step 3) adding ordinary sulfur into an internal mixer and mixing for 2.0 min;

[0177] Step 4) adding the mixed rubber into an open mill with the cooling water of the open mill kept on, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the high-performance adhesive rubber.

[0178] Example 6

[0179] A formula for an adhesive rubber comprising a non-phenolic environmentally friendly adhesive resin, bio-based phenol, and bio-based aldehyde suitable for use in rubber industrial cord fabric fibers is as follows:

[0180] Components parts by weight natural rubber 80 Styrene-butadiene rubber 10 Butadiene rubber 10 zinc oxide 10 stearic acid 2 Accelerator M 1 Carbon Black N550 30 Nano-aramid fiber 5 Polyester polyurethane resin 4 Tea polyphenols 0.5 Clove aldehyde 3 Ordinary sulfur 0.3 Insoluble sulfur IS-60 3.2

[0181] The preparation method comprises:

[0182] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0183] Step 1) adding natural rubber, styrene-butadiene rubber and butadiene rubber into an internal mixer and mixing for 2.5 minutes;

[0184] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 minutes;

[0185] Step 3) adding 1 / 3 of the carbon black N550 and nano-aramid fiber into an internal mixer and mixing for 1.5 minutes;

[0186] Step 4) adding 1 / 3 of the carbon black N550 and nano-aramid fiber into an internal mixer and mixing for 1.0 min;

[0187] Step 5) adding the remaining carbon black N550 and nano-aramid fiber into an internal mixer and mixing for 2.0 min;

[0188] Step 6) adding the mixed rubber to an open mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0189] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0190] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0191] Step 2) adding accelerator M, polyester polyurethane resin, tea polyphenols and syringaldehyde into an internal mixer and mixing for 2.0 min;

[0192] Step 3) adding ordinary sulfur and insoluble sulfur IS-60 into an internal mixer and mixing for 2.0 min;

[0193] Step 4) adding the mixed rubber into an open mill with the cooling water of the open mill kept on, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the high-performance adhesive rubber.

[0194] Example 7

[0195] A formula for an adhesive rubber comprising a non-phenolic environmentally friendly adhesive resin, bio-based phenol, and bio-based aldehyde suitable for use in rubber industrial cord fabric fibers is as follows:

[0196]

[0197]

[0198] The preparation method comprises:

[0199] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0200] Step 1) adding natural rubber, styrene-butadiene rubber and butadiene rubber into an internal mixer and mixing for 2.5 minutes;

[0201] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 minutes;

[0202] Step 3) adding 1 / 3 of carbon black N330, white carbon black, and carbon nanotubes into an internal mixer and mixing for 1.5 minutes;

[0203] Step 4) adding 1 / 3 of carbon black N330, white carbon black, and carbon nanotubes into an internal mixer and mixing for 1.0 min;

[0204] Step 5) adding the remaining carbon black N330, white carbon black, and carbon nanotubes into an internal mixer and mixing for 2.0 min;

[0205] Step 6) adding the mixed rubber to an open mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0206] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0207] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0208] Step 2) adding accelerator CZ, blocked isocyanate resin, eugenol and vanillin into an internal mixer and mixing for 2.0 min;

[0209] Step 3) adding ordinary sulfur into an internal mixer and mixing for 2.0 min;

[0210] Step 4) adding the mixed rubber into an open mill with the cooling water of the open mill kept on, and rolling out a 2 mm second-stage mixed rubber sheet to obtain the high-performance adhesive rubber.

[0211] Example 8

[0212] A formula for an adhesive rubber comprising a non-phenolic environmentally friendly adhesive resin, bio-based phenol, and bio-based aldehyde suitable for use in rubber industrial cord fabric fibers is as follows:

[0213]

[0214]

[0215] The preparation method comprises:

[0216] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0217] Step 1) adding natural rubber into an internal mixer and mixing for 2.5 minutes;

[0218] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 minutes;

[0219] Step 3) adding 1 / 3 of carbon black N550 and white carbon black into an internal mixer and mixing for 1.5 min;

[0220] Step 4) adding 1 / 3 of carbon black N550 and white carbon black into an internal mixer and mixing for 1.0 min;

[0221] Step 5) The remaining carbon black N550 and white carbon black were added to an internal mixer and mixed for 2.0 min;

[0222] Step 6) adding the mixed rubber to an open mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0223] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0224] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0225] Step 2) adding accelerator NOBS, polyester polyurethane resin, tea polyphenols and cinnamaldehyde into an internal mixer and mixing for 2.0 minutes;

[0226] Step 3) adding ordinary sulfur into an internal mixer and mixing for 2.0 min;

[0227] Step 4) adding the mixed rubber into an open mill with the cooling water of the open mill kept on, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the high-performance adhesive rubber.

[0228] Comparative Example 1

[0229] A petroleum-based phenolic adhesive rubber suitable for use in industrial tire cord fabrics, the formula of which is as follows:

[0230]

[0231]

[0232] The preparation method comprises:

[0233] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0234] Step 1) adding natural rubber into an internal mixer and mixing for 2.5 minutes;

[0235] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 minutes;

[0236] Step 3) 1 / 3 of carbon black N330 and white carbon black were added to an internal mixer and mixed for 1.5 min;

[0237] Step 4) adding 1 / 3 of carbon black N330 and white carbon black into an internal mixer and mixing for 1.0 min;

[0238] Step 5) The remaining carbon black N330 and white carbon black were added to an internal mixer and mixed for 2.0 min;

[0239] Step 6) adding the mixed rubber to an open mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0240] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0241] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0242] Step 2) Add accelerator M, adhesive A, and adhesive RS into an internal mixer and mix for 2.0 min;

[0243] Step 3) adding ordinary sulfur into an internal mixer and mixing for 2.0 min;

[0244] Step 4) adding the mixed rubber into an open mill with the cooling water of the open mill kept on, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the adhesive rubber.

[0245] Comparative Example 2

[0246] A petroleum-based phenolic adhesive rubber suitable for use in industrial tire cord fabrics, the formula of which is as follows:

[0247]

[0248]

[0249] The preparation method comprises:

[0250] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0251] Step 1) adding natural rubber into an internal mixer and mixing for 2.5 minutes;

[0252] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 minutes;

[0253] Step 3) adding 1 / 3 of the carbon black N330 into an internal mixer and mixing for 1.5 min;

[0254] Step 4) adding 1 / 3 of the carbon black N330 into an internal mixer and mixing for 1.0 min;

[0255] Step 5) adding the remaining carbon black N330 into an internal mixer and mixing for 2.0 min;

[0256] Step 6) adding the mixed rubber to an open mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0257] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0258] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0259] Step 2) adding accelerators CZ, SL3020, and RA65 into an internal mixer and mixing for 2.0 min;

[0260] Step 3) adding insoluble sulfur IS-7020 into an internal mixer and mixing for 2.0 min;

[0261] Step 4) adding the mixed rubber into an open mill with the cooling water of the open mill kept on, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the adhesive rubber.

[0262] Comparative Example 3

[0263] A petroleum-based phenolic adhesive rubber suitable for use in industrial tire cord fabrics, the formula of which is as follows:

[0264]

[0265]

[0266] The preparation method comprises:

[0267] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0268] Step 1) adding natural rubber and styrene-butadiene rubber into an internal mixer and mixing for 2.5 minutes;

[0269] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 minutes;

[0270] Step 3) adding 1 / 3 of the carbon black N330 into an internal mixer and mixing for 1.5 min;

[0271] Step 4) adding 1 / 3 of the carbon black N330 into an internal mixer and mixing for 1.0 min;

[0272] Step 5) adding the remaining carbon black N330 into an internal mixer and mixing for 2.0 min;

[0273] Step 6) adding the mixed rubber to an open mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0274] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0275] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0276] Step 2) Add accelerator M, SL3020, and RA65 to an internal mixer and mix for 2.0 min;

[0277] Step 3) adding ordinary sulfur into an internal mixer and mixing for 2.0 min;

[0278] Step 4) adding the mixed rubber into an open mill with the cooling water of the open mill kept on, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the adhesive rubber.

[0279] Comparative Example 4

[0280] A petroleum-based phenolic adhesive rubber suitable for use in industrial tire cord fabrics, the formula of which is as follows:

[0281]

[0282]

[0283] The preparation method comprises:

[0284] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0285] Step 1) adding natural rubber, styrene-butadiene rubber and butadiene rubber into an internal mixer and mixing for 2.5 minutes;

[0286] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 minutes;

[0287] Step 3) 1 / 3 of carbon black N330 and white carbon black were added to an internal mixer and mixed for 1.5 min;

[0288] Step 4) adding 1 / 3 of carbon black N330 and white carbon black into an internal mixer and mixing for 1.0 min;

[0289] Step 5) The remaining carbon black N330 and white carbon black were added to an internal mixer and mixed for 2.0 min;

[0290] Step 6) adding the mixed rubber to an open mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0291] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0292] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0293] Step 2) Add accelerator CZ, adhesive A, and adhesive RS into an internal mixer and mix for 2.0 min;

[0294] Step 3) adding ordinary sulfur into an internal mixer and mixing for 2.0 min;

[0295] Step 4) adding the mixed rubber into an open mill with the cooling water of the open mill kept on, and rolling out a 2 mm second-stage mixed rubber sheet to obtain the adhesive rubber.

[0296] Comparative Example 5

[0297] An adhesive rubber with a non-phenolic environmentally friendly adhesive resin added thereto suitable for use in rubber industry cord fabric fibers, the formula of which is as follows:

[0298] Components parts by weight natural rubber 80 Styrene-butadiene rubber 10 Butadiene rubber 10 zinc oxide 8 stearic acid 2 Accelerator CZ 1.5 Carbon black N330 35 Silica 5 carbon nanotubes 5 Blocked isocyanate resin 3 Ordinary sulfur 2.5

[0299] The preparation method comprises:

[0300] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0301] Step 1) adding natural rubber, styrene-butadiene rubber and butadiene rubber into an internal mixer and mixing for 2.5 minutes;

[0302] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 minutes;

[0303] Step 3) adding 1 / 3 of carbon black N330, white carbon black, and carbon nanotubes into an internal mixer and mixing for 1.5 minutes;

[0304] Step 4) adding 1 / 3 of carbon black N330, white carbon black, and carbon nanotubes into an internal mixer and mixing for 1.0 min;

[0305] Step 5) adding the remaining carbon black N330, white carbon black, and carbon nanotubes into an internal mixer and mixing for 2.0 min;

[0306] Step 6) adding the mixed rubber to an open mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0307] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0308] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0309] Step 2) adding accelerator CZ and blocked isocyanate resin into an internal mixer and mixing for 2.0 min;

[0310] Step 3) adding ordinary sulfur into an internal mixer and mixing for 2.0 min;

[0311] Step 4) adding the mixed rubber into an open mill with the cooling water of the open mill kept on, and rolling out a 2 mm second-stage mixed rubber sheet to obtain the adhesive rubber.

[0312] Performance Testing

[0313] The adhesive rubbers prepared in Examples 1-8 and Comparative Examples 1-5 were respectively combined with polyester fiber cords, nylon fiber cords, aramid fiber cords, and ultra-high molecular weight polyethylene fiber cords after traditional RFL dipping and non-RFL dipping treatments to prepare fiber / rubber composite material test specimens, and H extraction test, peel test, and fatigue life test were carried out.

[0314] The adhesive rubbers of Examples 7 and 8 and Comparative Examples 4 and 5 were tested for rubber self-adhesion using a RZN-II rubber self-adhesion tester.

[0315] The preparation method of H extraction test specimen is as follows:

[0316] With reference to GB / T2942-2009, the prepared adhesive rubber was completely coated on the dipped cord, wherein the embedding depth of nylon fiber, aramid fiber, and ultra-high molecular weight polyethylene fiber was 10 mm, and the embedding depth of polyester fiber was 5 mm. H-extraction specimens were prepared and placed on a flat vulcanizer for vulcanization at a vulcanization pressure of 15 MPa, a vulcanization temperature of 160°C, and a vulcanization time of 15 min.

[0317] The preparation method of the peeling force test strip is as follows:

[0318] Referring to the standard GB / T4075-2021, the adhesive rubber is completely covered on the dipped cord to prepare a peeling specimen, which is placed on a flat vulcanizer for vulcanization with a vulcanization pressure of 15 MPa, a vulcanization temperature of 160°C, and a vulcanization time of 15 min.

[0319] Fatigue life test specimen preparation and test conditions are as follows:

[0320] Referring to the GB / T39639-2020 standard, the rubber-coated rubber cord was completely covered with adhesive rubber and vulcanized on a flat-plate vulcanizer at a pressure of 15 MPa, a temperature of 160°C, and a time of 15 minutes to prepare fatigue specimens. Fatigue testing conditions were 80°C and 13 Hz.

[0321] In addition, compared with other types of fibers, polyester fibers also need to evaluate their persulfate performance. The vulcanization pressure of the H extraction test specimens, peel force test specimens, and fatigue life test specimens is 15 MPa, the vulcanization temperature is 160°C, and the vulcanization time is 1 hour.

[0322] With reference to standard GB / T528-2009, the adhesive rubbers prepared in Examples 1-8 and Comparative Examples 1-5 were placed on a flat vulcanizer for vulcanization at a vulcanization pressure of 15 MPa, a vulcanization temperature of 160° C., and a vulcanization time of 15 min to prepare test specimens for rubber tensile strength testing.

[0323] Rubber Adhesion Test Method: Place the rubber mix sample on the test platform of the RZN-II Rubber Adhesion Tester, ensuring full surface contact. Apply a specified initial pressure (0.5 MPa) and maintain it for a specified time (5 seconds) to ensure sufficient adhesion. Then, pull the sample apart at a constant speed (e.g., 20 cm / min). Record the maximum adhesion force during the pull-off process. Repeat the test three times, and take the average value as the final result.

[0324] The test results of Examples 1 and 2 and Comparative Example 1 are shown in Table 1.

[0325] The test results of Examples 3 and 4 and Comparative Example 2 are shown in Table 2.

[0326] The test results of Examples 5 and 6 and Comparative Example 3 are shown in Table 3.

[0327] The test results of Examples 7 and 8 and Comparative Examples 4 and 5 are shown in Table 4.

[0328] Table 1

[0329]

[0330] Table 2

[0331]

[0332] Table 3

[0333]

[0334]

[0335] Table 4

[0336]

[0337] In Tables 1-4, H extraction force represents H extraction performance, and a larger H extraction force indicates better H extraction performance; peeling force represents peeling performance, and a larger peeling force indicates better peeling performance; fatigue life represents dynamic fatigue performance, and a larger fatigue life value indicates better dynamic fatigue performance; a higher rubber self-adhesion value indicates better rubber self-adhesion performance.

[0338] The data in Table 1 show that:

[0339] For polyester fibers treated with a conventional RFL dipping system: Compared with Comparative Example 1 (polyester fibers bonded with petroleum-based phenolic rubber), the H extraction force of Examples 1 and 2 under normal vulcanization conditions increased by approximately 15-23%, the peel force increased by approximately 19-31%, and the fatigue life increased by approximately 38-46%; the H extraction force of Examples 1 and 2 under overvulcanization conditions increased by approximately 20-25%, the peel force increased by approximately 22-34%, and the fatigue life increased by approximately 38-45%.

[0340] For polyester fibers treated with the new non-RFL impregnation system: Compared with Comparative Example 1 (polyester fiber bonded with petroleum-based phenolic rubber), the H extraction force of Examples 1 and 2 under normal vulcanization conditions is increased by approximately 19-27%, the peel force is increased by approximately 16-24%, and the fatigue life is increased by approximately 46-50%; the H extraction force of Examples 1 and 2 under overvulcanization conditions is increased by approximately 22-28%, the peel force is increased by approximately 19-25%, and the fatigue life is increased by approximately 49-51%.

[0341] Compared with Comparative Example 1, the tensile strength, 100% modulus stress, and 300% modulus stress of Examples 1 and 2 are all improved.

[0342] From the data in Table 1, we can conclude that:

[0343] Comparative Example 1 uses petroleum-based phenolic formaldehyde as the adhesive resin; Examples 1 and 2 use non-phenolic environmentally friendly adhesive resins in combination with bio-based phenol and bio-based aldehyde to replace the petroleum-based phenolic formaldehyde as the adhesive resin, and simultaneously synergistically optimize the rubber system, activation system, sulfur-promoting system and filling system. The dynamic and static adhesion properties (H extraction force, peeling force, fatigue life) and persulfurization performance of the adhesive rubbers prepared in Examples 1 and 2 and polyester fibers (whether for RFL impregnation systems or non-RFL impregnation systems) are better than those of Comparative Example 1. In addition, the mechanical properties of Examples 1 and 2 are also better than those of Comparative Example 1. This shows that, for RFL-impregnated polyester fibers and non-RFL-impregnated polyester fibers, compared with petroleum-based phenolic formaldehyde, the dynamic and static adhesion properties of the adhesive rubbers prepared by using non-phenolic environmentally friendly adhesive resins and bio-based phenol and bio-based aldehyde as adhesive resins are significantly improved, and the mechanical properties are also improved.

[0344] The data in Table 2 show that:

[0345] For nylon fibers treated with traditional RFL dipping systems:

[0346] For 930 dtex / 2 nylon fiber, Examples 3 and 4 showed an increase in H extraction force by approximately 7-8%, an increase in peel force by approximately 10-19%, and an increase in fatigue life by approximately 38-42% compared to Comparative Example 2 (nylon fiber bonded with petroleum-based phenolic rubber). For 1400 dtex / 2 nylon cord, Examples 3 and 4 showed an increase in H extraction force by approximately 6-9%, an increase in peel force by approximately 17-18%, and an increase in fatigue life by approximately 47-50% compared to Comparative Example 2.

[0347] For nylon fibers treated with new non-RFL impregnation systems:

[0348] For 930 dtex / 2 nylon fiber, Examples 3 and 4 showed an increase in H-extraction force of approximately 6-8%, an increase in peel force of approximately 10-16%, and an increase in fatigue life of approximately 24-43% compared to Comparative Example 2. For 1400 dtex / 2 nylon cord, Examples 3 and 4 showed an increase in H-extraction force of approximately 2-7%, an increase in peel force of approximately 11-13%, and an increase in fatigue life of approximately 29-42% compared to Comparative Example 2.

[0349] Compared with Comparative Example 2, the tensile strength, 100% modulus of elongation, and 300% modulus of elongation of Examples 3 and 4 are all improved.

[0350] From the data in Table 2, we can conclude that:

[0351] Comparative Example 2 uses petroleum-based phenolic formaldehyde as the adhesive resin; Examples 3 and 4 use non-phenolic environmentally friendly adhesive resins in combination with bio-based phenol and bio-based aldehyde to replace the petroleum-based phenolic formaldehyde as the adhesive resin, and simultaneously synergistically optimize the rubber system, activation system, sulfur-promoted system and filling system. The dynamic and static adhesion properties (H extraction force, peeling force, fatigue life) of the adhesive rubbers prepared in Examples 3 and 4 and nylon fibers (whether for RFL impregnation systems or non-RFL impregnation systems) are better than those of Comparative Example 2. In addition, the mechanical properties of Examples 3 and 4 are also better than those of Comparative Example 2. This shows that, for RFL-impregnated nylon fibers and non-RFL-impregnated nylon fibers, compared with petroleum-based phenolic formaldehyde, the dynamic and static adhesion properties of the adhesive rubbers prepared by using non-phenolic environmentally friendly adhesive resins and bio-based phenol and bio-based aldehyde as adhesive resins are significantly improved, and the mechanical properties are also improved.

[0352] The data in Table 3 show that:

[0353] For aramid fibers treated with a conventional RFL dipping system, compared to Comparative Example 3 (aramid fibers bonded with petroleum-based phenolic rubber), Examples 5 and 6 showed an increase in H extraction force of approximately 8-9%, an increase in peel force of approximately 6-7%, and an increase in fatigue life of approximately 53-58%.

[0354] For aramid fibers treated with the new non-RFL impregnation system: compared with comparative example 4, the H extraction force of Examples 5 and 6 is increased by about 10-12%, the peeling force is increased by about 15-20%, and the fatigue life is increased by about 43-50%.

[0355] Compared with Comparative Example 3, the tensile strength, 100% modulus stress, and 300% modulus stress of Examples 5 and 6 are all improved.

[0356] From the data in Table 3, we can conclude that:

[0357] Comparative Example 3 uses petroleum-based phenolic formaldehyde as the adhesive resin; Examples 5 and 6 use non-phenolic environmentally friendly adhesive resins in combination with bio-based phenol and bio-based aldehyde to replace the petroleum-based phenolic formaldehyde as the adhesive resin, and simultaneously synergistically optimize the rubber system, activation system, sulfur-promoting system and filling system. The dynamic and static bonding properties (H extraction force, peeling force, fatigue life) of the adhesive rubbers prepared in Examples 5 and 6 and the aramid fiber (whether for the RFL impregnation system or the non-RFL impregnation system) are better than those of Comparative Example 3. In addition, the mechanical properties of Examples 5 and 6 are also better than those of Comparative Example 3. This shows that for RFL-impregnated aramid fibers and non-RFL-impregnated aramid fibers, compared with petroleum-based phenolic formaldehyde, the dynamic and static bonding properties of the adhesive rubbers prepared by using non-phenolic environmentally friendly adhesive resins and bio-based phenol and bio-based aldehyde as adhesive resins are significantly improved, and the mechanical properties are also improved.

[0358] The data in Table 4 show that:

[0359] For ultra-high molecular weight polyethylene fibers treated with a conventional RFL dipping system, the H extraction force of Examples 7 and 8 is increased by approximately 25-30%, the peel force is increased by approximately 23-33%, and the fatigue life is increased by approximately 25-31% compared to Comparative Example 4 (ultra-high molecular weight polyethylene fibers bonded with petroleum-based phenolic rubber).

[0360] For ultra-high molecular weight polyethylene fibers treated with the new non-RFL impregnation system: compared with comparative example 4, the H extraction force of Examples 7 and 8 is increased by about 15-25%, the peeling force is increased by about 21-44%, and the fatigue life is increased by about 20-35%.

[0361] For ultra-high molecular weight polyethylene fibers treated with a conventional RFL dipping system, the H extraction force of Examples 7 and 8 is increased by approximately 5-9%, the peel force is increased by approximately 7-16%, and the fatigue life is increased by approximately 2-7% compared to Comparative Example 5 (adhesive rubber to which a non-phenolic environmentally friendly adhesive resin is added alone).

[0362] For ultra-high molecular weight polyethylene fibers treated with the new non-RFL impregnation system: compared with comparative example 5, the H extraction force of Examples 7 and 8 is increased by about 5-14%, the peeling force is increased by about 11-32%, and the fatigue life is increased by about 4-17%.

[0363] Compared with Comparative Examples 4 and 5, the tensile strength, 100% modulus of elongation, 300% modulus of elongation, and rubber self-adhesion of Examples 7 and 8 are all improved. In particular, compared with Comparative Example 5, the rubber self-adhesion of Examples 7 and 8 is increased by about 315-320%, which is a significant improvement.

[0364] From the data in Table 4, we can conclude that:

[0365] Comparative Example 4 uses petroleum-based phenolic formaldehyde as the adhesive resin; Examples 7 and 8 use non-phenolic environmentally friendly adhesive resins in combination with bio-based phenol and bio-based aldehyde to replace the petroleum-based phenolic formaldehyde as the adhesive resin, and simultaneously synergistically optimize the rubber system, activation system, sulfur-promoted system and filling system. The dynamic and static adhesion properties (H extraction force, peeling force, fatigue life) of the adhesive rubbers prepared in Examples 7 and 8 and ultra-high molecular weight polyethylene fibers (whether for RFL impregnation systems or non-RFL impregnation systems) are better than those of Comparative Example 4. In addition, the mechanical properties of Examples 7 and 8 are also better than those of Comparative Example 4. This shows that, for RFL-impregnated ultra-high molecular weight polyethylene fibers and non-RFL-impregnated ultra-high molecular weight polyethylene fibers, compared with petroleum-based phenolic formaldehyde, the dynamic and static adhesion properties of the adhesive rubbers prepared by using non-phenolic environmentally friendly adhesive resins and bio-based phenol and bio-based aldehyde as adhesive resins are significantly improved, and the mechanical properties are also improved.

[0366] Comparative Example 5 uses a non-phenolic environmentally friendly adhesive resin as the adhesive resin; Examples 7 and 8 use a non-phenolic environmentally friendly adhesive resin in combination with bio-based phenol and bio-based aldehyde as the adhesive resin, and simultaneously synergistically optimize the rubber system, activation system, sulfur-promoting system and filling system. The dynamic and static adhesion properties (H extraction force, peeling force, fatigue life) of the adhesive rubber prepared in Examples 7 and 8 and the ultra-high molecular weight polyethylene fiber (whether for the RFL impregnation system or the non-RFL impregnation system) are better than those of Comparative Example 5. In addition, the self-adhesion of the rubber of Examples 7 and 8 is significantly better than that of Comparative Example 5, and the mechanical properties of Examples 7 and 8 are also better than that of Comparative Example 5. This shows that for RFL-impregnated ultra-high molecular weight polyethylene fibers and non-RFL-impregnated ultra-high molecular weight polyethylene fibers, compared with the addition of non-phenolic environmentally friendly adhesive resin alone, the dynamic and static adhesion properties of the adhesive rubber prepared by using non-phenolic environmentally friendly adhesive resin and bio-based phenol and bio-based aldehyde as adhesive resins are significantly improved, the self-adhesion of the rubber is significantly improved, and the mechanical properties are also improved.

[0367] In summary, it can be concluded that the present invention replaces the petroleum-based phenolic adhesive resin in the adhesive rubber with a non-phenolic environmentally friendly adhesive resin and a bio-based phenol, bio-based aldehyde system, and simultaneously synergistically optimizes the rubber system, activation system, sulfur-promoting system and filling system. The high-performance adhesive rubber obtained by combining the non-phenolic environmentally friendly adhesive resin with bio-based phenol and bio-based aldehyde has significantly better dynamic and static adhesion performance with various fibers than the phenolic adhesive rubber, greatly improving the interface performance of the composite material. The adhesive rubber formula of the present invention combining the non-phenolic environmentally friendly adhesive resin with bio-based phenol and bio-based aldehyde can achieve excellent interface dynamic and static adhesion performance with different types and specifications of rubber industrial cord fabric fibers without toxic and harmful components such as petroleum-based phenolic adhesive resins and without causing harm to the human body and the environment, and at the same time has good rubber mechanical properties and self-adhesive properties.

Claims

1. A high-performance adhesive rubber suitable for cord fabric fibers for rubber industry, characterized in that: The high-performance adhesive rubber is prepared from raw materials comprising the following components; the components and their weight parts are as follows: 100 parts by weight of base rubber; Activator 2-15 parts by weight, preferably 6-12 parts by weight; 10-50 parts by weight of reinforcing filler, preferably 21-43 parts by weight; 1-5 parts by weight of vulcanizing agent, preferably 1-3.5 parts by weight; Vulcanization accelerator 0.1-5 parts by weight, preferably 0.5-2 parts by weight; 0.5-20 parts by weight, preferably 3-7 parts by weight, of an environmentally friendly adhesive resin; 0.2-3 parts by weight of bio-based phenol, preferably 0.2-1 parts by weight; The bio-based aldehyde is 0.4-6 parts by weight, preferably 0.4-3 parts by weight.

2. The high-performance adhesive rubber according to claim 1, characterized in that The base rubber is natural rubber or a mixture of natural rubber, styrene-butadiene rubber and / or butadiene rubber; When the base rubber is a mixture of natural rubber, styrene-butadiene rubber and / or butadiene rubber, based on 100 parts by weight of the base rubber, the natural rubber accounts for 70-95 parts by weight, preferably 75-95 parts by weight, more preferably 80-90 parts by weight, and the balance is styrene-butadiene rubber and / or butadiene rubber.

3. The high performance adhesive rubber according to claim 1, characterized in that The activator is selected from one or more of zinc oxide and stearic acid; or / and, The reinforcing filler is selected from one or more of carbon black, white carbon black, carbon nanotubes, nano-aramid fibers, and graphene oxide; or / and, The vulcanizing agent is selected from one or more of common sulfur and insoluble sulfur; or / and, The vulcanization accelerator is selected from at least one of accelerator M, accelerator CZ, accelerator NS, and accelerator NOBS.

4. The high performance adhesive rubber according to claim 1, characterized in that The environmentally friendly adhesive resin is selected from at least one of functionalized unsaturated olefin resins, isocyanate resins, acrylic resins, epoxy resins, and polyurethane resins.

5. The high performance adhesive rubber according to claim 1, characterized in that The environmentally friendly adhesive resin is selected from at least one of maleic anhydride polybutadiene resin, blocked isocyanate resin, polyacrylic acid resin, butyl glycidyl ether, and polyester polyurethane resin.

6. The high performance adhesive rubber according to claim 1, characterized in that: The bio-based phenol is selected from at least one of tannic acid, eugenol and tea polyphenols.

7. The high performance adhesive rubber according to claim 1, characterized in that: The bio-based aldehyde is selected from at least one of vanillin, syringaldehyde, phenylacetaldehyde and cinnamaldehyde.

8. The high performance adhesive rubber according to claim 1, characterized in that: The weight ratio of the environmentally friendly adhesive resin to the total amount of the bio-based phenol and the bio-based aldehyde is (0.5-7):

1.

9. A method for preparing a high-performance adhesive rubber according to any one of claims 1 to 8, characterized in that: The preparation method comprises a first stage of internal kneading and a second stage of internal kneading; One-stage internal mixing: the base rubber, activator and reinforcing filler are internally mixed at 50-80°C and 40-70r / min for 8-15 minutes, and a mixed rubber sheet is obtained after cooling; Second stage internal mixing: the first stage mixed rubber sheet is internally mixed with a vulcanizing agent, a vulcanization accelerator, an environmentally friendly adhesive resin, a bio-based phenol, and a bio-based aldehyde at 30-80° C. and 40-70 r / min for 4-7 minutes, and the high-performance adhesive rubber is obtained after cooling.

10. Use of the high-performance adhesive rubber according to any one of claims 1 to 8 or the high-performance adhesive rubber prepared by the preparation method according to claim 9 in the rubber industry.

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