Non-phenolic adhesive rubber suitable for tire cord fabric fibers and application of non-phenolic adhesive rubber

Abstract

The invention relates to the technical field of preparation of bonding rubber for tire cord fabric fibers, in particular to non-phenolic bonding rubber suitable for the tire cord fabric fibers and application of the non-phenolic bonding rubber. According to the invention, a rubber system, an activation system, a sulfur promoting system, a reinforcing filling system and a bonding resin system of the bonding rubber are adjusted; the non-RF adhesive rubber which does not contain toxic phenolic aldehyde adhesive resin is obtained, and the dynamic and static adhesion performance of an interface adhered with different types and specifications of tire cord fabric fiber cords and the mechanical property of the rubber can reach or even exceed the level of RF adhesive rubber. The adhesive rubber provided by the invention does not contain RF adhesive resin, and a large amount of formaldehyde or resorcinol does not volatilize in the processing process; therefore, the technical problem that a large amount of resorcinol and formaldehyde are released in the use process of the bonding rubber for the tire cord fabric fibers at present, and the harm to human bodies and the environment is large is solved.

Description

Technical Field

[0001] The invention relates to the technical field of preparing adhesive rubber for tire cord fabric fibers, and further to a non-phenolic adhesive rubber suitable for tire cord fabric fibers and application thereof. Background Art

[0002] High-performance fiber-reinforced rubber composites have excellent comprehensive properties and are widely used in high-speed and high-load automobile and aircraft tires. However, due to factors such as high fiber crystallinity, chemical inertness, and large differences in polarity and modulus between the fiber and rubber, the fiber-rubber interface bonding is poor. Therefore, reinforcing the interface bonding between the cord fabric fiber and rubber has become the key to improving the comprehensive performance of the composite material.

[0003] On the one hand, in industry, fibers are usually impregnated and modified before being compounded with rubber. The traditional resorcinol-formaldehyde-latex (RFL) impregnation system contains a large amount of carcinogens, such as resorcinol and formaldehyde. Currently, many non-RFL impregnation systems have been developed, mainly using environmentally friendly resins such as epoxy resin, isocyanate, acrylic resin instead of phenolic resin as the main component of the impregnation system, such as US20200010741A1, US20150259560, and CN117988118A.

[0004] On the other hand, toxic phenolic (RF) adhesive resins (such as adhesives A / RS, SL3020, SL3022, etc.) are also added to the adhesive rubber components commonly used in tire cord fabric fibers to improve the interfacial bonding properties of fiber / rubber composites; the bonding mechanism is that the phenolic adhesive resin forms a phenolic resin network in the adhesive rubber, which can interact with the active groups (phenolic resin, epoxy resin, isocyanate) on the surface of the impregnated fiber. At the same time, the hydroxyl groups and hydroxymethyl groups in the phenolic resin will generate methylenequinone intermediates during the high-temperature vulcanization process, which interact with the active methylene in the rubber macromolecular chain. However, RF phenolic adhesive resins still release a large amount of resorcinol and formaldehyde during use, which is very harmful to the human body and the environment.

[0005] At present, a variety of modified RF adhesive resins have been disclosed for preparing RF adhesive rubbers, which can reduce toxicity and improve the various properties of fiber / rubber composite materials and pure rubber products. CN112300349A discloses a high-ortho-phenolic adhesive resin and a preparation method, which uses phenol as a raw material, zinc oxide, zinc hydroxide or organic acid zinc as a catalyst, and adds meta-cresol or resorcinol for modification. The prepared high-ortho-phenolic resin is used as an adhesive resin in a rubber composition, which can provide a good interface bonding effect and improve the comprehensive performance of the rubber. CN111333798A discloses a method for preparing a thermoplastic phenolic resin from hydroquinone, which is prepared by directly polymerizing hydroquinone with formaldehyde, or by mixing hydroquinone with different types of phenols and then polymerizing with formaldehyde, or by styrenating hydroquinone and then polymerizing with formaldehyde, or by mixing hydroquinone with different types of phenols and then polymerizing with formaldehyde and then modifying with bio-oil to prepare different types of thermoplastic phenolic resins for improving the bonding properties of fiber / rubber composite materials. CN113234300A discloses a cashew nut oil-modified bisphenol A phenolic resin and a preparation method thereof, which are used to improve the mechanical properties and aging properties of rubber.

[0006] However, the modified adhesive resins mentioned above are all RF adhesive resins, and the rubber prepared is still RF adhesive rubber. RF adhesive rubber has good interfacial properties with fiber bonding and excellent mechanical properties, but since the added RF adhesive resin still contains a large amount of formaldehyde and / or resorcinol volatilization during the processing, it is very harmful to the human body and the environment, so it is urgent to develop environmentally friendly adhesive resins. Summary of the invention

[0007] The technical problem solved by the present invention is that the adhesive rubber currently used for tire cord fabric fibers releases a large amount of resorcinol and formaldehyde during use, which causes great harm to human body and environment.

[0008] The present invention provides an adhesive rubber that does not contain RF adhesive resin and has better dynamic and static adhesion properties on the interface with tire cord fabric fibers and rubber mechanical properties than RF adhesive rubber by adding "one or more of functionalized unsaturated olefin resins, isocyanate resins, acrylic resins, epoxy resins, and polyurethane resins" and further optimizing the rubber system, activation system, sulfur-promoting system, and reinforcement filling system.

[0009] One of the objects of the present invention is to provide a non-phenolic adhesive rubber suitable for tire cord fabric fibers.

[0010] The non-phenolic adhesive rubber is prepared from raw materials comprising the following components; the components and their weight parts are as follows:

[0011] 100 parts by weight of base rubber;

[0012] Activator 2-15 parts by weight, preferably 6-12 parts by weight;

[0013] Vulcanization accelerator 0.1-5 parts by weight, preferably 0.5-2 parts by weight;

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

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

[0016] The environmentally friendly adhesive resin is 0.5-20 parts by weight, preferably 3-7 parts by weight.

[0017] The tire cord fabric fiber can be any existing tire cord fabric fiber used for preparing tires. Specifically, the tire cord fabric fiber can include nylon fiber, polyester fiber, aramid fiber, polyimide fiber, ultra-high molecular weight polyethylene fiber, etc.

[0018] The rubber can be any natural rubber or / and synthetic rubber currently used for preparing tires. As a preferred embodiment, the base rubber is natural rubber; or 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 70-100 parts by weight, preferably 75-100 parts by weight, more preferably 80-100 parts by weight, and the balance is styrene-butadiene rubber and / or butadiene rubber.

[0019] The activator can be selected from any one or more existing activators used for preparing tire rubber. As a preferred embodiment, the activator is selected from one or more of zinc oxide and stearic acid.

[0020] The vulcanization accelerator can be selected from any one or more existing vulcanization accelerators used to prepare tire rubber. As a preferred embodiment, the vulcanization accelerator is selected from one or more of accelerator M, accelerator CZ, accelerator NS, accelerator NOBS, accelerator DZ, accelerator DM and accelerator TMTD.

[0021] The reinforcing filler can be selected from any one or more existing reinforcing fillers used to prepare tire rubber. As a preferred embodiment, the reinforcing filler is selected from one or more of carbon black, white carbon black, carbon nanotubes, attapulgite, nano-aramid fiber, and graphene oxide.

[0022] The vulcanizing agent can be selected from any one or more existing vulcanizing agents used to prepare tire rubber. As a preferred embodiment, the vulcanizing agent is selected from one or more of common sulfur and insoluble sulfur. The insoluble sulfur can be one or more of insoluble sulfur IS-60, insoluble sulfur IS-90, and insoluble sulfur IS-7020.

[0023] 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.

[0024] 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, epoxy resin, epoxy acrylic resin, etc.; the polyurethane resin includes polyester polyurethane resin, aliphatic polyurethane resin, etc.

[0025] Therefore, as a preferred embodiment, the environmentally friendly adhesive resin is selected from one or more of epoxidized polybutadiene resin, maleic anhydride polybutadiene resin, blocked isocyanate resin, polyacrylic resin, epoxy resin, epoxy acrylic resin, polyester polyurethane resin, and aliphatic polyurethane resin.

[0026] The present invention adds "functionalized unsaturated olefin resin, isocyanate resin, acrylic resin, epoxy resin, polyurethane resin" to the adhesive rubber for the first time. Experiments have shown that compared with RF adhesive rubber, the interface performance of the non-phenolic adhesive rubber added with "functionalized unsaturated olefin resin, isocyanate resin, acrylic resin, epoxy resin, polyurethane resin" and the tire cord fiber cord is significantly improved, and the mechanical properties are equivalent or even better (for tire cord fibers treated with RFL impregnation system and non-RFL impregnation system). It can be seen that "functionalized unsaturated olefin resin, isocyanate resin, acrylic resin, epoxy resin, polyurethane resin" plays the role of adhesive resin in the present invention. Moreover, compared with RF adhesive resin, the performance of "functionalized unsaturated olefin resin, isocyanate resin, acrylic resin, epoxy resin, polyurethane resin" is significantly improved; specifically, the H extraction force, peeling force, dynamic fatigue life, and rubber mechanical properties are significantly improved.

[0027] The "functionalized unsaturated olefin resin, isocyanate resin, acrylic resin, epoxy resin, polyurethane resin" do not contain phenolic structure, and after being used to bond rubber, no large amount of formaldehyde and / or resorcinol will be volatilized during the processing. Therefore, "functionalized unsaturated olefin resin, isocyanate resin, acrylic resin, epoxy resin, polyurethane resin" is an environmentally friendly adhesive resin.

[0028] When the non-phenolic adhesive rubber with the environmentally friendly adhesive resin added is used for tire cord fabric fibers treated by RFL dipping system and non-RFL dipping system, the dynamic and static adhesive properties of the interface with the tire cord fabric fiber cords are significantly improved, and the mechanical properties are equivalent to or even better. Therefore, the non-phenolic adhesive rubber with the environmentally friendly adhesive resin added is suitable for tire cord fabric fibers treated by RFL dipping system and non-RFL dipping system.

[0029] The non-phenolic adhesive rubber does not contain RF adhesive resin. Therefore, a large amount of formaldehyde and / or resorcinol will not be volatilized during the processing, thereby solving the technical problem that "the adhesive rubber currently used for tire cord fabric fibers releases a large amount of resorcinol and formaldehyde during use, which is harmful to the human body and the environment."

[0030] It can be seen that the non-phenolic adhesive rubber provided by the present invention does not contain phenolic adhesive resin, and there will be no large amount of formaldehyde and / or resorcinol volatilization during the processing; at the same time, by adjusting the formula, its bonding performance with various tire fiber cords reaches the interface dynamic and static bonding performance and rubber mechanical properties equivalent to those of RF adhesive rubber. Therefore, the above non-phenolic adhesive rubber is suitable for various fiber cords (including but not limited to nylon fiber, polyester fiber, aramid fiber, polyimide fiber, ultra-high molecular weight polyethylene fiber, etc.) treated with traditional RFL and new non-RFL dipping systems.

[0031] The preparation method of the non-phenolic adhesive rubber can adopt the existing preparation method of adhesive rubber. Specifically, the preparation method includes a first stage of internal mixing and a second stage of internal mixing;

[0032] The first stage internal mixing includes: adding the base rubber, the activator and the reinforcing filler into the internal mixer and mixing them thoroughly to obtain a first stage mixed rubber sheet;

[0033] The second-stage internal mixing comprises: adding the first-stage mixed rubber sheet, the vulcanization accelerator, the vulcanizing agent, and the environmentally friendly adhesive resin into an internal mixer and mixing them fully to obtain the adhesive rubber.

[0034] The operation steps of the first stage and second stage internal mixing can adopt conventional operation; the process parameters of the first stage and second stage internal mixing can adopt conventional parameters; specifically,

[0035] The first stage of internal mixing includes: base rubber, activator and reinforcing filler are internally mixed at 50-80°C and 40-70r / min for 8-15min, then openly mixed and cooled to room temperature to obtain a mixed rubber sheet;

[0036] The second stage internal kneading includes: mixing rubber sheet, vulcanization accelerator, vulcanizing agent and environmentally friendly adhesive resin at 30-80°C and 40-70r / min for 4-7 minutes, then open kneading and cooling to room temperature to obtain the adhesive rubber.

[0037] The method for preparing the non-phenolic adhesive rubber, wherein a specific scheme comprises:

[0038] First stage internal mixing: set the temperature to 50-80℃, the speed to 40-70r / min

[0039] Step 1) adding natural rubber and styrene-butadiene rubber into an internal mixer and mixing for 2.5 minutes;

[0040] Step 2) adding the activator into an internal mixer and mixing for 1.5 min;

[0041] Step 3) adding about 1 / 3 of the reinforcing filler into an internal mixer and mixing for 1.5 min;

[0042] Step 4) adding about 1 / 3 of the reinforcing filler into an internal mixer and mixing for 1.0 min;

[0043] Step 5) adding the remaining reinforcing filler into an internal mixer and mixing for 2.0 min;

[0044] Step 6) adding the mixed rubber to an open mixing mill, rolling out a 1-10 mm mixed rubber sheet, and cooling at room temperature for about 2 hours;

[0045] Second stage internal mixing: set the temperature to 30-80℃, the speed to 40-70r / min

[0046] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0047] Step 2) adding the vulcanization accelerator and the environmentally friendly adhesive resin into an internal mixer and mixing for 2.0 min;

[0048] Step 3) adding the vulcanizing agent into an internal mixer and mixing for 2.0 min;

[0049] Step 4) adding the mixed rubber into an open mill, keeping the cooling water of the open mill open, and rolling out a 2 mm second-stage mixed rubber sheet to obtain the adhesive rubber.

[0050] The second object of the present invention is to provide the application of the non-phenolic adhesive rubber described in the first object of the invention in the field of automobile and aircraft tires, especially in the field of high-speed and high-load automobile and aircraft tires.

[0051] Specifically, the non-phenolic adhesive rubber is used for the fiber after RFL dipping and the fiber after non-RFL dipping. The fiber is selected from at least one of nylon fiber, polyester fiber, polyimide fiber, aramid fiber and ultra-high molecular weight polyethylene fiber.

[0052] Compared with the prior art, the present invention has the following beneficial effects:

[0053] The present invention proposes a novel non-RF bonding rubber suitable for tire cord fabric fibers.

[0054] The adhesive rubber formula of the present invention does not contain toxic and harmful components such as RF adhesive resin, and will not cause harm to human body and environment.

[0055] The adhesive rubber provided by the invention has excellent adhesive effect and can replace the traditional RF adhesive rubber.

[0056] The adhesive rubber formula provided by the invention adds an environmentally friendly adhesive resin, thereby further improving the bonding effect between the fiber and the rubber.

[0057] The mechanical strength of the adhesive rubber prepared by the present invention is improved, which is beneficial to its practical use performance.

[0058] In the present invention, the preparation process of the adhesive rubber is simple and is conducive to industrial production. DETAILED DESCRIPTION

[0059] The present invention is described in detail below in conjunction with specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the contents of the present invention still fall within the scope of protection of the present invention.

[0060] The raw materials used in the following examples and comparative examples can all be obtained commercially, among which:

[0061] Natural rubber, brand: Smoked sheet No. 1, purchased from Shanghai Cunsi Industrial Co., Ltd.

[0062] Styrene butadiene rubber, brand: 1500E, purchased from China National Petroleum Corporation

[0063] Butadiene rubber, CAS 9003-17-2, purchased from Jiangsu Runfeng Synthetic Technology Co., Ltd.

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

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

[0066] Accelerator CZ, purchased from Hebi Ruida Chemical Technology Co., Ltd.

[0067] Accelerator NS, purchased from Hebi Yuanhao Chemical Co., Ltd.

[0068] Accelerator NOBS, purchased from Jiangsu Runfeng Synthetic Technology Co., Ltd.

[0069] Accelerator DZ, purchased from Shanghai Jiacheng Chemical Co., Ltd.

[0070] Accelerator TMTD, purchased from Tianjin Yihua Chemical Co., Ltd.

[0071] Accelerator DM, purchased from Shandong Shangshun Chemical Co., Ltd.

[0072] Carbon black N330, purchased from Shanxi Sanqiang New Energy Technology Co., Ltd.

[0073] Carbon black N550, purchased from Shandong Kasong New Materials Co., Ltd.

[0074] Carbon black N326, purchased from Shanghai Zhupin Chemical Co., Ltd.

[0075] White carbon black, purchased from Shandong Kasong New Materials Co., Ltd.

[0076] Carbon nanotubes were purchased from Shandong Tanfeng New Materials Technology Co., Ltd.

[0077] Attapulgite, purchased from Baiyi Mineral Products Processing Plant in Lingshou County

[0078] Nano-aramid fiber, purchased from Jiangxi Shuobang New Material Technology Co., Ltd.

[0079] Graphene oxide, purchased from Zancheng Technology Co., Ltd.

[0080] Ordinary sulfur, purchased from Shanghai Ruiba New Material Technology Co., Ltd.

[0081] Insoluble sulfur IS-60, purchased from Guangdong Fengzheng New Materials Co., Ltd.

[0082] Insoluble sulfur IS-90, purchased from Guangdong Fengzheng New Materials Co., Ltd.

[0083] Insoluble sulfur IS-7020, purchased from Guangdong Fengzheng New Materials Co., Ltd.

[0084] Aliphatic polyurethane resin, brand name Viscolam PS202, purchased from Shanghai Yuanhe Chemical Co., Ltd.

[0085] Blocked isocyanate resin, CAS2556-36-7, purchased from Jiangsu Runfeng Synthetic Technology Co., Ltd.

[0086] Maleic anhydride polybutadiene resin, brand name Ricobond 1731HS, purchased from Shanghai Sendi Chemical Co., Ltd. Epoxidized polybutadiene resin, brand name jp100, purchased from Wuhan Kemik Biopharmaceutical Technology Co., Ltd.

[0087] Polyester polyurethane resin, brand name Bayhydrol UH XP 2592, purchased from Shanghai Yuanhe Chemical Co., Ltd. Epoxy acrylic resin, brand name Aropol L80305A, purchased from Shanghai Yinhuang Industrial Co., Ltd.

[0088] Polyacrylic acid resin, brand P756765, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0089] Epoxy resin, brand E875162, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0090] Adhesive A, purchased from Changzhou Xince Polymer Materials Co., Ltd.

[0091] Adhesive RS, purchased from Changzhou Xince Polymer Materials Co., Ltd.

[0092] Phenolic resin SL3020, purchased from Huaqi (China) Chemical Co., Ltd.

[0093] Phenolic resin SL3022, purchased from Huaqi (China) Chemical Co., Ltd.

[0094] Example 1

[0095] A formulation of a non-phenolic (RF) adhesive rubber suitable for tire cord fabric fibers is as follows:

[0096] Components Weight Natural rubber 100 Zinc Oxide 8 Stearic acid 2 Accelerator CZ 1.5 Carbon Black N330 35 White Carbon Black 5 Carbon Nanotubes 3 Aliphatic polyurethane resin 5 Common sulfur 2.5

[0097] The preparation method comprises:

[0098] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0099] Step 1) adding natural rubber into an internal mixer and mixing for 2.5 min;

[0100] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 min;

[0101] Step 3) adding 1 / 3 of carbon black N330, white carbon black and carbon nanotubes into an internal mixer and mixing for 1.5 min;

[0102] 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;

[0103] Step 5) adding the remaining carbon black N330, white carbon black and carbon nanotubes into an internal mixer and mixing for 2.0 min;

[0104] Step 6) adding the mixed rubber into an open mixing mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0105] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0106] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0107] Step 2) adding accelerator CZ and aliphatic polyurethane resin into an internal mixer and mixing for 2.0 min;

[0108] Step 3) adding common sulfur into an internal mixer and mixing for 2.0 min;

[0109] Step 4) adding the mixed rubber into an open mill, keeping the cooling water of the open mill open, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the adhesive rubber.

[0110] Example 2

[0111] A formulation of a non-phenolic (RF) adhesive rubber suitable for tire cord fabric fibers is as follows:

[0112]

[0113]

[0114] The preparation method comprises:

[0115] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0116] Step 1) adding natural rubber into an internal mixer and mixing for 2.5 min;

[0117] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 min;

[0118] Step 3) adding 1 / 3 of carbon black N550, carbon nanotubes, and graphene oxide into an internal mixer and mixing for 1.5 min;

[0119] Step 4) adding 1 / 3 of carbon black N550, carbon nanotubes, and graphene oxide into an internal mixer and mixing for 1.0 min;

[0120] Step 5) adding the remaining carbon black N550, carbon nanotubes, and graphene oxide into an internal mixer and mixing for 2.0 min;

[0121] Step 6) adding the mixed rubber into an open mixing mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0122] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0123] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0124] Step 2) adding accelerator NS and blocked isocyanate resin into an internal mixer and mixing for 2.0 min;

[0125] Step 3) adding insoluble sulfur IS-7020 into an internal mixer and mixing for 2.0 min;

[0126] Step 4) adding the mixed rubber into an open mill, keeping the cooling water of the open mill open, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the adhesive rubber.

[0127] Example 3

[0128] A formulation of a non-phenolic (RF) adhesive rubber suitable for tire cord fabric fibers is as follows:

[0129] Components Weight Natural rubber 90 Styrene Butadiene Rubber 10 Zinc Oxide 10 Stearic acid 2 Accelerator NS 0.8 Carbon Black N550 30 Attapulgite 5 Nano aramid fiber 5 Maleic anhydride polybutadiene resin 7 Insoluble Sulfur IS-7020 2.8

[0130] The preparation method comprises:

[0131] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0132] Step 1) adding natural rubber and styrene-butadiene rubber into an internal mixer and mixing for 2.5 minutes;

[0133] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 min;

[0134] Step 3) adding 1 / 3 of carbon black N550, attapulgite, and nano-aramid fiber into an internal mixer and mixing for 1.5 min;

[0135] Step 4) adding 1 / 3 of carbon black N550, attapulgite, and nano-aramid fiber into an internal mixer and mixing for 1.0 min;

[0136] Step 5) adding the remaining carbon black N550, attapulgite, and nano-aramid fiber into an internal mixer and mixing for 2.0 min;

[0137] Step 6) adding the mixed rubber into an open mixing mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0138] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0139] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0140] Step 2) adding accelerator NS and maleic anhydride polybutadiene resin into an internal mixer and mixing for 2.0 min;

[0141] Step 3) adding insoluble sulfur IS-7020 into an internal mixer and mixing for 2.0 min;

[0142] Step 4) adding the mixed rubber into an open mill, keeping the cooling water of the open mill open, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the adhesive rubber.

[0143] Example 4

[0144] A formulation of a non-phenolic (RF) adhesive rubber suitable for tire cord fabric fibers is as follows:

[0145] Components Weight Natural rubber 100 Zinc Oxide 10 Stearic acid 2 Accelerator NOBS 1 Accelerator DZ 1 Carbon Black N330 35 White Carbon Black 5 Carbon Nanotubes 3 Epoxidized polybutadiene resin 5 Common sulfur 0.3 Insoluble Sulfur IS-60 3.2

[0146] The preparation method comprises:

[0147] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0148] Step 1) adding natural rubber into an internal mixer and mixing for 2.5 min;

[0149] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 min;

[0150] Step 3) adding 1 / 3 of carbon black N330, white carbon black and carbon nanotubes into an internal mixer and mixing for 1.5 min;

[0151] 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;

[0152] Step 5) adding the remaining carbon black N330, white carbon black and carbon nanotubes into an internal mixer and mixing for 2.0 min;

[0153] Step 6) adding the mixed rubber into an open mixing mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0154] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0155] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0156] Step 2) adding accelerator NOBS, accelerator DZ and epoxidized polybutadiene resin into an internal mixer and mixing for 2.0 min;

[0157] Step 3) adding common sulfur and insoluble sulfur IS-60 into an internal mixer and mixing for 2.0 min;

[0158] Step 4) adding the mixed rubber into an open mill, keeping the cooling water of the open mill open, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the adhesive rubber.

[0159] Example 5

[0160] A formulation of a non-phenolic (RF) adhesive rubber suitable for tire cord fabric fibers is as follows:

[0161] Components Weight Natural rubber 80 Styrene Butadiene Rubber 10 Butadiene rubber 10 Zinc Oxide 4 Stearic acid 2 Accelerator CZ 1.5 Carbon Black N330 30 Carbon Nanotubes 5 Graphene oxide 5 Polyester polyurethane resin 4 Common sulfur 2.5

[0162] The preparation method comprises:

[0163] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0164] Step 1) adding natural rubber, styrene-butadiene rubber and butadiene rubber into an internal mixer and mixing for 2.5 minutes;

[0165] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 min;

[0166] Step 3) adding 1 / 3 of carbon black N330, carbon nanotubes, and graphene oxide into an internal mixer and mixing for 1.5 min;

[0167] Step 4) adding 1 / 3 of carbon black N330, carbon nanotubes, and graphene oxide into an internal mixer and mixing for 1.0 min;

[0168] Step 5) adding the remaining carbon black N330, carbon nanotubes, and graphene oxide into an internal mixer and mixing for 2.0 min;

[0169] Step 6) adding the mixed rubber into an open mixing mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0170] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0171] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0172] Step 2) adding accelerator CZ and polyester polyurethane resin into an internal mixer and mixing for 2.0 min;

[0173] Step 3) adding common sulfur into an internal mixer and mixing for 2.0 min;

[0174] Step 4) adding the mixed rubber into an open mill, keeping the cooling water of the open mill open, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the adhesive rubber.

[0175] Example 6

[0176] A formulation of a non-phenolic (RF) adhesive rubber suitable for tire cord fabric fibers is as follows:

[0177] Components Weight Natural rubber 90 Styrene Butadiene Rubber 10 Zinc Oxide 8 Stearic acid 2 Accelerator CZ 1.5 Carbon Black N550 30 Attapulgite 5 Nano aramid fiber 5 Epoxy acrylic resin 6.8 Common sulfur 0.3 Insoluble Sulfur IS-60 3.2

[0178] The preparation method comprises:

[0179] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0180] Step 1) adding natural rubber and styrene-butadiene rubber into an internal mixer and mixing for 2.5 minutes;

[0181] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 min;

[0182] Step 3) adding 1 / 3 of carbon black N550, attapulgite, and nano-aramid fiber into an internal mixer and mixing for 1.5 min;

[0183] Step 4) adding 1 / 3 of carbon black N550, attapulgite, and nano-aramid fiber into an internal mixer and mixing for 1.0 min;

[0184] Step 5) adding the remaining carbon black N550, attapulgite, and nano-aramid fiber into an internal mixer and mixing for 2.0 min;

[0185] Step 6) adding the mixed rubber into an open mixing mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0186] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0187] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0188] Step 2) adding accelerator CZ and epoxy acrylic resin into an internal mixer and mixing for 2.0 min;

[0189] Step 3) adding common sulfur and insoluble sulfur IS-60 into an internal mixer and mixing for 2.0 min;

[0190] Step 4) adding the mixed rubber into an open mill, keeping the cooling water of the open mill open, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the adhesive rubber.

[0191] Example 7

[0192] A formulation of a non-phenolic (RF) adhesive rubber suitable for tire cord fabric fibers is as follows:

[0193] Components Weight Natural rubber 100 Zinc Oxide 8 Stearic acid 2 Accelerator CZ 1.5 Carbon Black N330 35 White Carbon Black 5 Carbon Nanotubes 3 Polyacrylic acid resin 6.5 Common sulfur 2.5

[0194] The preparation method comprises:

[0195] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0196] Step 1) adding natural rubber into an internal mixer and mixing for 2.5 min;

[0197] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 min;

[0198] Step 3) adding 1 / 3 of carbon black N330, white carbon black and carbon nanotubes into an internal mixer and mixing for 1.5 min;

[0199] 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;

[0200] Step 5) adding the remaining carbon black N330, white carbon black and carbon nanotubes into an internal mixer and mixing for 2.0 min;

[0201] Step 6) adding the mixed rubber into an open mixing mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0202] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0203] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0204] Step 2) adding accelerator CZ and polyacrylic acid resin into an internal mixer and mixing for 2.0 min;

[0205] Step 3) adding common sulfur into an internal mixer and mixing for 2.0 min;

[0206] Step 4) adding the mixed rubber into an open mill, keeping the cooling water of the open mill open, and rolling out a 2 mm second-stage mixed rubber sheet to obtain the adhesive rubber.

[0207] Example 8

[0208] A formulation of a non-phenolic (RF) adhesive rubber suitable for tire cord fabric fibers is as follows:

[0209]

[0210]

[0211] The preparation method comprises:

[0212] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0213] Step 1) adding natural rubber and styrene-butadiene rubber into an internal mixer and mixing for 2.5 minutes;

[0214] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 min;

[0215] Step 3) adding 1 / 3 of carbon black N550, attapulgite, and nano-aramid fiber into an internal mixer and mixing for 1.5 min;

[0216] Step 4) adding 1 / 3 of carbon black N550, attapulgite, and nano-aramid fiber into an internal mixer and mixing for 1.0 min;

[0217] Step 5) adding the remaining carbon black N550, attapulgite, and nano-aramid fiber into an internal mixer and mixing for 2.0 min;

[0218] Step 6) adding the mixed rubber into an open mixing mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0219] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0220] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0221] Step 2) adding accelerator DM, accelerator TMTD and epoxy resin into an internal mixer and mixing for 2.0 min;

[0222] Step 3) adding common sulfur into an internal mixer and mixing for 2.0 min;

[0223] Step 4) adding the mixed rubber into an open mill, keeping the cooling water of the open mill open, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the adhesive rubber.

[0224] Example 9

[0225] A formulation of a non-phenolic (RF) adhesive rubber suitable for tire cord fabric fibers is as follows:

[0226]

[0227]

[0228] The preparation method comprises:

[0229] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0230] Step 1) adding natural rubber and styrene-butadiene rubber into an internal mixer and mixing for 2.5 minutes;

[0231] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 min;

[0232] Step 3) adding 1 / 3 of carbon black N326, carbon nanotubes, and graphene oxide into an internal mixer and mixing for 1.5 min;

[0233] Step 4) adding 1 / 3 of carbon black N326, carbon nanotubes, and graphene oxide into an internal mixer and mixing for 1.0 min;

[0234] Step 5) adding the remaining carbon black N326, carbon nanotubes, and graphene oxide into an internal mixer and mixing for 2.0 min;

[0235] Step 6) adding the mixed rubber into an open mixing mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0236] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0237] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0238] Step 2) adding accelerator DM, accelerator TMTD and aliphatic polyurethane resin into an internal mixer and mixing for 2.0 min;

[0239] Step 3) adding insoluble sulfur IS-90 into an internal mixer and mixing for 2.0 min;

[0240] Step 4) adding the mixed rubber into an open mill, keeping the cooling water of the open mill open, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the adhesive rubber.

[0241] Example 10

[0242] A formulation of a non-phenolic (RF) adhesive rubber suitable for tire cord fabric fibers is as follows:

[0243]

[0244]

[0245] The preparation method comprises:

[0246] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0247] Step 1) adding natural rubber, styrene-butadiene rubber and butadiene rubber into an internal mixer and mixing for 2.5 minutes;

[0248] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 min;

[0249] Step 3) adding 1 / 3 of carbon black N330, white carbon black and carbon nanotubes into an internal mixer and mixing for 1.5 min;

[0250] 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;

[0251] Step 5) adding the remaining carbon black N330, white carbon black and carbon nanotubes into an internal mixer and mixing for 2.0 min;

[0252] Step 6) adding the mixed rubber into an open mixing mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0253] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0254] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0255] Step 2) adding accelerator NS and blocked isocyanate resin into an internal mixer and mixing for 2.0 min;

[0256] Step 3) adding common sulfur and insoluble sulfur IS-60 into an internal mixer and mixing for 2.0 min;

[0257] Step 4) adding the mixed rubber into an open mill, keeping the cooling water of the open mill open, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the adhesive rubber.

[0258] Embodiment 11

[0259] A formulation of a non-phenolic (RF) adhesive rubber suitable for tire cord fabric fibers is as follows:

[0260] Components Weight Natural rubber 100 Zinc Oxide 10 Stearic acid 2 Accelerator NOBS 1 Accelerator DZ 1 Carbon Black N330 30 White Carbon Black 5 Carbon Nanotubes 3 Maleic anhydride polybutadiene resin 7 Common sulfur 2.5

[0261] The preparation method comprises:

[0262] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0263] Step 1) adding natural rubber into an internal mixer and mixing for 2.5 min;

[0264] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 min;

[0265] Step 3) adding 1 / 3 of carbon black N330, white carbon black and carbon nanotubes into an internal mixer and mixing for 1.5 min;

[0266] 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;

[0267] Step 5) adding the remaining carbon black N330, white carbon black and carbon nanotubes into an internal mixer and mixing for 2.0 min;

[0268] Step 6) adding the mixed rubber into an open mixing mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0269] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0270] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0271] Step 2) adding accelerator NOBS, accelerator DZ and maleic anhydride polybutadiene resin into an internal mixer and mixing for 2.0 min;

[0272] Step 3) adding common sulfur into an internal mixer and mixing for 2.0 min;

[0273] Step 4) adding the mixed rubber into an open mill, keeping the cooling water of the open mill open, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the adhesive rubber.

[0274] Example 12

[0275] A formulation of a non-phenolic (RF) adhesive rubber suitable for tire cord fabric fibers is as follows:

[0276] Components Weight Natural rubber 100 Zinc Oxide 8 Stearic acid 2 Accelerator DM 1.2 Accelerator TMTD 0.03 Carbon Black N550 30 White Carbon Black 5 Carbon Nanotubes 5 Aliphatic polyurethane resin 3 Insoluble Sulfur IS-60 3.2

[0277] The preparation method comprises:

[0278] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0279] Step 1) adding natural rubber into an internal mixer and mixing for 2.5 min;

[0280] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 min;

[0281] Step 3) adding 1 / 3 of carbon black N550, white carbon black and carbon nanotubes into an internal mixer and mixing for 1.5 min;

[0282] Step 4) adding 1 / 3 of carbon black N550, white carbon black and carbon nanotubes into an internal mixer and mixing for 1.0 min;

[0283] Step 5) adding the remaining carbon black N550, white carbon black and carbon nanotubes into an internal mixer and mixing for 2.0 min;

[0284] Step 6) adding the mixed rubber into an open mixing mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0285] Second stage internal mixing: set the temperature to 60℃ and the speed to 60r / min

[0286] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0287] Step 2) adding accelerator DM, accelerator TMTD and aliphatic polyurethane resin into an internal mixer and mixing for 2.0 min;

[0288] Step 3) adding insoluble sulfur IS-60 into an internal mixer and mixing for 2.0 min;

[0289] Step 4) adding the mixed rubber into an open mill, keeping the cooling water of the open mill open, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the adhesive rubber.

[0290] Comparative Example 1

[0291] An RF adhesive rubber, the formula of which is as follows:

[0292] Components Weight Natural rubber 90 Styrene Butadiene Rubber 10 Zinc Oxide 8 Stearic acid 2 Accelerator DM 1.2 Accelerator TMTD 0.03 Carbon Black N330 35 Adhesive A 0.8 Adhesive RS 0.96 Common sulfur 2.5

[0293] The preparation method comprises:

[0294] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0295] Step 1) adding natural rubber and styrene-butadiene rubber into an internal mixer and mixing for 2.5 minutes;

[0296] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 min;

[0297] Step 3) adding 1 / 3 of carbon black N330 into an internal mixer and mixing for 1.5 min;

[0298] Step 4) adding 1 / 3 of carbon black N330 into an internal mixer and mixing for 1.0 min;

[0299] Step 5) adding the remaining carbon black N330 into an internal mixer and mixing for 2.0 min;

[0300] Step 6) adding the mixed rubber into an open mixing mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0301] Second stage internal mixing: set the temperature to 80℃ and the speed to 60r / min

[0302] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0303] Step 2) adding accelerator DM, accelerator TMTD, adhesive A and adhesive RS into an internal mixer and mixing for 2.0 min;

[0304] Step 3) adding common sulfur into an internal mixer and mixing for 2.0 min;

[0305] Step 4) adding the mixed rubber into an open mill, keeping the cooling water of the open mill open, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the adhesive rubber.

[0306] Comparative Example 2

[0307] An RF adhesive rubber, the formula of which is as follows:

[0308] Components Weight Natural rubber 100 Zinc Oxide 4 Stearic acid 2 Accelerator M 1.2 Carbon Black N330 35 Phenolic resin SL3020 3.5 RA65 0.5 Common sulfur 2.5

[0309] The preparation method comprises:

[0310] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0311] Step 1) adding natural rubber into an internal mixer and mixing for 2.5 min;

[0312] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 min;

[0313] Step 3) adding 1 / 3 of carbon black N330 into an internal mixer and mixing for 1.5 min;

[0314] Step 4) adding 1 / 3 of carbon black N330 into an internal mixer and mixing for 1.0 min;

[0315] Step 5) adding the remaining carbon black N330 into an internal mixer and mixing for 2.0 min;

[0316] Step 6) adding the mixed rubber into an open mixing mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0317] Second stage internal mixing: set the temperature to 80℃ and the speed to 60r / min

[0318] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0319] Step 2) adding accelerator M, phenolic resin SL3020 and RA65 into an internal mixer and mixing for 2.0 min;

[0320] Step 3) adding common sulfur into an internal mixer and mixing for 2.0 min;

[0321] Step 4) adding the mixed rubber into an open mill, keeping the cooling water of the open mill open, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the adhesive rubber.

[0322] Comparative Example 3

[0323] An RF adhesive rubber, the formula of which is as follows:

[0324] Components Weight Natural rubber 100 Zinc Oxide 4 Stearic acid 2 Accelerator CZ 0.8 Carbon Black N330 35 Phenolic resin SL3020 5 RA65 0.75 Common sulfur 2.5

[0325] The preparation method comprises:

[0326] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0327] Step 1) adding natural rubber into an internal mixer and mixing for 2.5 min;

[0328] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 min;

[0329] Step 3) adding 1 / 3 of carbon black N330 into an internal mixer and mixing for 1.5 min;

[0330] Step 4) adding 1 / 3 of carbon black N330 into an internal mixer and mixing for 1.0 min;

[0331] Step 5) adding the remaining carbon black N330 into an internal mixer and mixing for 2.0 min;

[0332] Step 6) adding the mixed rubber into an open mixing mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0333] Second stage internal mixing: set the temperature to 80℃ and the speed to 60r / min

[0334] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0335] Step 2) adding accelerator CZ, phenolic resin SL3020 and RA65 into an internal mixer and mixing for 2.0 min;

[0336] Step 3) adding common sulfur into an internal mixer and mixing for 2.0 min;

[0337] Step 4) adding the mixed rubber into an open mill, keeping the cooling water of the open mill open, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the adhesive rubber.

[0338] Comparative Example 4

[0339] An RF adhesive rubber, the formula of which is as follows:

[0340]

[0341]

[0342] The preparation method comprises:

[0343] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0344] Step 1) adding natural rubber into an internal mixer and mixing for 2.5 min;

[0345] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 min;

[0346] Step 3) adding 1 / 3 of carbon black N330 into an internal mixer and mixing for 1.5 min;

[0347] Step 4) adding 1 / 3 of carbon black N330 into an internal mixer and mixing for 1.0 min;

[0348] Step 5) adding the remaining carbon black N330 into an internal mixer and mixing for 2.0 min;

[0349] Step 6) adding the mixed rubber into an open mixing mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0350] Second stage internal mixing: set the temperature to 80℃ and the speed to 60r / min

[0351] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0352] Step 2) adding accelerator CZ, adhesive A and adhesive RS into an internal mixer and mixing for 2.0 min;

[0353] Step 3) adding insoluble sulfur IS-90 into an internal mixer and mixing for 2.0 min;

[0354] Step 4) adding the mixed rubber into an open mill, keeping the cooling water of the open mill open, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the adhesive rubber.

[0355] Comparative Example 5

[0356] An RF adhesive rubber, the formula of which is as follows:

[0357] Components Weight Natural rubber 100 Zinc Oxide 4 Stearic acid 2 Accelerator NOBS 1 Accelerator DZ 1 Carbon Black N330 35 White Carbon Black 5 Carbon Nanotubes 3 Adhesive A 3 Adhesive RS 2.7 Insoluble Sulfur IS-7020 2.8

[0358] The preparation method comprises:

[0359] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0360] Step 1) adding natural rubber into an internal mixer and mixing for 2.5 min;

[0361] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 min;

[0362] Step 3) adding 1 / 3 of carbon black N330, white carbon black and carbon nanotubes into an internal mixer and mixing for 1.5 min;

[0363] 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;

[0364] Step 5) adding the remaining carbon black N330, white carbon black and carbon nanotubes into an internal mixer and mixing for 2.0 min;

[0365] Step 6) adding the mixed rubber into an open mixing mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0366] Second stage internal mixing: set the temperature to 80℃ and the speed to 60r / min

[0367] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0368] Step 2) adding accelerator NOBS, accelerator DZ, adhesive A and adhesive RS into an internal mixer and mixing for 2.0 min;

[0369] Step 3) adding insoluble sulfur IS-7020 into an internal mixer and mixing for 2.0 min;

[0370] Step 4) adding the mixed rubber into an open mill, keeping the cooling water of the open mill open, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the adhesive rubber.

[0371] Comparative Example 6

[0372] An RF adhesive rubber, the formula of which is as follows:

[0373] Components Weight Natural rubber 80 Styrene Butadiene Rubber 20 Zinc Oxide 5 Stearic acid 2 Accelerator CZ 0.2 Carbon Black N330 25 White Carbon Black 10 Phenolic resin SL3022 3 Insoluble Sulfur IS-7020 2.8

[0374] The preparation method comprises:

[0375] First stage internal mixing: set the temperature to 70℃ and the speed to 60r / min

[0376] Step 1) adding natural rubber and styrene-butadiene rubber into an internal mixer and mixing for 2.5 minutes;

[0377] Step 2) adding zinc oxide and stearic acid into an internal mixer and mixing for 1.5 min;

[0378] Step 3) adding 1 / 3 of carbon black N330 and white carbon black into an internal mixer and mixing for 1.5 min;

[0379] Step 4) adding 1 / 3 of carbon black N330 and white carbon black into an internal mixer and mixing for 1.0 min;

[0380] Step 5) adding the remaining carbon black N330 and white carbon black into an internal mixer and mixing for 2.0 min;

[0381] Step 6) adding the mixed rubber into an open mixing mill, rolling out a mixed rubber sheet, and cooling at room temperature for 2 hours;

[0382] Second stage internal mixing: set the temperature to 80℃ and the speed to 60r / min

[0383] Step 1) adding the cooled mixed film into an internal mixer and mixing for 1.0 min;

[0384] Step 2) adding accelerator CZ and phenolic resin SL3022 into an internal mixer and mixing for 2.0 min;

[0385] Step 3) adding insoluble sulfur IS-7020 into an internal mixer and mixing for 2.0 min;

[0386] Step 4) adding the mixed rubber into an open mill, keeping the cooling water of the open mill open, and rolling out a 2 mm thick two-stage mixed rubber sheet to obtain the adhesive rubber.

[0387] Performance Testing

[0388] With reference to the standard GB / T528-2009, the adhesive rubbers prepared in Examples 1-12 and Comparative Examples 1-6 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. The test results show that the mechanical properties of the non-phenolic adhesive rubbers of Examples 1-12 are better than those of the RF adhesive rubbers of Comparative Examples 1-6. Some of the test results are shown in Table 1-5.

[0389] The adhesive rubbers prepared in Examples 1-12 and Comparative Examples 1-6 were respectively combined with polyester fiber cords, nylon fiber cords, aramid fiber cords, polyimide fiber cords, and ultra-high molecular weight polyethylene fiber cords of different specifications after conventional RFL dipping and novel non-RFL dipping treatments to prepare test specimens, and H extraction tests and peeling tests were performed. The test results show that the non-phenolic adhesive rubbers of Examples 1-12 have better dynamic and static adhesion properties and persulfurization properties with different fibers than the RF adhesive rubbers of Comparative Examples 1-6. Among them, some test results are as follows.

[0390] The adhesive rubbers prepared in Examples 1-3 and Comparative Example 1 and the polyester fiber cords treated with conventional RFL and novel non-RFL dipping were prepared into test samples, and H extraction test, peeling test and dynamic adhesion performance test were carried out. The test results are shown in Table 1.

[0391] The adhesive rubbers prepared in Examples 4-6 and Comparative Examples 2 and 3 and the nylon fiber cords treated with conventional RFL and novel non-RFL dipping were prepared into test samples, and H extraction test, peeling test and dynamic adhesion performance test were carried out. The test results are shown in Table 2.

[0392] The adhesive rubber prepared in Examples 7, 8 and Comparative Example 4 and the aramid fiber cords treated with conventional RFL and novel non-RFL dipping were prepared into test samples, and H extraction test, peeling test and dynamic bonding performance test were carried out. The test results are shown in Table 3.

[0393] The adhesive rubber prepared in Examples 9, 10 and Comparative Example 5 and the polyimide fiber cords treated with conventional RFL and novel non-RFL dipping were prepared into test samples, and H extraction test, peeling test and dynamic bonding performance test were carried out. The test results are shown in Table 4.

[0394] The adhesive rubber prepared in Examples 11, 12 and Comparative Example 6 and the ultra-high molecular weight polyethylene fiber cords treated with conventional RFL and novel non-RFL dipping were prepared into test samples, and H extraction test and peeling test were carried out. The test results are shown in Table 5.

[0395] The preparation method of H extraction test specimen is as follows:

[0396] With reference to GB / T2942-2009, the prepared adhesive rubber is completely coated on the dipped cord, wherein the embedding depth of nylon fiber, aramid fiber, polyimide fiber, and ultra-high molecular weight polyethylene fiber is 10 mm, and the embedding depth of polyester fiber is 5 mm. H-extracted specimens are 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. The H-extracted specimens are then subjected to a dynamic fatigue performance test at 120°C and 10 Hz.

[0397] The preparation method of the peeling force test strip is as follows:

[0398] 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. The vulcanization pressure is 15 MPa, the vulcanization temperature is 160°C, and the vulcanization time is 15 min.

[0399] 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 and the peel force test specimens is 15 MPa, the vulcanization temperature is 160°C, and the vulcanization time is 1 h.

[0400] Table 1

[0401]

[0402] Table 2

[0403]

[0404] Table 3

[0405]

[0406] Table 4

[0407]

[0408] Table 5

[0409]

[0410] In Tables 1-5, 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.

[0411] The data in Table 1 show:

[0412] For polyester fibers treated with a conventional RFL dipping system: Compared with Comparative Example 1 (RF adhesive rubber for polyester fibers), the H extraction force of Examples 1-3 under normal vulcanization conditions is increased by about 17-35%, the peeling force is increased by about 12-34%, and the fatigue life is increased by about 25-43%. The H extraction force after vulcanization is increased by 11-32%, the peeling force after vulcanization is increased by 12-37%, and the fatigue life after vulcanization is increased by 43-56%.

[0413] For polyester fibers treated with the new non-RFL dipping system: Compared with Comparative Example 1 (RF adhesive rubber for polyester fibers), the H extraction force of Examples 1-3 under normal vulcanization conditions is increased by about 11-29%, the peeling force is increased by about 28-42%, and the fatigue life is increased by about 54-64%. The H extraction force after vulcanization is increased by 11-33%, the peeling force after vulcanization is increased by 20-39%, and the fatigue life after vulcanization is increased by 43-56%.

[0414] Compared with Comparative Example 1, the tensile strength, 100% modulus of elongation, and 300% modulus of elongation of Examples 1-3 are all improved.

[0415] From the data in Table 1, it can be concluded that in Examples 1-3, the RF adhesive resin in the adhesive rubber is removed and replaced with an environmentally friendly adhesive resin, and the rubber system, activation system, sulfur-promoting system and filling system are synergistically optimized, and the dynamic and static adhesive properties and persulfurization properties of the obtained non-phenolic adhesive rubber with polyester fiber are better than those of the RF adhesive rubber. In addition, the mechanical properties of the non-phenolic adhesive rubber in Examples 1-3 are also better than those of the RF adhesive rubber.

[0416] The data in Table 2 show:

[0417] For nylon fibers treated with traditional RFL dipping systems:

[0418] For 930dtex / 2 nylon cords, the H extraction force of Examples 4-6 is increased by about 9-12%, the peeling force is increased by about 10-27%, and the fatigue life is increased by about 36-49% compared with Comparative Example 2 (RF adhesive rubber for 930dtex / 2 nylon fibers). For 1400dtex / 2 nylon cords, the H extraction force of Examples 4-6 is increased by about 10-15%, the peeling force is increased by about 14-22%, and the fatigue life is increased by about 52-70% compared with Comparative Example 3 (RF adhesive rubber for 1400dtex / 2 nylon fibers).

[0419] For nylon fibers treated with new non-RFL impregnation systems:

[0420] For 930dtex / 2 nylon cords, the H extraction force of Examples 4-6 is increased by about 5-21%, the peeling force is increased by about 7-35%, and the fatigue life is increased by about 26-56% compared with that of Comparative Example 2. For 1400dtex / 2 nylon cords, the H extraction force of Examples 4-6 is increased by about 7-28%, the peeling force is increased by about 11-33%, and the fatigue life is increased by about 38-63% compared with that of Comparative Example 3.

[0421] Compared with Comparative Examples 2 and 3, the tensile strength, 100% modulus of elongation, and 300% modulus of elongation of Examples 4-6 are all improved.

[0422] From the data in Table 2, it can be concluded that in Examples 4-6, the RF adhesive resin in the adhesive rubber is removed and replaced with an environmentally friendly adhesive resin, and the rubber system, activation system, sulfur-promoting system and filling system are synergistically optimized, and the obtained non-phenolic adhesive rubber has better dynamic and static adhesive properties with nylon fibers of different specifications than the RF adhesive rubber. In addition, the mechanical properties of the non-phenolic adhesive rubber in Examples 4-6 are also better than those of the RF adhesive rubber.

[0423] The data in Table 3 show that:

[0424] For aramid fibers treated with a conventional RFL impregnation system: compared with Comparative Example 4 (RF adhesive rubber for aramid fibers), Examples 7-8 have an H extraction force that is increased by about 6-9%, a peeling force that is increased by about 4-7%, and a fatigue life that is increased by about 68-76%.

[0425] For nylon fibers treated with the new non-RFL impregnation system: compared with Comparative Example 4, the H extraction force of Examples 7-8 is increased by about 10-14%, the peeling force is increased by about 12-16%, and the fatigue life is increased by about 56-76%.

[0426] Compared with Comparative Example 4, the tensile strength, 100% modulus of elongation, and 300% modulus of Examples 7-8 are all improved.

[0427] From the data in Table 3, it can be concluded that in Examples 7-8, the RF adhesive resin in the adhesive rubber is removed and replaced with an environmentally friendly adhesive resin, and the rubber system, activation system, sulfur-promoting system and filling system are synergistically optimized, and the dynamic and static adhesive properties of the obtained non-phenolic adhesive rubber and aramid fiber are better than those of the RF adhesive rubber. In addition, the mechanical properties of the non-phenolic adhesive rubber in Examples 7-8 are also better than those of the RF adhesive rubber.

[0428] The data in Table 4 show that:

[0429] For polyimide fibers treated with a conventional RFL dipping system: Examples 9-10 have an H extraction force that is increased by about 3-22%, a peel force that is increased by about 5-26%, and a fatigue life that is increased by about 23-56% compared to Comparative Example 5 (RF adhesive rubber for polyimide fibers).

[0430] For polyimide fibers treated with a novel non-RFL impregnation system: compared with comparative example 5, the H extraction force of examples 9-10 is increased by about 21-35%, the peeling force is increased by about 27-33%, and the fatigue life is increased by about 36-43%.

[0431] Compared with Comparative Example 5, the tensile strength, 100% modulus of elongation, and 300% modulus of Examples 9-10 are all improved.

[0432] From the data in Table 4, it can be concluded that in Examples 9-10, the RF adhesive resin in the adhesive rubber is removed and replaced with an environmentally friendly adhesive resin, and the rubber system, activation system, sulfur-promoting system and filling system are synergistically optimized. The dynamic and static adhesive properties of the obtained non-phenolic adhesive rubber and polyimide fiber are better than those of the RF adhesive rubber. In addition, the mechanical properties of the non-phenolic adhesive rubber in Examples 9-10 are also better than those of the RF adhesive rubber.

[0433] The data in Table 5 show that:

[0434] For ultra-high molecular weight polyethylene fibers treated with a conventional RFL dipping system: Examples 11-12 have an H extraction force that is increased by about 24-36%, a peel force that is increased by about 20-40%, and a fatigue life that is increased by about 48-56% compared to Comparative Example 6 (RF adhesive rubber for ultra-high molecular weight polyethylene fibers).

[0435] For ultra-high molecular weight polyethylene fibers treated with the new non-RFL impregnation system: the H extraction force of Examples 11-12 is improved by about 31-45%, the peeling force is improved by about 37-56%, and the fatigue life is improved by about 39-46% compared with that of Comparative Example 6.

[0436] Compared with Comparative Example 6, the tensile strength, 100% modulus of elongation, and 300% modulus of Examples 11-12 are all improved.

[0437] From the data in Table 5, it can be concluded that in Examples 11-12, the RF adhesive resin in the adhesive rubber is removed and replaced with an environmentally friendly adhesive resin, and the rubber system, activation system, sulfur-promoting system and filling system are synergistically optimized, and the dynamic and static adhesive properties of the obtained non-phenolic adhesive rubber and the ultra-high molecular weight polyethylene fiber are better than those of the RF adhesive rubber. In addition, the mechanical properties of the non-phenolic adhesive rubber in Examples 11-12 are also better than those of the RF adhesive rubber.

[0438] In summary, it can be concluded that the present invention replaces the RF adhesive resin in the adhesive rubber with an environmentally friendly adhesive resin, and simultaneously synergistically optimizes the rubber system, activation system, sulfur-promoting system and filling system, and the obtained non-phenolic adhesive rubber has significantly better dynamic and static adhesive properties with various fibers than the RF adhesive rubber, greatly improving the interface performance of the composite material. The non-RF adhesive rubber formula of the present invention can achieve excellent interface dynamic and static adhesive properties with tire cord fabric fibers of different types and specifications without containing toxic and harmful components such as RF adhesive resin and causing harm to the human body and the environment.

Claims

1. A non-phenolic adhesive rubber suitable for tire cord fabric fibers, characterized in that: The non-phenolic 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; Vulcanization accelerator 0.1-5 parts by weight, preferably 0.5-2 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; The environmentally friendly adhesive resin is 0.5-20 parts by weight, preferably 3-7 parts by weight.

2. The non-phenolic 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; Based on 100 parts by weight of the base rubber, the natural rubber accounts for 70-100 parts by weight, preferably 75-100 parts by weight, more preferably 80-100 parts by weight, and the balance is styrene-butadiene rubber and / or butadiene rubber.

3. The non-phenolic adhesive rubber according to claim 1, characterized in that: The activator is selected from at least one of zinc oxide and stearic acid.

4. The non-phenolic adhesive rubber according to claim 1, characterized in that: The vulcanization accelerator is selected from at least one of accelerator M, accelerator CZ, accelerator NS, accelerator NOBS, accelerator DZ, accelerator DM and accelerator TMTD.

5. The non-phenolic adhesive rubber according to claim 1, characterized in that: The reinforcing filler is selected from one or more of carbon black, white carbon black, carbon nanotubes, attapulgite, nano-aramid fiber, and graphene oxide.

6. The non-phenolic adhesive rubber according to claim 1, characterized in that: The vulcanizing agent is selected from at least one of common sulfur and insoluble sulfur.

7. The non-phenolic adhesive rubber according to claim 1, characterized in that: 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; preferably, The environmentally friendly adhesive resin is selected from at least one of epoxidized polybutadiene resin, maleic anhydride polybutadiene resin, blocked isocyanate resin, polyacrylic resin, epoxy resin, epoxy acrylic resin, polyester polyurethane resin, and aliphatic polyurethane resin.

8. Use of the non-phenolic adhesive rubber according to any one of claims 1 to 7 in the field of automobile and aircraft tires.

9. The use according to claim 8, characterized in that The non-phenolic adhesive rubber is used for RFL-impregnated fibers and non-RFL-impregnated fibers.

10. The use according to claim 9, characterized in that The fiber is selected from at least one of nylon fiber, polyester fiber, polyimide fiber, aramid fiber, and ultra-high molecular weight polyethylene fiber.

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