CN113527776A - Rubber composite material, preparation method and application in shield machine main driving system sealing - Google Patents

Rubber composite material, preparation method and application in shield machine main driving system sealing Download PDF

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CN113527776A
CN113527776A CN202110900112.2A CN202110900112A CN113527776A CN 113527776 A CN113527776 A CN 113527776A CN 202110900112 A CN202110900112 A CN 202110900112A CN 113527776 A CN113527776 A CN 113527776A
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rubber
composite material
parts
clay
banburying
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CN113527776B (en
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李佳衡
龙伟漾
彭占杰
赵梦媛
张树祺
赵万里
赵明恩
韩铜楹
张新异
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China Railway Engineering Equipment Group Co Ltd CREG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract

The invention provides a rubber composite material, a preparation method thereof and application thereof in sealing of a main driving system of a shield tunneling machine. The raw material components for preparing the rubber composite material comprise, by weight, 100 parts of rubber, 8-15 parts of a molybdenum disulfide-clay composite material, 1-3 parts of a coupling agent, 60-110 parts of carbon black, 2-6 parts of nano zinc oxide, 1-6 parts of an anti-aging agent, 1-3 parts of an accelerator, 1-10 parts of a softener, 1-4 parts of a vulcanizing agent and 0.1-2 parts of a scorch retarder. The rubber composite material has better wear resistance and strength; the sealing device can be effectively suitable for sealing the main driving system of the shield machine, and has wide application prospect.

Description

Rubber composite material, preparation method and application in shield machine main driving system sealing
Technical Field
The invention belongs to the technical field of rubber sealing materials, and relates to a rubber composite material, a preparation method and application thereof in sealing of a main driving system of a shield tunneling machine.
Background
Along with the development of the shield machine, a host machine supporting manufacturer develops more and more shield machines suitable for complex working conditions, and particularly, the reliability and the service life of the seal of a main driving system of the shield machine are particularly critical in the face of the working conditions of large burial depth, high water pressure, long distance and complex and variable geological conditions. In the construction process, if the main driving system is sealed and fails, the main driving system is difficult to repair in a hole, engineering shutdown is caused, and once the condition happens, huge loss is brought to construction enterprises. The existing main driving sealing element mainly comes from import, and the production efficiency and the international competitiveness of domestic shield equipment are seriously restricted. At present, the main driving sealing material in the domestic market has low strength, no wear resistance and short service life, and in order to achieve the aim, the traditional sealing element needs to be modified, so that the strength, the wear resistance and the service life periodicity of the sealing element are improved, and the sealing effect of the shield tunneling machine is ensured.
The rubber industry uses a large amount of fillers as compounding agents, the dosage of the fillers is second to the consumption dosage of rubber, and the mineral clay material is an important component of the compounding agents because the mineral clay material has the advantages of abundant reserves in nature, low price, easy processing and the like. The mineral materials as fillers have different effects on the rubber function and the improvement effect according to different types and different amounts.
MoS2Is a typical layered hexagonal crystal, and the layers can generate slippage due to weak van der waals force fracture when receiving friction force, thereby forming a slippage surface to play a role in lubrication, and is known as 'the king of lubrication'. MoS2Compounded with rubber, the friction performance, thermal stability and the like of the rubber can be enhanced and improved.
In the processing of rubber, mineral clays and MoS are usually mixed2Separately added to the raw rubber for mixing, which results in clay and MoS2No bonding can be formed and no guarantee of mineral clay and MoS is obtained2The rubber reinforcing agent is uniformly dispersed in the raw rubber, and the composite material cannot well generate a synergistic effect, so that the reinforcing effect on the strength and the wear resistance of the rubber is greatly reduced.
Disclosure of Invention
Based on the defects of the prior art, the first purpose of the invention is to provide a rubber composite material; the second object of the present invention is to provide a method for preparing the rubber composite; the third purpose of the invention is to provide the application of the rubber composite material as a sealing material in the sealing of a main driving system of a shield machine.
The purpose of the invention is realized by the following technical scheme:
in one aspect, the invention provides a rubber composite material, which comprises the following raw material components in parts by weight:
Figure BDA0003199458640000021
the invention adopts molybdenum disulfide-clay composite material (MoS)2@ clay) is adopted to prepare the rubber composite material, and compared with the method of singly adopting molybdenum disulfide and clay raw materials, the rubber composite material has the advantage that the wear resistance and strength of the rubber are better improved.
In the above rubber composite material, preferably, the preparation method of the molybdenum disulfide-clay composite material comprises:
dissolving ammonium molybdate and thiourea in water and uniformly stirring to obtain a mixed solution;
then mixing the mixed solution and clay, and performing ultrasonic sanding dispersion to obtain a dispersion liquid;
and carrying out hydrothermal reaction on the dispersion solution, washing and drying a reaction product to obtain the molybdenum disulfide-clay composite material.
The invention adopts a one-pot hydrothermal method to uniformly grow the molybdenum disulfide on the clay mineral in situ, the ultrasonic-sand grinding coupling method is adopted in the preparation method to reduce the size of the clay, and simultaneously the dispersibility of the clay and the mixed solution is further improved, and the prepared molybdenum disulfide-clay composite material is mixed with other compounding agents such as rubber and the like, and then the rubber composite material is prepared by processes such as mixing, vulcanization and the like. In the molybdenum disulfide-clay composite material synthesized by the one-pot hydrothermal method and the ultrasonic sanding dispersion technology, the molybdenum disulfide and the clay form bonding, the self-agglomeration phenomenon is not easy to occur, the molybdenum disulfide-clay composite material is applied to the preparation of rubber materials, the synergistic effect of the molybdenum disulfide and the clay can be better exerted, the wear resistance of the rubber is improved, and the strength of the rubber is greatly improved.
In the above process, the ammonium molybdate ((NH)4)6Mo7O24·4H2O) and the thiourea (CH)4N2S) are all adopted as analytical reagents.
In the above rubber composite material, preferably, the mass ratio of the ammonium molybdate, the thiourea and the clay is (1-2): (1-2): 1.
in the rubber composite material, preferably, the time for dissolving ammonium molybdate and thiourea in water and stirring is 10-30 min.
In the above rubber composite material, preferably, the ultrasonic sanding and dispersing equipment is an ultrasonic-sand mill; the ultrasonic power is 200-800W, the rotational speed of sanding is 2000-2500 rpm, the temperature of sanding is 5-15 ℃, and the time of ultrasonic sanding is 10-30 min.
In the rubber composite material, preferably, the temperature rise rate of the hydrothermal reaction is 3-8 ℃/min, the temperature of the hydrothermal reaction is 100-280 ℃, and the heat preservation time of the hydrothermal reaction is 5-12 h.
In the above rubber composite material, preferably, the rubber includes one or more of nitrile rubber, fluororubber, hydrogenated nitrile rubber, styrene butadiene rubber, ethylene propylene rubber and silicone rubber.
In the above rubber composite material, preferably, the coupling agent includes one or more combinations of γ -methacryloxypropyltrimethoxysilane (KH570), γ -aminopropyltriethoxysilane (KH550), and tridecafluorooctyltriethoxysilane, but is not limited thereto.
In the above rubber composite material, preferably, the carbon black includes a combination of one or more of N774, N234, N326, N330, N550, and N660, but is not limited thereto.
In the above rubber composite material, preferably, the antioxidant includes a combination of one or more of antioxidant RD (2,2, 4-trimethyl-1, 2-dihydroquinoline polymer), antioxidant AW (6-ethoxy-2, 2, 4-trimethyl-1, 2-dihydroquinoline), antioxidant BLE (9, 9-dimethylacridine), antioxidant 4010NA (N-isopropyl-N '-phenyl-p-phenylenediamine), antioxidant D (N-phenyl-2-naphthylamine), and antioxidant H (N, N' -diphenyl-p-phenylenediamine), but is not limited thereto.
In the above rubber composite material, preferably, the accelerator includes one or a combination of more of an accelerator D (diphenylguanidine), an accelerator TMTD (tetramethylthiuram disulfide), an accelerator ZDC (zinc diethyldithiocarbamate), an accelerator NA-22 (ethylenethiourea), an accelerator M (2-mercaptobenzothiazole), an accelerator DM (2,2' -dithiodibenzothiazole), and an accelerator CZ (N-cyclohexyl-2-benzothiazolesulfenamide), but is not limited thereto.
In the above rubber composite material, preferably, the softener includes a combination of one or more of DBP (dibutyl phthalate), DOP (dioctyl phthalate), DOS (dioctyl dicaprylyl dicaprate), TCP (tricresyl phosphate), stearic acid, pine tar, rosin, ointment, and paraffin, but is not limited thereto.
In the above rubber composite, preferably, the vulcanizing agent includes a combination of one or more of sulfur, bisphenol AF (hexafluorobisphenol a) and DCP (dicumyl peroxide), but is not limited thereto.
In the above rubber composite material, preferably, the scorch retarder includes a combination of one or more of CTP (N-cyclohexylthiophthalimide), oxalic acid, succinic acid, lactic acid, phthalic anhydride, salicylic acid, benzoic acid, and oleic acid, but is not limited thereto.
On the other hand, the invention also provides a preparation method of the rubber composite material, which comprises the following steps:
according to the weight portion, firstly, putting rubber into an internal mixer for internal mixing, then adding nano zinc oxide and an anti-aging agent for continuous internal mixing, then adding a molybdenum disulfide-clay composite material and a coupling agent for continuous internal mixing, then adding half of carbon black and half of a softening agent for continuous internal mixing, finally adding the other half of carbon black and the other half of the softening agent for continuous internal mixing, and cleaning and discharging rubber after the internal mixing is finished to obtain rubber compound;
and (3) putting the rubber compound into an open mill to roll, adding a vulcanizing agent, an accelerator and an anti-scorching agent, mixing, and performing triangular wrapping and sheet discharging by using left and right cutters to obtain the rubber composite material.
In the preparation method, the banburying rotation speed of the banbury mixer is preferably 20 to 50r/min, and the banburying temperature is preferably 50 to 110 ℃.
In the preparation method, preferably, the rubber is added for banburying for 1-3 min; adding nano zinc oxide and an anti-aging agent, and continuously banburying for 1-3 min; adding a molybdenum disulfide-clay composite material and a coupling agent, and continuously banburying for 1-3 min; adding half of the carbon black and half of the softener, and continuously banburying for 1-3 min; adding the other half of carbon black and the other half of softener for continuously banburying for 1-3 min; and the time for cleaning after banburying is 1 min.
In the preparation method, the roller temperature of the roller coating of the rubber compound in the open mill is preferably 30-60 ℃; adding a vulcanizing agent, an accelerant and an anti-coking agent, and mixing at 100-180 ℃ for 30-80 min under the pressure of 5-20 MPa.
In the preparation method, the number of times of the left and right cutters is preferably 3-8; the triangular packaging is performed for 3-8 times.
In another aspect, the invention also provides an application of the rubber composite material as a sealing material in sealing of a main driving system of a shield tunneling machine.
The invention has the beneficial effects that:
in the rubber composite material, molybdenum disulfide uniformly grows on clay minerals in situ by adopting a one-pot hydrothermal method, the size of the clay can be reduced by adopting an ultrasonic-sanding coupling method in the preparation method, meanwhile, the dispersibility of the clay and a mixed solution is further improved, and the prepared molybdenum disulfide-clay composite material is mixed with other compounding agents such as rubber and the like and is subjected to processes such as mixing, vulcanization and the like to prepare the rubber composite material. In the molybdenum disulfide-clay composite material synthesized by the one-pot hydrothermal method and the ultrasonic sanding dispersion technology, molybdenum disulfide and clay form bonding, and the self-agglomeration phenomenon is not easy to occur, so that the molybdenum disulfide-clay composite material can better play the synergistic effect of molybdenum disulfide and clay when being applied to the preparation of rubber materials, the wear resistance of rubber is improved, and the strength of the rubber is greatly improved; the sealing device can be effectively suitable for sealing the main driving system of the shield machine, and has wide application prospect.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention. The starting materials used in the following examples are all commercially available in the art unless otherwise specified.
Example 1:
the embodiment provides a rubber composite material and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) take 1.24g of (NH)4)6Mo7O24·4H2O and 1.07g of CH4N2S is dissolved in 60mL of deionized water, stirred in a beaker for 30min and uniformly stirred to obtain a mixed solution;
(2) then pouring the mixed solution and 1g of clay into an ultrasonic-sand mill in sequence for ultrasonic sanding dispersion for 30min, wherein the ultrasonic power is 500W, the rotational speed of sanding is 2250rpm, and the temperature of sanding is 8 ℃ to obtain dispersion liquid;
(3) pouring the dispersion solution into a 100mL reaction kettle, then placing the reaction kettle into an oven for hydrothermal reaction, setting the temperature of the oven at 230 ℃, raising the temperature at 5 ℃/min, keeping the temperature for 12h, cooling the solution in the reaction kettle to room temperature after the reaction is finished, washing the solution for 3 times by using distilled water, and finally freeze-drying to obtain the molybdenum disulfide-clay composite material (MoS)2@clay)。
(4) Setting the rotating speed of an internal mixer to 35rpm, setting the initial temperature to 60 ℃, and firstly adding 100 parts of NBR3365 raw rubber for internal mixing for 1 min; then adding 4 parts of nano zinc oxide, 1 part of antioxidant 4010NA and 1 part of antioxidant RD, and continuously banburying for 1 min; then adding 12 parts of molybdenum disulfide-clay composite material and 1.2 parts of coupling agent KH570 for continuously banburying for 1.5 min; then adding 20 parts of carbon black N330, 20 parts of carbon black N774 and 5 parts of softener DOP for continuous banburying for 1.5 min; then adding 20 parts of carbon black N330, 20 parts of carbon black N774 and 5 parts of softener DOP for continuously banburying for 1.5 min; cleaning for 1min after banburying is finished, and discharging rubber to obtain rubber compound;
(5) setting the rotation speed of an open mill to be 20rpm, setting the roll temperature to be 40 ℃, and adding dense rubber into the open mill to wrap the roll; then adding 0.8 part of sulfur, 1.5 parts of peroxide vulcanizing agent DCP, 1.1 parts of accelerator CZ, 0.5 part of accelerator DM and 0.3 part of scorch retarder CTP, cutting the mixture 5 times left and right, wrapping the mixture in a triangular bag for 5 times, and then slicing to obtain the rubber composite material; wherein the vulcanization condition of the rubber compound is 155 ℃, the time is 20min and the pressure is 6 MPa.
Comparative example 1:
in the comparative example, the raw material molybdenum disulfide and clay are directly subjected to hydrothermal reaction to distinguish the in-situ hydrothermal reaction in the example 1, so that the molybdenum disulfide-clay composite material is prepared, and the rubber composite material is prepared by using the material. The preparation method comprises the following steps:
(1) 1.12g of MoS was taken2Dispersed in 60mL deionized water and stirred in a beaker for 30min to obtain MoS2An aqueous solution of (a);
(2) then MoS2The water solution and 1g of clay are poured into an ultrasonic-sand mill in sequence for ultrasonic sand grinding dispersion for 30min, the ultrasonic power is 500W, and the rotational speed of sand grinding is 2250rpm, and the sanding temperature is 8 ℃, so as to obtain dispersion liquid;
(3) and pouring the dispersion solution into a 100mL reaction kettle, then putting the reaction kettle into an oven for hydrothermal reaction, setting the temperature of the oven at 230 ℃, raising the temperature at 5 ℃/min, keeping the temperature for 12h, cooling the solution in the reaction kettle to room temperature after the reaction is finished, washing the solution for 3 times by using distilled water, and finally freeze-drying to obtain the molybdenum disulfide-clay composite material.
(4) Setting the rotating speed of an internal mixer to 35rpm, setting the initial temperature to 60 ℃, and firstly adding 100 parts of NBR3365 raw rubber for internal mixing for 1 min; then adding 4 parts of nano zinc oxide, 1 part of antioxidant 4010NA and 1 part of antioxidant RD, and continuously banburying for 1 min; then adding 12 parts of molybdenum disulfide-clay composite material and 1.2 parts of coupling agent KH570 for continuously banburying for 1.5 min; then adding 20 parts of carbon black N330, 20 parts of carbon black N774 and 5 parts of softener DOP for continuous banburying for 1.5 min; then adding 20 parts of carbon black N330, 20 parts of carbon black N774 and 5 parts of softener DOP for continuously banburying for 1.5 min; cleaning for 1min after banburying is finished, and discharging rubber to obtain rubber compound;
(5) setting the rotation speed of an open mill to be 20rpm, setting the roll temperature to be 40 ℃, and adding dense rubber into the open mill to wrap the roll; then adding 0.8 part of sulfur, 1.5 parts of peroxide vulcanizing agent DCP, 1.1 parts of accelerator CZ, 0.5 part of accelerator DM and 0.3 part of scorch retarder CTP, cutting the mixture 5 times left and right, wrapping the mixture in a triangular bag for 5 times, and then slicing to obtain the rubber composite material; wherein the vulcanization condition of the rubber compound is 155 ℃, the time is 20min and the pressure is 6 MPa.
Comparative example 2:
this comparative example was prepared by using ordinary ultrasonic dispersion in the preparation of the molybdenum disulfide-clay composite material, to distinguish the ultrasonic sand-milling dispersion of example 1, to obtain a molybdenum disulfide-clay composite material, and using this material to prepare a rubber composite material. The preparation method comprises the following steps:
(1) take 1.24g of (NH)4)6Mo7O24·4H2O and 1.07g of CH4N2S is dissolved in 60mL of deionized water, stirred in a beaker for 30min and uniformly stirred to obtain a mixed solution;
(2) adding 1g of clay into the mixed solution, and performing ultrasonic treatment for 30min to uniformly disperse the clay to obtain a dispersion solution;
(3) pouring the dispersion solution into a 100mL reaction kettle, then placing the reaction kettle into an oven for hydrothermal reaction, setting the temperature of the oven at 230 ℃, raising the temperature at 5 ℃/min, keeping the temperature for 12h, cooling the solution in the reaction kettle to room temperature after the reaction is finished, washing the solution for 3 times by using distilled water, and finally freeze-drying to obtain the molybdenum disulfide-clay composite material (MoS)2@clay)。
(4) Setting the rotating speed of an internal mixer to 35rpm, setting the initial temperature to 60 ℃, and firstly adding 100 parts of NBR3365 raw rubber for internal mixing for 1 min; then adding 4 parts of nano zinc oxide, 1 part of antioxidant 4010NA and 1 part of antioxidant RD, and continuously banburying for 1 min; then adding 12 parts of molybdenum disulfide-clay composite material and 1.2 parts of coupling agent KH570 for continuously banburying for 1.5 min; then adding 20 parts of carbon black N330, 20 parts of carbon black N774 and 5 parts of softener DOP for continuous banburying for 1.5 min; then adding 20 parts of carbon black N330, 20 parts of carbon black N774 and 5 parts of softener DOP for continuously banburying for 1.5 min; cleaning for 1min after banburying is finished, and discharging rubber to obtain rubber compound;
(5) setting the rotation speed of an open mill to be 20rpm, setting the roll temperature to be 40 ℃, and adding dense rubber into the open mill to wrap the roll; then adding 0.8 part of sulfur, 1.5 parts of peroxide vulcanizing agent DCP, 1.1 parts of accelerator CZ, 0.5 part of accelerator DM and 0.3 part of scorch retarder CTP, cutting the mixture 5 times left and right, wrapping the mixture in a triangular bag for 5 times, and then slicing to obtain the rubber composite material; wherein the vulcanization condition of the rubber compound is 155 ℃, the time is 20min and the pressure is 6 MPa.
Comparative example 3:
in the comparative example, the raw material molybdenum disulfide and clay are directly subjected to hydrothermal reaction, and common ultrasonic dispersion is adopted to distinguish the in-situ hydrothermal reaction and the ultrasonic sanding dispersion of the example 1, so that the molybdenum disulfide-clay composite material is prepared, and the rubber composite material is prepared by using the material. The preparation method comprises the following steps:
(1) 1.12g of MoS was taken2Dispersed in 60mL deionized water and stirred in a beaker for 30min to obtain MoS2An aqueous solution of (a);
(2) 1g of clay was added to M mentioned aboveoS2In the aqueous solution, evenly dispersing by ultrasonic for 30min to obtain a dispersion solution;
(3) and pouring the dispersion solution into a 100mL reaction kettle, then putting the reaction kettle into an oven for hydrothermal reaction, setting the temperature of the oven at 230 ℃, raising the temperature at 5 ℃/min, keeping the temperature for 12h, cooling the solution in the reaction kettle to room temperature after the reaction is finished, washing the solution for 3 times by using distilled water, and finally freeze-drying to obtain the molybdenum disulfide-clay composite material.
(4) Setting the rotating speed of an internal mixer to 35rpm, setting the initial temperature to 60 ℃, and firstly adding 100 parts of NBR3365 raw rubber for internal mixing for 1 min; then adding 4 parts of nano zinc oxide, 1 part of antioxidant 4010NA and 1 part of antioxidant RD, and continuously banburying for 1 min; then adding 12 parts of molybdenum disulfide-clay composite material and 1.2 parts of coupling agent KH570 for continuously banburying for 1.5 min; then adding 20 parts of carbon black N330, 20 parts of carbon black N774 and 5 parts of softener DOP for continuous banburying for 1.5 min; then adding 20 parts of carbon black N330, 20 parts of carbon black N774 and 5 parts of softener DOP for continuously banburying for 1.5 min; cleaning for 1min after banburying is finished, and discharging rubber to obtain rubber compound;
(5) setting the rotation speed of an open mill to be 20rpm, setting the roll temperature to be 40 ℃, and adding dense rubber into the open mill to wrap the roll; then adding 0.8 part of sulfur, 1.5 parts of peroxide vulcanizing agent DCP, 1.1 parts of accelerator CZ, 0.5 part of accelerator DM and 0.3 part of scorch retarder CTP, cutting the mixture 5 times left and right, wrapping the mixture in a triangular bag for 5 times, and then slicing to obtain the rubber composite material; wherein the vulcanization condition of the rubber compound is 155 ℃, the time is 20min and the pressure is 6 MPa.
Comparative example 4:
in the comparative example, the raw materials of molybdenum disulfide and clay are directly mixed and banburied to prepare the rubber composite material, so that the molybdenum disulfide-clay composite material is prepared in the first step in the difference of the example 1, and the specific preparation method is as follows:
(1) setting the rotating speed of an internal mixer to 35rpm, setting the initial temperature to 60 ℃, and firstly adding 100 parts of NBR3365 raw rubber for internal mixing for 1 min; then adding 4 parts of nano zinc oxide, 1 part of antioxidant 4010NA and 1 part of antioxidant RD, and continuously banburying for 1 min; followed by the addition of 6.4 parts of MoS2Continuously banburying 5.6 parts of clay and 1.2 parts of coupling agent KH570 for 1.5 min; then 20 parts of carbon black are addedN330, 20 parts of carbon black N774 and 5 parts of softener DOP, and continuously banburying for 1.5 min; then adding 20 parts of carbon black N330, 20 parts of carbon black N774 and 5 parts of softener DOP for continuously banburying for 1.5 min; cleaning for 1min after banburying is finished, and discharging rubber to obtain rubber compound;
(2) setting the rotation speed of an open mill to be 20rpm, setting the roll temperature to be 40 ℃, and adding dense rubber into the open mill to wrap the roll; then adding 0.8 part of sulfur, 1.5 parts of peroxide curing agent DCP, 1.1 parts of accelerator CZ, 0.5 part of accelerator DM and 0.3 part of scorch retarder DCT, cutting the mixture for 5 times by a left cutter and a right cutter, packaging the mixture in a triangular bag for 5 times, and then slicing the mixture to obtain the rubber composite material; wherein the vulcanization condition of the rubber compound is 155 ℃, the time is 20min and the pressure is 6 MPa.
Comparative example 5:
in this comparative example, the rubber composite material was prepared without adding the molybdenum disulfide-clay composite material, so as to distinguish the rubber composite material prepared by adding the molybdenum disulfide-clay composite material in example 1, the specific preparation method was as follows:
(1) setting the rotating speed of an internal mixer to 35rpm, setting the initial temperature to 60 ℃, and firstly adding 112 parts of NBR3365 raw rubber for internal mixing for 1 min; then adding 4 parts of nano zinc oxide, 1 part of antioxidant 4010NA and 1 part of antioxidant RD, and continuously banburying for 1 min; then adding 1.2 parts of coupling agent KH570 and continuously banburying for 1.5 min; then adding 20 parts of carbon black N330, 20 parts of carbon black N774 and 5 parts of softener DOP for continuous banburying for 1.5 min; then adding 20 parts of carbon black N330, 20 parts of carbon black N774 and 5 parts of softener DOP for continuously banburying for 1.5 min; cleaning for 1min after banburying is finished, and discharging rubber to obtain rubber compound;
(2) setting the rotation speed of an open mill to be 20rpm, setting the roll temperature to be 40 ℃, and adding dense rubber into the open mill to wrap the roll; then adding 0.8 part of sulfur, 1.5 parts of peroxide vulcanizing agent DCP, 1.1 parts of accelerator CZ, 0.5 part of accelerator DM and 0.3 part of scorch retarder CTP, cutting the mixture 5 times left and right, wrapping the mixture in a triangular bag for 5 times, and then slicing to obtain the rubber composite material; wherein the vulcanization condition of the rubber compound is 155 ℃, the time is 20min and the pressure is 6 MPa.
The rubber composite material prepared in example 1 of the present invention and the rubber composite materials prepared in comparative documents 1 to 5 were subjected to strength and wear resistance tests, and the experimental results are shown in table 1 below.
Table 1:
Figure BDA0003199458640000091
from the experimental data in table 1, it can be seen that: compared with comparative examples 1-5, the rubber composite material prepared by the scheme of the invention has more excellent strength performance and wear resistance.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (10)

1. The rubber composite material comprises the following raw material components in parts by weight:
Figure FDA0003199458630000011
2. the rubber composite of claim 1, wherein the molybdenum disulfide-clay composite is prepared by a process comprising:
dissolving ammonium molybdate and thiourea in water and uniformly stirring to obtain a mixed solution;
then mixing the mixed solution and clay, and performing ultrasonic sanding dispersion to obtain a dispersion liquid;
and carrying out hydrothermal reaction on the dispersion solution, washing and drying a reaction product to obtain the molybdenum disulfide-clay composite material.
3. The rubber composite material according to claim 2, wherein the mass ratio of the ammonium molybdate, the thiourea and the clay is (1-2): (1-2): 1.
4. the rubber composite material according to claim 2, wherein the ammonium molybdate and the thiourea are dissolved in water and stirred for 10-30 min;
preferably, the ultrasonic sanding and dispersing equipment is an ultrasonic-sand mill; the ultrasonic power is 200-800W, the rotational speed of sanding is 2000-2500 rpm, the temperature of sanding is 5-15 ℃, and the time of ultrasonic sanding is 10-30 min;
preferably, the temperature rise rate of the hydrothermal reaction is 3-8 ℃/min, the temperature of the hydrothermal reaction is 100-280 ℃, and the heat preservation time of the hydrothermal reaction is 5-12 h.
5. The rubber composite of claim 1, wherein the rubber comprises a combination of one or more of nitrile rubber, viton rubber, hydrogenated nitrile rubber, styrene butadiene rubber, ethylene propylene rubber, and silicone rubber;
preferably, the coupling agent comprises a combination of one or more of gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, and tridecafluorooctyltriethoxysilane;
preferably, the carbon black comprises a combination of one or more of N774, N234, N326, N330, N550 and N660.
6. The rubber composite of claim 1, wherein the antioxidant comprises a combination of one or more of antioxidant RD, antioxidant AW, antioxidant BLE, antioxidant 4010NA, antioxidant D, and antioxidant H;
preferably, the promoter comprises a combination of one or more of promoter D, promoter TMTD, promoter ZDC, promoter NA-22, promoter M, promoter DM and promoter CZ;
preferably, the softener comprises a combination of one or more of DBP, DOP, DOS, TCP, stearic acid, pine tar, rosin, ointment and paraffin;
preferably, the vulcanizing agent comprises a combination of one or more of sulfur, bisphenol AF and DCP;
preferably, the scorch retarder comprises a combination of one or more of CTP, oxalic acid, succinic acid, lactic acid, phthalic anhydride, salicylic acid, benzoic acid, and oleic acid.
7. A method of preparing a rubber composite as claimed in any one of claims 1 to 6, comprising the steps of:
according to the weight portion, firstly, putting rubber into an internal mixer for internal mixing, then adding nano zinc oxide and an anti-aging agent for continuous internal mixing, then adding a molybdenum disulfide-clay composite material and a coupling agent for continuous internal mixing, then adding half of carbon black and half of a softening agent for continuous internal mixing, finally adding the other half of carbon black and the other half of the softening agent for continuous internal mixing, and cleaning and discharging rubber after the internal mixing is finished to obtain rubber compound;
and (3) putting the rubber compound into an open mill to roll, adding a vulcanizing agent, an accelerator and an anti-scorching agent, mixing, and performing triangular wrapping and sheet discharging by using left and right cutters to obtain the rubber composite material.
8. The preparation method of claim 7, wherein the banburying speed of the banbury mixer is 20-50 r/min, and the banburying temperature is 50-110 ℃;
preferably, the rubber is added for banburying for 1-3 min; adding nano zinc oxide and an anti-aging agent, and continuously banburying for 1-3 min; adding a molybdenum disulfide-clay composite material and a coupling agent, and continuously banburying for 1-3 min; adding half of the carbon black and half of the softener, and continuously banburying for 1-3 min; adding the other half of carbon black and the other half of softener for continuously banburying for 1-3 min; and the time for cleaning after banburying is 1 min.
9. The method for preparing the rubber composition as claimed in claim 7, wherein the roll temperature of the rubber composition for roll coating in the open mill is 30 to 60 ℃; adding a vulcanizing agent, an accelerant and an anti-coking agent, and mixing at 100-180 ℃ for 30-80 min under the pressure of 5-20 MPa;
preferably, the number of times of the left and right cutters is 3-8; the triangular packaging is performed for 3-8 times.
10. Use of the rubber composite material according to any one of claims 1 to 6 as a sealing material in sealing a main driving system of a shield tunneling machine.
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