CN114672078A

CN114672078A - Modified rubber and preparation method thereof

Info

Publication number: CN114672078A
Application number: CN202210440341.5A
Authority: CN
Inventors: 施以进; 陈颖; 余昭军
Original assignee: Individual
Current assignee: Guangdong Border Crossing Intelligent Technology Co ltd
Priority date: 2022-04-26
Filing date: 2022-04-26
Publication date: 2022-06-28
Anticipated expiration: 2042-04-26
Also published as: CN114672078B

Abstract

The invention provides a modified rubber and a preparation method thereof, belonging to the technical field of rubber. The method comprises the following steps: s1, preparing modified graphite; s2, pretreating polyester fibers; s3, preparing a catalyst solution; s4, preparing polydopamine modified polyester fibers; s5, preparing modified polyester fibers; s6, processing an antioxidant; s7, preparing modified rubber. The raw materials of the invention have wide sources, the preparation method is simple, and the raw materials are mixed and vulcanized to form stable modified rubber, which has good aging resistance, low temperature performance, weather resistance, mechanical performance, processing performance and physicochemical performance, and has wide application prospect.

Description

Modified rubber and preparation method thereof

Technical Field

The invention relates to the technical field of rubber, in particular to modified rubber and a preparation method thereof.

Background

The rubber occupies an important position in daily life and social and economic construction, and is widely applied to tires, sealing parts, damping products, conveying belts and the like due to the advantages of high strength, good elasticity, wear resistance, good insulating property and the like. However, in practical applications, in order to further improve the properties of the rubber, some unsaturated rubbers, such as isoprene rubber, polybutadiene rubber (BR), styrene-butadiene rubber (SBR), etc., may be modified by introducing a specific functional group into a molecule through a chemical reaction of C = C bond.

In recent years, the rubber industry in our country has been rapidly developed, rubber products are widely applied to various industries, and Nitrile Butadiene Rubber (NBR) prepared by emulsion polymerization of butadiene and acrylonitrile has good oil resistance, heat resistance and strong adhesion due to the existence of acrylonitrile, and is widely applied to various oil resistant products, such as lubricating oil, fuel oil tanks, rubber parts of fluid media, sealing parts and the like. However, in the using process of the NBR, due to the change of factors such as heat, oxygen, light, water and the like in the environment, thermo-oxidative aging is easy to occur, so that the mechanical property and the physical and chemical properties are reduced, when the service performance of the product is influenced, the rubber can continuously degrade and crosslink molecular chains, and when the decomposition rate is too high, the molecular weight of the rubber is reduced, the product is sticky, and the strength is reduced; on the contrary, the surface is hardened and loses elasticity, and the aging is effectively delayed by adding the anti-aging agent into the rubber.

The Chinese invention patent 201810341505.2 provides a modified powdered nitrile rubber and an application thereof, wherein the modified powdered nitrile rubber comprises the following components in parts by weight: 60-70 parts of semi-crosslinked powder nitrile rubber, 10-20 parts of fully crosslinked powder nitrile rubber and 10-30 parts of calcium terephthalate. The preparation method of the modified powder nitrile rubber comprises the following process steps: mixing and heating calcium terephthalate in a high-speed mixer with a heating function to 50-60 ℃, adding fully-crosslinked powdered nitrile rubber, mixing for 5min, adding semi-crosslinked powdered nitrile rubber, and mixing for 3-5min to obtain the modified powdered nitrile rubber.

The Chinese patent 201410592735.8 provides a modified nitrile rubber and a preparation method thereof, which comprises the following mixed components: 100 parts of nitrile rubber; 5-10 parts of zinc oxide; 5-15 parts of magnesium oxide; 1-2 parts of stearic acid; 40-80 parts of carbon black; 10-45 parts by weight of strong grinding powder; 5-15 parts of a plasticizer; 2-3 parts of an anti-aging agent; 0.5 to 1.5 weight portions of vulcanizing agent; 3-5 parts of an accelerator. The preparation method comprises the following steps: and (3) uniformly mixing the magnesium oxide and the strong grinding powder in advance according to the dosage, and then mixing with other components according to the dosage to obtain the modified nitrile rubber.

The modified nitrile rubber obtained by the invention has the advantages of no obvious improvement on mechanical property and poor aging resistance due to uneven dispersion.

Disclosure of Invention

The invention aims to provide a modified rubber and a preparation method thereof, the modified rubber has wide raw material sources and simple preparation method, and the raw materials are mixed and vulcanized to form stable modified rubber which has good aging resistance, low-temperature performance, weather resistance, mechanical performance, processability and physicochemical performance and has wide application prospect.

The technical scheme of the invention is realized as follows:

the invention provides a preparation method of modified rubber, which comprises the following steps:

s1, preparing modified graphite: soaking graphite in alkali liquor, cleaning, drying, ball-milling, sieving, adding ionic liquid, heating and stirring by microwave, performing ultrasonic treatment, centrifuging, washing solids, and drying to obtain modified graphite;

s2, pretreatment of polyester fibers: adding polyester fiber into an ethanol aqueous solution containing alkali, heating to boil, filtering, and washing to obtain pretreated polyester fiber;

s3, preparing a catalyst solution: dissolving cobalt salt in Tris-HCl buffer solution to obtain catalyst solution;

s4, preparing polydopamine modified polyester fibers: dissolving dopamine hydrochloride in water, adding the pretreated polyester fiber prepared in the step S2, stirring at room temperature, dropwise adding the catalyst solution prepared in the step S3, heating for reaction, filtering, washing and drying to obtain polydopamine modified polyester fiber;

s5, preparing modified polyester fibers: dissolving a composite silane coupling agent in ethanol, adding the polydopamine modified polyester fiber prepared in the step S4, heating, stirring, reacting, filtering, washing and drying to obtain modified polyester fiber;

s6, antioxidant treatment: ball-milling the antioxidant, sieving, and drying to obtain antioxidant powder;

s7, preparing modified rubber: and (3) rolling the nitrile rubber after the first open milling, adding the modified graphite prepared in the step S1, the modified polyester fiber prepared in the step S5, the antioxidant powder prepared in the step S6, a plasticizer, a reinforcing filler and an anti-aging agent, mixing uniformly, adding an accelerator and a vulcanizing agent, carrying out second open milling, and vulcanizing to obtain the modified rubber.

As a further improvement of the invention, in the step S1, the ball milling time is 2-4h, and the mesh number of the screen is 500-700 meshes; the microwave heating temperature is 60-80 ℃, and the stirring is carried out for 30-40 min; the ultrasonic power is 1000-2000W, and the time is 1-3 h; the alkali liquor is 1-2mol/L NaOH solution or KOH solution; the ionic liquid is imidazolyl ionic liquid and is selected from at least one of 1-butyl-3-ethylimidazole chlorine, 1-butyl-3-ethylimidazole tetrafluoroboric acid, 1-butyl-3-ethylimidazole hexafluorophosphate, 1-butyl-3-ethylimidazole acetic acid, 1, 3-dimethyl imidazole tetrafluoroboric acid, 1-butyl-3-methylimidazole chlorine, 1-butyl-3-methylimidazole tetrafluoroboric acid, 1-butyl-3-methylimidazole hexafluorophosphate and 1-butyl-3-methylimidazole acetic acid.

As a further improvement of the invention, the ethanol aqueous solution containing alkali in the step S2 is ethanol aqueous solution containing 5-10wt% of NaOH or KOH, wherein the ethanol content is 30-50 wt%; the heating boiling time is 20-30 min.

As a further improvement of the present invention, in step S3, the cobalt salt is at least one selected from cobalt sulfate, cobalt chloride and cobalt bromide; the pH value of the Tris-HCl buffer solution is 7.8-8.2, and Co in the catalyst solution²⁺The ion concentration is 0.5-1.2 wt%.

As a further improvement of the invention, the mass ratio of the dopamine hydrochloride, the pretreated polyester fiber and the catalyst solution in the step S4 is (20-40): 100: (4-7); the heating temperature is 50-70 ℃ and the time is 3-5 h.

As a further improvement of the invention, the composite silane coupling agent in the step S5 is a mixture of a silane coupling agent with an amino group and a silane coupling agent with a hydroxyl group, wherein the silane coupling agent with an amino group is selected from KH550, A-1110, A-1120, KNM-602, Nanda-42, Nanda-73, A-1130, Y-5691, KH602 and KH 792; the silane coupling agent with hydroxyl is selected from at least one of 3- [ bis (2-hydroxyethyl) amino ] propane triethoxysilane and trimethylhydroxysilane; preferably, the compound silane coupling agent is a compound mixture of KH550 and 3- [ bis (2-hydroxyethyl) amino ] propane triethoxysilane, and the mass ratio is (3-7): 2; the mass ratio of the composite silane coupling agent to the polydopamine modified polyester fiber is (5-7): 50; the method comprises the following steps of; the heating temperature is 70-90 ℃, and the time is 1-3 h.

As a further improvement of the invention, the mesh number of the screen in the step S6 is 200-500 meshes; the antioxidant is at least one selected from antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 626 and antioxidant 3114; preferably, the antioxidant is a compound mixture of an antioxidant 1076 and an antioxidant 3114, and the mass ratio is (3-5): 1.

as a further improvement of the present invention, in step S7, the plasticizer is at least one selected from the group consisting of polyether plasticizers, polyester plasticizers, adipic acid ether ester plasticizers, and fatty plasticizers; the reinforcing filler is at least one selected from carbon nano tubes, carbon black, argil and nano calcium carbonate; the anti-aging agent is at least one selected from p-diphenylamine, N-nickel dibutyldithiocarbamate, 2, 4-trimethyl-1, 2-dihydroquinoline, 2-mercaptobenzimidazole, N-isopropyl-N-phenyl-p-phenylenediamine and 4,4 '-bis (a, a' -dimethylbenzyl) diphenylamine; the accelerator is selected from at least one of tetramethyl thiuram disulfide, triallyl cyanurate, N '-m-phenylene bismaleimide, 2' -dibenzothiazyl disulfide and N-cyclohexyl-2-benzothiazole sulfonamide; the vulcanizing agent is at least one selected from sulfur, ethylene thiourea, 2,4, 6-trithiol thiotriazine, dicumyl peroxide and di-o-tolylguanidine; the mass ratio of the nitrile rubber, the modified graphite, the modified polyester fiber, the antioxidant powder, the plasticizer, the reinforcing filler, the anti-aging agent, the accelerator and the vulcanizing agent is 100: (12-17): (15-22): (3-5): (2-7): (5-15): (0.2-0.7): (0.2-2): (0.5-1); the first open milling time is 10-15 min; the second open milling time is 3-5 min; the vulcanization condition is that the temperature is 165-175 ℃ for 20-30min under the pressure of 10-12 MPa; the mixing time is 20-40 min.

As a further improvement of the invention, the method specifically comprises the following steps:

s1, preparing modified graphite: soaking graphite in 1-2mol/L NaOH solution or KOH solution for 1-2h, cleaning, drying, ball-milling for 2-4h, sieving with a 500-ion-containing 700-mesh sieve, adding ionic liquid, heating with microwave at 60-80 ℃, stirring for 30-40min, performing 1000-ion-containing 2000W ultrasonic treatment for 1-3h, centrifuging, washing solids, and drying to obtain modified graphite;

s2, pretreatment of polyester fibers: adding polyester fiber into ethanol water solution containing 5-10wt% of NaOH or KOH, wherein the ethanol content is 30-50wt%, heating and boiling for 20-30min, filtering, and washing to obtain pretreated polyester fiber;

s3, preparing a catalyst solution: dissolving cobalt salt in Tris-HCl buffer solution with the pH value of 7.8-8.2 to obtain catalyst solution, wherein Co in the catalyst solution²⁺The ion concentration is 0.5-1.2 wt%;

s4, preparing polydopamine modified polyester fibers: dissolving 20-40 parts by weight of dopamine hydrochloride in water, adding 100 parts by weight of the pretreated polyester fiber prepared in the step S2, stirring at room temperature, dropwise adding 4-7 parts by weight of the catalyst solution prepared in the step S3, heating to 50-70 ℃, reacting for 3-5 hours, filtering, washing, and drying to obtain the polydopamine modified polyester fiber;

s5, preparing modified polyester fibers: dissolving 5-7 parts by weight of composite silane coupling agent in ethanol, adding 50 parts by weight of polydopamine modified polyester fiber prepared in the step S4, heating to 70-90 ℃, stirring for reaction for 1-3h, filtering, washing and drying to obtain modified polyester fiber;

s6, antioxidant treatment: ball-milling the antioxidant, sieving with a 200-sand 500-mesh sieve, and drying to obtain antioxidant powder;

s7, preparing modified rubber: and (2) milling 100 parts by weight of nitrile rubber for 10-15min, then roll wrapping, adding 12-17 parts by weight of the modified graphite prepared in the step S1, 15-22 parts by weight of the modified polyester fiber prepared in the step S5, 3-5 parts by weight of the antioxidant powder prepared in the step S6, 2-7 parts by weight of plasticizer, 5-15 parts by weight of reinforcing filler and 0.2-0.7 part by weight of anti-aging agent, mixing for 20-40min, adding 0.2-2 parts by weight of accelerator and 0.5-1 part by weight of vulcanizing agent after uniform mixing, milling for 3-5min, vulcanizing at the pressure of 10-12MPa and the temperature of 175 ℃ of 165-175 ℃ for 20-30min, and obtaining the modified rubber.

The invention further protects the modified rubber prepared by the preparation method.

The invention has the following beneficial effects: according to the invention, graphite is a non-polar layered simple substance and can generate cation-pi and pi-pi effects with imidazole-based cations of ionic liquid, so that the ionic liquid can be stably attached to the surface of the graphite, non-covalent bond modification is realized, and meanwhile, the structure of the graphite is not damaged or changed;

on the other hand, after the polyester fiber is subjected to alkali treatment, a plurality of hydroxyl structures are formed on the surface of the polyester fiber, dopamine is further easily loaded, a polydopamine molecular chain is generated in situ under the action of a catalyst, and the polydopamine molecular chain can be well dispersed in a matrix to form a filler network structure after the nitrile butadiene rubber matrix is added, meanwhile, the adhesion of the polyester fiber interface is obviously improved, and the toughness of the modified rubber can be obviously improved;

the polydopamine modified polyester fiber is further modified by a composite silane coupling agent, the composite silane coupling agent is a silane coupling agent with amino and a silane coupling agent with hydroxyl, a large number of hydroxyl and amino groups are formed on the surface of the fiber, the amino and hydroxyl positions can form hydrogen bonds with nitrogen on the imidazolyl group on the ionic liquid modified graphite particle and a CN group of the nitrile rubber, and simultaneously can form hydrogen bonds with the hydroxyl part of the antioxidant, so that the antioxidant, the modified polyester fiber and the modified graphite can form a stable network structure in a nitrile rubber matrix, and the mechanical property and the aging resistance of the nitrile rubber can be obviously improved.

The antioxidant is a compound mixture of the antioxidant 1076 and the antioxidant 3114, the antioxidant 1076 is a micromolecular antioxidant with hydroxyl, and the antioxidant 3114 is a micromolecular antioxidant with 3 hydroxyl which can form stable hydrogen bonds with hydroxyl or amino on the surface of the modified polyester fiber, so that the antioxidant is uniformly dispersed in a nitrile rubber matrix to form a network structure, and the thermal-oxidative aging resistance, the light aging resistance, the low-temperature performance and the weather resistance of the rubber are obviously improved.

The raw materials of the invention have wide sources, the preparation method is simple, and the raw materials are mixed and vulcanized to form stable modified rubber, which has good aging resistance, low temperature performance, weather resistance, mechanical performance, processing performance and physicochemical performance, and has wide application prospect.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

Fig. 1 is an SEM image of the polydopamine modified polyester fiber obtained in step S4 of example 1.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Butyl-3-ethylimidazole chloride, 99%, Shanghai Fujie chemical Co., Ltd; polyester fiber with the diameter of 10-25 mu m, the breaking strength of more than 500MPa, the breaking growth rate of more than 15 percent and the length of 5-7mm, and is made of a new material, Inc. of Shandong Haosen; graphite with carbon content over 97%, crystal grain size less than 0.1mm, Mohs hardness of 1-2, Shijiazhuang Huabang mineral products Co.

Example 1

The embodiment provides a preparation method of modified rubber, which specifically comprises the following steps:

s1, preparing modified graphite: adding 100 parts by weight of graphite into 200 parts by weight of 1mol/L NaOH solution, soaking for 1h, cleaning, drying at 70 ℃ for 2h, ball-milling for 2h, sieving with a 500-mesh sieve, adding 1-butyl-3-ethylimidazole chloride, heating with microwave to 60 ℃, stirring for 30min, performing 1000W ultrasonic treatment for 1h, centrifuging at 3000r/min for 15min, washing the solid with deionized water, and drying at 70 ℃ for 2h to obtain modified graphite;

s2, pretreatment of polyester fibers: adding 100 parts by weight of polyester fiber into 200 parts by weight of ethanol water solution containing 5wt% of NaOH, wherein the ethanol content is 30wt%, heating and boiling for 20min, filtering, and washing with deionized water to obtain pretreated polyester fiber;

s3, preparing a catalyst solution: dissolving cobalt sulfate in Tris-HCl buffer solution with the pH value of 7.8 to obtain catalyst solution, wherein Co in the catalyst solution²⁺The ion concentration is 0.5 wt%;

s4, preparing polydopamine modified polyester fibers: dissolving 20 parts by weight of dopamine hydrochloride in 100 parts by weight of water, adding 100 parts by weight of the pretreated polyester fiber prepared in the step S2, stirring for 30min at room temperature, dropwise adding 4 parts by weight of the catalyst solution prepared in the step S3, heating to 50 ℃, reacting for 3h, filtering, washing with deionized water, and drying at 70 ℃ for 2h to obtain polydopamine modified polyester fiber; fig. 1 is an SEM image of the prepared polydopamine modified polyester fiber, and it can be seen that a layer of polydopamine film is loaded on the surface of the polyester fiber.

S5, preparing modified polyester fibers: dissolving 5 parts by weight of composite silane coupling agent in 100 parts by weight of ethanol, adding 50 parts by weight of polydopamine modified polyester fiber prepared in the step S4, heating to 70 ℃, stirring and reacting for 1 hour, filtering, washing with deionized water, and drying at 70 ℃ for 2 hours to obtain modified polyester fiber; the composite silane coupling agent is a compound mixture of KH550 and 3- [ bis (2-hydroxyethyl) amino ] propane triethoxysilane, and the mass ratio is 3: 2;

s6, antioxidant treatment: ball-milling the antioxidant, sieving with a 200-mesh sieve, and drying at 70 deg.C for 2h to obtain antioxidant powder; the antioxidant is a compound mixture of an antioxidant 1076 and an antioxidant 3114, and the mass ratio is 3: 1;

s7, preparing modified rubber: and (2) milling 100 parts by weight of nitrile rubber for 10min, then rolling, adding 12 parts by weight of the modified graphite prepared in the step S1, 15 parts by weight of the modified polyester fiber prepared in the step S5, 3 parts by weight of the antioxidant powder prepared in the step S6, 2 parts by weight of plasticizer TP-759, 5 parts by weight of argil and 0.2 part by weight of N-isopropyl-N-phenyl-p-phenylenediamine, mixing for 20min, uniformly mixing, adding 0.2 part by weight of triallyl cyanurate and 0.5 part by weight of di-o-tolylguanidine, milling for 3min, vulcanizing for 20min at 165 ℃ under the pressure of 10MPa, and thus obtaining the modified rubber.

Example 2

s1, preparing modified graphite: adding 100 parts by weight of graphite into 200 parts by weight of 2mol/L KOH solution, soaking for 2h, cleaning, drying at 70 ℃ for 2h, ball-milling for 4h, sieving by a 700-mesh sieve, adding 1-butyl-3-ethylimidazole chloride, heating by microwave to 80 ℃, stirring for 40min, carrying out 2000W ultrasonic treatment for 3h, centrifuging at 3000r/min for 15min, washing the solid with deionized water, and drying at 70 ℃ for 2h to obtain modified graphite;

s2, pretreatment of polyester fibers: adding 100 parts by weight of polyester fiber into 200 parts by weight of ethanol water solution containing 10wt% of KOH, wherein the ethanol content is 50wt%, heating and boiling for 30min, filtering, and washing with deionized water to obtain pretreated polyester fiber;

s3, preparing a catalyst solution: dissolving cobalt bromide in Tris-HCl buffer solution with the pH value of 8.2 to obtain catalyst solution, wherein Co in the catalyst solution²⁺The ion concentration was 1.2 wt%;

s4, preparing polydopamine modified polyester fibers: dissolving 40 parts by weight of dopamine hydrochloride in 100 parts by weight of water, adding 100 parts by weight of the pretreated polyester fiber prepared in the step S2, stirring for 30min at room temperature, dropwise adding 7 parts by weight of the catalyst solution prepared in the step S3, heating to 70 ℃, reacting for 5h, filtering, washing with deionized water, and drying at 70 ℃ for 2h to obtain polydopamine modified polyester fiber;

s5, preparing modified polyester fibers: dissolving 7 parts by weight of composite silane coupling agent in 100 parts by weight of ethanol, adding 50 parts by weight of polydopamine modified polyester fiber prepared in the step S4, heating to 90 ℃, stirring and reacting for 3 hours, filtering, washing with deionized water, and drying at 70 ℃ for 2 hours to obtain modified polyester fiber; the composite silane coupling agent is a compound mixture of KH550 and 3- [ bis (2-hydroxyethyl) amino ] propane triethoxysilane, and the mass ratio is 7: 2;

s6, antioxidant treatment: ball-milling the antioxidant, sieving with a 500-mesh sieve, and drying at 70 deg.C for 2h to obtain antioxidant powder; the antioxidant is a compound mixture of an antioxidant 1076 and an antioxidant 3114, and the mass ratio is 5: 1;

s7, preparing modified rubber: and (2) milling 100 parts by weight of nitrile rubber for 15min, then wrapping the nitrile rubber by a roller, adding 17 parts by weight of the modified graphite prepared in the step S1, 22 parts by weight of the modified polyester fiber prepared in the step S5, 5 parts by weight of the antioxidant powder prepared in the step S6, 7 parts by weight of the plasticizer TP-90B, 15 parts by weight of the carbon nano tube and 0.7 part by weight of p-diphenylamine, mixing for 40min, uniformly mixing, adding 2 parts by weight of 2, 2' -dibenzothiazyl disulfide and 1 part by weight of dicumyl peroxide, milling for 5min, and vulcanizing for 30min at 175 ℃ under the pressure of 12MPa to obtain the modified rubber.

Example 3

s1, preparing modified graphite: adding 100 parts by weight of graphite into 200 parts by weight of 1.5mol/L NaOH solution, soaking for 1.5h, cleaning, drying at 70 ℃ for 2h, ball-milling for 3h, sieving with a 600-mesh sieve, adding 1-butyl-3-ethylimidazole chloride, heating to 70 ℃ by microwave, stirring for 35min, performing 1500W ultrasonic treatment for 3h, centrifuging at 3000r/min for 15min, washing the solid with deionized water, and drying at 70 ℃ for 2h to obtain modified graphite;

s2, pretreatment of polyester fibers: adding 100 parts by weight of polyester fiber into 200 parts by weight of ethanol water solution containing 7wt% of NaOH, wherein the ethanol content is 40wt%, heating and boiling for 25min, filtering, and washing with deionized water to obtain pretreated polyester fiber;

s3, preparing a catalyst solution: dissolving cobalt chloride in Tris-HCl buffer solution with the pH value of 8 to obtain catalyst solution, wherein Co in the catalyst solution²⁺The ion concentration was 0.9 wt%;

s4, preparing polydopamine modified polyester fibers: dissolving 30 parts by weight of dopamine hydrochloride in 100 parts by weight of water, adding 100 parts by weight of the pretreated polyester fiber prepared in the step S2, stirring for 30min at room temperature, dropwise adding 5 parts by weight of the catalyst solution prepared in the step S3, heating to 60 ℃, reacting for 4h, filtering, washing with deionized water, and drying at 70 ℃ for 2h to obtain polydopamine modified polyester fiber;

s5, preparing modified polyester fibers: dissolving 6 parts by weight of composite silane coupling agent in 100 parts by weight of ethanol, adding 50 parts by weight of polydopamine modified polyester fiber prepared in the step S4, heating to 80 ℃, stirring and reacting for 3 hours, filtering, washing with deionized water, and drying at 70 ℃ for 2 hours to obtain modified polyester fiber; the composite silane coupling agent is a compound mixture of KH550 and 3- [ bis (2-hydroxyethyl) amino ] propane triethoxysilane, and the mass ratio is 5: 2;

s6, antioxidant treatment: ball-milling the antioxidant, sieving with 350 mesh sieve, and drying at 70 deg.C for 2 hr to obtain antioxidant powder; the antioxidant is a compound mixture of an antioxidant 1076 and an antioxidant 3114, and the mass ratio is 4: 1;

s7, preparing modified rubber: and (2) rolling 100 parts by weight of nitrile rubber after 12min, adding 15 parts by weight of the modified graphite prepared in the step S1, 18 parts by weight of the modified polyester fiber prepared in the step S5, 4 parts by weight of the antioxidant powder prepared in the step S6, 5 parts by weight of the plasticizer RS-107, 10 parts by weight of carbon black and 0.5 part by weight of nickel N, N-dibutyl dithiocarbamate, mixing for 30min, adding 1 part by weight of tetramethyl thiuram disulfide and 0.7 part by weight of sulfur after uniform mixing, and vulcanizing for 25min at the pressure of 11MPa and the temperature of 170 ℃ under the condition of 4min after rolling to obtain the modified rubber.

Example 4

Compared with example 3, the antioxidant is antioxidant 1076, and other conditions are not changed.

Example 5

The antioxidant was 3114 as compared with example 3, and the other conditions were not changed.

Example 6

Compared with example 3, the composite silane coupling agent is KH550, and other conditions are not changed.

Example 7

Compared with the embodiment 3, the composite silane coupling agent is 3- [ bis (2-hydroxyethyl) amino ] propane triethoxysilane, and other conditions are not changed.

Comparative example 1

Compared with the example 3, the graphite in the step S1 is not modified by the ionic liquid 1-butyl-3-ethylimidazole chloride.

The method specifically comprises the following steps:

s1, preparing graphite powder: adding 100 parts by weight of graphite into 200 parts by weight of 1.5mol/L NaOH solution, soaking for 1.5h, cleaning, drying at 70 ℃ for 2h, ball-milling for 3h, sieving with a 600-mesh sieve, and drying at 70 ℃ for 2h to obtain graphite powder;

s3, preparing a catalyst solution: dissolving cobalt chloride in Tris-HCl buffer solution with the pH value of 8 to obtain catalyst solution, wherein Co in the catalyst solution²⁺The ion concentration is 0.9 wt%;

s7, preparing modified rubber: and (2) rolling 100 parts by weight of nitrile rubber after 12min, adding 15 parts by weight of graphite powder prepared in the step S1, 18 parts by weight of modified polyester fiber prepared in the step S5, 4 parts by weight of antioxidant powder prepared in the step S6, 5 parts by weight of plasticizer RS-107, 10 parts by weight of carbon black and 0.5 part by weight of nickel N, N-dibutyl dithiocarbamate, mixing for 30min, adding 1 part by weight of tetramethyl thiuram disulfide and 0.7 part by weight of sulfur after uniform mixing, and vulcanizing for 25min at the pressure of 11MPa and the temperature of 170 ℃ under the condition of 4min after rolling to obtain the modified rubber.

Comparative example 2

Compared with the modified graphite prepared in the example 3, the modified graphite prepared in the step S1 is not added, and other conditions are not changed.

The method specifically comprises the following steps:

s1, pretreatment of polyester fibers: adding 100 parts by weight of polyester fiber into 200 parts by weight of ethanol water solution containing 7wt% of NaOH, wherein the ethanol content is 40wt%, heating and boiling for 25min, filtering, and washing with deionized water to obtain pretreated polyester fiber;

s2, preparation of a catalyst solution: dissolving cobalt chloride in Tris-HCl buffer solution with the pH value of 8 to obtain catalyst solution, wherein Co in the catalyst solution²⁺The ion concentration was 0.9 wt%;

s3, preparing polydopamine modified polyester fibers: dissolving 30 parts by weight of dopamine hydrochloride in 100 parts by weight of water, adding 100 parts by weight of the pretreated polyester fiber prepared in the step S2, stirring for 30min at room temperature, dropwise adding 5 parts by weight of the catalyst solution prepared in the step S2, heating to 60 ℃, reacting for 4h, filtering, washing with deionized water, and drying at 70 ℃ for 2h to obtain polydopamine modified polyester fiber;

preparation of S4 modified polyester fiber: dissolving 6 parts by weight of composite silane coupling agent in 100 parts by weight of ethanol, adding 50 parts by weight of polydopamine modified polyester fiber prepared in the step S3, heating to 80 ℃, stirring and reacting for 3 hours, filtering, washing with deionized water, and drying at 70 ℃ for 2 hours to obtain modified polyester fiber; the composite silane coupling agent is a compound mixture of KH550 and 3- [ bis (2-hydroxyethyl) amino ] propane triethoxysilane, and the mass ratio is 5: 2;

s5, antioxidant treatment: ball-milling the antioxidant, sieving with 350 mesh sieve, and drying at 70 deg.C for 2 hr to obtain antioxidant powder; the antioxidant is a compound mixture of an antioxidant 1076 and an antioxidant 3114, and the mass ratio is 4: 1;

s6, preparing modified rubber: and (2) rolling 100 parts by weight of nitrile rubber after 12min, adding 33 parts by weight of the modified polyester fiber prepared in the step S4, 4 parts by weight of the antioxidant powder prepared in the step S5, 5 parts by weight of plasticizer RS-107, 10 parts by weight of carbon black and 0.5 part by weight of nickel N, N-dibutyl dithiocarbamate, mixing for 30min, adding 1 part by weight of tetramethyl thiuram disulfide and 0.7 part by weight of sulfur after uniformly mixing, and vulcanizing at 170 ℃ for 25min under the pressure of 11MPa after 4min and 11MPa, thereby obtaining the modified rubber.

Comparative example 3

Compared with the example 3, the polyester fiber obtained in the step S4 is not modified by polydopamine, and other conditions are not changed.

The method specifically comprises the following steps:

s3, preparing modified polyester fibers: dissolving 6 parts by weight of composite silane coupling agent in 100 parts by weight of ethanol, adding 50 parts by weight of the pretreated polyester fiber prepared in the step S2, heating to 80 ℃, stirring and reacting for 3 hours, filtering, washing with deionized water, and drying at 70 ℃ for 2 hours to obtain modified polyester fiber; the composite silane coupling agent is a compound mixture of KH550 and 3- [ bis (2-hydroxyethyl) amino ] propane triethoxysilane, and the mass ratio is 5: 2;

s4, processing an antioxidant: ball-milling the antioxidant, sieving with 350 mesh sieve, and drying at 70 deg.C for 2 hr to obtain antioxidant powder; the antioxidant is a compound mixture of an antioxidant 1076 and an antioxidant 3114, and the mass ratio is 4: 1;

s5, preparing modified rubber: and (2) rolling 100 parts by weight of nitrile rubber after 12min, adding 15 parts by weight of the modified graphite prepared in the step S1, 18 parts by weight of the modified polyester fiber prepared in the step S3, 4 parts by weight of the antioxidant powder prepared in the step S4, 5 parts by weight of the plasticizer RS-107, 10 parts by weight of carbon black and 0.5 part by weight of nickel N, N-dibutyl dithiocarbamate, mixing for 30min, adding 1 part by weight of tetramethyl thiuram disulfide and 0.7 part by weight of sulfur after uniform mixing, and vulcanizing for 25min at the pressure of 11MPa and the temperature of 170 ℃ under the condition of 4min after rolling to obtain the modified rubber.

Comparative example 4

The modification treatment described in step S5 was not performed, and other conditions were not changed, as compared with example 3.

The method specifically comprises the following steps:

s3, preparing a catalyst solution: will chloridizeDissolving cobalt in Tris-HCl buffer solution with the pH value of 8 to obtain catalyst solution, wherein Co in the catalyst solution²⁺The ion concentration is 0.9 wt%;

s4, preparing the polydopamine modified polyester fiber: dissolving 30 parts by weight of dopamine hydrochloride in 100 parts by weight of water, adding 100 parts by weight of the pretreated polyester fiber prepared in the step S2, stirring for 30min at room temperature, dropwise adding 5 parts by weight of the catalyst solution prepared in the step S3, heating to 60 ℃, reacting for 4h, filtering, washing with deionized water, and drying at 70 ℃ for 2h to obtain polydopamine modified polyester fiber;

s6, preparing modified rubber: and (2) rolling 100 parts by weight of nitrile rubber after 12min, adding 15 parts by weight of the modified graphite prepared in the step S1, 18 parts by weight of the polydopamine modified polyester fiber prepared in the step S4, 4 parts by weight of the antioxidant powder prepared in the step S5, 5 parts by weight of the plasticizer RS-107, 10 parts by weight of carbon black and 0.5 part by weight of N, N-dibutyl nickel dithiocarbamate, mixing for 30min, adding 1 part by weight of tetramethyl thiuram disulfide and 0.7 part by weight of sulfur after uniform mixing, and vulcanizing for 25min at the pressure of 11MPa and 170 ℃ to obtain the modified rubber.

Comparative example 5

Compared with the modified polyester fiber prepared in the example 3, the modified polyester fiber prepared in the step S5 is not added, and other conditions are not changed.

The method specifically comprises the following steps:

s2, antioxidant treatment: ball-milling the antioxidant, sieving with 350 mesh sieve, and drying at 70 deg.C for 2 hr to obtain antioxidant powder; the antioxidant is a compound mixture of an antioxidant 1076 and an antioxidant 3114, and the mass ratio is 4: 1;

s3, preparing modified rubber: and (2) rolling 100 parts by weight of nitrile rubber after being milled for 12min, adding 33 parts by weight of the modified graphite prepared in the step S1, 4 parts by weight of the antioxidant powder prepared in the step S2, 5 parts by weight of plasticizer RS-107, 10 parts by weight of carbon black and 0.5 part by weight of nickel N, N-dibutyl dithiocarbamate, mixing for 30min, adding 1 part by weight of tetramethyl thiuram disulfide and 0.7 part by weight of sulfur after uniformly mixing, milling for 4min, and vulcanizing for 25min at the pressure of 11MPa and the temperature of 170 ℃ to obtain the modified rubber.

Comparative example 6

Compared with the example 3, the antioxidant powder prepared in the step S6 is not added, and other conditions are not changed.

The method specifically comprises the following steps:

s6, preparing modified rubber: and (2) rolling 100 parts by weight of nitrile rubber after being open-milled for 12min, adding 15 parts by weight of the modified graphite prepared in the step S1, 18 parts by weight of the modified polyester fiber prepared in the step S5, 5 parts by weight of a plasticizer RS-107, 10 parts by weight of carbon black and 4.5 parts by weight of N, N-dibutyl nickel dithiocarbamate, mixing for 30min, adding 1 part by weight of tetramethyl thiuram disulfide and 0.7 part by weight of sulfur after uniformly mixing, opening for 4min, vulcanizing at 170 ℃ under the pressure of 11MPa for 25min to obtain the modified rubber.

Comparative example 7

The steps described in steps S1 to S5 were not performed, and other conditions were not changed, as compared with example 3.

The method specifically comprises the following steps:

s1, antioxidant treatment: ball-milling the antioxidant, sieving with 350 mesh sieve, and drying at 70 deg.C for 2 hr to obtain antioxidant powder; the antioxidant is a compound mixture of an antioxidant 1076 and an antioxidant 3114, and the mass ratio is 4: 1;

s2, preparing modified rubber: and (2) rolling 100 parts by weight of nitrile rubber for 12min, adding 4 parts by weight of the antioxidant powder prepared in the step S1, 5 parts by weight of plasticizer RS-107, 10 parts by weight of carbon black and 0.5 part by weight of nickel N, N-dibutyl dithiocarbamate, mixing for 30min, adding 1 part by weight of tetramethyl thiuram disulfide and 0.7 part by weight of sulfur after uniformly mixing, rolling for 4min, and vulcanizing for 25min at the pressure of 11MPa and the temperature of 170 ℃ to obtain the modified rubber.

Test example 1

The modified rubbers obtained in examples 1 to 7 of the present invention and comparative examples 1 to 7 were subjected to a performance test, and the results are shown in Table 1.

The tensile strength and the elongation are tested according to the method of GB/T528-;

the tear strength was tested according to GB/T529-,

the thickness is 2.0 plus or minus 0.2 mm, and the test is carried out at the speed of 500 mm/min;

the Shore hardness is tested by a Shore A durometer according to GB/T531.1-2008 & lt test method for pressing hardness of vulcanized rubber or thermoplastic rubber part 1: shore durometer test (shore hardness);

abrasion resistance the abrasion resistance of the test piece was measured in accordance with GB/T1689-2014 "determination of abrasion resistance of vulcanized rubber (Using Acron abrasion tester)".

TABLE 1

Group of	Hardness (Shao A)	Tensile Strength (MPa)	Elongation (%)	Tear Strength (N/mm)	Abrasion index (%)
						Example 1	68	28.45	582	96	9.2
Example 2	67	28.72	587	98	8.7
						Example 3	70	29.10	590	100	8.4
Example 4	65	28.10	576	92	12.4
						Example 5	66	27.87	570	90	11.7
Example 6	62	27.17	552	85	19.4
						Example 7	63	27.39	547	84	18.7
Comparative example 1	65	27.66	567	88	13.1
						Comparative example 2	62	25.84	540	82	15.7
Comparative example 3	64	27.22	510	83	17.4
						Comparative example 4	60	25.20	532	80	20.4
Comparative example 5	55	23.45	478	77	27.5
						Comparative example 6	63	27.10	565	87	13.5
Comparative example 7	52	22.70	452	72	30.2

As can be seen from the above table, the modified rubbers obtained in examples 1 to 3 of the present invention have good processability and mechanical properties.

Test example 2

The modified rubbers obtained in examples 1 to 7 of the present invention and comparative examples 1 to 7 were subjected to aging resistance tests and oil resistance tests, and the results are shown in Table 2.

Aging resistance: the modified rubber is made into a dumbbell shape and put into an aging test box under the condition of 100 ℃/70h, after aging is finished, the modified rubber is cooled at room temperature, the tensile strength, the elongation and the hardness are measured, and the change rate is calculated.

(tensile strength or elongation) change rate (%) = (parameter after test-parameter before test)/parameter before test × 100%

And (3) oil resistance test: volume change rate was measured on a 25mm by 50mm rectangle with Oil in accordance with ASTM Oil No. 1. The test temperature is 23 +/-2 ℃, and the soaking time is 168 h. The volume change rate after oil immersion is measured according to GB/T1690-2010 vulcanized rubber or thermoplastic rubber liquid resistance test method.

TABLE 2

As can be seen from the above table, the modified rubbers obtained in examples 1 to 3 of the present invention have good aging resistance and oil resistance. It can be seen that the modified rubber has increased tensile strength and decreased elongation after aging because the modified rubber exhibits a phenomenon of hardening after aging.

Compared with the embodiment 3, the embodiment 4 and the embodiment 5 have the advantages that the antioxidant is the antioxidant 1076 or the antioxidant 3114, the aging resistance and the oil resistance of the antioxidant are reduced, and the mechanical property is slightly reduced; compared with the example 3, the comparative example 6 has the advantages that the aging resistance and the oil resistance are obviously reduced and the mechanical property is slightly reduced without adding antioxidant powder; the antioxidant is a compound mixture of the antioxidant 1076 and the antioxidant 3114, the antioxidant 1076 is a micromolecule antioxidant with hydroxyl, the antioxidant 3114 is a micromolecule antioxidant with 3 hydroxyl, and the micromolecule antioxidant and the hydroxyl or the amino on the surface of the modified polyester fiber can form stable hydrogen bonds, so that the micromolecule antioxidant is uniformly dispersed in a nitrile butadiene rubber matrix to form a network structure, the thermal-oxidative aging resistance, the light-aging resistance, the low-temperature performance and the weather resistance of the rubber are obviously improved, and the two antioxidants have synergistic effect.

Compared with the example 3, the composite silane coupling agent of the examples 6 and 7 is single KH550 or 3- [ bis (2-hydroxyethyl) amino ] propane triethoxysilane, the mechanical property and the aging resistance are reduced, and compared with the example 3, the comparative example 4 has no modification treatment in the step S5, and the mechanical property and the aging resistance are obviously reduced. According to the invention, the polydopamine modified polyester fiber is modified by the composite silane coupling agent, the composite silane coupling agent is the silane coupling agent with amino and the silane coupling agent with hydroxyl, a large number of hydroxyl and amino are formed on the surface of the fiber, the amino structure can form a hydrogen bond with nitrogen on an imidazolyl group on an ionic liquid modified graphite particle and a CN group of nitrile rubber, and the hydroxyl structure can form a hydrogen bond with a hydroxyl part of an antioxidant, so that the antioxidant, the modified polyester fiber and the modified graphite can form a stable network structure in a nitrile rubber matrix, the mechanical property and the aging resistance of the nitrile rubber can be obviously improved, and the synergistic effect can be achieved after the two silane coupling agents are compounded.

Comparative example 1 compared with example 3, the graphite in step S1 was not modified with ionic liquid 1-butyl-3-ethylimidazole chloride, and its hardness and mechanical properties were decreased. According to the invention, the graphite can generate cation-pi and pi-pi effects with imidazole-based cations of the ionic liquid, so that the ionic liquid can be stably attached to the surface of the graphite, non-covalent bond modification is realized, the structure of the graphite cannot be damaged or changed, the graphite which is agglomerated together can be unwound and wound due to the fact that the imidazole-based branched chain has a high steric hindrance branched chain, the surface energy of the graphite is reduced, stable particles are formed and uniformly dispersed in a nitrile butadiene rubber matrix, interface interaction is generated between the graphite and the nitrile butadiene rubber, a compact and uniform cross-linked network structure is formed, and therefore, a good anti-aging effect can be achieved, and the mechanical property and the physicochemical property of the nitrile butadiene rubber are obviously improved.

Compared with the embodiment 3, the modified graphite prepared in the step S1 is not added, the hardness, the wear resistance and the mechanical property are obviously reduced, and the addition of the modified graphite can generate interface interaction with the nitrile rubber to form a compact and uniform cross-linked network structure, so that the good anti-aging effect can be achieved, and the mechanical property and the physicochemical property of the nitrile rubber can be obviously improved.

Compared with the example 3, the polyester fiber obtained in the step S4 has no polydopamine modification treatment, the elongation is obviously reduced, the mechanical properties are reduced, the polyester fiber of the invention has more hydroxyl structures formed on the surface after alkali treatment, dopamine is further easily loaded, polydopamine molecular chains are generated in situ under the action of a catalyst, and after the nitrile rubber matrix is added, the polydopamine molecular chains can be well dispersed in the matrix to form a filler network structure, meanwhile, the adhesion of the polyester fiber interface is obviously improved, and the toughness of the modified rubber can be obviously improved.

Compared with the example 3, the modified polyester fiber prepared without the step S5 has reduced added functionality, mechanical property, aging resistance and oil resistance, the invention modifies the polydopamine modified polyester fiber by the compound silane coupling agent, the composite silane coupling agent is a composite coupling agent of a silane coupling agent with amino and a silane coupling agent with hydroxyl, a large amount of hydroxyl and amino are formed on the surface of the fiber, the amino and hydroxyl positions can form hydrogen bonds with nitrogen on the imidazolyl group on the graphite particle modified by the ionic liquid and CN groups of the nitrile rubber, and simultaneously can form hydrogen bonds with the hydroxyl part of the antioxidant, therefore, the antioxidant, the modified polyester fiber and the modified graphite can form a stable network structure in the nitrile rubber matrix, and the mechanical property and the aging resistance of the nitrile rubber can be obviously improved.

Compared with the example 3, the comparative example 7 has no steps from S1 to S5, and the performances are obviously reduced, so that the addition of the modified graphite and the modified polyester fiber can obviously improve the performances of the modified rubber, and the prepared modified rubber has good aging resistance, low-temperature performance, weather resistance, mechanical performance, processability and physicochemical performance, and has wide application prospect.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims

1. A preparation method of modified rubber is characterized by comprising the following steps:

2. The method for preparing modified rubber according to claim 1, wherein the ball milling time in step S1 is 2-4h, and the mesh number of the screen is 500-700 mesh; the microwave heating temperature is 60-80 ℃, and the stirring is carried out for 30-40 min; the ultrasonic power is 1000-2000W, and the time is 1-3 h; the alkali liquor is 1-2mol/L NaOH solution or KOH solution; the ionic liquid is imidazolyl ionic liquid and is selected from at least one of 1-butyl-3-ethylimidazole chlorine, 1-butyl-3-ethylimidazole tetrafluoroboric acid, 1-butyl-3-ethylimidazole hexafluorophosphate, 1-butyl-3-ethylimidazole acetic acid, 1, 3-dimethyl imidazole tetrafluoroboric acid, 1-butyl-3-methylimidazole chlorine, 1-butyl-3-methylimidazole tetrafluoroboric acid, 1-butyl-3-methylimidazole hexafluorophosphate and 1-butyl-3-methylimidazole acetic acid.

3. The process for producing a modified rubber according to claim 1, wherein the aqueous ethanol solution containing an alkali used in step S2 is an aqueous ethanol solution containing 5 to 10wt% of NaOH or KOH, and the ethanol content is 30 to 50 wt%; the heating boiling time is 20-30 min.

4. The process for producing a modified rubber according to claim 1, wherein the cobalt salt in step S3 is at least one selected from the group consisting of cobalt sulfate, cobalt chloride and cobalt bromide; the pH value of the Tris-HCl buffer solution is 7.8-8.2, and Co in the catalyst solution²⁺The ion concentration is 0.5-1.2 wt%.

5. The method for preparing modified rubber according to claim 1, wherein the mass ratio of the dopamine hydrochloride, the pretreated polyester fiber and the catalyst solution in step S4 is (20-40): 100: (4-7); the heating temperature is 50-70 ℃ and the time is 3-5 h.

6. The method for producing a modified rubber according to claim 1, wherein the composite silane coupling agent in step S5 is a mixture of a silane coupling agent having an amino group selected from the group consisting of KH550, A-1110, A-1120, KNM-602, Nanda-42, Nanda-73, A-1130, Y-5691, KH602, KH 792; the silane coupling agent with hydroxyl is selected from at least one of 3- [ bis (2-hydroxyethyl) amino ] propane triethoxysilane and trimethylhydroxysilane; preferably, the compound silane coupling agent is a compound mixture of KH550 and 3- [ bis (2-hydroxyethyl) amino ] propane triethoxysilane, and the mass ratio is (3-7): 2; the mass ratio of the composite silane coupling agent to the polydopamine modified polyester fiber is (5-7): 50; the method comprises the following steps of; the heating temperature is 70-90 ℃ and the time is 1-3 h.

7. The method for preparing modified rubber according to claim 1, wherein the mesh number of the screen in step S6 is 200-500 meshes; the antioxidant is at least one selected from antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 626 and antioxidant 3114; preferably, the antioxidant is a compound mixture of an antioxidant 1076 and an antioxidant 3114, and the mass ratio is (3-5): 1.

8. the method for preparing modified rubber according to claim 1, wherein the plasticizer is at least one selected from the group consisting of polyether plasticizers, polyester plasticizers, adipic acid ether ester plasticizers and aliphatic plasticizers in step S7; the reinforcing filler is at least one selected from carbon nano tube, carbon black, pottery clay and nano calcium carbonate; the anti-aging agent is selected from at least one of p-diphenylamine, nickel N, N-dibutyl dithiocarbamate, 2, 4-trimethyl-1, 2-dihydroquinoline, 2-mercaptobenzimidazole, N-isopropyl-N-phenyl-p-phenylenediamine and 4,4 '-bis (a, a' -dimethylbenzyl) diphenylamine; the accelerator is selected from at least one of tetramethyl thiuram disulfide, triallyl cyanurate, N '-m-phenylene bismaleimide, 2' -dibenzothiazyl disulfide and N-cyclohexyl-2-benzothiazole sulfonamide; the vulcanizing agent is at least one selected from sulfur, ethylene thiourea, 2,4, 6-trithiol thiotriazine, dicumyl peroxide and di-o-tolylguanidine; the mass ratio of the nitrile rubber, the modified graphite, the modified polyester fiber, the antioxidant powder, the plasticizer, the reinforcing filler, the anti-aging agent, the accelerator and the vulcanizing agent is 100: (12-17): (15-22): (3-5): (2-7): (5-15): (0.2-0.7): (0.2-2): (0.5-1); the first open milling time is 10-15 min; the second open milling time is 3-5 min; the vulcanization condition is that the temperature is 165-175 ℃ for 20-30min under the pressure of 10-12 MPa; the mixing time is 20-40 min.

9. The method for preparing the modified rubber according to claim 1, comprising the steps of:

10. A modified rubber obtained by the production method as described in any one of claims 1 to 9.