CN114672078B - Modified rubber and preparation method thereof - Google Patents

Modified rubber and preparation method thereof Download PDF

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CN114672078B
CN114672078B CN202210440341.5A CN202210440341A CN114672078B CN 114672078 B CN114672078 B CN 114672078B CN 202210440341 A CN202210440341 A CN 202210440341A CN 114672078 B CN114672078 B CN 114672078B
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modified
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antioxidant
polyester fiber
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CN114672078A (en
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施以进
陈颖
余昭军
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Guangdong Border Crossing Intelligent Technology Co ltd
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Guangdong Border Crossing Intelligent Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

Abstract

The invention provides modified rubber and a preparation method thereof, and belongs to the technical field of rubber. The method comprises the following steps: s1, preparing modified graphite; s2, pretreatment of polyester fibers; s3, preparing a catalyst solution; s4, preparing polydopamine modified polyester fibers; s5, preparing modified polyester fibers; s6, treating an antioxidant; s7, preparing modified rubber. The invention has wide sources of raw materials and simple preparation method, and the raw materials are mixed and vulcanized to form stable modified rubber, so that the modified rubber has good ageing resistance, low-temperature performance, weather resistance, mechanical performance, processability 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
Rubber plays an important role in daily life and social and economic construction, and is widely applied to tires, sealing elements, damping products, conveyor belts and the like due to the advantages of high strength, high elasticity, good wear resistance, good insulating property and the like. However, in practical applications, to further improve the properties of the rubber, some unsaturated rubbers, such as isoprene rubber, polybutadiene rubber (BR), styrene-butadiene rubber (SBR), etc., may incorporate specific functional groups into the molecule by chemical reaction of c=c bonds to modify the rubber.
In recent years, the rubber industry in China has rapidly developed, and a large number of rubber products are applied to various industries, and Nitrile Butadiene Rubber (NBR) prepared by emulsion polymerization of butadiene and acrylonitrile has better oil resistance and heat resistance and strong adhesive force due to the existence of acrylonitrile, so that the NBR 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, NBR is easy to undergo thermooxidative aging due to the change of factors such as heat, oxygen, light and water in the environment in the use process, so that the mechanical property and the physical and chemical properties are reduced, when the rubber is aged and the service performance of the product is affected, the molecular chain of the rubber is continuously degraded and crosslinked, 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 an anti-aging agent is added into the rubber, so that the rubber is an effective method for delaying aging.
The Chinese patent 201810341505.2 provides a modified powder nitrile rubber and application thereof, wherein the modified powder 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 steps: mixing and heating the calcium terephthalate to 50-60 ℃ in a high-speed mixer with a heating function, adding the fully-crosslinked powder nitrile rubber, mixing for 5min, adding the semi-crosslinked powder nitrile rubber, and mixing for 3-5min to obtain the modified powder nitrile rubber.
Chinese patent 201410592735.8 provides a modified nitrile rubber and a preparation method thereof, wherein the modified nitrile rubber comprises the following mixed components: 100 parts by weight of nitrile rubber; 5-10 parts of zinc oxide; 5-15 parts of magnesium oxide; 1-2 parts by weight of stearic acid; 40-80 parts by weight of carbon black; strong grinding into 10-45 weight parts; 5-15 parts of plasticizer; 2-3 parts of an anti-aging agent; 0.5 to 1.5 parts by weight of vulcanizing agent; 3-5 parts of accelerator. The preparation method comprises the following steps: and (3) mixing the magnesium oxide and the strong grinding powder uniformly in advance according to the dosage, and 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 of mechanical properties and poor ageing resistance due to uneven dispersion.
Disclosure of Invention
The invention aims to provide modified rubber and a preparation method thereof, wherein the modified rubber has wide raw material sources, the preparation method is simple, and the stable modified rubber is formed after mixing and vulcanizing the raw materials, has good ageing 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, washing, drying, ball milling, sieving, adding ionic liquid, heating and stirring by microwaves, performing ultrasonic treatment, centrifuging, washing solids, and drying to obtain modified graphite;
s2, pretreatment of polyester fibers: adding the polyester fiber into an ethanol water solution containing alkali, heating and boiling, filtering and washing to obtain a pretreated polyester fiber;
s3, preparing a catalyst solution: dissolving cobalt salt in Tris-HCl buffer solution to obtain a 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, dripping the catalyst solution prepared in the step S3, heating for reaction, filtering, washing and drying to obtain the 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 the modified polyester fiber;
s6, antioxidant treatment: ball milling the antioxidant, sieving, and drying to obtain antioxidant powder;
S7, preparation of modified rubber: and (3) wrapping a roller after the first open milling of the nitrile rubber, 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), the plasticizer, the reinforcing filler and the anti-aging agent, mixing uniformly, adding the accelerator and the vulcanizing agent, and carrying out the second open milling and vulcanization to obtain the modified rubber.
As a further improvement of the invention, the ball milling time in the step S1 is 2-4 hours, and the mesh number of the sieves is 500-700 meshes; the microwave heating temperature is 60-80 ℃, and stirring is carried out for 30-40min; the ultrasonic power is 1000-2000W, and the time is 1-3h; the alkali liquor is NaOH solution or KOH solution with the concentration of 1-2 mol/L; the ionic liquid is imidazolyl ionic liquid and is at least one selected from 1-butyl-3-ethylimidazole chloride, 1-butyl-3-ethylimidazole tetrafluoroboric acid, 1-butyl-3-ethylimidazole hexafluorophosphoric acid, 1-butyl-3-ethylimidazole acetic acid, 1, 3-dimethyl imidazole tetrafluoroboric acid, 1-butyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole tetrafluoroboric acid, 1-butyl-3-methylimidazole hexafluorophosphoric acid and 1-butyl-3-methylimidazole acetic acid.
As a further improvement of the invention, the alkali-containing ethanol aqueous solution in the step S2 is an ethanol aqueous solution containing 5-10wt% of NaOH or KOH, wherein the ethanol content is 30-50wt%; the heating boiling time is 20-30min.
As a further improvement of the present invention, 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 solution 2+ The ion concentration is 0.5-1.2wt%.
As a further improvement of the present 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 heating time is 3-5h.
As a further improvement of the present invention, the composite silane coupling agent in the step S5 is a mixture of an amino-bearing silane coupling agent and a hydroxyl-bearing silane coupling agent, wherein the amino-bearing silane coupling agent is selected from KH550, A-1110, A-1120, KNM-602, nandina-42, nandina-73, A-1130, Y-5691, KH602, KH792; the silane coupling agent with hydroxyl is at least one selected from 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 said; the heating temperature is 70-90 ℃ and the heating time is 1-3h.
As a further improvement of the present invention, the screen mesh number in step S6 is 200-500 mesh; 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, the plasticizer in step S7 is at least one selected from the group consisting of polyether plasticizers, polyester plasticizers, adipic acid ether ester plasticizers, and aliphatic plasticizers; the reinforcing filler is at least one selected from carbon nano tube, carbon black, clay and nano calcium carbonate; the anti-aging agent is at least one selected from 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 at least one selected from tetramethylthiuram disulfide, triallyl cyanurate, N '-m-phenylene bismaleimide, 2' -dibenzothiazyl disulfide and N-cyclohexyl-2-benzothiazole sulfenamide; the vulcanizing agent is at least one selected from sulfur, ethylene thiourea, 2,4, 6-trithiol thiotriazine, dicumyl peroxide and di-o-toluene guanidine; the mass ratio of the nitrile rubber to the modified graphite to the modified polyester fiber to the antioxidant powder to the plasticizer to the reinforcing filler to the antioxidant to the accelerator to 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 mill time is 10-15min; the second open mill time is 3-5min; the vulcanization condition is that under the pressure of 10-12MPa, the temperature is 165-175 ℃ and the time is 20-30min; the mixing time is 20-40min.
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, washing, drying, ball milling for 2-4h, sieving with 500-700 mesh sieve, adding ionic liquid, heating to 60-80deg.C with microwave, stirring for 30-40min, ultrasonic treating for 1-3h with 1000-2000W, centrifuging, washing solid, and drying to obtain modified graphite;
s2, pretreatment of polyester fibers: adding the polyester fiber into an 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 pH value of 7.8-8.2 to obtain catalyst solution, wherein Co in the catalyst solution 2+ The ion concentration is 0.5-1.2wt%;
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, dripping 4-7 parts by weight of the catalyst solution prepared in the step S3, heating to 50-70 ℃, reacting for 3-5 hours, reacting, filtering, washing and drying to obtain the polydopamine modified polyester fiber;
S5, preparing modified polyester fibers: dissolving 5-7 parts by weight of a composite silane coupling agent in ethanol, adding 50 parts by weight of the polydopamine modified polyester fiber prepared in the step S4, heating to 70-90 ℃, stirring and reacting for 1-3 hours, filtering, washing and drying to obtain the modified polyester fiber;
s6, antioxidant treatment: ball milling the antioxidant, sieving with a 200-500 mesh sieve, and drying to obtain antioxidant powder;
s7, preparation of modified rubber: mixing 100 parts by weight of nitrile rubber for 10-15min, wrapping the nitrile rubber, adding 12-17 parts by weight of modified graphite prepared in the step S1, 15-22 parts by weight of modified polyester fiber prepared in the step S5, 3-5 parts by weight of 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 antioxidant, mixing for 20-40min, adding 0.2-2 parts by weight of accelerator and 0.5-1 part by weight of vulcanizing agent after mixing uniformly, and carrying out open mixing for 3-5min at 165-175 ℃ under the pressure of 10-12MPa, and vulcanizing for 20-30min to obtain 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 nonpolar lamellar simple substance, and can generate cation-pi and pi-pi actions with imidazolyl cations of ionic liquid, so that the ionic liquid can be stably attached to the surface of the graphite, thus non-covalent bond modification is realized, meanwhile, the structure of the graphite cannot be damaged or changed, and because the imidazolyl branched chains have large steric hindrance branched chains, the agglomerated graphite can be unwound, the surface energy of the graphite is reduced, stable particles are uniformly dispersed in a nitrile rubber matrix, interface interaction is generated between the graphite and the nitrile rubber, and a compact uniform cross-linked network structure is formed, so that a good anti-aging effect can be achieved, and the mechanical property and the physical and chemical properties of the nitrile rubber are obviously improved;
On the other hand, after the polyester fiber is subjected to alkali treatment, more hydroxyl structures are formed on the surface, dopamine is further easily loaded, polydopamine molecular chains are generated in situ under the action of a catalyst, and after the polydopamine molecular chains are added into a nitrile rubber matrix, the polydopamine molecular chains can be well dispersed in the matrix to form a filler network structure, meanwhile, the adhesiveness of the polyester fiber interface is obviously improved, and the toughness of the modified rubber can be obviously improved;
further, after the polydopamine modified polyester fiber is modified by the composite silane coupling agent, the composite silane coupling agent is a silane coupling agent with amino groups and a silane coupling agent with hydroxyl groups, a large number of hydroxyl groups and amino groups are formed on the surface of the fiber, the amino groups and the hydroxyl groups can form hydrogen bonds with nitrogen on imidazole groups on ionic liquid modified graphite particles and CN groups of nitrile rubber, and simultaneously can form hydrogen bonds with hydroxyl groups 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, and the mechanical property and the ageing 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 groups, the antioxidant 3114 is a micromolecular antioxidant with 3 hydroxyl groups, and the micromolecular antioxidant can form stable hydrogen bonds with hydroxyl groups or amino groups 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 thermo-oxidative aging resistance, photo-aging resistance, low-temperature performance and weather resistance of the rubber are obviously improved.
The invention has wide sources of raw materials and simple preparation method, and the raw materials are mixed and vulcanized to form stable modified rubber, so that the modified rubber has good ageing resistance, low-temperature performance, weather resistance, mechanical performance, processability and physicochemical performance and has wide application prospect.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
Fig. 1 is an SEM image of the polydopamine-modified polyester fiber prepared in step S4 of example 1.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Butyl-3-ethylimidazole chloride, 99%, shanghai Fujie chemical Co., ltd; the polyester fiber has the diameter of 10-25 mu m, the breaking strength of more than 500MPa, the breaking growth rate of more than 15%, the length of 5-7mm and Shandong Haoshen New Material Co., ltd; graphite with carbon content greater than 97%, crystal grain size less than 0.1mm, mohs hardness 1-2, shijia 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 1 hour, washing, drying at 70 ℃ for 2 hours, ball milling for 2 hours, sieving with a 500-mesh sieve, adding 1-butyl-3-ethylimidazole chloride, heating to 60 ℃ by microwaves, stirring for 30 minutes, performing 1000W ultrasonic for 1 hour, centrifuging for 15 minutes at 3000r/min, washing the solid with deionized water, and drying at 70 ℃ for 2 hours 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 pH value of 7.8 to obtain a catalyst solution, wherein Co in the catalyst solution 2+ Ion concentration is 0.5wt%;
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, dripping 4 parts by weight of the catalyst solution prepared in the step S3, heating to 50 ℃, reacting for 3h, reacting, filtering, washing with deionized water, and drying at 70 ℃ for 2h to obtain the polydopamine modified polyester fiber; fig. 1 is an SEM image of the prepared polydopamine-modified polyester fiber, and it can be seen from the figure that a polydopamine film is supported on the surface of the polyester fiber.
S5, preparing modified polyester fibers: dissolving 5 parts by weight of a composite silane coupling agent in 100 parts by weight of ethanol, adding 50 parts by weight of the polydopamine modified polyester fiber prepared in the step S4, heating to 70 ℃, stirring and reacting for 1h, filtering, washing with deionized water, and drying at 70 ℃ for 2h to obtain the modified polyester fiber; the compound silane coupling agent is a compound mixture of KH550 and 3- [ bis (2-hydroxyethyl) amino ] propane triethoxysilane, and the mass ratio is 3:2;
s6, antioxidant treatment: ball milling the antioxidant, sieving with a 200-mesh sieve, and drying at 70 ℃ for 2 hours 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, a step of;
S7, preparation of modified rubber: 100 parts by weight of nitrile rubber is subjected to open milling for 10min and then is wrapped by a roller, 12 parts by weight of modified graphite prepared in the step S1, 15 parts by weight of modified polyester fiber prepared in the step S5, 3 parts by weight of antioxidant powder prepared in the step S6, 2 parts by weight of plasticizer TP-759, 5 parts by weight of clay and 0.2 part by weight of N-isopropyl-N, -phenyl p-phenylenediamine are added, and after mixing uniformly, 0.2 part by weight of triallyl cyanurate and 0.5 part by weight of di-o-toluene guanidine are added, open milling is performed for 3min under 10MPa pressure, and vulcanization is performed for 20min at 165 ℃, thus obtaining the modified rubber.
Example 2
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 2mol/L KOH solution, soaking for 2 hours, cleaning, drying at 70 ℃ for 2 hours, ball milling for 4 hours, sieving with a 700-mesh sieve, adding 1-butyl-3-ethylimidazole chloride, heating to 80 ℃ by microwaves, stirring for 40 minutes, performing 2000W ultrasonic for 3 hours, centrifuging for 15 minutes at 3000r/min, washing the solid with deionized water, and drying at 70 ℃ for 2 hours 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: cobalt bromide is dissolved in Tris-HCl buffer solution with pH value of 8.2 to obtain catalyst solution, co in the catalyst solution 2+ The ion concentration was 1.2wt%;
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, dripping 7 parts by weight of the catalyst solution prepared in the step S3, heating to 70 ℃, reacting for 5h, reacting, filtering, washing with deionized water, and drying at 70 ℃ for 2h to obtain the polydopamine modified polyester fiber;
s5, preparing modified polyester fibers: dissolving 7 parts by weight of a composite silane coupling agent in 100 parts by weight of ethanol, adding 50 parts by weight of the polydopamine modified polyester fiber prepared in the step S4, heating to 90 ℃, stirring for reaction for 3 hours, filtering, washing with deionized water, and drying at 70 ℃ for 2 hours to obtain the modified polyester fiber; the compound 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 ℃ for 2 hours 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, a step of;
S7, preparation of modified rubber: 100 parts by weight of nitrile rubber is subjected to open milling for 15min and then is wrapped by a roller, 17 parts by weight of modified graphite prepared in the step S1, 22 parts by weight of modified polyester fiber prepared in the step S5, 5 parts by weight of antioxidant powder prepared in the step S6, 7 parts by weight of plasticizer TP-90B, 15 parts by weight of carbon nano tube and 0.7 part by weight of p-diphenylamine are added, and after being uniformly mixed, 2 parts by weight of 2,2' -dibenzothiazyl disulfide and 1 part by weight of dicumyl peroxide are added, and under the pressure of 5min and 12MPa, the temperature is 175 ℃ and the vulcanization is carried out for 30min, so that the modified rubber is obtained.
Example 3
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 1.5mol/L NaOH solution, soaking for 1.5 hours, cleaning, drying for 2 hours at 70 ℃, ball milling for 3 hours, sieving with a 600-mesh sieve, adding 1-butyl-3-ethylimidazole chloride, adding microwaves to heat for 70 ℃, stirring for 35 minutes, performing 1500W ultrasonic for 3 hours, centrifuging for 15 minutes at 3000r/min, washing the solid with deionized water, and drying for 2 hours at 70 ℃ 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: cobalt chloride is dissolved in Tris-HCl buffer solution with pH value of 8 to obtain catalyst solution, co in the catalyst solution 2+ Ion concentration was 0.9wt%;
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, dripping 5 parts by weight of the catalyst solution prepared in the step S3, heating to 60 ℃, reacting for 4h, reacting, filtering, washing with deionized water, and drying at 70 ℃ for 2h to obtain the polydopamine modified polyester fiber;
s5, preparing modified polyester fibers: dissolving 6 parts by weight of a composite silane coupling agent in 100 parts by weight of ethanol, adding 50 parts by weight of the polydopamine modified polyester fiber prepared in the step S4, heating to 80 ℃, stirring for reaction for 3 hours, filtering, washing with deionized water, and drying at 70 ℃ for 2 hours to obtain the modified polyester fiber; the compound 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 a 350-mesh sieve, and drying at 70 ℃ for 2 hours 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, a step of;
S7, preparation of modified rubber: 100 parts by weight of nitrile rubber is subjected to open milling for 12min and then is wrapped by a roller, 15 parts by weight of modified graphite 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 are added, and after mixing uniformly, 1 part by weight of tetramethylthiuram disulfide and 0.7 part by weight of sulfur are added, and under the pressure of 4min and 11MPa, the mixture is vulcanized for 25min at 170 ℃ to obtain the modified rubber.
Example 4
In comparison with example 3, the antioxidant was antioxidant 1076, and the other conditions were not changed.
Example 5
In comparison with example 3, the antioxidant was antioxidant 3114, and the other conditions were not changed.
Example 6
In comparison with example 3, the composite silane coupling agent was KH550, and the other conditions were not changed.
Example 7
In comparison with example 3, the compound silane coupling agent was 3- [ bis (2-hydroxyethyl) amino ] propane triethoxysilane, all other conditions being unchanged.
Comparative example 1
In contrast to example 3, the graphite in step S1 was not subjected to the ionic liquid 1-butyl-3-ethylimidazole chloride modification treatment.
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 1.5 hours, cleaning, drying at 70 ℃ for 2 hours, ball milling for 3 hours, sieving with a 600-mesh sieve, and drying at 70 ℃ for 2 hours to obtain graphite powder;
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: cobalt chloride is dissolved in Tris-HCl buffer solution with pH value of 8 to obtain catalyst solution, co in the catalyst solution 2+ Ion concentration was 0.9wt%;
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, dripping 5 parts by weight of the catalyst solution prepared in the step S3, heating to 60 ℃, reacting for 4h, reacting, filtering, washing with deionized water, and drying at 70 ℃ for 2h to obtain the polydopamine modified polyester fiber;
s5, preparing modified polyester fibers: dissolving 6 parts by weight of a composite silane coupling agent in 100 parts by weight of ethanol, adding 50 parts by weight of the polydopamine modified polyester fiber prepared in the step S4, heating to 80 ℃, stirring for reaction for 3 hours, filtering, washing with deionized water, and drying at 70 ℃ for 2 hours to obtain the modified polyester fiber; the compound 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 a 350-mesh sieve, and drying at 70 ℃ for 2 hours 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, a step of;
s7, preparation of modified rubber: 100 parts by weight of nitrile rubber is subjected to open milling for 12min and then is wrapped by a roller, 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 are added, and after mixing uniformly, 1 part by weight of tetramethylthiuram disulfide and 0.7 part by weight of sulfur are added, and under the pressure of 4min and 11MPa, the modified rubber is obtained through open milling at 170 ℃ and vulcanization for 25 min.
Comparative example 2
Compared with example 3, the modified graphite obtained in the step S1 was not added, and the other conditions were 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, preparing a catalyst solution: cobalt chloride is dissolved in Tris-HCl buffer solution with pH value of 8 to obtain catalyst solution, co in the catalyst solution 2+ Ion concentration was 0.9wt%;
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, dripping 5 parts by weight of the catalyst solution prepared in the step S2, heating to 60 ℃, reacting for 4h, reacting, filtering, washing with deionized water, and drying at 70 ℃ for 2h to obtain the polydopamine modified polyester fiber;
s4, preparation of modified polyester fibers: dissolving 6 parts by weight of a composite silane coupling agent in 100 parts by weight of ethanol, adding 50 parts by weight of the polydopamine modified polyester fiber prepared in the step S3, heating to 80 ℃, stirring for reaction for 3 hours, filtering, washing with deionized water, and drying at 70 ℃ for 2 hours to obtain the modified polyester fiber; the compound 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 a 350-mesh sieve, and drying at 70 ℃ for 2 hours 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, a step of;
S6, preparing modified rubber: mixing 100 parts by weight of nitrile rubber for 12min, wrapping the nitrile rubber, adding 33 parts by weight of modified polyester fiber prepared in the step S4, 4 parts by weight of 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 tetramethylthiuram disulfide and 0.7 part by weight of sulfur, mixing for 4min under the pressure of 11MPa, and vulcanizing for 25min at 170 ℃ to obtain modified rubber.
Comparative example 3
Compared with example 3, the polyester fiber in the step S4 is not subjected to polydopamine modification treatment, and other conditions are not changed.
The method specifically comprises the following steps:
s1, preparing modified graphite: adding 100 parts by weight of graphite into 200 parts by weight of 1.5mol/L NaOH solution, soaking for 1.5 hours, cleaning, drying for 2 hours at 70 ℃, ball milling for 3 hours, sieving with a 600-mesh sieve, adding 1-butyl-3-ethylimidazole chloride, adding microwaves to heat for 70 ℃, stirring for 35 minutes, performing 1500W ultrasonic for 3 hours, centrifuging for 15 minutes at 3000r/min, washing the solid with deionized water, and drying for 2 hours at 70 ℃ 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 modified polyester fibers: dissolving 6 parts by weight of a 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 for reaction for 3 hours, filtering, washing with deionized water, and drying at 70 ℃ for 2 hours to obtain a modified polyester fiber; the compound 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, antioxidant treatment: ball milling the antioxidant, sieving with a 350-mesh sieve, and drying at 70 ℃ for 2 hours 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, a step of;
s5, preparing modified rubber: 100 parts by weight of nitrile rubber is subjected to open milling for 12min and then is wrapped by a roller, 15 parts by weight of modified graphite prepared in the step S1, 18 parts by weight of modified polyester fiber prepared in the step S3, 4 parts by weight of antioxidant powder prepared in the step S4, 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 are added, and after mixing uniformly, 1 part by weight of tetramethylthiuram disulfide and 0.7 part by weight of sulfur are added, and under the pressure of 4min and 11MPa, the mixture is vulcanized for 25min at 170 ℃ to obtain the modified rubber.
Comparative example 4
In contrast to example 3, the modification treatment described in step S5 was not performed, and the other conditions were not changed.
The method specifically comprises the following steps:
s1, preparing modified graphite: adding 100 parts by weight of graphite into 200 parts by weight of 1.5mol/L NaOH solution, soaking for 1.5 hours, cleaning, drying for 2 hours at 70 ℃, ball milling for 3 hours, sieving with a 600-mesh sieve, adding 1-butyl-3-ethylimidazole chloride, adding microwaves to heat for 70 ℃, stirring for 35 minutes, performing 1500W ultrasonic for 3 hours, centrifuging for 15 minutes at 3000r/min, washing the solid with deionized water, and drying for 2 hours at 70 ℃ 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: cobalt chloride is dissolved in Tris-HCl buffer solution with pH value of 8 to obtain catalyst solution, co in the catalyst solution 2+ Ion concentration was 0.9wt%;
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, dripping 5 parts by weight of the catalyst solution prepared in the step S3, heating to 60 ℃, reacting for 4h, reacting, filtering, washing with deionized water, and drying at 70 ℃ for 2h to obtain the polydopamine modified polyester fiber;
S5, antioxidant treatment: ball milling the antioxidant, sieving with a 350-mesh sieve, and drying at 70 ℃ for 2 hours 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, a step of;
s6, preparing modified rubber: 100 parts by weight of nitrile rubber is subjected to open milling for 12min and then is wrapped by a roller, 15 parts by weight of modified graphite prepared in the step S1, 18 parts by weight of polydopamine modified polyester fiber prepared in the step S4, 4 parts by weight of 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 are added, and after mixing uniformly, 1 part by weight of tetramethylthiuram disulfide and 0.7 part by weight of sulfur are added, and under the pressure of 4min and 11MPa, the modified rubber is obtained through open milling at 170 ℃ and vulcanization for 25 min.
Comparative example 5
Compared with example 3, the modified polyester fiber obtained in the step S5 was not added, and the other conditions were not changed.
The method specifically comprises the following steps:
s1, preparing modified graphite: adding 100 parts by weight of graphite into 200 parts by weight of 1.5mol/L NaOH solution, soaking for 1.5 hours, cleaning, drying for 2 hours at 70 ℃, ball milling for 3 hours, sieving with a 600-mesh sieve, adding 1-butyl-3-ethylimidazole chloride, adding microwaves to heat for 70 ℃, stirring for 35 minutes, performing 1500W ultrasonic for 3 hours, centrifuging for 15 minutes at 3000r/min, washing the solid with deionized water, and drying for 2 hours at 70 ℃ to obtain modified graphite;
S2, antioxidant treatment: ball milling the antioxidant, sieving with a 350-mesh sieve, and drying at 70 ℃ for 2 hours 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, a step of;
s3, preparing modified rubber: mixing 100 parts by weight of nitrile rubber for 12min, wrapping the roller, adding 33 parts by weight of modified graphite prepared in the step S1, 4 parts by weight of 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 tetramethylthiuram disulfide and 0.7 part by weight of sulfur, mixing for 4min under the pressure of 11MPa, and vulcanizing for 25min at 170 ℃ to obtain modified rubber.
Comparative example 6
In comparison with example 3, the antioxidant powder obtained in step S6 was not added, and the other conditions were not changed.
The method specifically comprises the following steps:
s1, preparing modified graphite: adding 100 parts by weight of graphite into 200 parts by weight of 1.5mol/L NaOH solution, soaking for 1.5 hours, cleaning, drying for 2 hours at 70 ℃, ball milling for 3 hours, sieving with a 600-mesh sieve, adding 1-butyl-3-ethylimidazole chloride, adding microwaves to heat for 70 ℃, stirring for 35 minutes, performing 1500W ultrasonic for 3 hours, centrifuging for 15 minutes at 3000r/min, washing the solid with deionized water, and drying for 2 hours at 70 ℃ 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: cobalt chloride is dissolved in Tris-HCl buffer solution with pH value of 8 to obtain catalyst solution, co in the catalyst solution 2+ Ion concentration was 0.9wt%;
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, dripping 5 parts by weight of the catalyst solution prepared in the step S3, heating to 60 ℃, reacting for 4h, reacting, filtering, washing with deionized water, and drying at 70 ℃ for 2h to obtain the polydopamine modified polyester fiber;
s5, preparing modified polyester fibers: dissolving 6 parts by weight of a composite silane coupling agent in 100 parts by weight of ethanol, adding 50 parts by weight of the polydopamine modified polyester fiber prepared in the step S4, heating to 80 ℃, stirring for reaction for 3 hours, filtering, washing with deionized water, and drying at 70 ℃ for 2 hours to obtain the modified polyester fiber; the compound 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, preparing modified rubber: mixing 100 parts by weight of nitrile rubber for 12min, wrapping the roller, adding 15 parts by weight of modified graphite prepared in the step S1, 18 parts by weight of modified polyester fiber prepared in the step S5, 5 parts by weight of plasticizer RS-107, 10 parts by weight of carbon black and 4.5 parts by weight of nickel N, N-dibutyl dithiocarbamate, mixing for 30min, adding 1 part by weight of tetramethylthiuram disulfide and 0.7 part by weight of sulfur, mixing for 4min under the pressure of 11MPa, and vulcanizing for 25min at 170 ℃ to obtain modified rubber.
Comparative example 7
In contrast to example 3, the steps described in steps S1 to S5 were not performed, and the other conditions were not changed.
The method specifically comprises the following steps:
s1, treating an antioxidant: ball milling the antioxidant, sieving with a 350-mesh sieve, and drying at 70 ℃ for 2 hours 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, a step of;
s2, preparing modified rubber: and (3) carrying out open milling on 100 parts by weight of nitrile rubber for 12min, wrapping the roll, 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 tetramethylthiuram disulfide and 0.7 part by weight of sulfur after mixing uniformly, and carrying out open milling for 4min under the pressure of 11MPa, wherein the temperature is 170 ℃ and the vulcanization time is 25min to obtain the modified rubber.
Test example 1
The modified rubbers obtained in examples 1 to 7 and comparative examples 1 to 7 of the present invention were subjected to performance test, and the results are shown in Table 1.
Tensile strength and elongation were measured according to GB/T528-2009 method for measuring tensile stress Strain Properties of vulcanized rubber or thermoplastic rubber, using dumbbell-shaped test specimens at a speed of 500 mm/min;
tear strength was measured according to GB/T529-2008 method for determination of tear strength of vulcanized rubber or thermoplastic rubber (trouser, right-angle and crescent samples), using right-angle samples,
thickness was 2.0.+ -. 0.2. 0.2 mm, tested at a speed of 500 mm/min;
shore hardness is tested by using a Shore A durometer according to GB/T531.1-2008, part 1 of the method for testing indentation hardness of vulcanized rubber or thermoplastic rubber: shore durometer (Shore hardness) test;
abrasion resistance the abrasion resistance of the test specimens was measured according to GB/T1689-2014 determination of abrasion resistance of vulcanized rubber (with an Aldrich abrasion tester).
TABLE 1
Group of Hardness (Shore 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 shown in the table above, the modified rubbers prepared 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 and comparative examples 1 to 7 of the present invention were subjected to an aging resistance test and an oil resistance test, and the results are shown in Table 2.
Ageing resistance: the modified rubber is made into dumbbell shape and put into an aging test box under the condition of 100 ℃/70h, after aging, the tensile strength, the elongation and the hardness are measured after cooling under the condition of room temperature, and the change rate is calculated.
Change rate (%) = (parameter after test-parameter before test)/parameter before test×100%
Oil resistance test: the sample for measuring the volume change rate was a rectangle of 25mm by 50mm, and the Oil was ASTM Oil No.1. The test temperature is 23+/-2 ℃ and the soaking time is 168 hours. The volume change rate after oil immersion is measured according to GB/T1690-2010 "test method for liquid resistance of vulcanized rubber or thermoplastic rubber".
TABLE 2
As shown in the table above, the modified rubber prepared in the examples 1-3 of the invention has better ageing resistance and oil resistance. It can be seen that the tensile strength of the modified rubber increases and the elongation becomes smaller after aging because the modified rubber becomes hard after aging.
In examples 4 and 5, compared with example 3, the antioxidant is antioxidant 1076 or antioxidant 3114, the ageing resistance and oil resistance are reduced, and the mechanical properties are slightly reduced; compared with the comparative example 3, the ageing resistance and the oil resistance of the comparative example 6 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 micromolecular antioxidant with hydroxyl groups, the antioxidant 3114 is a micromolecular antioxidant with 3 hydroxyl groups, and the micromolecular antioxidant can form stable hydrogen bonds with hydroxyl groups or amino groups 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, the thermo-oxidative aging resistance, photo-aging resistance, low-temperature performance and weather resistance of the rubber are obviously improved, and the addition of the two antioxidants has a synergistic effect.
Examples 6 and 7 are compared with example 3, the composite silane coupling agent is single KH550 or 3- [ bis (2-hydroxyethyl) amino ] propane triethoxysilane, the mechanical property is reduced, the ageing resistance is reduced, and compared with example 3, comparative example 4 is not subjected to the modification treatment in step S5, and the mechanical property and the ageing resistance are obviously reduced. According to the invention, after the poly-dopamine modified polyester fiber is modified by the composite silane coupling agent, the composite silane coupling agent is a silane coupling agent with amino groups and a silane coupling agent with hydroxyl groups, a large number of hydroxyl groups and amino groups are formed on the surface of the fiber, an amino structure can form a hydrogen bond with nitrogen on imidazole groups on ionic liquid modified graphite particles and CN groups of nitrile rubber, and a hydroxyl structure can form a hydrogen bond with hydroxyl groups 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 ageing 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 the graphite in step S1 was not subjected to the ionic liquid 1-butyl-3-ethylimidazole chloride modification treatment, and its hardness and mechanical properties were reduced as compared with example 3. According to the invention, graphite can generate cation-pi and pi-pi actions with imidazole 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, the structure of the graphite cannot be damaged or changed, and because the imidazole branched chains have large steric hindrance branched chains, the agglomerated graphite can be unwound, the surface energy of the graphite is reduced, stable particles are uniformly dispersed in a nitrile rubber matrix, interface interaction is generated between the graphite and the nitrile rubber, and a compact uniform cross-linked network structure is formed, so that a good anti-aging effect can be achieved, and the mechanical property and the physical and chemical properties of the nitrile 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 of the modified graphite are obviously reduced, and the modified graphite can generate interface interaction with the nitrile rubber to form a compact and uniform cross-linked network structure, so that the modified graphite has a good anti-aging effect, and the mechanical property and the physical and chemical properties of the nitrile rubber are obviously improved.
Compared with the embodiment 3, the polyester fiber in the step S4 is not subjected to polydopamine modification treatment, the elongation is obviously reduced, the mechanical property is reduced, after the polyester fiber is subjected to alkali treatment, more hydroxyl structures are formed on the surface, dopamine is further easily loaded, the polydopamine molecular chain is generated in situ under the action of a catalyst, after the polydopamine molecular chain is added into a nitrile rubber matrix, the polyester fiber can be well dispersed in the matrix to form a filler network structure, and meanwhile, the adhesiveness of a polyester fiber interface is obviously improved, and the toughness of modified rubber can be obviously improved.
Compared with the embodiment 3, the modified polyester fiber prepared in the step 5 is not added, and the added functionality, mechanical property, ageing resistance and oil resistance of the modified polyester fiber are reduced.
Compared with the embodiment 3, the performance of the modified rubber is obviously improved by adding the modified graphite and the modified polyester fiber without performing the steps from the step S1 to the step S5, and the prepared modified rubber has good ageing resistance, low-temperature performance, weather resistance, mechanical performance, processing performance and physicochemical performance and wide application prospect.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (10)

1. The preparation method of the modified rubber is characterized by comprising the following steps:
s1, preparing modified graphite: soaking graphite in alkali liquor, washing, drying, ball milling, sieving, adding ionic liquid, heating and stirring by microwaves, performing ultrasonic treatment, centrifuging, washing solids, and drying to obtain modified graphite;
the ionic liquid is imidazolyl ionic liquid;
s2, pretreatment of polyester fibers: adding the polyester fiber into an ethanol water solution containing alkali, heating and boiling, filtering and washing to obtain a pretreated polyester fiber;
S3, preparing a catalyst solution: dissolving cobalt salt in Tris-HCl buffer solution to obtain a 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, dripping the catalyst solution prepared in the step S3, heating for reaction, filtering, washing and drying to obtain the 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 the modified polyester fiber;
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;
s6, antioxidant treatment: ball milling the antioxidant, sieving, and drying to obtain antioxidant powder;
the antioxidant is a compound mixture of an antioxidant 1076 and an antioxidant 3114, and the mass ratio is (3-5): 1, a step of;
s7, preparation of modified rubber: mixing the nitrile rubber with modified graphite prepared in the step S1, modified polyester fiber prepared in the step S5, antioxidant powder prepared in the step S6, plasticizer, reinforcing filler and anti-aging agent, uniformly mixing, adding an accelerator and a vulcanizing agent, performing secondary open mixing, and vulcanizing to obtain modified rubber; the mass ratio of the nitrile rubber to the modified graphite to the modified polyester fiber to the antioxidant powder to the plasticizer to the reinforcing filler to the antioxidant to the accelerator to 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).
2. The method for producing a modified rubber according to claim 1, wherein the ball milling time in step S1 is 2 to 4 hours and the mesh number is 500 to 700 mesh; heating with microwave at 60-80deg.C, and stirring for 30-40min; the ultrasonic power is 1000-2000W, and the time is 1-3h; the alkali liquor is NaOH solution or KOH solution with the concentration of 1-2 mol/L; the ionic liquid is at least one selected from 1-butyl-3-ethylimidazole chloride, 1-butyl-3-ethylimidazole tetrafluoroboric acid, 1-butyl-3-ethylimidazole hexafluorophosphoric acid, 1-butyl-3-ethylimidazole acetic acid, 1, 3-dimethyl imidazole tetrafluoroboric acid, 1-butyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole tetrafluoroboric acid, 1-butyl-3-methylimidazole hexafluorophosphoric acid and 1-butyl-3-methylimidazole acetic acid.
3. The method for producing a modified rubber according to claim 1, wherein the aqueous ethanol solution containing alkali in step S2 is an aqueous ethanol solution containing 5 to 10 wt.% NaOH or KOH, wherein the ethanol content is 30 to 50 wt.%; the heating boiling time is 20-30mi.
4. The method 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 solution 2+ The ion concentration is 0.5-1.2wt%.
5. The method for producing a modified rubber according to claim 1, wherein 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 heating time is 3-5h.
6. The method for preparing modified rubber according to claim 1, wherein the mass ratio of the composite silane coupling agent to the polydopamine modified polyester fiber in the step S5 is (5-7): 50; the heating temperature is 70-90 ℃ and the heating time is 1-3h.
7. The method for producing a modified rubber according to claim 1, wherein the mesh number in step S6 is 200 to 500.
8. The method for producing a modified rubber according to claim 1, wherein the plasticizer in step S7 is at least one selected from the group consisting of polyether plasticizers, polyester plasticizers, adipate plasticizers, and aliphatic plasticizers; the reinforcing filler is at least one selected from carbon nano tube, carbon black, clay and nano calcium carbonate; the anti-aging agent is at least one selected from p-diphenylamine, nickel N, N-dibutyl dithiocarbamate, 2-mercaptobenzimidazole, N-isopropyl-N, -phenyl-p-phenylenediamine and 4,4 '-bis (a, a' -dimethylbenzyl) diphenylamine; the accelerator is at least one selected from tetramethylthiuram disulfide, triallyl cyanurate, N '-m-phenylene bismaleimide, 2' -dibenzothiazyl disulfide and N-cyclohexyl-2-benzothiazole sulfenamide; the vulcanizing agent is at least one selected from sulfur, ethylene thiourea, 2,4, 6-trithiol thiotriazine, dicumyl peroxide and di-o-toluene guanidine; the first open mill time is 10-15min; the second open mill time is 3-5min; the vulcanization condition is 165-175 ℃ under the pressure of 10-12MPa for 20-30min.
9. The method for producing a modified rubber according to claim 1, comprising the steps of:
s1, preparing modified graphite: soaking graphite in 1-2mol/L NaOH solution or KOH solution for 1-2h, washing, drying, ball milling for 2-4h, sieving with 500-700 mesh sieve, adding ionic liquid, heating to 60-80deg.C with microwave, stirring for 30-40min, ultrasonic treating for 1-3h with 1000-2000W, centrifuging, washing solid, and drying to obtain modified graphite;
s2, pretreatment of polyester fibers: adding the polyester fiber into an 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 pH value of 7.8-8.2 to obtain catalyst solution, wherein Co in the catalyst solution 2+ The ion concentration is 0.5-1.2wt%;
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, dripping 4-7 parts by weight of the catalyst solution prepared in the step S3, heating to 50-70 ℃, reacting for 3-5 hours, reacting, filtering, washing and drying to obtain the polydopamine modified polyester fiber;
S5, preparing modified polyester fibers: dissolving 5-7 parts by weight of a composite silane coupling agent in ethanol, adding 50 parts by weight of the polydopamine modified polyester fiber prepared in the step S4, heating to 70-90 ℃, stirring and reacting for 1-3 hours, filtering, washing and drying to obtain the modified polyester fiber;
s6, antioxidant treatment: ball milling the antioxidant, sieving with a 200-500 mesh sieve, and drying to obtain antioxidant powder;
s7, preparation of modified rubber: mixing 100 parts by weight of nitrile rubber for 10-15min, wrapping the nitrile rubber, adding 12-17 parts by weight of modified graphite prepared in the step S1, 15-22 parts by weight of modified polyester fiber prepared in the step S5, 3-5 parts by weight of 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 antioxidant, mixing for 20-40min, adding 0.2-2 parts by weight of accelerator and 0.5-1 part by weight of vulcanizing agent after mixing uniformly, and carrying out open mixing for 3-5min at 165-175 ℃ under the pressure of 10-12MPa, and vulcanizing for 20-30min to obtain modified rubber.
10. A modified rubber produced by the production process according to any one of claims 1 to 9.
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CN105776187A (en) * 2016-01-27 2016-07-20 复旦大学 Method for green environmental-protection preparation of high-concentration ultra-clean graphene dispersion liquid
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