CN111635567A - Oxidation-resistant natural rubber compound and preparation method thereof - Google Patents
Oxidation-resistant natural rubber compound and preparation method thereof Download PDFInfo
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- CN111635567A CN111635567A CN202010625975.9A CN202010625975A CN111635567A CN 111635567 A CN111635567 A CN 111635567A CN 202010625975 A CN202010625975 A CN 202010625975A CN 111635567 A CN111635567 A CN 111635567A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses an oxidation-resistant natural rubber compound and a preparation method thereof, belonging to the field of natural rubber, and the key point of the technical scheme is that the oxidation-resistant natural rubber compound comprises the following raw materials by weight: 100 parts of natural rubber, 40-60 parts of carbon black, 3-6 parts of naphthenic oil, 3-6 parts of zinc oxide, 1-3 parts of stearic acid, 3-5 parts of protective wax, 1-3 parts of anti-aging agent, 1-3 parts of accelerator, 2-5 parts of sulfur, 1-3 parts of antiscorching agent CTP and 1-5 parts of functionalized graphene FEG. According to the invention, the antioxidant is added in the preparation process of the natural rubber, so that the oxidation resistance effect of the prepared rubber is improved, and the service life of the natural rubber product is prolonged under the condition of contacting with air.
Description
Technical Field
The invention relates to the field of natural rubber, and particularly relates to an oxidation-resistant natural rubber compound and a preparation method thereof.
Background
Natural rubber is a natural polymer compound, the main component of which is generally a polyolefin, and which contains other organic substances such as proteins, saccharides, and the like, and has been used for various articles for daily use and industry because of its excellent flexibility, strength, and electrical insulation properties. In addition, because the natural rubber has great elasticity, the natural rubber can be used for manufacturing different types of automobile articles, such as automobile tires, special adhesive tapes for agricultural machinery and the like.
As a non-synthetic elastomer, natural rubber is widely used in the production of industrial belts such as hexagonal belts and narrow V belts, rubber tracks such as engineering machine tracks and agricultural machine tracks, and various cut V belts. However, because the molecular structure of natural rubber contains unsaturated double bonds and active allyl hydrogen, the natural rubber and products thereof inevitably have polymer breakage and oxygen-containing groups during processing and use, seriously damage the physical and mechanical properties of the products and even lose the use value. Therefore, the ozone resistance effect of the natural rubber product is improved, and the ozone resistance effect has important significance for prolonging the service life of the natural rubber product in the process of contacting air.
Disclosure of Invention
The invention aims to provide an anti-oxidation natural rubber compound and a preparation method thereof.
The technical purpose of the invention is realized by the following technical scheme:
an oxidation-resistant natural rubber compound comprises the following raw materials in parts by weight: 100 parts of natural rubber, 40-60 parts of carbon black, 3-6 parts of naphthenic oil, 3-6 parts of zinc oxide, 1-3 parts of stearic acid, 3-5 parts of protective wax, 1-3 parts of an anti-aging agent, 1-3 parts of an accelerator, 2-5 parts of sulfur, 1-3 parts of an anti-scorching agent CTP, and 1-5 parts of functionalized graphene FEG.
Further, the functionalized graphene FEG is prepared by grafting tert-butyl-6-acrylic acid-4-methyl p-methyl methacrylate onto graphene through a coupling agent.
Further, the coupling agent is one of KH580 or KH 590.
Further, the carbon black comprises one or a mixture of carbon black N550 or carbon black N774.
Further, the protective wax is one of or a mixture of protective wax 654 or protective wax 9344.
Further, the anti-aging agent is one or a mixture of anti-aging agent 3100 and anti-aging agent 4020.
Further, the preparation method of the oxidation-resistant natural rubber compound comprises the following steps:
step S1: preparing a coupling agent solution, mixing the coupling agent solution with a graphene oxide solution, reacting for 6-8h at 90-95 ℃ under the condition of air isolation to obtain an intermediate product, and grafting tert-butyl-6-acrylic acid-4-methyl-p-methyl methacrylate onto graphene oxide according to the mass ratio of tert-butyl-6-acrylic acid-4-methyl-p-methyl methacrylate to graphene oxide of 1:1 to obtain functionalized graphene FEG for later use;
step S2: adding a dispersing agent to ultrasonically disperse the functional graphene FEG prepared in the step S1 in water to prepare a suspension, weighing natural rubber according to the mass ratio of 1:100, adding the natural rubber into the suspension, adding a calcium chloride solution to demulsify, filtering and washing to prepare a composite natural rubber;
step S3: setting a roller spacing of 0.5-1.5mm, plasticizing the composite natural rubber, standing for 30-40min, kneading the composite natural rubber, sequentially adding 40-60 parts of carbon black, 3-6 parts of naphthenic oil, 3-6 parts of zinc oxide, 1-3 parts of stearic acid, 3-5 parts of protective wax, 1-3 parts of an anti-aging agent, 1-3 parts of a promoter and 1-3 parts of an anti-scorching agent, and discharging rubber at the temperature of 110-120 ℃ to obtain a rubber compound;
step S4: adding the rubber compound into an open mill, adding 2-5 parts of sulfur, cutting for 5-8 times by a left cutter and a right cutter, beating for 7-10 times by a thin-pass triangular bag, and exhausting and discharging;
step S5: and vulcanizing the mixed rubber processed in the step S4 to obtain a vulcanized rubber material.
In conclusion, the invention has the following beneficial effects:
1. the functional graphene FEG is added into the rubber, and more curved surfaces appear on the surface of molecules of the functional graphene FEG compared with graphene oxide, so that the functional graphene FEG is doped into natural rubber, on one hand, oxygen is prevented from entering the functional graphene FEG by a lamella in the functional graphene FEG, on the other hand, the hindered phenol group and the thioether bond are synergistically antioxidant, and the antioxidant effect of the prepared rubber is further improved.
2. The functionalized graphene FEG is mixed with the natural rubber by an emulsion mixing method, so that the dispersion uniformity of the functionalized graphene FEG in the natural rubber is improved, and the thermal stability of the prepared rubber product is improved.
Detailed Description
Example 1:
an oxidation-resistant natural rubber compound comprises the following raw materials in parts by weight: 100 parts of natural rubber, 45 parts of carbon black, 3 parts of naphthenic oil, 3 parts of zinc oxide, 2 parts of stearic acid, 3 parts of protective wax, 3 parts of an anti-aging agent, 2 parts of an accelerator, 2 parts of sulfur, 2 parts of an anti-scorching agent CTP, and 1 parts of functionalized graphene FEG. The functionalized graphene FEG is prepared by grafting tert-butyl-6-acrylic acid-4-methyl-p-methyl methacrylate onto graphene through a coupling agent, wherein the tert-butyl-6-acrylic acid-4-methyl-p-methyl methacrylate is abbreviated as GM, and GM recorded in the subsequent documents is tert-butyl-6-acrylic acid-4-methyl-p-methyl methacrylate. Wherein the carbon black is a mixture of carbon black N550 and carbon black N774 in a mass ratio of 1:1, and the protective wax is a mixture of protective wax 654 and protective wax 9344 in a mass ratio of 1: 1. The anti-aging agent is a mixture of anti-aging agent 3100 and anti-aging agent 4020 in a mass ratio of 1: 1.
A method for preparing an oxidation-resistant natural rubber compound as described above, comprising the steps of:
step S1: preparing a coupling agent solution, wherein the coupling agent is KH590, mixing the coupling agent solution with a graphene oxide solution, reacting for 6 hours at 95 ℃ under the protection of nitrogen under the condition of air isolation to obtain an intermediate product, and grafting GM onto graphene oxide according to the mass ratio of 1:1 of GM to graphene oxide to obtain functionalized graphene FEG for later use;
step S2: adding a dispersing agent OP-10, ultrasonically dispersing the functional graphene FEG prepared in the step S1 in water to prepare a suspension, weighing natural rubber according to the mass ratio of 1:100, adding the natural rubber into the suspension, adding a calcium chloride solution for demulsification, filtering and washing to prepare a composite natural rubber, wherein the concentration of the calcium chloride solution is 5 mg/ml;
step S3: setting a roller spacing of 0.5mm, plasticizing the composite natural rubber, standing for 30min, kneading the composite rubber, sequentially adding 100 parts of natural rubber, 45 parts of carbon black, 3 parts of naphthenic oil, 3 parts of zinc oxide, 2 parts of stearic acid, 3 parts of protective wax, 3 parts of anti-aging agent, 2 parts of accelerant, 2 parts of sulfur, 2 parts of antiscorching agent CTP, 2 parts of functionalized graphene FEG, and discharging rubber at the temperature of 120 ℃ to obtain rubber compound;
step S4: adding the rubber compound into an open mill, adding 2 parts of sulfur, cutting for 6 times by a left cutter and a right cutter, performing thin-pass triangular bag making for 8 times, exhausting and discharging;
step S5, vulcanizing the mixed rubber processed in the step S4 under the vulcanization condition of 150 ℃/8MPa × (t)90+5min) to obtain the vulcanized rubber material.
Example 2:
an oxidation-resistant natural rubber compound comprises the following raw materials in parts by weight: 100 parts of natural rubber, 50 parts of carbon black, 4 parts of naphthenic oil, 3 parts of zinc oxide, 3 parts of stearic acid, 3 parts of protective wax, 4 parts of an anti-aging agent, 4 parts of an accelerator, 3 parts of sulfur, 3 parts of an anti-scorching agent CTP, and 2 parts of functionalized graphene FEG. The rest of the procedure is as in example 1.
Example 3:
an oxidation-resistant natural rubber compound comprises the following raw materials in parts by weight: 100 parts of natural rubber, 45 parts of carbon black, 3 parts of naphthenic oil, 3 parts of zinc oxide, 2 parts of stearic acid, 3 parts of protective wax, 3 parts of an anti-aging agent, 2 parts of an accelerator, 2 parts of sulfur, 2 parts of an anti-scorching agent CTP, and 3 parts of functionalized graphene FEG. The rest of the procedure is as in example 1.
Example 4:
an oxidation-resistant natural rubber compound comprises the following raw materials in parts by weight: 100 parts of natural rubber, 45 parts of carbon black, 3 parts of naphthenic oil, 3 parts of zinc oxide, 2 parts of stearic acid, 3 parts of protective wax, 3 parts of an anti-aging agent, 2 parts of an accelerator, 2 parts of sulfur, 2 parts of an anti-scorching agent CTP, and 4 parts of functionalized graphene FEG. The rest of the procedure is as in example 1.
Example 5:
an oxidation-resistant natural rubber compound comprises the following raw materials in parts by weight: 100 parts of natural rubber, 45 parts of carbon black, 3 parts of naphthenic oil, 3 parts of zinc oxide, 2 parts of stearic acid, 3 parts of protective wax, 3 parts of an anti-aging agent, 2 parts of an accelerator, 2 parts of sulfur, 2 parts of an anti-scorching agent CTP, and 5 parts of functionalized graphene FEG. The rest of the procedure is as in example 1.
Example 6:
an oxidation-resistant natural rubber compound comprises the following raw materials in parts by weight: 100 parts of natural rubber, 45 parts of carbon black, 3 parts of naphthenic oil, 3 parts of zinc oxide, 2 parts of stearic acid, 3 parts of protective wax, 3 parts of an anti-aging agent, 2 parts of an accelerator, 2 parts of sulfur, 2 parts of an anti-scorching agent CTP, and 0 parts of functionalized graphene FEG. The rest of the procedure is as in example 1.
As shown in table 1, six types of rubber compounds prepared according to the formulations in examples 1 to 6 are named as # 1, # 2, # 3, # 4, # 5 and # 6, respectively, wherein # 6 is used as a comparative example, no functionalized graphene FEG is added, and the rubber compound is tested for relevant performance by using a rheometer, which is used for testing the test conditions of 185 ℃ for 3min and the breaking time of a sample which is 20% 40 ℃ under the ozone concentration of 200pphm, and the test results are as follows:
table 1 rheometer test data for six compounds
The data in table 1 show that with the addition of the functionalized graphene FEG, the physical and mechanical properties of the prepared rubber product are improved, and particularly, the fracture time of the 1# to 5# rubber compound is increased compared with that of the 6# rubber compound, so that the functionalized graphene FEG provided by the invention is further illustrated, the ozone resistance effect of the prepared rubber is improved, and the functionalized graphene FEG has more curved surfaces on the surface of molecules compared with oxidized graphene, so that the functionalized graphene FEG is doped into natural rubber, on one hand, the sheet layer in the functionalized graphene FEG obstructs the entry of oxygen, on the other hand, the hindered phenol group and thioether bond synergistically resist oxidation, and thus the service life of the rubber product under the condition of long-term air contact is prolonged.
The present embodiment is only illustrative and not restrictive, and those skilled in the art can modify the present embodiment as required without inventive contribution after reading the present specification, but only protected by the scope of the claims of the present invention.
Claims (7)
1. An oxidation-resistant natural rubber compound is characterized by comprising the following raw materials in parts by weight: 100 parts of natural rubber, 40-60 parts of carbon black, 3-6 parts of naphthenic oil, 3-6 parts of zinc oxide, 1-3 parts of stearic acid, 3-5 parts of protective wax, 1-3 parts of anti-aging agent, 1-3 parts of accelerator, 2-5 parts of sulfur, 1-3 parts of antiscorching agent CTP and 1-5 parts of functionalized graphene FEG.
2. An oxidation-resistant natural mix as claimed in claim 1, characterized in that: the functionalized graphene FEG is prepared by grafting tert-butyl-6-acrylic acid-4-methyl p-methyl methacrylate onto graphene through a coupling agent.
3. An oxidation-resistant natural mix as claimed in claim 2, characterized in that: the coupling agent is one of KH580 or KH 590.
4. An oxidation-resistant natural mix as claimed in claim 1, characterized in that: the carbon black comprises one of carbon black N550 or carbon black N774 or a mixture of the two.
5. An oxidation-resistant natural mix as claimed in claim 1, characterized in that: the protective wax is one or a mixture of protective wax 654 or protective wax 9344.
6. An oxidation-resistant natural mix as claimed in claim 1, characterized in that: the anti-aging agent is one or a mixture of anti-aging agent 3100 and anti-aging agent 4020.
7. A method of preparing an oxidation resistant natural rubber mix according to claim 1, comprising the steps of:
step S1: preparing a coupling agent solution, mixing the coupling agent solution with a graphene oxide solution, reacting for 6-8 hours at 90-95 ℃ under the condition of air isolation to obtain an intermediate product, and grafting tert-butyl-6-acrylic acid-4-methyl-p-methyl methacrylate onto graphene oxide according to the mass ratio of tert-butyl-6-acrylic acid-4-methyl-p-methyl methacrylate to graphene oxide of 1:1 to obtain functionalized graphene FEG for later use;
step S2: adding a dispersing agent to ultrasonically disperse the functionalized graphene FEG prepared in the step S1 in water to prepare a suspension, weighing natural rubber according to the mass ratio of 1:100, adding the natural rubber into the suspension, adding a calcium chloride solution to demulsify, filtering and flushing to prepare a composite natural rubber;
step S3: setting a roller spacing of 0.5-1.5mm, plasticizing the composite natural rubber, standing for 30-40min, kneading the composite natural rubber, sequentially adding 40-60 parts of carbon black, 3-6 parts of naphthenic oil, 3-6 parts of zinc oxide, 1-3 parts of stearic acid, 3-5 parts of protective wax, 1-3 parts of an anti-aging agent, 1-3 parts of an accelerator and 1-3 parts of an anti-scorching agent CTP, and discharging rubber at the temperature of 110-;
step S4: adding the rubber compound into an open mill, adding 2-5 parts of sulfur, cutting for 5-8 times by a left cutter and a right cutter, beating for 7-10 times by a thin-pass triangular bag, and exhausting and discharging;
step S5: and (4) vulcanizing the mixed rubber processed in the step S4 to obtain a vulcanized rubber material.
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| KR20160077580A (en) * | 2014-12-23 | 2016-07-04 | 주식회사 포스코 | Graphene coating composition, graphene coated steel sheet and manufacturing method thereof |
| CN105801943A (en) * | 2016-05-31 | 2016-07-27 | 青岛双星轮胎工业有限公司 | Tread rubber composite material containing modified graphene oxide compound and preparation method of tread rubber composite material containing modified graphene oxide compound |
| CN106867031A (en) * | 2017-01-17 | 2017-06-20 | 东莞理工学院 | Graphene-based antioxidant and its preparation method and application |
| CN107857897A (en) * | 2017-10-30 | 2018-03-30 | 华南理工大学 | A kind of hindered phenol functionalization graphene and its preparation method and application |
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- 2020-07-01 CN CN202010625975.9A patent/CN111635567A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160077580A (en) * | 2014-12-23 | 2016-07-04 | 주식회사 포스코 | Graphene coating composition, graphene coated steel sheet and manufacturing method thereof |
| CN105801943A (en) * | 2016-05-31 | 2016-07-27 | 青岛双星轮胎工业有限公司 | Tread rubber composite material containing modified graphene oxide compound and preparation method of tread rubber composite material containing modified graphene oxide compound |
| CN106867031A (en) * | 2017-01-17 | 2017-06-20 | 东莞理工学院 | Graphene-based antioxidant and its preparation method and application |
| CN107857897A (en) * | 2017-10-30 | 2018-03-30 | 华南理工大学 | A kind of hindered phenol functionalization graphene and its preparation method and application |
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