CN107778553B - Rubber composite material and preparation method thereof - Google Patents
Rubber composite material and preparation method thereof Download PDFInfo
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- CN107778553B CN107778553B CN201711075955.3A CN201711075955A CN107778553B CN 107778553 B CN107778553 B CN 107778553B CN 201711075955 A CN201711075955 A CN 201711075955A CN 107778553 B CN107778553 B CN 107778553B
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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
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a rubber composite material and a preparation method thereof, wherein the rubber composite material comprises the following components: 100 parts of natural rubber, 40-50 parts of boron mud carbonization residue, 0.75-1.5 parts of accelerator, 5-10 parts of activator, 1-3 parts of stearic acid, 1.5-2.5 parts of sulfur, 3-5 parts of anti-aging agent and 5-10 parts of plasticizer. According to the invention, the boric sludge carbonization residue is applied to the rubber composite material, the compatibility between the boric sludge carbonization residue and rubber can be obviously improved through the optimization of each component in the formula and the optimization of the process, the prepared composite rubber material has better tensile strength and stress at definite elongation, can replace inorganic reinforcing fillers such as carbon black, argil, calcium carbonate and the like, not only can the production cost of rubber products be reduced, but also the characteristics of energy conservation and environmental protection are achieved, and the comprehensive utilization value of the boric sludge is greatly improved.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of solid wastes, and particularly relates to a rubber composite material and a preparation method thereof.
Background
The boron mud is alkaline solid waste generated in the borax production process by taking ascharite as a raw material, 4 tons of boron mud waste is generated along with the production of 1 ton of borax, the emission of the boron mud is large, a large amount of accumulated boron mud occupies land, and soda is added in the borax production process, so that the boron mud is strong in alkalinity and pollutes rivers.
At present, the treatment means of boron mud in China mainly utilizes boron mud waste to produce basic magnesium carbonate, boron-magnesium-phosphorus compound fertilizer, building bricks and the like. The process for preparing basic magnesium carbonate by using boron mud as a raw material through a carbonization method is the most mature, and the boron mud is used in the largest amount, but a large amount of calcium oxide is added in the process of producing the basic magnesium carbonate by using the method, so that almost equal amount of secondary solid waste (namely boron mud carbonization residue) can be generated. The main components of the material are 26.98 percent of magnesium oxide, 18.35 percent of calcium oxide, 4.09 percent of aluminum oxide, 2.53 percent of ferric oxide, 0.31 percent of potassium oxide, 0.14 percent of titanium oxide, 0.12 percent of manganese oxide and the like. The method is not favorable for comprehensive utilization of the boric sludge, and also does not accord with the national treatment principle of reduction, reutilization and resource utilization of waste resources. Therefore, the solid waste (namely the boron sludge carbonization residue) generated by the boron sludge for producing basic magnesium carbonate by the carbonization method must be further developed and utilized.
Through the analysis of the boron mud carbonization residue, the main chemical composition is as follows: magnesium oxide, silicon oxide, aluminum oxide, calcium oxide, iron oxide, sodium oxide, potassium oxide, and the like. The phase composition mainly comprises forsterite, calcite, quartz, pyrite, albite, potash feldspar and the like. At present, researches on using boron mud treated as rubber reinforcing filler have been reported, such as CN1044479, but the patent discloses a simple treatment mode of boron mud, and does not fully utilize effective components in boron mud.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide the rubber composite material, and the composite material adopts boric sludge carbonization residues as raw materials to replace argil, calcium carbonate and carbon black, so that the comprehensive utilization value of the boric sludge is greatly improved.
Another object of the present invention is to provide a method for preparing the above rubber composite material.
The invention is realized by the following technical scheme:
the rubber composite material comprises the following components in parts by weight:
100 parts of natural rubber, 40-50 parts of boron mud carbonization residue, 0.75-1.5 parts of accelerator, 5-10 parts of activator, 1-3 parts of stearic acid, 1.5-2.5 parts of sulfur, 3-5 parts of anti-aging agent and 5-10 parts of plasticizer.
The boron mud carbonization residue provided by the invention is solid waste generated in the process of producing basic magnesium carbonate by using boron mud as a raw material and adopting a carbonization method, and adopts a D8-FOCUS type X-ray diffractometer of Germany Bruker company, wherein the test conditions comprise that the scanning range is 5-70 degrees, the scanning speed is 2 degrees/min, Cu and K α are radiated, the wavelength is 1.54A, and the boron mud carbonization residue is analyzed to mainly comprise 25-27 percent of magnesium oxide, 17-20 percent of calcium oxide, 3-5 percent of aluminum oxide, 2-3 percent of ferric oxide, 0-0.5 percent of potassium oxide, 0-0.2 percent of titanium oxide, 0-0.2 percent of manganese oxide and the like, and the average grain size is tested to be less than 3 mu m by using a laser grain size analyzer.
Preferably, the boron mud carbonization residue is boron mud carbonization residue pretreated by a coupling agent, the addition amount of the coupling agent is 1-3 parts based on the total weight part of the whole rubber composite material, the coupling agent is one or a mixture of silane coupling agent, aluminate or stearic acid, and Si69 or KH560 is preferable. The surface pretreatment of the boron mud carbonization residue by using the coupling agent can improve the compatibility of the boron mud carbonization residue with a rubber matrix and further improve the mechanical property of the material.
The accelerator is one or a mixture of several of N-cyclohexyl-2-benzothiazole sulfonamide (accelerator CZ), symmetric diphenyl guanidine (accelerator D), 2-mercaptobenzothiazole (accelerator M) or tetramethyl thiuram disulfide (accelerator TMTD), and preferably N-cyclohexyl-2-benzothiazole sulfonamide (accelerator CZ) or symmetric diphenyl guanidine (accelerator D).
The active agent is one or the mixture of two of zinc oxide and magnesium oxide.
The anti-aging agent is one or a mixture of more of N-isopropyl-N' -phenyl-p-phenylenediamine (anti-aging agent 4010 NA), N-phenyl- β -naphthylamine (anti-aging agent D) or 2,2, 4-trimethyl-1, 2-dihydroquinoline (anti-aging agent RD).
The plasticizer is one or more of machine oil (such as No. 13 machine oil), paraffin, pine tar or coumarone resin.
The invention adopts the boron mud carbonization residue as the raw material, and has the advantages of fine particle size, large specific surface area and stable chemical property. The boron mud carbonization residue belongs to secondary waste residue, is alkaline, and has a pH value of 9.5-10, and the invention reasonably selects an accelerator aiming at the alkaline physical characteristics of the boron mud carbonization residue in the formula, and adopts a coupling agent to carry out surface pretreatment on the boron mud carbonization residue, thereby improving the compatibility of the boron mud carbonization residue with a rubber matrix and improving the mechanical property of the material.
The invention also provides a preparation method of the rubber composite material, which comprises the following steps:
(1) according to the mass ratio of the raw materials, placing the boron mud carbonization residue in a high-speed ball-milling mixer for pretreatment to obtain pretreated boron mud carbonization residue for later use;
(2) adjusting the roll spacing of an open mill, placing natural rubber between two rolls for plastication for 5-10 min, then sequentially adding an active agent, stearic acid, an accelerator, an anti-aging agent and a plasticizer step by step for mixing for 3-5 min, after uniform dispersion, adding pretreated boron mud carbonization residues, cutting and turning for many times after the powder consumption of rubber materials is finished, finally adding sulfur, after uniform mixing, thinly passing for 5-10 times, smashing rubber and discharging to obtain mixed rubber, and aging for later use;
(3) and putting the aged rubber compound into a flat vulcanizing machine for vulcanization to obtain the rubber composite material.
Preferably, in step (1), the pretreatment conditions are as follows: the rotating speed is 800 r/min-1000 r/min, the time is 10-30 min, and the temperature is 80-100 ℃.
Preferably, in the step (3), the vulcanization conditions are as follows: the temperature is 140-150 ℃, the pre-pressing pressure is 8-10MPa, the vulcanizing pressure is 13-15MPa, and the vulcanizing time is 10-15 min.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention applies the boron mud carbonization residue to the rubber composite material, and optimizes and works all components in the formula
The compatibility between the boric sludge carbonization residue and rubber can be obviously improved by optimizing the process, the prepared composite rubber material has better tensile strength and stress at definite elongation, can replace inorganic reinforcing fillers such as carbon black, argil, calcium carbonate and the like, can greatly reduce the use of the reinforcing fillers such as high-energy-consumption and high-pollution carbon black and the like, not only can reduce the production cost of rubber products, but also has the characteristics of energy conservation and environmental protection, and greatly improves the comprehensive utilization value of the boric sludge.
(2) The production method is simple, can effectively treat a large amount of waste materials generated in the process of producing basic magnesium carbonate from boron sludge, and accords with the national treatment principle of reduction, reutilization and resource utilization of waste resources.
Detailed Description
The following examples are given to specifically describe the present invention, but are not limited thereto.
B, boron mud carbonization residue: the method comprises the steps of using boron mud as a main raw material, adding calcium oxide to carry out digestion reaction, cooling a mixed solution, placing the cooled mixed solution in a high-pressure reaction kettle, pressurizing and introducing carbon dioxide to carry out carbonization reaction, stopping introducing the carbon dioxide when the pH of the mixed solution reaches 7, drying and grinding solid waste filtered by the mixed solution to obtain boron mud carbonization residues, and testing the average particle size of the boron mud carbonization residues to be 2.54 mu m by using a laser particle size analyzer.
Other raw materials used in the examples and comparative examples of the present invention were all commercially available.
Example 1 and comparative examples 1-3:
(1) as shown in Table 1, the boron sludge carbonization residue and the coupling agent are put into a high-speed ball mill mixer for pretreatment and pretreatment
The treatment conditions were: rotating at a speed of 800 r/min-1000 r/min for 10-30 min at a temperature of 80-100 ℃ to obtain pretreated boron mud carbonization residues for later use;
(2) adjusting the roller spacing of the open mill, placing the natural rubber between two rollers for plastication for 5-10 min, and then sequentially dividing
Adding an active agent, stearic acid, an accelerator, an anti-aging agent and a plasticizer, mixing for 3-5 min, after the materials are uniformly dispersed, adding pretreated boron mud carbonization residues, cutting and turning for many times after the materials are powdered, finally adding sulfur, after the materials are uniformly mixed, thinly passing for 5-10 times, smashing the materials, discharging to obtain mixed rubber, and aging for later use;
(3) placing the aged rubber compound into a flat vulcanizing machine for vulcanization to obtain a rubber composite material; conditions of vulcanization
Comprises the following steps: the temperature is 140-150 ℃, the pre-pressing pressure is 8-10MPa, the vulcanizing pressure is 13-15MPa, and the vulcanizing time is 10-15 min.
Examples 2 to 9:
as shown in Table 1, the boron sludge carbonization residue and the coupling agent are put into a high-speed ball mill mixer for pretreatment and pretreatment
The conditions of treatment are as follows: rotating at a speed of 800 r/min-1000 r/min for 10-30 min at a temperature of 80-100 ℃ to obtain pretreated boron mud carbonization residues for later use;
the rest is the same as example 1.
The obtained rubber composite material was subjected to a performance test according to the following method, and the test results are shown in table 2.
The performance test method comprises the following steps:
300% stress at definite elongation: the test is carried out according to GB/T528-2009 determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber, and the tensile rate is 500 mm/min.
Shore hardness: according to GB/T531-2008 Shore A hardness test method for vulcanized rubber or thermoplastic rubber.
Tensile strength at break: the test is carried out according to GB/T528-2009 determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber, and the tensile rate is 500 mm/min.
Density: the method A is selected for determination according to GB/T533-2008 determination of vulcanized rubber or thermoplastic rubber density.
Average particle size: a laser particle size analyzer is adopted, water is used as a medium, a certain amount of boron mud carbonization residue sample is added into a sample pool, sample particles are dispersed in the water through physical mechanical stirring, ultrasonic waves are started to disperse agglomerated particles, a circulating pump is started to uniformly distribute the particles in the system, the shading ratio is controlled to be 1-2 in the whole process, and the test is carried out.
TABLE 1 concrete compounding ratio (parts by weight) of each component in each example and comparative example
TABLE 2 Performance test data for each of the examples and comparative examples
As is clear from comparison between example 1 and comparative examples 1 to 3 in Table 2, the rubber composite material prepared from the boric sludge carbonized residue as a raw material has better properties than the comparative examples using general-purpose carbon black, calcium carbonate and kaolin as raw materials, and therefore the boric sludge carbonized residue can be completely used in the preparation of the rubber composite material instead of kaolin, calcium carbonate and carbon black.
Claims (9)
1. The rubber composite material is characterized by comprising the following components in parts by weight:
100 parts of natural rubber, 40-50 parts of boron mud carbonization residue, 0.75-1.5 parts of accelerator, 5-10 parts of activator, 1-3 parts of stearic acid, 1.5-2.5 parts of sulfur, 3-5 parts of anti-aging agent and 5-10 parts of plasticizer;
the boron mud carbonization residue is solid waste generated in the process of producing basic magnesium carbonate by using boron mud as a raw material through a carbonization method, and the average particle size of the boron mud carbonization residue is less than 3 mu m by using a laser particle size analyzer.
2. The rubber composite according to claim 1, wherein the boric sludge carbonization residue is a boric sludge carbonization residue pretreated with a coupling agent.
3. The rubber composite material as claimed in claim 2, wherein the coupling agent is added in an amount of 1-3 parts based on the total parts by weight of the entire rubber composite material, and the coupling agent is one or more of silane coupling agent, aluminate or stearic acid.
4. The rubber composite according to claim 3, wherein the coupling agent is Si69 or KH 560.
5. The rubber composite of claim 1, wherein the accelerator is one or a mixture of N-cyclohexyl-2-benzothiazolesulfenamide, diphenyl guanidine, 2-mercaptobenzothiazole, or tetramethylthiuram disulfide; the active agent is one or the mixture of two of zinc oxide and magnesium oxide.
6. The rubber composite of claim 5, wherein the accelerator is N-cyclohexyl-2-benzothiazolesulfenamide or symmetric diphenylguanidine.
7. The rubber composite material of claim 1, wherein the anti-aging agent is one or a mixture of N-isopropyl-N' -phenyl-p-phenylenediamine, N-phenyl- β -naphthylamine or 2,2, 4-trimethyl-1, 2-dihydroquinoline, and the plasticizer is one or a mixture of mechanical oil, paraffin, pine tar or coumarone resin.
8. A method for preparing a rubber composite according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) adjusting the roll spacing of an open mill, placing natural rubber between two rolls for plastication for 5-10 min, then sequentially adding an active agent, stearic acid, an accelerator, an anti-aging agent and a plasticizer step by step for mixing for 3-5 min, after the natural rubber is uniformly dispersed, adding boron mud carbonized residues, cutting and turning for many times after the rubber material is powdered, finally adding sulfur, after the natural rubber is uniformly mixed, thinly passing for 5-10 times, and smashing and slicing to obtain mixed rubber for aging for later use;
(2) and putting the aged rubber compound into a flat vulcanizing machine for vulcanization to obtain the rubber composite material.
9. The method for producing a rubber composite according to claim 8, wherein in the step (2), the vulcanization is carried out under the conditions of: the temperature is 140-150 ℃, the pre-pressing pressure is 8-10MPa, the vulcanizing pressure is 13-15MPa, and the vulcanizing time is 10-15 min.
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| CN108612741A (en) * | 2018-05-10 | 2018-10-02 | 昆山沃城胶辊有限公司 | a kind of corrosion-resistant rubber roller |
| CN111423620A (en) * | 2020-03-20 | 2020-07-17 | 河北旭龙液压密封件有限公司 | Rubber wear-resistant agent and preparation method thereof, wear-resistant and aging-resistant vulcanized rubber and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044479A (en) * | 1989-11-11 | 1990-08-08 | 姜国刚 | Application in boron mud powder production technique and the rubber item |
| CN101623904A (en) * | 2009-07-29 | 2010-01-13 | 沈阳化工学院 | Preparation method for synthesizing rubber pad by using boric sludge for filling neoprene and natural rubber |
| CN105566773A (en) * | 2014-10-13 | 2016-05-11 | 夏安娜 | Environment-friendly flame retardant rubber and preparation method thereof |
| CN106674800A (en) * | 2016-11-30 | 2017-05-17 | 安徽惠尔矿用设备有限公司 | Mine coated fabric with flame-retardant effect |
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2017
- 2017-11-06 CN CN201711075955.3A patent/CN107778553B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044479A (en) * | 1989-11-11 | 1990-08-08 | 姜国刚 | Application in boron mud powder production technique and the rubber item |
| CN101623904A (en) * | 2009-07-29 | 2010-01-13 | 沈阳化工学院 | Preparation method for synthesizing rubber pad by using boric sludge for filling neoprene and natural rubber |
| CN105566773A (en) * | 2014-10-13 | 2016-05-11 | 夏安娜 | Environment-friendly flame retardant rubber and preparation method thereof |
| CN106674800A (en) * | 2016-11-30 | 2017-05-17 | 安徽惠尔矿用设备有限公司 | Mine coated fabric with flame-retardant effect |
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