CN109627502B - Composite material of natural rubber and preparation method thereof - Google Patents
Composite material of natural rubber and preparation method thereof Download PDFInfo
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- CN109627502B CN109627502B CN201811337752.1A CN201811337752A CN109627502B CN 109627502 B CN109627502 B CN 109627502B CN 201811337752 A CN201811337752 A CN 201811337752A CN 109627502 B CN109627502 B CN 109627502B
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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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
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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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
Abstract
The invention relates to the technical field of natural rubber composite materials, in particular to a composite material of natural carageenan rubber and natural rubber and a preparation method thereof, wherein the preparation method comprises the following steps: (1) weighing natural latex, adding water to dilute, stirring uniformly, adding a surfactant while stirring, and then adding tetraethylenepentamine to prepare a latex mixed solution. (2) Methyl methacrylate monomer was added. (3) Heating the latex mixed solution to 40-60 ℃ in a water bath, dropwise adding an initiator, and reacting at a constant temperature for 3-7h to obtain a Tianjia rubber emulsion; adding natural latex into the latex, and then heating or adding acid for solidification to prepare mixed rubber of the natural rubber and the natural rubber; (4) and weighing the mixed rubber, the natural rubber, the silicon dioxide and other auxiliaries of the carbon black machine, mixing, and vulcanizing by adopting a mechanical dry blending process to prepare the natural rubber and natural rubber composite material. The composite material prepared by the invention has good processing performance and mechanical property.
Description
Technical Field
The invention relates to the technical field of natural rubber composite materials, in particular to a composite material of natural rubber and a preparation method thereof.
Background
Natural Rubber (NR) is widely used in tire tread rubber, especially in the field of engineering tires, due to its broad molecular weight distribution, good processability and excellent mechanical properties. Rubber articles must be able to be used by efficient reinforcement of the filler. Since the 20 th century, Carbon Black (CB) has been the most important reinforcing agent for rubber products, 90-95% of CB consumption is used in the rubber industry worldwide, and tires account for 67.5%. However, with the increasingly prominent energy and environmental crises, the high price of carbon black and the high environmental pollution caused by the processing process, the development of non-carbon black fillers, especially inorganic fillers capable of forming a nano composite structure with rubber, to replace or partially replace carbon black becomes an important development direction of the current rubber science and industry.
Wherein, SiO2Is an important substitute of carbon black and is widely used for rubber products. Because of SiO2The processing performance of rubber is improved, the dependence of a rubber loss factor (tan delta) on temperature can be increased, the heat generation and rolling resistance are reduced, and the wear resistance and wet skid resistance of rubber materials are improved, so that the 'green tire' developed by the method also becomes an important field of the current rubber industry.
High-dispersity SiO2Better overall performance (low viscosity, low rolling resistance and high wet skid and wear resistance) can be obtained for the tire, but SiO2The surface energy is large, and the rubber material is easy to agglomerate in a rubber matrix, so that the abrasion resistance of the rubber material is poor, and the hysteresis loss is large. Therefore, SiO is improved2The dispersibility of particles in NR is critical for the development of high performance NR masterbatches. The surface modification is an important way for obtaining the high-dispersity white carbon black, and the coupling agent is used for improving SiO2The main modifier of dispersibility. The silane coupling agent is added into the white carbon black sizing material, so that the three indexes of the tire can reach the bestAnd (4) balancing. In addition, in addition to SiO2Besides the surface properties, the properties of the rubber matrix also have an important influence on the dispersion of the white carbon black, which is shown in that the polar groups grafted on the nonpolar rubber matrix can generate strong action with the polar groups of the filler. In the NR system, the most typical is Epoxidized Natural Rubber (ENR) to improve SiO2In the case of dispersion in NR, ENR molecular chains have epoxy groups, have increased polarity, and interact strongly with filler particles, as compared to NR. However, this approach is not systematic, and the mechanism of the ENR as a compatibilizer needs further investigation. In addition, ENR is expensive, leading to increased production costs, and also inhibiting its use in the tire industry.
Compared with epoxidized natural rubber, the Tianjia rubber has lower cost and better application prospect. The polar monomer methyl methacrylate is used for grafting and modifying the nonpolar natural rubber, the prepared natural rubber and the prepared natural rubber can be mixed and dissolved in any proportion, and the obtained mixed rubber is used as an interface compatibilizer, so that the compatibility between the highly polar silicon dioxide and the nonpolar natural rubber can be improved, the interface bonding force between the highly polar silicon dioxide and the nonpolar natural rubber can be enhanced, a network structure with mutual permeation, tight bonding and mutual penetration between molecular chains of the silicon dioxide and the natural rubber is formed, and the important research value is realized.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a preparation method of a composite material of a natural rubber and a natural rubber, wherein the preparation method is used for preparing the natural rubber by introducing a polar group into a natural rubber molecular chain through a method of graft copolymerization with a polar monomer methyl methacrylate; according to the similar compatibility principle, the natural rubber is used as a compatibilizer to improve the compatibility between the nonpolar natural rubber and the polar filler silicon dioxide; and then the binding force between the rubber matrix and the filler is enhanced, so that the dispersibility of the filler in the matrix is promoted, and the mechanical property of the composite material is improved.
The invention also aims to provide a composite material of the natural rubber and the natural rubber, which has good processing performance and mechanical property, the stress at definite elongation, the tensile strength and the tearing strength of the composite material are far superior to those of the white carbon black/carbon black filled natural rubber, the reinforcing performance and the wear resistance of the composite material are equivalent to those of the white carbon black/carbon black filled rubber, and the heat generation and the rolling resistance of the composite material are obviously lower than those of the white carbon black/carbon black filled rubber.
The purpose of the invention is realized by the following technical scheme: a preparation method of a composite material of natural rubber and natural rubber comprises the following steps:
(1) weighing 100 parts by weight of natural latex, adding water to dilute the natural latex to a mass concentration of 20-45%, uniformly stirring, adding 0.01-10 parts by weight of surfactant while stirring, adding 0.03-5.0 parts by weight of tetraethylenepentamine, and preparing latex mixed solution;
(2) weighing 30-50 parts by weight of methyl methacrylate monomer, adding into the latex mixed solution, and stirring and dispersing;
(3) heating the latex mixed solution added with the methyl methacrylate monomer to 40-60 ℃ in a water bath, dropwise adding 0.03-5.0 parts by weight of initiator, and reacting at constant temperature for 3-7h to obtain a Tianjia rubber emulsion; adding 100 parts by weight of natural latex into the latex of the natural rubber, adding water to dilute the latex into 20-45% of emulsion by mass concentration, heating or adding acid to solidify the latex, curing, extruding, granulating, washing and drying the latex to obtain the mixed rubber of the natural rubber and the natural rubber;
(4) weighing 5-70 parts by weight of the mixed rubber, 30-95 parts by weight of natural rubber, 10-50 parts by weight of silicon dioxide, 10-50 parts by weight of carbon black, 0.1-5.0 parts by weight of silane coupling agent, 0.1-10 parts by weight of anti-aging agent, 0.1-10 parts by weight of sulfur, 0.1-5 parts by weight of accelerator, 0.1-15 parts by weight of zinc oxide and 0.1-10 parts by weight of stearic acid, mixing, and vulcanizing by adopting a mechanical dry blending process to prepare the composite material of the natural rubber and the natural rubber.
Preferably, the natural latex is natural latex of Hevea brasiliensis, concentrated natural latex with a total solid content of 55-65% by centrifugal concentration.
Preferably, the surfactant is sodium lauryl sulfate or oleylamine.
Preferably, the initiator is cumene hydroperoxide or tert-butyl hydroperoxide.
Preferably, the silica is nanosilica.
Preferably, the nano-silica is gas-phase nano-silica, precipitation nano-silica or sol-gel nano-silica.
Preferably, the silane coupling agent is bis- (gamma-triethoxysilylpropyl) tetrasulfide.
Preferably, the antioxidant is at least one of N-phenyl-alpha-aniline, N-phenyl-beta-naphthylamine, N-phenyl-N ' -isopropyl-p-phenylenediamine, N ' -diphenyl-p-phenylenediamine and 4, 4' -bis (2, 2-dimethylbenzyl) diphenylamine.
Preferably, the accelerator is N-tert-butyl-2-benzothiazole sulfonamide.
A composite material of natural rubber and natural rubber comprises the following components in parts by weight:
the invention has the beneficial effects that: according to the preparation method, a polar group is introduced into a natural rubber molecular chain by a method of graft copolymerization with a polar monomer methyl methacrylate to prepare the natural rubber; according to the similar compatibility principle, the natural rubber is used as a compatibilizer to improve the compatibility between the nonpolar natural rubber and the polar filler silicon dioxide; and then the binding force between the rubber matrix and the filler is enhanced, so that the dispersibility of the filler in the matrix is promoted, and the mechanical property of the composite material is improved.
According to the composite material, the natural rubber is replaced by the natural rubber, the natural rubber is used as the adhesive, the compatilizer and the toughening agent of a natural rubber/silicon dioxide/carbon black interface, and the natural rubber can also be used as the reinforcing agent of the natural rubber, so that the stress at definite elongation, the tensile strength, the tear strength and the aging resistance of the prepared novel composite material are superior to those of a white carbon black comparison sample, the tensile strength, the tear strength and the aging resistance of the prepared novel composite material are equivalent to those of the carbon black comparison sample, and the heat generation and the rolling resistance of the prepared novel. The novel composite material modified by the natural rubber has the advantages of low heat generation and low rolling resistance of white carbon black compared with a sample, and also has good mechanical properties of carbon black compared with a sample.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
A preparation method of a composite material of natural rubber and natural rubber comprises the following steps:
(1) weighing 100 parts by weight of natural latex, adding water to dilute the natural latex to a mass concentration of 20%, uniformly stirring, adding 0.4 part by weight of oleylamine while stirring, and then adding 0.2 part by weight of tetraethylenepentamine to prepare latex mixed liquid.
(2) 30 parts by weight of methyl methacrylate monomer was weighed and added to the latex mixture, and stirred and dispersed.
(3) Heating the latex mixed solution added with the methyl methacrylate monomer in a water bath to 50 ℃, dropwise adding 0.5 part by weight of tert-butyl hydroperoxide, and reacting in a water bath at the constant temperature of 60 ℃ for 6 hours to obtain a Tianjia rubber emulsion; adding 100 parts by weight of natural latex into the latex of the natural rubber, adding water to dilute the latex into 20% by mass concentration, heating or adding acid to solidify the latex, curing, extruding, granulating, washing and drying the latex to obtain the mixed rubber of the natural rubber and the natural rubber;
(4) weighing 10 parts by weight of the mixed rubber, 90 parts by weight of natural rubber, 50 parts by weight of silicon dioxide, 50 parts by weight of carbon black, 4 parts by weight of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide, 1 part by weight of anti-aging agent, 1.5 parts by weight of sulfur, 1 part by weight of N-tert-butyl-2-benzothiazole sulfenamide, 1.5 parts by weight of zinc oxide and 1 part by weight of stearic acid, and vulcanizing by adopting a mechanical dry blending process to prepare a composite material of the natural rubber and the natural rubber;
the silicon dioxide is gas phase method nano silicon dioxide;
the natural latex is concentrated natural latex with 60 percent of centrifugal concentration total solid content;
the anti-aging agent is N-phenyl-alpha-aniline, N-phenyl-beta-naphthylamine, N-phenyl-N ' -isopropyl-p-phenylenediamine, N ' -diphenyl-p-phenylenediamine or 4, 4' -bis (2, 2-dimethylbenzyl) diphenylamine.
Example 2
The specific preparation method is substantially the same as that of example 1, except that: the mass concentration of the latex was kept at 30%.
Example 3
The specific preparation method is basically the same as that of example 2, except that; the mass concentration of the latex is kept at 40%.
Example 4
The specific preparation method is substantially the same as that of example 1, except that: firstly, the reaction temperature is kept at 40 ℃, and secondly, the mass concentration of the latex is kept at 40%.
Example 5
The specific preparation method is substantially the same as that of example 1, except that: the amount of methyl methacrylate used is 50 parts.
Examples 6 to 9
The specific preparation method is substantially the same as that of example 1, except that: the weight ratio of the natural rubber to the natural rubber is respectively as follows: 10/90, 15/85, 20/80 and 30/70.
The performance tests of the composite of natural rubber and skyhook rubber made in example 9 are shown in the following table:
the above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (10)
1. A preparation method of a composite material of natural rubber and natural rubber is characterized by comprising the following steps: the method comprises the following steps:
(1) weighing 100 parts by weight of natural latex, adding water to dilute the natural latex to a mass concentration of 20-45%, uniformly stirring, adding 0.01-10 parts by weight of surfactant while stirring, adding 0.03-5.0 parts by weight of tetraethylenepentamine, and preparing latex mixed solution;
(2) weighing 30-50 parts by weight of methyl methacrylate monomer, adding into the latex mixed solution, and stirring and dispersing;
(3) heating the latex mixed solution added with the methyl methacrylate monomer to 40-60 ℃ in a water bath, dropwise adding 0.03-5.0 parts by weight of initiator, and reacting at constant temperature for 3-7h to obtain a Tianjia rubber emulsion; adding 100 parts by weight of natural latex into the latex of the natural rubber, adding water to dilute the latex into 20-45% of emulsion by mass concentration, heating or adding acid to solidify the latex, curing, extruding, granulating, washing and drying the latex to obtain the mixed rubber of the natural rubber and the natural rubber;
(4) weighing 5-70 parts by weight of the mixed rubber, 30-95 parts by weight of natural rubber, 10-50 parts by weight of silicon dioxide, 10-50 parts by weight of carbon black, 0.1-5.0 parts by weight of silane coupling agent, 0.1-10 parts by weight of anti-aging agent, 0.1-10 parts by weight of sulfur, 0.1-5 parts by weight of accelerator, 0.1-15 parts by weight of zinc oxide and 0.1-10 parts by weight of stearic acid, mixing, and vulcanizing by adopting a mechanical dry blending process to prepare the composite material of the natural rubber and the natural rubber.
2. The method of claim 1 for preparing a composite of natural rubber and caoutchouc, wherein the method comprises the steps of: the natural latex is natural latex of Hevea brasiliensis or concentrated natural latex.
3. The method of claim 1 for preparing a composite of natural rubber and caoutchouc, wherein the method comprises the steps of: the surfactant is sodium dodecyl sulfate or oleic acid amine.
4. The method of claim 1 for preparing a composite of natural rubber and caoutchouc, wherein the method comprises the steps of: the initiator is cumene hydroperoxide or tert-butyl hydroperoxide.
5. The method of claim 1 for preparing a composite of natural rubber and caoutchouc, wherein the method comprises the steps of: the silicon dioxide is nano silicon dioxide.
6. The method for preparing the composite material of the natural rubber and the celestial nail rubber according to the claim 5, wherein the method comprises the following steps: the nano-silica is gas phase method nano-silica, precipitation method nano-silica, sol-gel method nano-silica.
7. The method of claim 1 for preparing a composite of natural rubber and caoutchouc, wherein the method comprises the steps of: the silane coupling agent is bis- (gamma-triethoxysilylpropyl) tetrasulfide.
8. The method of claim 1 for preparing a composite of natural rubber and caoutchouc, wherein the method comprises the steps of: the anti-aging agent is at least one of N-phenyl-alpha-aniline, N-phenyl-beta-naphthylamine, N-phenyl-N ' -isopropyl-p-phenylenediamine, N ' -diphenyl-p-phenylenediamine and 4, 4' -bis (2, 2-dimethylbenzyl) diphenylamine.
9. The method of claim 1 for preparing a composite of natural rubber and caoutchouc, wherein the method comprises the steps of: the accelerator is N-tertiary butyl-2-benzothiazole sulfonamide.
10. A composite material of natural rubber and natural rubber is characterized in that: the composite material is prepared according to the preparation method of any one of claims 1 to 9, and comprises the following components in parts by weight:
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| CN113736400A (en) * | 2021-09-29 | 2021-12-03 | 福建友谊胶粘带集团有限公司 | Glue for bright blue protective film and bright blue protective film |
| CN115232373B (en) * | 2022-08-02 | 2023-08-22 | 泉州匹克鞋业有限公司 | Light rubber sole material and preparation method thereof |
| CN116515178B (en) * | 2023-06-07 | 2023-10-20 | 中国热带农业科学院农产品加工研究所 | Ageing-resistant heavenly stems and earthly branches rubber and natural rubber composite material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001302965A (en) * | 2000-04-21 | 2001-10-31 | Toyo Chem Co Ltd | Undercoating and adhesive tape |
| CN108017889A (en) * | 2017-12-15 | 2018-05-11 | 华南理工大学 | A kind of strong and unyielding balanced polylactic acid/methyl methacrylate rubber composite material and preparation method thereof |
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| US10000638B2 (en) * | 2013-10-03 | 2018-06-19 | Chandrasekaran Ramayya Pillai | Storage stabilized devulcanized tire rubber modified asphalt composition and the process for its preparation |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001302965A (en) * | 2000-04-21 | 2001-10-31 | Toyo Chem Co Ltd | Undercoating and adhesive tape |
| CN108017889A (en) * | 2017-12-15 | 2018-05-11 | 华南理工大学 | A kind of strong and unyielding balanced polylactic acid/methyl methacrylate rubber composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| In situ silica reinforcement of methyl methacrylate grafted natural rubber by sol-gel process;Natchamon Watcharakul 等;《J Sol-Gel Sci Technol》;20110201;第58卷;407-418 * |
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