CN114907627B - Preparation method of rubber nanocomposite, rubber nanocomposite and application - Google Patents

Preparation method of rubber nanocomposite, rubber nanocomposite and application Download PDF

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CN114907627B
CN114907627B CN202210501662.1A CN202210501662A CN114907627B CN 114907627 B CN114907627 B CN 114907627B CN 202210501662 A CN202210501662 A CN 202210501662A CN 114907627 B CN114907627 B CN 114907627B
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rubber
gutta
percha
mass
groups
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CN114907627A (en
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韩冬礼
张继川
张立群
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Shandong Light Chemical Zhiyuan New Material Technology Co ltd
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Beijing University of Chemical Technology
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/212—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase and solid additives
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2307/00—Characterised by the use of natural rubber
    • C08J2307/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2407/00—Characterised by the use of natural rubber
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides
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    • 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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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention provides a preparation method of a rubber nanocomposite, the rubber nanocomposite and application. The method comprises the following steps: (1) Dissolving gutta-percha in an organic solvent to prepare gutta-percha solution, filtering, adding an emulsifying agent, uniformly mixing, adding deionized water for emulsification, removing the organic solvent, adding a stabilizing agent, and regulating the pH value to 9-14 by using alkali to obtain gutta-percha emulsion; (2) Uniformly mixing the obtained gutta percha emulsion, natural rubber latex, a latex particle fusion agent and a rubber compounding agent to obtain mixed glue solution, and extracting a solid phase to obtain the rubber nanocomposite. The invention realizes the combination of gutta percha and natural rubber molecular chain scale, effectively improves the crystallization condition of gutta percha, improves the dispersion of gutta percha in a natural rubber matrix, improves the comprehensive performance of the rubber nanocomposite, in particular the fatigue resistance, and can be applied to the field of shock absorption products.

Description

Preparation method of rubber nanocomposite, rubber nanocomposite and application
Technical Field
The invention relates to the technical field of rubber composite materials, in particular to a preparation method of a rubber nanocomposite material, the rubber nanocomposite material and application.
Background
Gutta-percha (EUG) is a green renewable high polymer material, and has abundant eucommia ulmoides resources in China, which accounts for more than 95% of the total world. Gutta-percha has unique rubber-plastic dual property and is an excellent polymer material, and the chemical composition of the gutta-percha is completely the same as that of natural rubber (C 5 H 8 ) But the molecular structure is different, namely the isomer, the molecular structure of the eucommia ulmoides gum is trans-polyisoprene, and the molecular structure of the natural rubber is cis-polyisoprene. Because the methine groups are positioned at the two sides of the C=C double bond in the molecular structure of the gutta-percha, the atomic arrangement is relatively symmetricalMolecules are also more regularly soluble in the crystal structure, so that their physicochemical properties are also very different. The eucommia ulmoides rubber is solid at room temperature, has toughness, is crystalline hard plastic and is easy to crystallize. Gutta-percha pure rubber starts to crystallize at 10 ℃, starts to soften at 40-50 ℃ and shows elasticity and is easy to elongate; softening at 100 ℃ and having plasticity, but recovering the original properties after cooling.
Because the gutta-percha has unique crystallization performance, the gutta-percha has different performances under different temperatures and different vulcanization conditions, when the gutta-percha is blended with other rubbers such as natural rubber, styrene-butadiene rubber, butadiene rubber and the like, the gutta-percha can keep unique characteristics of the original rubber when being uniformly dispersed and has stronger interface effect with other rubber molecular chains, and can reduce blending heat, improve scorching characteristics, increase raw rubber strength, dynamic fatigue resistance, tensile strength and the like. However, the gutta-percha molecular chains have higher regularity and are extremely easy to crystallize, so that the gutta-percha is difficult to disperse in other rubber matrixes, and the gutta-percha cannot realize the interface effect on the molecular chain scale with other rubber molecular chains, so that the characteristic of gutta-percha cannot be fully exerted.
Natural rubber is a natural polymer material extracted from rubber-containing plants. The natural rubber is usually an elastic solid obtained by processing natural latex collected from Brazilian rubber tree by coagulation, drying, and the like. Natural rubber is a natural high molecular compound with cis-1, 4-polyisoprene as main component, its rubber hydrocarbon (cis-1, 4-polyisoprene) content is above 90%, and also contains small quantity of protein, fatty acid, sugar and ash. Natural rubber is an important strategic material, and is widely used in the fields of aerospace, heavy-duty automobiles, aircraft tires, medical sanitation and the like, along with coal, steel and petroleum, which are called as four basic industrial raw materials. The natural rubber has the characteristics of high strength, high modulus and high rebound, and also has the characteristic of strain-induced crystallization, and can form crystallization after being stretched under the action of external force. The self-reinforcement is very high; the average molecular weight is large, thus imparting high mechanical strength thereto.
The composite material prepared by blending the gutta-percha and the natural rubber can form microcrystals in a rubber matrix to prevent crack propagation and improve the fatigue resistance of the material, but in the prior art, the natural rubber and the gutta-percha are mostly processed by a traditional dry mixing mode, liquid phase mixing is also simply mixing, natural latex particles and the gutta-percha particles are independently dispersed in the liquid phase, and in the demulsification process, the gutta-percha and the natural rubber are more likely to be gathered together respectively due to the difference of affinities, and are still separated in structure in microcosmic view, so that the fatigue resistance of the composite material is poor. Therefore, a method for mixing gutta-percha and natural rubber is needed to be studied, and the dispersibility of the gutta-percha in a natural rubber matrix is improved, so that the dispersion of microcrystals in the matrix is improved, and the generation of cracks is better resisted.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a preparation method of a rubber nanocomposite, the rubber nanocomposite and application.
The invention prepares the high fatigue resistance rubber nano composite material by combining liquid phase latex mixing with wet mixing technology, and can be applied to the field of shock absorption products.
According to the invention, the gutta-percha emulsion, the natural rubber latex and the latex particle fusion agent are mixed in the liquid phase, so that the gutta-percha and the natural rubber latex particles are fused, the combination of the gutta-percha and the natural rubber molecular chain scale is realized, the crystallization condition of the gutta-percha is effectively improved, the dispersion of the gutta-percha in a natural rubber matrix is improved, and the comprehensive performance, particularly the fatigue resistance, of the rubber nanocomposite is improved.
The invention improves the interfacial effect between gutta-percha and natural rubber molecular chains to form a stable, firm and uniform interfacial layer, completes mixing with the filler and the complexing agent in a liquid phase, can realize uniform dispersion of the filler and the complexing agent in the gutta-percha/natural rubber dual-network structure, solves the problem of uneven dispersion of the complexing agent in two phases caused by the traditional mixing process, does not damage the original ecological structure of the gutta-percha and natural rubber molecular chains in the preparation process, and further improves the comprehensive performance of the rubber nanocomposite.
The invention aims at providing a preparation method of a rubber nanocomposite, which comprises the following steps:
(1) Dissolving gutta-percha in an organic solvent to prepare gutta-percha solution, filtering, adding an emulsifying agent, uniformly mixing, adding deionized water for emulsification, removing the organic solvent, adding a stabilizing agent, and regulating the pH value to 9-14 by using alkali to obtain gutta-percha emulsion;
(2) Uniformly mixing the gutta percha emulsion obtained in the step (1) with natural rubber latex, a latex particle fusion agent and a rubber compounding agent to obtain mixed glue solution, and extracting a solid phase to obtain the rubber nanocomposite.
In a preferred embodiment of the present invention,
step (1),
the gutta-percha is natural gutta-percha extracted from the bark, leaves or seeds of Du Zhongshu;
the organic solvent is good solvent of gutta percha, preferably at least one of toluene, xylene, benzene, cyclohexane, n-hexane, chloroform, acetone and petroleum ether; the above solvents may be used alone or in combination of two or more thereof;
the emulsifier is a surfactant, preferably at least one of paraffin-based carboxylic acid soap, fatty acid soap, disproportionated abietic acid soap, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate; more preferably at least one of disproportionated abietic acid soap, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate;
the stabilizer is at least one of alkylphenol ethoxylate phosphate (APE-10), alkylphenol ethoxylate (OP-10), fatty alcohol ethoxylate (AEO-9), polysorbate-80 emulsifier (Tween 80) and sorbitan fatty acid ester emulsifier (span 80); can be 1,2, 3, etc.; more preferably at least one of APE-10, OP-10, AEO-9;
the alkali is at least one of ammonia water, sodium hydroxide, potassium hydroxide and biomass alkali; the biomass alkali is at least one of betaine, ephedrine and colchicine; preferably ammonia.
In a preferred embodiment of the present invention,
step (1),
the mass concentration of the gutta-percha solution is 1% -60%; preferably 8% -30%;
the filtration was carried out by using a 45 μm (325 mesh) sieve, and undissolved gel and impurities were filtered off.
In a preferred embodiment of the present invention,
step (1),
the mass of the emulsifier is 0.2-5% of the mass of the gutta-percha; preferably 1.5% -3%; and/or the number of the groups of groups,
the mass of the stabilizing agent is 2% -30% of the mass of the gutta-percha; preferably 5% -20%; and/or the number of the groups of groups,
the concentration of the gutta-percha emulsion is 10% -70%; preferably 20% -60%; and/or the number of the groups of groups,
emulsifying, dispersing gutta-percha glue solution into a water phase by adopting a high-speed emulsifying machine with the rotating speed of 10000-20000 r/min; the emulsification time is 5 min-10 min;
the method for removing the organic solvent is a reduced pressure distillation method, and the organic solvent in the mixed solution is removed;
the mixing method in the step (1) is a stirring mixing method.
In a preferred embodiment of the present invention,
step (2),
the natural rubber latex is fresh latex or concentrated natural latex; the invention can use concentrated natural latex with various concentrations, and most of commercial products are concentrated natural rubber with the mass concentration of 60%, and are preferably selected;
the latex particle fusion agent is at least one of polyethylene glycol (PEG), dimethyl sulfoxide (DMSO), phytohemagglutinin (PHA) and glycerol; such as 1,2, 3 or 4; PEG is preferably PEG 1000-2000;
the rubber compounding agent is a conventional rubber auxiliary agent and comprises a filler, an active agent and an anti-aging agent; preferably further comprises an accelerator and a vulcanizing agent; the rubber compounding agent comprises, but is not limited to, the above types, and can be added according to the product performance requirements and the conventional dosage;
the vulcanizing agent is at least one of sulfur and dicumyl peroxide (DCP);
the accelerator is at least one of N-cyclohexyl-2-benzothiazole sulfenamide (CZ), N-dicyclohexyl-2-2 benzothiazole sulfenamide (NS), diphenyl guanidine (DPG) and tetramethylthiuram disulfide (TT);
the active agent is at least one of stearic acid, zinc oxide and magnesium oxide;
the anti-aging agent is at least one of N-phenyl-N ' -cyclohexyl p-phenylenediamine (anti-aging agent 4010), N- (1, 3-dimethyl) butyl-N ' -phenyl-p-phenylenediamine (anti-aging agent 4020), N-isopropyl-N ' -phenyl-p-phenylenediamine (anti-aging agent 4010 NA) and 2, 4-trimethyl-1, 2-dihydroquinoline polymer (anti-aging agent RD);
the filler is at least one of carbon black and white carbon black.
In a preferred embodiment of the present invention,
step (2),
the mass ratio of the gutta-percha to the dry rubber in the natural rubber latex is (0.01-0.5): 1, a step of; preferably (0.05 to 0.25): 1, a step of; and/or the number of the groups of groups,
the mass of the latex particle fusion agent is 2% -50% of the mass of the gutta-percha; preferably 5% -20%;
the mass of the gutta-percha refers to the mass of gutta-percha dry glue.
In a preferred embodiment of the present invention,
based on 100 parts by weight of the dry rubber in the natural rubber latex,
100 parts by weight of a dry rubber in natural rubber latex;
1-10 parts by weight of an active agent; preferably 1 to 7 parts by weight;
10-100 parts of filler; preferably 50 to 80 parts by weight;
1-10 parts of an anti-aging agent; preferably 1 to 5 parts by weight;
1-10 parts by weight of a promoter; preferably 1 to 5 parts by weight;
1-10 parts of sulfur; preferably 1 to 5 parts by weight.
The mixing method in the step (2) is a stirring mixing method.
In a preferred embodiment of the present invention,
step (2),
the extraction method comprises the steps of evaporating water in the mixed glue solution to dryness by spray drying equipment, wherein the outlet temperature is 95-105 ℃;
or adding acid, alkali or salt into the mixed glue solution to demulsify, co-precipitating and solidifying, and then extruding, dehydrating and drying;
or evaporating the water in the mixed glue solution by adopting a film drying mode, and drying at a low temperature in a normal pressure, reduced pressure or vacuum mode, wherein the drying temperature is 70-100 ℃;
the above 3 methods can be selected to extract the rubber nanocomposite, and the rubber nanocomposite can be obtained after the extraction.
The second object of the invention is to provide a rubber nanocomposite prepared by the method.
It is a further object of the present invention to provide a use of a rubber nanocomposite in a shock absorbing article.
The rubber nanocomposite prepared by the method has high fatigue resistance and can be used in shock absorption products.
According to the invention, the gutta-percha emulsion and the natural rubber latex are mixed in a liquid phase according to the mass ratio of the dry rubber, then a latex particle fusion agent is added into the mixed latex to fuse the gutta-percha latex particles and the natural rubber latex particles, then a rubber compounding agent and a filler which are emulsified and dispersed in advance are added into the emulsion, finally the rubber nanocomposite containing the gutta-percha, the natural rubber and the compounding agent is extracted from the liquid phase, and finally the natural rubber/gutta-percha rubber composite high fatigue-resistant rubber nanocomposite is obtained.
Compared with the prior art, the invention has the beneficial effects that:
the natural rubber and the gutta-percha are of isoprene structures, the physical and chemical properties of the natural rubber and the gutta-percha are greatly different due to the difference of cis-trans structures, the uniform compatibility of the natural rubber and the gutta-percha is difficult to realize through the traditional dry mixing, the liquid phase mixing in the prior art is also simply mixing, the natural rubber latex particles and the gutta-percha particles are independently dispersed in the liquid phase, the gutta-percha and the natural rubber are more easily gathered together respectively due to the difference of affinities in the demulsification process, and the structural separation is still shown on microcosmic scale.
The gutta-percha is added into the natural rubber, and the gutta-percha can form microcrystals in a rubber matrix to prevent crack propagation and improve the fatigue resistance of the material.
The invention improves the dispersion of the gutta-percha in the natural rubber matrix, and the prepared rubber nanocomposite has better physical and mechanical properties.
The invention utilizes wet mixing technology to complete mixing of rubber filler and compounding agent in blended latex, and then obtains master batch or rubber compound through co-precipitation or other devolatilization modes.
The invention introduces the devolatilization mode in the industry into the rubber industry, and can realize good extraction effect.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The raw materials used in examples and comparative examples were conventional commercially available raw materials.
Test method and standard:
tensile strength, 300% tensile stress, elongation at break: according to GB/T528-2009 test;
tear strength: according to GB/T529-2008 test;
flexural fatigue: according to GB/T13934-2006.
The parts indicated in the examples and comparative examples are parts by weight.
Example 1
Dissolving gutta-percha in cyclohexane to obtain gutta-percha solution with the mass fraction of 20%, filtering and removing impurities by a 325-mesh filter screen, adding disproportionated rosin acid soap with the mass fraction of 2% (calculated by dry colloid and the same applies below) of gutta-percha into the glue solution, adding deionized water for emulsification, emulsifying for 5min at the rotating speed of 20000r/min, removing the organic solvent by reduced pressure distillation, adding OP-10 with the mass fraction of gutta-percha into the gutta-percha solution, adding ammonia water to adjust the pH value to be 12, and obtaining stable gutta-percha emulsion with the concentration of 30%.
The eucommia latex and the concentrated natural latex with the mass concentration of 60 percent are mixed according to the mass ratio of 20:80 Mixing (the proportion of the dry glue), adding PEG1000 accounting for 10% of the mass of the gutta percha into the mixture after uniform mixing, grinding the mixture to obtain mixed glue solution, adding formic acid into the mixed glue solution for coprecipitation flocculation, and dehydrating and drying the mixture to obtain the rubber nanocomposite.
After 12h of parking, the performance was tested by vulcanization.
The rubber compounding agent comprises, by weight, 5 parts of zinc oxide, 2 parts of stearic acid, 50 parts of carbon black, 1.5 parts of accelerator CZ, 2 parts of anti-aging agent 4020 and 1.2 parts of sulfur, wherein the vulcanization condition is 150 ℃ for 20min, and the dry rubber in the natural latex is 100 parts.
Example 2
Dissolving gutta-percha in cyclohexane to obtain gutta-percha solution with the mass fraction of 20%, filtering and removing impurities by a 325-mesh filter screen, adding disproportionated rosin acid soap with the mass fraction of 2% (calculated by dry colloid and the same applies below) of gutta-percha into the glue solution, adding deionized water for emulsification, emulsifying for 5min at the rotating speed of 20000r/min, removing the organic solvent by reduced pressure distillation, adding OP-10 with the mass fraction of gutta-percha into the gutta-percha solution, adding ammonia water to adjust the pH value to be 12, and obtaining stable gutta-percha emulsion with the concentration of 30%.
The eucommia latex and the concentrated natural latex with the mass concentration of 60 percent are mixed according to the mass ratio of 20:80 Mixing (the proportion of the dry adhesive), adding PEG1000 accounting for 10 percent of the mass of the gutta-percha into the mixture after the mixture is uniformly mixed, grinding the mixture to obtain a mixed glue solution, and performing devolatilization by adopting spray drying equipment, wherein the outlet temperature is controlled at 105 ℃, thus obtaining the rubber nanocomposite.
After 12h of parking, the performance was tested by vulcanization.
The rubber compounding agent comprises, by weight, 5 parts of zinc oxide, 2 parts of stearic acid, 50 parts of carbon black, 1.5 parts of accelerator CZ, 2 parts of anti-aging agent 4020 and 1.2 parts of sulfur, wherein the dry rubber in natural latex is 100 parts, and the vulcanization condition is 150 ℃ x20min.
Example 3
Dissolving gutta-percha in cyclohexane to obtain gutta-percha solution with the mass fraction of 20%, filtering and removing impurities by a 325-mesh filter screen, adding disproportionated rosin acid soap with the mass fraction of 2% (calculated by dry colloid and the same applies below) of gutta-percha into the glue solution, adding deionized water for emulsification, emulsifying for 5min at the rotating speed of 20000r/min, removing the organic solvent by reduced pressure distillation, adding OP-10 with the mass fraction of gutta-percha into the gutta-percha solution, adding ammonia water to adjust the pH value to be 12, and obtaining stable gutta-percha emulsion with the concentration of 30%.
The eucommia latex and the concentrated natural latex with the mass concentration of 60 percent are mixed according to the mass ratio of 20:80 Mixing the materials according to the proportion of the dry glue, adding PEG1000 accounting for 10 percent of the mass of the gutta-percha into the mixture after the mixture is uniformly mixed, grinding the mixture to obtain a mixed glue solution, performing devolatilization by adopting a microwave film drying mode, performing low-temperature drying at normal pressure, and controlling the drying temperature to be about 90 ℃ to obtain the rubber nanocomposite.
After 12h of parking, the performance was tested by vulcanization.
The rubber compounding agent comprises, by weight, 5 parts of zinc oxide, 2 parts of stearic acid, 50 parts of carbon black, 1.5 parts of accelerator CZ, 2 parts of anti-aging agent 4020 and 1.2 parts of sulfur, wherein the vulcanization condition is 150 ℃ for 20min, and the dry rubber in the natural latex is 100 parts.
Example 4
Dissolving gutta-percha in cyclohexane to obtain gutta-percha solution with the mass fraction of 30%, filtering and removing impurities by a 325-mesh filter screen, adding sodium dodecyl sulfate with the mass of 2% of gutta-percha (calculated by dry colloid weight, the same applies below) into the glue solution, adding deionized water for emulsification, emulsifying for 5min at the rotating speed of 20000r/min in an emulsifying machine, removing the organic solvent by reduced pressure distillation, adding APE-10 with the mass of gutta-percha of 10% into the gutta-percha solution, adding ammonia water for regulating the pH value to be=12, and obtaining stable gutta-percha emulsion with the concentration of 30%.
The eucommia ulmoides latex and the concentrated natural latex with the mass concentration of 60% are mixed according to the mass ratio of 10:90 Mixing (the proportion of the dry adhesive), adding PEG2000 accounting for 10 percent of the mass of the gutta-percha into the mixture after the mixture is uniformly mixed, grinding the mixture to obtain a mixed glue solution, performing devolatilization by adopting a microwave film drying mode, performing low-temperature drying at normal pressure, and controlling the drying temperature to be about 90 ℃ to obtain the rubber nanocomposite.
After 12h of parking, the performance was tested by vulcanization.
The rubber compounding agent comprises, by weight, 5 parts of zinc oxide, 2 parts of stearic acid, 50 parts of carbon black, 1.5 parts of accelerator CZ, 2 parts of anti-aging agent 4020 and 1.2 parts of sulfur, wherein the vulcanization condition is 150 ℃ x20min, based on 100 parts of dry rubber in natural latex.
Example 5
Dissolving gutta-percha in cyclohexane to obtain gutta-percha solution with the mass fraction of 8%, filtering and removing impurities by a 325-mesh filter screen, adding sodium dodecyl sulfate with the mass of 1.5% (calculated by dry colloid weight, the same applies below) of gutta-percha into the glue solution, adding deionized water for emulsification, emulsifying for 10min at the rotating speed of 10000r/min in an emulsifying machine, removing the organic solvent by reduced pressure distillation, adding APE-10 with the mass of 20% of gutta-percha into the gutta-percha solution, adding ammonia water for regulating the pH value to be=9, and obtaining stable gutta-percha emulsion with the concentration of 60%.
The eucommia ulmoides latex and the concentrated natural latex with the mass concentration of 60% are mixed according to the mass ratio of 5:100 Mixing (the proportion of the dry glue), adding dimethyl sulfoxide accounting for 20% of the mass of the gutta-percha into the mixture after the mixture is uniformly mixed, grinding the mixture to obtain a mixed glue solution, performing devolatilization by adopting a microwave film drying mode, performing low-temperature drying at normal pressure, and controlling the drying temperature to be about 90 ℃ to obtain the rubber nanocomposite.
After 12h of parking, the performance was tested by vulcanization.
The rubber compounding agent comprises, by weight, 1 part of zinc oxide, 1 part of stearic acid, 65 parts of carbon black, 3 parts of accelerator NS, 2 parts of accelerator DPG, 1 part of anti-aging agent RD, 1 part of anti-aging agent 4010NA and 5 parts of sulfur, wherein the vulcanization condition is 150 ℃ for 20min, based on 100 parts of dry rubber in natural latex.
Example 6
Dissolving gutta-percha in cyclohexane to obtain gutta-percha solution with the mass fraction of 20%, filtering and removing impurities by a 325-mesh filter screen, adding sodium dodecyl sulfate with the mass of 3% of gutta-percha (calculated by dry colloid, the same applies below) into the glue solution, adding deionized water for emulsification, emulsifying for 10min at the rotating speed of 10000r/min in an emulsifying machine, removing the organic solvent by reduced pressure distillation, adding APE-10 with the mass of gutta-percha of 10% into the gutta-percha solution, adding ammonia water for regulating the pH value to be 14, and obtaining stable gutta-percha emulsion with the concentration of 20%.
The eucommia latex and the concentrated natural latex with the mass concentration of 60 percent are mixed according to the mass ratio of 0.25:1 (the proportion of the dry adhesive) is mixed, PEG2000 accounting for 5 percent of the mass of the gutta-percha is added after the mixture is uniformly mixed, the mixture is uniformly mixed with the ground and premixed compounding agent to obtain a mixed glue solution, then a microwave film drying mode is adopted for devolatilization, low-temperature drying is carried out at normal pressure, and the drying temperature is controlled at about 90 ℃ to obtain the rubber nanocomposite.
After 12h of parking, the performance was tested by vulcanization.
The rubber compounding agent comprises, by weight, 5 parts of zinc oxide, 2 parts of stearic acid, 80 parts of carbon black, 1.5 parts of accelerator CZ, 5 parts of anti-aging agent 4020 and 1.2 parts of sulfur, wherein the vulcanization condition is 150 ℃ for 20min, based on 100 parts of dry rubber in natural latex.
Comparative example 1
Comparative example 1 was compared with examples 1 to 3;
mixing 20 parts of gutta-percha, 80 parts of natural rubber, 5 parts of zinc oxide, 2 parts of stearic acid, 50 parts of carbon black, 1.5 parts of accelerator CZ, 2 parts of age resistor 4020 and 1.2 parts of sulfur in an internal mixer and an open mill in a sectional manner, mixing the weighed gutta-percha, the natural rubber, the zinc oxide, the stearic acid, the carbon black and the age resistor 4020 in the internal mixer at the rotating speed of 60r/min and the rubber discharging temperature of 145 ℃ to obtain a section of mixed rubber, standing for 12 hours, sequentially adding the accelerator and the sulfur in the section of mixed rubber through the open mill, uniformly mixing, discharging the sheets, standing to obtain a final rubber, standing for 12 hours, vulcanizing on a flat vulcanizing machine, and obtaining the eucommia ulmoides/natural rubber nanocomposite at the vulcanizing condition of 150 ℃ x20 minutes.
Comparative example 2
Comparative example 2 was compared with example 4;
10 parts of gutta-percha, 90 parts of natural rubber, 5 parts of zinc oxide, 2 parts of stearic acid, 50 parts of carbon black, 1.5 parts of accelerator CZ, 2 parts of age resistor 4020 and 1.2 parts of sulfur are mixed in sections on an internal mixer and an open mill, one section of the gutta-percha, the natural rubber, the zinc oxide, the stearic acid, the carbon black and the age resistor 4020 are mixed in the internal mixer at the rotating speed of 60r/min and the rubber discharging temperature of 145 ℃ to obtain one section of mixed rubber, after the mixed rubber is parked for 12 hours, the accelerator and the sulfur are sequentially added into one section of mixed rubber through the open mill, after the mixed rubber is uniformly mixed, the final mixed rubber is obtained, parked for 12 hours, the final mixed rubber is vulcanized on a flat vulcanizing machine, and the vulcanizing condition is 150 ℃ x20 minutes, thus obtaining the eucommia ulmoides/natural rubber nanocomposite.
Comparative example 3
Comparative example 3 was prepared by mixing the prepared gutta percha with the natural rubber emulsion without adding the latex particle fusion agent, then extracting gutta percha/natural rubber composite gum, and then adding the rubber fusion agent.
The preparation method comprises the following steps:
dissolving gutta percha in cyclohexane to obtain gutta percha solution with the mass fraction of 20%, filtering and removing impurities by a 325-mesh filter screen, adding disproportionated rosin acid soap with the mass of 2% of gutta percha (calculated by dry colloid and the same applies below) into the glue solution, adding deionized water for emulsification, emulsifying for 5min at the rotating speed of 20000r/min, removing the organic solvent by reduced pressure distillation, adding OP-10 with the mass of 5% of gutta percha into the gutta percha solution, adding ammonia water to adjust the pH value to be 12, and obtaining stable gutta percha emulsion with the concentration of 30%
The eucommia latex and the concentrated natural latex with the mass concentration of 60 percent are mixed according to the mass ratio of 20:80 Mixing (the proportion of the dry rubber), adding formic acid into the mixed glue solution after uniform mixing for coprecipitation flocculation, and dehydrating and drying to obtain the eucommia ulmoides/natural rubber compound rubber.
Mixing 100 parts of eucommia ulmoides/natural rubber composite rubber, 50 parts of carbon black, 1.5 parts of accelerator CZ, 40202 parts of antioxidant and 1.2 parts of sulfur in a mixing mill and an open mill in a sectionally mixing manner, wherein one section is mixing the weighed eucommia ulmoides rubber, natural rubber, zinc oxide, stearic acid, carbon black and antioxidant 4020 in the mixing mill at the rotating speed of 60r/min, the rubber discharging temperature of 145 ℃ to obtain one section of mixed rubber, standing for 12 hours, sequentially adding the accelerator and sulfur in the one section of mixed rubber through the open mill, standing after mixing uniformly to obtain a final rubber, standing for 12 hours, and vulcanizing in a flat vulcanizing machine under the vulcanizing condition of 150 ℃ x20 minutes to obtain the eucommia ulmoides/natural rubber nanocomposite.
Comparative example 4
Comparative example 4 was prepared from natural gum extracted from natural latex without compounding gutta percha.
The preparation method comprises the following steps:
adding a complexing agent which is ground and emulsified in advance into the concentrated natural latex with the mass concentration of 60%, uniformly mixing to obtain a mixed glue solution, adding formic acid into the mixed glue solution for coprecipitation flocculation, and dehydrating and drying to obtain the rubber nanocomposite.
After 12h of parking, the performance was tested by vulcanization.
The rubber compounding agent comprises, by weight, 5 parts of zinc oxide, 2 parts of stearic acid, 50 parts of carbon black, 1.5 parts of accelerator CZ, 2 parts of anti-aging agent 4020 and 1.2 parts of sulfur, wherein the vulcanization condition is 150 ℃ for 20min, and the dry rubber in the natural latex is 100 parts.
TABLE 1 results of Performance test of vulcanizates of examples 1 to 6, comparative examples 1 to 4
Figure GDA0004126069400000131
The formulation of comparative example 1 is exactly the same as that of examples 1 to 3, and comparative example 1 is dry-mixing, and as can be seen from Table 1, examples 1 to 3 have more excellent tensile strength properties, tensile stress, tear strength properties and flexural fatigue properties than comparative example 1, and examples 1 to 3 are proved to have better strength, modulus and fatigue resistance; also, the formulation of comparative example 2 is exactly the same as that of example 4, comparative example 2 is dry-kneading processing, and the strength, modulus and fatigue resistance of example 4 are better than those of comparative example 2; the data prove that the rubber nanocomposite prepared by the method has better mechanical property and fatigue resistance.
Comparative example 3 was exactly the same as the formulation of examples 1 to 3, but no latex particle fusion agent was added during the liquid phase mixing, a composite gel was prepared by blending eucommia latex and natural latex, and a rubber compounding agent was not added in the liquid phase, but was added to the prepared composite gel again, and a nanocomposite was prepared by dry kneading; comparative example 4 was different from comparative example 3 in that no eucommia ulmoides rubber was added, only natural rubber extracted from natural latex was used, then a rubber compounding agent exactly the same as the formulation of examples 1 to 3 was added thereto, and a nanocomposite was prepared by dry kneading; compared with comparative examples 3 and 4, examples 1 to 3 have more excellent tearing strength and flexural fatigue properties, which proves that the gutta percha has an effect of blocking crack growth after crystallization, and examples 1 to 3 improve dispersion of gutta percha in a matrix, thereby improving dispersion of microcrystals in the matrix and better resisting generation of cracks, and thus better fatigue resistance.
The test data of examples 1-6 demonstrate that the method of the present invention can be used to efficiently prepare highly fatigue resistant nanocomposites.

Claims (15)

1. A method for preparing a rubber nanocomposite, the method comprising:
(1) Dissolving gutta-percha in an organic solvent to prepare gutta-percha solution, filtering, adding an emulsifying agent, uniformly mixing, adding deionized water for emulsification, removing the organic solvent, adding a stabilizing agent, and regulating the pH value to 9-14 by using alkali to obtain gutta-percha emulsion;
(2) Uniformly mixing the gutta percha emulsion obtained in the step (1) with natural rubber latex, a latex particle fusion agent and a rubber compounding agent to obtain mixed glue solution, and extracting a solid phase to obtain the rubber nanocomposite;
in the step (1), the emulsifier is at least one of paraffin-based carboxylic acid soap, fatty acid soap, disproportionated rosin acid soap, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate; the stabilizer is at least one of alkylphenol polyoxyethylene ether phosphate, alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, polysorbate-80 emulsifier and sorbitan fatty acid ester emulsifier;
in the step (2), the latex particle fusion agent is at least one of polyethylene glycol, dimethyl sulfoxide, phytohemagglutinin and glycerol.
2. The method for preparing a rubber nanocomposite as claimed in claim 1, wherein:
step (1),
the organic solvent is at least one of toluene, xylene, benzene, cyclohexane, normal hexane, chloroform, acetone and petroleum ether; and/or the number of the groups of groups,
the alkali is at least one of ammonia water, sodium hydroxide, potassium hydroxide and biomass alkali; the biomass alkali is at least one of betaine, ephedrine and colchicine.
3. The method for preparing a rubber nanocomposite as claimed in claim 1, wherein:
step (1),
the mass concentration of the gutta-percha solution is 1% -60%.
4. A method of preparing a rubber nanocomposite as claimed in claim 3 wherein:
the mass concentration of the gutta-percha solution is 8% -30%.
5. The method for preparing a rubber nanocomposite as claimed in claim 1, wherein:
step (1),
the mass of the emulsifier is 0.2-5% of the mass of the gutta-percha; and/or the number of the groups of groups,
the mass of the stabilizing agent is 2% -30% of the mass of the gutta-percha; and/or the number of the groups of groups,
the concentration of the gutta-percha emulsion is 10% -70%; and/or the number of the groups of groups,
emulsifying by using an emulsifying machine with the rotating speed of 10000-20000 r/min; the emulsification time is 5 min-10 min.
6. The method for preparing a rubber nanocomposite as claimed in claim 5, wherein:
the mass of the emulsifier is 1.5-3% of the mass of the gutta-percha; and/or the number of the groups of groups,
the mass of the stabilizer is 5% -20% of the mass of the gutta-percha; and/or the number of the groups of groups,
the concentration of the gutta-percha emulsion is 20% -60%.
7. The method for preparing a rubber nanocomposite as claimed in claim 1, wherein:
step (2),
the natural rubber latex is fresh latex or concentrated natural latex; and/or the number of the groups of groups,
the rubber compounding agent comprises a filler, an active agent and an anti-aging agent; the active agent is at least one of stearic acid, zinc oxide and magnesium oxide; the anti-aging agent is at least one of N-phenyl-N ' -cyclohexyl p-phenylenediamine, N- (1, 3-dimethyl) butyl-N ' -phenyl p-phenylenediamine, N-isopropyl-N ' -phenyl p-phenylenediamine and 2, 4-trimethyl-1, 2-dihydroquinoline polymer; the filler is at least one of carbon black and white carbon black.
8. The method of preparing a rubber nanocomposite as claimed in claim 7, wherein:
the rubber compounding agent also comprises an accelerator and a vulcanizing agent; the vulcanizing agent is at least one of sulfur and dicumyl peroxide; the accelerator is at least one of N-cyclohexyl-2-benzothiazole sulfenamide, N-dicyclohexyl-2-benzothiazole sulfenamide, diphenyl guanidine and tetramethyl thiuram disulfide.
9. The method for preparing a rubber nanocomposite as claimed in claim 1, wherein:
step (2),
the mass ratio of the gutta-percha to the dry rubber in the natural rubber latex is (0.01-0.5): 1, a step of; and/or the number of the groups of groups,
the mass of the latex particle fusion agent is 2-50% of the mass of the gutta-percha.
10. The method of preparing a rubber nanocomposite as claimed in claim 9, wherein:
the mass ratio of the gutta-percha to the dry rubber in the natural rubber latex is (0.05-0.25): 1, a step of; and/or the number of the groups of groups,
the mass of the latex particle fusion agent is 5-20% of the mass of the gutta-percha.
11. The method of preparing a rubber nanocomposite as claimed in claim 8, wherein:
based on 100 parts by weight of the dry rubber in the natural rubber latex,
Figure FDA0004126069390000031
12. the method of preparing a rubber nanocomposite as claimed in claim 8, wherein:
based on 100 parts by weight of the dry rubber in the natural rubber latex,
Figure FDA0004126069390000032
13. the method for preparing a rubber nanocomposite as claimed in claim 1, wherein:
step (2),
the extraction method comprises the steps of evaporating water in the mixed glue solution to dryness by spray drying equipment, wherein the outlet temperature is 95-105 ℃;
or adding acid, alkali or salt into the mixed glue solution to demulsify, co-precipitating and solidifying, and then extruding, dehydrating and drying;
or low-temperature drying is carried out in normal pressure, reduced pressure or vacuum mode, and the drying temperature is 70-100 ℃.
14. A rubber nanocomposite produced by the production method according to any one of claims 1 to 13.
15. Use of the rubber nanocomposite material of claim 14 in a shock absorbing article.
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