CN105566692A - Natural rubber composite material and preparation method thereof - Google Patents
Natural rubber composite material and preparation method thereof Download PDFInfo
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- CN105566692A CN105566692A CN201610046452.2A CN201610046452A CN105566692A CN 105566692 A CN105566692 A CN 105566692A CN 201610046452 A CN201610046452 A CN 201610046452A CN 105566692 A CN105566692 A CN 105566692A
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- Prior art keywords
- carbon black
- tripoli
- white carbon
- composite material
- agent
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- 239000002131 composite material Substances 0.000 title abstract description 49
- 244000043261 Hevea brasiliensis Species 0.000 title abstract description 41
- 229920003052 natural elastomer Polymers 0.000 title abstract description 41
- 229920001194 natural rubber Polymers 0.000 title abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000006229 carbon black Substances 0.000 abstract description 114
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 107
- 229920001971 elastomer Polymers 0.000 abstract description 63
- 238000000034 method Methods 0.000 abstract description 28
- 239000000463 material Substances 0.000 abstract description 14
- 238000011049 filling Methods 0.000 abstract description 4
- 230000002787 reinforcement Effects 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract 3
- 238000005299 abrasion Methods 0.000 abstract 1
- 230000020169 heat generation Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 235000019241 carbon black Nutrition 0.000 description 113
- 239000010458 rotten stone Substances 0.000 description 88
- 239000003795 chemical substances by application Substances 0.000 description 69
- 239000006185 dispersion Substances 0.000 description 44
- 239000004594 Masterbatch (MB) Substances 0.000 description 42
- 239000000203 mixture Substances 0.000 description 33
- 230000003712 anti-aging effect Effects 0.000 description 29
- 239000007788 liquid Substances 0.000 description 26
- 239000007822 coupling agent Substances 0.000 description 20
- 238000002156 mixing Methods 0.000 description 19
- 230000001737 promoting effect Effects 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 238000005987 sulfurization reaction Methods 0.000 description 15
- 229920000126 latex Polymers 0.000 description 12
- 230000018044 dehydration Effects 0.000 description 10
- 238000006297 dehydration reaction Methods 0.000 description 10
- 239000013536 elastomeric material Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- 235000021355 Stearic acid Nutrition 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004816 latex Substances 0.000 description 7
- 238000010907 mechanical stirring Methods 0.000 description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000004513 sizing Methods 0.000 description 7
- 239000008117 stearic acid Substances 0.000 description 7
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000003490 calendering Methods 0.000 description 5
- 238000005304 joining Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 239000007970 homogeneous dispersion Substances 0.000 description 4
- 238000000265 homogenisation Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000012763 reinforcing filler Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 235000012489 doughnuts Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- -1 peptizer Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011814 protection agent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 150000001282 organosilanes Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
-
- 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
-
- 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
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
本发明提供一种天然橡胶复合材料及其制备方法。本发明提供的天然橡胶复合材料，以硅土代替部分白炭黑作为填充材料，具有低填充高补强的特点，少量的硅土即能明显降低胶料的生热，提高疲劳寿命，改善胶料的撕裂强度和耐磨性能。与未添加硅土的天然橡胶材料相比，升温值降低了37％，屈挠疲劳寿命提高了167％，撕裂强度提高了32％，磨耗量降低了51％。本发明提供的A+B法和一锅法制备天然橡胶复合材料，制备方法简便，实用，适用于大规模工业化生产。The invention provides a natural rubber composite material and a preparation method thereof. The natural rubber composite material provided by the invention uses silica instead of part of the white carbon black as the filling material, which has the characteristics of low filling and high reinforcement. A small amount of silica can significantly reduce the heat generation of the rubber, increase the fatigue life, and improve the rubber Tear strength and abrasion resistance of the material. Compared with the natural rubber material without adding silica, the temperature rise value is reduced by 37%, the flex fatigue life is increased by 167%, the tear strength is increased by 32%, and the wear amount is reduced by 51%. The A+B method and the one-pot method provided by the invention prepare the natural rubber composite material, and the preparation method is simple and practical, and is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to reinforcing rubber technical field, particularly a kind of native rubber composite material and preparation method thereof.
Background technology
Rubber applies to prepare doughnut, conveyor belts, various sealing device etc. because of its good elasticity, insulativity, resistance to air loss etc. widely.But along with the development of science and technology, the continuous expansion in rubber applications field, people are for rubbery intensity and functionally it is also proposed higher more requirement.Because elastomeric material much uses all in a dynamic condition, as doughnut, conveyor belts, dynamic seal etc., rubber item in dynamic use procedure due to hysteresis loss heat-dissipating, goods fatigue failure can be caused, work-ing life decline.Therefore, reduce the heat-dissipating of sizing material, will the work-ing life of improving rubber item be conducive to.
White carbon black is that a kind of high-specific surface area, high structure, highly active reinforcement and filler are material modified, because it has the physics-chem characteristic of special surface tissue and particle form structure and uniqueness, and is widely used in rubber materials by as reinforcing filler.At present, the main effective means reducing rubber item heat-dissipating uses white carbon black to carry out alternative carbon black in a large number.But a large amount of fillings of white carbon black can cause the wear resistance of sizing material to decline.
Summary of the invention
The object of the present invention is to provide a kind of native rubber composite material and preparation method thereof.Native rubber composite material provided by the invention, while reducing the heat-dissipating of elastomeric material in dynamic use procedure, improving fatigue lifetime, improves the wear resistance of elastomeric material.
The invention provides a kind of native rubber composite material, prepared by the raw material comprising following component:
100 parts by weight of natural rubber;
15 ~ 80 weight part white carbon blacks;
1 ~ 20 weight part tripoli;
0 ~ 80 parts by weight of carbon black per;
0 ~ 10 weight part coupling agent;
0 ~ 20 weight part tenderizer;
0.5 ~ 8 parts by weight of activated dose;
0.5 ~ 8 weight part anti-aging agent;
The promotor of totally 0.5 ~ 8 weight part and vulcanizing agent.
Preferably, described native rubber composite material is prepared by the raw material comprising following component:
100 parts by weight of natural rubber;
40 ~ 60 weight part white carbon blacks;
5 ~ 15 weight part tripoli;
30 ~ 50 parts by weight of carbon black per;
3 ~ 7 weight part coupling agents;
6 ~ 15 weight part tenderizers;
3 ~ 6 parts by weight of activated doses;
3 ~ 6 weight part anti-aging agent;
The promotor of totally 3 ~ 6 weight parts and vulcanizing agent.
Preferably, the particle diameter of described tripoli is 0.01 ~ 10 μm.
Preferably, described tenderizer is one or more in aromatic hydrocarbon oil and naphthenic oil.
Preferably, described promoting agent is at least one in zinc oxide and stearic acid.
Preferably, described anti-aging agent is one or more in p phenylenediamine type antioxidant, quinoline type antioxidant and physical protection agent.
Preferably, described promotor is one or more in sulfenamide type accelerators, thiazole accelerator, thiuram type accelerator and guanidine acclerators.
Preferably, described vulcanizing agent is one or more in Sulfur and sulphur-donor.
Present invention also offers a kind of preparation method of native rubber composite material, comprise the following steps:
By white carbon black dispersion liquid and the first natural rubber mix, obtain the mixture containing white carbon black;
The described mixture containing white carbon black is mixed with the first peptizer, after solidifying, obtains white carbon black master batch;
Tripoli dispersion liquid is mixed with the second natural rubber, obtains the mixture containing tripoli;
The described mixture containing tripoli is mixed with the second peptizer, after solidifying, obtains tripoli master batch;
By mixing to described white carbon black master batch, tripoli master batch and carbon black, coupling agent, tenderizer, anti-aging agent, promoting agent, promotor and vulcanizing agent and after sulfuration, obtain native rubber composite material;
Described white carbon black, first natural rubber, first peptizer, tripoli, second natural rubber, second peptizer, carbon black, coupling agent, tenderizer, anti-aging agent, promoting agent, promotor and vulcanizing agent quality and mass ratio be: (15 ~ 80): (70 ~ 90): (0.12 ~ 2): (1 ~ 20): (10 ~ 30): (0.02 ~ 0.6): (0 ~ 80): (0 ~ 10): (0 ~ 20): (0.5 ~ 8): (0.5 ~ 8): (0.5 ~ 8).
Present invention also offers a kind of preparation method of native rubber composite material, comprise the following steps:
White carbon black-tripoli dispersion liquid is mixed with natural rubber, obtains the mixture containing white carbon black and tripoli;
The described mixture containing white carbon black and tripoli is mixed with peptizer, obtains white carbon black-tripoli master batch;
By described white carbon black-tripoli master batch and carbon black, coupling agent, tenderizer, anti-aging agent, promoting agent, promotor and vulcanizing agent mixing and after sulfuration, obtain native rubber composite material;
Described white carbon black, tripoli, natural rubber, peptizer, carbon black, coupling agent, tenderizer, anti-aging agent, promoting agent, promotor and vulcanizing agent quality and mass ratio be: (15 ~ 80): (1 ~ 20): (100): (0.16 ~ 2.4): (0 ~ 80): (0 ~ 10): (0 ~ 20): (0.5 ~ 8): (0.5 ~ 8): (0.5 ~ 8).
The invention provides a kind of native rubber composite material, prepared by the raw material comprising following component: 100 parts by weight of natural rubber; 15 ~ 80 weight part white carbon blacks; 1 ~ 20 weight part tripoli; 0 ~ 80 parts by weight of carbon black per; 0 ~ 10 weight part coupling agent; 0 ~ 20 weight part tenderizer; 0.5 ~ 8 parts by weight of activated dose; 0.5 ~ 8 weight part anti-aging agent; The promotor of totally 0.5 ~ 8 weight part and vulcanizing agent.Native rubber composite material provided by the invention, using tripoli as packing material, have the HR highly reinforcing feature of low filling, a small amount of tripoli obviously can reduce the heat-dissipating of sizing material, improves fatigue lifetime, improves tear strength and the wear resisting property of sizing material.Experimental result shows, compared with the elastomeric material not adding tripoli, elastomeric material intensification value provided by the invention reduces 37%, and the flexing fatigue life-span improves 167%, and tear strength improves 32%, and wear loss reduces 51%.
Embodiment
The invention provides a kind of native rubber composite material, prepared by the raw material comprising following component:
100 parts by weight of natural rubber;
15 ~ 80 weight part white carbon blacks;
1 ~ 20 weight part tripoli;
0 ~ 80 parts by weight of carbon black per;
0 ~ 10 weight part coupling agent;
0 ~ 20 weight part tenderizer;
0.5 ~ 8 parts by weight of activated dose;
0.5 ~ 8 weight part anti-aging agent;
The promotor of totally 0.5 ~ 8 weight part and vulcanizing agent.
Native rubber composite material provided by the invention, replace part white carbon black as packing material using tripoli, have the HR highly reinforcing feature of low filling, a small amount of tripoli obviously can reduce the heat-dissipating of sizing material, improve fatigue lifetime, improve tear strength and the wear resisting property of sizing material.
Native rubber composite material provided by the invention comprises 100 parts by weight of natural rubber.In the present invention, described natural rubber, as rubber matrix, preferably adds with the form of nature rubber latex.The present invention does not have special requirement to described nature rubber latex, adopts the nature rubber latex that any form well known to those skilled in the art exists.In the present invention, in described nature rubber latex, the mass concentration of natural rubber is preferably 5 ~ 60wt%, is more preferably 20 ~ 40wt%, most preferably is 25 ~ 35wt%.In the present invention, described nature rubber latex is preferably fresh latex, that namely just taked from natural rubber tree, that period of storage is no more than 2 days natural rubber latex.
Native rubber composite material provided by the invention comprises 15 ~ 80 weight part white carbon blacks, is preferably 40 ~ 60 weight parts, is more preferably 45 ~ 55 weight parts, most preferably is 48 ~ 52 weight parts.In the present invention, described white carbon black is preferably white carbon black powder, white carbon black filter cake or white carbon black slurry.In the present invention, described white carbon black, as rubber reinforcing filler, can improve the intensity of elastomeric material, reduces rubber heat-dissipating.
Native rubber composite material provided by the invention comprises 1 ~ 20 weight part tripoli, is preferably 5 ~ 15 weight parts, is more preferably 8 ~ 12 weight parts.The present invention does not have special requirement to described tripoli, adopts commercially available tripoli well known to those skilled in the art.Tripoli is a kind of alumino-silicate minerals matter powder, and main chemical compositions is SiO
2, Al
2o
3and K
2o.The geologic media of its uniqueness makes mineral substance itself have small crystalline particle thickness, and this particle reassociates, be combined to form a kind of flaky texture of high slenderness ratio.In the present invention, described tripoli is preferably obtained through intercalation stripping, powder and super-refinement by tripoli mineral; The particle diameter of described tripoli is preferably 0.01 ~ 10 μm, is more preferably 0.1 ~ 5 μm.In the present invention, described tripoli preferably includes the component of following mass content: 70 ~ 90wt%SiO
2, 5 ~ 20wt%Al
2o
3, 0.4 ~ 3wt%K
2o.In the present invention, described tripoli replaces part white carbon black, and the flaky texture of tripoli can resist crack propagation on the one hand, improves the resistance to fatigue of sizing material; Tripoli lamella can induce the dispersion of white carbon black and carbon black on the other hand, and and form strong interaction between rubber, constraint rubber molecule chain movement, thus reduce heat-dissipating, raising wear resistance.
Native rubber composite material provided by the invention comprises 0 ~ 80 parts by weight of carbon black per, is preferably 3 ~ 50 weight parts, is more preferably 5 ~ 15 weight parts.The present invention does not have special requirement to described carbon black, adopts commercially available carbon black well known to those skilled in the art.In the present invention, described carbon black as rubber reinforcing filler, for improving the intensity of elastomeric material.
Native rubber composite material provided by the invention comprises 0 ~ 10 weight part coupling agent, is preferably 3 ~ 7 weight parts.The present invention does not have special requirement to described coupling agent, adopts coupling agent well known to those skilled in the art.In the present invention, described coupling agent is preferably organo silane coupling agent, is more preferably two (triethoxy propyl silane) tetrasulfide or two (triethoxy propyl silane) disulphide.In the present invention, described coupling agent can interaction between reinforcing filler and rubber matrix.
Native rubber composite material provided by the invention comprises 0 ~ 20 weight part tenderizer, is preferably 6 ~ 15 weight parts, is more preferably 8 ~ 12 weight parts.The present invention does not have special requirement to described tenderizer, adopts tenderizer well known to those skilled in the art.In the present invention, described tenderizer is preferably one or more in aromatic hydrocarbon oil and naphthenic oil, is more preferably environment-friendly aromatic oil.In the present invention, described tenderizer can improve the processing characteristics of rubber.
Native rubber composite material provided by the invention comprises 0.5 ~ 8 parts by weight of activated dose, is preferably 3 ~ 6 weight parts.The present invention does not have special requirement to described promoting agent, adopts promoting agent well known to those skilled in the art.In the present invention, described promoting agent is preferably at least one in zinc oxide and stearic acid.In the present invention, described promoting agent can improve the activity of vulcanization reaction.
Native rubber composite material provided by the invention comprises 0.5 ~ 8 weight part anti-aging agent, is preferably 3 ~ 6 weight parts.The present invention does not have special requirement to described anti-aging agent, adopts anti-aging agent well known to those skilled in the art.In the present invention, described anti-aging agent is preferably one or more in p phenylenediamine type antioxidant, quinoline type antioxidant and physical protection agent, is more preferably one or more in anti-aging agent RD, antioxidant 4020, anti-aging agent 6PPD and Microcrystalline Wax.In the present invention, described anti-aging agent can improve the ageing resistance of elastomeric material.
Native rubber composite material provided by the invention also comprises promotor and the vulcanizing agent of totally 0.5 ~ 8 weight part, is preferably 3 ~ 6 weight parts.The present invention does not have special requirement to described promotor and vulcanizing agent, adopts promotor well known to those skilled in the art and vulcanizing agent.In the present invention, described promotor is preferably one or more in sulfenamide type accelerators, thiazole accelerator, thiuram type accelerator and guanidine acclerators, is more preferably one or more in accelerator NS, accelerant CZ or vulkacit D PG.In the present invention, described promotor can shorten curing time, reduces curing temperature.In the present invention, described vulcanizing agent is preferably one or more in Sulfur and sulphur-donor, is more preferably one or more in common sulphur, insoluble sulfuy or oil-filled Sulfur.In the present invention, described vulcanizing agent can make rubber generation vulcanization crosslinking react, and make linear molecule form tridimensional network, plasticity-reduces, and elastic strength increases.In the present invention, the mass ratio of described promotor and vulcanizing agent is preferably (0.5 ~ 5): (0.3 ~ 2.5), is more preferably (1 ~ 3.5): (1 ~ 2).
Present invention also offers a kind of preparation method's (A+B method) of native rubber composite material, comprise the following steps:
By white carbon black dispersion liquid and the first natural rubber mix, obtain the mixture containing white carbon black;
The described mixture containing white carbon black is mixed with the first peptizer, after solidifying, obtains white carbon black master batch;
Tripoli dispersion liquid is mixed with the second natural rubber, obtains the mixture containing tripoli;
The described mixture containing tripoli is mixed with the second peptizer, after solidifying, obtains tripoli master batch;
By mixing to described white carbon black master batch, tripoli master batch and carbon black, coupling agent, tenderizer, anti-aging agent, promoting agent, promotor and vulcanizing agent and after sulfuration, obtain native rubber composite material;
Described white carbon black, first natural rubber, first peptizer, tripoli, second natural rubber, second peptizer, carbon black, coupling agent, tenderizer, anti-aging agent, promoting agent, promotor and vulcanizing agent quality and mass ratio be: (15 ~ 80): (70 ~ 90): (0.12 ~ 2): (1 ~ 20): (10 ~ 30): (0.02 ~ 0.6): (0 ~ 80): (0 ~ 10): (0 ~ 20): (0.5 ~ 8): (0.5 ~ 8): (0.5 ~ 8).
First the present invention provides white carbon black dispersion liquid.The present invention does not have special restriction to the described operation preparing dispersion liquid, adopts technical scheme prepared by dispersion liquid well known to those skilled in the art.In the present invention, in described dispersion liquid, the mass concentration of white carbon black is preferably 5 ~ 50%, is more preferably 20 ~ 35%, most preferably is 25 ~ 30%.In the present invention, the described white carbon black white carbon black slurries that are preferably white carbon black powder, white carbon black filter cake or directly take from carbon white production process.
In the present invention, when described white carbon black be white carbon black powder or white carbon black filter cake time, after preferably described white carbon black being mixed with water through dispersion, prepare white carbon black dispersion liquid.The present invention does not have particular requirement to described dispersing method, adopts the technical scheme of dispersion well known to those skilled in the art.In the present invention, described dispersion is preferably at least one in ultrasonic wave dispersion, high pressure homogenization dispersion, the homogeneous dispersion of high-shear or high-speed jet homogenous disperse.
In the present invention, when described be separated into ultrasonic wave dispersion time, preferably use ultrasonic wave separating apparatus to disperse.In the present invention, the ultrasonic frequency of described ultrasonic wave dispersion is preferably 15 ~ 60KHz, is more preferably 25 ~ 45KHz; The temperature of described ultrasonic wave dispersion is preferably 25 ~ 100 DEG C, is more preferably 40 ~ 80 DEG C, most preferably is 50 ~ 70 DEG C; The time of described ultrasonic wave dispersion is preferably 10 ~ 60min, is more preferably 20 ~ 50min, most preferably is 30 ~ 40min.
In the present invention, when described be separated into high pressure homogenization dispersion time, preferably use high pressure homogenizer to disperse.In the present invention, the operating pressure of described high pressure homogenization dispersion is preferably 10 ~ 200Mpa, is more preferably 40 ~ 130Mpa, most preferably is 70 ~ 100Mpa; The circular treatment number of times of described high pressure homogenization dispersion is preferably 1 ~ 100 time, is more preferably 20 ~ 80 times, most preferably is 40 ~ 60 times.
In the present invention, when described be separated into high-shear homogeneous dispersion time, preferably use high-shear homogenizing machine to disperse.In the present invention, the rotating speed of the homogeneous dispersion of described high-shear is preferably 1000 ~ 20000rpm, is more preferably 5000 ~ 15000rpm; The treatment time of the homogeneous dispersion of described high-shear is preferably 10min ~ 24h, is more preferably 3 ~ 15h, most preferably is 8 ~ 10h.
In the present invention, when described be separated into high-speed jet homogenous disperse time, preferably use Microfluidizer to disperse.In the present invention, the operating pressure of described high-speed jet homogenous disperse is preferably 20 ~ 400Mpa, is more preferably 60 ~ 300Mpa; The circular treatment number of times of described high-speed jet homogenous disperse is preferably 1 ~ 100 time, is more preferably 20 ~ 80 times, most preferably is 40 ~ 60 times.
In the present invention, when the white carbon black slurries in carbon white production process directly taken from by described white carbon black, preferably direct as dispersion liquid.
After obtaining white carbon black dispersion liquid, the present invention, by described white carbon black dispersion liquid and the first natural rubber mix, obtains the mixture containing white carbon black.The operation of the present invention to described mixing does not have special restriction, adopts the technical scheme of mixing well known to those skilled in the art.In the present invention, the white carbon black in described white carbon black dispersion liquid and the mass ratio of the first natural rubber are (15 ~ 80): (70 ~ 90), are preferably (40 ~ 60): (75 ~ 85).In the present invention, described mixing is preferably carried out under churned mechanically condition; The described churned mechanically time is preferably 1 ~ 60min, is more preferably 15 ~ 45min, most preferably is 25 ~ 35min; Described churned mechanically speed is preferably 100 ~ 1000rpm, is more preferably 300 ~ 800rpm, most preferably is 500 ~ 600rpm.
After obtaining the mixture containing white carbon black, the described mixture containing white carbon black mixes with the first peptizer by the present invention, obtains white carbon black master batch after solidifying.The present invention does not have special restriction to described operation of solidifying, and adopts technical scheme of solidifying well known to those skilled in the art.In the present invention, described in time of solidifying be preferably 1min ~ 100h, be more preferably 10min ~ 10h, most preferably be 20min ~ 5h.
In the present invention, the mass ratio of described first peptizer and the first natural rubber is preferably 1: 5 ~ 500, is more preferably 1: 20 ~ 300, most preferably is 1: 50 ~ 100.In the present invention, described first peptizer is preferably one or more in acids peptizer, alcohols peptizer and inorganic salts peptizer; Described acids peptizer is preferably one or more in hydrochloric acid, sulfuric acid, acetic acid and formic acid; Described alcohols peptizer is preferably at least one in methyl alcohol and ethanol; Described inorganic salts peptizer is preferably at least one in alkaline earth metal chloride, is more preferably at least one in calcium chloride and magnesium chloride.
Described first peptizer preferably mixes with the described mixture containing white carbon black by the present invention in form of an aqueous solutions; The mass concentration of the aqueous solution of described first peptizer is preferably 1 ~ 10wt%, is more preferably 3 ~ 8wt%.
The present invention preferably dewaters after solidification.The method of the present invention to described dehydration does not have special requirement, adopts the working method of dehydration well known to those skilled in the art.In the present invention, described dehydration preferably includes ironed, crepe, granulation operations.In the present invention, described ironed, crepe, granulation operations do not have special restriction, according to actual needs, adopt ironed, crepe, granulation operations well known to those skilled in the art.
The present invention preferably carries out drying after dewatering.The method of the present invention to described drying does not have special requirement, adopts the working method of drying well known to those skilled in the art.In the present invention, described drying temperature is preferably 50 ~ 130 DEG C, is more preferably 80 ~ 100 DEG C; Described time of drying is preferably 1 ~ 24h, is more preferably 5 ~ 20h, most preferably is 10 ~ 15h.
The invention provides tripoli dispersion liquid, described dispersion liquid is mixed with the second natural rubber, obtain the mixture containing tripoli; The described mixture containing tripoli is mixed with the second peptizer, after dehydration, drying, obtains tripoli master batch.The present invention does not have special requirement to the described method preparing tripoli master batch, adopts the method preparing tripoli master batch well known to those skilled in the art.In the present invention, preferably tripoli master batch is prepared according to the method preparing white carbon black master batch described in technique scheme.In the present invention, the preparation of described white carbon black master batch and described tripoli master batch does not have sequencing.In the present invention, the mass ratio of described tripoli and the second natural rubber is (1 ~ 20): (10 ~ 30), is preferably (5 ~ 15): (15 ~ 25).In the present invention, in described tripoli dispersion liquid, the mass concentration of tripoli is preferably 5 ~ 50%, is more preferably 20 ~ 35%, most preferably is 25 ~ 30%.
In the present invention, the summation of described first natural rubber and the second natural rubber is the natural rubber in component described in technique scheme; In other words, in the present invention, the natural rubber in described component adds in batches, and white carbon black master batch prepared by a part of natural rubber and white carbon black, and tripoli master batch prepared by remainder natural rubber and tripoli.
In the present invention, the mass ratio of described second peptizer and the second natural rubber is preferably 1: 5 ~ 500, is more preferably 1: 20 ~ 300, most preferably is 1: 50 ~ 100.In the present invention, described second peptizer is preferably one or more in acids peptizer, alcohols peptizer and inorganic salts peptizer; Described acids peptizer is preferably one or more in hydrochloric acid, sulfuric acid, acetic acid and formic acid; Described alcohols peptizer is preferably at least one in methyl alcohol and ethanol; Described inorganic salts peptizer is preferably at least one in alkaline earth metal chloride, is more preferably at least one in calcium chloride and magnesium chloride.
Described second peptizer preferably mixes with the described mixture containing tripoli by the present invention in form of an aqueous solutions; The mass concentration of the aqueous solution of described second peptizer is preferably 1 ~ 10wt%, is more preferably 3 ~ 8wt%.
After obtaining white carbon black master batch and tripoli master batch, the present invention, by after mixing to described white carbon black master batch, tripoli master batch and carbon black, anti-aging agent, promoting agent, promotor and vulcanizing agent and sulfuration, obtains native rubber composite material.The present invention does not have special requirement to described mixing and vulcanisation operation, adopts the operation of mixing and sulfuration well known to those skilled in the art.
In the present invention, described white carbon black, tripoli, carbon black, coupling agent, tenderizer, anti-aging agent, promoting agent, promotor and vulcanizing agent quality and mass ratio be (15 ~ 80): (1 ~ 20): (0 ~ 80): (0 ~ 10): (0 ~ 20): (0.5 ~ 8): (0.5 ~ 8): (0.5 ~ 8), be preferably (40 ~ 60): (5 ~ 15): (3 ~ 50): (3 ~ 7): (6 ~ 15): (3 ~ 6): (3 ~ 6): (3 ~ 6), be more preferably (45 ~ 55): (8 ~ 12): (5 ~ 15): (4 ~ 6): (8 ~ 12): (4 ~ 5): (4 ~ 5): (4 ~ 5).
Present invention also offers a kind of preparation method's (one kettle way) of native rubber composite material, comprise the following steps:
White carbon black-tripoli dispersion liquid is mixed with natural rubber, obtains the mixture containing white carbon black and tripoli;
The described mixture containing white carbon black and tripoli is mixed with peptizer, obtains white carbon black-tripoli master batch;
By described white carbon black-tripoli master batch and carbon black, coupling agent, tenderizer, anti-aging agent, promoting agent, promotor and vulcanizing agent mixing and after sulfuration, obtain native rubber composite material;
Described white carbon black, tripoli, natural rubber, peptizer, carbon black, coupling agent, tenderizer, anti-aging agent, promoting agent, promotor and vulcanizing agent quality and mass ratio be: (15 ~ 80): (1 ~ 20): (100): (0.16 ~ 2.4): (0 ~ 80): (0 ~ 10): (0 ~ 20): (0.5 ~ 8): (0.5 ~ 8): (0.5 ~ 8).
First the present invention provides white carbon black-tripoli dispersion liquid.The present invention does not have special restriction to the described operation preparing dispersion liquid, adopts technical scheme prepared by dispersion liquid well known to those skilled in the art.The present invention preferably prepares white carbon black-tripoli dispersion liquid according to the method preparing white carbon black dispersion liquid.In the present invention, in described dispersion liquid, total mass concentration of white carbon black and tripoli is preferably 5 ~ 50%, is more preferably 20 ~ 35%, most preferably is 25 ~ 30%.
After obtaining white carbon black-tripoli dispersion liquid, described white carbon black-tripoli dispersion liquid mixes with natural rubber by the present invention, obtains the mixture containing white carbon black and tripoli; The described mixture containing white carbon black and tripoli is mixed with peptizer, after solidifying, obtains white carbon black-tripoli master batch; By described white carbon black-tripoli master batch and carbon black, coupling agent, tenderizer, anti-aging agent, promoting agent, promotor and vulcanizing agent mixing and after sulfuration, obtain native rubber composite material.The present invention to describedly preparing mixture, solidify, operation that is mixing and sulfuration do not have special restriction, according to well known to those skilled in the artly preparing mixture, solidify, the technical scheme of mixing and sulfuration.In the present invention, preferably prepare white carbon black-tripoli master batch according to method described in A+B method, described white carbon black-tripoli master batch solidified, mixing and sulfuration.
In the present invention, the mass ratio of described white carbon black, tripoli and natural rubber is (15 ~ 80): (1 ~ 20): (100), be preferably (40 ~ 60): (5 ~ 15): (100), are more preferably (45 ~ 55): (8 ~ 12): (100).
In the present invention, the mass ratio of described peptizer and natural rubber is preferably 1: 5 ~ 500, is more preferably 1: 20 ~ 300, most preferably is 1: 50 ~ 100.In the present invention, described peptizer is preferably one or more in acids peptizer, alcohols peptizer and inorganic salts peptizer; Described acids peptizer is preferably one or more in hydrochloric acid, sulfuric acid, acetic acid and formic acid; Described alcohols peptizer is preferably at least one in methyl alcohol and ethanol; Described inorganic salts peptizer is preferably at least one in alkaline earth metal chloride, is more preferably at least one in calcium chloride and magnesium chloride.
Described peptizer preferably mixes with the described mixture containing white carbon black and tripoli by the present invention in form of an aqueous solutions; The mass concentration of the aqueous solution of described peptizer is preferably 1 ~ 10wt%, is more preferably 3 ~ 8wt%.
In the present invention, described white carbon black, tripoli, carbon black, coupling agent, tenderizer, anti-aging agent, promoting agent, promotor and vulcanizing agent quality and mass ratio be (15 ~ 80): (1 ~ 20): (0 ~ 80): (0 ~ 10): (0 ~ 20): (0.5 ~ 8): (0.5 ~ 8): (0.5 ~ 8), be preferably (40 ~ 60): (5 ~ 15): (3 ~ 50): (3 ~ 7): (6 ~ 15): (3 ~ 6): (3 ~ 6): (3 ~ 6), be more preferably (45 ~ 55): (8 ~ 12): (5 ~ 15): (4 ~ 6): (8 ~ 12): (4 ~ 5): (4 ~ 5): (4 ~ 5).
In order to further illustrate the present invention, below in conjunction with embodiment, native rubber composite material provided by the invention is described in detail, but they can not be interpreted as limiting the scope of the present invention.
Comparative example:
By 100g natural rubber, 50g white carbon black VN3,5g carbon black N330, urge CZ, 2g urge D and 1.5g sulphur with two (triethoxy propyl silane) tetrasulfide of 4g, 1g anti-aging agent RD, 4gTDAE oil, 1g stearic acid, 3gZnO, 1.5g, calendering process is mixing and sulfuration obtains rubber composite routinely.
Embodiment 1:
45g white carbon black powder is added in 360g water, adopt high-shear homogenizing machine, under 10000rpm, 30min dispersion treatment is carried out to obtained mixture, joining 400g does containing in the fresh latex of 20%, 500rpm mechanical stirring 30min, add massfraction be 5% acetic acid solution 32g carry out solidifying 10min, through dehydration, obtain white carbon black master batch after 100 DEG C of dry 4h; 5g tripoli is added in 50g water, adopt high-shear homogenizing machine, under 10000rpm, 30min dispersion treatment is carried out to obtained mixture, joining 100g does containing in the fresh latex of 20%, 500rpm mechanical stirring 30min, add massfraction be 5% acetic acid solution 8g carry out solidifying 10min, through dehydration, obtain white carbon black master batch after 100 DEG C of dry 4h.Tripoli master batch prepared by the white carbon black master batch prepared by 125g again and 25g, urge CZ, 2g urge D and 1.5g sulphur with two (triethoxy propyl silane) tetrasulfide of 5g carbon black N330,4g, 1g anti-aging agent RD, 4gTDAE oil, 1g stearic acid, 3gZnO, 1.5g, calendering process is mixing and sulfuration obtains rubber composite routinely.
Embodiment 2:
45g white carbon black powder and 5g tripoli are added in 360g water, adopt Microfluidizer, under 200MPa, dispersion treatment is carried out to obtained mixture, cycle index is 5 times, joining 500g does containing in the fresh latex of 20%, 500rpm mechanical stirring 30min, add massfraction be 2% formic acid solution 40g carry out solidifying 30min, through dehydration, obtain white carbon black/tripoli master batch after 100 DEG C of dry 4h.The white carbon black again prepared by 150g/tripoli master batch, urge CZ, 2g urge D and 1.5g sulphur with two (triethoxy propyl silane) tetrasulfide of 5g carbon black N330,4g, 1g anti-aging agent RD, 4gTDAE oil, 1g stearic acid, 3gZnO, 1.5g, calendering process is mixing and sulfuration obtains rubber composite routinely.
Embodiment 3:
Get white carbon black mass concentration be 60% white carbon black filter cake 67g be added in 133g water, mechanical stirring 1h, then high pressure homogenizer is adopted, under 50MPa, dispersion treatment is carried out to obtained mixture, cycle index is join 400g for 5 times to do containing in the fresh latex of 20%, 500rpm mechanical stirring 30min, add massfraction be 10% ethanolic soln 100g carry out solidifying 2h, through dehydration, obtain white carbon black master batch after 100 DEG C of dry 4h; 10g tripoli is added in 50g water, then high pressure homogenizer is adopted, under 50MPa, dispersion treatment is carried out to obtained mixture, cycle index is 5 times, joining 100g does containing in the fresh latex of 20%, 500rpm mechanical stirring 30min, add massfraction be 10% ethanolic soln 30g carry out solidifying 2h, through dehydration, obtain white carbon black master batch after 100 DEG C of dry 4h.Tripoli master batch prepared by the white carbon black master batch prepared by 120g again and 30g, urge CZ, 2g urge D and 1.5g sulphur with two (triethoxy propyl silane) tetrasulfide of 5g carbon black N330,4g, 1g anti-aging agent RD, 4gTDAE oil, 1g stearic acid, 3gZnO, 1.5g, calendering process is mixing and sulfuration obtains rubber composite routinely.
Embodiment 4:
Directly getting 200g dry matter content is 20wt% white carbon black slurries, add 10g tripoli, adopt ultrasonic wave separating apparatus, 30min is processed under ultrasonic frequency 25KHz, temperature 50 C, joining 500g does containing in the fresh latex of 20%, 500rpm mechanical stirring 30min, add massfraction be 10% calcium chloride 20g solidify, through dehydration, obtain white carbon black/tripoli master batch after 100 DEG C of dry 4h.The white carbon black again prepared by 150g/tripoli master batch, urge CZ, 2g urge D and 1.5g sulphur with two (triethoxy propyl silane) tetrasulfide of 5g carbon black N330,4g, 1g anti-aging agent RD, 4gTDAE oil, 1g stearic acid, 3gZnO, 1.5g, calendering process is mixing and sulfuration obtains rubber composite routinely.
The performance of the present invention to native rubber composite material prepared by embodiment and comparative example detects: the method specified according to GB/T528-2009, detects the stress at definite elongation of native rubber composite material and tensile strength; According to the method that GB/T529-2008 specifies, the tear strength of native rubber composite material is detected; According to the method that GB/T9867-2008 specifies, the wear loss of native rubber composite material is detected; According to the method that GB/T1687-1993 specifies, the temperature rise value of native rubber composite material is detected; According to the method that GB/T13934-2006 specifies, the flexing fatigue life-span of native rubber composite material is detected.Detected result is in table 1.
Carry out performance test by obtaining native rubber composite material in comparative example and embodiment, test result is as shown in table 1.
Native rubber composite material performance test results in table 1 comparative example of the present invention and embodiment
| Performance | Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| 300% stretches surely, Mpa | 9.92 | 12.25 | 12.83 | 13.20 | 13.75 |
| Tensile strength, Mpa | 21.57 | 29.34 | 30.53 | 32.30 | 31.56 |
| Tear strength, kN/m | 97.65 | 123.57 | 129.25 | 125.10 | 127.80 |
| Wear loss, cm 3/1.61km | 0.471 | 0.323 | 0.279 | 0.267 | 0.230 |
| Temperature rise value, DEG C | 29.0 | 20.1 | 19.5 | 18.2 | 18.5 |
| The flexing fatigue life-span, ten thousand times/6 grades | 7.5 | 18.0 | 20.0 | 17.5 | 16.0 |
As can be seen from Table 1, the native rubber composite material that the embodiment of the present invention prepares, compared with not adding the elastomeric material of tripoli in comparative example, 300% tensile modulus, tensile strength, tear strength and flexing fatigue life-span are all improved significantly, and wear loss and temperature rise value all have remarkable reduction.
As can be seen from above comparative example and embodiment, native rubber composite material provided by the invention, compared with the elastomeric material not adding tripoli, temperature rise value reduces 37%, the flexing fatigue life-span improves 167%, tear strength improves 32%, and wear loss reduces 51%, has low-heat-generation, high fatigue life, tear strength and wear resisting property.
The above is only the preferred embodiment of the present invention, not does any pro forma restriction to the present invention.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a native rubber composite material, comprises following component:
100 parts by weight of natural rubber;
15 ~ 80 weight part white carbon blacks;
1 ~ 20 weight part tripoli;
0 ~ 80 parts by weight of carbon black per;
0 ~ 10 weight part coupling agent;
0 ~ 20 weight part tenderizer;
0.5 ~ 8 parts by weight of activated dose;
0.5 ~ 8 weight part anti-aging agent;
The promotor of totally 0.5 ~ 8 weight part and vulcanizing agent.
2. native rubber composite material according to claim 1, is characterized in that, comprises following component:
100 parts by weight of natural rubber;
40 ~ 60 weight part white carbon blacks;
5 ~ 15 weight part tripoli;
30 ~ 50 parts by weight of carbon black per;
3 ~ 7 weight part coupling agents;
6 ~ 15 weight part tenderizers;
3 ~ 6 parts by weight of activated doses;
3 ~ 6 weight part anti-aging agent;
The promotor of totally 3 ~ 6 weight parts and vulcanizing agent.
3. native rubber composite material according to claim 1 and 2, is characterized in that, the particle diameter of described tripoli is 0.01 ~ 10 μm.
4. native rubber composite material according to claim 1 and 2, is characterized in that, described tenderizer is one or more in aromatic hydrocarbon oil and naphthenic oil.
5. native rubber composite material according to claim 1 and 2, is characterized in that, described promoting agent is at least one in zinc oxide and stearic acid.
6. native rubber composite material according to claim 1 and 2, is characterized in that, described anti-aging agent is one or more in p phenylenediamine type antioxidant, quinoline type antioxidant and physical protection agent.
7. native rubber composite material according to claim 1 and 2, is characterized in that, described promotor is one or more in sulfenamide type accelerators, thiazole accelerator, thiuram type accelerator and guanidine acclerators.
8. native rubber composite material according to claim 1 and 2, is characterized in that, described vulcanizing agent is one or more in Sulfur and sulphur-donor.
9. a preparation method for native rubber composite material, comprises the following steps:
By white carbon black dispersion liquid and the first natural rubber mix, obtain the mixture containing white carbon black;
There is the mixture of white carbon black to mix with the first peptizer described conjunction, after solidifying, obtain white carbon black master batch;
Tripoli dispersion liquid is mixed with the second natural rubber, obtains the mixture closing tripoli;
The described mixture containing tripoli is mixed with the second peptizer, after solidifying, obtains tripoli master batch;
By mixing to described white carbon black master batch, tripoli master batch and carbon black, coupling agent, tenderizer, anti-aging agent, promoting agent, promotor and vulcanizing agent and after sulfuration, obtain native rubber composite material;
Described white carbon black, first natural rubber, first peptizer, tripoli, second natural rubber, second peptizer, carbon black, coupling agent, tenderizer, anti-aging agent, promoting agent, promotor and vulcanizing agent quality and mass ratio be: (15 ~ 80): (70 ~ 90): (0.12 ~ 2): (1 ~ 20): (10 ~ 30): (0.02 ~ 0.6): (0 ~ 80): (0 ~ 10): (0 ~ 20): (0.5 ~ 8): (0.5 ~ 8): (0.5 ~ 8).
10. a preparation method for native rubber composite material, comprises the following steps:
White carbon black-tripoli dispersion liquid is mixed with natural rubber, obtains the mixture closing white carbon black and tripoli;
The described mixture containing white carbon black and tripoli is mixed with peptizer, obtains white carbon black-tripoli master batch;
By described white carbon black-tripoli master batch and carbon black, coupling agent, tenderizer, anti-aging agent, promoting agent, promotor and vulcanizing agent mixing and after sulfuration, obtain native rubber composite material;
Described white carbon black, tripoli, natural rubber, peptizer, carbon black, coupling agent, tenderizer, anti-aging agent, promoting agent, promotor and vulcanizing agent quality and mass ratio be: (15 ~ 80): (1 ~ 20): (100): (0.16 ~ 2.4): (0 ~ 80): (0 ~ 10): (0 ~ 20): (0.5 ~ 8): (0.5 ~ 8): (0.5 ~ 8).
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| CN106633218A (en) * | 2016-10-21 | 2017-05-10 | 安徽理工大学 | Natural rubber composite material and preparation method thereof |
| CN106674633A (en) * | 2016-12-23 | 2017-05-17 | 太仓冠联高分子材料有限公司 | Natural rubber material for vacuum pipeline of high-speed rail and preparation method thereof |
| CN107602953A (en) * | 2017-10-11 | 2018-01-19 | 岭南师范学院 | A kind of tripoli/Heveatex compound cutan and its preparation method and application |
| CN115490919A (en) * | 2021-11-24 | 2022-12-20 | 江苏锐巴新材料科技有限公司 | Flexing and cracking resistant agent composition for shoe material and application thereof |
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| CN106084323A (en) * | 2016-06-20 | 2016-11-09 | 岭南师范学院 | A kind of tripoli/natural rubber masterbatch and preparation method thereof |
| CN106633218A (en) * | 2016-10-21 | 2017-05-10 | 安徽理工大学 | Natural rubber composite material and preparation method thereof |
| CN106674633A (en) * | 2016-12-23 | 2017-05-17 | 太仓冠联高分子材料有限公司 | Natural rubber material for vacuum pipeline of high-speed rail and preparation method thereof |
| CN107602953A (en) * | 2017-10-11 | 2018-01-19 | 岭南师范学院 | A kind of tripoli/Heveatex compound cutan and its preparation method and application |
| CN107602953B (en) * | 2017-10-11 | 2019-11-12 | 岭南师范学院 | A kind of silica/natural rubber latex composite adhesive film and its preparation method and application |
| CN115490919A (en) * | 2021-11-24 | 2022-12-20 | 江苏锐巴新材料科技有限公司 | Flexing and cracking resistant agent composition for shoe material and application thereof |
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