CN105199171A - Preparation method of white carbon black masterbatch, obtained product and application of product to high-wear-resistance white carbon black reinforcing material for rubber - Google Patents
Preparation method of white carbon black masterbatch, obtained product and application of product to high-wear-resistance white carbon black reinforcing material for rubber Download PDFInfo
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- CN105199171A CN105199171A CN201510664292.3A CN201510664292A CN105199171A CN 105199171 A CN105199171 A CN 105199171A CN 201510664292 A CN201510664292 A CN 201510664292A CN 105199171 A CN105199171 A CN 105199171A
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- white carbon
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 249
- 229920001971 elastomer Polymers 0.000 title claims abstract description 84
- 239000005060 rubber Substances 0.000 title claims abstract description 84
- 239000006229 carbon black Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 45
- 239000012779 reinforcing material Substances 0.000 title abstract 2
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 86
- 239000007822 coupling agent Substances 0.000 claims abstract description 80
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 74
- 239000006185 dispersion Substances 0.000 claims abstract description 70
- 239000000463 material Substances 0.000 claims abstract description 51
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 238000003756 stirring Methods 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 239000007965 rubber solvent Substances 0.000 claims abstract description 24
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 229960001866 silicon dioxide Drugs 0.000 claims description 70
- 239000003795 chemical substances by application Substances 0.000 claims description 55
- 238000005299 abrasion Methods 0.000 claims description 33
- -1 polyoxyethylene Polymers 0.000 claims description 25
- 238000012986 modification Methods 0.000 claims description 24
- 230000004048 modification Effects 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 16
- 239000000194 fatty acid Substances 0.000 claims description 16
- 229930195729 fatty acid Natural products 0.000 claims description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- 238000000889 atomisation Methods 0.000 claims description 12
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 12
- 239000000344 soap Substances 0.000 claims description 12
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 claims description 9
- 238000005304 joining Methods 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 238000004807 desolvation Methods 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 150000004665 fatty acids Chemical class 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 229920001195 polyisoprene Polymers 0.000 claims description 7
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 6
- 244000043261 Hevea brasiliensis Species 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 229920003052 natural elastomer Polymers 0.000 claims description 6
- 229920001194 natural rubber Polymers 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 150000002191 fatty alcohols Chemical class 0.000 claims description 5
- 229920005862 polyol Polymers 0.000 claims description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- 239000010692 aromatic oil Substances 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 239000005543 nano-size silicon particle Substances 0.000 claims description 3
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 claims description 3
- 239000000779 smoke Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims description 3
- 229960004418 trolamine Drugs 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 4
- 229940105289 carbon black Drugs 0.000 description 67
- 235000019241 carbon black Nutrition 0.000 description 67
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 31
- 239000000243 solution Substances 0.000 description 17
- 238000004513 sizing Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 8
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- 230000003014 reinforcing effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
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- 238000004886 process control Methods 0.000 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000008118 PEG 6000 Substances 0.000 description 3
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 3
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
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- 230000007547 defect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
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- 230000002787 reinforcement Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229930182558 Sterol Natural products 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- 108090000623 proteins and genes Proteins 0.000 description 2
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- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
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- 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
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-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
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 101100364280 Oryza sativa subsp. japonica RSS3 gene Proteins 0.000 description 1
- 101100150875 Oryza sativa subsp. japonica SUS1 gene Proteins 0.000 description 1
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- 101100478972 Oryza sativa subsp. japonica SUS3 gene Proteins 0.000 description 1
- 101100004663 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) BRR2 gene Proteins 0.000 description 1
- 101100504519 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) GLE1 gene Proteins 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
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- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of white carbon black masterbatch, an obtained product and an application of the product to a high-wear-resistance white carbon black reinforcing material for rubber. The method comprises steps as follows: adding a coupling agent to stirred silicon dioxide in an atomizing manner to modify the silicon dioxide; mixing rubber and a solvent to obtain a rubber-solvent homogeneous system; adding the modified silicon dioxide to the rubber-solvent homogeneous system, removing the solvent after evenly stirring the mixture, adding a dispersant to an obtained dry material, fully and evenly mixing the mixture, and tableting or granulating the mixture to obtain the white carbon black masterbatch. With the adoption of the method, the silicon dioxide cannot agglomerate again easily, the dispersion uniformity and the uniformity degree of silicon dioxide particles are further improved, the obtained product is added to tire tread rubber, the mechanical strength and the wear resistance of the rubber are substantially improved, and the heat build-up and the hysteresis loss are obviously reduced.
Description
Technical field
The present invention relates to a kind of preparation method of white carbon black master batch, also relate to white carbon black master batch obtained in this way and the application as rubber white carbon black high abrasion supporting material thereof, belong to rubber and white carbon black technical field.
Background technology
From Article 1 " green tire " since meter Qi Lin researchs and develops successfully, except rubber base material, add anti-slippery that white carbon black can improve tire, the performance that reduces rolling resistance and improve the aspect such as wear-resisting generally acknowledge by people.But initial white carbon black and coupling agent addition manner for add several times in rubber mixing process, white carbon black and coupling agent reaction modifying i.e. in-situ modified in rubber mixing process, this is that dry method is mixing, exist white carbon black addition can not white carbon black particle after excessive and dispersion agglomeration is serious again, sizing material mooney viscosity large, need multistage mixing, the shortcomings that the loaded down with trivial details and energy consumption of technique is high, compound viscosity rebound phenomena serious, heat-dissipating conference causes the security of processing bad, filler reinforcement effect white carbon black being lost should have.
Some patent reports, the aqueous phase such as natural rubber latex or styrene-butadiene latex breakdown of emulsion is adopted to prepare white carbon black master batch, although the method plays certain improvement dispersiveness effect to white carbon black, but still there is following defect: containing a large amount of moisture in natural rubber latex, and there is extremely strong water-absorbent because of white carbon black, unfavorable to final drying, thus cause sizing material in the rubber product production processes such as tire can produce bubble or pore, cause that product is defective or defect ware rate is high; Containing nonrubber compositions such as protein, fat, wax, sterol, sterol ester, phosphatide and the variable valency metal such as copper, manganese compounds in natural rubber latex, organic non-rubber component has a negative impact to the mechanics of sizing material and processing characteristics, and also containing compositions such as more nonrubber hydrocarbon in synthetic latex, wherein the nonrubber hydrocarbon such as protein affects the linked reaction of coupling agent and white carbon black, the ageing-resistant performance of variable valency metal compounds affect sizing material, belongs to restricted; The initial hardness of white carbon black master batch prepared by natural rubber latex is very large, and the processing directly had influence on from now on uses and disperses, and in use procedure, heat-dissipating is high and very easily damage mixing facilities moment, etc. these defects directly have influence on its development from now on and application.
Applicant has applied for a kind of patent of invention for tire tread high abrasion supporting material and preparation method thereof by name in 2014, application number is CN201410715546.5, this patent adopts natural rubber to be raw material, overcomes the deficiency of latex, achieves good effect.The compositions such as white carbon black, dispersion agent, coupling agent directly join in rubber solutions by this product in the preparation, but product is confined to use in the rubber item formula based on natural rubber, and chemical modification is not in advance carried out to white carbon black, although carry out in the liquid phase mixing the dispersion that can improve mixing process, but because the dilute solution shearing force of rubber is low, once white carbon black gathering of reuniting has occurred at early stage, then cannot be opened in follow-up liquid-phase mixing.
Therefore, make white carbon black in rubber dispersion, have the higher degree that is uniformly dispersed, effectively prevent the reunion collection of its particle, develop more high performance the rubber item particularly significant and sense of urgency in the supporting material of tire, the poisonous and harmful source of reducing in preparation process, this has great economic and social benefit to safety and environmental protection etc.
Summary of the invention
For the mixing deficiency existed with natural rubber latex dispersion technology of existing dry method, the invention provides a kind of preparation method of white carbon black master batch, the method does not produce " three wastes ", environmental protection is feasible, the dispersiveness of white carbon black can be increased, not only increase the dispersiveness of white carbon black in Rubber processing process in sizing material, also significantly improve the reinforcing effect of white carbon black to sizing material.
Present invention also offers the application as rubber white carbon black high abrasion supporting material of the white carbon black master batch that obtains according to the method described above and this master batch, this master batch wear resisting property and reinforcing property all good, can as rubber industry high abrasion supporting material.
The present invention is the further modification on CN201410715546.5 basis, by the adjustment of the preparation method of dialogue carbonblack master batch, widen the kind (being not limited only to natural rubber) of rubber, improve the dispersiveness of white carbon black, control the reunion collection of white carbon black particle in rubber matrix, reach the white carbon black master batch of gained under same recipe condition and have the object of more high-wear resistance and reinforcing property, especially the preparation of " green tire " tread rubber provides new thinking.
The concrete technical scheme of the present invention is as follows:
The preparation method of a kind of white carbon black (i.e. silicon-dioxide, lower same) master batch, comprises the following steps:
(1) modification of silicon-dioxide: coupling agent is added in the silicon-dioxide of stirring in the mode of atomization, continues after adding to stir, obtain the silicon-dioxide of modification;
(2) preparation of rubber-solvent homogeneous system: by rubber and solvent, heated and stirred is dissolved completely to rubber, obtains rubber-solvent homogeneous system;
(3) preparation of white carbon black master batch: the silicon-dioxide of modification is under agitation slowly joined in rubber-solvent homogeneous system continuously, be uniformly mixed, then heat up desolvation, obtain dry material, in gained dry material, add dispersion agent fully mix, through compressing tablet or granulation, obtain white carbon black master batch.
In above-mentioned preparation method, first carry out mixed and modified with silicon-dioxide by coupling agent in the mode of atomization, energy consumption when avoiding use and the solvent recuperation of organic solvent and loss, add cost, the feature of environmental protection is better.
When modification, coupling agent adds in the mode of atomization, and the atomization of coupling agent can adopt routine techniques now to realize, such as, liquid silane coupling agent is passed through Double-fluid atomization nozzle, control atmospheric pressure 0.3MPa-1.0MPa, liquid pressure 0.2-0.5MPa realizes the atomization of coupling agent.
In above-mentioned preparation method, in order to ensure that silicon-dioxide fully mixes with coupling agent, reaction, for coupling agent add speed, the stirring velocity of silicon-dioxide has strict requirement, once control bad, the dispersiveness of silicon-dioxide and reinforcing property will be subject to extreme influence.Through lot of experiments, the present invention obtains following processing parameter: coupling agent constantly adds in silicon-dioxide with the form of spraying according to uniform speed, and its joining day is that 10min-1.5h is better, best during joining day 1h; Silane coupling agent is atomized in the process and whole silica modified process added, and maintenance stirring velocity is 1000-2000rpm, and optimum stirring velocity is 1500rpm.By the cooperation of joining day and stirring velocity, make coupling agent and the abundant blending dispersion of silicon-dioxide even, ensure that carrying out smoothly of modification.
Further, after coupling agent has added, continue under this stirring velocity, to stir 0-30min, preferred 1-30min, optimum 10min, guarantee fully completing of modification.
Further, the temperature of the adition process of coupling agent and the whole process of modification is 100 DEG C-150 DEG C, preferably 110 DEG C-120 DEG C.
In above-mentioned preparation method, adopt rubber-solvent homogeneous system to mix with improved silica, white carbon black is fully disperseed, improves its use properties further.Preferably, in step (2), rubber and solvent mix at 50-80 DEG C, and mixing time is 1-10 hour.
In above-mentioned steps (3), desolvation at 80 ~ 120 DEG C.The solvent removed can reclaim rear recycling, avoids the waste of solvent.
In above-mentioned preparation method, each raw material dosage is as follows by weight: silica 1 ~ 100 part, coupling agent 1 ~ 10 part, rubber 1 ~ 100 part, solvent 500 ~ 1500 parts, dispersion agent 1 ~ 10 part.Preferably, when adopting following weight part consumption, effect is better: silicon-dioxide 50-60 part, coupling agent 5 parts, rubber 100 parts, solvent 1000 parts, dispersion agent 10 parts.
In above-mentioned each raw material dosage relation, the mass ratio of coupling agent and silicon-dioxide is within the scope of 1:1-1:10.
In above-mentioned each raw material dosage relation, the mass ratio of silicon-dioxide and rubber is 1-100:100, reaches as high as 1:1, preferred 2-8:10, most preferably 5-6:10.
In above-mentioned preparation method, described silicon-dioxide is any one in ordinary precipitation process silicon-dioxide, nano silicon and high dispersive silicon-dioxide, and being preferably specific surface area is 161m
2/ g ~ 210m
2the ordinary precipitation process silicon-dioxide of/g.
In above-mentioned preparation method, described coupling agent is at least one in silane coupling agent, titanate coupling agent, aluminate coupling agent, bimetal coupling agent, xylogen coupling agent and tin coupling agent.Wherein, every class coupling agent comprises multiple heterogeneity, and every class coupling agent performance is similar.In a preferred embodiment of the invention, coupling agent is preferably the silane coupling agent (such as Si69, Si75) of the silane coupling agent (such as Si69, Si75) of mass ratio 4:1 and the mixture of titanate coupling agent or mass ratio 5:1 and the mixture of bimetal coupling agent;
In above-mentioned preparation method, described rubber is at least one in caoutchouc standard glue, smoke sheet rubber, rubber crepe sheet, solution polymerized butadiene styrene rubber, emulsion polymerized styrene butadiene rubber, cis-1,4-polybutadiene rubber, chloroprene rubber, polyisoprene rubber, epoxy natural rubber and ethylene-propylene rubber(EPR).Wherein, have different models in all kinds of rubber, every class rubber performance is similar.In the preferred embodiment of the present invention, it is the solution polymerized butadiene styrene rubber of 70:30 and the mixture of cis-1,4-polybutadiene rubber that rubber is preferably mass ratio, or mass ratio is the solution polymerized butadiene styrene rubber of 80:20 and the mixture of polyisoprene rubber.The present invention adopts solid rubber to replace latex, can reduce the carbon black modified interference of nonrubber hydrocarbon impurity dialogue in latex and impact, improve product reinforcing and dispersing property.
In above-mentioned preparation method, described solvent is industrial naptha, C
5~ C
9aliphatic hydrocarbon, turps, C
2-C
5at least one in straight-chain fatty alcohol, wherein C
5~ C
9aliphatic hydrocarbon comprises hexanaphthene, normal heptane etc., C
2-C
5straight-chain fatty alcohol comprises ethanol, Virahol and butanols etc.This solvent low toxicity, security are high, improve operating environment.
Preferably, solvent is the turps of mass ratio 60:40 and the mixture of industrial naptha.
In above-mentioned preparation method, described dispersion agent plays dispersion and activation, is at least one in the composite dispersing agent of polyoxyethylene glycol, trolamine, soap class dispersion agent, fatty acid ester dispersion agent, fatty alcohol, fatty acid soaps class and fatty acid ester, fatty acid soaps class and fatty acid acyl amine composite dispersing agent, fatty acid acyl amine dispersion agent, fatty acid dispersion agent, aromatic oil dispersion agent, aliphatic hydrocarbon oils dispersion agent, aliphatic polyol alcohols dispersion agent, aliph polyols ethers dispersion agent, aliphatic group sodium sulfate, aliphatic group benzene sulfonic acid sodium salt and sodium alkyl naphthalene sulfonate.Wherein, all kinds of dispersion agent has different models, and all kinds of dispersing agent performance is similar.In a preferred embodiment of the invention, dispersion agent is preferably mass ratio is the soap class dispersion agent of 5:3 and the mixture of polyoxyethylene glycol.
Can obtain white carbon black master batch according to the method described above, gained white carbon black Masterbatch Dispersion of the present invention is good, and not easily reunite, reinforcing property is good, also within protection scope of the present invention.
Present invention also offers the application of above-mentioned white carbon black master batch as rubber white carbon black high abrasion supporting material.White carbon black master batch of the present invention can be used alone, and provides sizing material and white carbon black simultaneously; Also can use with other natural rubber, synthetic rubber and their carbonblack master batch.
White carbon black is first mixed pre-modification with atomised form to coupling agent by the present invention, then join under whipped state in the homodisperse system of rubber-solvent, be uniformly mixed, then distill desolvation and obtain dry material, again dry material and dispersion agent are fully mixed the twice dispersing realizing white carbon black in mixing roll, last compressing tablet or granulation, obtain white carbon black master batch.This concise in technology, environmental protection, easily realize large-scale industrial produce.
Products obtained therefrom of the present invention can as rubber industry high abrasion supporting material, have the following advantages: the silicon-dioxide of modification is placed in the rubber-solvent dispersion system of few nonrubber hydrocarbon interference by the method to be disperseed, silicon-dioxide is not easy to reunite again, dispersion agent add the mobility that can increase improved silica and rubber stock, improve mixing efficiency and curability, the dispersing uniformity of silicon dioxide granule and degree of uniformity are got a promotion further.White carbon black master batch of the present invention adds to after in tire tread glue, the viscosity rebound phenomena of sizing material can no longer occur, and can further improve wear resistance and the wet-sliding resistant performance of glue, reduce rolling resistance, make wear resistance, anti-slippery and lowly roll resistance " Magic triangle " and obtain reasonable balance.In addition, the rubber item sizing material that application this law mixes particularly tire tread compound physical strength and wear resisting property significantly promotes, and heat generation and hysteresis loss obviously reduce.
Accompanying drawing explanation
Fig. 1 the inventive method process flow sheet.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed, it is to be understood that following explanation is only exemplary, its content is not limited.If no special instructions, in following embodiment, each raw material dosage is weight part.
In following embodiment, various raw material used all can have been bought from market.
embodiment 1
High abrasion supporting material---the formula of white carbon black master batch is as follows: silicon-dioxide 50 parts, coupling agent 5 parts, rubber 100 parts, solvent 1000 parts, dispersion agent 4 parts, and described silicon-dioxide is specific surface area is 161m
2/ g ~ 210m
2the ordinary precipitation process silicon-dioxide (such as NEWSIL 115 etc.) of/g, described coupling agent is silane coupling agent (the such as Si69 of mass ratio 4:1, Si75 etc.) and titanate coupling agent (such as KR-TTS, TC-TTS, KR-38 etc.) mixture, described rubber is solution polymerized butadiene styrene rubber (the such as SSBR4525 of mass ratio 70:30, SSBRT2000R, SSBR1205 etc.) and cis-1,4-polybutadiene rubber (such as BR9000, BR9002, BR-9004A, BR-9004B, BR-550, BR-1207) mixture, described solvent is the turps of mass ratio 60:40 and the mixture of industrial naptha, described dispersion agent is soap class dispersion agent (the such as H60EF of mass ratio 5:3, HST, HPP etc.) and polyoxyethylene glycol (such as PEG2000, PEG4000, PEG6000 etc.) mixture.
Preparation method is:
, silicon-dioxide mixing, modification: silicon-dioxide is joined in the mixing machine heated with plough coulter type mechanical stirring and chuck, or add with chuck heating high-speed mixer in, join in silicon-dioxide by coupling agent in the mode of atomization while stirring, coupling agent at the uniform velocity adds, and the joining day is 1h, add rear continuation and stir 10min, obtain the silicon-dioxide of modification, whole process control temp is 110-120 DEG C, and control stirring velocity is 1500rpm.
, rubber-solvent dispersion system preparation: joined by rubber in the still with condensation reflux device and whipping appts, then add solvent, control temperature 60 DEG C stirs 5 hours, to rubber solution, obtains rubber-solvent homogeneous system.
, high abrasion supporting material preparation: will
the improved silica obtained slowly joins continuously under whipped state
rubber-solvent homogeneous system in, be uniformly mixed, after mixing, obtain dry material at 100 DEG C of desolvations, recovered solvent reuses, then dry material and dispersion agent are fully mixed in mixing roll, last compressing tablet or granulation, high abrasion supporting material can be obtained.
embodiment 2
High abrasion supporting material---the formula of white carbon black master batch: with embodiment 1.
Preparation method is as follows:
, silicon-dioxide mixing, modification: silicon-dioxide is joined in the mixing machine heated with plough coulter type mechanical stirring and chuck, or add with chuck heating high-speed mixer in, join in silicon-dioxide by coupling agent in the mode of atomization while stirring, coupling agent at the uniform velocity adds, and the joining day is 10min, add rear continuation and stir 30min, obtain the silicon-dioxide of modification, whole process control temp is 110-120 DEG C, and control stirring velocity is 2000rpm.
, rubber-solvent dispersion system preparation: with embodiment 1.
, high abrasion supporting material preparation: with embodiment 1.
embodiment 3
High abrasion supporting material---the formula of white carbon black master batch: with embodiment 1.
Preparation method is as follows:
, silicon-dioxide mixing, modification: silicon-dioxide is joined in the mixing machine heated with plough coulter type mechanical stirring and chuck, or add with chuck heating high-speed mixer in, join in silicon-dioxide by coupling agent in the mode of atomization while stirring, coupling agent at the uniform velocity adds, and the joining day is 1.5h, add rear continuation and stir 5min, obtain the silicon-dioxide of modification, whole process control temp is 110-120 DEG C, and control stirring velocity is 1000rpm.
, rubber-solvent dispersion system preparation: with embodiment 1.
, high abrasion supporting material preparation: with embodiment 1.
embodiment 4
High abrasion supporting material---the formula of white carbon black master batch: with embodiment 1.
Preparation method is as follows:
, silicon-dioxide mixing, modification: silicon-dioxide is joined in the mixing machine heated with plough coulter type mechanical stirring and chuck, or add with chuck heating high-speed mixer in, join in silicon-dioxide by coupling agent in the mode of atomization while stirring, coupling agent at the uniform velocity adds, and the joining day is 0.5h, add rear continuation and stir 15min, obtain the silicon-dioxide of modification, whole process control temp is 150 DEG C, and control stirring velocity is 1200rpm.
, rubber-solvent dispersion system preparation: joined by rubber in the still with condensation reflux device and whipping appts, then add solvent, control temperature 50 DEG C stirs 8 hours, to rubber solution, obtains rubber-solvent homogeneous system.
, high abrasion supporting material preparation: will
the improved silica obtained slowly joins continuously under whipped state
rubber-solvent homogeneous system in, be uniformly mixed, after mixing, obtain dry material at 120 DEG C of desolvations, recycling design reuses, then dry material and dispersion agent are fully mixed in mixing roll, last compressing tablet or granulation, high abrasion supporting material can be obtained.
embodiment 5
High abrasion supporting material---the formula of white carbon black master batch: with embodiment 1.
Preparation method is as follows:
, silicon-dioxide mixing, modification: silicon-dioxide is joined in the mixing machine heated with plough coulter type mechanical stirring and chuck, or add with chuck heating high-speed mixer in, join in silicon-dioxide by coupling agent in the mode of atomization while stirring, coupling agent at the uniform velocity adds, and the joining day is 1.5h, add rear continuation and stir 1min, obtain the silicon-dioxide of modification, whole process control temp is 100 DEG C, and control stirring velocity is 1800rpm.
, rubber-solvent dispersion system preparation: joined by rubber in the still with condensation reflux device and whipping appts, then add solvent, control temperature 80 DEG C stirs 3 hours, to rubber solution, obtains rubber-solvent homogeneous system.
, high abrasion supporting material preparation: will
the improved silica obtained slowly joins continuously under whipped state
rubber-solvent homogeneous system in, be uniformly mixed, after mixing, obtain dry material at 100 DEG C of desolvations, recycling design reuses, then dry material and dispersion agent are fully mixed in mixing roll, last compressing tablet or granulation, high abrasion supporting material can be obtained.
embodiment 6
High abrasion supporting material---the formula of white carbon black master batch is as follows: silicon-dioxide 60 parts, coupling agent 5 parts, rubber 100 parts, solvent 1000 parts, dispersion agent 4 parts, and described silicon-dioxide is specific surface area is 161m
2/ g ~ 210m
2the ordinary precipitation process silicon-dioxide (such as NEWSIL 115 etc.) of/g, described coupling agent is silane coupling agent (the such as Si69 of mass ratio 5:1, Si75 etc.) and the mixture of bimetal coupling agent (such as TPM etc.), described rubber is solution polymerized butadiene styrene rubber (the such as SSBR4525 of mass ratio 70:30, SSBRT2000R, SSBR1205 etc.) and cis-1,4-polybutadiene rubber (such as BR9000, BR9002, BR-9004A, BR-9004B, BR-550, BR-1207) mixture, described solvent is the turps of mass ratio 60:40 and the mixture of industrial naptha, described dispersion agent is soap class dispersion agent (the such as H60EF of mass ratio 5:3, HST, HPP etc.) and polyoxyethylene glycol (such as PEG2000, PEG4000, PEG6000 etc.) mixture.
Preparation method is with embodiment 1.
embodiment 7
High abrasion supporting material---the formula of white carbon black master batch is as follows: silica 1 00 part, coupling agent 10 parts, rubber 100 parts, solvent 1500 parts, dispersion agent 10 parts, and described silicon-dioxide is specific surface area is 161m
2/ g ~ 210m
2the ordinary precipitation process silicon-dioxide (such as NEWSIL 115 etc.) of/g, described coupling agent is silane coupling agent Si69 and titanate coupling agent (the such as KR-TTS of mass ratio 4:1, TC-TTS, KR-38 etc.) mixture, described rubber is solution polymerized butadiene styrene rubber (the such as SSBR4525 of mass ratio 70:30, SSBRT2000R, SSBR1205 etc.) and cis-1,4-polybutadiene rubber (such as BR9000, BR9002, BR-9004A, BR-9004B, BR-550, BR-1207) mixture, described solvent is the turps of mass ratio 60:40 and the mixture of industrial naptha, described dispersion agent is (the such as H60EF of mass ratio 5:3, HST, HPP etc.) and polyoxyethylene glycol (such as PEG2000, PEG4000, PEG6000 etc.) mixture.
Preparation method is with embodiment 1.
embodiment 8
High abrasion supporting material---the formula of white carbon black master batch is as follows: silica 1 00 part, coupling agent 10 parts, rubber 100 parts, solvent 1500 parts, dispersion agent 10 parts, described silicon-dioxide is high dispersive silicon-dioxide (such as NEWSIL HD165GR), described coupling agent is titanate coupling agent (the such as KR-TTS of mass ratio 3:1, TC-TTS, KR-38 etc.) and the mixture of bimetal coupling agent (such as TPM etc.), described rubber is caoutchouc standard glue (such as SCR5# etc.), described solvent is hexanaphthene, described dispersion agent is fatty acid soaps class (such as H60EF, HST, HPP etc.) and fatty acid acyl amine composite dispersing agent (such as HT16, WB16 etc.).
Preparation method is with embodiment 1.
embodiment 9
High abrasion supporting material---the formula of white carbon black master batch is as follows: silicon-dioxide 20 parts, coupling agent 2 parts, rubber 80 parts, solvent 1000 parts, dispersion agent 5 parts, described silicon-dioxide is nano silicon, described coupling agent is aluminate coupling agent (such as SG-Al821, DL-411D, DL-411DF etc.), described rubber is the smoke sheet rubber (such as No. RSS1 of mass ratio 1:1, RSS2#, RSS3# etc.) and the mixture of white crepe (such as one-level is white), described solvent is Virahol, described dispersion agent is the trolamine of mass ratio 1:1:1, aromatic oil dispersion agent (such as TDAE, RAE etc.) and the mixture of aliphatic group benzene sulfonic acid sodium salt (such as Sodium dodecylbenzene sulfonate etc.).
Preparation method is with embodiment 1.
embodiment 10
High abrasion supporting material---the formula of white carbon black master batch is as follows: silicon-dioxide 50 parts, coupling agent 5 parts, rubber 100 parts, solvent 1000 parts, dispersion agent 5 parts, described silicon-dioxide is ordinary precipitation process silicon-dioxide, described coupling agent is the xylogen of mass ratio 1:1 and the mixture of tin coupling agent, described rubber is ethylene-propylene rubber(EPR) (such as Ethylene Propylene Terpolymer 4770R, 4725 etc.), described solvent is normal heptane, and described dispersion agent is the aliph polyols ethers dispersion agent of mass ratio 2:3 and the mixture of sodium alkyl naphthalene sulfonate (such as Sodium dodecylbenzene sulfonate etc.).
Preparation method is with embodiment 1.
comparative example 1
High abrasion supporting material---the formula of white carbon black master batch: with embodiment 7.
Method with reference to patent CN201410715546.5 is prepared, and step is as follows:
1, rubber is dropped in solvent, at 60 DEG C, with the rotating speed of 200rpm, be stirred to rubber solution, obtain rubber-solvent dispersion system;
2, silicon-dioxide, coupling agent and dispersion agent are added successively in above-mentioned rubber-solvent dispersion system under the rotating speed of 200rpm stirs, be uniformly mixed, obtain mixture;
3, mixture is warming up to 100 DEG C ± 2 DEG C, volatilizes solvent fast, obtain dry material in 2h, recycling design reuses;
4, dry material is carried out granulation, to obtain final product.
comparative example 2
The formula of white carbon black master batch: silicon-dioxide 500g, coupling agent 50g, rubber 1000g, solvent 10kg, dispersion agent 40g, described silicon-dioxide is specific surface area is 161m
2/ g ~ 210m
2the ordinary precipitation process silicon-dioxide (such as NEWSIL 115) of/g, described coupling agent is the silane coupling agent (such as Si69 or Si75) of mass ratio 4:1 and the mixture of titanate coupling agent (such as KR-TTS), described rubber is the solution polymerized butadiene styrene rubber (such as SSBR4525) of mass ratio 70:30 and the mixture of cis-1,4-polybutadiene rubber (such as BR9000), described solvent is the turps of mass ratio 60:40 and the mixture of industrial naptha, and described dispersion agent is the soap class dispersion agent (such as H60EF) of mass ratio 5:3 and the mixture of polyoxyethylene glycol (such as PEG2000).
Preparation process is as follows:
1, white carbon black water slurry preparation: add coupling agent in 3.6L deionized water.Take precipitated silica, join in solution by the white carbon black weighed up, turbid solution is at the uniform velocity stirred to make it in turbid solution each component disperses even, stir speed (S.S.) should be 1000rpm, and churning time is obtain white carbon black water slurry in 2 hours.
2, the mixture (by rubber dry glue convert as 1000g) of white carbon black water slurry with styrene-butadiene latex and cis-1,4-polybutadiene rubber latex is mixed, under the stirring velocity of 1000rpm, stir and obtain mixed solution in 2 hours.
3, disperse the mixed solution ultrasonic wave that step 2 obtains, ultrasonic time is 30min, carries out 6 times altogether, after each ultrasonic disperse, stirs 10min under mixed solution being placed in the stirring velocity of 300rpm, makes mixture system temperature be down to room temperature.Mixed solution is joined under stirring, mass concentration is flocculate in the calcium chloride solution of 1%, stirring velocity is 300rpm, until after no longer including new throw out generation in mixing solutions, after the micelle trickle washing of the white carbon black/rubber obtained that flocculates, drying 24 hours in 50 DEG C of baking ovens, dry solid materials is white carbon black master batch.
application examples
In order to verify that above-described embodiment and comparative example gained white carbon black master batch are as the reinforcement of high abrasion supporting material and abrasion resistant effect, carry out following experiment:
Respectively using each embodiment and comparative example products obtained therefrom as high abrasion supporting material, according to high abrasion supporting material 100 parts ,-805 parts, zinc oxide, stearic acid 1.5 parts, vulkacit D PG-802 part, accelerator NS 1 part, Sulfur-802 parts, antioxidant 4020 1 part, the formula that anti-aging agent RD is 1 part carries out feeding, then each material carried out banburying according to GB/T6038-2006, open refining and sulfuration, obtain testing sizing material, verified the advantage of each high abrasion supporting material by the related performance indicators testing each experiment sizing material.
The performance test results of each experiment sizing material sees the following form 1.
Table 1
Note: tensile strength, stress at definite elongation, elongation at break are tested by GB/T528-2009, DIN abrasion are tested by GB/T9867-2008.
As can be seen from the performance test results of above-mentioned each experiment sizing material, the white carbon black master batch adopting formula of the present invention and method to prepare has very strong reinforcement and wear resisting property.
Claims (10)
1. a preparation method for white carbon black master batch, is characterized in that comprising the following steps:
(1) modification of silicon-dioxide: coupling agent is added in the silicon-dioxide of stirring in the mode of atomization, continues after adding to stir, obtain the silicon-dioxide of modification;
(2) preparation of rubber-solvent homogeneous system: by rubber and solvent, heated and stirred is dissolved completely to rubber, obtains rubber-solvent homogeneous system;
(3) preparation of white carbon black master batch: the silicon-dioxide of modification is under agitation slowly joined in rubber-solvent homogeneous system continuously, be uniformly mixed, then heat up desolvation, obtain dry material, in gained dry material, add dispersion agent fully mix, through compressing tablet or granulation, obtain white carbon black master batch.
2. preparation method according to claim 1, is characterized in that: in step (1), and described coupling agent average rate joins in the silicon-dioxide of stirring, and the joining day of coupling agent is 10min-1.5h, preferred 1h.
3. preparation method according to claim 1, is characterized in that: in step (1), after coupling agent adds, and continues to stir 0-30min, preferred 10min.
4. preparation method according to claim 1, is characterized in that: in step (1) coupling agent add and the temperature of the whole process of modification is 100 DEG C-150 DEG C, preferably 110 DEG C-120 DEG C.
5. the preparation method according to claim 1,2 or 3, is characterized in that: in step (1), and in whole silica modified process, maintenance stirring velocity is 1000-2000rpm, and preferred stirring velocity is 1500rpm.
6. preparation method according to claim 1, is characterized in that: in step (2), and rubber and solvent mix at 50-80 DEG C, and mixing time is 1-10 hour.
7. preparation method according to claim 1, is characterized in that: in step (3), desolvation at 80 ~ 120 DEG C.
8. the preparation method according to any one of claim 1-7, is characterized in that: each raw material dosage is as follows by weight: silica 1 ~ 100 part, coupling agent 1 ~ 10 part, rubber 1 ~ 100 part, solvent 500 ~ 1500 parts, dispersion agent 1 ~ 10 part; Preferably, each raw material dosage is as follows by weight: silicon-dioxide 50-60 part, coupling agent 5 parts, rubber 100 parts, solvent 1000 parts, dispersion agent 10 parts.
9. the preparation method according to any one of claim 1-8, is characterized in that:
Described silicon-dioxide is any one in ordinary precipitation process silicon-dioxide, nano silicon and high dispersive silicon-dioxide, and being preferably specific surface area is 161m
2/ g ~ 210m
2the ordinary precipitation process silicon-dioxide of/g;
Described coupling agent is at least one in silane coupling agent, titanate coupling agent, aluminate coupling agent, bimetal coupling agent, xylogen coupling agent and tin coupling agent, is preferably the silane coupling agent Si69 of mass ratio 4:1 and the silane coupling agent Si75 of the mixture of titanate coupling agent or mass ratio 5:1 and the mixture of bimetal coupling agent;
Described rubber is at least one in caoutchouc standard glue, smoke sheet rubber, rubber crepe sheet, solution polymerized butadiene styrene rubber, emulsion polymerized styrene butadiene rubber, cis-1,4-polybutadiene rubber, chloroprene rubber, polyisoprene rubber, epoxy natural rubber and ethylene-propylene rubber(EPR), being preferably mass ratio is the solution polymerized butadiene styrene rubber of 70:30 and the mixture of cis-1,4-polybutadiene rubber, or mass ratio is the solution polymerized butadiene styrene rubber of 80:20 and the mixture of polyisoprene rubber;
Described solvent is industrial naptha, C
5~ C
9aliphatic hydrocarbon, turps, C
2-C
5at least one in straight-chain fatty alcohol, is preferably the turps of mass ratio 60:40 and the mixture of industrial naptha;
Described dispersion agent is polyoxyethylene glycol, trolamine, soap class dispersion agent, fatty acid ester dispersion agent, fatty alcohol, the composite dispersing agent of fatty acid soaps class and fatty acid ester, fatty acid soaps class and fatty acid acyl amine composite dispersing agent, fatty acid acyl amine dispersion agent, fatty acid dispersion agent, aromatic oil dispersion agent, aliphatic hydrocarbon oils dispersion agent, aliphatic polyol alcohols dispersion agent, aliph polyols ethers dispersion agent, aliphatic group sodium sulfate, at least one in aliphatic group benzene sulfonic acid sodium salt and sodium alkyl naphthalene sulfonate, being preferably mass ratio is the soap class dispersion agent of 5:3 and the mixture of polyoxyethylene glycol.
10. according to the white carbon black master batch that the preparation method of the white carbon black master batch according to any one of claim 1-9 obtains, and this white carbon black master batch is as the application of rubber white carbon black high abrasion supporting material.
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| US12024615B2 (en) | 2019-06-10 | 2024-07-02 | Eneos Corporation | Silane coupling agent composition comprising silane compound and protein modifying agent, and rubber composition comprising the same |
| CN113924334B (en) * | 2019-06-10 | 2024-08-16 | 引能仕株式会社 | Silane coupling agent composition comprising a silane compound and a protein denaturant, and rubber composition comprising the silane coupling agent composition |
| CN115720584A (en) * | 2020-06-18 | 2023-02-28 | 引能仕株式会社 | Silane coupling agent composition and rubber composition containing same |
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