CN105273252A - Method for preparing tread rubber from carbon black dry method masterbatch/white carbon black wet method masterbatch and application - Google Patents
Method for preparing tread rubber from carbon black dry method masterbatch/white carbon black wet method masterbatch and application Download PDFInfo
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- CN105273252A CN105273252A CN201510777522.7A CN201510777522A CN105273252A CN 105273252 A CN105273252 A CN 105273252A CN 201510777522 A CN201510777522 A CN 201510777522A CN 105273252 A CN105273252 A CN 105273252A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
The invention relates to a method for preparing tread rubber from carbon black dry method masterbatch/white carbon black wet method masterbatch. The method includes the following steps that a, carbon black dry method masterbatch, white carbon black wet method masterbatch and additives including one or more of a coupling agent, antiager, an activating agent, oil and other processing auxiliaries are added into an internal mixer, and then vulcanizer and accelerant are added and evenly mixed to obtain a tread rubber compound; b, the rubber compound is vulcanized to obtain the vulcanized tread rubber. As white carbon black is combined into the vulcanized tread rubber, on the premise of guaranteeing the wear resistance, the rolling resistance of a tire is reduced, and the wet skid resistance of the tire is improved.
Description
Technical field
The present invention relates to Tire rubber material production field, particularly relate to a kind of preparation method and application of tread rubber sizing material.
Background technology
Take carbon black as the tread rubber of filler, wear resisting property is good, but hysteresis loss is high, and rolling resistance is large, and white carbon black significantly can reduce rolling resistance, improves wet-sliding resistant performance simultaneously, but wear resisting property is poorer than carbon black.So, in tire industry, often utilize carbon black/white carbon black and be used for balancing various performance, to manufacturing the tire of excellent combination property.Especially be today that people pay close attention to day by day at the energy-conservation and safe of tire, this and mode have important value.
In recent years, wet method mixing technology due to its fillers dispersed degree high, equipment investment is few, environmental protection, and the advantage of less energy-consumption is subject to extensive concern both domestic and external.Initial wet method is mixing to be realized by coprecipitation method, fillers dispersed is mixed with rubber latex in water, after adding flocculation agent precipitation, dehydration, drying, obtains rubber master batch, the mixing patent CN102153792A of domestic wet method, CN102516418A, CN102634083A) still continue to use this method; PKU Pulverkautschuk Union GmbH of Germany prepares Powdered rubber master batch: after latex and filler precipitate, then adds partial filler dispersion rubber master batch, prevents adhesion (CN101182376A); Cabot Co., Ltd of the U.S. utilizes rubber latex/filler liquid phase continuous mixing to prepare rubber master batch (US19970823411); EVE Rubber Institute Co., Ltd. utilizes rubber solutions/filler liquid phase continuous mixing to prepare rubber master batch (CN103203810A).But these wet method mixing technologies only concentrate on the preparation of single filler rubber master batch.CN102807689A utilizes the mixing white carbon black rubber master batch of wet method and improves the performance of mine tire tread glue with carbon black, but utilize the mixing white carbon black rubber master batch of wet method and carbon black dry method rubber master batch and patent and document do not have report.
Summary of the invention
The present invention by also improving the performance of carbon black dry method rubber master batch with white carbon black wet method rubber master batch, and is applied to tire tread glue, under the prerequisite ensureing wear resisting property, reduces tire drag, improves tire wet-sliding resistant performance.
A kind of rubber combination, is characterized in that: adopt carbon black dry method rubber master batch and obtain with the preparation of white carbon black wet method rubber master batch.
As preferably: wet method rubber master batch is obtained by least one of the preparation method of latex/filler coprecipitation method, powdered rubber, latex/mixing method of filler Continuous Liquid Phase, rubber solutions/mixing method of filler Continuous Liquid Phase.
As preferably: dry method rubber master batch adopts at least one equipment in mill, Banbury mixer, milling machine, continuous mixer or screw rubber mixing machine to obtain.
As preferably: prepare that the rubber that rubber master batch uses is natural rubber, one or more in polybutadiene rubber, polyisoprene rubber, styrene-butadiene rubber, second third glue, butyl rubber, butadiene-acrylonitrile rubber, neoprene latex, silicon rubber, viton, urethanes, chlorosulfonated polyethylene rubber, acrylic elastomer.
As preferably: the total consumption of rubber is 100 weight parts, and total consumption of filler is 20 ~ 120 weight parts, preferably 30 ~ 70 weight parts, and wherein carbon black and white carbon black weight ratio are 1: 20 to 20: 1, preferably 1: 10 to 10: 1.
As preferably: the specific surface area of carbon black is 4 to 350m
2/ g, preferably 30 to 260m
2/ g, the oil-absorption(number) of-carbon black is 20 to 250ml/100g, preferably 25 to 200ml/100g, more preferably 30 to 150ml/100g.
As preferably: white carbon black specific surface area is 10 to 500m
2/ g, preferably 45 to 400m
2/ g, more preferably 70 to 300m
2/ g, oil-absorption(number) is 20 to 350ml/100g, preferably 25 to 300ml/100g, more preferably 30 to 290ml/100g, and white carbon black directly adds or adopts that coupling agent is modified in advance to add.
As preferably: also comprise the two-phase carbon black that consumption is 1-50 part in rubber combination.
As preferably: also comprise one or more of coupling agent, anti-aging agent, promoting agent, oil and other processing aids in rubber combination.
As preferably:
Organo silane coupling agent with following general formula represents:
(R
n-(RO)
3-nSi-(Alk)
m-(Ar)
p)
q(A)(I)
R
n’(RO)
3-nSi-(Alk)(II)
R
n’(RO)
3-nSi-(Alk
enyl)(III)
Or R
n' (RO)
3-nsi-(Alk)-S-(C=O) R
1(IV)
In formula, as q=1, A is-SCN ,-SH ,-Cl ,-NH
2;
As q=2, A is-S
x-;
The alkyl that R and R ' is the branching of carbon atom from 1 to 15 or straight chain or phenolic group, R with R ' can be identical, also can be different;
N is 0,1 or 2;
Alk is the straight or branched alkyl containing 1 to 6 carbon atom;
Alk
enyl is the straight or branched thiazolinyl containing 1 to 6 carbon atom;
R
1it is the straight or branched alkyl containing 1 to 30 carbon atom;
M is 0 or 1;
Ar is the aryl containing 6 to 12 carbon atoms;
P be 0 or 1, p and m can not be 0 simultaneously;
X is 2 to 8;
Wherein the most frequently used is two (triethoxy propyl silane) tetrasulfide and disulphide, 3-thiocyanogen propyl-triethoxysilane, γ-mercapto propyl-trimethoxysilane, 3-Octanoylthio-1-propyl-triethoxysilicane, [2-(4-chloromethyl phenyl) ethyl]-triethoxyl silane, (3-mercaptopropyi)-two [trideceth (5) base]-Ethoxysilane, zirconium ester coupling agent, titanate coupling agent, nitro coupling agent, alcohol compound, described alcohol compound comprises unit alcohol, dibasic alcohol, polyvalent alcohol, described alcohol compound comprises propyl alcohol, butanols, ethylene glycol, polyoxyethylene glycol and derivative thereof, the total consumption of coupling agent is 1% to 20% of white carbon black consumption, preferably 5% to 15%.
As preferably: anti-aging agent be selected from amines antioxidants, phenolic type antioxidant and protection wax one or more, total consumption of anti-aging agent is 0.2 to 11 weight part, preferably 1 to 9 weight part.
As preferably: promoting agent comprises zinc oxide and stearic acid, and total consumption of promoting agent is 0.5 to 10 weight part, preferably 1 to 8 weight part.
As preferably: oil comprises the rubber processing operations oil of the aromatic hydrocarbon oil of petroleum, naphthenic oil and other types, and total consumption of oil is 0 to 30 weight part, preferably 0 to 20 weight part, more preferably 0 to 15 weight part.
As preferably: vulcanizing agent comprise in Sulfur, sulfur donor and superoxide one or more, the consumption of vulcanizing agent is 0.2 to 5 weight part, preferably 0.5 to 3 weight part.
As preferably: promotor comprise in thiazoles, sulfenamide, thiurams, thiocarbamates class, hexichol guanidine acclerators, vulkacit H one or more, the consumption of promotor is 0.2 to 5 weight part, preferably 0.5 to 3 weight part.
The present invention also provides and utilizes carbon black dry method rubber master batch and the method preparing cross-linked rubber with white carbon black wet method rubber master batch, comprises following steps:
In Banbury mixer, add carbon black dry method rubber master batch, white carbon black wet method rubber master batch, add additive again and comprise one or more of coupling agent, anti-aging agent, promoting agent, oil and other processing aids, then add after vulcanizing agent and promotor mix and obtain tread rubber rubber unvulcanizate; By rubber unvulcanizate sulfuration, obtain tread rubber cross-linked rubber; Or one or more of coupling agent, anti-aging agent, promoting agent, oil and other processing aids add when prepared by carbon black dry method rubber master batch or white carbon black wet method rubber master batch.
The present invention also provides the tire tread glue sizing material adopting above-mentioned rubber combination to prepare.
The technology of the present invention effect:
And with after white carbon black wet method rubber master batch, carbon black dry method rubber master batch hysteresis loss significantly reduces, wear resisting property is without obvious decline simultaneously, and wet-sliding resistant performance improves.
Specific embodiments
Further describe the present invention by embodiment below, but scope of the present invention is not by the restriction of these embodiments.
(1) embodiment uses following plant and instrument and measuring method to measure:
Plant and instrument prepared by table 1 rubber sample
| Sequence number | Device name | Specifications and models | Manufacturer |
| 1 | Banbury mixer | BR1600 | Farrel Corp. (US) 25 Main Street, Ansonia, CT 06401, U.S.A. of the U.S. |
| 2 | Mill | Polymix 150L | SERVITEC company of Germany |
| 3 | Vulcanizing press | P-V-200-3RT-2-PCD | Huge rock oil pressure Industrial Co., Ltd |
The testing method of table 2 properties of rubber and instrument
(2) embodiment and comparative example
Raw material:
Isoamyl glue, IR70, Yikesi New-material Co., Ltd., Qingdao;
White carbon black, NewsilHD165MP, Q & C Silicon Chemical Co., Ltd.;
Two-phase carbon black, CSDPF2125, Cabot (Shanghai) Investment Co., Ltd;
Carbon black, N234, Cabot (Shanghai) Investment Co., Ltd;
Zinc oxide, Dalian zinc oxide factory;
Stearic acid, PF1808, Malaysian Li Cheng company limited;
N-(1,3-dimethyl) butyl-N '-diphenyl-para-phenylene diamine (antioxidant 4020), Flexsys company;
2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer (anti-aging agent RD), Nanjing Chemical Industry Co., Ltd., SINOPEC chemical plant;
Protection wax, Paramelt Specialty Chemicals (Suzhou) Co., Ltd.;
Two (triethoxy propyl silane) tetrasulfide (TESPT), NanJing Shuguang Chemical Group Co., Ltd.;
N-cyclohexyl 2-benzothiazole sulfonamide (accelerant CZ), vulkacit D (vulkacit D PG), Shandong Sunsine Chemical Co., Ltd.;
Sulfur S, Lin Yiluo village Sulfur factory.
Comparative example 1
In Banbury mixer, add 100 parts of isoamyl glue, 50 parts of carbon black N234 mixing after obtain carbon black rubber master batch.150 parts of carbon black rubber master batch, 3 parts of stearic acid, 5 parts of zinc oxide, 1.5 parts of protection waxes, 1.5 parts of anti-aging agent RDs, 1.5 parts of antioxidant 4020s are added in Banbury mixer, mixing, after binder removal parks 4 hours, add 1.2 parts of accelerant CZs again, 1.0 parts of common Sulfurs, mixing evenly rear binder removal, parks with vulcanizing press sulfuration under 150 DEG C of conditions after 4 hours, obtained tread rubber comparative example 1.
Comparative example 2
50 parts of white carbon black 165MP, 5 parts of TESPT are joined in the hexane solution of 100 parts of isoamyl glue and mix, cohesion in continuous injection knockouts, white carbon black wet method rubber master batch is obtained after desolventizing drying afterwards, rubber master batch is added in Banbury mixer, add 3 parts of stearic acid, 5 parts of zinc oxide, 1.5 parts of protection waxes, 1.5 parts of anti-aging agent RDs, 1.5 parts of mixing rear binder removals of antioxidant 4020 again, after parking 4 hours, add 2.0 parts of accelerant CZs, 1.6 parts of common Sulfurs, mixing evenly rear binder removal, park with vulcanizing press sulfuration under 150 DEG C of conditions after 4 hours, obtained tread rubber comparative example 2.
Comparative example 3
In Banbury mixer, add 100 parts of isoamyl glue, 50 parts of CSDPF2125,2 parts of TESPT, 3 parts of stearic acid, 5 parts of zinc oxide, 1.5 parts of protection waxes, 1.5 parts of anti-aging agent RDs, 1.5 parts of antioxidant 4020s are mixing, melting temperature reaches more than 140 DEG C and keeps 2 minutes, binder removal, after parking 4 hours, adds 1.2 parts of accelerant CZs, 1.4 parts of common Sulfurs, mixing evenly rear binder removal, parks with vulcanizing press sulfuration under 150 DEG C of conditions after 4 hours, obtained tread rubber comparative example 3.
Embodiment 1
50 parts of white carbon black 165MP, 5 parts of TESPT are joined in 100 parts of isoamyl glue hexane solutions after mixing, inject cohesion in knockouts continuously, afterwards desolventizing drying obtains white carbon black wet method rubber master batch.Add in Banbury mixer 100 isoamyl glue, 50 parts of carbon black N234 mixing after obtain carbon black rubber master batch.75 parts of carbon black rubber master batch are added, 77.5 parts of white carbon black wet method rubber master batch, stearic acid 2.5 parts in Banbury mixer, 4.5 parts, zinc oxide, protection wax 1.5 parts, anti-aging agent RD 1.5 parts, antioxidant 4020 2.0 parts, mixing evenly rear binder removal, after parking 4 hours, add accelerant CZ 2.0 parts, common Sulfur 1.6 parts, vulkacit D PG0.5 part, mixing evenly rear binder removal, park with vulcanizing press sulfuration under 150 DEG C of conditions after 4 hours, obtained tread rubber embodiment 1.
Embodiment 2
50 parts of white carbon black 165MP, 5 parts of TESPT are joined in 100 parts of isoamyl glue hexane solutions after mixing, inject cohesion in knockouts continuously, afterwards desolventizing drying obtains white carbon black wet method rubber master batch.Add in Banbury mixer 100 parts of isoamyl glue, 50 parts of carbon black N234 mixing after obtain carbon black rubber master batch.30 parts of isoamyl glue are added, 15 parts of CSDPF2125,0.6 part of TESPT in Banbury mixer, 45 parts of carbon black rubber master batch, 62 parts of white carbon black wet method rubber master batch, stearic acid 3 parts, 5 parts, zinc oxide, protection wax 1.5 parts, anti-aging agent RD 1.5 parts, antioxidant 4020 1.5 parts, mixing evenly rear binder removal, after parking 4 hours, add accelerant CZ 1.5 parts, common Sulfur 1.4 parts, mixing evenly rear binder removal, park with vulcanizing press sulfuration under 150 DEG C of conditions after 4 hours, obtained tread rubber embodiment 2.
The physicals of table 3 cross-linked rubber
As seen from the above table, dry method carbon black rubber master batch with after wet method white carbon black rubber master batch, resilience raises 9 values, and temperature rise reduces by 12.4 DEG C, hysteresis loss reduces by 49%, wears away result from DIN, with white carbon black recipe ratio comparatively, wear resisting property raising 9%.
Embodiment 2 performance is three kinds of coefficient results of carbon black, its wear resisting property and carbon black close, better than the wear resisting property of wet method white carbon black cross-linked rubber (comparative example 2) and dry method two-phase carbon black compound rubber (comparative example 3), and compared with carbon black formula, hysteresis loss reduces by 40%.
Claims (17)
1. a rubber combination, is characterized in that: adopt carbon black dry method rubber master batch and obtain with the preparation of white carbon black wet method rubber master batch.
2. rubber combination according to claim 1, is characterized in that: wet method rubber master batch is obtained by least one of the preparation method of latex/filler coprecipitation method, powdered rubber, latex/mixing method of filler Continuous Liquid Phase, rubber solutions/mixing method of filler Continuous Liquid Phase.
3. rubber combination as claimed in claim 1, is characterized in that: dry method rubber master batch adopts at least one equipment in mill, Banbury mixer, milling machine, continuous mixer or screw rubber mixing machine to obtain.
4. rubber combination according to claim 1, is characterized in that: prepare that the rubber that rubber master batch uses is natural rubber, one or more in polybutadiene rubber, polyisoprene rubber, styrene-butadiene rubber, second third glue, butyl rubber, butadiene-acrylonitrile rubber, neoprene latex, silicon rubber, viton, urethanes, chlorosulfonated polyethylene rubber, acrylic elastomer.
5. rubber combination according to claim 1, it is characterized in that: the total consumption of rubber is 100 weight parts, total consumption of filler is 20 ~ 120 weight parts, preferably 30 ~ 70 weight parts, wherein carbon black and white carbon black weight ratio are 1: 20 to 20: 1, preferably 1: 10 to 10: 1.
6. rubber combination according to claim 1, is characterized in that: the specific surface area of carbon black is 4 to 350m
2/ g, preferably 30 to 260m
2/ g, the oil-absorption(number) of carbon black is 20 to 250ml/100g, preferably 25 to 200ml/100g, more preferably 30 to 150ml/100g.
7. rubber combination as claimed in claim 1, is characterized in that: the specific surface area of described white carbon black is 10 to 500m
2/ g, preferably 45 to 400m
2/ g, more preferably 70 to 300m
2/ g, the oil-absorption(number) of described white carbon black is 20 to 350ml/100g, preferably 25 to 300ml/100g, more preferably 30 to 290ml/100g, white carbon black directly add or adopt coupling agent modified after add.
8. rubber combination as claimed in claim 1, is characterized in that: also comprise the two-phase carbon black that consumption is 1-50 part in rubber combination.
9. rubber combination as claimed in claim 1, is characterized in that: also comprise one or more of coupling agent, anti-aging agent, promoting agent, oil and other processing aids in rubber combination.
10. rubber combination according to claim 9, it is characterized in that: coupling agent comprises two (triethoxy propyl silane) tetrasulfide and disulphide, 3-thiocyanogen propyl-triethoxysilane, γ-mercapto propyl-trimethoxysilane, 3-Octanoylthio-1-propyl-triethoxysilicane, [2-(4-chloromethyl phenyl) ethyl]-triethoxyl silane, (3-mercaptopropyi)-two [trideceth (5) base]-Ethoxysilane, zirconium ester coupling agent, titanate coupling agent, nitro coupling agent, alcohol compound, described alcohol compound comprises unit alcohol, dibasic alcohol, polyvalent alcohol, described alcohol compound comprises propyl alcohol, butanols, ethylene glycol, polyoxyethylene glycol and derivative thereof, the total consumption of coupling agent is 1% to 20% of white carbon black consumption, preferably 5% to 15%.
11. rubber combinations according to claim 9, is characterized in that: anti-aging agent be selected from amines antioxidants, phenolic type antioxidant and protection wax one or more, total consumption of anti-aging agent is 0.2 to 11 weight part, preferably 1 to 9 weight part.
12. rubber combinations according to claim 9, is characterized in that: promoting agent comprises zinc oxide and stearic acid, and total consumption of promoting agent is 0.5 to 10 weight part, preferably 1 to 8 weight part.
13. rubber combinations according to claim 9, it is characterized in that: oil comprises the rubber processing operations oil of the aromatic hydrocarbon oil of petroleum, naphthenic oil and other types, total consumption of oil is 0 to 30 weight part, preferably 0 to 20 weight part, more preferably 0 to 15 weight part.
14. rubber combinations according to claim 9, is characterized in that: vulcanizing agent comprise in Sulfur, sulfur donor and superoxide one or more, the consumption of vulcanizing agent is 0.2 to 5 weight part, preferably 0.5 to 3 weight part.
15. rubber combinations according to claim 9, it is characterized in that: promotor comprise in thiazoles, sulfenamide, thiurams, thiocarbamates class, hexichol guanidine acclerators, vulkacit H one or more, the consumption of promotor is 0.2 to 5 weight part, preferably 0.5 to 3 weight part.
16. utilize carbon black dry method rubber master batch and prepare the method for cross-linked rubber with white carbon black wet method rubber master batch, comprise following steps:
In Banbury mixer, add carbon black dry method rubber master batch, white carbon black wet method rubber master batch, add additive again and comprise one or more of coupling agent, anti-aging agent, promoting agent, oil and other processing aids, then add after vulcanizing agent and promotor mix and obtain tread rubber rubber unvulcanizate; By rubber unvulcanizate sulfuration, obtain tread rubber cross-linked rubber; Or one or more of coupling agent, anti-aging agent, promoting agent, oil and other processing aids add when prepared by carbon black dry method rubber master batch or white carbon black wet method rubber master batch.
Tire tread glue sizing material prepared by the rubber combination as described in 17. employings are as arbitrary in claim 1-15.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510777522.7A CN105273252A (en) | 2015-11-13 | 2015-11-13 | Method for preparing tread rubber from carbon black dry method masterbatch/white carbon black wet method masterbatch and application |
| PCT/CN2016/105482 WO2017080513A1 (en) | 2015-11-13 | 2016-11-11 | Wet mixing master batch, rubber composition prepared from filler or master batch, and preparation method |
| ZA2018/03959A ZA201803959B (en) | 2015-11-13 | 2018-06-13 | Rubber composition of wet masterbatch and fillers or masterbatches and preparation process thereof |
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|---|---|---|---|
| CN201510777522.7A CN105273252A (en) | 2015-11-13 | 2015-11-13 | Method for preparing tread rubber from carbon black dry method masterbatch/white carbon black wet method masterbatch and application |
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| CN108178852A (en) * | 2016-12-08 | 2018-06-19 | 中国石油化工股份有限公司 | Rubber composition and vulcanization rubber and its preparation method and application |
| CN114292450A (en) * | 2022-01-04 | 2022-04-08 | 中策橡胶集团股份有限公司 | Dry mixing method of tire rubber composition, tread composition and low rolling resistance high-performance tire |
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Application publication date: 20160127 |