CN105419004A - High-heat-conductive rubber composition, preparation method thereof and tyre - Google Patents
High-heat-conductive rubber composition, preparation method thereof and tyre Download PDFInfo
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- CN105419004A CN105419004A CN201510988624.3A CN201510988624A CN105419004A CN 105419004 A CN105419004 A CN 105419004A CN 201510988624 A CN201510988624 A CN 201510988624A CN 105419004 A CN105419004 A CN 105419004A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- 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
- C08K2201/003—Additives being defined by their diameter
-
- 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
- C08K2201/004—Additives being defined by their length
-
- 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
- C08K2201/006—Additives being defined by their surface area
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The application discloses a high-heat-conductive rubber composition, a preparation method thereof and a tyre. The high-heat-conductive rubber composition includes, by weight, 100 parts of rubber, 20-75 parts of carbon black, 0-25 parts of white carbon black, 0.1-10 parts of carbon nano tubes, and 0.1-10 parts of graphene. The tyre, on the basis of original processing performance and conventional physical performance maintained, is improved in heat-conductivity of total materials and is reduced in vulcanizing time, and meanwhile is improved in durability when being used for long time under high load.
Description
Technical field
The application belongs to field of material technology, particularly relates to a kind of high heat conductive rubber composition, is mainly used in tire.
Background technology
Along with the develop rapidly of economy, the quantity of automobile grows with each passing day, and tire is as composition important in automobile, and the demand of tire is also increase year by year, and a series of energy problem so caused by tire and safety problem will be subject to paying close attention to greatly and paying attention to.Tire needs to carry out sulfuration in process of production just can reach required intensity and use value, if tire sizing material has good heat conductivility, so obviously can shorten curing time in sulfidation, in use squeegee action can be produced simultaneously heat release go out thus reduce the traveling temperature of tire, ensure that the work-ing life of tire.
Carbon nanotube has the character of many uniquenesses, such as: very large length-to-diameter ratio, very high tensile strength, excellent electrical and thermal conductivity performance etc.Its excellent thermal property can give the special performance of material in hot while improving material mechanical performance, can be the heat conduction level that material reaches higher by the interpolation of carbon nanotube.
Graphene is a kind of novel material of the individual layer sheet structure be made up of carbon atom, and the thermal conductivity of Graphene, up to 5300W/mK, is a kind of thermally conductive material preferably.But single-layer graphene is difficult to obtain in actual production process, be mostly that a few layer graphene is superimposed and the graphene film obtained.
Summary of the invention
The object of the present invention is to provide a kind of high heat conductive rubber composition, its preparation method and tire, to overcome deficiency of the prior art.
For achieving the above object, the invention provides following technical scheme:
The embodiment of the present application discloses a kind of high heat conductive rubber composition, comprises according to weight part:
The rubber of 100 weight parts;
The carbon black of 20 ~ 75 weight parts;
The white carbon black of 0 ~ 25 weight part;
The carbon nanotube of 0.1 ~ 10 weight part;
The Graphene of 0.1 ~ 10 weight part.
Preferably, in above-mentioned high heat conductive rubber composition, the softening agent of 0 ~ 15phr is also comprised; The antioxidant of 2 ~ 5phr; The promotor of 0.5 ~ 5phr; The promoting agent of 1 ~ 12phr; And the sulphur of 0.5 ~ 6phr.
Preferably, in above-mentioned high heat conductive rubber composition, the length of described carbon nanotube 0.5 ~ 100 μm, diameter is 5 ~ 200nm.
Preferably, in above-mentioned high heat conductive rubber composition, the described Graphene number of plies is 1-20 layer, and specific surface area is 40 ~ 300m
2/ g.
Preferably, in above-mentioned high heat conductive rubber composition, the content of described carbon nanotube is 1 ~ 5 weight part.
Preferably, in above-mentioned high heat conductive rubber composition, the content of described Graphene is 1 ~ 7 weight part.
Preferably, in above-mentioned high heat conductive rubber composition, described rubber is polydiene.
Preferably, in above-mentioned high heat conductive rubber composition, the content of described white carbon black is 5 ~ 15 weight parts.
Preferably, in above-mentioned high heat conductive rubber composition, the content of described carbon black is 30 ~ 40 weight parts.
Accordingly, disclosed herein as well is a kind of preparation method of high heat conductive rubber composition, comprising:
(1) female refining:
Female refining is carried out in Banbury mixer, starting temperature is 20-80 DEG C, rotating speed is 30-80 rev/min, pressure is 3-8bar, order of addition(of ingredients) is: rubber is initially adding, 10-60 adds white carbon black, carbon black, carbon nanotube, Graphene, coupling agent, anti-aging agent, zinc oxide, Microcrystalline Wax, stearic acid and softening agent after second, finally the binder removal when 140-175 DEG C;
(2) refining eventually:
Eventually refining carries out in Banbury mixer, order of addition(of ingredients): at the first rubber master batch of beginning, 10-60 adds promotor and sulphur after second, binder removal after 100-400 second.
Disclosed herein as well is a kind of tire, comprise described high heat conductive rubber composition.
Compared with prior art, the invention has the advantages that: tire product of the present invention is on the basis maintaining original processing characteristics and Typical physical performance, improve the heat conductivility of integral material, shorten curing time, improve endurance quality when the long-term high loading of tire uses simultaneously.
Embodiment
The embodiment of the present application discloses a kind of high heat conductive rubber composition, comprises according to weight part:
The rubber of 100 weight parts;
The carbon black of 20 ~ 75 weight parts;
The white carbon black of 0 ~ 25 weight part;
The carbon nanotube of 0.1 ~ 10 weight part;
The Graphene of 0.1 ~ 10 weight part.
In above-mentioned high heat conductive rubber composition, rubbery system preferably uses polydiene, and wherein polydiene calculates with 100 parts by weight (phr).
Polydiene comprises natural rubber and other various synthetic rubber, wherein elastomericly can comprise cis-1,4-polybutadiene rubber (cis-1,4-polyhutadiene), polyisoprene rubber (cis-1,4-polyprene, comprise natural rubber and synthesis polyisoprene rubber), isoprene-isobutylene rubber (comprising conventional butyl rubbers, chlorinated butyl rubber, brominated butyl rubber and carboxylate butyl rubber), styrene-butadiene rubber(SBR) (butadiene/styrene copolymers comprises emulsion polymerized styrene butadiene rubber and solution polymerized butadiene styrene rubber).Preferred natural rubber.
In above-mentioned high heat conductive rubber composition, the content of carbon black is 20 ~ 75 weight parts, is preferably 20 ~ 55 weight parts, more preferably 30 ~ 40 weight parts.
In the present embodiment, carbon black includes, but are not limited to: N110, N121, N134, N220, N231, N234, N242, N293, N299, N315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N660, N683, N754, N762, N765, N770, N774, N787, N907, N908, N990, N991.It is 15-150m that these carbon blacks have specific surface area
2the absorption value of/g, DBP is 30-150cm
3the feature of/100g.
In above-mentioned high heat conductive rubber composition, the content of white carbon black is 0 ~ 25 weight part, preferably 5 ~ 11 weight parts.Preferably, white carbon black comprises gas-phase silica and precipitated silica, preferred precipitated silica.In the present embodiment, industry can not use white carbon black.
In above-mentioned high heat conductive rubber composition, the content of carbon nanotube is 0.1 ~ 10 part, preferably 1 ~ 5 part.Preferably, the purity >=95wt% of carbon nanotube.Carbon nanotube has the diameter of 5 ~ 200nm.Carbon nanotube has the length of 0.5 ~ 100 μm.Carbon nanotube is untreatment carbon nanotube or surface treated carbon nanotube, process group wherein can comprise unsaturated carbon-carbon double bond group, carboxyl and hydroxyl etc., if the process of unsaturated double-bond group, on the main chain that unsaturated double-bond can be positioned at modified group or on side chain.Carbon nanotube comprises Single Walled Carbon Nanotube and multi-walled carbon nano-tubes.
In above-mentioned high heat conductive rubber composition, Graphene content is 0.1 ~ 10 part, preferably 1 ~ 7 part.Preferably, the specific surface area of Graphene is 30 ~ 200m
2/ g, preferably 40 ~ 120m
2/ g.The number of plies of Graphene is 1 ~ 20 Rotating fields, preferably 10 ~ 15 layers.Graphene comprises untreated and surface treated Graphene.
In above-mentioned high heat conductive rubber composition, also can comprise various additive:
Rubber combination also can comprise the softening agent of 0 ~ 15 weight part.Softening agent can be added in rubber mix process, also can be contained in rubber.Described softening agent comprises various oil known in the art, comprises the various wet goods of aromatic hydrocarbon oil, naphthenic oil, paraffin oil, department of botany, and various resin known in the art, comprises the various resins etc. of carbon five, carbon nine, terpenes and department of botany.Also softening agent can not be added in the present embodiment.
Rubber combination also can comprise additive: antioxidant, and its consumption is generally 2-5 weight part, and oxidation inhibitor used in the present invention has various physics and chemistry anti-aging agent; Promoting agent 1-12 weight part.
Rubber combination also can comprise vulcanization accelerator to control time and the temperature of sulfuration, improves processing and the use properties of rubber.Preferably, two kinds of promotor, i.e. primary accelerator and secondary accelerator is used.Wherein the consumption of primary accelerator is generally 0.5-3 weight part, and the consumption of secondary accelerator is less, is generally 0.05-2 weight part.The kind that can be used for the promotor of the present embodiment has thiazoles, thiurams, sulfenamide, dithiocarbamate(s), xanthan acids, guanidine class, Thiourea etc.Preferably, primary accelerator is sulfenamide, and secondary accelerator is guanidine class.
The embodiment of the present application also discloses a kind of tire, and it comprises above-mentioned high heat conductive rubber composition.Rubber combination is applied to tyre surface, basic glue, sidewall, tire shoulder, triangle rubber, belt compound, carcass glue, transition layer glue, the air/tight layer rubber etc. of tire, is preferably applied to tyre surface.
The present invention is described further by the following example: according to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, concrete material ratio, processing condition and result thereof described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
The preparation of rubber combination:
Prepared the rubber combination with following composition by mixing method, describedly mixingly to comprise:
(1) female refining:
Female refining is carried out in X (S) M-1.6 × (0 ~ 180) type Banbury mixer, and starting temperature is 50 DEG C, and rotating speed is 70 turns/min, and pressure is 7bar.Order of addition(of ingredients) is: rubber is initially adding, and adds white carbon black, carbon black, carbon nanotube, Graphene, coupling agent, anti-aging agent, zinc oxide, Microcrystalline Wax, stearic acid and softening agent after 30s, finally the binder removal when 155C.
(2) refining eventually:
Refining carries out in X (S) M-1.6 × (0 ~ 180) type Banbury mixer eventually, order of addition(of ingredients): at the first rubber master batch of beginning, add promotor promotor and sulphur, binder removal after 180s after 20s.
Starting material and equipment:
Natural rubber (TSR20), white carbon black (NewsilHD165MP, purchased from Wuxi Que Chenggui company limited), carbon black (N234, purchased from American Cabot company limited), softening agent (environment-friendly aromatic oil TDAE, holy purchased from the German Chinese), carbon nanotube (on one's own account), Graphene (on one's own account), coupling agent is two-(γ-triethoxyl silane propyl group)-tetrasulfide, anti-aging agent N-(1, 3-dimethyl) butyl-N'-diphenyl-para-phenylene diamine, Microcrystalline Wax, zinc oxide, stearic acid, promotor vulkacit D, accelerant N-cyclohexyl-2-benzothiazole sulfonamide and sulphur are commercially available.
X (S) M-1.6 × (0 ~ 180) type Banbury mixer, height rubber and plastics machine technical equipment company limited of Qingdao section; The mill of XK-200 type, height rubber and plastics machine technical equipment company limited of Qingdao section; XLB-400 type vulcanizing press, height rubber and plastics machine technical equipment company limited of Qingdao section; MV3000 mooney viscosity instrument, German Montech; D-MDR3000 rheometer, German Montech; Z010 universal tensile testing machine, German Zwick; ShoreA hardness tester, German Zwick.
Testing standard and instrument:
(i) mooney viscosity: ASTMD1646-2007; Adopt the MV3000 mooney viscosity instrument of German Montech company;
Mooney viscosity index=embodiment mooney viscosity/comparative example mooney viscosity × 100
(ii) mooney scorch: ASTMD1646-2007; Adopt the MV3000 mooney viscosity instrument of German Montech company;
Mooney scorch time index=embodiment Mooney scorch time/comparative example Mooney scorch time × 100
(iii) Shore A hardness: ASTMD2240-2010; Adopt the Z3130 sclerometer of German Zwick company
Hardness number=embodiment hardness/comparative example hardness × 100
(iv) tensile strength index: ASTMD412-2006, sample is dumbbell shape, and test speed is 500mm/min, and test environment temperature is 23 ± 2 DEG C; Adopt German ZwickZ010 tension testing machine.
Tensile strength × 100 of the tensile strength/comparative example of tensile strength index=embodiment
(v) swelling index: rebound performance is tested according to GB/T1681-2009, probe temperature 25 DEG C.
Swelling index=embodiment resilience/comparative example resilience × 100
(vi) anti tear index: ASTMD624-2007, adopt square sample, test speed is 500mm/min, and test environment temperature is 23 ± 2 DEG C; Adopt German ZwickZ010 tension testing machine.
Tear strength × 100 of the tear strength/comparative example of anti tear index=embodiment
(vii) thermal conductivity index: adopt quasi steady state method test.Reference standard ASTME1530
Thermal conductivity × 100 of the thermal conductivity/comparative example of thermal conductivity index=embodiment
Embodiment 1
In embodiment 1, adopt natural rubber as rubbery system, add the carbon nanotube of different amounts, Graphene and filler (carbon black, the white carbon black) contribution to system heat conductivility by formula adjustment.The diameter of carbon nanotube used is 5 ~ 20nm, length 3-50 μm, specific surface area 200-300m
2/ g; Graphene specific surface area 40 ~ 100m
2/ g, purity > 97wt%, thickness < 30nm.
Table 1: the performance of embodiment 1 laboratory test.
As can be seen from upper table 1:
1) comparative example 1-1 is the formula in tire actual production process, the carbon black only having maintenance higher and white carbon black content can meet normal production and service requirements, although add the heat conductivility that relatively large carbon nanotube and Graphene also can maintain cross-linked rubber in comparative example 1-2 and comparative example 1-3, but certain impact can be brought to processing characteristics, affect normal process for processing, therefore best cooperation must be the performance that a certain amount of carbon black (or white carbon black)/carbon nano tube/graphene synergy effectively could improve cross-linked rubber.When the consumption of carbon black is greater than 20phr, adds and be less than the over-all properties that the carbon nanotube of 10phr and Graphene just effectively can improve cross-linked rubber, meet production and the service requirements of tire.
2) adding carbon nanotube and Graphene in an embodiment, to reduce the mooney viscosity of rubber unvulcanizate after carbon black and white carbon black consumption in a slight decrease simultaneously, can improve processing characteristics; Time of scorch extends simultaneously, improves processing safety.Carbon nanotube and Graphene have very high thermal conductivity, and the consumption of carbon black is more simultaneously, and can form good heat conduction network path, therefore the thermal conductivity of cross-linked rubber significantly improves.
Embodiment 2
In example 2, adopt natural rubber as rubbery system, added carbon nanotube and the Graphene of different amount by formula adjustment, keep the comparatively high filler loading capacity (consumption is 40 weight parts) of carbon black to verify that carbon nanotube and Graphene compound use are on the impact of system heat conductivility simultaneously.Specific embodiments is in table 2.
Table 2: the performance of embodiment 2 laboratory test
Can be found by table 2, after adding carbon nanotube and Graphene, mooney viscosity, time of scorch and hardness can remain unchanged substantially, tensile strength and rebound performance obviously improve simultaneously, but tear strength has reduction, found by test heat conduction data, after carbon nanotube and Graphene compound share, heat conductivility obviously improves, and can improve more than 10%.
Finally, also it should be noted that, term " comprises ", " comprising " or its any other variant are intended to contain comprising of nonexcludability, thus make to comprise the process of a series of key element, method, article or equipment and not only comprise those key elements, but also comprise other key elements clearly do not listed, or also comprise by the intrinsic key element of this process, method, article or equipment.
Claims (10)
1. a high heat conductive rubber composition, is characterized in that, comprise according to weight part:
The rubber of 100 weight parts;
The carbon black of 20 ~ 75 weight parts;
The white carbon black of 0 ~ 25 weight part;
The carbon nanotube of 0.1 ~ 10 weight part;
The Graphene of 0.1 ~ 10 weight part.
2. high heat conductive rubber composition according to claim 1, is characterized in that: the softening agent also comprising 0 ~ 15phr; The antioxidant of 2 ~ 5phr; The promotor of 0.5 ~ 5phr; The promoting agent of 1 ~ 12phr; And the sulphur of 0.5 ~ 6phr.
3. high heat conductive rubber composition according to claim 1, it is characterized in that: the length of described carbon nanotube 0.5 ~ 100 μm, diameter is 5 ~ 200nm.
4. high heat conductive rubber composition according to claim 1, it is characterized in that: the described Graphene number of plies is 1 ~ 20 layer, specific surface area is 40 ~ 300m
2/ g.
5. high heat conductive rubber composition according to claim 1, is characterized in that: the content of described carbon nanotube is 1 ~ 5 weight part.
6. high heat conductive rubber composition according to claim 1, is characterized in that: the content of described Graphene is 1 ~ 7 weight part.
7. high heat conductive rubber composition according to claim 1, is characterized in that: described rubber is polydiene.
8. high heat conductive rubber composition according to claim 1, is characterized in that: the content of described white carbon black is 5 ~ 15 weight parts, and the content of described carbon black is 30 ~ 40 weight parts.
9. the preparation method of the arbitrary described high heat conductive rubber composition of claim 1 to 8, is characterized in that, comprising:
(1) female refining:
Female refining is carried out in Banbury mixer, starting temperature is 20-80 DEG C, rotating speed is 30-80 rev/min, pressure is 3-8bar, order of addition(of ingredients) is: rubber is initially adding, 10-60 adds white carbon black, carbon black, carbon nanotube, Graphene, coupling agent, anti-aging agent, zinc oxide, Microcrystalline Wax, stearic acid and softening agent after second, finally the binder removal when 140-175 DEG C;
(2) refining eventually:
Eventually refining carries out in Banbury mixer, order of addition(of ingredients): at the first rubber master batch of beginning, 10-60 adds promotor and sulphur after second, binder removal after 100-400 second.
10. a tire, is characterized in that, comprises the arbitrary described high heat conductive rubber composition of claim 1 to 8.
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| CN105754157A (en) * | 2016-04-13 | 2016-07-13 | 上海众力汽车部件有限公司 | Automobile chassis bush rubber composition |
| CN105924705A (en) * | 2016-05-13 | 2016-09-07 | 赛轮金宇集团股份有限公司 | Highly filled white carbon black tread rubber having good electric and thermal conductivity and used for pneumatic tire |
| CN106146932A (en) * | 2016-09-27 | 2016-11-23 | 钟光 | A kind of carbon nano ring protects rubber composite and preparation method thereof |
| CN106957463A (en) * | 2017-06-03 | 2017-07-18 | 明光速耐德实心轮胎有限公司 | A kind of press-fit solid tyre tread rubber and preparation method |
| CN107043475A (en) * | 2017-04-21 | 2017-08-15 | 厦门正新橡胶工业有限公司 | Graphene pickering emulsion optimization rubber composition and preparation method thereof |
| CN108003489A (en) * | 2017-12-22 | 2018-05-08 | 恒力盛泰（厦门）石墨烯科技有限公司 | A kind of high thermal conductivity tube formula of graphene-containing |
| CN108162226A (en) * | 2017-12-25 | 2018-06-15 | 山东西水永橡胶有限公司 | A kind of preparation method of high heat conduction type tire curing bladder |
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| CN108802096A (en) * | 2018-04-16 | 2018-11-13 | 山东大学 | A kind of graphene rubber spring and its dynamic heat build up real-time monitoring device |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105754157A (en) * | 2016-04-13 | 2016-07-13 | 上海众力汽车部件有限公司 | Automobile chassis bush rubber composition |
| CN105924705A (en) * | 2016-05-13 | 2016-09-07 | 赛轮金宇集团股份有限公司 | Highly filled white carbon black tread rubber having good electric and thermal conductivity and used for pneumatic tire |
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Application publication date: 20160323 |