CN107266733A - A kind of carbon carbon/rubber composite preparation method - Google Patents
A kind of carbon carbon/rubber composite preparation method Download PDFInfo
- Publication number
- CN107266733A CN107266733A CN201710680483.8A CN201710680483A CN107266733A CN 107266733 A CN107266733 A CN 107266733A CN 201710680483 A CN201710680483 A CN 201710680483A CN 107266733 A CN107266733 A CN 107266733A
- Authority
- CN
- China
- Prior art keywords
- carbon
- master batch
- rubber
- rubber master
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 116
- 239000005060 rubber Substances 0.000 title claims abstract description 116
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000011203 carbon fibre reinforced carbon Substances 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 48
- 230000008569 process Effects 0.000 claims abstract description 27
- 239000002002 slurry Substances 0.000 claims abstract description 27
- 239000000839 emulsion Substances 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 238000005516 engineering process Methods 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 42
- 239000006229 carbon black Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000003292 glue Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 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 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000004880 explosion Methods 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000008267 milk Substances 0.000 claims 2
- 210000004080 milk Anatomy 0.000 claims 2
- 235000013336 milk Nutrition 0.000 claims 2
- 239000000084 colloidal system Substances 0.000 claims 1
- 239000007921 spray Substances 0.000 claims 1
- 239000000945 filler Substances 0.000 abstract description 30
- 238000002156 mixing Methods 0.000 abstract description 22
- 238000001035 drying Methods 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- 238000013329 compounding Methods 0.000 description 9
- 229920000049 Carbon (fiber) Polymers 0.000 description 7
- 235000021355 Stearic acid Nutrition 0.000 description 7
- 239000004917 carbon fiber Substances 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 7
- 239000008117 stearic acid Substances 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 6
- 244000043261 Hevea brasiliensis Species 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- 229920003052 natural elastomer Polymers 0.000 description 5
- 229920001194 natural rubber Polymers 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 239000002296 pyrolytic carbon Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical class [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/005—Methods for mixing in batches
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention belongs to rubber wet method mixing technology field, specifically related to a kind of carbon carbon/rubber composite preparation method, technical process includes preparing rubber master batch mixed liquor, prepare rubber master batch and prepare composite totally three steps, filler is stirred first and the technological means of ultrasonic atomizatio pre-processes to form filler slurry, then using the rapid warm crushing technology of filler predispersion, filler slurry is sprayed filler slurry by gas high pressure, it is ejected into high temp objects surface, suddenly heat is crushed filler emulsion droplet, realize twice dispersing of the filler in rubber matrix, high temperature expansion drying technology is used again, the wet method elastomeric compound prepared after disperseing through the rapid temperature of filler predispersion is broken is placed in moisture flash evapn therein in hot environment, solidify filler good dispersion in rubber matrix, filler/rubber composite is finally prepared using conventional banbury；Its scientific in principle is reliable, practical simplicity, and preparation efficiency is high, has a extensive future, and use environment is friendly.
Description
Technical field：
The invention belongs to rubber wet method mixing technology field, and in particular to a kind of carbon carbon/rubber composite preparation method,
It is combined using carbon carbon latex predispersion with wet method elastomeric compound drying process and realizes that carbon carbon is dispersed with dividing in latex
Cloth, the aggregation after anti-blocking carbon is scattered is made carbon carbon and is evenly distributed and well dispersed, good mechanical performance, comprehensive mechanical property
Carbon carbon/the rubber composite significantly improved with dynamic mechanical.
Background technology：
With the continuous progress and the sustainable development of material subject of science and technology, the material that the mankind use also is updating and entered
Every field, industry-by-industry and each department that step, high polymer material and its product have been captured in life, fly greatly to space flight
Some part of machine, small to one screw, is likely to use high polymer material；Rubber is used as a kind of important strategic thing
Money, is widely used in the fields such as national economy, new and high technology and defence and military, but be due to that rubbery intensity is low, modulus is low, wear-resisting
Property and fatigue resistance it is poor, without practicality, so most rubber are required for packing strengthening agent.In the prior art, carbon black
It is widely used in white carbon as main reinforcing agent in rubber, including graphene, CNT and carbon carbon composite wood
The preparation and application of emerging filler/rubber composite of material etc. also turn into study hotspot.
The process of rubber composite preparation process most critical is mixing, and the essence of compounding procedure is exactly by various compounding ingredients
It is mixed into rubber, is also mixing and dispersion process of the rubber with various compounding ingredients with the process for the elastomeric compound that uniform quality is made；
It can be said that mixing be in rubber process first be also a most important procedure, the quality of mix quality is straight
Connect the quality for having influence on rubber, performance and its service life；At present, it is many using banbury more than the mixing of China's rubber industry
Segmentation compounding process, due to the high-elastic characteristic of high polymer, result in the process that mixing process is a continuous heat heating, is anti-
Only sizing material incipient scorch destroys the performance of sizing material and reaches the dispersed purpose of compounding ingredient, and mixing process has to be repeated, right
The performance of rubber generates irreversible influence；In order to improve melting efficiency, new compounding process and process layer goes out not
Thoroughly, including low-temperature primary method, tandem mixing and continuous mixing etc., these new mixing technologies are in melting efficiency and mixing
Upper to have good portfolio effect, still, the scattered grade of the filler in these mechanically milling technologies can not reach the journey of setting
Degree, even if extension mixing time, the mixing of sizing material will not also be greatly improved.In order to obtain preferably mixing matter
Amount, people are attempted the new energy injection such as ultrasonic wave and Solid dry ice into mixing process to break the aggregation of filler, are improved
Compounding rubber quality, finds that these new technological means simply improve the microcosmic scattered of filler to a certain extent by studying
Degree, but a certain distance is still suffered from the requirement of high-end rubber, for the preparation of carbon carbon/rubber composite, machine
The technological means of tool mixing can not meet the scattered demand of filler；Carbon/carbon compound material is carbon fiber and its enhanced carbon of fabric
Matrix composite, with low-density (<2.0g/cm3), high intensity, high ratio modulus, high-termal conductivity, low-expansion coefficient, frictional property
Nowadays the advantages of energy is good, and thermal shock resistance is good, dimensional stability is high, be in the alternative materials of minority of 1650 DEG C of use above
Material, highest theoretical temperatures are more up to 2600 DEG C, it is considered to be one of most promising high-temperature material.
At present, the wet method of rubber nano composite material prepares main using chemical method processing brand-new material and latex breast
Nano filling, is dispersed in latex by liquid using the mode of stirring, then flocculates and wet method elastomeric compound is made, this method and
Chemical reagent is added in technique, very big influence is generated on properties of rubber, the quality and service life of rubber is reduced；
The preparation method of wet process mixed natural rubber material for example disclosed in Chinese patent 201110064299.3, it is to traditional mixing technology
Improved, acetic acid flocculation is added in the latex solution produced, wash glue and dehydration through rubber washing machine, then dried in drying box
4-6h, can obtain the glue stuff compounding of natural rubber after drying.There is the defect being difficult to avoid that in strong acid flocculation, can not only influence behaviour
Make the healthy of personnel, etching apparatus, the long time drying after flocculation easily produces the sour gas of influence environment, if by force
Sour clear do not wash clean can also influence vulcanization under follow-up cure time, sour environment to cause curing time lag.Therefore, research and develop
A kind of carbon carbon/rubber composite preparation method for improving carbon carbon degree of scatter in wet method mixing process, is flocculated using anacidity
Method, the reunion after preventing carbon carbon scattered, shortens the production cycle, improves the performance and intensity of rubber, has very much science and apply valency
Property, it may have good society and application prospect.
The content of the invention：
It is an object of the invention to overcome the shortcoming that prior art is present, the carbon carbon hardly possible in wet method mixing process is solved scattered
The problem of with easy reunite, while solving in wet method mixing process to flocculate properties of rubber caused by elastomeric compound by adding acid ingredient
The problems such as variation, a kind of new wet method compounding process of R ＆ D design and technique, are crushed by the rapid temperature of carbon carbon emulsion droplet predispersion
Technology realizes that carbon carbon is dispersed in emulsion, reaches the microcosmic degree of scatter of nanoscale of carbon carbon, passes through high temperature expansion drying
Technology realizes the rapid draing of wet method elastomeric compound, prevents the microcosmic aggregation of carbon carbon, so as to prepare high performance wet method elastomeric compound, is
High-performance tire, the system of high-end rubber are with the practicable approach of offer.
Carbon carbon/rubber composite preparation method of the present invention, which obtains technical process, to be included preparing rubber master batch mixed liquor, system
Standby rubber master batch and prepare composite totally three steps：
(1) rubber master batch mixed liquor is prepared：
The carbon carbon composite aqueous solution is prepared first：In temperature it is 25-100 DEG C and work(by carbon carbon composite powder and water
The carbon carbon composite aqueous solution is made in rate ultrasound 15min-12h under conditions of 500-1500W；
Then carbon black slurry is prepared：The water and carbon black that set mass fraction are mixed, and handled with high speed dispersor
The black slurry that finely dispersed mass percent concentration is 20-30% is obtained, at omnidirectional planetary ball mill
Reason black slurry 4-6h obtains carbon black slurry；
Finally prepare rubber master batch mixed liquor：The carbon carbon composite aqueous solution and 200g natural emulsions are added in carbon black slurry
5-30min mechanical agitation processing is carried out, rubber master batch mixed liquor is obtained, completes the preparation of rubber master batch mixed liquor；
(2) rubber master batch, is prepared：The surface temperature of high temperature plate is adjusted to 150 DEG C, the jet velocity of nozzle is adjusted to 15m/s,
The ejection flow of nozzle is adjusted to 3L/h, and the horizontal range of nozzle distance high temperature plate is adjusted to 100mm, and rubber master batch mixed liquor is from spraying
The emulsion droplet that device is ejected into high temperature plate surface realizes microcosmic scattered, the black slurry in rubber master batch mixed liquor by explosion and splashing
Handled by the broken dispersing technology of rapid temperature and cause the moment under the high temperature positice ground effect of high temperature plate of the moisture in black slurry
Evaporation, the showing of high temperature plate to form rubber master batch, completes the preparation of rubber master batch；
(3) composite is prepared：It is placed in mill and is plasticated after rubber master batch is scraped with scraper plate, obtains the mother of sheet
Glue, sheet rubber master batch is cut into the block rubber master batch being sized, in favor of kneading and preventing the excessive infringement machine of rubber master batch stress, will
1.8g ZnO, 1.8g SAD, 1.8g antioxidant 4020 and 1.24g accelerant CZ are made into small powder, by the initial of banbury
Temperature adjustment is 90 °, and initial speed is adjusted to 90r/min, and the 2/3,40s of rubber master batch prepared by step (2) is added in banbury
Small powder and remaining 1/3 rubber master batch are added into banbury afterwards, obtain carrying bolt 2s after mixed material, 40s, the temperature of mixed material rises
To after 120 °, bolt 2s is carried after the rotating speed of banbury is brought up into 100r/min operatings 140s, the rotating speed of banbury is down to 90r/
Min, the temperature of mixed material rises to refining glue 1min after 145 °, and the temperature of mixed material, which rises to, carries out dumping after 147 °, obtain
To elastomeric compound, the total time of banburying is less than 6min, the S of 165g elastomeric compound, 1.29g accelerant CZ and 1.1g is put into gap
It is adjusted to beat triangle bag in the mill after bag roller 4 times, the elastomeric compound tabletting after triangle bag will be played into the thickness of setting and in room
16h is stood under warm environment, the preparation of composite is completed.
Carbon carbon/rubber composite prepared by the present invention is respectively 100,35,5,2,0.7 and 2.25 including mass fraction
Natural emulsion, carbon black N330, ZnO, SAD, accelerant CZ and S, the compound derivative material of carbon carbon is variable；Heveatex is what Thailand produced
Mass percent concentration is 60% natural emulsion；White carbon is the white carbon of Qingdao Rhodia Ltd production；ZnO
Addition with SAD is the 0.3-2% of natural emulsion quality；Antioxidant 4020, accelerant CZ and S are commercially available technical grade
Product.
The present invention compared with prior art, is stirred to filler and the technological means of ultrasonic atomizatio pre-processes to be formed first
Filler slurry, then using the rapid warm crushing technology of filler predispersion, filler slurry is sprayed filler slurry by gas high pressure
Go out, be ejected into high temp objects surface, heat is crushed filler emulsion droplet suddenly, quick-fried after drop is held up due to the steam cushion on high temperature surface
It is broken, further break the network structure of filler and filler in the blasting process of emulsion droplet, realize filler in rubber matrix
Twice dispersing, improve the microcosmic scattered grade of filler, will be suddenly warm through filler predispersion then using high temperature expansion drying technology
Crush the wet method elastomeric compound prepared after disperseing to be placed in moisture flash evapn therein in hot environment, solidification filler is in rubber-based
Good dispersion in body, finally prepares filler/rubber composite using conventional banbury；Its scientific in principle is reliable, practical letter
Just, preparation efficiency is high, has a extensive future, and use environment is friendly.
Brief description of the drawings：
Fig. 1 is that carbon carbon composite addition of the present invention is respectively 0 part, 5 parts and 10 parts of carbon carbon/rubber combined
Material tire dynamic mechanical correlation curve schematic diagram.
Fig. 2 is that carbon carbon composite addition of the present invention is respectively 0 part, 5 parts and 10 parts of carbon carbon/rubber combined
Material tire wet-sliding resistant performance contrasts column schematic diagram.
Fig. 3 is that carbon carbon composite addition of the present invention is respectively 0 part, 5 parts and 10 parts of carbon carbon/rubber combined
Material tire rolling resistance performance comparison column schematic diagram.
Fig. 4 is that carbon carbon composite addition of the present invention is respectively 0 part, 5 parts and 10 parts of carbon carbon/rubber combined
The scanning electron microscope (SEM) photograph of material tire (wherein, a addition is 0 part, and b addition is 5 parts, and c addition is 10 parts).
Embodiment：
The present invention is described further below by embodiment and with reference to accompanying drawing.
Embodiment 1：
Carbon carbon/rubber composite preparation method that the present embodiment is related to is also referred to as atomization drying method, its technical process bag
Include and prepare rubber master batch mixed liquor, prepare rubber master batch and prepare composite totally three steps：
(1) rubber master batch mixed liquor is prepared：
The carbon carbon composite aqueous solution is prepared first：In temperature it is 25-100 DEG C and work(by carbon carbon composite powder and water
The carbon carbon composite aqueous solution is made in rate ultrasound 15min-12h under conditions of 500-1500W；
Then carbon black slurry is prepared：The water and carbon black that set mass fraction are mixed, and handled with high speed dispersor
The black slurry that finely dispersed mass percent concentration is 20-30% is obtained, at omnidirectional planetary ball mill
Reason black slurry 4-6h obtains carbon black slurry；
Finally prepare rubber master batch mixed liquor：The carbon carbon composite aqueous solution and 200g natural emulsions are added in carbon black slurry
5-30min mechanical agitation processing is carried out, rubber master batch mixed liquor is obtained, completes the preparation of rubber master batch mixed liquor；
(2) rubber master batch, is prepared：The surface temperature of high temperature plate is adjusted to 150 DEG C, the jet velocity of nozzle is adjusted to 15m/s,
The ejection flow of nozzle is adjusted to 3L/h, and the horizontal range of nozzle distance high temperature plate is adjusted to 100mm, and rubber master batch mixed liquor is from spraying
The emulsion droplet that device is ejected into high temperature plate surface realizes microcosmic scattered, the black slurry in rubber master batch mixed liquor by explosion and splashing
Handled by the broken dispersing technology of rapid temperature and cause the moment under the high temperature positice ground effect of high temperature plate of the moisture in black slurry
Evaporation, the showing of high temperature plate to form rubber master batch, completes the preparation of rubber master batch；
The evaporation curable of moisture in black slurry carbon black and natural emulsion it is microcosmic scattered, it is therefore prevented that carbon black
Coacervation process, the alkaline components volatilization in natural emulsion under high temperature action, it is to avoid sizing material quality caused by sour flucculation process
The problem of variation；
(3) composite is prepared：It is placed in mill and is plasticated after rubber master batch is scraped with scraper plate, obtains the mother of sheet
Glue, sheet rubber master batch is cut into the block rubber master batch being sized, in favor of kneading and preventing the excessive infringement machine of rubber master batch stress, will
1.8g ZnO (zinc oxide), 1.8g SAD (stearic acid), 1.8g antioxidant 4020 and 1.24g accelerant CZ are made into small
Material, is adjusted to 90 °, initial speed is adjusted to 90r/min by the initial temperature of banbury, and step (2) system is added in banbury
Small powder and remaining 1/3 rubber master batch are added into banbury after 2/3,40s of standby rubber master batch, obtain carrying bolt 2s after mixed material, 40s,
The temperature of mixed material is risen to after 120 °, and bolt 2s is carried after the rotating speed of banbury is brought up into 100r/min operatings 140s, will be close
The rotating speed of mill is down to 90r/min, and the temperature of mixed material rises to refining glue 1min after 145 °, and the temperature of mixed material rises to
Dumping is carried out after 147 °, elastomeric compound is obtained, the total time of banburying is less than 6min, by 165g elastomeric compound, 1.29g accelerant CZ
It is put into 1.1g S (sulphur) in the mill that gap is adjusted to after bag roller and beats triangle bag 4 times, the mixing glue laminated after triangle bag will be beaten
Piece into setting thickness and stand under room temperature environment 16h, complete the preparation of composite.
Carbon carbon/rubber composite manufactured in the present embodiment is respectively 100,35,5,2,0.7 and 2.25 including mass fraction
Natural emulsion, carbon black N330, ZnO, SAD, accelerant CZ and S, the compound derivative material of carbon carbon is variable；Heveatex produces for Thailand
Mass percent concentration be 60% natural emulsion；White carbon is the white carbon of Qingdao Rhodia Ltd production；
ZnO and SAD addition is the 0.3-2% of natural emulsion quality；Antioxidant 4020, accelerant CZ and S are commercially available work
Industry level product.
During carbon carbon/rubber composite testing inspection manufactured in the present embodiment, 0 part, 5 parts and 10 parts carbon carbon is combined respectively
Material, which is added in carbon carbon/rubber composite tire, to be tested tire, and the dynamic mechanical of tire is using Germany
DMA (full-automatic Dynamic Mechanical Analyzer) tests of GABO companies, test condition is as follows：Frequency is 10HZ, and static strain is
5%, static stress is 70N, and dynamic strain is 0.25%, and dynamic stress is 60N, and temperature range is -65 to 65 DEG C, temperature rise rate
For 2 DEG C/min, using stretch mode；Carbon carbon composite addition is respectively 0 part, 5 parts and 10 parts of carbon carbon/rubber combined material
Material wheel tire dynamic mechanical correlation curve is as shown in Figure 1：The rolling resistance of tire, anti-slippery, anti-wear performance three, which exist, to be write
Devil's triangle relation of name, improves any one performance in three, and how together will necessarily influenceing remaining, both have the trend of variation,
Tri- performances of Shi Tigao are always the objective of the struggle of people, for fixed formula, and good calendering process then can be a certain in lifting
Kind or while two kinds of performances so that the downward trend of another performance is tried one's best reduction；The dynamic mechanical of tread mix
There can be obvious dependency relation with the performance of finished tire, the wet-sliding resistant performance of tire is characterized using 0 DEG C of Tan δ,
Tan δ are bigger, and wet-sliding resistant performance is better, and rolling resistance performance is characterized using 60 DEG C of Tan δ, and Tan δ are smaller, and rolling resistance is lower：
Carbon carbon composite addition is respectively 0 part, 5 parts and 10 parts of carbon carbon/rubber composite tire wet-sliding resistant performance contrast post
Shape figure is as shown in Fig. 2 carbon carbon composite addition is respectively 0 part, 5 parts and 10 parts of carbon carbon/rubber composite tire rolling
Performance comparison block diagram is hindered as shown in figure 3, being learnt by Fig. 2 and 3, and with the increase of carbon carbon composite number, carbon carbon/rubber is multiple
The anti-slippery ability of condensation material tire is significantly improved, and in the case where carbon carbon composite addition is 5 parts, carbon carbon/rubber is multiple
The rolling resistance increase of condensation material tire is few；Carbon carbon composite addition is respectively 0 part, 5 parts and 10 parts of carbon carbon/rubber combined
The scanning electron microscope (SEM) photograph of material tire is as shown in figure 4, wherein, a addition is 0 part, and b addition is 5 parts, and c addition is
10 parts, carbon carbon composite addition is more regular for the brittle failure face of 0 part of carbon carbon/rubber composite tire, only exists one
A little rough textures, this is due to that inequality of being exerted oneself in brittle failure is caused, and carbon carbon composite addition is 5 parts of carbon
The surface of carbon/rubber composite tire is relatively smooth, the carbon fiber dispersion ratio in carbon carbon composite it is more uniform and
Orientation ratio is more regular, can preferably be combined with rubber matrix, helps to strengthen the mechanical property of carbon carbon/rubber composite tire
Can, carbon carbon composite addition is 10 parts of carbon carbon/rubber composite tire with the increasing of carbon carbon composite consumption
Many, there is agglomeration in carbon fiber in carbon carbon composite, and some cellular eyelets are have also appeared on brittle failure surface, and this is carbon
Pyrolytic carbon in carbon composite generates aggregation, and in brittle failure, particle comes off from section produces space, secondly, on brittle failure surface
Some circular holes are showed, reason is, because carbon fiber and rubber matrix binding ability decline, to cause adhesion small during brittle failure
In the breaking tenacity of carbon fiber, and then carbon fiber pulls out generation circular hole from brittle failure face；Carbon carbon composite addition is respectively 0
Part, carbon carbon/rubber composites of 5 parts and 10 parts is to the influence such as following table of natural rubber (NR) composite heat conductivility：
For composite, thermal conductivity is taken mainly certainly in the collective effect of rubber and conductive filler, and filler is at it
In occupy leading role, interaction has been begun with as loading increases, between filler grain, has been formd in system similar
The form of netted and chain, referred to as heat conduction network chain, as seen from the above table, with increasing for carbon carbon composite addition, naturally
The trend risen is presented in the thermal conductivity of rubber composite, and reason has two：One is that pyrolytic carbon has in itself in carbon carbon composite
Excellent electric conductivity, two be increasing with carbon carbon composite addition, and pyrolytic carbon and carbon fiber, which contact with each other, becomes many, carbon
More heat conduction network chain is formed between carbon composite and carbon carbon composite, so as to form passage of heat, natural rubber is combined
The thermal conductivity of material is significantly lifted.
Claims (2)
1. a kind of carbon carbon/rubber composite preparation method, it is characterised in that technical process includes preparing rubber master batch mixed liquor, preparation
Rubber master batch and prepare composite totally three steps：
(1) rubber master batch mixed liquor is prepared：
The carbon carbon composite aqueous solution is prepared first：It is 25-100 DEG C in temperature by carbon carbon composite powder and water with power to exist
The carbon carbon composite aqueous solution is made in ultrasound 15min-12h under conditions of 500-1500W；
Then carbon black slurry is prepared：The water and carbon black that set mass fraction are mixed, and obtained with high speed dispersor processing
Finely dispersed mass percent concentration is 20-30% black slurry, utilizes omnidirectional planetary ball mill processing carbon
Heisui River dispersion 4-6h obtains carbon black slurry；
Finally prepare rubber master batch mixed liquor：The carbon carbon composite aqueous solution and 200g natural emulsions are added in carbon black slurry and carried out
5-30min mechanical agitation processing, obtains rubber master batch mixed liquor, completes the preparation of rubber master batch mixed liquor；
(2) rubber master batch, is prepared：The surface temperature of high temperature plate is adjusted to 150 DEG C, the jet velocity of nozzle is adjusted to 15m/s, nozzle
Ejection flow be adjusted to 3L/h, the horizontal range of nozzle distance high temperature plate is adjusted to 100mm, and rubber master batch mixed liquor sprays from sprayer
The emulsion droplet for being mapped to high temperature plate surface realizes microcosmic scattered, the black slurry process in rubber master batch mixed liquor by explosion and splashing
The rapid broken dispersing technology of temperature, which is handled, causes the flash evapn under the high temperature positice ground effect of high temperature plate of the moisture in black slurry,
The showing of high temperature plate to form rubber master batch, completes the preparation of rubber master batch；
(3) composite is prepared：It is placed in mill and is plasticated after rubber master batch is scraped with scraper plate, obtains the rubber master batch of sheet, will
Sheet rubber master batch is cut into the block rubber master batch being sized, in favor of kneading and preventing the excessive infringement machine of rubber master batch stress, by 1.8g
ZnO, 1.8g SAD, 1.8g antioxidant 4020 and 1.24g accelerant CZ be made into small powder, by the initial temperature of banbury
90 ° are adjusted to, initial speed is adjusted to 90r/min, being added in banbury after 2/3,40s of rubber master batch prepared by step (2) will
Small powder and remaining 1/3 rubber master batch add banbury, obtain carrying bolt 2s after mixed material, 40s, the temperature of mixed material rises to
After 120 °, bolt 2s is carried after the rotating speed of banbury is brought up into 100r/min operatings 140s, the rotating speed of banbury is down to 90r/
Min, the temperature of mixed material rises to refining glue 1min after 145 °, and the temperature of mixed material, which rises to, carries out dumping after 147 °, obtain
To elastomeric compound, the total time of banburying is less than 6min, the S of 165g elastomeric compound, 1.29g accelerant CZ and 1.1g is put into gap
It is adjusted to beat triangle bag in the mill after bag roller 4 times, the elastomeric compound tabletting after triangle bag will be played into the thickness of setting and in room
16h is stood under warm environment, the preparation of composite is completed.
2. carbon carbon/rubber composite preparation method according to claim 1, it is characterised in that the carbon carbon/rubber is multiple
Condensation material includes the natural emulsion that mass fraction is respectively 100,35,5,2,0.7 and 2.25, carbon black N330, ZnO, SAD, promotion
Agent CZ and S, the compound derivative material of carbon carbon is variable；Heveatex is the genuine milk that the mass percent concentration that Thailand produces is 60%
Glue；White carbon is the white carbon of Qingdao Rhodia Ltd production；ZnO and SAD addition is genuine milk colloid
The 0.3-2% of amount；Antioxidant 4020, accelerant CZ and S are commercially available technical grade product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710680483.8A CN107266733B (en) | 2017-08-10 | 2017-08-10 | A kind of carbon carbon/rubber composite material preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710680483.8A CN107266733B (en) | 2017-08-10 | 2017-08-10 | A kind of carbon carbon/rubber composite material preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107266733A true CN107266733A (en) | 2017-10-20 |
| CN107266733B CN107266733B (en) | 2018-10-12 |
Family
ID=60079695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710680483.8A Active CN107266733B (en) | 2017-08-10 | 2017-08-10 | A kind of carbon carbon/rubber composite material preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107266733B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485929A (en) * | 2018-11-09 | 2019-03-19 | 青岛双星轮胎工业有限公司 | Tread rubber and preparation method thereof for all-steel load-bearing radial tire |
| CN110003577A (en) * | 2019-04-24 | 2019-07-12 | 青岛科技大学 | A kind of GO/CNT/IIR high-heat-conductive composite material preparation method |
| CN110014527A (en) * | 2019-03-21 | 2019-07-16 | 青岛科技大学 | A kind of GR-SiO2/ IIR material preparation method and glue-spraying device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010009654A1 (en) * | 1997-04-30 | 2001-07-26 | Masayuki Kawazoe | Process for production of modified carbon black for rubber reinforcement and process of production of rubber composition containing modified carbon black |
| CN101851360A (en) * | 2010-06-18 | 2010-10-06 | 北京化工大学 | Method for preparing easily mixed high filling clay/rubber nano composite material |
| CN102050973A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Tread rubber composite material and preparation method thereof |
| CN102585309A (en) * | 2012-01-04 | 2012-07-18 | 北京化工大学 | Method for preparing high-dispersion white carbon black/rubber nano composite material |
| CN103203810A (en) * | 2013-01-10 | 2013-07-17 | 怡维怡材料研究院有限公司 | Continuous manufacturing method for rubber masterbatch, rubber masterbatch prepared by using continuous manufacturing method and rubber product |
-
2017
- 2017-08-10 CN CN201710680483.8A patent/CN107266733B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010009654A1 (en) * | 1997-04-30 | 2001-07-26 | Masayuki Kawazoe | Process for production of modified carbon black for rubber reinforcement and process of production of rubber composition containing modified carbon black |
| CN102050973A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Tread rubber composite material and preparation method thereof |
| CN101851360A (en) * | 2010-06-18 | 2010-10-06 | 北京化工大学 | Method for preparing easily mixed high filling clay/rubber nano composite material |
| CN102585309A (en) * | 2012-01-04 | 2012-07-18 | 北京化工大学 | Method for preparing high-dispersion white carbon black/rubber nano composite material |
| CN103203810A (en) * | 2013-01-10 | 2013-07-17 | 怡维怡材料研究院有限公司 | Continuous manufacturing method for rubber masterbatch, rubber masterbatch prepared by using continuous manufacturing method and rubber product |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485929A (en) * | 2018-11-09 | 2019-03-19 | 青岛双星轮胎工业有限公司 | Tread rubber and preparation method thereof for all-steel load-bearing radial tire |
| CN110014527A (en) * | 2019-03-21 | 2019-07-16 | 青岛科技大学 | A kind of GR-SiO2/ IIR material preparation method and glue-spraying device |
| CN110014527B (en) * | 2019-03-21 | 2021-01-01 | 青岛科技大学 | GR-SiO2/IPreparation method of IR material and glue spraying device |
| CN110003577A (en) * | 2019-04-24 | 2019-07-12 | 青岛科技大学 | A kind of GO/CNT/IIR high-heat-conductive composite material preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107266733B (en) | 2018-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107325343B (en) | A kind of graphene/rubber composite material preparation method | |
| CN107457933B (en) | A kind of filler/rubber composite material preparation method | |
| CN107312208B (en) | A kind of white carbon black/rubber composite material preparation method | |
| CN105459284B (en) | The liquid phase continuous mixing technique and its rubber product of high dispersive carbon nanotube masterbatch | |
| CN107266733B (en) | A kind of carbon carbon/rubber composite material preparation method | |
| CN104086824B (en) | Elastic composite and manufacture method thereof | |
| CN103275524B (en) | Preparation method of graphene kaolin composite nanometer rubber fillers | |
| CN105710983B (en) | A kind of rubber wet method compounding process for premixing atomization and remixing | |
| CN107337815B (en) | A kind of preparation method of silicon carbon black/native rubber composite material | |
| CN102617918B (en) | Method for preparing high-ductility conductive polymer composite material | |
| CN103435820B (en) | Pre-treatment method of asphalt and spherical graphite negative electrode material coated by using asphalt | |
| CN109810323B (en) | Preparation method of white carbon black/graphene oxide nano hybrid filler, nano hybrid filler and application of nano hybrid filler | |
| CN100457812C (en) | Process for preparing attapulgite and natural rubber nano composite material | |
| CN105419095B (en) | A kind of production method of carbon black composite powder material | |
| CN106084332A (en) | The preparation method of the pre-dispersed rubber master batch of graphene microchip and process units | |
| CN109517195A (en) | A kind of method that wet process is kneaded preparation carbon black rubber master batch | |
| CN105419009A (en) | Method for preparing high-filling composite masterbatch through semi-open type superheated steam spray-drying method | |
| CN103819760A (en) | Process method for preparing high-performance carbon black masterbatch | |
| CN103289143A (en) | Energy-saving tire tread rubber composition and preparation method thereof | |
| CN105949536A (en) | {0><}0{>Preparation method of high-strength natural rubber (NR)/carbon nano tube (CNT) conductive composite film | |
| CN109651891A (en) | A kind of graphene water-based composition, preparation method and graphene water-soluble conducting ink | |
| CN109251327B (en) | Method and device for preparing rubber compound by continuous spraying and mixing | |
| CN114407266A (en) | Preparation method of carbon black/natural latex composite material | |
| CN108299657B (en) | Preparation method and application of high-dispersion modified lignin | |
| CN104961930B (en) | A kind of latex doped with Graphene and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Wang Chuansheng Inventor after: Li Haitao Inventor after: Wen Nannan Inventor after: Liu Jie Inventor after: Bian Huiguang Inventor after: Shen Bo Inventor after: Yin Fengfu Inventor after: Li Shaoming Inventor before: Wang Chuansheng Inventor before: Li Haitao Inventor before: Wen Nannan Inventor before: Liu Jie Inventor before: Bian Huiguang Inventor before: Shen Bo Inventor before: Yin Fengfu Inventor before: Li Shaoming |