CN103419291A - Continuous preparation method for rubber masterbatch and rubber masterbatch prepared thereby - Google Patents
Continuous preparation method for rubber masterbatch and rubber masterbatch prepared thereby Download PDFInfo
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- CN103419291A CN103419291A CN2013103375599A CN201310337559A CN103419291A CN 103419291 A CN103419291 A CN 103419291A CN 2013103375599 A CN2013103375599 A CN 2013103375599A CN 201310337559 A CN201310337559 A CN 201310337559A CN 103419291 A CN103419291 A CN 103419291A
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- 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
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
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- 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
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
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- 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
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
- B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing rubber
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- 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
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
- C08J3/212—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase and solid additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2321/00—Characterised by the use of unspecified rubbers
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a continuous preparation method of a rubber masterbatch and the rubber masterbatch prepared thereby. The preparation method comprises the following steps: (1), adding a filler into a rubber solution and forming a rubber/filler/solvent mixture by stirring; (2), directly feeding the rubber/filler/solvent mixture in the step (1) into a heating medium with the temperature higher than the boiling point of a solvent, agglomerating the mixture and deswelling when the polarity of the heating medium is different from that of the used solvent, and quickly volatilizing the solvent to form a heating medium-containing mixture of a rubber/filler compound and the solvent; (3), removing the solvent and drying the mixture to obtain the rubber/filler masterbatch. The preparation method does not have special requirements on rubber and the filler and is wider in application range; production equipment and process are simple, continuous, efficient, low in energy consumption, low in manpower and lower in cost; the masterbatch prepared by the method is very superior in processing, physical mechanical performance and product quality.
Description
Technical field
The present invention relates to rubber materials, the rubber masterbatch that particularly prepared by the method for continuously producing of rubber masterbatch and the method.
Background technology
In rubber/filler/additive/dicyandiamide solution, the cohesion of rubber/filler/additive from solvent is to manufacture critical step in rubber/filler/additive rubber master batch.This process described in WO98/58985 is that large-scale blade-carrying worm gear drying machine carries out in per minute 400/1200 device turned, and the cohesion speed of this method is slower, and technical process is long, consumes energy high.The present invention relates to several mixed at high speed/condensing methods, wherein condense medium and comprise gas, especially high-temperature gas and liquid mixed with rubber/filler/additive agent mixture moment under the state of high energy turbulent flow, due to the high-temperature effect of gas and the difference of liquid medium and solvent polarity aspect, the rubber/filler in rubber/filler/additive/solvent mixture/additive will produce desolvation agent phenomenon and condense in solvent.Due to the high velocity turbulent flow effect, mixture and cohesion medium are that being blended in the very short time of desolvation agent medium can complete.Because the interface of desolvation agent medium and rubber/filler/additive/solvent increases greatly, the cohesion speed of rubber/filler/additive in solvent is very fast, if the temperature of desolvation agent medium is higher, solvent will volatilize rapidly in coacervation process, cause condensing micelle less, so the solvent evaporates effect of coagel is further accelerated.Therefore, compared with the conventional method, the designed condensing method of the application has characteristics efficient, energy-conservation and mixing and cohesion continued operation.
Summary of the invention
For the problem of prior art, the purpose of this invention is to provide a kind of method for continuously producing of rubber masterbatch and rubber masterbatch prepared by the method.Another object of the present invention is to provide a kind of rubber that uses rubber masterbatch of the present invention to prepare.
The advantage of the method for continuously producing of rubber masterbatch of the present invention is:
1) continuous high-efficient;
2) mix and cohesion evenly and speed fast;
3) significantly improve the physical and mechanical properties of vulcanizate and the quality of rubber;
4) with the condensation technique during existing wet method is mixing, compare, the present invention to rubber, filler without specific (special) requirements, applied widely to the contamination of rubber and filler and additive;
5) production equipment and process very simple and continuously, efficient, consume energy low, few manually, thereby cost is lower;
6) rubber master batch that uses the method to prepare is all very superior on processing characteristics, physical and mechanical properties, product quality.
The invention further relates to following embodiment:
A kind of method for continuously producing of rubber masterbatch, comprise the steps:
Step 1): filler is joined in rubber solutions, by stirring, form rubber/filler/solvent mixture;
Step 2): the rubber/filler in step 1)/solvent mixture is directly passed in the heat medium of temperature higher than solvent boiling point, the polarity of this heat medium is different from the polarity of solvent for use, mixture coagulated deswelling, and solvent volatilizees rapidly, thus rubber/filler compound that formation contains this heat medium and the mixture of solvent;
Step 3): desolvation also carries out drying to described mixture, obtains rubber/filler masterbatch.
Preferably, step 2 wherein) can implement with any container.
Preferably, step 2 wherein) implement the pref. cylindrical tank container in tank container.
Preferably, optional recycling step 3 wherein) solvent removed, recycle.
Preferably, wherein in step 1) and/or step 2) in optional add one or more and be selected from the additive of oil, age resistor, coupling agent, activating agent, antioxidant, fire retardant, heat stabilizer, light stabilizer, dyestuff, pigment, vulcanizing agent and promoter.
Preferably, wherein said heat medium is water vapour, in dried solid mixture, can contain water, then obtains rubber/filler masterbatch through vacuum drying, heat drying or extruding heat drying except after anhydrating.
Preferably, wherein said heat medium is water, described solvent be boiling point lower than 100 ℃ of varsols, can contain water in dried solid mixture, then obtain rubber/filler masterbatch through vacuum drying, heat drying or extruding heat drying except after anhydrating.
More preferably, wherein said heat drying is for drying or air-dry.
More preferably, wherein said extruding heat drying removes after heat medium further dry again for first extruding.
More preferably, wherein said further drying is air-dry, oven dry or mechanical drying.
More preferably, wherein said mechanical drying is for being used mill, masticator, banbury, continuous internal mixer, single screw extrusion machine, and double screw extruder carries out drying.
The present invention also provides a kind of rubber masterbatch prepared according to said method.
Further, the present invention also provides a kind of rubber that adopts above-mentioned masterbatch to prepare.
The method for continuously producing of rubber masterbatch of the present invention comprises the steps:
Step 1): filler is joined in rubber solutions, by stirring, form rubber/filler/solvent mixture;
Step 2): the rubber/filler in step 1)/solvent mixture is directly passed in the heat medium of temperature higher than solvent boiling point, the polarity of this heat medium is different from the polarity of solvent for use, mixture coagulated deswelling, and solvent volatilizees rapidly, thus rubber/filler compound that formation contains this heat medium and the mixture of solvent;
Step 3): desolvation also carries out drying to described mixture, thereby obtains rubber/filler masterbatch.
The method for continuously producing of rubber masterbatch of the present invention also optionally comprises recycling step 3) step of solvent to recycle that remove.In addition, in step 1) and/or step 2) in optional add one or more and be selected from the additive of oil, age resistor, coupling agent, activating agent, antioxidant, dyestuff, light stabilizer, fire retardant, heat stabilizer, pigment, vulcanizing agent and promoter.
Step 1) can be used method well known in the art to realize.Stirring described in step 1) can be used general mixer to complete, and includes but not limited to blade paddle mixer, trough mixer, planetary stirring machine, Z-blade mixer etc.
Step 1) can further include finely divided step, described finely divided can enforcement in the following way: by the mixture of above-mentioned stirring gained by a nozzle in the situation that the high pressure high shear spray, to improve the dispersion of filler and/or additive; Make above-mentioned ejecta make mixed liquor clash into the dispersiveness that increases filler and/or additive at the Guan Zhongyu tube wall by swan neck more than; Or make ejecta convert by the bore pipeline that repeatedly folding and unfolding changes the dispersion that shear stress increases filler and/or additive.Pressure limit used is from 0.1MPa to 60MPa, preferably 10MPa to 40MPa.
Described finely divided rear formed mixture can also disperse further to improve filler and/or the dispersion of additive in rubber solutions by following essence:
I. described finely divided mixture is afterwards added continuously in ball mill and/or colloid mill and disperseed, make filler and/or additive be dispersed in uniformly in rubber solutions;
Ii. described finely divided mixture is afterwards joined continuously in grinder and ground so that filler and/or additive are well dispersed in rubber solutions, this grinder has the plane mill of one or more groups high speed rotating and is fixed on the grinder sleeve and fixing pin or the price fixing alternate with the plane mill.
Iii. described finely divided mixture is afterwards joined in grinder and ground continuously, this grinder has two blades of direction of rotation, described blade has the pore chute, under high pressure can improve filler and/or the degree of scatter of additive in rubber solutions by the blade of rotation.Pressure limit used is from 0.1MPa to 60MPa, preferably 10MPa to 40MPa.
Iv. described finely divided mixture is afterwards joined in multi-layer high-voltage slit dispersion machine continuously, mixture is under high pressure extruded slit between two-layer, and the strong shearing force now produced can improve filler and/or the degree of scatter of additive in rubber solutions.Pressure limit used is from 0.1MPa to 60MPa, preferably 10MPa to 40MPa.
V. described finely divided mixture is afterwards joined continuously in the power decentralized device and disperseed, many radially-arranged slits or hole are arranged on the rotor of the High Rotation Speed of described power decentralized device, mixture with high-speed impact on stator surface so that filler and/or additive be evenly dispersed in rubber solutions.
Two or more in above-mentioned five kinds of finely divided methods use of can mutually connecting.
Described rubber solutions can directly directly obtain from prepare the solution polymerized rubber production line, also the dry glue of any type can be dissolved in the solvent of this glue to preparation.When with dry glue, preparing rubber solutions, described dry glue can be the rubber of any kind used in the art, as natural polymer or synthetic polymer.Described natural polymer includes but not limited to natural gum, gutta-percha, guayule etc.; Described synthetic polymer includes but not limited to that monomer polymerization gained (containing intermingle with rubber), monomer polymerization gained (being emulsion polymerized rubber), monomer body in emulsion in solution carries out the polymerization gained.When described rubber solutions directly obtains from prepare the solution polymerized rubber production line, described solution polymerized rubber is for using ethene, propylene, butylene, amylene, alkene, heptene, the triolefin of the diene of a 4-7 carbon atom or 6-7 carbon atom, or containing homopolymerization or the copolymerized polymer of the vinyl monomer of other atom or functional group, described other atoms or functional group are silicon atom, fluorine atom, the chlorine atom, nitrogen-atoms, oxygen atom, sulphur atom, ester group, the amino ester group, cyano group, also comprise the homopolymers and the copolymer that contain above-mentioned monomer, comprising but be not limited to polybutadiene, polyisoprene, butadiene-styrene rubber, second the third glue, butyl rubber, NBR, neoprene, silicon rubber, fluorubber, polyurethane rubber, CSM, ACM etc.The molecular weight of rubber is 1,000 to 4,000 ten thousand, preferably 5,000 to 3,000 ten thousand, more preferably 10,000 to 8,000,000.
Solvent in described rubber solutions is the good solvent of various rubber.Solvent can be specifically aliphatic solvent, aromatic hydrocarbon solvent, chlorinated hydrocarbon solvent, ketones solvent, ether solvent and esters solvent, described aliphatic solvent includes, but are not limited to various industrial napthas, cycloalkane, substituted ring alkane, normal alkane, described aromatic hydrocarbon solvent includes but not limited to benzene,toluene,xylene, styrene, and described chlorinated hydrocarbon solvent includes but not limited to carrene, chloroform, carbon tetrachloride, dichloroethanes, chlorobenzene, tetrachloro-ethylene, chlorotoluene.The concentration range of rubber in solution is 1% weight to 60% weight, preferably 5% weight to 40% weight, more preferably 10% weight to 30% weight.
Described filler includes but not limited to various solid powdery reinforcing agents and filler used in rubber, as the nanometer materials of all kinds of carbon blacks, silica, metal oxide, salt, different resins and above-mentioned filler.Wherein said metal oxide includes, but are not limited to aluminium oxide, magnesia, zinc oxide etc., and described salt includes, but are not limited to the nanometer materials of calcium carbonate, potter's clay and above-mentioned filler.The specific area of filler is 0.1 to 800m
2/ g, preferably 1 to 500m
2/ g, more preferably 5 to 300m
2/ g.For carbon black, silica (white carbon), its oil factor is 20 to 250ml/100g, preferably 25 to 200ml/100g, more preferably 30 to 150ml/100g, wherein said filler comprises their mixture, as heterogeneous filler, comprising but be not limited to two-phase or the heterogeneous filler that carbon black, silica, aluminium oxide, magnesia, zinc oxide, calcium oxide, titanium oxide, boron oxide etc. form, for two-phase or heterogeneous filler, its oil factor is 20 to 250ml/100g, preferably 25 to 200ml/100g, and more preferably 30 to 150ml/100g.The consumption of filler is 5 to 300 weight portions (take rubber as 100 weight portions), preferably 10 to 200 weight portions, more preferably 30 to 150 weight portions.That described filler also comprises in above-mentioned filler two or more and use thing.
Described filler also comprises their surface modifying stuffing.Wherein said surface modification can be certain functional group is connected on to filling surface or by mixing or adsorbing, modifier is combined on filling surface by physics mode by chemical reaction.Described modification, can be dissolved in modifier after solvent mixing with filler and carry out the liquid phase modification, as Wang W, Nanse G, Vidal A, et al.K.G.K[J], 1994, described in 47:493, also modifier and filler Hybrid Heating can be carried out to solid-state modification, as Wang MJ, Wolff.S.R.C.T[J], described in 1992,65:715.Surface modification is carried out before also can be in filler is added to rubber solutions, or modifier is joined in the mixture of rubber solutions and filler and carry out surface modification.The modifier that described modifier is this area routine, such as the organo silane coupling agent meaned with following general formula:
(R
n-(RO)
3-nSi-(Alk)
m-(Ar)
p)
q(A) （I）
R
n’(RO)
3-nSi-(Alk) （II）
Or R
n' (RO)
3-nSi-(Alk
enyL) (III)
In formula, when q=1, A is-SCN ,-SH ,-Cl ,-NH
2
When q=2, A is-S
x-;
The branching that R and R ' they are carbon atom from 1 to 4 or alkyl or the phenolic group of straight chain, and R and R ' can be identical, also can be different;
N is 0,1 or 2;
Alk is the straight or branched alkyl that contains 1 to 6 carbon atom;
Alk
enyL is the straight or branched thiazolinyl that contains 1 to 6 carbon atom;
M is 0 or 1;
Ar is the aryl that contains 6 to 12 carbon atoms;
P be 0 or 1, p and n can not be 0 simultaneously;
X is 2 to 8;
Wherein the most frequently used is two (triethoxy propyl silane) tetrasulfides and disulphide, 3-thiocyanogen propyl group-triethoxysilane, γ-sulfydryl-trimethoxy silane, zirconium ester coupling agent, phthalate ester coupling agent, nitro coupling agent, alcohol compound, described alcohol compound includes but not limited to unit alcohol, dihydroxylic alcohols, polyalcohol, and described alcohol compound includes but not limited to propyl alcohol, butanols, ethylene glycol, polyethylene glycol and derivative thereof.
Step 1) of the present invention can directly join filler and/or additive in rubber solutions, also can be first filler and/or additive is joined in the solvent identical or different with rubber solutions after being mixed to form uniform suspension and adds and sneak in rubber solutions by stirring.Additive can optionally comprise one or more in the additive of oil, age resistor, coupling agent, activating agent, antioxidant, heat stabilizer, light stabilizer, fire retardant, dyestuff, pigment, vulcanizing agent or promoter.The consumption of additive therefor is conventional amount used, or is adjusted according to the requirement of actual conditions.
In step 2) in, by the rubber/filler in step 1)/solvent mixture or through finely divided mixture, directly pass in the heat medium of temperature higher than solvent boiling point.When the character of heat medium, when from solvent for use character, especially polarity is different, mixture condenses and deswelling, and the heat medium temperature is during higher than solvent boiling point, solvent rapidly volatilization form the masterbatch that contains heat medium.This masterbatch after heat medium is removed in heating the masterbatch product, during the solvent volatilized in this process and rubber are synthetic, unreacted monomer enters in condenser and fractionating column and is reclaimed, the cohesion mixture of gained with heat medium, separate after filtration and dry after the rubber master batch product.Above-mentioned heat medium includes but not limited to water.When water is cooked heat medium, described solvent is that boiling point is lower than 100 ℃ of solvents.Then during the solvent that volatilized and rubber are synthetic, unreacted monomer and water vapour enter in condenser and fractionating column and are reclaimed.Described drying can be vacuum drying, comprises normal-temperature vacuum drying, vacuum freezedrying and heating, vacuum drying, can be also general drying mode, for example oven dry or air-dry.Described drying also can remove after heat medium further dry again for first extruding, wherein said further drying is air-dry, oven dry or mechanical drying, described mechanical drying is for being used mill, masticator, banbury, continuous internal mixer, single screw extrusion machine, and double screw extruder carries out drying.
Step 2) cohesion can be implemented with any container; Preferably, with the knockouts of any particular design, do not implement; Step 2) cohesion can be implemented in tank container, the tank container of pref. cylindrical.
Step 2) cohesion in also can be implemented with knockouts, the knockouts used can be for having the tubular type knockouts of one or more charging aperture, the feedstock direction of wherein said charging aperture can with tubular type, to condense the axial direction of organ pipe parallel, the end of outlet in pipe, the axial direction that also can condense organ pipe with tubular type is 1-180 ° of angle, preferably be 20-120 ° of angle, more preferably be 70-100 ° of angle, most preferably be 85-95 ° of angle.When charging aperture, while being a plurality of, the feedstock direction of part charging aperture is parallel with the axial direction of tubular type cohesion organ pipe; The axial direction of the cylinder of the feedstock direction of remaining charging aperture and tubular type knockouts is 1-180 ° of angle, preferably be 20-120 ° of angle, more preferably be 70-100 ° of angle, most preferably be 85-95 ° of angle, the radial direction that be projected as this cross section of the feedstock direction of each charging aperture on the cross section vertical with the tubular axis heart is to any direction between the tangential direction of this cross section, be preferably radial direction, or be tangential direction.Described charging aperture all on the axial perpendicular same plane from pipe or described charging aperture on different planes.
Step 2) knockouts used in the knockouts that two or three above concentric pipes mutually form of also can serving as reasons, wherein each pipe has one or more charging aperture, the feedstock direction of described charging aperture is to be parallel to the axial direction of pipe or is the tangential direction of pipe, the end of outlet in pipe.Fluid can directly pass into, and also can pass into from the tangential direction of tube wall.The end of the charging aperture of each pipe can be in same plane, also from inside to outside the end of the charging aperture of each pipe successively elongated the or end charging aperture of each pipe from inside to outside shorten successively.
Step 2) knockouts used in can be also the cartridge type knockouts, and this cartridge type knockouts only has a charging aperture, and this charging aperture is positioned on the upper end or barrel of cartridge type knockouts, the lower end of outlet in cylinder.Fluid can directly inject knockouts by charging aperture, also can inject knockouts with the direction of tangent line along barrel.
Step 2) knockouts used in also can be for top is tubular, and bottom is cone shape cone type structure, and has one or more charging aperture.The feedstock direction of charging aperture can be the tangential direction of barrel; Each charging aperture can be in same plane, also can be in Different Plane.The feedstock direction of charging aperture also can be vertical with the axial direction of cylinder or be 1-180 ° of angle with the axial direction of cylinder, preferred 20-110 ° of angle, more preferably 70-100 ° of angle, 85-95 ° of angle most preferably, the feedstock direction of each charging aperture to any direction between the tangential direction of this cross section, is preferably the tangential direction of this cross section at the radial direction that is projected as this cross section of the cross section vertical with the cylinder axle center.
Preferably, step 2) use the tank container of arbitrary shape, more preferably use columniform tank container.
The method of described recovery solvent can be used any known method in this area, as the method for the solvent by vaporization by surface condensation or direct condensation by contact reclaimed.When using the method for direct condensation contact, cooling agent can adopt water.
Technical characterstic of the present invention has following 3 points:
I. technical characterstic of the present invention is that Technological adaptability is strong: both can with technique is simple, the slightly poor rubber solutions of fillers dispersed and properties of product have generally mixed with filler, additive and directly heating means prepare rubber/filler/additive rubber master batch, the rubber/filler of the higher but better performances of dispersal device, mixing knockouts and the mechanical drying method manufacturing cost that can utilize again particular design/additive rubber master batch; Masterbatch prepared by different process can reasonably adapt to the needs of different rubbers.
Ii. technical characterstic of the present invention is the cohesion of rubber/filler/additive/solvent mixture and the mode of desolventizing: rubber/filler/additive/solvent mixture directly pass into character especially the liquid medium of polarity and solvent for use different in kind make mixture deswelling cohesion, and medium temperature is during higher than solvent boiling point, solvent rapidly volatilization form the masterbatch that contains heat medium.This masterbatch after heat medium is removed in heating the masterbatch product, liquid medium used includes but not limited to water.
Iii. technical characterstic of the present invention is that agglomeration step technique is simple, does not require baroque knockouts, and equipment cost is low.
The specific embodiment
Below with embodiment, further describe the present invention, but scope of the present invention is not subject to the restriction of these embodiment.
(1) in embodiment, experimental data is measured with following instrument and equipment and assay method:
Instrument and equipment prepared by table 1 rubber sample
| Sequence number | Device name | Specifications and models | Manufacturer |
| 1 | Banbury | XSM-1/10-120 | Shanghai Kechuang rubber and plastics machine equipment Co., Ltd |
| 2 | Mill | 152.5*320 | Zhanjiang Machine Factory, Guangdong Prov. |
| 3 | Vulcanizing press | XLB-D600*600 | East, Huzhou, Zhejiang machinery Co., Ltd |
The method of testing of table 2 vulcanizating glue physical performance and instrument
(2) embodiment and Comparative Examples
Raw material:
Synthetic polyisoprenes rubber, IR-70, her Cohan new material Co., Ltd of Qingdao;
White carbon, NEWSIL1165-MP, Wuxi really becomes silicon industry Co., Ltd;
Zinc oxide, Dalian zinc oxide factory;
Stearic acid, PF1808, Co., Ltd is found into by Malaysia;
Antioxidant 4020, the holy chemical Co., Ltd difficult to understand in Jiangsu;
Silane coupler Si69, NanJing Shuguang Chemical Group Co., Ltd.;
Accelerant CZ, Shandong is Shun's chemical industry Co., Ltd still;
Diphenylguanidine PG, Dan County, Shandong chemical industry Co., Ltd;
Sulfur, Wudi Jin Sheng chemical industry Co., Ltd.
Comparative Examples 1
In banbury, 56 parts of white carbons, 5.6 parts of silane coupler Si69 are joined in 100 parts of synthesizing cis polyisoprene, carry out mixing, after filler is sneaked into rubber, add discharging from banbury in mixing 4 minutes again after 3.5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of antioxidant 4020s, then in mill, cross sheet under roller and obtain premixing glue.After parking 8 hours, 2 parts of accelerant CZs, 1 part of diphenylguanidine PG and 1.8 parts of Sulfurs are added in premixing glue and make elastomeric compound in mill.Sheet under mill after parking 8 hours, vulcanizes to optimum cure in 150 ℃ of vulcanizing presses, makes dry method vulcanizate 1.
Embodiment 1
56 parts of white carbons, 5.6 parts of silane coupler Si69,3.5 parts of zinc oxide are joined in the normal hexane solution of 100 part of 12% cis-polyisoprene, after its rubber/white carbon/Si69/ normal hexane mixture just mixes with blade paddle mixer, mixture is sprayed into to swan neck more than by a nozzle and make mixed liquor clash into the dispersion that increases filler at the Guan Zhongyu tube wall.Then mixture is joined in grinder continuously and carry out essence and disperse, obtain smart dispersed mixture, then mixture is directly sprayed into continuously under the pressure of 0.2MPa approximately in the water of 95 ℃ and condense.By cohesion the micelle of desolventizing after filtration, drying obtains rubber master batch 1.
Embodiment 2
56 parts of white carbons, 5.6 parts of silane coupler Si69,3.5 parts of zinc oxide are joined in the normal hexane solution of 100 part of 12% cis-polyisoprene, after its rubber/white carbon/Si69/ normal hexane mixture just mixes with blade paddle mixer, mixture is sprayed into to swan neck more than by a nozzle and make mixed liquor clash into the dispersion that increases filler at the Guan Zhongyu tube wall.After mixture is joined continuously in grinder and carries out essence and disperse, obtain smart dispersed mixture, then mixture is directly sprayed under the pressure of 30MPa in the water of 95 ℃ and is condensed.By cohesion the micelle of desolventizing after filtration, obtain rubber master batch 2 after drying.
Comparative Examples 2
56 parts of white carbons, 5.6 parts of silane coupler Si69,3.5 parts of zinc oxide are joined in the normal hexane solution of 100 part of 12% cis-polyisoprene, after its rubber/white carbon/Si69/ normal hexane mixture just mixes with blade paddle mixer, mixture is sprayed into to swan neck more than by a nozzle and make mixed liquor clash into the dispersion that increases filler at the Guan Zhongyu tube wall.After mixture is joined continuously in grinder and carries out essence and disperse, obtain smart dispersed mixture, then mixture is injected in knockouts under the pressure of 30MPa to the nitrogen that is simultaneously 180 ℃ by two other entrance implantation temperature through two entrances in the cone cartridge type knockouts that four entrances are arranged.The gained mixture sprays into continuously and is filled with approximately drier desolventizing, the drying of 150 ℃ of nitrogen, forms the solid powdery material, and rubber master batch 3.
The rubber master batch of above-mentioned gained 1, rubber master batch 2 and rubber master batch 3 are added to discharging from banbury in mixing 4 minutes again after 2 parts of stearic acid, 2 parts of antioxidant 4020s in banbury, and sizing material is crossed roller, lower in mill.Mixing parking after 8 hours adds discharging from banbury in mixing 1.5 minutes again after 2 parts of accelerant CZs, 1 part of diphenylguanidine and 1.8 parts of Sulfurs again in banbury.Sheet under mill after parking 8 hours, vulcanizes to optimum cure in 150 ℃ of vulcanizing presses, makes respectively wet method vulcanizate 1,2 and 3.
The physical property of table 3 vulcanizate
As known from Table 3, under same recipe, the different cured properties that prepare of condensing method that adopt due to the wet method elastomeric compound also have difference, with maskerbatch of dry process, compare, in wet masterbatch, the degree of scatter of filler in rubber improved greatly, the hot strength of vulcanizate, resilience and wearability obviously improve, and the compression fatigue heat-dissipating decreases.Wet method vulcanizate 1,2 is compared performance with wet method vulcanizate 3 and is more or less the same, but embodiment 1 compares with the preparation method of Comparative Examples 2 with 2 preparation method, does not use the knockouts of particular design, has advantage cheaply.
Claims (13)
1. the method for continuously producing of a rubber masterbatch, comprise the steps:
Step 1): filler is joined in rubber solutions, by stirring, form rubber/filler/solvent mixture;
Step 2): the rubber/filler in step 1)/solvent mixture is directly passed in the heat medium of temperature higher than solvent boiling point, the polarity of this heat medium is different from the polarity of solvent for use, mixture coagulated deswelling, and solvent volatilizees rapidly, thus rubber/filler compound that formation contains this heat medium and the mixture of solvent;
Step 3): desolvation also carries out drying to described mixture, obtains rubber/filler masterbatch.
2. method according to claim 1, wherein step 2) can implement with any container.
3. method according to claim 1, wherein step 2) implement the pref. cylindrical tank container in tank container.
4. method according to claim 1, wherein optional recycling step 3) solvent that removes, recycle.
5. method according to claim 1, wherein in step 1) and/or step 2) in optionally add one or more and be selected from the additive of oil, age resistor, coupling agent, activating agent, antioxidant, fire retardant, heat stabilizer, light stabilizer, dyestuff, pigment, vulcanizing agent and promoter.
6. according to the arbitrary described method of claim 1-5, wherein said heat medium is water vapour, in dried solid mixture, can contain water, then obtains rubber/filler masterbatch through vacuum drying, heat drying or extruding heat drying except after anhydrating.
7. according to the arbitrary described method of claim 1-5, wherein said heat medium is water, described solvent is that boiling point is lower than 100 ℃ of varsols, can contain water in dried solid mixture, then obtain rubber/filler masterbatch through vacuum drying, heat drying or extruding heat drying except after anhydrating.
8. according to the arbitrary described method of claim 6-7, wherein said heat drying is oven dry or air-dry.
9. according to the arbitrary described method of claim 6-7, wherein said extruding heat drying removes after heat medium further dry again for first extruding.
10. method according to claim 9, wherein said further drying is air-dry, oven dry or mechanical drying.
11. method according to claim 10, wherein said mechanical drying is for being used mill, masticator, banbury, continuous internal mixer, single screw extrusion machine, and double screw extruder carries out drying.
12. the rubber masterbatch prepared according to the described method of claim 1-11.
13. a rubber, it uses rubber masterbatch according to claim 12 to prepare.
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| CN201310337559.9A CN103419291B (en) | 2013-08-05 | 2013-08-05 | Rubber masterbatch prepared by the method for continuously producing of rubber masterbatch and the method |
| MX2016001563A MX2016001563A (en) | 2013-08-05 | 2014-07-22 | Continuous manufacturing process for rubber masterbatch and rubber masterbatch prepared therefrom. |
| PCT/CN2014/082711 WO2015018279A1 (en) | 2013-08-05 | 2014-07-22 | Continuous manufacturing process for rubber masterbatch and rubber masterbatch prepared therefrom |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277255A (en) * | 2014-11-03 | 2015-01-14 | 怡维怡橡胶研究院有限公司 | Application of rubber master batch prepared continuously in hard bead filler of truck tyre |
| CN104311929A (en) * | 2014-11-03 | 2015-01-28 | 怡维怡橡胶研究院有限公司 | Application of continuously prepared rubber masterbatch in sedan tire tread rubber |
| WO2015018279A1 (en) * | 2013-08-05 | 2015-02-12 | 怡维怡橡胶研究院有限公司 | Continuous manufacturing process for rubber masterbatch and rubber masterbatch prepared therefrom |
| CN104387625A (en) * | 2014-11-03 | 2015-03-04 | 怡维怡橡胶研究院有限公司 | Application of continuously-prepared rubber masterbatch in soft bead filler of truck tire |
| CN104387628A (en) * | 2014-11-03 | 2015-03-04 | 怡维怡橡胶研究院有限公司 | Application of continuously prepared rubber master batch in sidewall rubber of truck tires |
| CN104742268A (en) * | 2015-04-01 | 2015-07-01 | 苏州第一元素纳米技术有限公司 | Preparation method of master batch |
| WO2017041753A1 (en) * | 2015-09-11 | 2017-03-16 | 怡维怡橡胶研究院有限公司 | Continuous manufacturing method of rubber masterbatch, and rubber masterbatch manufactured by same |
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| CN115975269A (en) * | 2023-02-16 | 2023-04-18 | 江苏通用科技股份有限公司 | Composition for preparing eucommia ulmoides gum base rubber composite material and preparation method thereof |
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| CN103419291B (en) * | 2013-08-05 | 2016-04-27 | 怡维怡橡胶研究院有限公司 | Rubber masterbatch prepared by the method for continuously producing of rubber masterbatch and the method |
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- 2013-08-05 CN CN201310337559.9A patent/CN103419291B/en active Active
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| CN103205001A (en) * | 2013-01-10 | 2013-07-17 | 怡维怡材料研究院有限公司 | Dispersion method for filling material in rubber solution |
| 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 |
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| CN103224659A (en) * | 2013-03-25 | 2013-07-31 | 怡维怡材料研究院有限公司 | Filler, synthetic rubber and wet rubber compound integrated production method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2015018279A1 (en) * | 2013-08-05 | 2015-02-12 | 怡维怡橡胶研究院有限公司 | Continuous manufacturing process for rubber masterbatch and rubber masterbatch prepared therefrom |
| CN104277255A (en) * | 2014-11-03 | 2015-01-14 | 怡维怡橡胶研究院有限公司 | Application of rubber master batch prepared continuously in hard bead filler of truck tyre |
| CN104311929A (en) * | 2014-11-03 | 2015-01-28 | 怡维怡橡胶研究院有限公司 | Application of continuously prepared rubber masterbatch in sedan tire tread rubber |
| CN104387625A (en) * | 2014-11-03 | 2015-03-04 | 怡维怡橡胶研究院有限公司 | Application of continuously-prepared rubber masterbatch in soft bead filler of truck tire |
| CN104387628A (en) * | 2014-11-03 | 2015-03-04 | 怡维怡橡胶研究院有限公司 | Application of continuously prepared rubber master batch in sidewall rubber of truck tires |
| CN104277255B (en) * | 2014-11-03 | 2017-01-25 | 怡维怡橡胶研究院有限公司 | Application of rubber master batch prepared continuously in hard bead filler of truck tyre |
| CN104387625B (en) * | 2014-11-03 | 2017-04-12 | 怡维怡橡胶研究院有限公司 | Application of continuously-prepared rubber masterbatch in soft bead filler of truck tire |
| CN104742268A (en) * | 2015-04-01 | 2015-07-01 | 苏州第一元素纳米技术有限公司 | Preparation method of master batch |
| WO2017041753A1 (en) * | 2015-09-11 | 2017-03-16 | 怡维怡橡胶研究院有限公司 | Continuous manufacturing method of rubber masterbatch, and rubber masterbatch manufactured by same |
Also Published As
| Publication number | Publication date |
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| WO2015018279A1 (en) | 2015-02-12 |
| CN103419291B (en) | 2016-04-27 |
| MX2016001563A (en) | 2016-11-25 |
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