CN103600434B - Rubber masterbatch prepared by the method for continuously producing of rubber masterbatch and the method - Google Patents
Rubber masterbatch prepared by the method for continuously producing of rubber masterbatch and the method Download PDFInfo
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- CN103600434B CN103600434B CN201310337578.1A CN201310337578A CN103600434B CN 103600434 B CN103600434 B CN 103600434B CN 201310337578 A CN201310337578 A CN 201310337578A CN 103600434 B CN103600434 B CN 103600434B
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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
- B29B7/002—Methods
- B29B7/007—Methods for continuous mixing
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/02—Chemical or physical treatment of rubber latex before or during concentration
- C08C1/075—Concentrating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/14—Coagulation
-
- 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
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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
-
- 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
- C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
-
- 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
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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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
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/06—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices
- B29B7/10—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary
-
- 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
Abstract
The invention discloses rubber masterbatch prepared by the method for continuously producing of rubber masterbatch and the method, manufacture method comprises the steps: step 1): joined by filler in rubber solutions, forms rubber/filler/solvent mixture by stirring; Step 2): the rubber/filler/solvent mixture in step 1) is condensed, obtains the mixture of rubber/filler compound and solvent; Step 3): desolvation also carries out drying to described mixture, obtains rubber/filler masterbatch.The invention still further relates to masterbatch prepared by a kind of said method and the rubber using this masterbatch to prepare.Compared with dry technology in mixing with existing wet method, the present invention is to rubber, filler without particular/special requirement, and the scope of application is wider.Production technology continuously, efficient, consume energy low, few artificial, thus cost is lower.The masterbatch using the method to prepare is all very superior in processing characteristics, physical and mechanical properties, product quality.
Description
Technical field
The present invention relates to rubber materials, particularly the rubber masterbatch prepared of the method for continuously producing of rubber masterbatch and the method.
Background technology
In rubber/filler/additive/dicyandiamide solution, rubber/filler/additive is manufacture critical step in rubber/filler/additive rubber master batch from the cohesion solvent.This process described in WO98/58985 is that large-scale blade-carrying worm gear drying machine carries out in the device of 400/1200 turn per minute, and the cohesion of this method and rate of drying are comparatively slow, and technical process is long, consumes energy high.The present invention relates to several mixed at high speed/condensing method, wherein condense medium and comprise gas, especially high-temperature gas and liquid mix under the state of high energy turbulent flow instantaneously with rubber/filler/additive agent mixture, due to the high-temperature effect of gas and the difference of liquid medium and solvent polarity aspect, the rubber/filler/additive in rubber/filler/additive/solvent mixture will produce desolvation agent phenomenon in a solvent and condense.Due to high velocity turbulent flow effect, namely mixture and cohesion medium move back being blended in the very short time of solvent medium and can complete.Because the interface of moving back solvent medium and rubber/filler/additive/solvent increases greatly, rubber/filler/additive cohesion speed in a solvent quickly, if the temperature of moving back solvent medium is higher, solvent will volatilize rapidly in coacervation process, cause cohesion micelle less, therefore coagel solvent volatilization and desiccation accelerate further.Therefore, compared with the conventional method, the drying means designed by the application has feature that is efficient, energy-conservation and continued operation.
Summary of the invention
For the problem of prior art, the object of this invention is to provide rubber masterbatch prepared by a kind of method for continuously producing of rubber masterbatch and the method.Another object of the present invention is to provide a kind of rubber using 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) uniform drying and speed is fast;
3) physical and mechanical properties of vulcanizate and the quality of rubber is significantly improved;
4) compared with the condensation technique in mixing with existing wet method, the present invention to rubber, filler without particular/special requirement, 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 artificial, thus cost is lower;
6) rubber master batch using the method to prepare is all very superior in processing characteristics, physical and mechanical properties, product quality.
The invention further relates to following embodiment:
A method for continuously producing for rubber masterbatch, comprises the steps:
Step 1): joined by filler in rubber solutions, forms rubber/filler/solvent mixture by stirring;
Step 2): the rubber/filler/solvent mixture in step 1) is condensed, obtains the mixture of rubber/filler compound and solvent;
Step 3): desolvation also carries out drying to described mixture, obtains rubber/filler masterbatch;
Wherein, drying in step 3) refers to step 2) in the mixture that obtains proceed in heating belt type drying machine, heat drying under vacuum or inert gas, during the solvent volatilized and rubber synthesize, unreacted monomer enters in condenser and fractionating column and reclaims; Or the drying in step 3) refers to step 2) in the mixture that obtains carry out spraying dry or flash distillation, heat medium used is inert gas or water vapour, and during the solvent volatilized and rubber synthesize, unreacted monomer enters in condenser and fractionating column and reclaims.
Preferably, wherein in step 2) described in cohesion can for flocculant flocculence, heating, the one of moving back in solvent method, multiple or combination.
Preferably, wherein optional recycling step 3) solvent that removes, recycle.
Preferably, wherein in step 1) and/or step 2) in optional add the additive that one or more are selected from oil, age resistor, coupling agent, activating agent, antioxidant, fire retardant, heat stabilizer, light stabilizer, dyestuff, pigment, vulcanizing agent and promoter.
Preferably, wherein use water vapour to be heat medium, in dried solid mixture, can water be contained, then obtain rubber/filler masterbatch after vacuum drying, heat drying or extruding heat drying.
Preferably, wherein said inert gas is nitrogen.
More preferably, wherein said heat drying is oven dry or air-dry.
More preferably, wherein said extruding heat drying is dry further again after first extruding removes water.
More preferably, wherein said further drying be air-dry, dry or mechanical drying.
More preferably, wherein said mechanical drying is for using 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, present invention also offers a kind of rubber adopting above-mentioned masterbatch to prepare.
The method for continuously producing of rubber masterbatch of the present invention comprises the steps:
Step 1): joined by filler in rubber solutions, forms rubber/filler/solvent mixture by stirring;
Step 2): the rubber/filler/solvent mixture in step 1) is condensed, obtains the mixture of rubber/filler compound and solvent;
Step 3): desolvation also carries out drying to described mixture, obtains rubber/filler masterbatch;
Wherein, drying in step 3) refers to step 2) in the mixture that obtains proceed in heating belt type drying machine, heat drying under vacuum or inert gas, during the solvent volatilized and rubber synthesize, unreacted monomer enters in condenser and fractionating column and reclaims; Or the drying in step 3) refers to step 2) in the mixture that obtains carry out spraying dry or flash distillation, heat medium used is inert gas or water vapour, and during the solvent volatilized and rubber synthesize, unreacted monomer enters in condenser and fractionating column and reclaims.
Wherein in step 2) described in condensing method can use any known method in this area, as flocculant flocculence, heating, move back solvent method etc. one, multiple or combination.The method for continuously producing of rubber masterbatch of the present invention also optionally comprises recycling step 3) solvent that removes is with the step recycled.In addition, in step 1) and/or step 2) in optional add the additive that one or more are selected from oil, age resistor, coupling agent, activating agent, antioxidant, fire retardant, heat stabilizer, light stabilizer, dyestuff, pigment, vulcanizing agent and promoter.
Step 1) can use method well known in the art to realize.Stirring described in step 1) can use 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 dividedly can to implement in the following way: sprayed, to improve the dispersion of filler and/or additive when high pressure high shear by a nozzle by the mixture of above-mentioned stirring gained; Above-mentioned ejecta is made to make mixed liquor clash into the dispersiveness increasing filler and/or additive at Guan Zhongyu tube wall by swan neck more than; Or make ejecta convert shear stress by the bore pipeline that repeatedly folding and unfolding changes and increase the dispersion of filler and/or additive.Pressure limit used from 0.1MPa to 60MPa, preferred 10MPa to 40MPa.
Described finely divided rear formed mixture can also improve filler and/or the dispersion of additive in rubber solutions further by following essence dispersion:
I. by described finely divided after mixture add continuously in ball mill and/or colloid mill and disperse, filler and/or additive are dispersed in rubber solutions uniformly;
Ii. by described finely divided after mixture join continuously in grinder and carry out grinding to make filler and/or additive be well dispersed in rubber solutions, this grinder has the plane mill of one or more groups high-speed rotation and to be fixed on grinder sleeve and the fixing pin alternate with plane mill or price fixing.
Iii. by described finely divided after mixture join in grinder continuously and grind, this grinder has two contrary blades of rotation direction, described blade has pore chute, under high pressure can improve filler and/or the degree of scatter of additive in rubber solutions by the blade rotated.Pressure limit used from 0.1MPa to 60MPa, preferred 10MPa to 40MPa.
Iv. by described finely divided after mixture join in multi-layer high-voltage slit dispersion machine continuously, mixture is under high pressure extruded from slit between two-layer, and the Strong shear power now produced can improve filler and/or the degree of scatter of additive in rubber solutions.Pressure limit used from 0.1MPa to 60MPa, preferred 10MPa to 40MPa.
V. by described finely divided after mixture join continuously in power decentralized device and disperse, the rotor of the High Rotation Speed of described power decentralized device has many radially-arranged slits or hole, mixture with high-speed impact on stator surface to make filler and/or additive be evenly dispersed in rubber solutions.
Two or more use of can mutually connecting in above-mentioned five kinds of finely divided methods.
Described rubber solutions can directly directly obtain from preparing solution polymerized rubber production line, also the dry glue of any type can be dissolved preparation in the solvent of this glue.When preparing rubber solutions with dry glue, 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 is polymerized gained (i.e. solution polymerized rubber) in the solution, monomer is polymerized gained (i.e. emulsion polymerized rubber) in emulsion, monomer body carries out polymerization gained.When described rubber solutions directly from prepare obtain solution polymerized rubber production line time, described solution polymerized rubber is for using ethene, propylene, butylene, amylene, hexene, heptene, the triolefin of the diene of 4-7 carbon atom or 6-7 carbon atom, or containing the homopolymerization of the vinyl monomer of other atom or functional group or copolymerized polymer, other atoms described or functional group are silicon atom, fluorine atom, chlorine atom, nitrogen-atoms, oxygen atom, sulphur atom, ester group, amino ester group, cyano group, also the homopolymers containing above-mentioned monomer and copolymer is comprised, comprising but be not limited to polybutadiene, polyisoprene, butadiene-styrene rubber, second third glue, butyl rubber, NBR, neoprene, silicon rubber, fluorubber, polyurethane rubber, CSM, ACM etc.The molecular weight of rubber is 1 thousand to 4,000 ten thousand, preferably 5 thousand to 3,000 ten thousand, more preferably 1 ten thousand to 800 ten thousand.
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 naptha, 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.Rubber concentration range is in the solution 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 agent used in rubber and filler, as the nanometer materials of all kinds of carbon black, 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 the two-phase of the composition such as carbon black, silica, aluminium oxide, magnesia, zinc oxide, calcium oxide, titanium oxide, boron oxide or heterogeneous filler, for two-phase or heterogeneous filler, its oil factor is 20 to 250ml/100g, preferably 25 to 200ml/100g, more preferably 30 to 150ml/100g.The consumption of filler is 5 to 300 weight portions (be 100 parts by weight with rubber), preferably 10 to 200 weight portions, more preferably 30 to 150 weight portions.That described filler also to comprise in above-mentioned filler two or more and use thing.
Described filler also comprises their surface modifying stuffing.Wherein said surface modification can be by chemical reaction certain functional group be connected on filling surface or be combined on filling surface by physics mode by modifier by mixing or adsorb.Described modification, mixes with filler after modifier can being dissolved in solvent and carries out liquid phase modification, as WangW, NanseG, VidalA, etal.K.G.K [J], 1994, described in 47:493, also modifier and filler Hybrid Heating can be carried out solid-state modification, as WangMJ, Wolff.S.R.C.T [J], described in 1992,65:715.Surface modification also can be carried out before adding in rubber solutions by filler, or carried out surface modification in mixture modifier being joined rubber solutions and filler.Described modifier is the modifier of this area routine, such as with the organo silane coupling agent that following general formula represents:
(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, as q=1, A is-SCN ,-SH ,-Cl ,-NH
2;
As q=2, A is-S
x-;
The alkyl that R and R ' is the branching of carbon atom from 1 to 4 or straight chain or phenolic group, R with R ' can be identical, also can be different;
N is 0,1 or 2;
Alk is the straight or branched alkyl containing 1 to 6 carbon atom;
Alk
enyl is the straight or branched thiazolinyl containing 1 to 6 carbon atom;
M is 0 or 1;
Ar is the aryl containing 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) tetrasulfide and disulphide, 3-thiocyanogen propyl-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.
Filler and/or additive can directly join in rubber solutions by step 1) of the present invention, also first filler and/or additive can be joined and to add after being mixed to form uniform suspension in the solvent identical or different with rubber solutions again and to be mixed in rubber solutions by stirring.Additive can optionally comprise in the additive of oil, age resistor, coupling agent, activating agent, antioxidant, heat stabilizer, light stabilizer, fire retardant, dyestuff, pigment, vulcanizing agent or promoter one or more.The consumption of additive therefor is conventional amount used, or adjusts according to the requirement of actual conditions.
Step 2) described in cohesion can for flocculant flocculence, heating, the one of moving back in solvent method, multiple or combination.
Preferably, in step 2) in the rubber/filler in step 1)/solvent mixture is sent in knockouts, and contact with nitrogen, steam, water, filler water slurry and one or more fluid-phases in oil in knockouts and mix rear cohesion, obtain the mixture of rubber/filler compound and solvent.
Step 2) the middle knockouts used can for having the tubular type knockouts of one or more charging aperture, the feedstock direction of wherein said charging aperture can to condense the axial direction of organ pipe parallel with tubular type, outlet is in the end of pipe, the axial direction that also can condense organ pipe with tubular type is 1-180 ° of angle, preferably in 20-120 ° of angle, more preferably in 70-100 ° of angle, most preferably in 85-95 ° of angle.When charging aperture is multiple, the feedstock direction of part charging aperture is parallel with the axial direction that tubular type condenses organ pipe; The axial direction of the feedstock direction of remaining charging aperture and the cylinder of tubular type knockouts is 1-180 ° of angle, preferably in 20-120 ° of angle, more preferably in 70-100 ° of angle, most preferably in 85-95 ° of angle, the feedstock direction of each charging aperture radial direction being projected as this cross section on the cross section of pipe axis perpendicular to this cross section tangential direction between any direction, be preferably radial direction, or be tangential direction.Described charging aperture is all on the same plane perpendicular from the axis of pipe or described charging aperture is in different planes.
Step 2) in the knockouts that uses also can be by two or three above knockouts of forming of mutually concentric pipes, wherein each pipe has one or more charging aperture, the feedstock direction of described charging aperture is be parallel to the axial direction of pipe or the tangential direction for pipe, and outlet is in the end of 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 in same plane, also can from inside to outside the charging aperture of each pipe end successively end that the is elongated or charging aperture of each pipe from inside to outside shorten successively.
Step 2) in the knockouts that uses also can be cartridge type knockouts, this cartridge type knockouts only has a charging aperture, on the upper end that this charging aperture is positioned at cartridge type knockouts or barrel, exports the lower end being in cylinder.Fluid directly can inject knockouts by charging aperture, also can inject knockouts along barrel with the direction of tangent line.
Step 2) in use knockouts can be also tubular for top, 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 ° angle, more preferably 70-100 ° of angle, most preferably 85-95 ° of angle, the feedstock direction of each charging aperture the cross section of cylinder axis perpendicular the radial direction being projected as this cross section to this cross section tangential direction between any direction, be preferably the tangential direction of this cross section.
Step 2) described in nitrogen, steam, water, filler water slurry and oil in one or more fluids and step 1) in rubber/filler/solvent mixture of obtaining enter knockouts by one or more charging aperture, wherein the temperature of nitrogen is 20-300 DEG C, the temperature of steam is 100-300 DEG C, the temperature of liquid water is 20-100 DEG C, the temperature of oil is 20-300 DEG C, and the temperature of filler water slurry is 20-100 DEG C.Described oil is that rubber materials manufactures the conventional oil of oil-extended rubber.In step 1) the optional oil used can with step 2) in the oil that uses identical or different.The filler used in step 1) can with step 2) in the filler that uses identical or different.
Drying in step 3) refers to step 2) in the mixture that obtains proceed in heating belt type drying machine, heat drying under vacuum or inert gas (such as nitrogen), during the solvent volatilized and rubber synthesize, unreacted monomer enters in condenser and fractionating column and reclaims; Or by step 2) in the mixture that obtains carry out spraying dry or flash distillation, heat medium used is inert gas (such as nitrogen) or water vapour, and in the solvent volatilized and rubber synthesis, unreacted monomer enters in condenser and fractionating column and reclaims.
Wherein when using water vapour for heat medium, in dried solid mixture, can water be contained, then obtain rubber/filler masterbatch after vacuum drying, heat drying or extruding heat drying.It is dry that described vacuum drying comprises normal-temperature vacuum drying, vacuum freezedrying and heating, vacuum.Described heat drying can be general drying mode, such as oven dry or air-dry.Described extruding heat drying is dry further again after first extruding removes heat medium, wherein said further drying be air-dry, dry or mechanical drying, described mechanical drying is for using mill, masticator, banbury, continuous internal mixer, single screw extrusion machine, and double screw extruder carries out drying.
The method of described recycling design can use any known method in this area, as the method for the solvent of vaporization by surface condensation or direct condensation by contact reclaimed.When using the method for direct chilled contact, cooling agent can adopt water.
Technical characterstic following points of the present invention:
I. technical characterstic of the present invention is that Technological adaptability is strong: both can be simple by technique and filler dispersed and properties of product are slightly poor rubber solutions generally mixes with filler, additive and directly heating means prepare rubber/filler/additive rubber master batch, can utilize again the dispersal device of particular design, mix knockouts and the higher but rubber/filler/additive rubber master batch of better performances of mechanical drying method manufacturing cost; Masterbatch prepared by different process reasonably can adapt to the needs of different rubber.
Ii. technical characterstic of the present invention is the knockouts adopting particular design, and it is one and exports by one or more import and one device formed.When the rubber/filler/additive/solvent mixture through essence dispersion injects knockouts under the state of the high turbulent flow of high speed, because speed is very high, according to hydrodynamics and turbulent fluid mechanics principle, the hurried decline of mixture internal pressure.Under high shear forces, mix logistics will form fine drop, the low boiling point solvent in addition under low pressure in liquid mixture may reach its boiling point, and solvent accelerates volatilization, and solvent is separated with mixture.This separation process also can, by the mixture droplets containing a large amount of solvent vapo(u)r being gushed out from knockouts realization by a narrow and small outlet, make pressure greatly decline due to the increase of flow velocity, thus the gasification rate of solvent and degree strengthen greatly.When this fluid-mixing sprays in the drying device of high-temperature gas such as nitrogen, the rising of temperature makes solvent be diffused into rapidly in hot atmosphere by mixture drying efficiency is improved greatly.
Iii. the mode of above-mentioned cohesion desolventizing of the present invention is one or two injection rubber/filler/additive/solvent mixture in multiple imports of knockouts, and passes into nitrogen by other one or more imports.When the mixture entered and gas are all in high energy and high speed turbulence state, both mixing can complete within several milliseconds of times to several ms and mixture becomes drop at this moment.Solvent in drop is undergoes rapid expansion gasification under the low pressure of turbulent flow, and makes the rubber in mixture/hurried cohesion of filler/additive component and form the solid-liquid/gas three-phase mixture of dispersion.In the process, when injecting the nitrogen temperature in knockouts and being higher, the cohesion speed of the expansion of solvent, gasification and solid will improve greatly, and liquid phase composition declines greatly.In extreme circumstances, solid, the gas two-phase only had solid condensation product and formed by nitrogen and solvent vapo(u)r is become.When three-phase or two-phase mixture are by outlet that knockouts is narrow and small, make due to the increase of flow velocity fluid pressure reduce further and cause the gasification degree of solvent and speed greatly to increase, liquid phase reduces rapidly.After fluid-mixing sprays into the drying device of high-temperature gas such as nitrogen atmosphere, the rising due to temperature make to remain in solvent in rubber/filler/additive condensation product further rapidly volatilization diffuse in hot phase, and drying efficiency is improved greatly.
Iv. a mode of above-mentioned cohesion of the present invention and desolventizing is if when additive comprises oil, by being injected rubber/filler/additive (wherein do not contain or only contain the required oil of part sizing material)/solvent mixture under high-voltage high-speed by one or two in multiple imports of knockouts, and inject oil by other one or more imports.The amount of oil is used the difference of oil mass in rubber master batch formula aequum and rubber/filler/additive/solvent mixture.Mixture and oil mix rapidly when high energy turbulent flow and condense, and the low pressure of high velocity turbulent flow fluid will make solvent gasify rapidly and be separated with rubber/filler/additive compound.As improved the temperature of oil, because the thermal capacity of oil is large, the gasification of solvent will speed up.After formed solid, liquid, gas smoke-like mixture sprays at a high speed the drying device containing high-temperature gas by narrow and small outlet, smoke-like solid liquid phase dispersity makes it increase the contact area with gas phase further due to the reduction of fluid pressure during ejection, thus the gasification rate of solvent is accelerated, high-temperature atmosphere also will improve the efficiency of desolventizing greatly simultaneously.
V. a mode of the above-mentioned cohesion of the present invention and desolventizing under high-voltage high-speed, injects rubber/filler/additive/solvent mixture by one or two import in the multiple import of knockouts, and inject high-pressure water vapor by other one or more entrances.Water move back solvent action and high temperature action under, rubber/filler/additive completes cohesion in a solvent in several milliseconds to several ms, and under low pressure in smoke-like, solvent volatilizees in a large number.Due to the latent heat of steam liquefied, the speed that solvent is gasified is fast compared with hot nitrogen many.But also add moisture in the smoke-like solid, liquid, gas three-phase mixture formed.When this mixture under high pressure sprays into high-temperature gas at a high speed by the narrow and small outlet of knockouts, due to the reduction of pressure and the further rising of temperature, water gasifies with solvent and is separated with solid phase rubber/filler/additive compound and enters gas phase, and the drying efficiency of compound is improved.
Vi. a kind of mode of the above-mentioned cohesion of the present invention and desolventizing is by rubber/filler/additive/solvent mixture one or two injection mixing/knockouts under the condition of high-voltage high-speed in the multiple import of knockouts, and water especially high-temperature water is injected knockouts in the condition of high-voltage high-speed from all the other imports simultaneously.Under the state of high energy turbulent flow, water moves back solvent action to rubber solutions in addition, and rubber/filler/additive completes cohesion within several milliseconds of times to several ms.Due to the low pressure property of high energy turbulent flow, especially when using high-temperature water, solvent reaches rapidly its boiling point and volatilizees, and water is partial gasification also.When after the drying device that the outlet that the solid, liquid, gas three-phase mixture in knockouts is under high pressure narrow and small by it is ejected to containing high temperature air or nitrogen, because the low-pressure fluid formed at a high speed will be dispersed in high-temperature hot air or hot nitrogen with vaporific.The moisture made wherein and solvent volatilize again by huge specific area and the low pressure of the rubber/filler condensed in smog/additive solid-liquid phase further, and solid composite moisture and solvent seasoning effect are increased.As the dilutional hyponatremia injected in knockouts, the complex after rubber/filler/additive cohesion may be blended in water.Now, the compound of moisture content is separated with water by general separation method such as filters, centrifugal etc., then carries out drying.
Vii. a kind of mode of the above-mentioned cohesion of the present invention and desolventizing is that one or several when high-voltage high-speed in the multiple import of knockouts of rubber/filler/additive/solvent mixture is injected knockouts, and by filler water slurry, preferred high temperature filler water slurry, under the condition of high-voltage high-speed, also inject knockouts from other imports simultaneously.Under the state of high energy turbulent flow, water moves back solvent action to rubber solutions in addition, and rubber/filler/additive/solvent and filler water slurry Homogeneous phase mixing, condensing upon in several milliseconds to several ms of rubber/filler/additive completes.Due to the low pressure property of high energy turbulent flow, when especially using high temperature filler water slurry, namely solvent reaches rapidly its boiling point and volatilizees, and water is partial gasification also.When the solid, liquid, gas three-phase mixture in mixing/knockouts under high pressure by its narrow and small outlet after entering gathering-device, because the low-pressure fluid formed at a high speed will be dispersed in high temperature air or nitrogen with vaporific.On the one hand because pressure is very low, on the other hand because the contact surface of solid, liquid phase and gas increases greatly, solvent and moisture are wherein diffused into rapidly in gas phase.As injected the dilutional hyponatremia of the filler water slurry of knockouts and the water after spraying can not volatilize completely, complex after rubber/filler/additive cohesion may be blended in water, now by general separation method, the compound of moisture content is separated with water by such as filter, centrifugal etc., then carries out drying.
Viii. technical characterstic of the present invention the solid rubber master batch particle of cohesion, desolventizing in knockouts can be separated to obtain masterbatch through separator with solvent gas when passing into high temperature inert gas in knockouts.Separator includes but not limited to cyclone separator.This kind of technology makes not contact water in whole rubber master batch manufacture process.
Ix. when technical characterstic of the present invention is moisture in complex after the cohesion of any rubber/filler/additive, by filtering, extruding and dewater, more at high temperature by mechanical means drying.Dry equipment therefor is mill, masticator, banbury, continuous internal mixer, single screw extrusion machine, double screw extruder.This kind of method can make the dispersion of filler and additive improve further.
Detailed description of the invention
Further describe the present invention by embodiment below, but scope of the present invention is not by the restriction of these embodiments.
(1) in embodiment, experimental data following instrument and equipment and assay method measures:
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 | Zhejiang Huzhou east Machinery Co., Ltd. |
The method of testing of table 2 vulcanizating glue physical performance and instrument
(2) embodiment and comparative example
Raw material:
Synthetic polyisoprenes rubber, IR-70, her Cohan new material Co., Ltd of Qingdao;
White carbon, NEWSIL1165-MP, Wuxi Que Chenggui industry Co., Ltd;
Zinc oxide, Dalian zinc oxide factory;
Stearic acid, PF1808, Malaysian Li Cheng Co., Ltd;
Antioxidant 4020, Jiangsu Sheng Ao Chemical Co., Ltd.;
Silane coupler Si69, NanJing Shuguang Chemical Group Co., Ltd.;
Accelerant CZ, Shandong Sunsine Chemical Co., Ltd.;
Diphenylguanidine PG, Dan County, Shandong Chemical Co., Ltd.;
Sulfur, Wudi Jin Sheng Chemical Co., Ltd..
Comparative example 1
In banbury, 56 parts of white carbons, 5.6 parts of silane coupler Si69 are joined carry out in 100 parts of synthesizing cis polyisoprene mixing, after filler is mixed 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 cross roller bottom sheet on a mill until and obtain premixing glue.After parking 8 hours, 2 parts of accelerant CZs, 1 part of diphenylguanidine PG and 1.8 part Sulfur are added obtained elastomeric compound in premixing glue on a mill until.Through mill bottom sheet, after parking 8 hours, in 150 DEG C of vulcanizing presses, sulfuration is to optimum cure, obtained dry pre-sulfiding glue 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 hexane solution of 100 part of 12% cis-polyisoprene, after its rubber/white carbon/Si69/ hexane mixture just mixes with blade paddle mixer, mixture is sprayed into swan neck more than by a nozzle and makes mixed liquor clash into the dispersion increasing filler at Guan Zhongyu tube wall.After mixture joined in grinder continuously carry out essence dispersion, obtain smart dispersed mixture, then being passed through under the pressure of 30MPa by mixture has in the cone type knockouts of four entrances two entrances to inject continuously in knockouts, be about the nitrogen of 180 DEG C from the continuous implantation temperature of two other entrance simultaneously, then gained mixture is sprayed into continuously in the drier of the nitrogen being filled with about 150 DEG C, namely volatilize from the droplet that rubber/white carbon/Si69/ n-hexane expands at 1-10 internal solvent second, form the micelle of desolventizing, nitrogen containing powdery micelle is separated to obtain powder rubber master batch 1 with solvent mixture through cyclone separator with micelle.
Embodiment 2
56 parts of white carbons, 5.6 parts of silane coupler Si69,3.5 parts of zinc oxide are joined in the hexane solution of 100 part of 12% cis-polyisoprene, after its rubber/white carbon/Si69/ hexane mixture just mixes with blade paddle mixer, mixture is sprayed into swan neck more than by a nozzle and makes mixed liquor clash into the dispersion increasing filler at Guan Zhongyu tube wall.Then mixture is joined continuously in grinder and carry out essence dispersion, obtain smart dispersed mixture, then being passed through under the pressure of 30MPa by mixture has in the cone type knockouts of four entrances two entrances to inject continuously in knockouts, simultaneously from the water of the continuous implantation temperature of two other entrance about 95 DEG C, make mixture coagulated.By cohesion and through collecting to obtain rubber master batch 2 after the vacuum drier inner drying 20min of the micelle of desolventizing after filtering under vacuum is-0.08MPa.
Embodiment 3
56 parts of white carbons, 5.6 parts of silane coupler Si69,3.5 parts of zinc oxide are joined in the hexane solution of 100 part of 12% cis-polyisoprene, after its rubber/white carbon/Si69/ hexane mixture just mixes with blade paddle mixer, mixture is sprayed into swan neck more than by a nozzle and makes mixed liquor clash into the dispersion increasing filler at Guan Zhongyu tube wall.After mixture joined in grinder continuously carry out essence dispersion, obtain smart dispersed mixture, then being passed through under the pressure of 30MPa by mixture has in the cone type knockouts of four entrances two entrances to inject continuously in knockouts, simultaneously from the water of the continuous implantation temperature of two other entrance about 95 DEG C, make mixture coagulated.The micelle that will condense also desolventizing obtains rubber master batch 3 after filtering after single screw extrusion machine inner drying 3min.
The rubber master batch 1-3 of above-mentioned gained is added in banbury discharging from banbury in mixing 4 minutes again after 2 parts of stearic acid, 2 parts of antioxidant 4020s, sizing material crosses roller on a mill until, bottom sheet.Mixing park 8 hours after in banbury, add 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.Through mill bottom sheet, after parking 8 hours, in 150 DEG C of vulcanizing presses, sulfuration is to optimum cure, respectively obtained wet method vulcanizate 1-3.
The physical property of table 3 vulcanizate
As known from Table 3, under same recipe, the drying means adopted due to wet method elastomeric compound is different and cured properties that is preparation also has difference, compared with maskerbatch of dry process, in wet masterbatch, the degree of scatter of filler in rubber is improved greatly, the hot strength of vulcanizate, resilience and wearability significantly improve, and compression fatigue heat-dissipating decreases.
Claims (9)
1. a method for continuously producing for rubber masterbatch, comprises the steps:
Step 1): 56 parts of white carbons, 5.6 parts of silane coupler Si69,3.5 parts of zinc oxide being joined in the normal hexane solution of 100 part of 12% cis-polyisoprene, forming rubber/white carbon/Si69/ hexane mixture by stirring;
Step 2): by step 1) in rubber/white carbon/Si69/ hexane mixture condense, obtain the mixture of rubber/white carbon/Si69 compound and n-hexane;
Step 3): remove n-hexane and drying is carried out to described mixture, obtaining rubber/white carbon/Si69 masterbatch;
Wherein, in step 2) described in cohesion can for flocculant flocculence, heating, the one of moving back in solvent method, multiple or combination;
Wherein, step 3) in drying refer to step 2) in the mixture that obtains proceed in heating belt type drying machine, heat drying under vacuum or inert gas, during the n-hexane volatilized and rubber synthesize, unreacted monomer enters in condenser and fractionating column and reclaims; Or step 3) in drying refer to step 2) in the mixture that obtains carry out spraying dry or flash distillation, heat medium used is inert gas or water vapour, and during the n-hexane volatilized and rubber synthesize, unreacted monomer enters in condenser and fractionating column and reclaims.
2. method according to claim 1, wherein optional recycling step 3) n-hexane that removes, recycle.
3. method according to claim 1, wherein in step 1) and/or step 2) in optional add the additive that one or more are selected from oil, age resistor, coupling agent, activating agent, antioxidant, fire retardant, heat stabilizer, light stabilizer, dyestuff, pigment, vulcanizing agent and promoter.
4. according to the arbitrary described method of claim 1-3, wherein use water vapour to be heat medium, in dried solid mixture, can water be contained, then obtain rubber/filler masterbatch after vacuum drying, heat drying or extruding heat drying.
5., according to the arbitrary described method of claim 1-3, wherein said inert gas is nitrogen.
6. method according to claim 4, wherein said heat drying is oven dry or air-dry.
7. method according to claim 4, wherein said extruding heat drying is dry further again after first extruding removes water.
8. method according to claim 7, wherein said further drying be air-dry, dry or mechanical drying.
9. method according to claim 8, wherein said mechanical drying is for using masticator, single screw extrusion machine, and double screw extruder carries out drying.
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| CN201310337578.1A CN103600434B (en) | 2013-08-05 | 2013-08-05 | Rubber masterbatch prepared by the method for continuously producing of rubber masterbatch and the method |
| RU2016107597A RU2678061C2 (en) | 2013-08-05 | 2014-07-22 | Continuous manufacturing process for rubber masterbatch and rubber masterbatch prepared therefrom |
| PCT/CN2014/082710 WO2015018278A1 (en) | 2013-08-05 | 2014-07-22 | Continuous manufacturing process for rubber masterbatch and rubber masterbatch prepared therefrom |
| SG11201600905PA SG11201600905PA (en) | 2013-08-05 | 2014-07-22 | Continuous manufacturing process for rubber masterbatch and rubber masterbatch prepared therefrom |
| ZA2016/01523A ZA201601523B (en) | 2013-08-05 | 2016-03-04 | Continuous method for manufacturing rubber masterbatch and rubber masterbatch prepared thereby |
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| CN103600434B (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 |
| CN105459284B (en) * | 2014-08-25 | 2019-04-05 | 山东大展纳米材料有限公司 | The liquid phase continuous mixing technique and its rubber product of high dispersive carbon nanotube masterbatch |
| CN104371120A (en) * | 2014-11-03 | 2015-02-25 | 怡维怡橡胶研究院有限公司 | Application of continuously prepared rubber masterbatches in car tire belt compound |
| 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 |
| 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 |
| CN104371122A (en) * | 2014-11-03 | 2015-02-25 | 怡维怡橡胶研究院有限公司 | Application of continuously prepared rubber master batch in truck tire base |
| CN105131307A (en) * | 2015-09-11 | 2015-12-09 | 怡维怡橡胶研究院有限公司 | Continuous preparation method for rubber masterbatch and rubber masterbatch prepared by method |
| CN105602047A (en) * | 2015-09-11 | 2016-05-25 | 怡维怡橡胶研究院有限公司 | Continuous making method of rubber masterbatch and rubber masterbatch prepared by the same |
| CN105199171A (en) * | 2015-10-15 | 2015-12-30 | 山东阳谷华泰化工股份有限公司 | Preparation method of white carbon black masterbatch, obtained product and application of product to high-wear-resistance white carbon black reinforcing material for rubber |
| CN105690587B (en) * | 2016-03-17 | 2018-08-17 | 青岛科技大学 | It is a kind of to be first atomized the rubber wet method mixing method remixed |
| CN105729654B (en) * | 2016-03-17 | 2019-01-04 | 青岛科技大学 | A kind of gas auxiliary rubber wet process mixing producing device |
| CN111113709A (en) * | 2019-12-30 | 2020-05-08 | 中国科学院长春应用化学研究所 | Continuous wet mixing method and device for isoprene rubber |
| CN113442320A (en) * | 2020-03-27 | 2021-09-28 | 海南天然橡胶产业集团股份有限公司 | Method for preparing elastomer composite material and product prepared by method |
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| WO2015018278A1 (en) | 2015-02-12 |
| RU2016107597A3 (en) | 2018-05-07 |
| ZA201601523B (en) | 2017-08-30 |
| RU2678061C2 (en) | 2019-01-22 |
| CN103600434A (en) | 2014-02-26 |
| SG11201600905PA (en) | 2016-03-30 |
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