CN103419291B - 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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- CN103419291B CN103419291B CN201310337559.9A CN201310337559A CN103419291B CN 103419291 B CN103419291 B CN 103419291B CN 201310337559 A CN201310337559 A CN 201310337559A CN 103419291 B CN103419291 B CN 103419291B
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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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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses rubber masterbatch prepared by the method for continuously producing of rubber masterbatch and the method, manufacture method comprises: 1): joined by filler in rubber solutions, forms rubber/filler/solvent mixture by stirring; 2): the rubber/filler/solvent mixture in step 1) is directly passed into temperature higher than in the heat medium of 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 formed containing the rubber/filler compound of this heat medium and the mixture of solvent; 3): desolvation also carries out drying to described mixture, obtains rubber/filler masterbatch.The present invention is to rubber, filler without particular/special requirement, and the scope of application is wider.Production equipment and process simple and continuously, efficient, consume energy low, few artificial, cost is lower.Very superior in the masterbatch processing using the method to prepare, physical and mechanical properties, product quality.<!-- 2 -->
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 speed of this method is 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 the solvent volatilization of coagel is accelerated further.Therefore, compared with the conventional method, the condensing method designed by the application has efficient, energy-conservation and mixing and cohesion continued operation feature.
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) mixing and cohesion are evenly 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 directly passed into temperature higher than in the heat medium of 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 formed containing the rubber/filler compound of this heat medium and the mixture of solvent;
Step 3): desolvation also carries out drying to described mixture, obtains rubber/filler masterbatch.
Preferably, wherein step 2) any container can be used implement.
Preferably, wherein step 2) implement in tank container, pref. cylindrical tank container.
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 said heat medium is water vapour, can contain water in dried solid mixture, then after anhydrating, obtains rubber/filler masterbatch through vacuum drying, heat drying or extruding heat drying.
Preferably, wherein said heat medium is water, described solvent be boiling point lower than 100 DEG C of varsols, can water be contained in dried solid mixture, then through vacuum drying, heat drying or extruding heat drying after anhydrating, obtain rubber/filler masterbatch.
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 heat medium.
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 directly passed into temperature higher than in the heat medium of 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 formed containing the rubber/filler compound of this heat medium and the mixture of solvent;
Step 3): desolvation also carries out drying to described mixture, thus obtains rubber/filler masterbatch.
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, dyestuff, light stabilizer, fire retardant, heat stabilizer, 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, alkene, 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.
In step 2) in, directly pass into temperature higher than in the heat medium of solvent boiling point by the rubber/filler/solvent mixture in step 1) or through finely divided mixture.When especially polarity is different from solvent for use character for the character of heat medium, namely mixture condenses and deswelling, and heating medium temperature higher than solvent boiling point time, namely solvent volatilizees rapidly the masterbatch formed containing heat medium.This masterbatch through heating removing heat medium after masterbatch product, in solvent volatilized in the process and rubber synthesis, unreacted monomer enters in condenser and fractionating column and reclaims, the cohesion mixture of gained be separated with heat medium after filtration and dry after rubber master batch product.Above-mentioned heat medium includes but not limited to water.When doing heat medium with water, described solvent is that boiling point is lower than 100 DEG C of solvents.Then during volatilized solvent and rubber synthesize, unreacted monomer and water vapour enter in condenser and fractionating column and reclaim.Described drying can be vacuum drying, and comprising normal-temperature vacuum drying, vacuum freezedrying and heating, vacuum dry, also can be general drying mode, such as oven dry or air-dry.Described drying also can be 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.
Step 2) cohesion can use any container to implement; Preferably, do not use the knockouts of any particular design to implement; Step 2) cohesion can implement in tank container, the tank container of pref. cylindrical.
Step 2) in cohesion also can use knockouts to implement, the 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.
Preferably, step 2) use the tank container of arbitrary shape, more preferably use columniform tank container.
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 of the present invention has following 3 points:
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 rubber/filler/cohesion of additive/solvent mixture and the mode of desolventizing: the liquid medium that rubber/filler/additive/solvent mixture directly passes into character especially polarity and solvent for use different in kind makes mixture deswelling and condenses, and medium temperature higher than solvent boiling point time, namely solvent volatilizees rapidly the masterbatch formed containing heat medium.This masterbatch through heating removing heat medium after 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, and do not require baroque knockouts, equipment cost is low.
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 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 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 mixture is directly sprayed into continuously in the water of about 95 DEG C under the pressure of 0.2MPa and condense.Will 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 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 mixture directly sprayed under the pressure of 30MPa in the water of 95 DEG C and condense.Will cohesion the micelle of desolventizing after filtration, obtain rubber master batch 2 after drying.
Comparative example 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 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 two entrances in the cone cartridge type knockouts of four entrances to inject in knockouts, is the nitrogen of 180 DEG C by two other entrance implantation temperature simultaneously.Gained mixture spray into continuously be filled with about 150 DEG C of nitrogen drier desolventizing, drying, form solid powdery material, i.e. rubber master batch 3.
The rubber master batch 1 of above-mentioned gained, rubber master batch 2 and rubber master batch 3 are 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 1,2 and 3.
The physical property of table 3 vulcanizate
As known from Table 3, under same recipe, the condensing method 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.Wet method vulcanizate 1,2 performance compared with wet method vulcanizate 3 is more or less the same, but embodiment 1 with 2 preparation method compared with the preparation method of comparative example 2, do not use the knockouts of particular design, there is the advantage of low cost.
Claims (8)
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/ normal hexane mixture by stirring;
Step 2): by step 1) in rubber/white carbon/Si69/ normal hexane mixture directly pass in the heat medium of temperature higher than normal hexane boiling point, the polarity of this heat medium is different from the polarity of normal hexane, mixture coagulated deswelling, and normal hexane volatilizees rapidly, thus formed containing the rubber/white carbon/Si69 compound of this heat medium and the mixture of normal hexane;
Wherein step 2) described in heat medium be water vapour; Or step 2) described in heat medium be water; Wherein step 2) implement in tank container;
Step 3): remove normal hexane and to described mixture through vacuum drying, heat drying or extruding heat drying except anhydrating, obtain rubber/white carbon/Si69 masterbatch.
2. method according to claim 1, wherein step 2) in tank container be cylindrical tank container.
3. method according to claim 1, wherein optional recycling step 3) n-hexane that removes, recycle.
4. 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.
5., according to the arbitrary described method of claim 1, wherein said heat drying is oven dry or air-dry.
6., according to the arbitrary described method of claim 1, wherein said extruding heat drying is dry further again after first extruding removes heat medium.
7. method according to claim 6, wherein said further drying be air-dry, dry or mechanical drying.
8. method according to claim 7, wherein said mechanical drying carries out drying for using masticator, single screw extrusion machine or double screw extruder.
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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 |
| PCT/CN2014/082711 WO2015018279A1 (en) | 2013-08-05 | 2014-07-22 | Continuous manufacturing process for rubber masterbatch and rubber masterbatch prepared therefrom |
| MX2016001563A MX2016001563A (en) | 2013-08-05 | 2014-07-22 | Continuous manufacturing process for rubber masterbatch and rubber masterbatch prepared therefrom. |
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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 |
| 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 |
| 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 |
| 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 |
| CN104742268B (en) * | 2015-04-01 | 2017-06-09 | 苏州第一元素纳米技术有限公司 | A kind of preparation method of masterbatch |
| 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 |
| 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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| CN103113597A (en) * | 2013-01-30 | 2013-05-22 | 怡维怡材料研究院有限公司 | Continuous manufacturing method of rubber masterbatch and rubber masterbatch prepared by same |
| 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 |
| 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 |
| 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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| 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 |
| 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 |
| CN103113597A (en) * | 2013-01-30 | 2013-05-22 | 怡维怡材料研究院有限公司 | Continuous manufacturing method of rubber masterbatch and rubber masterbatch prepared by same |
| 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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