CN105602047A

CN105602047A - Continuous making method of rubber masterbatch and rubber masterbatch prepared by the same

Info

Publication number: CN105602047A
Application number: CN201510577390.3A
Authority: CN
Inventors: 王梦蛟; 宋建军; 王正; 和富金; 贾维杰; 张红霞; 张秀彬
Original assignee: EVE RUBBER RESEARCH INSTITUTE Co Ltd
Current assignee: EVE RUBBER RESEARCH INSTITUTE Co Ltd
Priority date: 2015-09-11
Filing date: 2015-09-11
Publication date: 2016-05-25
Also published as: WO2017041754A1; ZA201802336B

Abstract

The invention relates to a continuous making method of rubber masterbatch and rubber masterbatch prepared by the same. The continuous making method of the rubber masterbatch consists of: step A): adding a filler or filler/additive into a rubber solution, performing stirring to form a rubber/filler (or filler/additive)/solvent mixture; and step B): step A) introducing the obtained rubber/filler (or filler/additive)/solvent mixture directly into a gas medium to carry out coagulation and solvent separation to obtain rubber/filler (or filler/additive) masterbatch. According to the invention, coagulation is carried out in a gas medium, the coagulation medium is easy to separate, the process is simplified, and energy can be saved.

Description

Rubber masterbatch prepared by a kind of method for continuously producing of rubber masterbatch and the method

Technical field

The present invention relates to rubber materials, particularly prepared by a kind of method for continuously producing of rubber masterbatch and the methodRubber masterbatch.

Background technology

Mixing is the critical process of rubber size processing, and is the operation of energy consumption maximum in process always, its energy consumptionAccount for the more than half of whole rubber processing energy consumption. Otherness between the mixing every batch of sizing material of common dry method is larger, usually to follow-up workThe very large impact of the mass formation of order, due to the kneading repeatedly of rubber, molecular weight rubber declines, and filler is at rubber simultaneouslyIn the unequal reason of dispersion cause properties of rubber to decline, also can produce a large amount of dust and cause the pollution of environment. So, wetMethod calendering process arises at the historic moment, and this process is to save the energy than the significant advantage of existing dry method calendering process, fills outMaterial and additive can be better in rubber, more homodisperse while properties of product are greatly improved. Mixed in wet methodIn sweetening process, most important technical process is agglomeration step.

CN103113597A discloses the wet method compounding process that uses the knockouts of particular design to carry out high-efficiency and continuous cohesion,Cohesion medium comprises nitrogen, steam, water, filler water slurry and oil, but this knockouts is high to equipment material requirement, techniqueCost is higher; CN103419291A discloses the method that makes water do heat medium, but follow-up need to separation through separatorDewater, caused micelle breakage, rubber master batch has loss. US7307121B2 discloses a kind of stripping (steamstripping)Method desolvation, specific practice is that white carbon/rubber composition is pumped in stripper plant to cohesion desolvation,The method passes into water vapour during because of stripping, needs dehydration and dry.

Summary of the invention

For solve in prior art water and steam as cohesion medium, need to dehydrate complex procedures and causingThe problem of rubber master batch loss, the object of this invention is to provide a kind of method for continuously producing and the method preparation of rubber masterbatchRubber masterbatch. Another object of the present invention is to provide a kind of rubber system that uses rubber masterbatch of the present invention to prepareProduct.

The present invention directly passes into rubber/filler/additive agent mixture in gas, work simplification of the present invention, the saving energy, improve fillers dispersed performance and vulcanization of rubber characteristic, strengthen filler-interpolymer interaction, thus the rubber system of makingProduct performance boost.

The method for continuously producing that the invention discloses following several rubber masterbatch, comprising:

1, a method for continuously producing for rubber masterbatch, comprises the steps:

Steps A): filler is joined in rubber solutions, form rubber/filler/solvent mixture by stirring;

Step B): by steps A) rubber/filler/solvent mixture of obtaining directly passes in gas medium and condensesAnd separated from solvent, obtain rubber/filler masterbatch.

2, a method for continuously producing for rubber masterbatch, comprises the steps:

Step B): by steps A) rubber/filler/solvent mixture of obtaining directly passes in gas medium and condensesAnd partial solvent is separated, obtain the mixture of rubber/filler compound and solvent;

Step C): to step B) mixture that obtains carries out separated from solvent, described separated from solvent step is specially will be mixedCompound separates solvent by evaporation, or is dried and is separated solvent by low-voltage vacuum, or separates solvent by the mode of heating,Or separate solvent by spray-dired mode, or separate solvent by the mode of expansion drying, or by the side of flash distillationFormula separates solvent, thereby obtains rubber/filler masterbatch.

3, a method for continuously producing for rubber masterbatch, comprises the steps:

Step D): the mixture that previous step is obtained is dried, and obtains rubber/filler masterbatch; Described being dried isHeat drying and/or mechanical drying.

4, a method for continuously producing for rubber masterbatch, comprises the steps:

Step C): to step B) mixture that obtains carries out separated from solvent, described separated from solvent step is specially will be mixedCompound separates solvent by evaporation, or is dried and is separated solvent by low-voltage vacuum, or separates solvent by the mode of heating,Or separate solvent by spray-dired mode, or separate solvent by the mode of expansion drying, or by the side of flash distillationFormula separates solvent;

Wherein step C) described in be evaporated to and use baking oven or drying plate to evaporate; Described spray-dired atomizing typeFor centrifugal atomizing, pressure atomization or twin fluid atomization; The mode of described expansion drying is for first heating then sudden outburstPressure; The mode of described flash distillation is at least one of atmospheric flashing or vacuum flashing, and flash distillation progression is 1-3 level. Wherein stepRapid C) described in low-voltage vacuum be dried in vacuum to solvent flashing or suction filtration under lower than an atmospheric pressure, instituteState be preferably-0.1MPa to 0 of pressure, more preferably-0.09MPa to 0, most preferably is-0.08MPa to 0. Step C)Described in expansion drying for make solvent flashing gasification, preferably screw expansion dryer by screw expansion dryer0-20MPa, more preferably pushes along axle under 1-10MPa, and pitch is successively decreased, frictional heat, and outlet pressure rapid drawdown, adhesive tape is swollenSwollen loosening, the solvent flashing gasification in adhesive tape.

Wherein step D) described heat drying for dry or air-dry; Described mechanical drying for use mill, masticator,Banbury, continuous internal mixer, single screw extrusion machine, double screw extruder is dried, and the operating temperature of mechanical drying is10 DEG C to 250 DEG C; Step D) can first carry out carrying out again mechanical drying after heat drying, also can first carry out mechanical dryAfter dry, carry out again heat drying. Step D) select when mechanical drying heat drying simultaneously, temperature is 10 DEG C to 250 DEG C;Select when heat drying, can in gas medium, heat, described gas medium comprise air, nitrogen, steam,CO₂At least one.

Wherein steps A) in join and also comprise additive in rubber solutions, form rubber/filler/interpolation by stirringAgent/solvent mixture. Steps A) can directly filler and/or additive be joined in rubber solutions, also can be first byFiller and/or additive join and in the solvent identical or different with rubber solutions, form filler and or additive/solventThing. This filler and or additive/solvent mixture can directly mix with rubber solutions, also can park after certain hour andRubber solutions mixes, and heats or do not heat in the time parking, and in the time of heating, temperature is 10 DEG C to 200 DEG C, adds when above-mentionedHot temperature degree is during higher than the boiling point of solvent, and heating need be carried out in pressure vessel. Steps A) rubber/filler of obtaining and orAdditive/solvent mixture, can enter next step immediately, also can first park certain hour, in the time parking heating orPerson does not heat, and when when heating, temperature is 10 DEG C to 200 DEG C, when above-mentioned heating-up temperature is during higher than the boiling point of solvent, and heatingNeed in pressure vessel, carry out. Described additive can optionally comprise oil, age resistor, coupling agent, activating agent, anti-oxidantAgent, heat stabilizer, light stabilizer, fire retardant, dyestuff, pigment, plasticizer, softening agent, processing aid, vulcanizing agentOr one or more in the additive of promoter. The consumption of additive therefor is conventional amount used, or according to actual conditionsRequirement adjust.

Steps A) can use method well known in the art to realize. Steps A) described in stirring can use generally and stirThe machine of mixing completes, and includes but not limited to blade paddle mixer, trough mixer, planetary stirring machine, Z-blade mixer etc.

Steps A) can further include finely divided step, described finely divided can enforcement in the following way: incite somebody to actionThe mixture of above-mentioned stirring gained sprays the high pressure high shear in the situation that by a nozzle, to improve filler and/or to addAdd the dispersion of agent; Make above-mentioned ejecta by swan neck more than make mixed liquor Guan Zhongyu tube wall clash into increase filler and/Or the dispersiveness of additive; Or make ejecta by a bore repeatedly folding and unfolding change pipeline convert shear stress andIncrease the dispersion of filler and/or additive. Pressure limit used is from 0.1MPa to 100MPa, and preferably 10MPa extremely80MPa。

Described finely divided rear formed mixture can also disperse further to improve filler and/or interpolation by following essenceThe dispersion of agent in rubber solutions:

I. described mixture after finely divided is added continuously in ball mill and/or colloid mill and is disperseed, make filler and/Or additive is dispersed in rubber solutions uniformly;

Ii. described finely divided mixture is afterwards joined continuously in grinder and ground so that filler and/or additiveBe well dispersed in rubber solutions, this grinder has the plane mill of one or more groups high speed rotating and is fixed on grinderOn sleeve and fixing pin or the price fixing alternate with plane mill.

Iii. described finely divided mixture is afterwards joined in grinder and ground continuously, this grinder has rotationTwo blades of opposite direction, described blade has pore chute, under high pressure can improve filler by the blade of rotationAnd/or the degree of scatter of additive in rubber solutions. Pressure limit used is from 0.1MPa to 100MPa, preferably 10MPaTo 80MPa.

Iv. described finely divided mixture is afterwards joined in multi-layer high-voltage slit dispersion machine continuously, mixture is existedUnder high pressure, between two-layer, slit, extrude, the strong shearing force now producing can improve filler and/or additive is molten at rubberDegree of scatter in liquid. Pressure limit used is from 0.1MPa to 100MPa, preferably 10MPa to 80MPa.

V. described finely divided mixture is afterwards joined continuously in power decentralized device and disperseed, described power dividesOn the rotor of the High Rotation Speed of loose device, have many radially-arranged slits or hole, mixture with high-speed impact on stator surfaceSo that filler and/or additive are evenly dispersed in rubber solutions.

Two or more in above-mentioned five kinds of finely divided methods use of can mutually connecting.

Described rubber solutions can directly directly obtain from prepare solution polymerized rubber production line, also can doing any typeGlue dissolves preparation in the solvent of this glue. In the time preparing rubber solutions with dry glue, described dry glue can be to use in this areaThe rubber of any kind, as natural polymer or synthetic polymer. Described natural polymer include but not limited to natural gum,Gutta-percha, guayule etc.; Described synthetic polymer include but not limited to monomer in solution polymerization gained (being solution polymerized rubber),Monomer polymerization gained (being emulsion polymerized rubber), monomer body in emulsion carry out polymerization gained. When described rubber solutions directWhile acquisition from prepare solution polymerized rubber production line, described solution polymerized rubber for ethene, propylene, butylene, amylene, alkene,The diene of heptene, a 4-7 carbon atom or the triolefin of 6-7 carbon atom or containing the vinyl monomer of other atom or functional groupHomopolymerization or copolymerized polymer, described other atoms or functional group are silicon atom, fluorine atom, chlorine atom, nitrogen-atoms, oxygenAtom, sulphur atom, ester group, amino ester group, cyano group, also comprises the homopolymers and the copolymer that contain above-mentioned monomer,Comprising but be not limited to polybutadiene, polyisoprene, butadiene-styrene rubber, second the third glue, butyl rubber, NBR, neopreneGlue, silicon rubber, fluorubber, polyurethane rubber, CSM, ACM etc. The molecule of rubberAmount is 1,000 to 4,000 ten thousand, preferably 5,000 to 3,000 ten thousand, more preferably 10,000 to 8,000,000.

Solvent in described rubber solutions is the good solvent of various rubber. Solvent can be specifically aliphatic solvent, fragranceHydrocarbon solvent, chlorinated hydrocarbon solvent, ketones solvent, ether solvent and esters solvent, described aliphatic solvent comprises but does not limitIn various industrial napthas, cycloalkane, substituted ring alkane, normal alkane, described aromatic hydrocarbon solvent includes but not limited to benzene, firstBenzene, dimethylbenzene, styrene, described chlorinated hydrocarbon solvent include but not limited to carrene, chloroform, carbon tetrachloride,Dichloroethanes, chlorobenzene, tetrachloro-ethylene, chlorotoluene. The concentration range of rubber in solution is 1% weight to 60% weight,Preferably 5% weight to 40% weight, more preferably 10% weight to 30% weight.

Described filler includes but not limited to various solid powdery reinforcing agents and filler used in rubber, as all kinds of charcoalsThe nanometer materials of black, silica, metal oxide, salt, different resins and above-mentioned filler. Wherein said metalOxide includes, but are not limited to aluminium oxide, magnesia, zinc oxide etc., described salt include, but are not limited to calcium carbonate,The nanometer materials of potter's clay and above-mentioned filler. The specific area of filler is 0.1 to 800m²/ g, preferably 1 to 500m²/g，More preferably 5 to 300m²/ g. For carbon black, silica (white carbon), its oil factor is 20 to 250ml/100g,Preferably 25 to 200ml/100g, and more preferably 30 to 150ml/100g, wherein said filler comprise they mixture andHeterogeneous filler, heterogeneous filler includes, but are not limited to carbon black, silica, aluminium oxide, magnesia, zinc oxide, oxidationTwo-phase or the heterogeneous filler of the composition such as calcium, titanium oxide, boron oxide, for two-phase or heterogeneous filler, its oil factor is20 to 250ml/100g, and preferably 25 to 200ml/100g, and more preferably 30 to 150ml/100g. The consumption of filler is 5To 300 weight portions (taking rubber as 100 weight portions), preferably 10 to 200 weight portions, more preferably 30 to 150 weightsAmount part. That described filler also comprises in above-mentioned filler two or more and use thing.

Described filler also comprises their surface modifying stuffing. Wherein said surface modification can be to pass through chemical reactionCertain functional group is connected on to filling surface or by mixing or adsorbing, modifier is combined in to filler by physics modeOn surface. Described modification, can be, but not limited to modifier to be dissolved in after solvent and to mix with filler and carry out liquid phase modification,As WangW, NanseG, VidalA, etal.K.G.K[J], described in 1994,47:493, also can be, but not limited to changeProperty agent and filler Hybrid Heating are carried out solid-state modification, as WangMJ, and Wolff.S.R.C.T[J], described in 1992,65:715.Surface modification is carried out before also can be in filler is added to rubber solutions, or modifier is joined to rubber solutions and fillerMixture in carry out surface modification. Described modifier is the modifier of this area routine, such as what represent with following general formulaOrgano silane coupling agent:

(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, in the time of q=1, A is-SCN ,-SH ,-Cl ,-NH₂；

In the time of q=2, A is-S_x-；

R and R ' are the branching of carbon atom from 1 to 4 or alkyl or the phenolic group of straight chain, and R and R ' can be identical, also canDifferent;

N is 0,1 or 2;

Alk is the straight or branched alkyl that contains 1 to 6 carbon atom;

Alk_enyL is the straight or branched thiazolinyl that contains 1 to 6 carbon atom;

M is 0 or 1;

Ar is the aryl that contains 6 to 12 carbon atoms;

P be 0 or 1, p and n can not be 0 simultaneously;

X is 2 to 8;

Wherein the most frequently used is two (triethoxy propyl silane) tetrasulfides and disulphide, 3-thiocyanogen propyl group-tri-secondTMOS, γ-mercapto propyl group-trimethoxy silane, zirconium ester coupling agent, titanate coupling agent, nitro coupling agent, alcoholCompounds, described alcohol compound includes but not limited to unit alcohol, dihydroxylic alcohols, polyalcohol, described alcohol compound bagDraw together but be not limited to propyl alcohol, butanols, ethylene glycol, polyethylene glycol and derivative thereof.

To step B), step C) and step D) solvent carry out recycle and reuse; Described recovery by condenser,Fractionating column and sprinkling equipment are implemented. The method of described recovery solvent can be used any known method in this area, asThe solvent of vaporization is reclaimed by the method for surface condensation or direct condensation by contact. When using the side of direct condensation contactWhen method, cooling agent can adopt water, homogeneous solvent.

Wherein step B) can implement with any container. Step B) in tank container, implement pref. cylindricalTank container. At step B) in optional add one or more and be selected from oil, age resistor, coupling agent, activating agent, antioxygenAgent, fire retardant, heat stabilizer, light stabilizer, dyestuff, pigment, plasticizer, softening agent, processing aid, sulfurationThe additive of agent and promoter. Step B) described in gas medium comprise nitrogen, carbon dioxide, steam, airAt least one. Step B) described in the temperature of gas medium be more than solvent boiling point temperature, preferably 50-250 DEG C,More preferably 70-180 DEG C.

Wherein at step B) before or after further implementation step B1): the mixture that previous step is obtained is sent into solidifyingIn poly-device, and in knockouts one or more fluid-phases in optional and nitrogen, steam, water, filler water slurry and oilContact and mix rear cohesion, obtaining the mixture of rubber/filler/additive compound and solvent. At step B) before orFurther implementation step B2 afterwards): the mixture that previous step is obtained directly passes into the heating of temperature higher than solvent boiling pointIn medium, the polarity of this heat medium is different from the polarity of solvent for use, mixture coagulated desolvation agent, and solvent is fastSpeed volatilization, thereby rubber/filler/additive compound that formation contains this heat medium and the mixture of solvent. Described systemMaking method comprises step B1 simultaneously), step B2) and step B).

Step B1) the middle knockouts using can be for having the tubular type knockouts of one or more charging aperture, whereinThe feedstock direction of described charging aperture can to condense the axial direction of organ pipe parallel with tubular type, and the end of outlet in pipe, also canTo be 1-180 ° of angle with the axial direction of tubular type cohesion organ pipe, be preferably 20-120 ° of angle, be more preferably 70-100 ° of angle,Most preferably be 85-95 ° of angle. When charging aperture is while being multiple, the axle of the feedstock direction of part charging aperture and tubular type cohesion organ pipeParallel to direction; The axial direction of the cylinder of the feedstock direction of remaining charging aperture and tubular type knockouts is 1-180 ° of angle, excellentChoosing is 20-120 ° of angle, is more preferably 70-100 ° of angle, is most preferably 85-95 ° of angle, and the feedstock direction of each charging aperture existsAnd the radial direction that is projected as this cross section on the vertical cross section of the tubular axis heart is between the tangential direction of this cross sectionAny direction, is preferably radial direction, or is tangential direction. All axially perpendicular in pipe of described charging apertureSame plane on or described charging aperture in different planes.

Step B1) in the knockouts that uses two or three above knockouts of concentric pipes composition mutually of also can serving as reasons,Wherein each pipe has one or more charging aperture, and the feedstock direction of described charging aperture is the axial side who is parallel to pipeTo or be the tangential direction of pipe, the end of outlet in pipe. Fluid can directly pass into, also can be from the tangent line side of tube wallTo passing into. The end of the charging aperture of each pipe can be in same plane, also the charging aperture of each pipe from inside to outsideEnd successively the end elongated or charging aperture of each pipe from inside to outside shortens successively.

Step B1) in use knockouts can be also cartridge type knockouts, this cartridge type knockouts only has a charging aperture,This charging aperture is positioned on the upper end or barrel of cartridge type knockouts, the lower end of outlet in cylinder. Fluid can be straight by charging apertureConnect injection knockouts, also can inject knockouts with the direction of tangent line along barrel.

Step B1) the middle knockouts using also can be for top is tubular, and bottom is cone shape cone type structure, andThere is one or more charging aperture. The feedstock direction of charging aperture can be the tangential direction of barrel; Each charging aperture is passableIn same plane, also can be in Different Plane. The feedstock direction of charging aperture also can be vertical with the axial direction of cylinder orBe 1-180 ° of angle with the axial direction of cylinder, preferably 20-110 ° of angle, more preferably 70-100 ° of angle, most preferably 85-95 °Angle, the feedstock direction of each charging aperture at the radial direction that is projected as this cross section of the cross section vertical with cylinder axle center to this horizontal strokeAny direction between the tangential direction in cross section, is preferably the tangential direction of this cross section.

Step B1) described in nitrogen, steam, water, filler water slurry and oil in one or more fluids and stepA) rubber/filler/solvent mixture obtaining in enters knockouts by one or more charging apertures, wherein the temperature of nitrogenDegree is 20-300 DEG C, and the temperature of steam is 100-300 DEG C, and the temperature of liquid water is 20-100 DEG C, and the temperature of oil is20-300 DEG C, the temperature of filler water slurry is 20-100 DEG C. Described oil is that rubber materials is manufactured the conventional oil of oil-extended rubber. StepRapid A) in the optional oil using can with step B1) in the oil that uses identical or different. Steps A) middle filling out of usingMaterial can with step B1) in use filler identical or different.

At step B2) in, the mixture that previous step is obtained directly passes into the heat medium of temperature higher than solvent boiling pointIn. When the character of heat medium is when especially polarity is different from solvent for use character, mixture condenses and desolvation agent, andHeat medium temperature is during higher than solvent boiling point, solvent rapidly volatilization form the masterbatch that contains heat medium. This masterbatchThrough heating remove after heat medium masterbatch product, not anti-during the solvent volatilizing in this process and rubber are syntheticThe monomer of answering enters in condenser and fractionating column and reclaims, and the cohesion mixture of gained separates also with heat medium after filtrationAfter dry rubber master batch product. Above-mentioned heat medium includes but not limited to water. In the time that water is cooked heat medium, described solventFor boiling point is lower than 100 DEG C of solvents. Then during the solvent that volatilized and rubber are synthetic, unreacted monomer and water vapour enterEnter in condenser and fractionating column and reclaim.

Step B2) cohesion can implement with any container; Preferably, do not use the knockouts of any particular designImplement; Step B2) cohesion can in tank container, implement. Preferably, step B2) use the tank of arbitrary shapeShape container, more preferably uses columniform tank container.

Step B) for mixture is directly passed in gas medium and to be condensed. Step B) can come with any containerImplement; Preferably, do not implement with the knockouts of any particular design; Step B) cohesion can be in tank containerImplement. Preferably, step B) use the tank container of arbitrary shape, more preferably use columniform tank container.

Technique effect of the present invention is

I. rubber/filler (or filler/additive)/cohesion of solvent mixture and the mode of desolventizing: rubber/filler (orFiller/additive)/solvent mixture directly passes in gas medium and makes mixture coagulated, do not need the cohesion of particular designDevice, cohesion medium are that gas is easily separated, and raw material is easy to get; And while containing nitrogen in gas medium, add a certain amount of moistureCan increase filler-rubber interactions, reduce filler and assemble, improve the Micro-disperse State of filler in rubber.

Ii. rubber/filler (or filler/additive)/solvent mixture does not need liquid medium to condense, and has reduced techniqueCost.

Iii. condensation product, in thermal medium, does not need through separator, gets final product and separated from solvent, can ensure to the full extent female refiningThe physical property of glue.

Iv. separated from solvent mode disclosed by the invention (separates solvent by mixture by evaporation, or does by low-voltage vacuumDry separation solvent, or separate solvent by the mode of heating, or separate solvent by spray-dired mode, or by swollenSwollen dry mode separates solvent, or separates solvent by the mode of flash distillation) can realize the separation completely of solvent, and shouldSeparation can complete rapidly, has avoided rubber molecule Yin Gaowen that deterioration by oxidation phenomenon occurs, and has strengthened the benefit of filler to rubberPotent fruit.

V. Technological adaptability is strong: both can be simple by technique and rubber solutions that properties of product are slightly poor and filler, additiveGeneral mix and directly heating means prepare rubber/filler/additive rubber master batch, can utilize again particular design dispersal device,Mix cohesion process and the higher but rubber/filler/additive rubber master batch of better performances of mechanical drying method manufacturing cost; DifferentMasterbatch prepared by technique can reasonably adapt to the needs of different rubbers.

Detailed description of the invention

Further describe the present invention with embodiment below, but scope of the present invention is not subject to the restriction of these embodiment.

(1) in embodiment, experimental data is measured with following instrument and equipment and assay method:

Instrument and equipment prepared by table 1 rubber sample

Sequence number	Device name	Specifications and models	Manufacturer
				1	Banbury	BR1600	Farrel Corp. (US) 25 Main Street, Ansonia, CT 06401, U.S.A. of the U.S.
2	Mill	Polymix 150L	SERVITEC company of Germany
				3	Vulcanizing press	P-V-200-3RT-2-PCD	Huge rock oil pressure Industrial Co., Ltd

The method of testing of table 2 vulcanizating glue physical performance and instrument

(2) embodiment and comparative example

Raw material:

Solution polymerized butadiene styrene rubber, Tai Xiang Co., Ltd;

Oil-filled solution polymerized butadiene styrene rubber (37.5 parts of oil-filled amounts), VSL4526-OHM, LANXESS produces;

Butadiene rubber, BR9000, Qilu Co., Ltd., China Petrochemical Corp;

White carbon, NewsilHD165MP, Q & C Silicon Chemical Co., Ltd.

Silane coupler Si69, NanJing Shuguang Chemical Group Co., Ltd.;

Stearic acid, PF1808, Malaysian Li Cheng Co., Ltd;

Zinc oxide, Dalian zinc oxide factory;

Paraffin, Paramelt Specialty Chemicals (Suzhou) Co., Ltd.;

Anti-aging agent RD, Nanjing Chemical Industry Co., Ltd., SINOPEC chemical plant;

Antioxidant 4020, Jiangsu Sheng Ao Chemical Co., Ltd.;

Accelerant CZ, Shandong Sunsine Chemical Co., Ltd.;

Diphenylguanidine PG, Dan County, Shandong Chemical Co., Ltd.;

Sulfur, Lin Yiluo Zhuan Xin Anhua factory.

Comparative example 1

96.3 parts of oil-filled solution polymerized butadiene styrene rubbers, 30 parts of butadiene rubbers are added in banbury, after broken glue half a minute, by 78Part white carbon, 6.4 parts of silane coupler Si69 and 1.8 parts of oil contents add in rubber for twice. When above-mentioned substance is sneaked into rubberGlue also makes temperature reach the mixing time that extends again 2 minutes after 150 DEG C, and binder removal is crossed roller, thin-pass six times in millRear lower sheet is first paragraph premixing glue. This glue is parked after 8 hours and is put into the broken glue of banbury again, adds 3.5 parts of oxidationsZinc, 2 parts of stearic acid, 2 parts of paraffin, 2 parts of antioxidant 4020s after mixing 2 minutes binder removal be second segment premixing glue.Park and after 8 hours, in banbury, add again 2.0 parts of accelerant CZs, 2.1 parts of diphenylguanidine PG and 1.4 parts of Sulfurs,Elastomeric compound is crossed roller on the machine of thawing, and thin-pass descends for six times sheet to be finished composition afterwards. This glue is parked after 8 hours at 165 DEG COn vulcanizing press, vulcanize to optimum cure, make dry method vulcanizate.

Comparative example 2

70 parts of solution polymerized butadiene styrene rubbers and 30 parts of butadiene rubbers are dissolved in to the rubber solutions that makes 20% in hexane, then will78 parts of white carbons, 6.4 parts of silane coupler Si69,28 parts of oil, 2 parts of age resistor taking 100 parts of rubber as basis4020,3.5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of paraffin are sneaked into and in rubber solutions, are formed mixture. This mixture warpAfter mixing, under the pressure of 30MPa, process has in two entrance injecting tube bevel-type knockouts in four imports, and simultaneouslyUnder the pressure of 10MPa, inject the water of 90-100 DEG C from two other entrance, gained solid-liquid/gas three-phase mixture passes throughAn outlet of knockouts sprays into drier, forms solid powder substance, then is after drying masterbatch 1.

Embodiment 1

70 parts of solution polymerized butadiene styrene rubbers and 30 parts of butadiene rubbers are dissolved in to the rubber solutions that makes 20% in hexane, then will78 parts of white carbons, 6.4 parts of silane coupler Si69,28 parts of oil, 2 parts of age resistor taking 100 parts of rubber as basis4020,3.5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of paraffin are sneaked into and in rubber solutions, are formed mixture. This mixture is mixedAfter closing dispersion, directly pass into 180 DEG C of N₂In complete cohesion and desolventizing (" devolatilization "), obtain masterbatch 2.

Embodiment 2

70 parts of solution polymerized butadiene styrene rubbers and 30 parts of butadiene rubbers are dissolved in to the rubber solutions that makes 20% in hexane, then will78 parts of white carbons, 6.4 parts of silane coupler Si69,28 parts of oil, 2 parts of age resistor taking 100 parts of rubber as basis4020,3.5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of paraffin are sneaked into and in rubber solutions, are formed mixture. This mixture warpBlade mixer just mixes, curved tube disperser carefully mixes after homogenizer essence is mixed and directly passes into and be filled with 180 DEG C of nitrogen, CO₂TankIn, in tank, also containing 1% moisture, after mixture desolventizing, drying is masterbatch 3 again.

Embodiment 3

70 parts of solution polymerized butadiene styrene rubbers and 30 parts of butadiene rubbers are dissolved in to the rubber solutions that makes 20% in hexane, then will78 parts of white carbons, 6.4 parts of silane coupler Si69,28 parts of oil, 2 parts of age resistor taking 100 parts of rubber as basis4020,3.5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of paraffin are sneaked into and in rubber solutions, are formed mixture. This mixture is straightConnect in the water that sprays into approximately 95 DEG C and pass into 150 DEG C of air simultaneously, gained solid-liquid/gas three-phase mixture is dried by hot-air ovenAfter be masterbatch 4.

Embodiment 4

70 parts of solution polymerized butadiene styrene rubbers and 30 parts of butadiene rubbers are dissolved in to the rubber solutions that makes 20% in hexane, then will78 parts of white carbons, 6.4 parts of silane coupler Si69,28 parts of oil, 2 parts of age resistor taking 100 parts of rubber as basis4020,3.5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of paraffin are sneaked into and in rubber solutions, are formed mixture. This mixture warpTwo entrances that pass through under the pressure of 30MPa after mixing in the cone type knockouts that has four entrances inject solidifying continuouslyIn poly-device, be about the nitrogen of 180 DEG C from the continuous implantation temperature of two other entrance simultaneously, gained mixture is dry through sprayingDry mode separates solvent, makes masterbatch 5.

Embodiment 5

70 parts of solution polymerized butadiene styrene rubbers and 30 parts of butadiene rubbers are dissolved in to the rubber solutions that makes 20% in hexane, then will78 parts of white carbons, 6.4 parts of silane coupler Si69,28 parts of oil, 2 parts of age resistor taking 100 parts of rubber as basis4020,3.5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of paraffin are sneaked into and in rubber solutions, are formed mixture. This mixture warpGrinder directly passes in the container that is filled with 150 DEG C of nitrogen after mixing, and the rubber/filler/solvent mixture after cohesion is through addingAfter thermal release solvent, then after expansion drying, be masterbatch 6.

Above-mentioned gained masterbatch 1～6 is wrapped after roller in mill, add 2.0 parts of accelerant CZs, 2.1 parts of promoterAfter DPG and 1.4 parts of Sulfurs, sheet under thin-pass, parked after 8 hours, in the vulcanizing press of 165 DEG C, vulcanized to sulfuricChange, make wet method vulcanizate 1～6.

Table 3 is wet, the physical property of dry method vulcanizate

Table 3 is that the embodiment 1-5 of wet masterbatch under different formulations and technique and the comparative example of dry method elastomeric compound are (rightRatio 1) physical property of the vulcanizate that obtains. Therefrom can find out, under same recipe, wet masterbatch is with dryMethod masterbatch is compared, and the dispersiveness of filler in rubber improves greatly, and the hardness of vulcanizate is lower, hot strength and pulling apartPercentage elongation is higher, and elasticity is high, and hysteresis loss is low, and anti-wear performance is better. Relatively the data of comparative example 2 and embodiment 1 canTo find out, under same recipe, the wet masterbatch in the present invention is without drying steps, except hysteresis loss is slightly high, DINOutside abrasion index is lower slightly, can with the publication number patent that is CN103113597 in wet masterbatch performance suitable, this methodCan greatly save energy, reduction processing step, is applicable to the less demanding situation of rubber master batch anti-wear performance. More rightThe data of ratio 2 and embodiment 2-5 can find out, under same recipe, and the wet masterbatch in the present invention and publication numberFor the wet masterbatch in the patent of CN103113597 is compared, the dispersiveness of filler in rubber improves, vulcanizateHardness is lower, and hot strength and elongation at break are suitable, and elasticity is high, and hysteresis loss is low, and anti-wear performance is good.

Claims

1. a method for continuously producing for rubber masterbatch, comprises the steps:

2. a method for continuously producing for rubber masterbatch, comprises the steps:

3. a method for continuously producing for rubber masterbatch, comprises the steps:

Steps A): filler is joined in rubber solutions, form rubber/filler solvent mixture by stirring;

4. a method for continuously producing for rubber masterbatch, comprises the steps:

5. according to the method described in claim 1-4 any one, wherein steps A) in rubber/filler/solvent mixtureCan enter immediately step B), also can park certain hour, in the time parking, heat or do not heat; In the time of heating, temperatureDegree is 10 DEG C to 200 DEG C.

6. according to the method described in claim 2 or 4, wherein step C) described in be evaporated to and use baking oven or drying plateEvaporate; Described spray-dired atomizing type is centrifugal atomizing, pressure atomization or twin fluid atomization; Described expansion is dryDry mode is for first heating then sudden outburst pressure; The mode of described flash distillation be atmospheric flashing or vacuum flashing extremelyFew a kind of, flash distillation progression is 1-3 level.

7. according to the method described in claim 2 or 4, wherein step C) described in low-voltage vacuum be dried as veryEmpty extremely lower than solvent flashing or suction filtration under an atmospheric pressure.

8. according to the method described in claim 2 or 4, wherein step C) described in expansion drying for passing through screw rodExpansion-exsiccation machine makes solvent flashing gasification.

9. according to the method described in claim 3 or 4, wherein step D) described heat drying is for drying or air-dry;Described mechanical drying is for using mill, masticator, banbury, continuous internal mixer, single screw extrusion machine or twin-screwExtruder is dried, and the operating temperature of mechanical drying is 10 DEG C to 250 DEG C; Step D) can first carry out heat dryingAfter carry out again mechanical drying, also can first carry out carrying out heat drying after mechanical drying.

10. according to the method described in claim 3 or 4, wherein step D) can add while selecting mechanical drying simultaneouslyHeated drying, temperature is 10 DEG C to 250 DEG C; While selecting heat drying, can in gas medium, heat described gasMedium comprises air, nitrogen, steam, CO₂At least one.

11. according to the method described in claim 1-4 any one, wherein steps A) in join in rubber solutions alsoComprise additive, form rubber/filler/additive/solvent mixture by stirring; Filler and additive can directly joinIn rubber solutions, or first filler and additive are joined in the solvent identical or different with rubber solutions, then directJoin in rubber solutions or park certain hour after join in rubber solutions, while parking heating or do not heat; When addingWhen heat, temperature is 10 DEG C to 200 DEG C.

12. methods according to claim 11, wherein said additive is selected from oil, anti-old for one or moreAgent, coupling agent, activating agent, antioxidant, fire retardant, heat stabilizer, light stabilizer, dyestuff, pigment, plasticizer,The additive of softening agent, processing aid, vulcanizing agent and promoter.

13. method according to claim 11, wherein steps A) in rubber/filler and additive/solvent mixedCompound can enter step B immediately), also can park certain hour, in the time parking, heat or do not heat; In the time of heating,Temperature is 10 DEG C to 200 DEG C.

14. according to the method described in claim 1-4 any one, wherein at step B) in optional add one or moreBe selected from oil, age resistor, coupling agent, activating agent, antioxidant, fire retardant, heat stabilizer, light stabilizer, dyestuff,The additive of pigment, plasticizer, softening agent, processing aid, vulcanizing agent and promoter.

15. according to the method described in claim 1-4 any one, wherein step B) described in gas medium comprise nitrogenAt least one of gas, carbon dioxide, steam, air.

16. according to the method described in claim 1-4 any one, wherein step B) described in the temperature of gas mediumMore than the boiling temperature for solvent.

17. according to the method described in claim 1-4 any one, wherein at step B) before or after further implementStep B1): the mixture that previous step is obtained is sent in knockouts, and in knockouts optional and nitrogen, steam,Water, filler water slurry and one or more fluid-phases in oil contact and mix rear cohesion, obtain rubber/filler/additive multipleThe mixture of compound and solvent.

18. according to the method described in claim 1-4 any one, wherein at step B) before or after further implementStep B2): the mixture that previous step is obtained directly passes in the heat medium of temperature higher than solvent boiling point, this heatingThe polarity of medium is different from the polarity of solvent for use, mixture coagulated desolvation agent, and solvent volatilizees rapidly, contains thereby formThere are rubber/filler/additive compound of this heat medium and the mixture of solvent.

19. according to the method described in claim 1-4 any one, and wherein said manufacture method comprises step B1 simultaneously),Step B2) and step B).

20. according to the method described in claim 1-4 any one, wherein to step B), step C) and step D)Solvent carry out recycle and reuse; Described recovery is implemented by condenser, fractionating column and sprinkling equipment.

21. 1 kinds of rubber masterbatch of preparing according to the method described in claim 1-20 any one.

22. 1 kinds of rubbers, it uses rubber masterbatch according to claim 21 to prepare.