CN103419292B - 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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- CN103419292B CN103419292B CN201310337560.1A CN201310337560A CN103419292B CN 103419292 B CN103419292 B CN 103419292B CN 201310337560 A CN201310337560 A CN 201310337560A CN 103419292 B CN103419292 B CN 103419292B
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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
-
- 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
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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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
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
Abstract
The invention discloses rubber masterbatch prepared by the method for continuously producing of rubber masterbatch and the method, manufacture method comprises: 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 passed into temperature higher than in the heat medium of solvent boiling point, polarity and the solvent for use character of this medium are when especially polarity is different, namely mixture condenses and deswelling, and medium temperature higher than solvent boiling point time, solvent rapidly i.e. volatilization and 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.Compared with condensation technique during the present invention is mixing with existing wet method, to rubber, filler without particular/special requirement, the scope of application is wider.Production technology simple and continuously, efficient, consume energy low, few artificial, cost is lower.<!-- 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 is to rubber, filler without particular/special requirement, and the scope of application is wider.
5) production technology very simple and continuously, efficient, consume energy low, few artificial, thus cost is lower;
6) masterbatch using the method to prepare is 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 remaining mixture, obtains rubber/filler masterbatch;
Wherein, during the solvent volatilized in step 3) and rubber synthesize, unreacted monomer enters in condenser and fractionating column and reclaims, separated heating medium, the mixture separated from heat medium proceeds in heating belt type drying machine again, in vacuum, inert gas or air, carry out drying; Or in the solvent volatilized in step 3) and rubber synthesis, unreacted monomer enters in condenser and fractionating column and reclaims, and then carries out extruding heat drying to remaining mixture.
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, optionally after vacuum drying, heat drying or extruding heat drying, obtain rubber/filler masterbatch again.
Preferably, wherein said inert gas is nitrogen.
Preferably, wherein said heat medium is water, described solvent be boiling point lower than 100 DEG C of varsols, optionally again 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.9, method according to claim 8, 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.
Present invention also offers a kind of rubber masterbatch prepared according to said method.
Further, present invention also offers a kind of a kind of rubber adopting above-mentioned rubber 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 passed into temperature higher than in the heat medium of solvent boiling point, the polarity of this medium and the character of solvent for use are when especially polarity is different, namely mixture condenses and deswelling, and during medium temperature point mixed higher than solvent, solvent i.e. volatilization and formed containing the rubber/filler compound of this heat medium and the mixture of solvent rapidly;
Step 3): desolvation also carries out drying to remaining mixture, obtains rubber/filler masterbatch;
Wherein, during the solvent volatilized in step 3) and rubber synthesize, unreacted monomer enters in condenser and fractionating column and reclaims, separated heating medium, the mixture separated from heat medium proceeds in heating belt type drying machine again, in vacuum, inert gas or air, carry out drying; Or in the solvent volatilized in step 3) and rubber synthesis, unreacted monomer enters in condenser and fractionating column and reclaims, and then carries out extruding heat drying to remaining mixture.
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:
(Rn-(RO)
3-nSi-(Alk)m-(Ar)p)q(A)（I）
Rn’(RO)3-nSi-(Alk)（II）
Or Rn ' (RO) 3-nSi-(Alkenyl) (III)
In formula, as q=1, A is-SCN ,-SH ,-Cl ,-NH2;
As q=2, A is-Sx-;
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;
Alkenyl 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 medium, namely mixture condenses and deswelling, 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, 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 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) do not require the knockouts using any particular design, any container can be used implement, preferred tank container, more preferably cylindrical tank container.
Drying in step 3) to refer in the solvent that volatilizes in step 3) and rubber synthesis that unreacted monomer enters in condenser and fractionating column and reclaims, separated heating medium, the mixture separated from heat medium proceeds in heating belt type drying machine again, in vacuum, inert gas (such as nitrogen) or air, carry out drying; Or in the solvent volatilized in step 3) and rubber synthesis, unreacted monomer enters in condenser and fractionating column and reclaims, and then carries out extruding heat drying to remaining mixture.Wherein when using water vapour for heat medium, in dried solid mixture, can contain water, more optional through vacuum drying, heat drying or extrude after heat drying and obtain rubber/filler masterbatch.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 can be dry further again after first extruding removes liquid heating 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 of the present invention has following 2 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 cohesion process 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.
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.Then mixture is joined continuously in grinder and carry out essence dispersion, obtain smart dispersed mixture, then mixture is directly passed in the tank of the water being filled with about 95 DEG C and condense.To condense and proceed to after the dehydration of the micelle of desolventizing in heating belt type drying machine, heat drying obtains rubber master batch 1 under vacuo.
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 mixture is directly passed in the tank of the water being filled with about 95 DEG C and carry out condensing and solvent is volatilized, then solvent enters condenser recovery, containing micelle and water in tank, after screening, obtain moisture micelle, then this micelle is proceeded in single screw extrusion machine to dehydrate and obtain rubber master batch 2.
The rubber master batch 1,2 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 1,2.
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.
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 n-hexane boiling point, the polarity of this heat medium is different from the polarity of n-hexane, mixture coagulated deswelling, and n-hexane volatilizees rapidly, thus formed containing the rubber/white carbon/Si69 compound of this heat medium and the mixture of normal hexane;
Step 3): remove normal hexane and drying is carried out to remaining mixture, obtaining rubber/white carbon/Si69 masterbatch;
Wherein, step 2) in use water vapour to be heat medium, optionally after vacuum drying, heat drying or extruding heat drying, obtain rubber/filler masterbatch again;
Or, wherein step 2) described in heat medium be water, optionally again through vacuum drying, heat drying or extruding heat drying after anhydrating, obtain rubber/filler masterbatch;
Wherein, in step 3) in the n-hexane that volatilizes and rubber synthesis unreacted monomer enter in condenser and fractionating column and reclaim, separated heating medium, the mixture separated from heat medium proceeds in heating belt type drying machine again, in vacuum, inert gas or air, carry out drying; Or in step 3) in the n-hexane that volatilizes and rubber synthesis unreacted monomer enter in condenser and fractionating column and reclaim, then extruding heat drying is carried out to remaining mixture.
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 said inert gas is nitrogen.
5. method according to claim 4, wherein said heat drying is oven dry or air-dry.
6. method according to claim 4, 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 is for using masticator, single screw extrusion machine, and double screw extruder carries out drying.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310337560.1A CN103419292B (en) | 2013-08-05 | 2013-08-05 | Rubber masterbatch prepared by the method for continuously producing of rubber masterbatch and the method |
| CA2920409A CA2920409C (en) | 2013-08-05 | 2014-07-22 | Continuous method for manufacturing rubber masterbatch and rubber masterbatch prepared thereby |
| MYPI2016000228A MY193024A (en) | 2013-08-05 | 2014-07-22 | Continuous method for manufacturing rubber masterbatch and rubber masterbatch prepared thereby |
| PCT/CN2014/082714 WO2015018281A1 (en) | 2013-08-05 | 2014-07-22 | Continuous manufacturing process for rubber masterbatch and rubber masterbatch prepared therefrom |
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| CN201310337560.1A CN103419292B (en) | 2013-08-05 | 2013-08-05 | Rubber masterbatch prepared by the method for continuously producing of rubber masterbatch and the method |
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| CN (1) | CN103419292B (en) |
| CA (1) | CA2920409C (en) |
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| WO (1) | WO2015018281A1 (en) |
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| CN103419292B (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 |
| 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 |
| FR3045621B1 (en) * | 2015-12-16 | 2017-11-17 | Michelin & Cie | PROCESS FOR THE PREPARATION OF A MASTER MIXTURE, COMPRISING A DIENE ELASTOMER, A REINFORCING ORGANIC CHARGE AND AN ANTIOXIDANT AGENT |
| FR3045620B1 (en) * | 2015-12-16 | 2017-11-17 | Michelin & Cie | PROCESS FOR THE PREPARATION OF A MASTER MIXTURE, COMPRISING A DIENE ELASTOMER, A REINFORCING ORGANIC LOAD, AND, POSSIBLY, ANTIOXIDANT AGENT |
| CN106750389A (en) * | 2016-11-17 | 2017-05-31 | 北京化工大学 | A kind of method that wet method prepares white carbon black/solution polymerized butadiene styrene rubber rubber master batch |
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| TW360585B (en) * | 1996-04-01 | 1999-06-11 | Cabot Corp | Elastomeric compositions and methods and apparatus for producing same |
| CN101463149B (en) * | 2007-12-19 | 2011-11-09 | 北京化工大学 | Preparation of wear resistant rubber composite material |
| JP5651062B2 (en) * | 2011-03-31 | 2015-01-07 | 東洋ゴム工業株式会社 | Rubber composition, method for producing the same, and pneumatic tire |
| CN103159990B (en) * | 2011-12-08 | 2014-12-31 | 中国石油化工股份有限公司 | Master batch and preparation method thereof, and vulcanized rubber and applications thereof |
| CN103113597B (en) * | 2013-01-30 | 2018-07-27 | 怡维怡橡胶研究院有限公司 | Rubber masterbatch prepared by the method for continuously producing and this method of rubber masterbatch |
| CN103419292B (en) * | 2013-08-05 | 2016-04-27 | 怡维怡橡胶研究院有限公司 | Rubber masterbatch prepared by the method for continuously producing of rubber masterbatch and the method |
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| Publication number | Publication date |
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| CA2920409A1 (en) | 2015-02-12 |
| WO2015018281A1 (en) | 2015-02-12 |
| MY193024A (en) | 2022-09-22 |
| CA2920409C (en) | 2018-09-04 |
| CN103419292A (en) | 2013-12-04 |
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