CN103203810A - Continuous manufacturing method for rubber masterbatch, rubber masterbatch prepared by using continuous manufacturing method and rubber product - Google Patents
Continuous manufacturing method for rubber masterbatch, rubber masterbatch prepared by using continuous manufacturing method and rubber product Download PDFInfo
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Abstract
The invention relates to a continuous manufacturing method for rubber masterbatch, the rubber masterbatch prepared by using the continuous manufacturing method and a rubber product. The manufacturing method comprises the following steps: 1) adding a filling material into a rubber solution, carrying out stirring so as to form a rubber/filling material/solvent mixture and subjecting the rubber/filling material/solvent mixture to further fine dispersion and refined dispersion so as to improve the dispersion degree of the filling material in the rubber solution; 2) subjecting rubber and the filling material in the rubber/filling material/solvent mixture having undergone refined dispersion in step 1) to hetero-coagulation so as to obtain a mixture of a rubber/filling material compound and a solvent; and 3) removing the solvent and drying the mixture so as to obtain the rubber/filling material masterbatch. The invention further provides the masterbatch prepared by using the manufacturing method and the rubber product prepared from the masterbatch. Compared with a conventional wet rubber compounding technology, the invention has the following advantages: there are no special requirements on rubber and the filling material, the prepared masterbatch has a wide application scope, and dispersity of the filling material in a rubber compound is accordingly improved.
Description
Technical field
The present invention relates to rubber materials, particularly rubber masterbatch and the rubber of the preparation of a kind of method for continuously producing of rubber masterbatch and this method.
Background technology
In the modern rubber industry, the sizing material that manufactures a product contains the fine particle pulverulent filler more than 99%, their application is the supporting material as rubber on the one hand, claim reinforcing agent again, improve physical and mechanical properties such as tensile stress, tensile strength, elongation at break, the tear resistance of rubber, and improve the serviceability of rubber product, such as anti-wear performance, frictional behaviour, dynamic antivibration (hysteresis) performance, anti-stabbing etc.; Can give rubber some special functions on the other hand again, such as conduction and insulating properties, heat conduction and heat-insulating property, radiation resistance, magnetic property, and improve the resistant to chemical media aggressivity of rubber, reduce the swellability of rubber in solvent and increase air-tightness etc.In addition, add the volume that filler can increase sizing material in the sizing material, compare the lower filler of price with used rubber substrate for the unit volume price, their application also can make the cost of rubber descend.Therefore, filler is only second to rubber itself and occupies second always at the raw-material consumption of rubber.In addition, also needing to add various additives in making the required sizing material of rubber makes rubber cross or improves the processing characteristics of sizing material and some characteristic of rubber.
In making the sizing material of rubber, most important technology is added in filler and additive exactly and makes it reach even dispersion in the rubber in rubbery parent substance.In fact, want to optimize filler to application performances such as reinforcing rubber or fillings, and the function of performance additive, at first to make it reach fine dispersion.Disperse bad meeting to make rubber bring other problems, in some cases, be used for to disperse filler with the additive cost than the cost of filler itself taller go out many.
The conventional approach that filler and additive are sneaked in the rubber is with large-scale mixing facilities, comprising banbury, masticator and opening rubber mixing machine filler and the additive of Powdered or liquid are sneaked in the solid rubber, this kind technology mixing time is long, power consumption is high, dust is many and dispersed extreme difference, thereby the physical and mechanical properties of vulcanizate and rubber product quality are very restricted.
States such as the U.S., Britain, Malaysia, India and China all once attempted to make carbonblack master batch with latex in history, but suitability for industrialized production all is unrealized, mainly contain the preparation method (CN99807464, CN99807105, CN99127509, CN99125587, CN00103762, CN00117904, CN200710199527) of the powdered rubber of German PKU Pulverkautschuk Union GmbH over the past two decades at this a few thing on the one hand, the technical characterstic of the method is: rubber latex is mixed back adding chemicals reach cohesion with the carbon black water slurry.The method is batch production, except complex technical process, waste time and energy, production efficiency low outside, to be that masterbatch viscosity is high especially be difficult to processing to its product major defect, and the anti-wear performance of vulcanizate and goods thereof is relatively poor.Although its reason mainly is because carbon black scattered, thereby a large amount of non-rubber components is adsorbed onto the interaction that filling surface has destroyed rubber-filler in carbon black dispersion and latex mixed process.Need coupling agent to increase the interactional filler of rubber/filler for some, the absorption of non-rubber component has also hindered the coupling reaction of rubber molecule and filling surface.These problems until the early 1990s in last century U.S. Cabot Corporation developed liquid phase with Heveatex and carbon black water slurry and make the technology of natural gum/carbonblack master batch continuously and just solved (US19970823411, CN97195156, CN98811684, CN00808002, CN02825969).The method that this liquid phase continuous mixing prepares rubber/filler masterbatch has simplified rubber mixing technique, mixing time, has reduced energy consumption and artificial, but used packing variety and content is restricted in the rubber master batch preparation.When continuity method is mixed cohesion continuously by latex and filler water slurry, when using the strong filler of hydrophily such as white carbon, the cohesion back is more at the residual filler of aqueous phase, increase the difficulty of water treatment, and amount of filler too high or too low all can not be effectively with condensation product and moisture from, the method also can not directly be used for rubber solutions and filler are prepared filler/rubber masterbatch.
Summary of the invention
Rubber masterbatch and the rubber of the method for continuously producing of rubber masterbatch of the present invention and the preparation of this method, at prior art problems and the purpose of its invention provides the rubber masterbatch of a kind of method for continuously producing of rubber masterbatch and the preparation of this method, in the hope of improving the decentralization of filler in rubber size, production technology is continuous, efficient, low power consuming, few artificial, thereby cost is lower.
Another goal of the invention is, a kind of rubber that uses rubber masterbatch preparation of the present invention is provided, thereby improve the rubber master batch of use the method preparation in processing characteristics, physical and mechanical properties and product quality, and can save the postprocessing working procedures after the existing solution polymerized rubber polymerisation.
The advantage of rubber masterbatch method for continuously producing of the present invention is: 1) continuous high-efficient; 2) good dispersion of filler and additive; 3) mix and cohesion evenly and speed fast; 4) owing to there is not the adding of water in the mixed process, the therefore desolventizing drying and be not subjected to the interference of water rapidly of the mixture after the cohesion; 5) because the high dispersive of filler and additive and do not have other materials and disturb can significantly improve the physical and mechanical properties of vulcanizate and the quality of rubber; 6) when making masterbatch with solution polymerized rubber, can save that rubber solutions mixes, heats a series of last handling processes such as coacervation process, separated from solvent and recovery, rubber dehydration, drying, packing in the solution polymerized rubber production technology with water, reduce the manufacturing cost of solution polymerized rubber greatly; 7) the method for the invention applied widely to the kind of rubber and filler and additive and content.
The invention further relates to following embodiment:
1, a kind of method for continuously producing of rubber masterbatch comprises the steps:
Step 1): filler is joined in the rubber solutions, by stir forming rubber/filler/solvent mixture, and to described rubber/filler/solvent mixture further finely divided and smart dispersion with the degree of scatter of raising filler in rubber solutions;
Step 2): rubber and filler in the rubber/filler/solvent mixture after essence is disperseed in the step 1) are condensed altogether, obtain the mixture of rubber/filler compound and solvent;
Step 3): remove solvent and described mixture is carried out drying, obtain rubber/filler masterbatch.
2, according to embodiment 1 described method, optional recycling step 3 wherein) solvent that removes is recycling.
3, according to embodiment 1 described method, wherein in step 1) and/or step 2) in optional add one or more and be selected from the additive of oil, age resistor, coupling agent, activating agent, antioxidant, fire retardant, heat stabilizer, light stabilizer, dyestuff, pigment, vulcanizing agent and promoter.
4, according to the described method of embodiment 1-3, finely divided as described below described in the step 1) wherein:
I). the rubber/filler after will stirring/solvent mixture or rubber/filler/additive/solvent mixture is by spraying under the nozzle situation under high pressure, and used pressure limit is from 2MPa to 60MPa, preferred 10MPa to 40MPa;
II). make above-mentioned I) in ejecta make rubber/filler/solvent mixture or rubber/filler/additive/solvent mixture increase the dispersiveness of filler at Guan Zhongyu tube wall bump by swan neck more than; Or
III). make above-mentioned I) in ejecta by bore pipeline of changing of folding and unfolding repeatedly, come the conversion shear stress and increase the dispersiveness of filler.
5, according to the described method of embodiment 1-3, wherein the essence described in the step 1) is separated into and disperses adding continuously in ball mill and/or the colloid mill through the mixture after finely divided.
6, according to the described method of embodiment 1-3, wherein the essence described in the step 1) is separated into and grinds joining in the grinder continuously through the mixture after finely divided, and this grinder has the plane mill of one or more groups high-speed rotation and is fixed on the grinder sleeve and fixing pin or the price fixing alternate with the plane mill.
7, according to the described method of embodiment 1-3, wherein the essence described in the step 1) is separated into and grinds joining in the grinder continuously through the mixture after finely divided, this grinder has two blades of direction of rotation, and described blade has the pore chute.
8, according to the described method of embodiment 1-3, wherein the essence described in the step 1) is separated into and will joins continuously in the multi-layer high-voltage slit dispersion machine through the mixture after finely divided, mixture is under high pressure extruded the slit between two-layer, used pressure limit is from 2MPa to 60MPa, preferred 10MPa to 40MPa.
9, according to the described method of embodiment 1-3, wherein the essence described in the step 1) is separated into and disperses joining continuously in the power decentralized device through the mixture after finely divided, and radially-arranged slit or hole are arranged on the rotor of power decentralized device.
10, according to the described method of embodiment 5-9, wherein with two or more use of connecting mutually in the described smart process for dispersing of embodiment 5-9.
11, according to the described method of embodiment 1-10, wherein said rubber solutions is directly to obtain from preparation solution polymerized rubber production line, or the dried glue of any kind is dissolved preparation in the good solvent of this rubber.
12, according to embodiment 11 described methods, when wherein preparing rubber solutions with dried glue, described dried glue is natural polymer or synthetic polymer, described natural polymer comprises natural gum, gutta-percha, guayule, and described synthetic polymer is that monomer polymerization gained, monomer polymerization gained or monomer body in emulsion in solution carries out the polymerization gained.
13, according to embodiment 11 described methods, when wherein said rubber solutions directly obtains from preparation solution polymerized rubber production line, described solution polymerized rubber is the triolefin of the diene of ethene, propylene, butylene, amylene, hexene, heptene, a 4-7 carbon atom or 6-7 carbon atom or homopolymerization or the copolymerized polymer that contains the vinyl monomer of other atom or functional group, described other atoms or functional group are silicon atom, fluorine atom, chlorine atom, nitrogen-atoms, oxygen atom, sulphur atom, ester group, the amino ester group, cyano group.
14, according to embodiment 13 described methods, the rubber in the wherein said rubber solutions is polybutadiene, polyisoprene, butadiene-styrene rubber, second third glue, butyl rubber, NBR, neoprene, silicon rubber, fluorubber, polyurethane rubber, CSM, ACM.
15, according to the described method of embodiment 1-14, wherein the concentration range of rubber in solution is 1% weight to 60% weight, preferred 5% weight to 40% weight, more preferably 10% weight to 30% weight.
16, according to the described method of embodiment 1-15, the molecular weight of rubber is 1,000 to 4,000 ten thousand in the wherein said rubber solutions, and is preferred 5,000 to 3,000 ten thousand, more preferably 10,000 to 8,000,000.
17, according to the described method of embodiment 1-16, the solvent in the wherein said rubber solutions is the good solvent of various rubber.
18, according to embodiment 1 described method, wherein said filler is solid powdery reinforcing agent and/or filler used in the rubber.
19, according to embodiment 18 described methods, wherein said filler contains the nanometer materials of carbon black, silica, metal oxide, calcium carbonate, potter's clay and/or resin and above-mentioned filler; Or described filler is two-phase or the heterogeneous filler of carbon black, silica, aluminium oxide, magnesia, zinc oxide, calcium oxide, titanium oxide, boron oxide composition; Or described above-mentioned filler and use mixture.
20, according to embodiment 18 described methods, the specific area of wherein said filler is 0.1 to 800m
2/ g, preferred 1 to 500m
2/ g, more preferably 5 to 300m
2/ g.
21, according to embodiment 19 described methods, the oil factor of wherein said carbon black and silica is 20 to 250ml/100g, and preferred 25 to 200ml/100g, and more preferably 30 to 150ml/100g.
22, according to embodiment 1 described method, wherein choose wantonly described filler is carried out surface modification.
23, according to embodiment 22 described methods, wherein said surface modification is for to be connected on filling surface by chemical reaction with functional group, or by mixing or absorption is combined in filling surface with modifier.
24, according to embodiment 22 described methods, wherein said surface modification was carried out before adding filler in the rubber solutions, or modifier was joined in the mixture of rubber solutions and filler and carry out surface modification.
25, according to the described method of embodiment 1-3, wherein in step 1), directly filler dry powder and/or additive dry powder are joined in the rubber solutions, or earlier filler and/or additive are joined with the identical or different solvent of rubber solutions in join rubber solutions again after mixing formation uniform filler/solvent suspension liquid or filler/additive/solvent suspension liquid, sneak in the rubber solutions by stirring; Liquid additive can directly join in the rubber solutions.
26, according to embodiment 1 described method, wherein the stirring in the step 1) is finished by mixer.
27, method according to claim 25, wherein said mixer are blade paddle mixer, trough mixer, planetary stirring machine, Z-blade mixer.
28, a kind of rubber masterbatch according to the described method preparation of embodiment 1-27.
29, a kind of rubber, its use prepares according to embodiment 28 described rubber masterbatch.
The method for continuously producing of rubber masterbatch of the present invention comprises the steps:
Step 1): filler is joined in the rubber solutions, by stir forming rubber/filler/solvent mixture, and to described rubber/filler/solvent mixture further finely divided and smart dispersion with the degree of scatter of raising filler in rubber solutions;
Step 2): rubber and filler in the rubber/filler/solvent mixture after essence is disperseed in the step 1) are condensed altogether, obtain the mixture of rubber/filler compound and solvent;
Step 3): remove solvent and described mixture is carried out drying, obtain rubber/filler masterbatch.
The method for continuously producing of rubber masterbatch of the present invention is the optional recycling step 3 that comprises also) solvent that removes is with recycling step.In addition, in step 1) and/or step 2) in optional add one or more and be selected from the additive of oil, age resistor, coupling agent, activating agent, antioxidant, fire retardant, heat stabilizer, light stabilizer, dyestuff, pigment, vulcanizing agent and promoter.
Stirring described in the step 1) can use general mixer to finish, and includes but not limited to blade paddle mixer, trough mixer, planetary stirring machine, Z-blade mixer etc.
Finely divided can enforcement in the following way described in the step 1): the mixture of above-mentioned stirring gained is sprayed under the situation of high pressure high shear by a nozzle, to improve the dispersion of filler and/or additive; And then make above-mentioned ejecta make mixed liquor increase the dispersiveness of filler and/or additive at Guan Zhongyu tube wall bump by swan neck more than; Or make ejecta by a bore repeatedly the pipeline that changes of folding and unfolding come the conversion shear stress to increase the dispersion of filler and/or additive.Used pressure limit is from 2MPa to 60MPa, preferred 10MPa to 40MPa.
Can also further improve filler and/or the dispersion of additive in rubber solutions by following smart dispersion at the formed mixture in finely divided back described in the step 1):
I. described finely divided mixture is afterwards added in ball mill and/or the colloid mill continuously and disperse, make filler and/or additive be dispersed in the rubber solutions uniformly;
Ii. described finely divided mixture is afterwards joined continuously and grind in the grinder so that filler and/or additive are well dispersed in the rubber solutions, this grinder has the plane mill of one or more groups high-speed rotation and is fixed on the grinder sleeve and fixing pin or the price fixing alternate with the plane mill.
Iii. described finely divided mixture is afterwards joined in the grinder continuously and grind, this grinder has two blades of direction of rotation, described blade has the pore chute, under high pressure can improve filler and/or the degree of scatter of additive in rubber solutions by the blade of rotation.Used pressure limit is from 2MPa to 60MPa, preferred 10MPa to 40MPa.
Iv. described finely divided mixture is afterwards joined in the multi-layer high-voltage slit dispersion machine continuously, mixture is under high pressure extruded the slit between two-layer, and the strong shearing force that produce this moment can improve filler and/or the degree of scatter of additive in rubber solutions.Used pressure limit is from 2MPa to 60MPa, preferred 10MPa to 40MPa.
V. described finely divided mixture is afterwards joined in the power decentralized device continuously and disperse, many radially-arranged slits or hole are arranged on the high speed rotor rotated of described power decentralized device, mixture with high-speed impact on stator surface so that filler and/or additive be evenly dispersed in the rubber solutions.
Two or more of above-mentioned five kinds of finely divided methods use of can connecting mutually.
Described rubber solutions can directly directly obtain from preparation solution polymerized rubber production line, also the dried glue of any kind can be dissolved preparation in the solvent of this glue.When preparing rubber solutions with dried glue, described dried glue can be the rubber of any kind of used in the art, as natural polymer or synthetic polymer.Described natural polymer includes but not limited to natural gum, gutta-percha, guayule etc.; Described synthetic polymer includes but not limited to that monomer polymerization gained (namely containing intermingle with rubber), monomer polymerization gained (being emulsion polymerized rubber), monomer body in emulsion in solution carries out the polymerization gained.When described rubber solutions directly obtains from preparation solution polymerized rubber production line, described solution polymerized rubber includes, but are not limited to polybutadiene, polyisoprene, butadiene-styrene rubber, second third glue, butyl rubber, NBR, neoprene etc. for the triolefin of the diene of ethene, propylene, butylene, amylene, hexene, heptene, a 4-7 carbon atom or 6-7 carbon atom or contain homopolymerization or the copolymerized polymer of the vinyl monomer of other atom or functional group.The molecular weight of rubber is 1,000 to 4,000 ten thousand, and is preferred 5,000 to 3,000 ten thousand, more preferably 10,000 to 8,000,000.
Solvent in the described rubber solutions is the good solvent of various rubber.Solvent is specifically as follows aliphatic solvent, aromatic hydrocarbon solvent, chlorinated hydrocarbon solvent, ketones solvent, ether solvent and esters solvent, described aliphatic solvent includes, but are not limited to all kinds of solvents gasoline, cycloalkane, substituted ring alkane, normal alkane, described aromatic hydrocarbon solvent includes but not limited to benzene,toluene,xylene, styrene, and described chlorinated hydrocarbon solvent includes but not limited to carrene, chloroform, carbon tetrachloride, dichloroethanes, chlorobenzene, tetrachloro-ethylene, chlorotoluene.The concentration range of rubber in solution is 1% weight to 60% weight, preferred 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 the rubber, as all kinds of carbon blacks, silica, metal oxide, salt, different resins and various fine particle solid powder substance.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, preferred 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, preferred 25 to 200ml/100g, more preferably 30 to 150ml/100g, wherein said filler comprises their mixture, as heterogeneous filler, comprising but be not limited to two-phase or the heterogeneous filler that carbon black, silica, aluminium oxide, magnesia, zinc oxide, calcium oxide, titanium oxide, boron oxide etc. are formed, for two-phase or heterogeneous filler, its oil factor is 20 to 250ml/100g, preferred 25 to 200ml/100g, and more preferably 30 to 150ml/100g.The consumption of filler is 5 to 300 weight portions (be 100 weight portions in rubber), preferred 10 to 200 weight portions, more preferably 30 to 150 weight portions.That described filler also comprises in the above-mentioned filler two or more and use thing.
Described filler also comprises their surface modifying stuffing.Wherein said surface modification can be certain functional group to be connected on filling surface or by mixing or absorption and modifier is combined on the filling surface by physics mode by chemical reaction.Described surface modification can be carried out before adding filler in the rubber solutions, or modifier was joined in the mixture of rubber solutions and filler and carry out surface modification.Described modifier is the modifier of this area routine, such as the organo silane coupling agent of representing with following general formula:
(R
n-(RO)
3-nSi-(Alk)
m-(Ar)
p)
q(A) (I)
R
n’(RO)
3-nSi-(Alk) (II)
Or R
n' (RO)
3-nSi-(Alk
EnyL) (III)
In the formula, when q=1, A is-SCN-SH ,-Cl ,-NH
2
When 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 can be different;
N is 0,1 or 2;
Alk is the straight or branched alkyl that contains 1 to 6 carbon atom;
Alk
EnyL is the straight or branched thiazolinyl that contains 1 to 6 carbon atom;
M is 0 or 1;
Ar is the aryl that contains 6 to 12 carbon atoms;
P be 0 or 1, p and n can not be 0 simultaneously;
X is 2 to 8;
Wherein the most frequently used is two (triethoxy propyl silane) tetrasulfides and disulphide, 3-thiocyanogen propyl group-triethoxysilane, γ-sulfydryl-trimethoxy silane, zirconium ester coupling agent, phthalate ester coupling agent, nitro coupling agent, alcohol compound, described alcohol compound includes but not limited to unit alcohol, dihydroxylic alcohols, polyalcohol, and described alcohol compound includes but not limited to propyl alcohol, butanols, ethylene glycol, polyethylene glycol and derivative thereof.
Step 1) of the present invention can directly join filler dry powder and/or additive in the rubber solutions, also can be earlier with filler and/or additive join with the identical or different solvent of rubber solutions in mix to form and add again behind the uniform suspension and sneak in the rubber solutions by stirring.Additive can be chosen one or more in the additive that comprises oil, age resistor, coupling agent, activating agent, antioxidant, heat stabilizer, light stabilizer, fire retardant, dyestuff, pigment, vulcanizing agent or promoter wantonly.The consumption of additive therefor is conventional amount used, or adjusts according to practical requirements.
The method that rubber, filler and/or additive in the mixture after the finely divided and smart dispersion are condensed altogether can be used any known method in this area, as flocculant flocculence, heating, move back solvent method etc.
Drying means in the step 3) can use any known method in this area, dry, drying under reduced pressure, spray-drying, fluidized drying, freeze drying, infrared drying, microwave drying, hygroscopic desiccation etc. of pressing dry as usual.
The method of described recovery solvent can be used any known method in this area, as solvent that will vaporization by surface condensation or directly the method for condensation by contact reclaimed.Cooling agent can adopt water when using the method for direct condensation contact.
Compare with existing wet method elastomeric compound technology, the present invention does not have specific (special) requirements to rubber, filler, and the scope of application is wider.In addition, the decentralization height of filler in rubber size, production technology is continuous, efficient, low power consuming, few artificial, thereby cost is lower.Simultaneously, use the rubber master batch of the method preparation all very superior on processing characteristics, physical and mechanical properties, product quality, and can save the postprocessing working procedures after the existing solution polymerized rubber polymerisation.
The specific embodiment
Further describe the present invention with embodiment below, but scope of the present invention is not subjected to the restriction of these embodiment.
(1) embodiment uses following instrument and equipment and assay method to measure:
The instrument and equipment of table 1 rubber sample preparation
| Sequence number | Device name | Specifications and models | Manufacturer |
| 1 | Banbury | XSM-1/10-120 | Shanghai Kechuang rubber and plastics machine equipment Co., Ltd |
| 2 | Mill | 152.5*320 | Zhanjiang Machine Factory, Guangdong Prov. |
| 3 | Vulcanizing press | XLB-D600*600 | East, Huzhou, Zhejiang machinery Co., Ltd |
The method of testing of table 2 vulcanizating glue physical performance and instrument
(2) embodiment and Comparative Examples
Raw material:
Synthetic polyisoprenes rubber, IR-70, her Cohan new material Co., Ltd of Qingdao;
Solution polymerized butadiene styrene rubber, VSL4526-OHM, LANXESS produces;
Butadiene rubber, BR9000, Qilu Co., Ltd., China Petrochemical Corp;
White carbon, Newsil HD165MP really becomes chemistry of silicones limited company;
Carbon black N234, Cabot (China) Investment Co., Ltd;
Zinc oxide, Dalian zinc oxide factory;
The boron resin acid, PF1808, Co., Ltd is found into by Malaysia;
Age resistor 4020, Flexsys Chemical (M) Sdn Bhd;
Antioxidant 264, Huangyan, Zhejiang East Zhejiang province rubber chemicals Co., Ltd;
Anti-aging agent RD, Nanjing Chemical Industry Co., Ltd., SINOPEC chemical plant;
Silane coupler Si69, NanJing Shuguang Chemical Group Co., Ltd.;
Accelerant CZ, Shandong be Shun's chemical industry Co., Ltd still;
Diphenylguanidine, Dan County, Shandong chemical industry Co., Ltd;
Sulfur, Lin Yiluo Zhuan Xin Anhua factory;
Antiscorching agent (CTP), Shandong Yanggu Huatai Chemical Co., Ltd..
Umber is weight portion described in following examples and the Comparative Examples.
Embodiment 1
60 parts of white carbons, 6 parts of silane coupler Si69 are joined in the hexane solution of 100 part of 8% cis-polyisoprene, after its rubber/white carbon/Si69/ n-hexane mixture mixes by first mixed, the thin mixed smart mode of mixing shown in the table 3, inject cohesion in the knockouts continuously, spray into the interior desolventizing of drier and drying afterwards and obtain rubber master batch 1.
With rubber master batch 1 mill bag roller evenly after, add 3.5 parts of zinc oxide, 1 part of stearic acid, 1.5 parts of anti-aging agent RDs, 2 parts of age resistor 4020,1.6 parts of antiscorching agent, after adding 2 parts of accelerant CZs, 1 part of diphenylguanidine, 1.6 parts of Sulfurs again, cross roller, following sheet, park that the vulcanizing press with 150 ℃ vulcanizes to optimum cure after 8 hours, make wet method vulcanizate 1.
Comparative Examples 1
In banbury, 60 parts of white carbons, 6 parts of silane couplers joined carry out in the middle of 100 parts the cis-polyisoprene mixing, mixing certain hour, add 3.5 parts of zinc oxide, 1 part of stearic acid, 1.5 parts of anti-aging agent RDs, 2 parts of age resistor 4020,1.6 parts of antiscorching agent, elastomeric compound is parked and is added 2 parts of accelerant CZs, 1 part of diphenylguanidine, 1.6 parts of Sulfurs after 8 hours again, elastomeric compound parks that the vulcanizing press with 150 ℃ vulcanizes to optimum cure after 8 hours, makes dry method vulcanizate 1.
Embodiment 2
78 parts of white carbons, 6.4 parts of silane coupler Si69 and antioxidant 264 are joined in the hexane solution of 70 parts of solution polymerized butylbenzene glue and 30 parts of cis-butadiene cements, after its rubber/white carbon/Si69/ antioxidant 264/n-hexane mixture mixes by first mixed, the thin mixed smart mode of mixing shown in the table 3, inject cohesion in the knockouts continuously, spray into the interior desolventizing of drier and drying afterwards and obtain rubber master batch 2 through the further drying of double screw extruder.
With rubber master batch 2 mill bag roller evenly after, add 28 parts of high aromatic oils, 3.5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of age resistor 4020,2 parts of paraffin, sheet under after mixing, park after 8 hours again after mill adds 1.3 parts of accelerant CZs, 0.3 part of diphenylguanidine, 1.4 parts of Sulfurs, cross roller, following sheet, elastomeric compound parks that the vulcanizing press with 150 ℃ vulcanizes to optimum cure after 8 hours, makes wet method vulcanizate 2.
Comparative Examples 2
In banbury, with 78 parts of white carbons, 6.4 parts of silane couplers join carry out in 70 parts of solution polymerized butylbenzene glue and the 30 parts of cis-butadiene cements mixing, mixing certain hour, add 28 parts of high aromatic oils, 3.5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of age resistor 4020,2 parts of paraffin, elastomeric compound park after 8 hours in banbury, add again behind 1.3 parts of accelerant CZs, 0.3 part of diphenylguanidine, the 1.4 parts of Sulfurs mixing, elastomeric compound parks that the vulcanizing press with 150 ℃ vulcanizes to optimum cure after 8 hours, makes dry method vulcanizate 2.
Embodiment 3
78 parts of white carbons, 6.4 parts of silane coupler Si69,28 parts of high aromatic oils, 3.5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of antioxidant 264s and 2 parts of paraffin are joined in the hexane solution of 70 parts of solution polymerized butylbenzene glue and 30 parts of cis-butadiene cements, after its rubber/white carbon/additive/n-hexane mixture mixes by first mixed, the thin mixed smart mode of mixing shown in the table 3, inject cohesion in the knockouts continuously, spray into desolventizing and dry in the drier afterwards, and obtain rubber master batch 3 through the further drying of double screw extruder.
With rubber master batch 3 mill bag roller evenly after, adds 1.3 parts of accelerant CZs, 0.3 part of diphenylguanidine, 1.4 parts of Sulfurs after, cross roller, time sheet, elastomeric compound parks that the vulcanizing press with 150 ℃ vulcanizes to optimum cure after 8 hours, makes wet method vulcanizate 3.
The technological process of table 3 continuous mixing
| Sequence number | Just mix | Thin mixing | Smart mixing |
| Rubber master batch 1 | The blade mixer | The curved tube disperser | Kinetic dispersion mill |
| Rubber master batch 2 | Planetary stirring machine | Caliber changes disperser | Multi-layer high-voltage slit dispersion machine |
| Rubber master batch 3 | Z-blade mixer | The curved tube disperser | Ball mill |
Table 4 is wet, the physical property of dry method vulcanizate
Table 4 is the physical property of the resulting vulcanizate of Comparative Examples of the embodiment of wet masterbatch under different formulations and technology and dry method elastomeric compound, therefrom as can be seen, under same recipe, wet masterbatch is compared with maskerbatch of dry process, and the degree of scatter of filler in rubber improves greatly, and the hardness of vulcanizate is lower, hot strength and elongation at break are higher, the elasticity height, dynamic compression is given birth to hot low, and anti-wear performance is better.
Claims (29)
1. the method for continuously producing of a rubber masterbatch is characterized in that: comprises the steps,
Step 1) joins filler in the rubber solutions, by stir forming rubber/filler/solvent mixture, and to described rubber/filler/solvent mixture further finely divided and smart dispersion with the degree of scatter of raising filler in rubber solutions;
Step 2), rubber and filler in the rubber/filler/solvent mixture after essence is disperseed in the step 1) are condensed altogether, obtain the mixture of rubber/filler compound and solvent;
Step 3) removes solvent and described mixture is carried out drying, obtains rubber/filler masterbatch.
2. the method for continuously producing of rubber masterbatch according to claim 1 is characterized in that: optional recycling step 3 wherein) solvent that removes, recycling.
3. the method for continuously producing of rubber masterbatch according to claim 1 is characterized in that: wherein in step 1) and/or step 2) in optional add one or more and be selected from the additive of oil, age resistor, coupling agent, activating agent, antioxidant, fire retardant, heat stabilizer, light stabilizer, dyestuff, pigment, vulcanizing agent and promoter.
4. according to the method for continuously producing of claim 1,2 or 3 described rubber masterbatch, it is characterized in that: finely divided as described below described in the step 1) wherein,
I). the rubber/filler after will stirring/solvent mixture or rubber/filler/additive/solvent mixture is by spraying under the nozzle situation under high pressure, and used pressure limit is from 2MPa to 60MPa, preferred 10MPa to 40MPa;
II). make above-mentioned I) in ejecta make rubber/filler/solvent mixture or rubber/filler/additive/solvent mixture increase the dispersiveness of filler at Guan Zhongyu tube wall bump by swan neck more than; Or
III). make above-mentioned I) in ejecta by bore pipeline of changing of folding and unfolding repeatedly, come the conversion shear stress and increase the dispersiveness of filler.
5. according to the method for continuously producing of claim 1,2 or 3 described rubber masterbatch, it is characterized in that: wherein the essence described in the step 1) is separated into and disperses adding continuously in ball mill and/or the colloid mill through the mixture after finely divided.
6. according to the method for continuously producing of claim 1,2 or 3 described rubber masterbatch, it is characterized in that: wherein the essence described in the step 1) is separated into and grinds joining in the grinder continuously through the mixture after finely divided, and this grinder has the plane mill of one or more groups high-speed rotation and is fixed on the grinder sleeve and fixing pin or the price fixing alternate with the plane mill.
7. according to the method for continuously producing of claim 1,2 or 3 described rubber masterbatch, it is characterized in that: wherein the essence described in the step 1) is separated into and grinds joining in the grinder continuously through the mixture after finely divided, this grinder has two blades of direction of rotation, and described blade has the pore chute.
8. according to the method for continuously producing of claim 1,2 or 3 described rubber masterbatch, it is characterized in that: wherein the essence described in the step 1) is separated into and will joins continuously in the multi-layer high-voltage slit dispersion machine through the mixture after finely divided, mixture is under high pressure extruded the slit between two-layer, used pressure limit is from 2MPa to 60MPa, preferred 10MPa to 40MPa.
9. according to the method for continuously producing of claim 1,2 or 3 described rubber masterbatch, it is characterized in that: wherein the essence described in the step 1) is separated into and disperses joining continuously in the power decentralized device through the mixture after finely divided, and radially-arranged slit or hole are arranged on the rotor of power decentralized device.
10. according to the method for continuously producing of any described rubber masterbatch of claim in the claim 5 to 9, it is characterized in that: wherein with two or more use of connecting mutually in the described smart process for dispersing of claim 5-9.
11. the method for continuously producing according to any described rubber masterbatch of claim in the claim 1 to 10, it is characterized in that: wherein said rubber solutions is directly to obtain from preparation solution polymerized rubber production line, or the dried glue of any kind is dissolved preparation in to the good solvent of this glue.
12. the method for continuously producing of rubber masterbatch according to claim 11, it is characterized in that: when wherein preparing rubber solutions with dried glue, described dried glue is natural polymer or synthetic polymer, described natural polymer comprises natural gum, gutta-percha, guayule, and described synthetic polymer is that monomer polymerization gained, monomer polymerization gained or monomer body in emulsion in solution carries out the polymerization gained.
13. the method for continuously producing of rubber masterbatch according to claim 11, it is characterized in that: when wherein said rubber solutions directly obtains from preparation solution polymerized rubber production line, described solution polymerized rubber is the triolefin of the diene of ethene, propylene, butylene, amylene, hexene, heptene, a 4-7 carbon atom or 6-7 carbon atom or homopolymerization or the copolymerized polymer that contains the vinyl monomer of other atom or functional group, described other atoms or functional group are silicon atom, fluorine atom, chlorine atom, nitrogen-atoms, oxygen atom, sulphur atom, ester group, the amino ester group, cyano group.
14. the method for continuously producing of rubber masterbatch according to claim 13 is characterized in that: the rubber in the wherein said rubber solutions is polybutadiene, polyisoprene, butadiene-styrene rubber, second third glue, butyl rubber, NBR, neoprene, silicon rubber, fluorubber, polyurethane rubber, CSM, ACM.
15. the method for continuously producing according to any described rubber masterbatch of claim in the claim 1 to 14, it is characterized in that: wherein the concentration range of rubber in solution is 1% weight to 60% weight, preferred 5% weight to 40% weight, more preferably 10% weight to 30% weight.
16. according to any method for continuously producing of the described rubber masterbatch of claim in the claim 1 to 15, it is characterized in that: the molecular weight of rubber is 1,000 to 4,000 ten thousand in the wherein said rubber solutions, and is preferred 5,000 to 3,000 ten thousand, more preferably 10,000 to 8,000,000.
17. according to the method for continuously producing of any described rubber masterbatch of claim in the claim 1 to 16, it is characterized in that: the solvent in the wherein said rubber solutions is the good solvent of various rubber.
18. the method for continuously producing of rubber masterbatch according to claim 1 is characterized in that: wherein said filler is solid powdery reinforcing agent and/or filler used in the rubber.
19. the method for continuously producing of rubber masterbatch according to claim 18 is characterized in that: wherein said filler contains the nanometer materials of carbon black, silica, metal oxide, calcium carbonate, potter's clay and/or resin and above-mentioned filler; Or described filler is two-phase or the heterogeneous filler of carbon black, silica, aluminium oxide, magnesia, zinc oxide, calcium oxide, titanium oxide, boron oxide composition; Or described above-mentioned filler and use mixture.
20. the method for continuously producing of rubber masterbatch according to claim 18 is characterized in that: the specific area of wherein said filler is 0.1 to 800m
2/ g, preferred 1 to 500m
2/ g, more preferably 5 to 300m
2/ g.
21. the method for continuously producing of rubber masterbatch according to claim 19 is characterized in that: the oil factor of wherein said carbon black and silica is 20 to 250ml/100g, and preferred 25 to 200ml/100g, and more preferably 30 to 150ml/100g.
22. the method for continuously producing of rubber masterbatch according to claim 1 is characterized in that: wherein choose wantonly described filler is carried out surface modification.
23. the method for continuously producing of rubber masterbatch according to claim 22 is characterized in that: wherein said surface modification is for to be connected on filling surface by chemical reaction with functional group, or by mixing or absorption is combined in filling surface with modifier.
24. the method for continuously producing of rubber masterbatch according to claim 22, it is characterized in that: wherein said surface modification was carried out before adding filler in the rubber solutions, or modifier was joined in the mixture of rubber solutions and filler and carry out surface modification.
25. the method for continuously producing according to claim 1,2 or 3 described rubber masterbatch, it is characterized in that: wherein in step 1), directly filler dry powder and/or additive dry powder are joined in the rubber solutions, or earlier filler and/or additive are joined with the identical or different solvent of rubber solutions in join rubber solutions again after mixing formation uniform filler/solvent suspension liquid or filler/additive/solvent suspension liquid, sneak in the rubber solutions by stirring; Liquid additive can directly join in the rubber solutions.
26. the method for continuously producing of rubber masterbatch according to claim 1 is characterized in that: wherein the stirring in the step 1) is finished by mixer.
27. the method for continuously producing of rubber masterbatch according to claim 25 is characterized in that: wherein said mixer is blade paddle mixer, trough mixer, planetary stirring machine, Z-blade mixer.
28. rubber masterbatch according to the described method preparation of claim 1-27.
29. a rubber, it uses rubber masterbatch according to claim 28 to prepare.
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