CN103205001A - Dispersion method for filling material in rubber solution - Google Patents
Dispersion method for filling material in rubber solution Download PDFInfo
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- CN103205001A CN103205001A CN2013100270025A CN201310027002A CN103205001A CN 103205001 A CN103205001 A CN 103205001A CN 2013100270025 A CN2013100270025 A CN 2013100270025A CN 201310027002 A CN201310027002 A CN 201310027002A CN 103205001 A CN103205001 A CN 103205001A
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Abstract
The invention relates to a dispersion method for a filling material in a rubber solution. The dispersion method comprises the following steps: adding the filling material into the rubber solution and 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. Compared with dispersing performance obtained in a conventional wet rubber compounding technology, the filling material has a high dispersion degree in a rubber compound according to the invention; and the dispersion method provided by the invention has the advantages of a continuous process, high efficiency, low energy consumption and little manual work, so cost is low. Meanwhile, a masterbatch prepared by using the method has superior processing performance, physical and mechanical properties and product quality.
Description
Technical field
The present invention relates to rubber materials, particularly the dispersing method of a kind of filler in rubber solutions.
Background technology
Rubber especially prepares the used rubber of doughnut, and most important technology is exactly that filler is added in the rubber to improve the physical and mechanical properties of its cross-linked rubber, could satisfy the service requirements of cross-linked rubber goods.In traditional rubber industry, adopting solid rubber and strengthening agent powder is raw material, with mechanical mixing method namely do the refining method with fillers dispersed in rubber matrix to produce rubber unvulcanizate.This method needs through operations such as cutting glue, plasticate, be mixing, and facility investment is big, and it is even with fillers dispersed only to rely on the mechanical shearing effect to be difficult to, thereby influences the physical and mechanical properties of cross-linked rubber.
In recent years, in order to solve the scattering problem of filler in rubber, scientific research institutions and the enterprise mixing technology of wet method that begins one's study both at home and abroad.Add tensio-active agent during the dispersed paste solution that record obtains natural rubber latex and disperse black carbon in water among the CN101883812 mixes, apply mechanical shear stress and disperse.Propose among the CN102775618 a kind of disperses in water with natural rubber latex and silicon sol or nano silicon after, the dispersing method that after heating in water bath is warmed up to melting temperature, carries out the constant temperature stirring.Disclosed method is as follows among the CN102516418: filler, processing aid etc. are made into mixture by adding dispersion agent, oxidation inhibitor, anti-sedimentation agent, wetting agent, water, after long-time the grinding, in being 20 rev/mins stirrer, 90-95 ℃, stirring velocity be prefabricated into dispersion, after mixing with revertex, add that acid etc. is condensed, washing, drying.
Make a general survey of both at home and abroad about the dispersion technology of filler in rubber, roughly the hybrid mode of Cai Yonging substantially all is to use stirrer, wherein commonly used is blade mixer, trough mixer, planetary stirring machine and Z-blade mixer, the shortcoming of this type of stirrer is batch operation on the one hand, can't realize continuous production; Then exist dispersing property not good on the other hand, directly influence the physical and mechanical properties of rubber item.
Summary of the invention
At prior art problems, the purpose of this invention is to provide the dispersing method of a kind of filler in rubber solutions.
Adopt the dispersing method advantage of filler of the present invention in rubber solutions to be: the 1) good dispersity of filler and additive; 2) 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 cross-linked rubber and the quality of rubber item; 3) 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, the dispersing method of a filler in rubber solutions, comprise the steps: 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.
2, according to embodiment 1 described method, one or more are selected from the additive of oil, antioxidant, anti-aging agent, coupling agent, promoting agent, fire retardant, thermo-stabilizer, photostabilizer, dyestuff, pigment, vulcanizing agent and promotor wherein to choose interpolation wantonly.
3, according to the described method of embodiment 1-2, wherein said finely divided as described below:
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 range 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.
4, according to the described method of embodiment 1-2, wherein said essence is separated into disperses adding continuously in ball mill and/or the colloidal mill through the mixture after finely divided.
5, according to the described method of embodiment 1-2, wherein said essence is separated into grinds joining in the shredder continuously through the mixture after finely divided, and this shredder has the plane mill of one or more groups high-speed rotation and is fixed on the shredder sleeve and fixing pin or the price fixing alternate with the plane mill.
6, according to the described method of embodiment 1-2, wherein said essence is separated into grinds joining in the shredder continuously through the mixture after finely divided, and this shredder has two blades of direction of rotation, and described blade has the pore chute.
7, according to the described method of embodiment 1-2, wherein said essence 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 range is from 2MPa to 60MPa, preferred 10MPa to 40MPa.
8, according to the described method of embodiment 1-2, wherein said essence is separated into disperses joining continuously in the power decentralized device through the mixture after finely divided, and the rotation of power decentralized device is changeed in last radially-arranged slit or a hole.
9, according to the described method of embodiment 4-8, wherein with two or more use of connecting mutually in the described smart dispersing method of claim 4-8.
10, according to the described method of embodiment 1-9, 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.
11, according to embodiment 10 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.
12, according to embodiment 10 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 Siliciumatom, fluorine atom, chlorine atom, nitrogen-atoms, Sauerstoffatom, sulphur atom, ester group, the amino ester group, cyano group.
13, according to embodiment 12 described methods, the rubber in the wherein said rubber solutions is polyhutadiene, polyisoprene, butadiene-styrene rubber, second third glue, butyl rubber, butadiene-acrylonitrile rubber, neoprene latex, silicon rubber, viton, urethanes, chlorosulfonated polyethylene rubber, acrylic elastomer.
14, according to the described method of embodiment 1-13, 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.
15, according to the described method of embodiment 1-14, 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.
16, according to the described method of embodiment 1-15, the solvent in the wherein said rubber solutions is the good solvent of various rubber.
17, according to embodiment 1 described method, wherein said filler is solid powdery strengthening agent and/or weighting agent used in the rubber.
18, according to embodiment 17 described methods, wherein said filler contains the nanometer materials of carbon black, silicon-dioxide, 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, silicon-dioxide, aluminum oxide, magnesium oxide, zinc oxide, calcium oxide, titanium oxide, boron oxide composition; Or described above-mentioned filler and use mixture.
19, according to embodiment 17 described methods, the specific surface 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.
20, according to embodiment 18 described methods, the oil-absorption(number) of wherein said carbon black and silicon-dioxide is 20 to 250ml/100g, and preferred 25 to 200ml/100g, and more preferably 30 to 150ml/100g.
21, according to embodiment 1 described method, wherein choose wantonly described filler is carried out surface modification.
22, according to embodiment 21 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 properties-correcting agent.
23, according to embodiment 21 described methods, wherein said surface modification was carried out before adding filler in the rubber solutions, or properties-correcting agent was joined in the mixture of rubber solutions and filler and carry out surface modification.
24, according to the described method of embodiment 1-2, wherein 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; Fluid additive can directly join in the rubber solutions.
25, according to embodiment 1 described method, stirring is wherein finished by stirrer.
26, according to embodiment 24 described methods, wherein said stirrer is blade mixer, trough mixer, planetary stirring machine, Z-blade mixer.
The dispersing method of filler of the present invention in rubber solutions comprises the steps: filler is joined in the rubber solutions, form rubber/filler/solvent mixture by stirring, and further finely divided to improve the degree of scatter of filler in rubber solutions to described rubber/filler/solvent mixture.
One or more are selected from the additive of oil, antioxidant, anti-aging agent, coupling agent, promoting agent, fire retardant, thermo-stabilizer, photostabilizer, dyestuff, pigment, vulcanizing agent and promotor to choose interpolation wantonly in aforesaid method.Described stirring can use general stirrer to finish, and includes but not limited to blade mixer, trough mixer, planetary stirring machine, Z-blade mixer etc.
Described finely divided can enforcement in the following way: 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 solution 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 range is from 2MPa to 60MPa, preferred 10MPa to 40MPa.
The formed mixture in described finely divided back can also further improve filler and/or the dispersion of additive in rubber solutions by following smart dispersion:
I. described finely divided mixture is afterwards added in ball mill and/or the colloidal 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 shredder so that filler and/or additive are well dispersed in the rubber solutions, this shredder has the plane mill of one or more groups high-speed rotation and is fixed on the shredder sleeve and fixing pin or the price fixing alternate with the plane mill.
Iii. described finely divided mixture is afterwards joined in the shredder continuously and grind, this shredder 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 range 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 range 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 rotor of the high speed rotating 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 is for using ethene, propylene, butylene, amylene, hexene, heptene, the triolefin of the diene of a 4-7 carbon atom or 6-7 carbon atom or contain the homopolymerization of vinyl monomer of other atom or functional group or described other atoms of copolymerized polymer or functional group are Siliciumatom, fluorine atom, the chlorine atom, nitrogen-atoms, Sauerstoffatom, sulphur atom, ester group, the amino ester group, cyano group includes, but are not limited to polyhutadiene, polyisoprene; butadiene-styrene rubber; second third glue; butyl rubber; butadiene-acrylonitrile rubber; neoprene latex; silicon rubber; viton; urethanes; chlorosulfonated polyethylene rubber; acrylic elastomer etc.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 solvents, aromatic hydrocarbon solvent, chlorinated hydrocarbon solvent, ketones solvent, ether solvent and esters solvent, described aliphatic solvents includes, but are not limited to all kinds of SOLVENTS gasoline, naphthenic hydrocarbon, substituted ring alkane, normal alkane, described aromatic hydrocarbon solvent includes but not limited to benzene,toluene,xylene, vinylbenzene, and described chlorinated hydrocarbon solvent includes but not limited to methylene dichloride, trichloromethane, tetracol phenixin, ethylene dichloride, chlorobenzene, zellon, toluene(mono)chloride.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 strengthening agents and weighting agent used in the rubber, as the nanometer materials of all kinds of carbon blacks, silicon-dioxide, metal oxide, salt, different resins and above-mentioned filler.Wherein said metal oxide includes, but are not limited to aluminum oxide, magnesium oxide, zinc oxide etc., and described salt includes, but are not limited to calcium carbonate, potter's clay.The specific surface 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, silicon-dioxide (white carbon black), its oil-absorption(number) 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, silicon-dioxide, aluminum oxide, magnesium oxide, zinc oxide, calcium oxide, titanium oxide, boron oxide etc. are formed, for two-phase or heterogeneous filler, its oil-absorption(number) 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 parts (be 100 weight parts in rubber), preferred 10 to 200 weight parts, more preferably 30 to 150 weight parts.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 properties-correcting agent 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 properties-correcting agent was joined in the mixture of rubber solutions and filler and carry out surface modification.Described properties-correcting agent is the properties-correcting agent 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-triethoxyl silane, 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, dibasic alcohol, polyvalent alcohol, and described alcohol compound includes but not limited to propyl alcohol, butanols, ethylene glycol, polyoxyethylene glycol and derivative thereof.
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, anti-aging agent, coupling agent, promoting agent, antioxidant, thermo-stabilizer, photostabilizer, fire retardant, dyestuff, pigment, vulcanizing agent or promotor wantonly.The consumption of additive therefor is conventional amount used, or adjusts according to practical requirements.
Compare with the dispersion technology of existing filler in rubber, the present invention can realize the dispersity height of filler in rubber size, production technique continuously, efficiently uses the rubber master batch of this method preparation all very superior on processing characteristics, physical and mechanical properties, quality product simultaneously.
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 plant and instrument and measuring method to measure:
The plant and instrument of table 1 rubber sample preparation
| Sequence number | Device name | Specifications and models | Manufacturer |
| 1 | Banbury mixer | XSM-1/10-120 | Shanghai Kechuang rubber and plastics machine equipment company limited |
| 2 | Mill | 152.5*320 | Zhanjiang Machine Factory, Guangdong Prov. |
| 3 | Vulcanizing press | XLB-D600*600 | East, Huzhou, Zhejiang machinery company limited |
The testing method of table 2 vulcanizating glue physical performance and instrument
(2) embodiment and Comparative Examples
Raw material:
Synthetic polyisoprenes rubber, IR-70, her Cohan novel material company limited of Qingdao;
White carbon black, Newsil HD165MP really becomes chemistry of silicones limited-liability company;
Zinc oxide, Dalian zinc oxide factory;
Stearic acid, PF1808, company limited is found into by Malaysia;
Anti-aging agent 4020, Flexsys Chemical (M) Sdn Bhd;
Antioxidant 264, Huangyan, Zhejiang East Zhejiang province rubber ingredients company limited;
Silane coupling agent Si69, NanJing Shuguang Chemical Group Co., Ltd.;
Accelerant CZ, Shandong be Shun's chemical industry company limited still;
Sulfur, Lin Yiluo Zhuan Xin Anhua factory;
Comparative Examples 1
60 parts of white carbon blacks, 6 parts of silane coupling agent Si69 are joined in the hexane solution of 100 part of 8% cis-polyisoprene, after its rubber/white carbon black/Si69/ normal hexane mixture just mixes with blade mixer, inject cohesion in the knockouts continuously, spray into desolventizing and the dry rubber master batch 1 that obtains Comparative Examples 1 in the moisture eliminator afterwards.
Embodiment 1
With 60 parts of white carbon blacks, 6 parts of silane coupling agent Si69 join in the hexane solution of 100 part of 8% cis-polyisoprene, after its rubber/white carbon black/Si69/ normal hexane mixture just mixes with blade mixer, mixture is sprayed into swan neck more than by a nozzle makes mixture increase the dispersion of filler at Guan Zhongyu tube wall bump, then with mixture by a nozzle spray into a bore repeatedly the pipeline that changes of folding and unfolding change the dispersion that shear-stress increases filler and additive, then mixture is injected in the knockouts continuously and condense, spray into desolventizing and the dry rubber master batch 2 that obtains embodiment 1 in the moisture eliminator afterwards.
Embodiment 2
60 parts of white carbon blacks, 6 parts of silane coupling agent Si69 are joined in the hexane solution of 100 part of 8% cis-polyisoprene, after its rubber/white carbon black/Si69/ normal hexane mixture just mixes with blade mixer, mixture is sprayed into swan neck more than by a nozzle make mixture increase the dispersion of filler at Guan Zhongyu tube wall bump.Then mixture is joined continuously and carry out the essence dispersion in the shredder, this shredder has the plane mill of one or more groups high-speed rotation and is fixed on the sleeve and fixed wafer or the pin alternate with the plane mill, namely get smart dispersed mixture, then mixture is injected in the knockouts continuously and condense, spray into desolventizing and the dry rubber master batch 3 that obtains embodiment 2 in the moisture eliminator afterwards.
Embodiment 3
60 parts of white carbon blacks, 6 parts of silane coupling agent Si69 are joined in the hexane solution of 100 part of 8% cis-polyisoprene, after its rubber/white carbon black/Si69/ normal hexane mixture just mixes with blade mixer, mixture is sprayed into swan neck more than by a nozzle make mixed solution increase the dispersion of filler at Guan Zhongyu tube wall bump.Then mixture is joined continuously and carry out the essence dispersion in the shredder, this shredder has two blades of direction of rotation, described blade has the pore chute, under high pressure can improve the degree of scatter of filler in rubber by the blade of rotation, namely get smart dispersed mixture, then mixture is injected in the knockouts continuously and condense, spray into desolventizing and the dry rubber master batch 4 that obtains embodiment 3 in the moisture eliminator afterwards.
Embodiment 4
60 parts of white carbon blacks, 6 parts of silane coupling agent Si69 are joined in the hexane solution of 100 part of 8% cis-polyisoprene, after its rubber/white carbon black/Si69/ normal hexane mixture just mixes with blade mixer, mixture is sprayed into swan neck more than by a nozzle make mixed solution increase the dispersion of filler at Guan Zhongyu tube wall bump.Mixture is joined continuously in the multi-layer high-voltage slit dispersion machine then, mixture is under high pressure extruded the slit between two-layer, namely get smart dispersed mixture, then mixture is injected in the knockouts continuously and condense, spray into desolventizing and the dry rubber master batch 5 that obtains embodiment 4 in the moisture eliminator afterwards.
Embodiment 5
60 parts of white carbon blacks, 6 parts of silane coupling agent Si69 are joined in the hexane solution of 100 part of 8% cis-polyisoprene, after its rubber/white carbon black/Si69/ normal hexane mixture just mixes with blade mixer, mixture is sprayed into swan neck more than by a nozzle make mixed solution increase the dispersion of filler at Guan Zhongyu tube wall bump.Then mixture is joined in the power decentralized device continuously and disperse, many radially-arranged slits or hole are arranged on the rotor of the high speed rotating of described power decentralized device, mixture with high-speed impact on stator surface so that filler and additive be evenly dispersed in the rubber solutions, namely get smart dispersed mixture, then mixture is injected in the knockouts continuously and condense, spray into desolventizing and the dry rubber master batch 6 that obtains embodiment 5 in the moisture eliminator afterwards.
Embodiment 6
60 parts of white carbon blacks, 6 parts of silane coupling agent Si69 are joined in the hexane solution of 100 part of 8% cis-polyisoprene, after its rubber/white carbon black/Si69/ normal hexane mixture just mixes with blade mixer, mixture is sprayed into swan neck more than by a nozzle make mixed solution increase the dispersion of filler at Guan Zhongyu tube wall bump.Then mixture is added continuously and carry out the essence dispersion in the colloidal mill, namely get smart dispersed mixture, mixture is injected in the knockouts continuously condense then, spray into desolventizing and the dry rubber master batch 7 that obtains embodiment 6 in the moisture eliminator afterwards.
With the rubber master batch 1-7 of above-mentioned gained mill bag roller evenly after, adds 3.5 parts of zinc oxide, 1 part of stearic acid, 2 parts of anti-aging agent 4020,1.3 parts of accelerant CZs, 0.3 part of vulkacit D and 1.4 parts of Sulfurs after, mistake roller, following sheet.Mixingly park that the vulcanizing press with 150 ℃ vulcanizes to plateau cure after 8 hours, the gained cross-linked rubber is respectively Comparative Examples cross-linked rubber 1, embodiment cross-linked rubber 2-7.
The influence that table 3 dispersing method disperses in cross-linked rubber white carbon black
Table 3 is the contrast with fillers dispersed in the different dispersing method gained cross-linked rubbers, therefrom as can be seen, after with finely divided method, the dispersiveness of filler is better than general method gained sizing material, and filler disperses its dispersing property of back to improve further again by essence simultaneously.
The physicals of table 4 cross-linked rubber 1-7
As known from Table 4, because the improvement of dispersing characteristic, sizing material tensile strength, tensile yield, rebound resilience and wear resistance obviously improve, and the living heat of compression fatigue decreases.
Claims (26)
1. the dispersing method of a filler in rubber solutions, its thing is levied and is: comprises the steps,
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.
2. the dispersing method of filler according to claim 1 in rubber solutions, its thing is levied and is: wherein optionally add one or more and be selected from the additive of oil, antioxidant, anti-aging agent, coupling agent, promoting agent, fire retardant, thermo-stabilizer, photostabilizer, dyestuff, pigment, vulcanizing agent and promotor.
3. the dispersing method of filler according to claim 1 and 2 in rubber solutions, its thing is levied and is: wherein said finely divided as described below,
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 range 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.
4. the dispersing method of filler according to claim 1 and 2 in rubber solutions, its thing is levied and is: wherein said essence is separated into disperses adding continuously in ball mill and/or the colloidal mill through the mixture after finely divided.
5. the dispersing method of filler according to claim 1 and 2 in rubber solutions, its thing is levied and is: wherein said essence is separated into grinds joining in the shredder continuously through the mixture after finely divided, and this shredder has the plane mill of one or more groups high-speed rotation and is fixed on the shredder sleeve and fixing pin or the price fixing alternate with the plane mill.
6. the dispersing method of filler according to claim 1 and 2 in rubber solutions, its thing is levied and is: wherein said essence is separated into grinds joining in the shredder continuously through the mixture after finely divided, this shredder has two blades of direction of rotation, and described blade has the pore chute.
7. the dispersing method of filler according to claim 1 and 2 in rubber solutions, its thing is levied and is: wherein said essence 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 range is from 2MPa to 60MPa, preferred 10MPa to 40MPa.
8. the dispersing method of filler according to claim 1 and 2 in rubber solutions, its thing is levied and is: wherein said essence is separated into 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.
9. according to any dispersing method of the described filler of claim in rubber solutions in the claim 4 to 8, its thing is levied and is: wherein with two or more use of connecting mutually in the described smart dispersing method of claim 4-8.
10. according to any dispersing method of the described filler of claim in rubber solutions in the claim 1 to 9, its thing is levied and is: 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.
11. the dispersing method of filler according to claim 10 in rubber solutions, its thing is levied and is: 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.
12. the dispersing method of filler according to claim 10 in rubber solutions, its thing is levied and is: 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 Siliciumatom, fluorine atom, chlorine atom, nitrogen-atoms, Sauerstoffatom, sulphur atom, ester group, the amino ester group, cyano group.
13. the dispersing method of filler according to claim 12 in rubber solutions, its thing is levied and is: the rubber in the wherein said rubber solutions is polyhutadiene, polyisoprene, butadiene-styrene rubber, second third glue, butyl rubber, butadiene-acrylonitrile rubber, neoprene latex, silicon rubber, viton, urethanes, chlorosulfonated polyethylene rubber, acrylic elastomer.
14. according to any dispersing method of the described filler of claim in rubber solutions in the claim 1 to 13, its thing is levied and is: 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.
15. according to any dispersing method of the described filler of claim in rubber solutions in the claim 1 to 14, its thing is levied and is: 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.
16. according to any dispersing method of the described filler of claim in rubber solutions in the claim 1 to 15, its thing is levied and is: the solvent in the wherein said rubber solutions is the good solvent of various rubber.
17. the dispersing method of filler according to claim 1 in rubber solutions, its thing is levied and is: wherein said filler is solid powdery strengthening agent and/or weighting agent used in the rubber.
18. the dispersing method of filler according to claim 17 in rubber solutions, its thing is levied and is: wherein said filler contains the nanometer materials of carbon black, silicon-dioxide, 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, silicon-dioxide, aluminum oxide, magnesium oxide, zinc oxide, calcium oxide, titanium oxide, boron oxide composition; Or described above-mentioned filler and use mixture.
19. the dispersing method of filler according to claim 17 in rubber solutions, its thing is levied and is: the specific surface 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.
20. the dispersing method of filler according to claim 18 in rubber solutions, its thing is levied and is: the oil-absorption(number) of wherein said carbon black and silicon-dioxide is 20 to 250ml/100g, and preferred 25 to 200ml/100g, and more preferably 30 to 150ml/100g.
21. the dispersing method of filler according to claim 1 in rubber solutions, its thing is levied and is: wherein choose wantonly described filler is carried out surface modification.
22. the dispersing method of filler according to claim 21 in rubber solutions, its thing is levied and is: 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 properties-correcting agent.
23. the dispersing method of filler according to claim 21 in rubber solutions, its thing is levied and is: wherein said surface modification was carried out before adding filler in the rubber solutions, or properties-correcting agent was joined in the mixture of rubber solutions and filler and carry out surface modification.
24. the dispersing method of filler according to claim 1 and 2 in rubber solutions, its thing is levied and is: wherein 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; Fluid additive can directly join in the rubber solutions.
25. the dispersing method of filler according to claim 1 in rubber solutions, its thing is levied and is: stirring is wherein finished by stirrer.
26. the dispersing method of filler according to claim 24 in rubber solutions, its thing is levied and is: wherein said stirrer is blade mixer, trough mixer, planetary stirring machine, Z-blade mixer.
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| CN103419291A (en) * | 2013-08-05 | 2013-12-04 | 怡维怡材料研究院有限公司 | Continuous preparation method for rubber masterbatch and rubber masterbatch prepared thereby |
| CN104327315A (en) * | 2014-11-03 | 2015-02-04 | 怡维怡橡胶研究院有限公司 | Application of continuously-prepared rubber masterbatch in car tire base rubber |
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| CN104356443A (en) * | 2014-11-28 | 2015-02-18 | 山东阳谷华泰化工股份有限公司 | High-wear-resistant reinforced material for tire tread and preparation method of highly-wear-resistant reinforced material |
| CN104962069A (en) * | 2015-07-07 | 2015-10-07 | 青岛泰联科高分子材料研发有限公司 | Flame-retardant rubber |
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| CN106479006A (en) * | 2015-08-25 | 2017-03-08 | 中国石油天然气股份有限公司 | Elastic composites |
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| CN103419291A (en) * | 2013-08-05 | 2013-12-04 | 怡维怡材料研究院有限公司 | Continuous preparation method for rubber masterbatch and rubber masterbatch prepared thereby |
| CN103419291B (en) * | 2013-08-05 | 2016-04-27 | 怡维怡橡胶研究院有限公司 | Rubber masterbatch prepared by the method for continuously producing of rubber masterbatch and the method |
| CN105459284A (en) * | 2014-08-25 | 2016-04-06 | 山东大展纳米材料有限公司 | Liquid phase continuous mixing process of high dispersion carbon nanotube masterbatch and rubber product thereof |
| CN105459284B (en) * | 2014-08-25 | 2019-04-05 | 山东大展纳米材料有限公司 | The liquid phase continuous mixing technique and its rubber product of high dispersive carbon nanotube masterbatch |
| CN104327315A (en) * | 2014-11-03 | 2015-02-04 | 怡维怡橡胶研究院有限公司 | Application of continuously-prepared rubber masterbatch in car tire base rubber |
| CN104327317A (en) * | 2014-11-03 | 2015-02-04 | 怡维怡橡胶研究院有限公司 | Application of continuously prepared rubber master batch in sedan tire rubber |
| CN104356443A (en) * | 2014-11-28 | 2015-02-18 | 山东阳谷华泰化工股份有限公司 | High-wear-resistant reinforced material for tire tread and preparation method of highly-wear-resistant reinforced material |
| CN104962069A (en) * | 2015-07-07 | 2015-10-07 | 青岛泰联科高分子材料研发有限公司 | Flame-retardant rubber |
| CN106479006A (en) * | 2015-08-25 | 2017-03-08 | 中国石油天然气股份有限公司 | Elastic composites |
| CN106479005A (en) * | 2015-08-25 | 2017-03-08 | 中国石油天然气股份有限公司 | The preparation method of elastic composites |
| CN115926207A (en) * | 2022-11-23 | 2023-04-07 | 辽宁维航基业科技有限公司 | Preparation method of soft wear-resistant glue |
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