CN103203810B - Rubber masterbatch and rubber prepared by the method for continuously producing and the method for rubber masterbatch - Google Patents

Rubber masterbatch and rubber prepared by the method for continuously producing and the method for rubber masterbatch Download PDF

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CN103203810B
CN103203810B CN201310027024.1A CN201310027024A CN103203810B CN 103203810 B CN103203810 B CN 103203810B CN 201310027024 A CN201310027024 A CN 201310027024A CN 103203810 B CN103203810 B CN 103203810B
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rubber
filler
continuously producing
masterbatch
rubber masterbatch
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CN201310027024.1A
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CN103203810A (en
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王梦蛟
宋建军
戴德盈
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怡维怡橡胶研究院有限公司
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Abstract

Rubber masterbatch and rubber prepared by the method for continuously producing and the method for rubber masterbatch of the present invention, its manufacture method comprise the following steps:Step 1), filler is added in rubber solutions, rubber/filler/solvent mixture is formed by stirring, and further finely divided to the rubber/filler/solvent mixture and smart disperse to improve degree of scatter of the filler in rubber solutions;Step 2), make step 1) in essence dispersion after rubber/filler/solvent mixture in rubber and filler co-agglomeration, obtain the mixture of rubber/filler compound and solvent;Step 3), desolvation and described mixture is dried, obtain rubber/filler masterbatch.The masterbatch prepared by above-mentioned manufacture method and the rubber prepared using the masterbatch.It is wider using scope to rubber, filler without particular/special requirement compared with existing wet method elastomeric compound technology, correspondingly improve decentralization of the filler in rubber size.

Description

Rubber masterbatch prepared by the method for continuously producing and the method for rubber masterbatch with Rubber

Technical field

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

Background technology

In modern rubber industry, the sizing material more than 99% for manufacturing product contains fine particle pulverulent filler, their application On the one hand the supporting material of rubber is used as, also known as reinforcing agent, the physical and mechanical properties such as tensile stress, anti-tensile of rubber is improved It is intensity, elongation at break, tear resistance, and improve the performance of rubber product, such as anti-wear performance, frictional behaviour, dynamic State damping (delayed) performance, anti-stabbing etc.;On the other hand can assign rubber some special functions again, it is such as conductive and Insulating properties, heat conduction and heat-insulating property, radiation resistance, magnetic property, and improve the resistant to chemical media aggressivity of rubber, drop Low rubber swellability in a solvent and increase air-tightness etc..Additionally, addition filler can increase the body of sizing material in sizing material Product, for unit volume price compared with rubber substrate used for the relatively low filler of price, their application can also make rubber The cost of glue product declines.Therefore, filler is only second to rubber and occupies in itself and always in the consumption of rubber raw material Two.In addition, being also required to add various additives to make rubber cross or improve adding for sizing material in sizing material needed for manufacturing rubber Some characteristics of work performance and rubber.

Manufacture rubber sizing material in, most important technique exactly filler and additive are added in rubber make its Reached in rubbery parent substance dispersed.In fact, wanting optimization filler to application performances such as reinforcing rubber or fillings, and play The function of additive, first has to reach fine dispersion.Dispersion is bad to make rubber bring other problemses, in some feelings Under condition, for dispersed filler and cost of the additive cost than filler in itself it is taller go out many.

By the conventional approach that filler and additive are mixed into rubber be with large-scale mixing facilities, including banbury, Be mixed into solid rubber for powdered or liquid filler and additive by masticator and opening rubber mixing machine, when this kind of technique is kneaded Between long, power consumption is high, dust is more and dispersed extreme difference, thus the physical and mechanical properties and rubber product quality of vulcanizate be subject to very Big limitation.

The state such as the U.S., Britain, Malaysia, India and China all attempts to manufacture carbon black masterbatching with latex in history Glue, but industrialized production is not implemented, a few thing in this regard mainly has German powdered rubber to join over the past two decades Close limited company powdered rubber preparation method (CN99807464, CN99807105, CN99127509, CN99125587, CN00103762, CN00117904, CN200710199527), the technical characterstic of the method is:By rubber glue Breast adds chemicals to reach cohesion after mixing with carbon black water slurry.The method is batch production, time-consuming to take except complex technical process Outside power, low production efficiency, its product major defect is difficult to for masterbatching adhesiveness is especially high, and vulcanizate and its product Anti-wear performance it is poor.Although its reason is primarily due to the scattered of carbon black, in carbon black dispersion and latex mixed process In substantial amounts of non-rubber component be adsorbed onto filler surface so as to destroy the interaction of rubber-filler.Coupling is needed for some Agent increases for the filler that rubber/filler interacts, and the absorption of non-rubber component also hampers rubber molecule with filler surface Coupling reaction.These problems are until the early 1990s in last century Cabot Corporation of U.S. Heveatex and carbon black water slurry are developed Liquid phase continuously manufacture natural gum/carbonblack master batch technique be just addressed (US19970823411, CN97195156, CN98811684、CN00808002、CN02825969).The method that this liquid phase continuous mixing prepares rubber/filler masterbatch subtracts Change rubber mixing technique, mixing time, reduce energy consumption and artificial, but packing variety used in rubber master batch preparation and content are subject to Limitation.When continuity method continuously mixes cohesion by latex and filler water slurry, during using hydrophily strong filler such as white carbon, after cohesion In water phase remain filler it is more, increase water process difficulty, and amount of filler it is too high or too low can not effectively will coagulate Polymers and water are separated, and the method can not also be used directly to for rubber solutions and filler to prepare filler/rubber masterbatch.

The content of the invention

Rubber masterbatch and rubber prepared by the method for continuously producing and the method for rubber masterbatch of the present invention Product, for problem of the prior art, the purpose of its invention is to provide a kind of method for continuously producing of rubber masterbatch and is somebody's turn to do Rubber masterbatch prepared by method, to improve decentralization of the filler in rubber size, production technology is continuous, efficient, low consumption , can lack artificial, thus cost is relatively low.

Another goal of the invention is to provide a kind of rubber prepared using rubber masterbatch of the invention, so as to improve Using the rubber master batch of the method preparation in processing characteristics, physical and mechanical properties and product quality, and existing solution polymerized rubber can be saved Postprocessing working procedures after polymerisation.

The advantage of rubber masterbatch method for continuously producing of the present invention is:1) continuous high-efficient;2) filler and addition The good dispersion of agent;3) mix and cohesion is uniform and speed is fast;4) due to the addition for not having water in mixed process, therefore after cohesion Mixture can rapidly desolventizing drying without being disturbed by water;5) due to the high dispersive of filler and additive and without other things Matter is disturbed, and is remarkably improved the physical and mechanical properties of vulcanizate and the quality of rubber;6) when manufacturing masterbatching with solution polymerized rubber During glue, can save rubber solutions in solution polymerized rubber production technology separated with water mixing, heating aggregation process, solvent and reclaimed, rubber A series of last handling processes such as glue dehydration, dry, packaging, substantially reduce the manufacturing cost of solution polymerized rubber;7) side of the present invention Method is applied widely to the species and content of rubber and filler and additive.

The invention further relates to scheme is implemented as follows:

1st, a kind of method for continuously producing of rubber masterbatch, comprises the following steps:

Step 1):Filler is added in rubber solutions, rubber/filler/solvent mixture is formed by stirring, and to institute The further finely divided and smart dispersion of rubber/filler/solvent mixture is stated to improve degree of scatter of the filler in rubber solutions;

Step 2):Make step 1) in essence dispersion after rubber/filler/solvent mixture in rubber and filler co-agglomeration, Obtain the mixture of rubber/filler compound and solvent;

Step 3):Desolvation is simultaneously dried to described mixture, obtains rubber/filler masterbatch.

2nd, the method according to embodiment 1, wherein optional recycling step 3) solvent that is removed, recycle.

3rd, the method according to embodiment 1, wherein in step 1) and/or step 2) in optionally addition one or more Selected from oil, age resistor, coupling agent, activating agent, antioxidant, fire retardant, heat stabilizer, light stabilizer, dyestuff, pigment, vulcanization Agent and the additive of accelerator.

4th, the method according to embodiment 1-3, wherein step 1) described in it is finely divided as described below:

I) rubber/filler/solvent mixture after stirring or rubber/filler/additive/solvent mixture are passed through one by Individual nozzle under high pressure in the case of spray, pressure limit used from 2MPa to 60MPa, preferably 10MPa to 40MPa;

II) makes above-mentioned I) in ejecta rubber/filler/solvent mixture or rubber/fill out are made by swan neck more than Material/additive/solvent mixture clashes into Guan Zhongyu tube walls increases the dispersiveness of filler;Or

III) makes above-mentioned I) in ejecta shearing is converted by pipeline that the multiple folding and unfolding of bore changes should Power and increase the dispersiveness of filler.

5th, the method according to embodiment 1-3, wherein step 1) described in essence be separated into after finely divided Mixture be continuously added to be disperseed in ball mill and/or colloid mill.

6th, the method according to embodiment 1-3, wherein step 1) described in essence be separated into after finely divided Mixture be added continuously to be ground in grinder, the grinder have one or more groups of high-speed rotations plane mill and It is fixed on fixing pin or price fixing on grinder sleeve and alternate with plane mill.

7th, the method according to embodiment 1-3, wherein step 1) described in essence be separated into after finely divided Mixture be added continuously to be ground in grinder, the grinder has two opposite blades of rotation direction, the leaf Piece has pore chute.

8th, the method according to embodiment 1-3, wherein step 1) described in essence be separated into after finely divided Mixture be continuously added in multi-layer high-voltage slit dispersion machine, make mixture under high pressure between two-layer in slit squeeze Go out, pressure limit used from 2MPa to 60MPa, preferably 10MPa to 40MPa.

9th, the method according to embodiment 1-3, wherein step 1) described in essence be separated into after finely divided Mixture be continuously added to be disperseed in power decentralized device, have radially-arranged narrow on the rotor of power decentralized device Seam or hole.

10th, the method according to embodiment 5-9, wherein by two in the smart process for dispersing described in embodiment 5-9 Plant or two or more being serially connected uses.

11st, the method according to embodiment 1-10, wherein the rubber solutions for directly from prepare solution polymerized rubber life Obtained in producing line, or any kind of dry glue is dissolved into preparation in the good solvent of the rubber.

12nd, the method according to embodiment 11, wherein when preparing rubber solutions with dry glue, the dry glue is natural poly- Compound or synthetic polymer, the natural polymer include natural gum, gutta-percha, guayule, and the synthetic polymer is monomer Polymerization gained, monomer are in the emulsion obtained by polymerization or obtained by monomer body is polymerized in the solution.

13rd, the method according to embodiment 11, wherein the rubber solutions are directly from preparing solution polymerized rubber production line During middle acquisition, the solution polymerized rubber be ethene, propylene, butylene, amylene, hexene, heptene, 4-7 carbon atom diene or 6-7 it is individual The homopolymerization of the triolefin of carbon atom or the vinyl monomer containing other atoms or functional group or copolymerized polymer, described other atoms or official It is silicon atom, fluorine atom, chlorine atom, nitrogen-atoms, oxygen atom, sulphur atom, ester group, amino ester group, cyano group that can roll into a ball.

14th, the method according to embodiment 13, wherein the rubber in the rubber solutions is polybutadiene, poly- isoamyl Diene, butadiene-styrene rubber, the glue of second third, butyl rubber, NBR, neoprene, silicon rubber, fluorubber, polyurethane rubber, chlorosulfonated polyethylene Rubber, ACM.

15th, the method according to embodiment 1-14, wherein rubber concentration range in the solution be 1% weight extremely 60% weight, preferably 5% weight are to 40% weight, more preferably 10% weight to 30% weight.

16th, the method according to embodiment 1-15, wherein in the rubber solutions rubber molecular weight for 1,000 to 40000000, preferably 5,000 to 30,000,000, more preferably 10,000 to 8,000,000.

17th, the method according to embodiment 1-16, wherein the solvent in the rubber solutions is various rubber Good solvent.

18th, the method according to embodiment 1, wherein described filler are solid powdery reinforcing agent used in rubber And/or filler.

19th, the method according to embodiment 18, wherein described filler contain carbon black, silica, metal oxide, The nanometer materials of calcium carbonate, potter's clay and/or resin and above-mentioned filler;Or described filler be carbon black, silica, aluminum oxide, Magnesia, zinc oxide, calcium oxide, titanium oxide, the two-phase of boron oxide composition or many phase fillings;Or the above-mentioned filler and with mixed Compound.

20th, the method according to embodiment 18, the wherein specific surface area of described filler are 0.1 to 800m2/ g, preferably 1 to 500m2/ g, more preferably 5 to 300m2/g。

21st, the method according to embodiment 19, wherein the oil factor of the carbon black and silica be 20 to 250ml/100g, preferably 25 to 200ml/100g, more preferably 30 to 150ml/100g.

22nd, the method according to embodiment 1, wherein surface is optionally carried out to described filler being modified.

23rd, the method according to embodiment 22, wherein described surface is modified as by chemically reacting functional group Filler surface is connected on, or is combined on filler surface modifying agent by mixing or adsorbing.

24th, the method according to embodiment 22, wherein the surface be modified by filler add rubber solutions in it Before carry out, or modifying agent is added to carries out surface in the mixture of rubber solutions and filler and be modified.

25th, the method according to embodiment 1-3, wherein in step 1) in directly by filler dry powder and/or additive Dry powder is added in rubber solutions, or first filler and/or additive be added in the solvent identical or different with rubber solutions Rubber solutions are then added to after being mixed to form uniform filler/solvent suspension liquid or filler/additive/solvent suspension liquid, are passed through Stirring is mixed into rubber solutions;Liquid additive can be added directly into rubber solutions.

26th, the method according to embodiment 1, wherein step 1) in stirring by mixer complete.

27th, method according to claim 25, wherein the mixer is blade paddle mixer, trough mixer, Planetary stirring machine, Z-blade mixer.

28th, rubber masterbatch prepared by a kind of method according to embodiment 1-27.

29th, a kind of rubber, it is prepared using the rubber masterbatch according to embodiment 28.

The method for continuously producing of rubber masterbatch of the invention comprises the following steps:

Step 1):Filler is added in rubber solutions, rubber/filler/solvent mixture is formed by stirring, and to institute The further finely divided and smart dispersion of rubber/filler/solvent mixture is stated to improve degree of scatter of the filler in rubber solutions;

Step 2):Make step 1) in essence dispersion after rubber/filler/solvent mixture in rubber and filler co-agglomeration, Obtain the mixture of rubber/filler compound and solvent;

Step 3):Desolvation is simultaneously dried to described mixture, obtains rubber/filler masterbatch.

The method for continuously producing of rubber masterbatch of the invention also optionally includes recycling step 3) solvent that is removed with The step of recycling.Additionally, in step 1) and/or step 2) in optionally addition one or more be selected from oil, age resistor, coupling The additive of agent, activating agent, antioxidant, fire retardant, heat stabilizer, light stabilizer, dyestuff, pigment, vulcanizing agent and accelerator.

Step 1) described in stirring can be completed using general mixer, including but not limited to blade paddle mixer, groove Formula mixer, planetary stirring machine, Z-blade mixer etc..

Step 1) described in finely divided can implement in the following way:Mixture obtained by above-mentioned stirring is passed through one Individual nozzle sprays in the case of high pressure high shear, to improve the dispersion of filler and/or additive;Then above-mentioned ejecta is made again Mixed liquor is clashed into Guan Zhongyu tube walls by swan neck more than increases the dispersiveness of filler and/or additive;Or make ejection Thing converts shear stress and increases the dispersion of filler and/or additive by the pipeline that the multiple folding and unfolding of bore changes. Pressure limit used from 2MPa to 60MPa, preferably 10MPa to 40MPa.

In step 1) described in it is finely divided after the mixture that is formed can also further be improved by following essence dispersions The dispersion of filler and/or additive in rubber solutions:

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

Ii. by it is described it is finely divided after mixture be added continuously to be ground in grinder so as to filler and/or add Plus agent is well dispersed in rubber solutions, the grinder has the plane mill of one or more groups of high-speed rotations and is fixed on grinding Mantle cylinder is gone up and the fixing pin or price fixing alternate with plane mill.

Iii. by it is described it is finely divided after mixture be added continuously to be ground in grinder, the grinder have turn Dynamic two blades in opposite direction, the blade has pore chute, can improve filler by the blade for rotating under high pressure And/or degree of scatter of the additive in rubber solutions.Pressure limit used from 2MPa to 60MPa, preferably 10MPa to 40MPa.

Iv. by it is described it is finely divided after mixture be continuously added in multi-layer high-voltage slit dispersion machine, make mixture Extruded in slit between two-layer under high pressure, the Strong shear power for now producing can improve filler and/or additive is molten in rubber Degree of scatter in liquid.Pressure limit used from 2MPa to 60MPa, preferably 10MPa to 40MPa.

V. by it is described it is finely divided after mixture be continuously added to be disperseed in power decentralized device, the power point Have many radially-arranged slits or a hole on the rotor of the high speed rotation for dissipating device, mixture with high-speed impact on stator surface with Filler and/or additive is set to be evenly dispersed in rubber solutions.

Two or more of above-mentioned five kinds of finely divided methods can be serially connected and use.

Described rubber solutions can be directly obtained directly from solution polymerized rubber production line is prepared, also can will be any kind of Dry glue dissolves preparation in the solvent of the glue.When rubber solutions are prepared with dry glue, the dry glue can be used in this area Any kind of rubber, such as natural polymer or synthetic polymer.The natural polymer includes but is not limited to natural gum, Du Secondary glue, guayule etc.;The synthetic polymer include but is not limited to monomer be polymerized in the solution gained (i.e. solution polymerized rubber), monomer Obtained by (i.e. emulsion polymerized rubber), monomer body are polymerized obtained by polymerization in emulsion.When the rubber solutions are directly molten from preparing When being obtained in poly- rubber production line, the solution polymerized rubber is former with ethene, propylene, butylene, amylene, hexene, heptene, 4-7 carbon Homopolymerization or the copolymerized polymer of the diene of son or the triolefin of 6-7 carbon atom or the vinyl monomer containing other atoms or functional group, Including but not limited to polybutadiene, polyisoprene, butadiene-styrene rubber, the glue of second third, butyl rubber, NBR, neoprene etc..Rubber Molecular weight is 1,000 to 40,000,000, preferably 5,000 to 30,000,000, more preferably 10,000 to 8,000,000.

Solvent in the rubber solutions is the good solvent of various rubber.Solvent is specifically as follows aliphatic solvent, virtue Fragrant hydrocarbon solvent, chlorinated hydrocarbon solvent, ketones solvent, ether solvent and esters solvent, the aliphatic solvent are included but is not limited to Various industrial napthas, cycloalkane, substitution cycloalkane, normal alkane, the aromatic hydrocarbon solvent include but is not limited to benzene, toluene, diformazan Benzene, styrene, the chlorinated hydrocarbon solvent include but is not limited to dichloromethane, chloroform, carbon tetrachloride, dichloroethanes, chlorobenzene, Tetrachloro-ethylene, chlorotoluene.Rubber concentration range in the solution is 1% weight to 60% weight, preferably 5% weight to 40% weight Amount, more preferably 10% weight to 30% weight.

Described filler includes but is not limited to various solid powdery reinforcing agents and filler used in rubber, such as all kinds of charcoals Black, silica, metal oxide, salt, different resins and various fine particle solid powder substances.Wherein described metal oxygen Thing includes but is not limited to aluminum oxide, magnesia, zinc oxide etc., the salt include but is not limited to calcium carbonate, potter's clay and on State the nanometer materials of filler.The specific surface area of filler is 0.1 to 800m2/ g, preferably 1 to 500m2/ g, more preferably 5 to 300m2/ g.For carbon black, silica (white carbon), its oil factor be 20 to 250ml/100g, preferably 25 to 200ml/100g, More preferably 30 to 150ml/100g, wherein described filler include their mixture, such as many phase fillings, including but not It is limited to the two-phase or multiphase of the compositions such as carbon black, silica, aluminum oxide, magnesia, zinc oxide, calcium oxide, titanium oxide, boron oxide Filler, for two-phase or many phase fillings, its oil factor be 20 to 250ml/100g, preferably 25 to 200ml/100g, it is more excellent Select 30 to 150ml/100g.The consumption of filler is 5 to 300 weight portions (being counted by 100 weight portions of rubber), preferably 10 to 200 weights Amount part, more preferably 30 to 150 weight portions.It is that described filler also includes in above-mentioned filler two or more and use thing.

Described filler also includes their surface modifying stuffing.It can be by chemical anti-that wherein described surface is modified Certain functional group should be connected on filler surface or by mixing or absorption by modifying agent by physics mode with reference in filler On surface.The surface is modified can be carried out before filler is added in rubber solutions, or that modifying agent is added into rubber is molten Surface is carried out in the mixture of liquid and filler to be modified.The modifying agent is the conventional modifying agent in this area, such as uses below general formula The organo silane coupling agent of expression:

(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-;

R and R ' is branched or straight chain alkyl or phenolic group of the carbon atom from 1 to 4, and R and R ' can be with identical, it is also possible to different;

N is 0,1 or 2;

Alk is to contain 1 to 6 straight or branched alkyl of carbon atom;

AlkenyL is to contain 1 to 6 straight or branched alkenyl of carbon atom;

M is 0 or 1;

Ar is to contain 6 to 12 aryl of carbon atom;

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

X is 2 to 8;

Most common of which is double (triethoxy propyl silane) tetrasulfides and disulphide, 3- thiocyanogens propyl group-three Ethoxysilane, γ-sulfydryl-trimethoxy silane, zirconium ester coupling agent, phthalate ester coupling agent, nitro coupling agent, alcohols chemical combination Thing, the alcohol compound includes but is not limited to unit alcohol, dihydroxylic alcohols, polyalcohol, and the alcohol compound is included but is not limited to Propyl alcohol, butanol, ethylene glycol, polyethylene glycol and its derivative.

Step 1 of the present invention) directly filler dry powder and/or additive can be added in rubber solutions, it is also possible to first will Filler and/or additive are added in the solvent identical or different with rubber solutions after being mixed to form uniform suspension and add And be mixed into rubber solutions by stirring.Additive can optionally include oil, age resistor, coupling agent, activating agent, antioxidant, heat One or more in the additive of stabilizer, light stabilizer, fire retardant, dyestuff, pigment, vulcanizing agent or accelerator.It is used to add Plus the consumption of agent is conventional amount used, or it is adjusted according to the requirement of actual conditions.

Step 2) in make the side of rubber, filler and/or additive co-agglomeration in the mixture after finely divided and smart dispersion Method, it is possible to use any of method in this area, such as flocculant flocculence, heating, move back solvent method.

Step 3) in drying means can using any of method in this area, such as constant pressure and dry, drying under reduced pressure, Spray drying, fluidized drying, freeze-drying, infrared drying, microwave drying, hygroscopic desiccation etc..

The method of described recycling design such as can be passed through the solvent of vaporization using any of method in this area Surface condensation or the method for directly contact condensation are reclaimed.When the method using direct chilled contact, cooling agent can be used Water.

Compared with existing wet method elastomeric compound technology, the present invention to rubber, filler without particular/special requirement, it is wider using scope.Remove Outside this, decentralization of the filler in rubber size is high, production technology is continuous, efficiently, it is low power consuming, few artificial, thus cost compared with It is low.Meanwhile, the rubber master batch prepared using the method is all very superior in processing characteristics, physical and mechanical properties, product quality, and The postprocessing working procedures after existing solution polymerized rubber polymerisation can be saved.

Specific embodiment

The present invention is further described with embodiment below, but the scope of the present invention is not restricted by the embodiments.

(1) embodiment is determined using following instrument and equipment and assay method:

Instrument and equipment prepared by the rubber sample of table 1

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 and instrument of the vulcanizating glue physical performance of table 2

(2) embodiment and comparative example

Raw material:

Synthetic polyisoprenes rubber, IR-70, her Cohan new material Co., Ltd of Qingdao;

Solution polymerized butadiene styrene rubber, VSL4526-OHM, LANXESS production;

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

White carbon, Newsil HD165MP, Q & C Silicon Chemical Co., Ltd.;

Carbon black N234, Cabot (China) Investment Co., Ltd;

Zinc oxide, Dalian zinc oxide factory;

Co., Ltd is found into by boron resin acid, PF1808, Malaysia;

Antioxidant 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 Sunsine Chemical Co., Ltd.;

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

Sulfur, Lin Yiluo Zhuan Xin Anhua factory;

Antiscorching agent (CTP), Shandong Yanggu Huatai Chemical Co., Ltd..

Number is weight portion described in following examples and comparative example.

Embodiment 1

The n-hexane that 60 parts of white carbons, 6 parts of silane coupler Si69 are added into 100 part of 8% cis-polyisoprene is molten In liquid, after first mixed, the thin mixed mode of mixing essence of its rubber/white carbon/Si69/ hexane mixture as shown in table 3 mixes, continuously Cohesion in ground injection knockouts, sprays into drier desolventizing and be dried to obtain rubber master batch 1 afterwards.

By rubber master batch 1 after bag roller is uniform on a mill, 3.5 parts of zinc oxide, 1 part of stearic acid, 1.5 parts of anti-aging agent RDs, 2 are added Part antioxidant 4020,1.6 parts of antiscorching agent, after adding 2 parts of accelerant CZs, 1 part of diphenylguanidine, 1.6 parts of Sulfurs, cross roller, bottom sheet, Vulcanized to optimum cure with 150 DEG C of vulcanizing press after parking 8 hours, wet method vulcanizate 1 is obtained.

Comparative example 1

In banbury, 60 parts of white carbons, 6 parts of silane couplers are added in the middle of 100 parts of cis-polyisoprene Kneaded, kneaded 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 antioxidant 4020s, 1.6 parts of antiscorching agent, elastomeric compound adds 2 parts of accelerant CZs, 1 part of diphenylguanidine, 1.6 parts of Sulfurs after parking 8 hours, elastomeric compound stops Vulcanized to optimum cure with 150 DEG C of vulcanizing press after putting 8 hours, dry pre-sulfiding glue 1 is obtained.

Embodiment 2

78 parts of white carbons, 6.4 parts of silane coupler Si69 and antioxidant 264 are added to 70 parts of Butadiene-Styrene Rubbers and 30 parts In the hexane solution of cis-butadiene cement, its rubber/white carbon/Si69/ antioxidant 264s/hexane mixture is first as shown in table 3 It is mixed, thin to mix after the mixed mode of essence mixes, be continuously injected into cohesion in knockouts, spray into afterwards in drier desolventizing and it is dry simultaneously It is further dried through double screw extruder and obtains rubber master batch 2.

By rubber master batch 2 after bag roller is uniform on a mill, 28 parts of high aromatic oils, 3.5 parts of zinc oxide, 2 parts of stearic acid, 2 are added Part antioxidant 4020,2 parts of paraffin, bottom sheet after kneading, added on a mill again after parking 8 hours 1.3 parts of accelerant CZs, After 0.3 part of diphenylguanidine, 1.4 parts of Sulfurs, cross roller, bottom sheet, elastomeric compound park 8 hours after with 150 DEG C of vulcanizing press vulcanize to After optimum cure, wet method vulcanizate 2 is obtained.

Comparative example 2

In banbury, 78 parts of white carbons, 6.4 parts of silane couplers are added to 70 parts of Butadiene-Styrene Rubbers and 30 parts of suitable fourths Kneaded in glue, kneaded certain hour, added 28 parts of high aromatic oils, 3.5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of age resistor 4020th, 2 parts of paraffin, elastomeric compound adds 1.3 parts of accelerant CZs, 0.3 part of diphenylguanidine, 1.4 in banbury again after parking 8 hours Kneaded after part Sulfur, elastomeric compound is vulcanized to optimum cure after parking 8 hours with 150 DEG C of vulcanizing press, be obtained dry pre-sulfiding Glue 2.

Embodiment 3

By 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 Part antioxidant 264 and 2 parts of paraffin are added in 70 parts of Butadiene-Styrene Rubbers and 30 parts of hexane solutions of cis-butadiene cement, its rubber/white After first mixed, the thin mixed mode of mixing essence of the carbon black/additive/hexane mixture as shown in table 3 mixes, knockouts is continuously injected into Interior cohesion, sprays into desolventizing and drying in drier, and be further dried through double screw extruder and obtain rubber master batch 3 afterwards.

By rubber master batch 3 after bag roller is uniform on a mill, 1.3 parts of accelerant CZs, 0.3 part of diphenylguanidine, 1.4 parts of Sulfurs are added Afterwards, roller, bottom sheet are crossed, elastomeric compound is vulcanized to optimum cure after parking 8 hours with 150 DEG C of vulcanizing press, wet method vulcanizate is obtained 3。

The continuous mixing technological process of table 3

Sequence number It is just mixed It is thin mixed Essence is mixed Rubber master batch 1 Blade stirrer 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 Curved tube disperser Ball mill

Table 4 is wet, dry pre-sulfiding glue physical property

Table 4 is under different formulations and technique obtained by the comparative example of the embodiment of wet masterbatch and dry method elastomeric compound The physical property of vulcanizate, there it can be seen that under same recipe, compared with maskerbatch of dry process, filler exists wet masterbatch Degree of scatter in rubber is greatly improved, and the hardness of vulcanizate is relatively low, and tensile strength and elongation at break are higher, and elasticity is high, is moved State compression heat generation is low, and anti-wear performance is preferable.

Claims (38)

1. a kind of method for continuously producing of rubber masterbatch, it is characterised in that:Comprise the following steps,
Step 1), filler is added in rubber solutions, rubber/filler/solvent mixture is formed by stirring, and to the rubber Glue/filler/solvent mixture is further finely divided and smart disperses improving degree of scatter of the filler in rubber solutions;
Step 2), make step 1) in essence dispersion after rubber/filler/solvent mixture in rubber and filler co-agglomeration, obtain The mixture of rubber/filler compound and solvent;
Step 3), desolvation is simultaneously dried to described mixture, obtains rubber/filler masterbatch;
Wherein step 1) described in it is finely divided as described below,
I) sprays the rubber/filler/solvent mixture after stirring or rubber/filler/additive/solvent mixture by one Mouth under high pressure in the case of spray, pressure limit used is from 2MPa to 60MPa;
II) makes above-mentioned I) in ejecta by swan neck more than make rubber/filler/solvent mixture or rubber/filler/ Additive/solvent mixture clashes into Guan Zhongyu tube walls increases the dispersiveness of filler;Or
III) makes above-mentioned I) in ejecta convert shear stress by pipeline that the multiple folding and unfolding of bore changes and Increase the dispersiveness of filler.
2. the method for continuously producing of rubber masterbatch according to claim 1, it is characterised in that:Wherein optionally reclaim step The rapid solvent for 3) being removed, recycles.
3. the method for continuously producing of rubber masterbatch according to claim 1, it is characterised in that:Wherein in step 1) And/or step 2) in optionally addition one or more be selected from oil, age resistor, coupling agent, activating agent, antioxidant, fire retardant, heat The additive of stabilizer, light stabilizer, dyestuff, pigment, vulcanizing agent and accelerator.
4. the method for continuously producing of rubber masterbatch according to claim 1, it is characterised in that:Wherein step 1) in institute That states is finely divided as described below:
I) sprays the rubber/filler/solvent mixture after stirring or rubber/filler/additive/solvent mixture by one Mouth under high pressure in the case of spray, pressure limit used is from 10MPa to 40MPa;
II) makes above-mentioned I) in ejecta by swan neck more than make rubber/filler/solvent mixture or rubber/filler/ Additive/solvent mixture clashes into Guan Zhongyu tube walls increases the dispersiveness of filler;Or
III) makes above-mentioned I) in ejecta convert shear stress by pipeline that the multiple folding and unfolding of bore changes and Increase the dispersiveness of filler.
5. the method for continuously producing of rubber masterbatch according to claim 1, it is characterised in that:Wherein step 1) in institute The essence stated is separated into during the mixture after finely divided is continuously added into ball mill and/or colloid mill is disperseed.
6. the method for continuously producing of rubber masterbatch according to claim 1, it is characterised in that:Wherein step 1) in institute The essence stated to be separated into be added continuously to the mixture after finely divided and is ground in grinder, and the grinder has one group Or multigroup high-speed rotation plane mill and be fixed on fixing pin or price fixing on grinder sleeve and alternate with plane mill.
7. the method for continuously producing of rubber masterbatch according to claim 1, it is characterised in that:Wherein step 1) in institute The essence stated to be separated into be added continuously to the mixture after finely divided and is ground in grinder, and the grinder has rotation Two blades in opposite direction, the blade has pore chute.
8. the method for continuously producing of rubber masterbatch according to claim 1, it is characterised in that:Wherein step 1) in institute The essence stated is separated into and the mixture after finely divided is continuously added in multi-layer high-voltage slit dispersion machine, mixture is existed Extruded in slit between two-layer under high pressure, pressure limit used is from 2MPa to 60MPa.
9. the method for continuously producing of rubber masterbatch according to claim 8, it is characterised in that:Wherein step 1) in essence Dispersion pressure limit used is from 10MPa to 40MPa.
10. the method for continuously producing of rubber masterbatch according to claim 1, it is characterised in that:Wherein step 1) in Described essence to be separated into be continuously added to the mixture after finely divided is disperseed in power decentralized device, power decentralized There are radially-arranged slit or hole on the rotor of device.
The method for continuously producing of 11. rubber masterbatch according to any one of claim 5 to 10, it is characterised in that: Two or more being serially connected in smart process for dispersing described in claim 5-10 is used.
The method for continuously producing of 12. rubber masterbatch according to any one of claim 1 to 10, it is characterised in that: Wherein described rubber solutions are directly obtained from solution polymerized rubber production line is prepared, or by any kind of dry glue to the glue Good solvent in dissolve prepare.
The method for continuously producing of 13. rubber masterbatch according to claim 12, it is characterised in that:Wherein use dry glue system During standby rubber solutions, the dry glue is natural polymer or synthetic polymer, and the natural polymer includes natural gum, the bark of eucommia Glue, guayule, the synthetic polymer are polymerized gained, monomer in the emulsion obtained by polymerization or monomer body in the solution for monomer Obtained by being polymerized.
The method for continuously producing of 14. rubber masterbatch according to claim 12, it is characterised in that:Wherein described rubber Solution directly from prepare obtained in solution polymerized rubber production line when, the solution polymerized rubber be ethene, propylene, butylene, amylene, hexene, Heptene, the diene of 4-7 carbon atom or the 6-7 homopolymerization of the triolefin or the vinyl monomer containing other atoms or functional group of carbon atom Or copolymerized polymer, described other atoms or functional group be silicon atom, fluorine atom, chlorine atom, nitrogen-atoms, oxygen atom, sulphur atom, Ester group, amino ester group or cyano group.
The method for continuously producing of 15. rubber masterbatch according to claim 14, it is characterised in that:Wherein described rubber Rubber in solution is polybutadiene, polyisoprene, butadiene-styrene rubber, the glue of second third, butyl rubber, NBR, neoprene, silicon rubber, Fluorubber, polyurethane rubber, CSM or ACM.
The method for continuously producing of 16. rubber masterbatch according to claim 15, it is characterised in that:Wherein rubber is molten Concentration range in liquid is 1% weight to 60% weight.
The method for continuously producing of 17. rubber masterbatch according to claim 16, it is characterised in that:Wherein rubber is molten Concentration range in liquid is 5% weight to 40% weight.
The method for continuously producing of 18. rubber masterbatch according to claim 17, it is characterised in that:Wherein rubber is molten Concentration range in liquid is 10% weight to 30% weight.
The method for continuously producing of 19. rubber masterbatch according to claim 16, it is characterised in that:Wherein described rubber The molecular weight of rubber is 1,000 to 40,000,000 in solution.
The method for continuously producing of 20. rubber masterbatch according to claim 19, it is characterised in that:Wherein described rubber The molecular weight of rubber is 5,000 to 30,000,000 in solution.
The method for continuously producing of 21. rubber masterbatch according to claim 20, it is characterised in that:Wherein described rubber The molecular weight of rubber is 10,000 to 8,000,000 in solution.
The method for continuously producing of 22. rubber masterbatch according to claim 19, it is characterised in that:Wherein described rubber Solvent in solution is the good solvent of various rubber.
The method for continuously producing of 23. rubber masterbatch according to claim 1, it is characterised in that:Wherein described filler It is solid powdery reinforcing agent used in rubber and/or filler.
The method for continuously producing of 24. rubber masterbatch according to claim 23, it is characterised in that:Wherein described filler Nanometer materials containing carbon black, silica, metal oxide, calcium carbonate, potter's clay and/or resin and above-mentioned filler;Or institute State the two-phase or many that filler is constituted for carbon black, silica, aluminum oxide, magnesia, zinc oxide, calcium oxide, titanium oxide, boron oxide Phase filling;Or the above-mentioned filler and use mixture.
The method for continuously producing of 25. rubber masterbatch according to claim 23, it is characterised in that:Wherein described filler Specific surface area be 0.1 to 800m2/g。
The method for continuously producing of 26. rubber masterbatch according to claim 25, it is characterised in that:Wherein described filler Specific surface area be 1 to 500m2/g。
The method for continuously producing of 27. rubber masterbatch according to claim 26, it is characterised in that:Wherein described filler Specific surface area be 5 to 300m2/g。
The method for continuously producing of 28. rubber masterbatch according to claim 24, it is characterised in that:Wherein described carbon black It is 20 to 250ml/100g with the oil factor of silica.
The method for continuously producing of 29. rubber masterbatch according to claim 28, it is characterised in that:Wherein described carbon black It is 25 to 200ml/100g with the oil factor of silica.
The method for continuously producing of 30. rubber masterbatch according to claim 29, it is characterised in that:Wherein described carbon black It is 30 to 150ml/100g with the oil factor of silica.
The method for continuously producing of 31. rubber masterbatch according to claim 1, it is characterised in that:Wherein optionally to institute State filler carry out surface be modified.
The method for continuously producing of 32. rubber masterbatch according to claim 31, it is characterised in that:Wherein described table Face is modified as be connected on filler surface by functional group by chemically reacting, or is combined in filler table modifying agent by mixing or adsorbing Face.
The method for continuously producing of 33. rubber masterbatch according to claim 31, it is characterised in that:Wherein described surface Being modified before filler is added in rubber solutions is carried out, or modifying agent is added in the mixture of rubber solutions and filler Row surface is modified.
The method for continuously producing of 34. rubber masterbatch according to claim 1,2 or 3, it is characterised in that:Wherein in step It is rapid 1) in directly filler dry powder and/or additive dry powder are added in rubber solutions, or first filler and/or additive added Uniform filler/solvent suspension liquid or filler/additive/solvent are mixed to form in the solvent identical or different with rubber solutions Rubber solutions are then added to after suspension, are mixed into rubber solutions by stirring;It is molten that liquid additive can be added directly into rubber In liquid.
The method for continuously producing of 35. rubber masterbatch according to claim 1, it is characterised in that:Wherein step 1) in Stirring by mixer complete.
The method for continuously producing of 36. rubber masterbatch according to claim 34, it is characterised in that:Wherein described stirring Machine is blade paddle mixer, trough mixer, planetary stirring machine or Z-blade mixer.
A kind of 37. rubber masterbatch prepared according to any described methods of claim 1-36.
A kind of 38. rubbers, it is prepared using the rubber masterbatch according to claim 37.
CN201310027024.1A 2013-01-10 2013-01-10 Rubber masterbatch and rubber prepared by the method for continuously producing and the method for rubber masterbatch CN103203810B (en)

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