WO2015018279A1 - 橡胶母炼胶的连续式制造方法及该方法制备的橡胶母炼胶 - Google Patents

橡胶母炼胶的连续式制造方法及该方法制备的橡胶母炼胶 Download PDF

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Publication number
WO2015018279A1
WO2015018279A1 PCT/CN2014/082711 CN2014082711W WO2015018279A1 WO 2015018279 A1 WO2015018279 A1 WO 2015018279A1 CN 2014082711 W CN2014082711 W CN 2014082711W WO 2015018279 A1 WO2015018279 A1 WO 2015018279A1
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Prior art keywords
rubber
solvent
drying
mixture
filler
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PCT/CN2014/082711
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English (en)
French (fr)
Inventor
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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Priority to MX2016001563A priority Critical patent/MX2016001563A/es
Publication of WO2015018279A1 publication Critical patent/WO2015018279A1/zh

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
    • B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/212—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase and solid additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2321/00—Characterised by the use of unspecified rubbers

Definitions

  • the invention relates to the field of rubber, in particular to a continuous manufacturing method of rubber masterbatch and a rubber masterbatch prepared by the method.
  • the agglomeration of the rubber/filler from the solvent is an important step in the manufacture of rubber/filler/additive masterbatch.
  • the process described in W098/58985 is carried out in a large bladed worm gear dryer at 400/1200 rpm, which is a slower, longer process and consumes more energy.
  • the invention relates to several high-speed mixing/coacervation methods, wherein the coalescence medium comprises a gas, in particular a high-temperature gas and a liquid and a rubber/filler/additive mixture are instantaneously mixed in a high-energy turbulent state, due to the high temperature effect of the gas and the liquid medium and the solvent electrode
  • the difference in properties, the rubber/filler/addition of the rubber/filler/additive in the solvent mixture will cause a solvent-free phenomenon in the solvent. Due to the high velocity turbulence effect, the mixing of the mixture with the suspected polymerization medium, the desolvent medium, can be accomplished in a very short period of time.
  • the agglomeration method designed by the present application is characterized by high efficiency, energy saving, and mixing and coagulation continuous operation as compared with the prior art.
  • the present invention has no requirements for t rubber and filler, and a wide range of applications for the types and contents of fillers and additives;
  • the masterbatch prepared by this method is superior in processability, physical and mechanical properties, and product quality.
  • the invention further relates to the following embodiments:
  • a continuous manufacturing method of rubber masterbatch includes the following steps: Step 1): adding the filler to the rubber solution, the ship is stirred to form a crucible mixture; Step 2): directly passing the rubber/filler/solvent mixture in step 1) into a heating medium having a temperature higher than the boiling point of the solvent, The polarity of the heating medium is different from the polarity of the solvent used, the mixture agglomerates and swells, and the solvent evaporates rapidly, thereby forming a mixture of the rubber wrist composite containing the heating medium and the solvent;
  • Step 3 The solvent is removed and the mixture of M is dried to obtain a tJt/filler masterbatch.
  • step ⁇ 12 can be carried out using any container.
  • step 2) is carried out in a can container, preferably a cylindrical can container.
  • the solvent removed in step 3) is optionally recovered and recycled.
  • step 1) wherein one or more selected from the group consisting of oil, antioxidant, coupling agent, active agent, antioxidant, flame retardant, heat stabilizer, light are optionally added in step 1) and/or step 2) Additives for stabilizers, dyes, pigments, vulcanizing agents and accelerators.
  • the heating medium is water vapor
  • the dried solid mixture contains water, and then dried by vacuum drying, heating and drying, and heated to remove water to obtain a rubber JK filler master batch.
  • the heating medium is water
  • the solvent is a hydrocarbon solvent having a boiling point of less than 100 ° C
  • the dried solid mixture has water, and then dried by vacuum drying, heating drying or extrusion drying to remove water. Get the rubber masterbatch rubber.
  • heat drying is drying or air drying.
  • the extrusion heat drying is performed by first removing the heating medium and then drying it. More preferably, the drying step is air drying, drying or mechanical drying.
  • the mechanical drying is carried out using an open mill, a kneader, an internal mixer, a continuous internal mixer, a single-screw extruder, and twin-screw extrusion.
  • the invention also provides a t-size masterbatch prepared according to the above method.
  • the present invention also provides a rubber article prepared by using the above masterbatch.
  • the continuous manufacturing method of the rubber master batch of the present invention comprises the following steps:
  • Step 1) adding the filler to the rubber solution and forming the oak/solvent mixture by stirring;
  • Step 2) directly feeding the rubber filler/solvent mixture in step 1) into a heating medium having a boiling point higher than the boiling point of the solvent The polarity of the heating medium is different from the polarity of the solvent used, the mixture agglomerates and swells, and the solvent evaporates rapidly, thereby forming a mixture of the rubber filler composite containing the heating medium and the solvent;
  • Step 3 The solvent is removed and the mixture is dried to obtain a tJt/filler masterbatch.
  • the continuous manufacturing process of the rubber masterbatch of the present invention optionally further comprises the step of recovering the solvent removed in step 3) for recycling. Further, optionally adding one or more selected from the group consisting of oil, anti-aging agent, pourant, active agent, antioxidant, dye, light stabilizer, flame retardant, heat stable in step 1) and/or step 2) Agents, pigments, vulcanizing agents and Additive for the accelerator.
  • Step 1) can be carried out using methods well known in the art.
  • the agitation described in the step 1) can be carried out using a general agitator, including but not limited to a vane type agitation type agitation type planetary mixer, a zigzag type mixer, and the like.
  • Step 1) may further comprise a fine dispersion step, wherein the fine dispersion of M may be carried out as follows: The mixture obtained by the above agitation is sprayed through a nozzle under high pressure and high shear to improve the filler and/or the additive. Dispersing; causing the above-mentioned effluent to pass through a multi-bend tube to cause the mixture to collide with the tube wall in the tube to increase the dispersibility of the filler and/or the additive; or to cause the effluent to pass through a tube having a plurality of tubes To shift the shear stress to increase the dispersion of the filler and/or additive.
  • the pressure used ranges from 0.1 MPa to 60 MPa, preferably 10 MPa to 0 MPa.
  • the mixture formed after the fine dispersion can further improve the dispersion of the filler and/or the additive in the rubber solution by the following fine dispersion:
  • the finely dispersed mixture is continuously added to a grinder for grinding to sufficiently disperse the filler and/or the additive in the rubber solution, the grinder having one or more sets of high-speed rotating flat grinding discs and fixed in the grinding A fixing pin or plate on the casing and between the flat grinding discs.
  • the pressure used ranges from 0.1 MPa to 60 MPa, preferably 10 MPa to 40 MPa.
  • the mixture after finely dispersing the legs is continuously added to the multi-layer high-pressure slit disperser, and the mixture is extruded under high pressure from the slit between the two layers, and the strong shear force generated at this time can increase the filler and / or the degree of dispersion of the additive in the rubber solution.
  • the pressure used ranges from 0.1 MPa to 60 MPa, preferably 10 MPa to 0 MPa.
  • v. Dispersing the finely dispersed mixture continuously into a power disperser having a plurality of radially distributed slits or holes on the high speed rotating rotor, the mixture impinging on the stator surface at high speed
  • the top layer is such that the filler and/or the additive are uniformly dispersed in the gum solution.
  • Two or more of the above five fine dispersion methods may be used in series with each other.
  • the rubber solution of M can be directly obtained from the preparation of the solution rubber production line, and any type of dry glue can be prepared by dissolving in the solvent of the glue.
  • the dry glue may be any kind of rubber used in the art, such as a natural polymer or a synthetic polymer.
  • the natural polymer includes, but is not limited to, natural rubber, gutta percha, silver chrysanthemum, etc.; synthetic polymers including, but not limited to, monomers obtained by polymerization in a solution (ie, a solution rubber), and polymerization of monomers in an emulsion ( That is, the latex rubber) and the monomer body are obtained by polymerization.
  • the M-soluble rubber is ethylene, propylene, butene, pentene, hexene, a homopolymer or copolymer of heptene, a diene of 4 to 7 carbon atoms or a triene of 6 to 7 carbon atoms, or an ethylenic monomer having other atoms or functional groups, and other atoms or functional groups of the leg are silicon atoms.
  • a fluorine atom a chlorine atom, a nitrogen atom, an oxygen atom, a sulfur atom, an ester group, an amino ester group, a cyano group, and also a homopolymer and a copolymer containing the above monomers, including but not limited to polybutylene Diene, polyisoprene, styrene butadiene rubber, ethylene propylene rubber, butyl rubber, nitrile rubber, neoprene, silicone rubber, fluororubber, urethane rubber, chlorosulfonated polyethylene rubber, acrylate rubber, and the like.
  • the amount of rubber is from 1 to 40 million, preferably from 5,000 to 30,000,000, more preferably from 10,000 to 8,000,000.
  • the solvent in the Mt solution is a good solvent for various t-gels.
  • the solvent may specifically be an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a chlorinated hydrocarbon solvent, a ketone solvent, an ether solvent, and an ester solvent, and the aliphatic hydrocarbon solvent includes, but is not limited to, various solvents such as gasoline, cycloalkane, and substituted cycloalkane.
  • M aromatic hydrocarbon solvent including but not limited to benzene, toluene, xylene, styrene, the chlorinated hydrocarbon solvent including but not limited to dichloromethane, chloroform, carbon tetrachloride, dichloroethane Alkane, chlorobenzene, tetrachloroethylene, chlorotoluene.
  • concentration of the rubber in the solution ranges from 1% by weight to 60% by weight, preferably from 5% by weight to 0% by weight, more preferably from 10% by weight to 30% by weight.
  • the fillers include, but are not limited to, various solid powdered reinforcing agents and fillers used in rubber, such as various types of carbon black, silica, metal oxides, salts, different resins, and nanoscale materials of the above fillers.
  • the metal oxides include, but are not limited to, alumina, magnesia, zinc oxide, etc.
  • the salts include, but are not limited to, carbonic acid, clay, and nanoscale materials of the above fillers.
  • the specific surface area of the filler is 0.1 to 800m 2 / g, preferably from 1 to 500 m 2 / g, more preferably 5 to 300 m 2 / g.
  • the oil absorption value is from 20 to 250 ml / 100 g, preferably from 25 to 200 ml / 100 g, more preferably from 30 to 150 ml / 100 g, wherein the filler comprises a mixture thereof,
  • multiphase fillers including but not limited to carbon black, silica, alumina, magnesia, zinc oxide, oxidized titanium oxide, boron oxide, etc., for two-phase or multi-phase fillers, for two-phase or multi-phase
  • the oil absorption value is from 20 to 250 ml/100 g, preferably from 25 to 200 ml/100 g, more preferably from 30 to 150 ml/100 g.
  • the filler is used in an amount of 5 to 300 parts by weight (based on 100 parts by weight of the rubber), preferably 10 to 200 parts by weight, more preferably 30 to 150 parts by weight.
  • the filler also includes a combination of two or more of the above fillers.
  • the filler of the legs also includes their surface modifying fillers.
  • the surface modification of the legs may be a ship chemical reaction in which a certain functional group is attached to the surface of the filler or the modifier is physically bonded to the surface of the filler by mixing or adsorption.
  • the modifier can be dissolved in a solvent and mixed with a filler, such as Wang W, Nanse G, Vidal A, et al. K. GK [J], 1994, 47:493 In the middle of the household; 3 ⁇ 4, the modifier and the filler may also be mixed and heated for solid phase modification, as described in Wang MJ, Wolff. SRCT [J], 1992, 65:715.
  • the surface modification may also be carried out before the filler is added to the rubber solution, or the modifier may be added to the mixture of the rubber solution and the filler for surface modification.
  • the modifier is a conventional modifier in the art, such as an organosilane coupling agent represented by the following formula:
  • R and R' are a branched or linear alkyl or phenol group having from 1 to 4 carbon atoms, and R and R' may be the same or different;
  • n 0, 1 or 2;
  • Alk is a linear or branched hydrocarbon group having 1 to 1 carbon atom
  • ⁇ 13 ⁇ 4 ⁇ 1 is a linear or branched alkenyl group having 1 to 1 carbon atom
  • n 0 or 1
  • Ar is an aryl group having 6 to 12 carbon atoms
  • p is 0 or 1, p and n cannot be 0 at the same time;
  • X is 2 to 8;
  • the most commonly used are bis(triethoxypropylsilane) tetrasulfide and disulfide, 3-thiocyanopropyl-triethoxysilane, ⁇ -mercapto-trimethoxysilane, zirconate a coupling agent, a phthalate coupling agent, a nitro coupling agent, an alcohol compound, including but not limited to a unit alcohol, a glycol, a polyol, and a compound such as, but not limited to, propanol , butanol, ethylene glycol, polyethylene glycol and its derivatives.
  • Step 1) of the present invention may directly add the filler and/or the additive to the rubber solution, or may first add the filler and/or the additive to the same or different solvent as the rubber solution to form a uniform suspension, and then add and pass through. Stir in the rubber solution.
  • the additive may optionally include one or more of an oil, an antioxidant, a coupling agent, an active agent, an antioxidant, a heat stabilizer, a light stabilizer, a flame retardant, a dye, a pigment, a vulcanizing agent, or an additive for an accelerator. .
  • the amount of the additive used is a conventional amount or adjusted according to actual conditions.
  • step 2) the rubber/filler/solvent mixture or the finely divided mixture in step 1) is passed directly into a heating medium having a temperature above the boiling point of the solvent.
  • a heating medium having a temperature above the boiling point of the solvent.
  • the nature of the heating medium is different from the nature of the solvent used, especially the polarity, the mixture agglomerates and swells.
  • the temperature of the heating medium is higher than the boiling point of the solvent, the solvent volatilizes to form a master batch containing a heating medium.
  • the masterbatch is heated to remove the heating medium to form a masterbatch product.
  • the solvent and the unreacted monomer in the rubber synthesis are recovered into the condenser and the column, and the obtained agglomerated mixture is recovered.
  • the filter is separated from the heating medium and dried to form a masterbatch product.
  • heating media include, but are not limited to, water.
  • the solvent has a boiling point lower than that of the lore solvent.
  • the volatilized solvent and the unreacted monomer in the t-gel synthesis and water vapor are then recovered in the condenser and fractionation column for recovery.
  • the drying may be vacuum drying, including normal temperature vacuum drying, freeze vacuum drying, and heating vacuum drying, or may be a general drying method such as drying or air drying.
  • the drying may also be performed by first extruding and removing the heating medium and then further drying, wherein the drying is performed by air drying, drying or mechanical drying, and the legs are dried to use an open mill, a kneader, an internal mixer, Continuous Mixer, single screw extruder, twin-screw extrusion.
  • the agglomeration of step 2) can be carried out using any container; preferably, it is carried out without using any specially designed agglomerator; the agglomeration of the step can be carried out in a can-shaped container, preferably a cylindrical can-shaped container.
  • the agglomeration in step 2) can also be carried out using a coalescer, which can be a tubular agglomerator with one or more feed ports, wherein the feed direction of the feed port can be condensed with the tube
  • a coalescer which can be a tubular agglomerator with one or more feed ports, wherein the feed direction of the feed port can be condensed with the tube
  • the axial direction of the tube is parallel, the outlet is at the end of the tube, and may be at an angle of 1-180° to the axial direction of the tube agglomerator tube, preferably at an angle of 20-120°, more preferably; it 70-100° angle Most preferably at an angle of 85-95°.
  • the feed direction of some of the feed ports is parallel to the axial direction of the tube agglomerator tube; the feed direction of the other feed ports is the axial direction of the tube of the tube agglomerator An angle of 1-180°, preferably at an angle of 20-120°, more preferably at an angle of 70400°, optimal; it 85-95.
  • the projection of the feed direction of each feed port on a cross section perpendicular to the axis of the tube is any direction between the radial direction of the cross section to the tangential direction of the cross section, preferably a radial direction, or a tangent direction.
  • the feed ports are all in the same plane perpendicular to the axial direction of the tube or the feed ports are on different planes.
  • the agglomerator used in step 2) may also be an agglomerator consisting of two or more mutually concentric tubes, wherein each tube has one or more feed ports, and the feed direction of the feed port is Parallel to the axial direction of the tube or the tangential direction of the tube, the outlet is at the end of the tube.
  • the fluid can be passed directly or through the tangential direction of the tube wall.
  • the ends of the feed ports of each tube may be in the same plane, or may be lengthened from the ends of the feed ports of the inner and outer tubes or sequentially shortened from the inner and outer ends of the feed ports of each tube.
  • the agglomerator used in step 2) may also be a cylindrical agglomerator having only one feed port located at the upper end of the barrel agglomerator or on the wall of the barrel, the outlet being at the lower end of the barrel.
  • the fluid can be injected directly into the agglomerator through the feed port or injected into the agglomerator in a tangential direction along the wall of the vessel.
  • the agglomerator used in step 2) may also have a cylindrical shape at the upper portion and a cone-shaped structure with a conical shape at the lower portion and one or more feed ports.
  • the feed direction of the feed port may be the tangential direction of the barrel wall; each feed port may be in the same plane or in a different plane.
  • the feed direction of the feed port may also be perpendicular to the axial direction of the barrel or at an angle of 1-180° to the axial direction of the barrel, preferably 20-110°, more preferably 70-100°, most preferably 85-95.
  • the projection direction of the feed direction of each feed port in a cross section perpendicular to the axis of the cylinder is any direction between the radial direction of the cross section to the tangential direction of the cross section, preferably the tangential direction of the cross section .
  • step 2) uses a can-shaped container of any shape, more preferably a cylindrical can-shaped container.
  • the method of recovering the solvent may be carried out by any method known in the art, such as by vaporizing the solvent through surface suspicion or direct contact with cold doubt.
  • the coolant may be water when using a direct cold contact method.
  • the technical feature of the invention is that the process adaptability is strong: the process can be simple, the filler dispersibility and the product property
  • the rubber solution/filler/additive masterbatch can be prepared by mixing the rubber solution with the filler, the additive and the direct heating method, and the fC3 ⁇ 4, the mixing agglomerator and the mechanical drying method can be used to manufacture the higher cost but the performance is better.
  • the technical feature of the present invention is the way of suspected poly-polymerization and solvent removal of t-glue/filler/additive/solvent mixture: Rubber JK/filler/additive/solvent mixture directly into the liquid, especially the liquid with different polarity and solvent properties The medium dehydrates and agglomerates the mixture, and when the temperature of the medium is higher than the boiling point of the solvent, the solvent rapidly evaporates to contain heat.
  • the masterbatch is heated to remove the heating medium to form a masterbatch product, and the liquid medium used includes, but is not limited to, water.
  • the technical feature of the present invention is that the agglomeration step is simple in process, does not require a structure agglomerator, and has low equipment cost.
  • Antioxidant 020 Jiangsu Shengao Chemical Co., Ltd.;
  • Silane coupling agent Si69 Nanjing Shuguang Chemical Group Co., Ltd.
  • Example 1 After being placed in the open mill for 8 hours, it was vulcanized to a positive vulcanization in a 15 CTC flat vulcanizer to obtain a dry vulcanizate.
  • Example 1 After being placed in the open mill for 8 hours, it was vulcanized to a positive vulcanization in a 15 CTC flat vulcanizer to obtain a dry vulcanizate.
  • the mixture was continuously added to a grinder for fine dispersion, that is, a finely dispersed mixture was obtained, and then the mixture was directly sprayed into water at about 95 ° C under a pressure of 0.2 MPa to coagulate.
  • the coagulated and desolvated colloidal particles are filtered and dried to obtain a masterbatch 1.
  • Spraying the mixture through a nozzle into a multi-bend tube causes the mixture to collide with the tube wall in the tube to increase the dispersion of the filler.
  • the mixture is continuously added to the mill for fine dispersion, that is, the mixture is refined, and then the mixture is injected into the agglomerator through two inlets of a cone-type agglomerator having four inlets under a pressure of 30 MPa, and the ship is simultaneously
  • two inlets were injected with nitrogen gas at a temperature of 18 CTC.
  • the resulting mixture was continuously sprayed into a desiccant desiccant filled with about 15 CTC of nitrogen, and dried to form a solid powdery substance, i.e., a masterbatch 3.
  • the masterbatch 1, the masterbatch 2 and the masterbatch 3 obtained above are added to the internal mixer by adding 2 parts of stearic acid, 2 parts of the antioxidant 4020, and then kneading for 4 minutes to discharge from the internal mixer. Open il ⁇ over the roller, the next piece. After mixing for 8 hours, add 2 parts of leg CZ, 1 part of leg D and 1. 8 wounds, yellow and then mix in the mixer. 1. Discharge from the mixer for 5 minutes. After being placed in the open mill for 8 hours, it was vulcanized to a positive vulcanization in a 150 ° C plate vulcanizer to prepare wet vulcanizates 1, 2 and 3, respectively.
  • the special design of the agglomerator is not used, which has the advantage of low cost.

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Abstract

本发明公开了橡胶母炼胶的连续式制造方法及该方法制备的橡胶母炼胶，制造方法包括：1）：将填料加入到橡胶溶液中，通过搅拌形成橡胶/填料/溶剂混合物；2）：将步骤1）中的橡胶/填料/溶剂混合物直接通入温度高于溶剂沸点的加热介质中，该加热介质的极性与所用溶剂的极性不同，混合物凝聚并退溶胀，并且溶剂迅速挥发，从而形成含有该加热介质的橡胶/填料复合物与溶剂的混合物；3）：脱除溶剂并对所述的混合物进行干燥，得到橡胶/填料母炼胶。本发明对橡胶、填料无特殊要求，使用范围较广。生产设备及工艺简单、且连续、高效、耗能低、少人工，成本较低。使用此方法制备的母炼胶加工、物理机械性能、产品质量上十分优越。

Description

橡胶母炼胶的连续式制造方法及该方法制备的橡胶母炼胶
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本发明涉及橡胶领域，特别涉及橡胶母炼胶的连续式制造方法及该方法制备的橡胶 母炼胶。
背景: fcfe^
在橡胶 /填料 /添加剂 /溶剂体系中， 橡胶 /填料垂剂从溶剂中的凝聚是制造橡胶 /填 料 /添加剂母胶中很重要的步骤。 W098/58985中所述的这一过程为大型带有叶片的蜗轮 干燥机在每分钟 400/1200转的 ¾¾中进行， 这种方法的凝聚 «较慢， 工艺过程长， 耗能高。 本发明涉及几种高速混合 /凝聚方法， 其中凝聚介质包括气体， 尤其是高温气 体和液体与橡胶 /填料 /添加剂混合物在高能湍流的状态下瞬间混合， 由于气体的高温效 应及液体介质与溶剂极性方面的差异， 橡胶 /填料 /添加弃 溶剂混合物中的橡胶 /填料 /添 加剂将在溶剂中产生退溶剂现象而疑聚。由于高速湍流效应，混合物和疑聚介质即退溶 剂介质的混合在非常短的时间内即可完成。 由于退溶剂介质和橡胶 /填料 /添加 溶剂的 界面大大增加， t胶 /填料 /添加剂在溶剂中的疑聚速度非常快， 如果退溶剂介质的温度 较高， 溶剂将在凝聚过程中通挥发， 导致凝聚胶粒较小， 因此凝聚胶的溶剂挥发作用 进一步加速。 因此， 与现有方法相比， 本申请所设计的凝聚方法具有高效、节能而且混 合及凝聚连续操作的特点。
发明内容
针对现有技术的问题，本发明的目的是提供一种t胶母炼胶的连续式制造方法及该 方法制备的橡胶母炼胶。本发明的另一个目的是提供一种使用本发明的t胶母炼胶制备 的橡胶制品。
本发明腿的橡胶母炼胶的连续式制造方法的优点为：
1 )连续高效；
2)混合和凝聚均匀且速率快；
3 )显著提高硫化胶的物理机械性能和橡胶制品的质量；
4)与现有湿法混炼中的疑聚技术相比， 本发明对t胶、 填料无 ¾要求， 和填料及添加剂的种类及含量的适用范围广；
5)生产设备及工艺十分简单、 且连续、 高效、 耗能低、 少人工， 因而成本较低；
6)使用此方法制备的母胶在加工性能、 物理机械性能、 产品质量上都十分优越。 本发明进一步涉及如下实施方案：
一种橡胶母炼胶的连续式制造方法， 包括如下步骤： 步骤 1 ): 将填料加入到橡胶溶液中， 舰搅拌形成樾扁斗翻混合物； 步骤 2): 将步骤 1 ) 中的橡胶 /填料 /溶剂混合物直接通入温度高于溶剂沸点的加热 介质中， 该加热介质的极性与所用溶剂的极性不同，混合物凝聚并退溶胀， 并且溶剂迅 速挥发， 从而形成含有该加热介质的橡腕料复合物与溶剂的混合物；
步骤 3): 脱除溶剂并对戶; M的混合物进行干燥， 得到tJt/填料母炼胶。
优选的是， 其中步 §12)可以使用任何容器来实施。
优选的是， 其中步骤 2)在罐状容器中实施， 优选圆柱形罐状容器。
优选的是， 其中任选回收步骤 3)所脱除的溶剂， 循环利用。
优选的是， 其中在步骤 1 )和 /或步骤 2) 中任选添加一种或多种选自油、 防老剂、 偶联剂、 活性剂、 抗氧化剂、 阻燃剂、 热稳定剂、 光稳定剂、 染料、颜料、硫化剂和促 进剂的添加剂。
优选的是， 其中所述加热介质为水蒸汽， 干燥后的固体混合物中会含有水， 再经 过真空干燥、 加热干燥謝齐压加热干燥除去水后得到橡 JK填料母炼胶。
优选的是， 其中所述加热介质为水， 所述溶剂为沸点低于 100°C烃类溶剂， 干燥后 的固体混合物中 有水，再经过真空干燥、加热干燥或挤压加热干燥除去水后得到橡 鹏料母炼胶。
更为优选的是， 其中所述加热干燥为烘干或风干。
更为优选的是， 其中所述挤压加热干燥为先挤压脱除加热介质后再进一步干燥。 更为优选的是， 其中所 一步干燥为风干、 烘干或机械干燥。
更为优选的是， 其中所述机械干燥为使用开炼机、 捏炼机、 密炼机、 连续密炼机 、 单螺杆挤出机， 双螺杆挤出«行干燥。
本发明还提供一种†艮据上述方法制备的t胶母炼胶。
进一步地， 本发明还提供了采用上述母炼胶制备的一种橡胶制品。
本发明的橡胶母炼胶的连续式制造方法包括如下步骤：
步骤 1): 将填料加入到橡胶溶液中， 通过搅拌形成橡鹏料 /溶剂混合物； 步骤 2):将步骤 1 )中的橡臉填料 /溶剂混合物直接通入 ¾¾t高于溶剂沸点的加热介 质中， 该加热介质的极性与所用溶剂的极性不同， 混合物凝聚并退溶胀， 并且溶剂迅速 挥发， 从而形成含有该加热介质的橡臉填料复合物与溶剂的混合物；
步骤 3): 脱除溶剂并对所述的混合物进行干燥， 从而得到tJt/填料母炼胶。
本发明的橡胶母炼胶的连续式制造方法还任选包括回收步骤 3)所脱除的溶剂以循 环利用的步骤。 此外， 在步骤 1 )和 /或步骤 2) 中任选添加一种或多种选自油、 防老剂 、 倾关剂、 活性剂、 抗氧化剂、 染料、 光稳定剂、 阻燃剂、 热稳定剂、 颜料、 硫化剂和 促进剂的添加剂。
步骤 1 )可以使用本领域公知的方法实现。 步骤 1 ) 中所述的搅拌可以使用一般搅 拌机完成^包括但不限于叶片式搅拌 槽式搅拌札行星式搅拌机， 曲拐式搅拌机等。
步骤 1 )还可以进一步包括细分散步骤， 戶; M的细分散可以 如下方式实施： 将 上述搅拌所得的混合物通过一个喷嘴在高压高剪切的情况下喷出， 以改善填料和 /或添 加剂的分散； 使上述喷出物通过一个多弯头管使混合液在管中与管壁撞击增加填料和 / 或添加剂的分散性;或使喷出物通过一个管内径多次收放变化的管路来变换剪切应力而 增加填料和 /或添加剂的分散。所用压力范围从 O.lMPa至 60MPa，优选 lOMPa至 0MPa。
所述的细分散后所形成的混合物还可以通过下述精分散进一步改善填料和 /或添加 剂在橡胶溶液中的分散：
i. 将戶; M细分散之后的混合物连续加入球磨机和 l交体磨中进行分散， 使填料和 / 或添加剂均匀的分散在橡胶溶液中 ·'
ϋ. 将所述细分散之后的混合物连续加入到研磨机中进行研磨以使填料和 /或添加剂 充分分散在橡胶溶液中，该研磨机具有一组或多组高速转动的平面磨盘和固定在研磨机 套筒上并与平面磨盘相间的固定销钉或定盘。
iii. 将戶; M细分散之后的混合物连续加入到研磨机中进行研磨， 该研磨机具有转动 方向相反的两个叶片，所述叶片具有细孔流槽，在高压下可以通过旋转的叶片提高填料 和 /或添加剂在橡胶溶液中的分散程度。所用压力范围从 O.lMPa至 60MPa，优选 lOMPa 至 40MPa。
iv. 将腿细分散之后的混合物连续地加入到多层高压狭缝分散机中， 使混合物在 高压下从两层之间狭缝中挤出， 此时产生的强剪切力可提高填料和 /或添加剂在橡胶溶 液中的分散程度。 所用压力范围从 O.lMPa至 60MPa， 优选 lOMPa至 0MPa。
v. 将所述细分散之后的混合物连续地加入到动力分散器中进行分散， 所述动力分 散器的高速旋转的转子上有许多径向分布的狭缝或孔，混合物以高速撞击在定子表面上 以使填料和 /或添加剂均匀地分散在^ f胶溶液中。
上述五种细分散方法中的两种或两种以上可以相互串联使用。
戶; M的橡胶溶液可以直接从制备溶聚橡胶生产线中直接获得，亦可将任何类型的干 胶在该胶的溶剂中溶解制备。当用干胶制备橡胶溶液时， 干胶可以是本领域中使用 的任何种类的橡胶，如天然聚合物或合成聚合物。所述天然聚合物包括但不限于天然胶、 杜仲胶、银菊胶等;舰合成聚合物包括但不限于单体在溶液中聚合所得(即溶聚橡胶)、 单体在乳液中聚合所得（即乳聚橡胶)、 单体本体进行聚合所得。 当所述橡胶溶載接 从制备溶聚橡胶生产线中获得时， 戶; M溶聚橡胶为用乙烯、 丙烯、 丁烯、 戊烯、 已烯、 庚烯、 4-7个碳原子的双烯或 6-7个碳原子的三烯、 或含其它原子或官能团的烯类单体 的均聚或共聚聚合物， 腿其他原子或官能团为硅原子、氟原子、氯原子、氮原子、氧 原子、 硫原子、 酯基团， 氨基酯基团， 氰基， 也包括含有上述单体的均聚物和共聚物， 其中包括但并不限于聚丁二烯、 聚异戊二烯、 丁苯胶、 乙丙胶、 丁基胶、 丁腈胶、氯丁 胶、硅橡胶、氟橡胶、 聚氨酯橡胶、氯磺化聚乙烯橡胶、丙烯酸酯橡胶等。橡胶的 量为 1千至 4000万， 优选 5千至 3000万， 更优选 1万至 800万。
戶; Mt胶溶液中的溶剂均为各种t胶的良溶剂。溶剂具体可以是脂肪烃溶剂、芳香 烃溶剂、氯化烃溶剂、酮类溶剂、醚类溶剂和酯类溶剂， 所述脂肪烃溶剂包括但并不限 于各种溶剂汽油、环烷烃、取代环烷烃、正烷烃， 戶; M芳香烃溶剂包括但不限于苯、 甲 苯、 二甲苯、 苯乙烯， 所述氯化烃溶剂包括但不限于二氯甲烷、 三氯甲烷、 四氯化碳、 二氯乙烷、氯苯、 四氯乙烯、氯甲苯。橡胶在溶液中的浓度范围为 1%重量至 60%重量， 优选 5%重量至 0%重量， 更优选 10%重量至 30%重量。
所述填料包括但不限于橡胶中所用的各种固体粉末状补强剂和填充剂， 如各类炭 黑、二氧化硅、金属氧化物、盐类、不同树脂及上述填料的纳米级材料。其中所述金属 氧化物包括但并不限于氧化铝、 氧化镁、 氧化锌等， 所述盐类包括但并不限于碳酸 、 陶土及上述填料的纳米级材料。 填料的比表面积为 0.1至 800m2/g， 优选 1至 500 m2/g， 更优选 5至 300 m2/g。对于炭黑、二氧化硅（白炭黑)来说，其吸油值为 20至 250ml/100g， 优选 25至 200ml/100g， 更优选 30至 150ml/100g， 其中所述的填料包括它们的混合物， 如多相填料，其中包括但并不限于炭黑、二氧化硅、氧化铝、氧化镁、氧化锌、氧化^ 氧化钛、 氧化硼等组成的双相或多相填料， 对于双相或多相填料来讲， 其吸油值为 20 至 250ml/100g， 优选 25至 200ml/100g， 更优选 30至 150ml/100g。 填料的用量为 5至 300重量份 (以橡胶为 100重量份计)， 优选 10至 200重量份， 更优选 30至 150重量 份。 所述填料也包括上述填料中两种或多种的并用物。
腿的填料也包括它们的表面改性填料。其中腿的表面改性可以是舰化学反应 将一定的官能团接在填料表面或通过混合或吸附而将改性剂通过物理方式结合在填料 表面上。戶; M改性来讲，可以将改性剂溶于溶剂后与填料混 行液相改性，如 Wang W, Nanse G , VidalA, et al. K. G K [J], 1994, 47:493中戶； ¾，也可以将改性剂与填料混合加热 进行固相改性， 如 Wang MJ, Wolff .S. R.C.T [J], 1992, 65:715中所述。表面改性也可以在 将填料加入橡胶溶液中之前进行，或将改性剂加入到橡胶溶液和填料的混合物中进行表 面改性。 所述改性剂为本领域常规的改性剂， 诸如用以下通式表示的有机硅烷偶联剂：
( n- ( O )3-„Si- (Alk)m- ( Ar)p)q (A) (I )
Figure imgf000005_0001
(Π) 或！^ ！^：^ ^ ) (m) 式中， 当 q=l时， A为 -SCN， -SH, -Cl， -NH2;
当 q=2时， A为 -Sx -;
R和 R'为碳原子从 1至 4的支化或直链的烷基或酚基， R和 R'可以相同， 也可以 不同；
n为 0， 1或 2;
Alk是含有 1至 ό个碳原子的直链或支链烃基；
Α1¾ηγ1是含有 1至 ό个碳原子的直链或支链烯基；
m为 0或 1;
Ar是含有 6至 12个碳原子的芳基；
p为 0或 1， p和 n不能同时为 0;
X为 2至 8;
其中最常用的为双（三乙氧基丙基硅烷）四硫化物和二硫化物、 3-硫氰基丙基 -三乙 氧基硅烷、 γ -巯基-三甲氧基硅烷、 锆酸酯偶联剂、 酞酸酯偶联剂、 硝基偶联剂、 醇类 化合物， 所述醇类化合物包括但不限于单元醇、二元醇、 多元醇， 戶細享类化合物包括 但不限于丙醇、 丁醇、 乙二醇、 聚乙二醇及其衍生物。
本发明步骤 1 )可以直接将填料和 /或添加剂加入到橡胶溶液中，也可以先将填料和 /或添加剂加入到与橡胶溶液相同或不同的溶剂中混合形成均匀的悬浮液后再加入并通 过搅拌混入橡胶溶液中。 添加剂可任选包括油、 防老剂、 偶联剂、 活性剂、 抗氧化剂、 热稳定剂、光稳定剂、阻燃剂、染料、颜料、硫化剂或促进剂的添加剂中的一种或多种。 所用添加剂的用量均为常规用量， 或根据实际情况的要求进行调整。
在步骤 2)中，将步骤 1 )中的橡胶 /填料 /溶剂混合物或经过细分散的混合物直接通 入温度高于溶剂沸点的加热介质中。当加热介质的性质与所用溶剂性质尤其是极性不同 时， 混合物即凝聚并退溶胀， 而加热介质温度高于溶剂沸点时， 溶剂即通挥发而成含 有加热介质的母炼胶。该母炼胶经加热除去加热介质后即成母炼胶产品，在此过程中所 挥发出的溶剂和橡胶合成中未反应的单体进入冷凝器和 留塔中进行回收，所得的凝聚 混合物经过滤与加热介质分离并干燥后即成母胶产品。 上述加热介质包括但不限于水。 当用水做加热介质时， 所述溶剂为沸点低于 lore溶剂。然后所挥发出的溶剂和t胶合 成中未反应的单体以及水蒸汽进入冷凝器和分馏塔中进行回收。所述干燥可以为真空干 燥， 包括常温真空干燥、冷冻真空干燥及加热真空干燥， 也可以为一般的干燥方式， 例 如烘干或风干。所述干燥也可以为先挤压脱除加热介质后再进一步干燥，其中所 ¾¾一 步干燥为风干、烘干或机械干燥， 腿几械干燥为使用开炼机、捏炼机、密炼机、连续 密炼机、 单螺杆挤出机， 双螺杆挤出霞行干燥。
步骤 2) 的凝聚可以使用任何容器来实施； 优选， 不使用任何特殊设计的凝聚器来 实施； 步 ) 的凝聚可以在罐状容器中实施， 优选圆柱形的罐状容器。
步骤 2) 中的凝聚也可以使用凝聚器来实施， 使用的凝聚器可以为具有一个或两个 以上进料口的管式凝聚器，其中所述进料口的进料方向可以与管式凝聚器管的轴向方向 平行， 出口处于管的末端， 也可以与管式凝聚器管的轴向方向呈 1-180° 角， 优选呈 20-120° 角， 更优; it 70-100° 角， 最优选呈 85-95° 角。当进料口为多个时， 部分进料 口的进料方向与管式凝聚器管的轴向方向平行;其余的进料口的进料方向与管式凝聚器 的筒的轴向方向呈 1-180° 角，优选呈 20-120° 角，更优选呈 70400° 角，最优； it 85-95 。 角，各进料口的进料方向在与管轴心垂直的横截面上的投影为该横截面的半径方向至 该横截面的切线方向之间的任何方向，优选为半径方向， 或者为切线方向。所述的进料 口均处于与管的轴向相垂直的同一平面上或者所述的进料口处于不同的平面上。
步骤 2) 中使用的凝聚器也可以为由两个或三个以上相互同心的管组成的凝聚器， 其中每个管具有一个或两个以上的进料口， 进料口的进料方向为平行于管的轴向方 向或为管的切线方向， 出口处于管的末端。流体可以直接通入， 也可以从管壁的切线方 向通入。每个管的进料口的末端可以在同一平面内，也可以由内向外^ ^管的进料口的 末端依次变长或由内向外每个管的进料口的末端依次变短。
步骤 2) 中使用的凝聚器也可以为筒式凝聚器， 该筒式凝聚器只有一个进料口， 该 进料口位于筒式凝聚器的上端或筒壁上， 出口处于筒的下端。流体可以通过进料口直接 注入凝聚器， 也可以沿筒壁以切线的方向注入凝聚器。
步骤 2) 中使用的凝聚器也可以为上部是筒状， 下部是圆锥状的筒锥式结构， 并具 有一个或两个以上进料口。进料口的进料方向可以为筒壁的切线方向；各进料口可以处 于同一平面，也可以处于不同平面。进料口的进料方向也可以与筒的轴向方向垂直或与 筒的轴向方向呈 1-180° 角， 优选 20-110° 角， 更优选 70-100° 角， 最优选 85-95° 角， 各进料口的进料方向在与筒轴心垂直的横截面的投影为该横截面的半径方向至该横截 面的切线方向之间的任何方向， 优选为该横截面的切线方向。
优选， 步骤 2)使用任意形状的罐状容器， 更优选使用圆柱形的罐状容器。
所述的回收溶剂的方法可以使用本领域中任何已知的方法，如将汽化的溶剂通过表 面冷疑或直接接触冷疑的方法加以回收。当使用直接冷疑接触的方法时冷却剂可以采用 水。
本发明的技术特点有如下三点：
i. 本发明的技术特点是工艺适应性强： 既可以用工艺简单而填料分散性及产品性 能稍差的橡胶溶液与填料、 添加剂一般混合和直接加热方法制备橡胶 /填料 /添加剂母 胶，又可利用辦朱设计的分 fC¾置、混合凝聚器和机械干燥方法制造成本较高但性能较
195 好的橡胶 /填料 /添加剂母胶； 不同工艺制备的母炼胶可合理地适应不同橡胶制品的需 要。
ϋ. 本发明的技术特点是t胶 /填料 /添加剂 /溶剂混合物的疑聚和脱溶剂的方式： 橡 JK/填料 /添加剂 /溶剂混合物直接通入性质尤其是极性与所用溶剂性质不同的液体介 质使混合物退溶胀并凝聚，而介质温度高于溶剂沸点时，溶剂即迅速挥发而成含有加热
200 介质的母炼胶。该母炼胶经加热除去加热介质后即成母炼胶产品，所用液体介质包括但 不限于水。
iii. 本发明的技术特点是凝聚步骤工艺简单， 不要求结构复杂的凝聚器， 设备成本 低。
具 施方式
下面用实施例进一步描述本发明， 但是本发明的范围不受这些实施例的限制。 (一）实施例中实验数据用以下仪器设备及测定方法测定：
Figure imgf000008_0002
Figure imgf000008_0001
序
测试项目 测 示准 设备名称 规格型号 生产厂家 号
胶料中的
1 - 炭黑分散仪 GT-505-CBD 高铁检测仪器公司 分散
2 硬度 GB T 531.1-2008 硬度计（邵 A) LX-A 上海六菱仪器厂 伺月画拉力实
3 拉伸弓艘 (MPa) GB T 528-2009 A1-3000 高铁检测仪器公司 验机
伺月画拉力实
4 扯断伸长率 (%) GB T 528-2009 A1-3000 高铁检测仪器公司 验机
5 回弹性 (%) GB/T 1681-2009 回弹性测试仪 GT-7042-RE 高铁检测仪器公司
6 疲劳生热 GB/T 1687-1993 压缩生热 几 RH-2000N 高铁检测仪器公司
7 磨耗 几 GB T1689-1998 DIN磨耗 佥机 GT7012-A 高铁检测仪器公司 210 (二）实施例颜比例
原料：
合成聚异戊二烯橡胶， IR-70, 青岛伊科思新材料有限公司；
白炭黑， NEWSIL1165-MP， 无锡确成硅业有限公司；
mm, 大连氧化锌厂；
215 硬脂酸， PF1808, 马来西亚立成有限公司；
防老剂 020， 江苏圣奥化学有限公司；
硅烷偶联剂 Si69， 南京曙光化工集团有限公司；
促进剂 CZ， 山东尚舜化工有限公司；
促进剂 DPG， 山东单县化工有限公司；
220 硫黄， 无棣金盛化工有限公司。
对比例 1
在密炼机内将 56份白炭黑、 5.6份硅烷偶联剂 Si69加入到 100份合成顺式聚异戊 二烯中进行混炼，当填料混入橡胶后，力口入 3.5份氧化锌、 2份硬脂酸、 2份防老剂 4020 后再混炼 4分钟从密炼机中卸料， 然后在开炼机上过辊下片得预混胶。 停放 8小时后， 225 将 2份 剂 CZ、 1份 剂 DPG和 1.8份硫黄在开炼il±加入预混胶中制得混炼胶。
经开炼机下片， 停放 8小时后， 在 15CTC平板硫化机中硫化至正硫化， 制得干法硫化胶 实施例 1
将 56份白炭黑、 5. 6份硅烷偶联剂 Si69、 3. 5份氧化锌加入到 100份 12%顺式聚异 230 戊二烯的正已烷溶液中， 其橡胶 /白炭黑 /Si69/正已烷混合物用叶片式搅拌机初混后， 将混合物通过一个喷嘴喷入一个多弯头管使混合液在管中与管壁撞击增加填料的分散。 然后将混合物连续加入到研磨机中进行精分散， 即得精分散混合物， 然后将混合物在 0. 2MPa的压力下直接连续喷入约 95°C的水中凝聚。 将凝聚并脱溶剂的胶粒经过滤、 干 燥得到母胶 1。
235 实施例 2
将 56份白炭黑、 5. 6份硅烷偶联剂 Si69、 3. 5份氧化锌加入到 100份 12%顺式聚异 戊二烯的正已烷溶液中， 其橡胶 /白炭黑 /Si69/正已烷混合物用叶片式搅拌机初混后， 将混合物通过一个喷嘴喷入一个多弯头管使混合液在管中与管壁撞击增加填料的分散。 后将混合物连续加入到研磨机中进行精分散，即得精分散混合物，然后将混合物在 30MPa 240 的压力下直接喷入 95°C的水中进行凝聚。 将凝聚并脱溶剂的胶粒经过滤、 干燥后得到 母胶 2。 对比例 2
将 56份白炭黑、 5. 6份硅烷偶联剂 Si69、 3. 5份氧化锌加入到 100份 12%顺式聚异 戊二烯的正已烷溶液中， 其橡胶 /白炭黑 /Si69/正已烷混合物用叶片式搅拌机初混后，
245 将混合物通一个喷嘴喷入一个多弯头管使混合液在管中与管壁撞击增加填料的分散。
后将混合物连续加入到研磨机中进行精分散，即得精分散混合物，然后将混合物在 30MPa 的压力下经过有四个入口的锥筒式凝聚器中的两个入口注入凝聚器内，同时舰另夕卜两 个入口注入温度为 18CTC的氮气。 所得混合物连续喷入充有约 15CTC氮气的干燥器脱溶 剂、 干燥， 形成固体粉末状物质， 即母胶 3。
250 将上述所得的母胶 1、母胶 2和母胶 3在密炼机内加入 2份硬脂酸、 2份防老剂 4020 后再混炼 4分钟从密炼机中卸料，胶料在开炼il±过辊， 下片。 混炼停放 8小时后再在 密炼机内加入 2份腿剂 CZ、 1份腿剂 D和 1. 8伤、 黄后再混炼 1. 5分钟从密炼机中 卸料。 经开炼机下片， 停放 8小时后， 在 150°C平板硫化机中硫化至正硫化， 分别制得 湿法硫化胶 1、 2和 3。
表 3硫化胶的物理性能
Figure imgf000010_0001
从表 3可知， 在相同配方下， 由于湿法混炼胶所采用的疑聚方法不同而制备的 化胶性能亦有不同，与干法母炼胶相比，湿法母炼胶中填料在橡胶中的分散程度大大改 进， 硫化胶的拉伸强度、 回弹性及耐磨性明显提高， 压缩疲劳生热有所降低。湿法硫化 胶 1， 2与湿法硫化胶 3相比性能相差不大，但实施例 1和 2的制备方法与对比例 2的制
260 备方法相比， 不使用特殊设计的凝聚器， 具有低成本的优势。

Claims

WO 2015/018279 权 利 要 求 书 PCT/CN2014/082711
1、 一种橡胶母炼胶的连续式制造方法， 包括如下步骤：
步骤 1 ): 将填料加入到橡胶溶液中， 舰搅拌形成樾扁斗翻混合物； 步骤 2): 将步骤 1 ) 中的橡胶 /填料 /溶剂混合物直接通入温度高于溶剂沸点的加热 介质中， 该加热介质的极性与所用溶剂的极性不同，混合物凝聚并退溶胀， 并且溶剂迅 速挥发， 从而形成含有该加热介质的橡腕料复合物与溶剂的混合物；
步骤 3): 脱除溶剂并对戶; M的混合物进行干燥， 得到tJt/填料母炼胶。
2、 根据权利要求 1所述的方法， 其中步骤 2)可以使用任何容器来实施。
3、 根据权利要求 1戶; M的方法， 其中步骤 2)在罐状容器中实施， 优选圆柱形罐状 容器。
4、 根据权利要求 1所述的方法， 其中任选回收步骤 3)所脱除的溶剂， 循环利用。
5、 根据权利要求 1所述的方法， 其中在步骤 1 )和 /或步骤 2) 中任选添加一种或多 种选自油、 防老剂、 偶联剂、 活性剂、 抗氧化剂、 阻燃剂、 热稳定剂、 光稳定剂、 染料 、 颜料、 硫化剂和碰剂的添加剂。
6、根据权利要求 1-5任一腦勺方法，其中所述加热介质为水蒸汽， 干燥后的固体 混合物中会含有水， 再经过真空干燥、 加热干燥或挤压加热干燥除去水后得到橡胶 /填 料母炼胶。
7、†艮据权利要求 1-5任一戶 的方法，其中所述加热介质为水， 戶; M溶剂为沸点低 于 100°C烃类溶剂， 干燥后的固体混合物中 有水， 再经过真空干燥、 加热干燥或挤 压加热干燥除去水后得到橡臉填料母炼胶。
8、 †艮据权利要求 6-7任一戶 的方法， 其中所述加热干燥为烘干或风干。
9、根据权利要求 6-7任一所述的方法，其中所述挤压加热干燥为先挤压脱除加热介 质后再进一步干燥。
10、 †艮据权利要求 9戶; M的方法， 其中所 一步干燥为风干、 烘干或 械干燥。
11、 根据权利要求 10所述的方法， 其中所述机械干燥为使用开炼机、 捏炼机、 密 炼机、 连续密炼机、 单螺杆挤出机， 双螺杆挤出 亍干燥。
12、 一种†艮据权利要求 1-11所述的方法制备的橡胶母炼胶。
13、 一种t胶制品， 其使用†艮据权利要求 12戶; ¾的橡胶母炼胶制备得到。
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