WO2015018280A1 - 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
WO2015018280A1
WO2015018280A1 PCT/CN2014/082712 CN2014082712W WO2015018280A1 WO 2015018280 A1 WO2015018280 A1 WO 2015018280A1 CN 2014082712 W CN2014082712 W CN 2014082712W WO 2015018280 A1 WO2015018280 A1 WO 2015018280A1
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Prior art keywords
rubber
drying
filler
masterbatch
mixture
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PCT/CN2014/082712
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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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Application filed by 怡维怡橡胶研究院有限公司 filed Critical 怡维怡橡胶研究院有限公司
Priority to KR1020157034587A priority Critical patent/KR101795203B1/ko
Priority to ES14834055T priority patent/ES2861825T3/es
Priority to EP14834055.7A priority patent/EP3031590B1/en
Priority to US14/910,221 priority patent/US10125229B2/en
Priority to JP2016532219A priority patent/JP6397021B2/ja
Publication of WO2015018280A1 publication Critical patent/WO2015018280A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • 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
    • C08J3/12—Powdering or granulating
    • C08J3/122—Pulverisation by spraying
    • 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
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons

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 rubber/filler/additive is included in the solvent.
  • the process described in W098/58985 is carried out in a large, bladed worm gear dryer at 400/1200 rpm, which results in slower agglomeration, long process life and high energy consumption.
  • the present invention omits the agglomeration step, simplifies the process, and reduces costs.
  • Another object of the present invention is to provide a continuous manufacturing method of a rubber master batch and a t-size masterbatch prepared by the method. Another object of the present invention is to provide a rubber article prepared using the t-size masterbatch of the present invention.
  • the present invention has no requirements for rubber and filler, and the invention has a wide application range for the types and contents of rubber, fillers and additives;
  • a continuous manufacturing method of a rubber masterbatch comprising the following steps:
  • the drying in the step 2) means transferring the mixture obtained in the step 1) into a heated conveyor belt dryer, Heating and drying under vacuum or inert gas, the solvent and the unreacted monomer in the rubber synthesis are recycled into the condenser and the fractionation column for recovery; or the drying in step 2) means the step 1)
  • the mixture is spray dried or flashed.
  • the heating medium used is an inert gas or water vapor, and the volatilized solvent and unreacted monomers in the rubber synthesis enter the condenser and the column for recovery.
  • step 1) wherein one or more selected from the group consisting of oils, antioxidants, antioxidants, coupling agents, active agents, flame retardants, heat stabilizers, light stabilizers, dyes, pigments are optionally added in step 1) , vulcanizing agents and additives for the agent.
  • step 1) specifically adds a filler to the rubber solution, forms a rubber/filler/solvent mixture by stirring, and further finely disperses and finely disperses the rubber/filler/solvent mixture to increase the filler in the rubber solution. The degree of dispersion in the middle.
  • the heating medium described in the step 2) is water vapor
  • the solid mixture in the dry state has water therein, and then dried under vacuum, heated and dried, and heated to remove water to obtain a rubber/filler masterbatch. gum. More preferably, wherein the 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 provides a rubber article prepared using a rubber masterbatch.
  • the continuous manufacturing method of the rubber master batch of the present invention comprises the following steps:
  • the drying in the step 2) means transferring the mixture obtained in the step 1) into a heated conveyor belt dryer, Heating and drying under vacuum or inert gas, the solvent and the unreacted monomer in the rubber synthesis are recycled into the condenser and the fractionation column for recovery; or the drying in step 2) means the step 1)
  • the mixture is spray dried or flashed.
  • the heating medium used is an inert gas or water vapor, and the volatilized solvent and unreacted monomers in the rubber synthesis enter the condenser and the column for recovery.
  • the continuous manufacturing process of the rubber masterbatch of the present invention optionally further comprises the step of recovering the solvent removed in step 2) for recycling. Further, in step 1), one or more selected from the group consisting of oils, antioxidants, coupling agents, active agents, antioxidants, dyes, light stabilizers, flame retardants, heat stabilizers, pigments, and vulcanizing agents are optionally added. And ⁇ leg additive.
  • 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, the fine dispersion of the ruthenium 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 filler and/or addition by the following fine dispersion.
  • Dispersion of the agent in the rubber solution is a mixture formed after the fine dispersion of the agent in the rubber solution:
  • 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.
  • the household; M finely dispersed mixture is continuously added to the power disperser for dispersion, the high-speed rotating rotor of the M-power disperser has a plurality of radially distributed slits or holes, and the mixture hits at a high speed.
  • the surface of the stator is such that the filler and/or 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 a diene using ethylene, propylene, butene, pentene, hexene, heptene, 4-7 carbon atoms.
  • a homopolymer or copolymer of 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, fluorine atoms, chlorine atoms, nitrogen atoms, oxygen atoms.
  • sulfur atom, ester group, amino ester group, cyano group also includes homopolymers and copolymers containing the above monomers, including but not limited to polybutadiene, polyisoprene, styrene-butadiene rubber , Ethylene-propylene rubber, butyl rubber, nitrile rubber, neoprene, silicone rubber, fluorine rubber, urethane rubber, chlorosulfonated polyethylene rubber, acrylate rubber, etc.
  • the amount of rubber is from 1 to 40 million, preferably from 5,000 to 30 million, 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, A Benzene, xylene, styrene, the chlorinated hydrocarbon solvent includes, but is not limited to, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, 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 500m 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 leg 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: ( n- ( O ) 3- constructiveSi- (Alk) m - ( Ar) p ) q ( A) (I)
  • A is -SCN, -SH, -CI, -NH 2 ;
  • 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 t-gel solution to form a uniform suspension, and then add and Mix into the rubber solution by stirring.
  • 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.
  • Drying in step 2) means transferring the mixture obtained in step 1) into a heated conveyor belt dryer, heating and drying under vacuum or an inert gas (for example, nitrogen), and the solvent and the rubber compound are not reacted in the synthesis.
  • the monomer is charged into the condenser and the column for recovery; or the mixture obtained in step 1) is spray dried or flashed, and the heating medium used is an inert gas (such as nitrogen) or water vapor, and the solvent and rubber are volatilized.
  • the unreacted monomer in the synthesis enters the condenser and the column for recovery.
  • water vapor is used as the heating medium, the dried solid mixture may contain water, and then dried under vacuum, dried by heating or extruded and heated to obtain a rubber/filler masterbatch.
  • the vacuum drying includes vacuum drying at room temperature, freeze vacuum drying, and heating under vacuum.
  • the heat drying may be a general drying method such as drying or air drying.
  • the extrusion heating and drying is performed by first removing and removing the heating medium, and then further drying, wherein the household is further dried to be air-dried, dried or mechanically dried, and the household is operated by using an open mill, a kneader, an internal mixer. , continuous mixer, single screw extruder, twin screw extruder for drying.
  • the method of recovering the solvent can be recovered by any method known in the art, such as by vaporizing the solvent by surface condensation or direct contact condensation.
  • the coolant may be water when the direct condensation contact method is used.
  • the invention is further described by the following examples, but the scope of the invention is not limited by the examples. (1) The examples were determined using the following apparatus and measuring methods:
  • Butadiene rubber BR9000, Sinopec Qilu Co., Ltd.;
  • Antioxidant 020 Jiangsu Shengao Chemical Co., Ltd.;
  • Antioxidant 264 Zhejiang Huangyan Zhedong Rubber Additive Co., Ltd.;
  • Antioxidant RD chemical plant of Sinopec Nanjing Chemical Industry Co., Ltd.
  • Silane coupling agent Si69 Nanjing Shuguang Chemical Group Co., Ltd.
  • silica and silane coupling agent are added to 100 parts of cis-polyisoprene for kneading, mixing for a certain period of time, and 3.5 parts of zinc oxide are added.
  • the masterbatch 2 is added to the internal mixer by adding 2 parts of stearic acid, 2 parts of the antioxidant 020, and then kneading 2, discharging from the internal mixer, and the rubber is passed through the roll on the open mill and the lower piece. After mixing for 8 hours, add 2 parts of CZ, 1 part of D and 1.6 parts of sulfur in the mixer and mix again 1.5 ⁇ ! Discharged from the mixer. After being placed in the open mill for 8 hours, it was vulcanized to a positive pressure in a 15 CTC flat vulcanizer to obtain a wet vulcanizate 2 .
  • Table 3 shows the physical properties of the vulcanizate obtained from the examples of the wet master batch and the dry mix in different formulations and processes. It can be seen that in the same formulation, the wet masterbatch Compared with the dry masterbatch, the dispersion of the filler in the rubber is greatly improved, the hardness of the vulcanizate is lower, the tensile strength and the elongation at break are higher, the elasticity is high, the dynamic compression heat generation is low, and the wear resistance is low. better.

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  • Mechanical Engineering (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

本发明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，制造方法包括如下步骤：步骤1）：将填料加入到橡胶溶液中，通过搅拌形成橡胶/填料/溶剂混合物；步骤2）：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。本发明还涉及一种上述方法制备的母炼胶以及使用该母炼胶制备得到的橡胶制品。与现有湿法混炼胶技术相比，本发明对橡胶、填料无特殊要求，使用范围较广。除此之外，填料在橡胶胶料中的分散度高，生产工艺连续、高效、低耗能、少人工，因而成本较低。

Description

纖胶的连续式制造方法及该方法制备的橡胶母炼胶
¾ ^领域
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 /填料垂齐赚 1J体系中， 均包含橡胶 /填料 /添加剂从溶剂中的凝聚步骤。
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转的装 置中进行， 这种方法的凝聚速度较慢， 工艺过程长， 耗能高。 本发明省略了凝聚步骤， 简化了工艺， 降低成本。
发明内容
针对现有技术的问题， 本发明的目的是提供一种橡胶母炼胶的连续式制造方法及 该方法制备的t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)省略了凝聚步骤， 简化工艺降低成本；
3)与现有湿法混炼胶技术相比， 本发明对橡胶、 填料无 ¾要求， 本发明戶; M方 法对橡胶和填料及添加剂的种类及含量的适用范围广；
4)填料在橡胶胶料中的分散度高， 生产工艺连续、 高效、 低耗能、 少人工， 因而 成本较低。
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， 其包括如下步骤：
步骤 1 ): 将填料加入到橡胶溶液中， 舰搅拌形成橡鹏料翻混合物；
) 脱除溶剂并对戶; M的混合物进行干燥， 得到橡臉填料母炼胶； 其中， 步骤 2) 中的干燥是指将步骤 1 ) 中得到的混合物转入加热运输带式干燥机 内，在真空或隋性气体下加热干燥，所挥发出的溶剂和橡胶合成中未反应的单体进入冷 凝器和分馏塔中进行回收； 或步骤 2)中的干燥是指将步骤 1 )中得到的混合物进行喷雾 干燥或闪蒸，所用加热介质为惰性气体或水蒸汽，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。
优选的是， 其中在步骤 1 )中任选添加一种或多种选自油、抗氧化剂、 防老剂、偶 联剂、活性剂、阻燃剂、热稳定剂、光稳定剂、染料、颜料、硫化剂和^ ί剂的添加剂。 优选的是， 其中步骤 1 )具体为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， 并对所述橡胶 /填料 /溶剂混合物进一步细分散和精分散以提高填料在橡 胶溶液中的分散程度。
优选的是， 其中步骤 2)所述的加热介质为水蒸汽时， 此时干燥后的固体混合物中 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胶 /填料母炼胶。 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 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 亍干燥。
本发明还提供了一种 t艮据上述方法制备的t胶母炼胶。
进一步地， 本发明提供了采用橡胶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， 舰搅拌形成樾扁斗翻混合物；
) 脱除溶剂并对戶; M的混合物进行干燥， 得到橡臉填料母炼胶； 其中， 步骤 2) 中的干燥是指将步骤 1 ) 中得到的混合物转入加热运输带式干燥机 内，在真空或隋性气体下加热干燥，所挥发出的溶剂和橡胶合成中未反应的单体进入冷 凝器和分馏塔中进行回收； 或步骤 2)中的干燥是指将步骤 1 )中得到的混合物进行喷雾 干燥或闪蒸，所用加热介质为惰性气体或水蒸汽，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。
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 2)所脱除的溶剂以循 环利用的步骤。 此外， 在步骤 1 ) 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、 染料、 光稳定剂、 阻燃剂、 热稳定剂、颜料、硫化剂和 ί腿剂的添加 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; Μ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. 将戶; M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， 戶; M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^ t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 500m2/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
或！^ ！^：^ ^ ) (ΠΙ)
式中， 当 q=l时， A为 -SCN， -SH， -CI, -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t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。
步骤 2) 中的干燥是指将步骤 1) 中得到的混合物转入加热运输带式干燥机内， 在 真空或惰性气体（例如氮气）下加热干燥， 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； 或将步骤 1 ) 中得到的混合物进行喷雾干燥或闪蒸， 所用加热介质为惰性气体（例如氮气）或水蒸汽， 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。其中当使用水蒸汽为加热介质时，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后得到橡胶 /填料母 炼胶。所述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^所述加热干燥 可以为一般的干燥方式，例如烘干或风干。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， 其中戶 进一步干燥为风干、烘干或机械干燥， 戶; Mi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， 双螺杆挤出机进行干燥。
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 面冷凝或直接接触冷凝的方法加以回收。 当使用直接冷凝接触方法时冷却剂可采用水。 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）实施例使用以下仪器设备及测定方法测定：
表 1橡胶样品制备的仪器设备
序号 设备名称 规格型号 生产厂家
1 密舰 XSM-1/10-120 上爾斗创橡塑机械设备有限公司
2 开嵐几 152.5*320 广东省湛江机械厂
3 平板硫化机 XLB-D600*600 浙江湖少 H东崖戒有限公司 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
(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；
溶聚丁苯橡胶， VSL 526-OHM, LANXESS生产；
顺丁橡胶， BR9000， 中国石化齐鲁股份有限公司；
白炭黑， NewsilHD165MP, 确成硅化学股份有限公司；
mm, 大连氧化锌厂；
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；
防老剂 264， 浙江黄岩浙东橡胶助剂有限公司；
防老剂 RD， 中国石化集团南京化学工业有限公司化工厂；
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 D， 山东单县化工有限公司；
硫黄， 无棣金盛化工有限公司；
防焦剂 (CTP), 山东阳谷华泰化工有限公司。
以下实施例和对比例中所述份数均为重量份。
实施例 1
将 60份白炭黑、 6份硅烷偶联剂 Si69加入到 100份 8%顺式聚异戊二烯的正已烷 溶液中， 其橡胶 /白炭黑 / Si69/正已烷混合物通叶片搅拌机混合后喷入充有约 15CTC的 氮气的干燥器内，形成脱溶剂的胶粒，含有粉状胶粒的氮气和溶剂混合物经旋风分离器 与胶粒分离得粉末母胶 1。
180 将母胶 1在开炼机上包辊均匀后， 加入 3.5份氧化锌、 1份硬脂酸、 1.5份防老剂
RD、 2份防老剂棚、 1.6份防焦剂， 再加入 2份腿剂 CZ、 1份碰剂 D、 1.6份硫 黄后， 过辊、 下片， 停放 8小时后用 15CTC的平板硫化机硫化至正硫化， 制得湿法硫化 胶 1。
对比例 1
185 在密炼机内， 将 60份白炭黑、 ό份硅烷偶联剂加入到 100份的顺式聚异戊二烯当 中进行混炼， 混炼一定时间， 力口入 3.5份氧化锌、 1份硬脂酸、 1.5份防老剂 RD、 2份 防老剂 020、 1.6份防焦剂，混炼胶停放 8小时后再加入 2份促进剂 CZ、 1份促进剂 D、 1.6 混炼胶停放 8小时后用 15CTC的平板硫化机硫化至正硫化， 制得干法 化 胶 1。
190 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物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， 然后将混合物在真空度为 -0. 08MPa下的
195 真空干燥机内干燥 20min后经收集得母胶 2。
将母胶 2在密炼机内加入 2份硬脂酸、 2份防老剂 020后再混炼 2 中从密炼机 中卸料，胶料在开炼机上过辊， 下片。 混炼停放 8小时后再在密炼机内加入 2份碰剂 CZ、 1份碰剂 D和 1.6份硫黄后再混炼 1.5 ^！中从密炼机中卸料。 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， 制得湿法硫化胶 2。
200 对比例 2
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， 将 2份 剂 CZ、 1份 剂 DPG和 1.8份硫黄在密炼il±加入预混胶中制得混炼胶。
205 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 2。
210 表 3湿、 干法硫化胶的物理性能
Figure imgf000009_0001
表 3为在不同配方及工艺下湿法母炼胶的实施例和干法混炼胶的对比例所得到的 硫化胶的物理性能， 从中可以看出， 在相同配方下， 湿法母炼胶与干法母炼胶相比， 填 料在橡胶中的分散程度大大提高，硫化胶的硬度较低， 拉伸强度和扯断伸长率较高， 弹 性高， 动态压缩生热低， 耐磨性能较好。

Claims

权 利 要 求 书 WO 2015/018280 PCT/CN2014/082712
1、 一种橡胶母炼胶的连续式制造方法， 其包括如下步骤：
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；
脱除溶剂并对戶; M的混合物进行干燥， 得到tJt/填料母炼胶；
其中， 步骤 2) 中的干燥是指将步骤 1 ) 中得到的混合物转入加热运输带式干燥机 内，在真空或隋性气体下加热干燥，所挥发出的溶剂和橡胶合成中未反应的单体进入冷 凝器和分馏塔中进行回收； 或步骤 2)中的干燥是指将步骤 1 )中得到的混合物进行喷雾 干燥或闪蒸，所用加热介质为惰性气体或水蒸汽，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。
2、 根据权利要求 1所述的方法， 其中在步骤 1 ) 中任选添加一种或多种选自油、 抗氧化剂、 防老剂、 偶联剂、 活性剂、 阻燃剂、 热稳定剂、 光稳定剂、 染料、颜料、硫 化剂和 剂的添加剂。
3、 根据权利要求 1-2任一所述的方法， 其中步骤 1 )具体为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，并对) 5；¾橡胶 /填料 /溶剂混合物进一步细分 散和精分散以提高填料在橡胶溶液中的分散程度。
4、†艮据权利要求 1-3任一所述的方法， 其中步骤 2)所述的加热介质为水蒸汽时， 此时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。
5、 †艮据权利要求 4戶; ¾的方法， 其中戶 加热干燥为烘干或风干。
6、 根据权利要求 4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。
7、 †艮据权利要求 6戶; M的方法， 其中戶; M¾—步干燥为风干、 烘干或 械干燥。
8、 †艮据权利要求 7所述的方法， 其中所述 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， 双螺杆挤出机进行干燥。
9、 一种根据权利要求 1-8所述的方法制备的橡胶母炼胶。
10、 一种t胶制品， 其使用†艮据权利要求 9戶; ¾的t胶母炼胶制备得到。
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