WO2017041754A1 - 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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WO2017041754A1
WO2017041754A1 PCT/CN2016/098636 CN2016098636W WO2017041754A1 WO 2017041754 A1 WO2017041754 A1 WO 2017041754A1 CN 2016098636 W CN2016098636 W CN 2016098636W WO 2017041754 A1 WO2017041754 A1 WO 2017041754A1
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Prior art keywords
solvent
rubber
filler
drying
mixture
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PCT/CN2016/098636
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English (en)
French (fr)
Inventor
王梦蛟
宋建军
王正
和富金
贾维杰
张红霞
张秀彬
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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
Publication of WO2017041754A1 publication Critical patent/WO2017041754A1/zh
Priority to ZA2018/02336A priority Critical patent/ZA201802336B/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions 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 a rubber master batch and a rubber masterbatch and a rubber product prepared by the method.
  • CN103113597A discloses a wet mixing method for efficient continuous coagulation using a specially designed agglomerator comprising nitrogen, water vapor, water, filler water slurry and oil, but the agglomerator has high requirements on equipment materials and high process cost.
  • CN103419291A discloses a method of using water as a heating medium, but the subsequent separation and removal of water by a separator causes damage of the rubber particles and loss of the mother rubber.
  • US 7,307,121 B2 discloses a steam stripping process for solvent removal by pumping a silica/rubber mixture into a stripping unit to coagulate and remove solvent, which is required for steam to be introduced during stripping. Dehydrated and dried.
  • the primary object of the present invention is to provide a continuous manufacturing method of a rubber master batch. Another object of the present invention is to provide a rubber masterbatch prepared by the above method. It is still another object of the present invention to provide a rubber article prepared by using the above rubber masterbatch.
  • the invention directly integrates the rubber/filler and/or additive mixture into the gas to achieve agglomeration and solvent separation.
  • the process of the invention simplifies, saves energy, improves the dispersion property of the filler and the vulcanization property of the rubber, and enhances the filler-polymer interaction. Thereby the performance of the rubber product is improved.
  • the invention discloses the following continuous manufacturing methods of rubber master batches, including:
  • a continuous manufacturing method of rubber masterbatch includes the following steps:
  • a continuous manufacturing method of rubber masterbatch includes the following steps:
  • the solvent is separated, or the solvent is separated by expansion drying, or the solvent is separated by flash evaporation to obtain a rubber/filler masterbatch.
  • a continuous manufacturing method of rubber masterbatch includes the following steps:
  • a continuous manufacturing method of rubber masterbatch includes the following steps:
  • the evaporation in the step C) is carried out by using an oven or a drying plate; the atomization method of the spray drying is centrifugal atomization, pressure atomization or two-fluid atomization; the expansion and drying method is first heating and then suddenly The pressure is released; the flashing method is at least one of atmospheric flash evaporation or vacuum flash evaporation, and the number of flash stages is 1-3.
  • the low pressure vacuum drying described in the step C) is to volatilize the solvent or suction filtration under a vacuum to a pressure lower than one atmosphere, and the pressure is preferably -0.1 MPa to 0. It is more preferably -0.09 MPa to 0, and most preferably -0.08 MPa to 0.
  • the expansion and drying described in the step C) is to flash-vaporize the solvent by a screw expansion dryer, preferably a screw expansion dryer, 0-20 MPa, more preferably 1-10 MPa, along the axis, the pitch decreases, the friction heat generation, the outlet pressure After the drop, the strip expands and relaxes, and the solvent in the strip flashes and vaporizes.
  • a screw expansion dryer preferably a screw expansion dryer, 0-20 MPa, more preferably 1-10 MPa
  • the heating drying in step D) is drying or air drying;
  • the mechanical drying is drying using an open mill, a kneader, an internal mixer, a continuous internal mixer, a single screw extruder, and a twin screw extruder.
  • the mechanical drying temperature is from 10 ° C to 250 ° C;
  • the step D) may be followed by heating and drying, followed by mechanical drying, or mechanical drying before heating and drying.
  • Step D) selecting mechanical drying may be simultaneously heated and dried at a temperature of 10 ° C to 250 ° C; when heating and drying is selected, heating may be performed in a gaseous medium comprising at least one of air, nitrogen, water vapor, and CO 2 .
  • a gaseous medium comprising at least one of air, nitrogen, water vapor, and CO 2 .
  • step A) immediately enters step B), or is parked for a certain period of time and then proceeds to step B), with or without heating during parking; when heated, the temperature is between 10 ° C and 200 ° C.
  • step A) further comprises adding an additive to the rubber solution to form a rubber/filler/additive/solvent mixture by stirring.
  • Step A) 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 the filler and/or the additive/solvent mixture.
  • the filler and/or the additive/solvent mixture may be directly mixed with the rubber solution, or may be mixed with the rubber solution after being parked for a certain period of time, heated or not heated during parking, and when heated, the temperature is 10 ° C to 200 ° C, when the above heating When the temperature is higher than the boiling point of the solvent, the heating is carried out in a pressure vessel.
  • the rubber/filler and/or additive/solvent mixture obtained in step A) can be immediately moved to the next step, or it can be parked for a certain period of time, heated or not heated during parking, and when heated, the temperature is 10 ° C to 200 ° C, When the above heating temperature is higher than the boiling point of the solvent, the heating is carried out in a pressure vessel.
  • the additive may optionally include 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 plasticizer, a softener, a processing aid, One or more of a vulcanizing agent or an additive to a promoter.
  • the amount of the additive used is a conventional amount or adjusted according to actual conditions.
  • Step A) can be carried out using methods well known in the art.
  • the agitation described in step A) can be accomplished using a conventional mixer including, but not limited to, a blade mixer, a tank mixer, a planetary mixer, a sigma mixer, and the like.
  • the step A) may further comprise a fine dispersion step, which may be carried out by spraying the mixture obtained by the above agitation through a nozzle under high pressure and high shear to improve the filler and/or the additive.
  • Dispersing causing the above-mentioned ejected material to pass through a multi-bend tube to cause the mixed liquid to collide with the tube wall in the tube to increase the dispersibility of the filler and/or the additive; or to cause the ejected material to pass through the inner diameter of the tube for multiple times.
  • the pressure used ranges from 0.1 MPa to 100 MPa, preferably from 10 MPa to 80 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:
  • Iv. continuously adding the finely dispersed mixture to a multi-layer high-pressure slit disperser, and extruding the mixture from the slit between the two layers under high pressure, 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 100 MPa, preferably from 10 MPa to 80 MPa.
  • Two or more of the above five fine dispersion methods may be used in series with each other.
  • the rubber solution 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 gum, gutta percha, silver inulin, etc.
  • the synthetic polymer includes, but is not limited to, a monomer obtained by polymerizing in a solution (ie, a solution rubber), and a monomer obtained by polymerization in an emulsion. (ie, latex rubber), the monomer body is obtained by polymerization.
  • the solution rubber is diene or 6 using ethylene, propylene, butene, pentene, hexene, heptene, 4-7 carbon atoms.
  • a homopolymer or copolymerized polymer of a triene of -7 carbon atoms or an ethylenic monomer having other atoms or functional groups, such as a silicon atom, a fluorine atom, a chlorine atom, a nitrogen atom, an oxygen atom, Sulfur atoms, ester groups, amino ester groups, cyano groups also include 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, chloro
  • the solvent in the rubber solution is a good solvent for various rubbers.
  • 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, including but not limited to various solvents such as gasoline, cycloalkane, and substituted cycloalkane.
  • the aromatic hydrocarbon solvent includes, but not limited to, benzene, toluene, xylene, styrene
  • the chlorinated hydrocarbon solvent includes, but not limited to, dichloromethane, chloroform, carbon tetrachloride, dichloroethane , chlorobenzene, tetrachloroethylene, chlorotoluene.
  • the concentration of the rubber in the solution ranges from 1% by weight to 60% by weight, preferably from 5% by weight to 40% by weight, More preferably, it is 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, calcium carbonate, 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 300m 2 / g.
  • the oil absorption value is 20 to 250 ml / 100 g, preferably 25 to 200 ml / 100 g, more preferably 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, calcium oxide, titanium oxide, boron oxide, etc., for biphasic or heterogeneous
  • 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 fillers also include their surface modifying fillers.
  • the surface modification described therein may be that a certain functional group is attached to the surface of the filler by a chemical reaction or the modifier is physically bonded to the surface of the filler by mixing or adsorption.
  • the modification may, but is not limited to, dissolving the modifier in a solvent and mixing with the filler for liquid phase modification, such as WangW, Nanse G, Vidal A, et al. KGK [J], 1994, 47:493.
  • the method may also be, but is not limited to, mixing and heating the modifier with the filler 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:
  • A is -SCN, -SH, -Cl, -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 6 carbon atoms
  • Alk eny l is a linear or branched alkenyl group having 1 to 6 carbon atoms
  • 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 2 to 8
  • the most commonly used ones are bis(triethoxypropylsilane) tetrasulfide and disulfide, 3-thiocyanopropyl-triethoxysilane, ⁇ -mercaptopropyl-trimethoxysilane, zirconate
  • An ester coupling agent, a titanate coupling agent, a nitro coupling agent, an alcohol compound, and the alcohol compound includes, but not limited to, a unit alcohol, a glycol, a polyol, and the alcohol compound includes but is not limited to Propanol, butanol, ethylene glycol, polyethylene glycol and derivatives thereof.
  • step B), step C) and step D) is recycled for recycling; the recovery is carried out by means of a condenser, a fractionation column and a spraying device.
  • 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. When the method of direct condensation contact is used, the coolant may be water or the same solvent.
  • step B) can be carried out using any container.
  • Step B) is carried out in a can container, preferably a cylindrical can container.
  • the gaseous medium described in step B) includes at least one of nitrogen, carbon dioxide, water vapor, and air.
  • the temperature of the gaseous medium described in step B) is above the boiling point of the solvent, preferably from 50 to 250 ° C, more preferably from 70 to 180 ° C.
  • step B1) is further carried out before or after step B): the mixture obtained in the previous step is fed into the agglomerator and optionally in the agglomerator with nitrogen, water vapor, water, water slurry and oil The fluid or a plurality of fluids are contacted and mixed to form a mixture of the rubber/filler and or additive complex and the solvent.
  • Step B2) is further carried out before or after step B): the mixture obtained in the previous step is directly passed into a heating medium having a temperature higher than the boiling point of the solvent, the polarity of the heating medium being different from the polarity of the solvent used, and the mixture is agglomerated and The solvent is removed and the solvent is rapidly volatilized to form a mixture of rubber/filler and or additive complex and solvent containing the heating medium.
  • Step B1) and/or step B2) are further carried out before or after step B).
  • the agglomerator used in step B1) may be a tubular agglomerator having one or more feed ports, wherein the feed port may be fed in a direction parallel to the axial direction of the tubular agglomerator tube, and the outlet is at The end of the tube may also be at an angle of 1-180° to the axial direction of the tubular agglomerator tube, preferably at an angle of 20-120°, more preferably at an angle of 70-100°, and most preferably at an angle of 85-95°.
  • the feed direction of the partial feed port is parallel to the axial direction of the tube agglomerator tube; the feed direction of the other feed ports is opposite to the axial direction of the tube of the tube agglomerator 1-180° angle, preferably at an angle of 20-120°, more preferably at an angle of 70-100°, most preferably at an angle of 85-95°, the feed direction of each feed port being perpendicular to the axis of the tube axis
  • the projection is in any direction between the radial direction of the cross section to the tangential direction of the cross section, preferably a radial direction, or a tangential direction.
  • the feed ports are all on the same plane perpendicular to the axial direction of the tube or the feed ports are at different planes on.
  • the agglomerator used in step B1) may also be an agglomerator consisting of two or more mutually concentric tubes, wherein each tube has one or more feed ports, the feed of which is fed The direction is parallel to the axial direction of the tube or the tangential direction of the tube, and 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 the ends of the feed ports of each tube may be lengthened from the inside to the outside or the ends of the feed ports of each tube from the inside to the outside may be shortened.
  • the agglomerator used in step B1) 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 it can be injected into the agglomerator in a tangential direction along the wall of the barrel.
  • the agglomerator used in the step B1) may also have a cylindrical shape with an upper portion and a conical tubular structure with a lower portion and one or more feed ports.
  • the feed direction of the feed port may be the tangential direction of the tube wall; each feed port may be in the same plane or in different planes.
  • 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 an angle of 20-110°, more preferably an angle of 70-100°, most preferably 85-95.
  • the projection 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 .
  • One or more of the nitrogen, steam, water, filler slurry and oil described in step B1) and the rubber/filler/solvent mixture obtained in step A) are condensed through one or more feed ports
  • the temperature of the nitrogen gas is 20-300 ° C
  • the temperature of the water vapor is 100-300 ° C
  • the temperature of the liquid water is 20-100 ° C
  • the temperature of the oil is 20-300 ° C
  • the temperature of the filler water slurry is 20-100. °C.
  • the oil is a commonly used oil for the manufacture of oil-filled rubber in the rubber field.
  • the oil optionally used in step A) may be the same as or different from the oil used in step B1).
  • the filler used in step A) may be the same as or different from the filler used in step B1).
  • step B2) the mixture obtained in the previous step is passed directly into a heating medium having a temperature higher than 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 desorbs the solvent, and when the temperature of the heating medium is higher than the boiling point of the solvent, the solvent rapidly 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 fractionation column for recovery, and the obtained agglomerated mixture is obtained.
  • 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 is a solvent having a boiling point of less than 100 °C. The solvent and the unreacted monomer in the rubber synthesis and the water vapor are then introduced into the condenser and the fractionation column for recovery.
  • step B2) can be carried out using any container; preferably, it is carried out without using any specially designed agglomerator; the agglomeration of step B2) can be carried out in a can container.
  • step B2) uses a can-shaped container of any shape, more preferably a cylindrical can-shaped container.
  • Step B) is to agglomerate the mixture directly into a gaseous medium.
  • Step B) can be carried out using any container; preferably, it is carried out without using any specially designed agglomerator; the agglomeration of step B) can be carried out in a can container.
  • step B) uses a can-shaped container of any shape, more preferably a cylindrical can-shaped container.
  • the invention also provides a rubber masterbatch prepared according to the above method.
  • the present invention also provides a rubber article which is prepared using the rubber masterbatch described above.
  • Rubber/filler (or filler/additive)/solvent mixture agglomeration and solvent removal rubber/filler (or filler/additive)/solvent mixture directly into the gaseous medium to agglomerate the mixture without special design condensation
  • the condensing medium is easy to separate the gas, and the raw material is easy to obtain; while the gaseous medium contains nitrogen, adding a certain amount of water can increase the filler-rubber interaction, reduce the aggregation of the filler, and improve the microscopic dispersion of the filler in the rubber.
  • Rubber/filler (or filler/additive)/solvent mixture can be agglomerated without the need for a liquid medium, reducing process costs.
  • the condensate can be separated from the solvent in the heat medium without passing through the separator, which can ensure the physical properties of the masterbatch to the greatest extent.
  • the solvent separation method disclosed in the present invention (the mixture is separated by evaporation, or the solvent is separated by low pressure vacuum drying, or the solvent is separated by heating, or the solvent is separated by spray drying, or the solvent is separated by expansion drying) , or by separating the solvent by flashing, the complete separation of the solvent can be achieved, and the separation can be completed quickly, the oxidative aging phenomenon of the rubber molecules due to high temperature is avoided, and the reinforcing effect of the filler on the rubber is enhanced.
  • Oil-filled polystyrene-butadiene rubber (37.5 parts oil-filled), VSL4526-OHM, LANXESS production;
  • Butadiene rubber BR9000, Sinopec Qilu Co., Ltd.;
  • Silane coupling agent Si69 Nanjing Shuguang Chemical Group Co., Ltd.
  • Zinc oxide Dalian zinc oxide plant
  • Antioxidant RD chemical plant of Sinopec Nanjing Chemical Industry Co., Ltd.
  • Antioxidant 4020 Jiangsu Shengao Chemical Co., Ltd.;
  • the glue After adding 3.5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of paraffin, and 2 parts of anti-aging agent 4020 for 2 minutes, the glue is the second stage. Mixing glue. After 8 hours of parking, 2.0 parts of accelerator CZ, 2.1 parts of accelerator DPG and 1.4 parts of sulfur were added to the internal mixer, and the mixture was passed through a roller on the freezer. After six passes, the lower piece was the final rubber. After the gel was allowed to stand for 8 hours, it was vulcanized to a positive vulcanization on a plate vulcanizer at 165 ° C to obtain a dry vulcanizate.
  • Table 3 shows the physical properties of the vulcanizates obtained in Examples 1-5 of the wet master batches and the comparative examples of the dry mixes (Comparative Example 1) under different formulations and processes. It can be seen that, under the same formula, the dispersibility of the filler in the rubber is greatly improved compared with the dry masterbatch, and the hardness of the vulcanizate is low, tensile strength and elongation at break. Higher, high elasticity, low hysteresis loss and good wear resistance. Comparing the data of Comparative Example 2 and Example 1, it can be seen that the wet master batch in the present invention can be equivalent to the wet master batch in the patent of CN103113597 without the drying step under the same formulation.
  • the wet masterbatch of the present invention has a filler in rubber compared to the wet masterbatch in the patent of CN103113597.
  • the dispersibility is improved, the hardness of the vulcanized rubber is low, the tensile strength and the elongation at break are equivalent, the elasticity is high, the hysteresis loss is low, and the wear resistance is good.

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Abstract

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和橡胶制品，包括如下步骤：步骤A）：将填料加入到橡胶溶液中，通过搅拌形成橡胶/填料/溶剂的混合物；步骤B）：将步骤A）得到的橡胶/填料/溶剂混合物直接通入气体介质中进行凝聚和溶剂分离，得到橡胶/填料母炼胶。还提供上述方法得到的橡胶母炼胶及其橡胶制品。其中凝聚在气体介质中进行，凝聚介质易分离，工艺简化，节约能源。

Description

[根据细则37.2由ISA制定的发明名称]　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 技术领域
本发明涉及橡胶领域，特别涉及一种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和橡胶制品。
背景技术
混炼是橡胶胶料加工的关键工序，且一直是加工过程中能耗最大的工序，其能耗占整个橡胶加工能耗的大半。普通干法混炼每批胶料之间的差异性较大，常常对后续工序的质量产生很大影响，同时由于橡胶的反复捏炼，橡胶分子量下降，以及填料在橡胶中的分散不均等原因造成胶料性能下降，还会产生大量粉尘造成环境的污染。故此，湿法混炼工艺应运而生，此工艺方法比现有的干法混炼工艺的显著优势在于节省能源，填料和添加剂在橡胶中能够更好、更均匀分散的同时产品性能得到极大的提升。在湿法混炼工艺中，最重要的工艺过程即是凝聚步骤。
CN103113597A公开了使用特殊设计的凝聚器进行高效连续凝聚的湿法混炼方法，凝聚介质包括氮气、水蒸气、水、填料水浆和油，但该凝聚器对设备材质要求高，工艺成本较高；CN103419291A公开了使用水做加热介质的方法，但后续需要经分离器分离除水，造成了胶粒破损，母胶有损失。US7307121B2公开了一种汽提(steam stripping)的方法脱除溶剂，具体做法是将白炭黑/橡胶混合物泵入汽提装置中凝聚并脱除溶剂，该方法因汽提时通入水蒸汽，需要脱水和干燥。
发明内容
为了解决现有技术中水和水蒸气作为凝聚介质、需要脱水干燥，工序复杂且造成母胶损失的问题，本发明的首要目的是提供一种橡胶母炼胶的连续式制造方法。本发明的另一目的在于提供上述方法制备得到的橡胶母炼胶。本发明的再一个目的是提供一种使用上述橡胶母炼胶制备得到的橡胶制品。
本发明将橡胶/填料和/或添加剂混合物直接通入气体中实现凝聚和溶剂分离，本发明的工艺简化、节约能源，改善了填料分散性能和橡胶硫化特性，增强了填料-聚合物相互作用，从而使橡胶制品性能提升。
本发明公开了如下几种橡胶母炼胶的连续式制造方法，包括：
一种橡胶母炼胶的连续式制造方法，包括如下步骤：
步骤A)：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B)：将步骤A)得到的橡胶/填料/溶剂混合物直接通入气体介质中进行凝聚和溶剂分离，得到橡胶/填料母炼胶。
一种橡胶母炼胶的连续式制造方法，包括如下步骤：
步骤A)：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B)：将步骤A)得到的橡胶/填料/溶剂混合物直接通入气体介质中进行凝聚并使部分溶剂分离，得到橡胶/填料复合物与溶剂的混合物；
步骤C)：对步骤B)得到的混合物进行溶剂分离，所述溶剂分离步骤具体为将混合物通过蒸发分离溶剂，或通过低压真空干燥分离溶剂，或通过加热的方式分离溶剂，或通过喷雾干燥的方式分离溶剂，或通过膨胀干燥的方式分离溶剂，或者通过闪蒸的方式分离溶剂，从而得到橡胶/填料母炼胶。
一种橡胶母炼胶的连续式制造方法，包括如下步骤：
步骤A)：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B)：将步骤A)得到的橡胶/填料/溶剂混合物直接通入气体介质中进行凝聚并使部分溶剂分离，得到橡胶/填料复合物与溶剂的混合物；
步骤D)：对上一步骤得到的混合物进行干燥，得到橡胶/填料母炼胶；所述干燥为加热干燥和/或机械干燥。
一种橡胶母炼胶的连续式制造方法，包括如下步骤：
步骤A)：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B)：将步骤A)得到的橡胶/填料/溶剂混合物直接通入气体介质中进行凝聚并使部分溶剂分离，得到橡胶/填料复合物与溶剂的混合物；
步骤C)：对步骤B)得到的混合物进行溶剂分离，所述溶剂分离步骤具体为将混合物通过蒸发分离溶剂，或通过低压真空干燥分离溶剂，或通过加热的方式分离溶剂，或通过喷雾干燥的方式分离溶剂，或通过膨胀干燥的方式分离溶剂，或者通过闪蒸的方式分离溶剂；
步骤D)：对上一步骤得到的混合物进行干燥，得到橡胶/填料母炼胶；所述干燥为加热干燥和/或机械干燥。
其中步骤C)所述蒸发为使用烘箱或干燥板进行蒸发；所述喷雾干燥的雾化方式为离心雾化、压力雾化或二流体雾化；所述膨胀干燥的方式为先进行加热然后突然释放压力；所述闪蒸的方式为常压闪蒸或减压闪蒸的至少一种，闪蒸级数为1-3级。其中步骤C)中所述的低压真空干燥为在真空至低于一个大气压的压力下挥发溶剂或抽滤，所述压力优选为-0.1MPa至0， 更优选为-0.09MPa至0，最优选为-0.08MPa至0。步骤C)中所述的膨胀干燥为通过螺杆膨胀干燥机使溶剂闪蒸气化，优选螺杆膨胀干燥机0-20MPa，更优选1-10MPa下沿轴推送，螺距递减，摩擦生热，出口压力骤降，胶条膨胀放松，胶条内的溶剂闪蒸气化。
其中步骤D)所述加热干燥为烘干或风干；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，双螺杆挤出机进行干燥，机械干燥的工作温度为10℃至250℃；步骤D)可以先进行加热干燥后再进行机械干燥，也可以先进行机械干燥后再进行加热干燥。步骤D)选择机械干燥时可以同时加热干燥，温度为10℃至250℃；选择加热干燥时，可在气体介质中进行加热，所述气体介质包括空气、氮气、水蒸气、CO2的至少一种。
其中步骤A)中的橡胶/填料/溶剂混合物立即进入步骤B)，或者停放一定时间再进入步骤B)，在停放时加热或者不加热；当加热时，温度为10℃至200℃。其中步骤A)中还包括将添加剂加入到橡胶溶液中，通过搅拌形成橡胶/填料/添加剂/溶剂混合物。步骤A)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形成填料和/或添加剂/溶剂混合物。该填料和/或添加剂/溶剂混合物可直接与橡胶溶液混合，也可以停放一定时间后与橡胶溶液混合，在停放时加热或者不加热，当加热时，温度为10℃至200℃，当上述加热温度高于溶剂的沸点时，加热需在压力容器中进行。步骤A)得到的橡胶/填料和/或添加剂/溶剂混合物，可立即进入下一步骤，也可以先停放一定时间，在停放时加热或者不加热，当加热时，温度为10℃至200℃，当上述加热温度高于溶剂的沸点时，加热需在压力容器中进行。所述的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、增塑剂、软化剂、加工助剂、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A)可以使用本领域公知的方法实现。步骤A)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机，槽式搅拌机，行星式搅拌机，曲拐式搅拌机等。
步骤A)还可以进一步包括细分散步骤，所述的细分散可以通过如下方式实施：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0.1MPa至100MPa，优选10MPa至80MPa。
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.将所述细分散之后的混合物连续加入球磨机和/或胶体磨中进行分散，使填料和/或添加 剂均匀的分散在橡胶溶液中；
ii.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.将所述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0.1MPa至100MPa，优选10MPa至80MPa。
iv.将所述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0.1MPa至100MPa，优选10MPa至80MPa。
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橡胶溶液中。
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。
所述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，所述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；所述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。当所述橡胶溶液直接从制备溶聚橡胶生产线中获得时，所述溶聚橡胶为用乙烯、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，所述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。橡胶的分子量为1千至4000万，优选5千至3000万，更优选1万至800万。
所述橡胶溶液中的溶剂均为各种橡胶的良溶剂。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，所述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40％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钙、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300m2/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及多相填料，多相填料包括但并不限于炭黑、二氧化硅、氧化铝、氧化镁、氧化锌、氧化钙、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。
所述的填料也包括它们的表面改性填料。其中所述的表面改性可以是通过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。所述改性来讲，可以但不限于将改性剂溶于溶剂后与填料混合进行液相改性，如WangW，Nanse G，VidalA，et al.K.G.K[J]，1994，47：493中所述，也可以但不限于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：
(Rn-(RO)3-nSi-(Alk)m-(Ar)p)q(A)         (I)
Rn’(RO)3-nSi-(Alk)          (II)
或Rn’(RO)3-nSi-(Alkenyl)      (III)
式中，当q＝1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6个碳原子的直链或支链烃基；
Alkenyl是含有1至6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-巯丙基-三甲氧基硅烷、锆酸酯偶联剂、钛酸酯偶联剂、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，所述醇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。
对步骤B)、步骤C)和步骤D)的溶剂进行回收循环利用；所述回收通过冷凝器、分馏塔和喷淋设备实施。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的方法时冷却剂可以采用水、同种溶剂。
其中步骤B)可以使用任何容器来实施。步骤B)在罐状容器中实施，优选圆柱形罐状容器。在步骤B)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、增塑剂、软化剂、加工助剂、硫化剂和促进剂的添加剂。步骤B)中所述的气体介质包括氮气、二氧化碳、水蒸气、空气的至少一种。步骤B)中所述的气体介质的温度为溶剂沸点温度以上，优选50-250℃，更优选70-180℃。
其中在步骤B)之前或之后进一步实施步骤B1)：将上一步骤得到的混合物送入凝聚器中，并在凝聚器中任选与氮气、水蒸气、水、填料水浆和油中的一种或多种流体相接触并混合后凝聚，得到橡胶/填料和或添加剂复合物与溶剂的混合物。在步骤B)之前或之后进一步实施步骤B2)：将上一步骤得到的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，混合物凝聚并退溶剂，并且溶剂迅速挥发，从而形成含有该加热介质的橡胶/填料和或添加剂复合物与溶剂的混合物。其中在步骤B)之前或之后进一步实施步骤B1)和/或步骤B2)。
步骤B1)中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，更优选呈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70-100°角，最优选呈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B1)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，所述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，也可以由内向外每个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B1)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B1)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。
步骤B1)中所述的氮气、水蒸气、水、填料水浆和油中的一种或多种流体和步骤A)中得到的橡胶/填料/溶剂混合物通过一个或多个进料口进入凝聚器，其中氮气的温度为20-300℃，水蒸气的温度为100-300℃，液体水的温度为20-100℃，油的温度为20-300℃，填料水浆的温度为20-100℃。所述油为橡胶领域制造充油橡胶常用的油。步骤A)中任选使用的油可以与步骤B1)中使用的油相同或不同。步骤A)中使用的填料可以与步骤B1)中使用的填料相同或不同。
在步骤B2)中，将上一步骤得到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剂，而加热介质温度高于溶剂沸点时，溶剂即迅速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分馏塔中进行回收，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100℃溶剂。然后所挥发出的溶剂和橡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。
步骤B2)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；步骤B2)的凝聚可以在罐状容器中实施。优选，步骤B2)使用任意形状的罐状容器，更优选使用圆柱形的罐状容器。
步骤B)为将混合物直接通入气体介质中进行凝聚。步骤B)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；步骤B)的凝聚可以在罐状容器中实施。优选，步骤B)使用任意形状的罐状容器，更优选使用圆柱形的罐状容器。本发明还提供一种根据上述方法制备得到的橡胶母炼胶。本发明还提供一种橡胶制品，其使用上述的橡胶母炼胶制备得到。
本发明的技术效果为
i.橡胶/填料(或填料/添加剂)/溶剂混合物的凝聚和脱溶剂的方式：橡胶/填料(或填料/添加剂)/溶剂混合物直接通入气体介质中使混合物凝聚，不需要特殊设计的凝聚器、凝聚介质为气体易分离，原料易得；而气体介质中含有氮气时，添加一定量的水分可增加填料-橡胶相互作用，减少填料聚集，改善填料在橡胶中的微观分散性。
ii.橡胶/填料(或填料/添加剂)/溶剂混合物不需要液体介质即可凝聚，减少了工艺成本。
iii.凝聚物在热介质中，不需经分离器，即可与溶剂分离，可最大程度上保证母炼胶的物理性能。
iv.本发明公开的溶剂分离方式(将混合物通过蒸发分离溶剂，或通过低压真空干燥分离溶剂，或通过加热的方式分离溶剂，或通过喷雾干燥的方式分离溶剂，或通过膨胀干燥的方式分离溶剂，或者通过闪蒸的方式分离溶剂)可实现溶剂的完全分离，且该分离能够迅速完成，避免了橡胶分子因高温发生氧化老化现象，增强了填料对橡胶的补强效果。
v.工艺适应性强：既可以用工艺简单而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(或填料/添加剂)母胶，又可利用特殊设计的分散装置、混合凝聚工艺和机械干燥方法制造成本较高但性能较好的橡胶/填料(或填料/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。
具体实施方式
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：
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 密炼机 BR1600 美国法雷尔公司
2 开炼机 Polymix 150L 德国SERVITEC公司
3 平板硫化机 P-V-200-3RT-2-PCD 磐石油压工业有限公司
表2硫化胶物理性能的测试方法及仪器
Figure PCTCN2016098636-appb-000001
Figure PCTCN2016098636-appb-000002
(二)实施例及对比例
原料：
溶聚丁苯橡胶，台橡股份有限公司；
充油溶聚丁苯橡胶(充油量37.5份)，VSL4526-OHM，LANXESS生产；
顺丁橡胶，BR9000，中国石化齐鲁股份有限公司；
白炭黑，Newsil HD165MP，确成硅化学股份有限公司
硅烷偶联剂Si69，南京曙光化工集团有限公司；
硬脂酸，PF1808，马来西亚立成有限公司；
氧化锌，大连氧化锌厂；
石蜡，百瑞美特殊化学品(苏州)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；
防老剂4020，江苏圣奥化学有限公司；
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；
硫黄，临沂罗庄新安化工厂。
对比例1
将96.3份充油溶聚丁苯橡胶、30份顺丁橡胶加入密炼机内，破胶半分钟后，将78份白炭黑、6.4份硅烷偶联剂Si69和1.8份油分两次加入橡胶中。当上述物质混入橡胶并使温度达到150℃后再延长2分钟的混炼时间，排胶，在开炼机上过辊，薄通六次后下片即为第一段预混胶。该胶停放8小时后再放入密炼机中破胶，加入3.5份氧化锌、2份硬脂酸、2份石蜡、2份防老剂4020混炼2分钟后排胶即为第二段预混胶。停放8小时后再在密炼机内加入2.0份促进剂CZ、2.1份促进剂DPG和1.4份硫黄，混炼胶在开冻机上过辊，薄通六次后下片即为终炼胶。该胶停放8小时后在165℃的平板硫化机上硫化至正硫化，制得干法硫化胶。
对比例2
将70份溶聚丁苯橡胶和30份顺丁橡胶溶于己烷中制得20％的橡胶溶液，再将以100份橡胶为基础的78份白炭黑、6.4份硅烷偶联剂Si69、28份油、2份防老剂4020、3.5份氧化锌、2份硬脂酸、2份石蜡混入橡胶溶液中形成混合物。该混合物经混合后在30MPa的压力下经过有四个进口中的两个入口注入筒锥式凝聚器内，而同时从另外两个入口在10MPa的压力下注入90-100℃的水，所得固/液/气三相混合物通过凝聚器的一个出口喷入干燥器，形成固体粉末物质，再经干燥后即为母炼胶1。
实施例1
将70份溶聚丁苯橡胶和30份顺丁橡胶溶于己烷中制得20％的橡胶溶液，再将以100份橡胶为基础的78份白炭黑、6.4份硅烷偶联剂Si69、28份油、2份防老剂4020、3.5份氧化锌、2份硬脂酸、2份石蜡混入橡胶溶液中形成混合物。该混合物混合分散后直接通入180℃N2中完成凝聚并脱溶剂(“脱挥”)，得到母炼胶2。
实施例2
将70份溶聚丁苯橡胶和30份顺丁橡胶溶于己烷中制得20％的橡胶溶液，再将以100份橡胶为基础的78份白炭黑、6.4份硅烷偶联剂Si69、28份油、2份防老剂4020、3.5份氧化锌、2份硬脂酸、2份石蜡混入橡胶溶液中形成混合物。该混合物经叶片搅拌机初混、曲管分散器细混和均质机精混后直接通入充有180℃氮气、CO2的罐内，罐内还含有1％的水分，混合物脱溶剂后再经干燥即为母炼胶3。
实施例3
将70份溶聚丁苯橡胶和30份顺丁橡胶溶于己烷中制得20％的橡胶溶液，再将以100 份橡胶为基础的78份白炭黑、6.4份硅烷偶联剂Si69、28份油、2份防老剂4020、3.5份氧化锌、2份硬脂酸、2份石蜡混入橡胶溶液中形成混合物。该混合物直接喷入约95℃的水中同时通入150℃空气，所得固/液/气三相混合物通过热风烘箱干燥后即为母炼胶4。
实施例4
将70份溶聚丁苯橡胶和30份顺丁橡胶溶于己烷中制得20％的橡胶溶液，再将以100份橡胶为基础的78份白炭黑、6.4份硅烷偶联剂Si69、28份油、2份防老剂4020、3.5份氧化锌、2份硬脂酸、2份石蜡混入橡胶溶液中形成混合物。该混合物经混合后在30MPa的压力下经过有四个入口的筒锥式凝聚器中的两个入口连续注入凝聚器内，同时从另外两个入口连续注入温度约为180℃的氮气，将所得混合物经喷雾干燥的方式分离溶剂，制得母炼胶5。
实施例5
将70份溶聚丁苯橡胶和30份顺丁橡胶溶于己烷中制得20％的橡胶溶液，再将以100份橡胶为基础的78份白炭黑、6.4份硅烷偶联剂Si69、28份油、2份防老剂4020、3.5份氧化锌、2份硬脂酸、2份石蜡混入橡胶溶液中形成混合物。该混合物经研磨机混合后直接通入充有150℃氮气的容器中，凝聚后的橡胶/填料/溶剂混合物经加热分离溶剂后，再经膨胀干燥后即为母炼胶6。
将上述所得母炼胶1～6在开炼机上包辊后，加入2.0份促进剂CZ、2.1份促进剂DPG和1.4份硫黄后薄通下片，停放8小时后，在165℃的平板硫化机中硫化至正硫化，制得湿法硫化胶1～6。
表3湿、干法硫化胶的物理性能
Figure PCTCN2016098636-appb-000003
Figure PCTCN2016098636-appb-000004
表3为在不同配方及工艺下湿法母炼胶的实施例1-5和干法混炼胶的对比例(对比例1)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性大大提高，硫化胶的硬度较低，拉伸强度和扯断伸长率较高，弹性高，滞后损失低，耐磨性能较好。比较对比例2和实施例1的数据可以看出，在相同配方下，本发明中的湿法母炼胶不经干燥步骤，可与公开号为CN103113597的专利中的湿法母炼胶性能相当，此法可大大节省能量消耗，缩减工艺步骤，应用范围广阔。比较对比例2和实施例2-5的数据可以看出，在相同配方下，本发明中的湿法母炼胶与公开号为CN103113597的专利中的湿法母炼胶相比，填料在橡胶中的分散性提高，硫化胶的硬度较低，拉伸强度和扯断伸长率相当，弹性高，滞后损失低，耐磨性能好。

Claims (25)

  1. 一种橡胶母炼胶的连续式制造方法，其特征在于包括如下步骤：
    步骤A)：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B)：将步骤A)得到的橡胶/填料/溶剂混合物直接通入气体介质中进行凝聚和溶剂分离，得到橡胶/填料母炼胶。
  2. 一种橡胶母炼胶的连续式制造方法，其特征在于包括如下步骤：
    步骤A)：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B)：将步骤A)得到的橡胶/填料/溶剂混合物直接通入气体介质中进行凝聚并使部分溶剂分离，得到橡胶/填料复合物与溶剂的混合物；
    步骤C)：对步骤B)得到的混合物进行溶剂分离，所述溶剂分离步骤具体为将混合物通过蒸发分离溶剂，或通过低压真空干燥分离溶剂，或通过加热的方式分离溶剂，或通过喷雾干燥的方式分离溶剂，或通过膨胀干燥的方式分离溶剂，或者通过闪蒸的方式分离溶剂，从而得到橡胶/填料母炼胶。
  3. 一种橡胶母炼胶的连续式制造方法，其特征在于包括如下步骤：
    步骤A)：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B)：将步骤A)得到的橡胶/填料/溶剂混合物直接通入气体介质中进行凝聚并使部分溶剂分离，得到橡胶/填料复合物与溶剂的混合物；
    步骤D)：对步骤B)得到的混合物进行干燥，得到橡胶/填料母炼胶；所述干燥为加热干燥和/或机械干燥。
  4. 一种橡胶母炼胶的连续式制造方法，其特征在于包括如下步骤：
    步骤A)：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B)：将步骤A)得到的橡胶/填料/溶剂混合物直接通入气体介质中进行凝聚并使部分溶剂分离，得到橡胶/填料复合物与溶剂的混合物；
    步骤C)：对步骤B)得到的混合物进行溶剂分离，所述溶剂分离步骤具体为将混合物通过蒸发分离溶剂，或通过低压真空干燥分离溶剂，或通过加热的方式分离溶剂，或通过喷雾干燥的方式分离溶剂，或通过膨胀干燥的方式分离溶剂，或者通过闪蒸的方式分离溶剂；
    步骤D)：对步骤C)得到的混合物进行干燥，得到橡胶/填料母炼胶；所述干燥为加热干燥和/或机械干燥。
  5. 根据权利要求1-4任一项所述的方法，其特征在于其中步骤A)中的橡胶/填料/溶剂混合物立即进入步骤B)，或者停放一定时间再进入步骤B)，在停放时加热或者不加热；当加热时，温 度为10℃至200℃。
  6. 根据权利要求2或4所述的方法，其特征在于其中步骤C)所述蒸发为使用烘箱或干燥板进行蒸发；所述喷雾干燥的雾化方式为离心雾化、压力雾化或二流体雾化；所述膨胀干燥的方式为先进行加热然后突然释放压力；所述闪蒸的方式为常压闪蒸和减压闪蒸中的至少一种，闪蒸级数为1-3级。
  7. 根据权利要求2或4所述的方法，其特征在于其中步骤C)中所述的低压真空干燥为在真空至低于一个大气压的压力下挥发溶剂或抽滤。
  8. 根据权利要求2或4所述的方法，其特征在于其中步骤C)中所述的膨胀干燥为通过螺杆膨胀干燥机使溶剂闪蒸气化。
  9. 根据权利要求3或4所述的方法，其特征在于其中步骤D)所述加热干燥为烘干或风干；所述机械干燥为使用开炼机、捏炼机、密炼机、连续密炼机、单螺杆挤出机或者双螺杆挤出机进行干燥，机械干燥的工作温度为10℃至250℃；步骤D)先进行加热干燥后再进行机械干燥，或者先进行机械干燥后进行加热干燥。
  10. 根据权利要求3或4所述的方法，其特征在于其中步骤D)所述干燥为机械干燥时同时加热干燥，温度为10℃至250℃；所述干燥为加热干燥时，在气体介质中进行加热，所述气体介质包括空气、氮气、水蒸气和CO2中的至少一种。
  11. 根据权利要求1-4任一项所述的方法，其特征在于其中步骤A)中还包括将添加剂加入到橡胶溶液中，通过搅拌形成橡胶/填料/添加剂/溶剂混合物；所述填料和添加剂直接加入到橡胶溶液中，或者先将所述填料和添加剂加入到与橡胶溶液相同或不同的溶剂中，然后直接加入到橡胶溶液中或停放一定时间后加入到橡胶溶液中，停放时加热或者不加热；当加热时，温度为10℃至200℃。
  12. 根据权利要求11所述的方法，其特征在于其中所述的添加剂为一种或多种选自油、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、增塑剂、软化剂、加工助剂、硫化剂和促进剂的添加剂。
  13. 根据权利要求11所述的方法，其特征在于其中步骤A)中所述的橡胶/填料和添加剂/溶剂混合物立即进入步骤B)，或者停放一定时间再进入步骤B)，在停放时加热或者不加热；当加热时，温度为10℃至200℃。
  14. 根据权利要求1-4任一项所述的方法，其特征在于其中在步骤B)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、增塑剂、软化剂、加工助剂、硫化剂和促进剂的添加剂。
  15. 根据权利要求1-4任一项所述的方法，其特征在于其中步骤B)中所述的气体介质包括氮气、二氧化碳、水蒸气和空气中的至少一种。
  16. 根据权利要求1-4任一项所述的方法，其特征在于其中步骤B)中所述的气体介质的温度为溶剂的沸点温度以上。
  17. 根据权利要求1-4任一项所述的方法，其特征在于其中在步骤B)之前或之后进一步实施步骤B1)：将上一步骤得到的混合物送入凝聚器中，并在凝聚器中任选与氮气、水蒸气、水、填料水浆和油中的一种或多种流体相接触并混合后凝聚，得到橡胶/填料复合物与溶剂的混合物。
  18. 根据权利要求1-4任一项所述的方法，其特征在于其中在步骤B)之前或之后进一步实施步骤B2)：将上一步骤得到的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，混合物凝聚并退溶剂，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。
  19. 根据权利要求1-4任一项所述的方法，其特征在于其中在步骤B)之前或之后进一步实施步骤B1)和/或步骤B2)。
  20. 根据权利要求1所述的方法，其特征在于其中对步骤B)的溶剂进行回收循环利用；所述回收通过冷凝器、分馏塔和喷淋设备实施。
  21. 根据权利要求2所述的方法，其特征在于其中对步骤B)和步骤C)的溶剂进行回收循环利用；所述回收通过冷凝器、分馏塔和喷淋设备实施。
  22. 根据权利要求3所述的方法，其特征在于其中对步骤B)和步骤D)的溶剂进行回收循环利用；所述回收通过冷凝器、分馏塔和喷淋设备实施。
  23. 根据权利要求4所述的方法，其特征在于其中对步骤B)、步骤C)和步骤D)的溶剂进行回收循环利用；所述回收通过冷凝器、分馏塔和喷淋设备实施。
  24. 一种根据权利要求1-23任一项所述的方法制备的橡胶母炼胶。
  25. 一种橡胶制品，其特征在于其使用根据权利要求24所述的橡胶母炼胶制备得到。
PCT/CN2016/098636 2015-09-11 2016-09-10 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 WO2017041754A1 (zh)

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CN105131307A (zh) * 2015-09-11 2015-12-09 怡维怡橡胶研究院有限公司 一种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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