CN1261843A - Mill mixing process for compounding gas-phase produced elastomers - Google Patents

Mill mixing process for compounding gas-phase produced elastomers Download PDF

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Publication number
CN1261843A
CN1261843A CN98806830A CN98806830A CN1261843A CN 1261843 A CN1261843 A CN 1261843A CN 98806830 A CN98806830 A CN 98806830A CN 98806830 A CN98806830 A CN 98806830A CN 1261843 A CN1261843 A CN 1261843A
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Prior art keywords
mill
compound
synthetic rubber
mixing
compounding process
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Chinese (zh)
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E·T·伊塔利尔安德
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Union Carbide Chemicals and Plastics Technology LLC
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Union Carbide Chemicals and Plastics Technology LLC
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    • 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
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/52—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices with rollers or the like, e.g. calenders
    • B29B7/56—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices with rollers or the like, e.g. calenders with co-operating rollers, e.g. with repeated action, i.e. the material leaving a set of rollers being reconducted to the same set or being conducted to a next set
    • 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
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/52—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices with rollers or the like, e.g. calenders
    • B29B7/56—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices with rollers or the like, e.g. calenders with co-operating rollers, e.g. with repeated action, i.e. the material leaving a set of rollers being reconducted to the same set or being conducted to a next set
    • B29B7/562—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices with rollers or the like, e.g. calenders with co-operating rollers, e.g. with repeated action, i.e. the material leaving a set of rollers being reconducted to the same set or being conducted to a next set with means for axially moving the material on the rollers
    • 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
    • B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
    • B29B7/22—Component parts, details or accessories; Auxiliary operations
    • B29B7/24—Component parts, details or accessories; Auxiliary operations for feeding
    • B29B7/242—Component parts, details or accessories; Auxiliary operations for feeding in measured doses
    • B29B7/244—Component parts, details or accessories; Auxiliary operations for feeding in measured doses of several materials
    • 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
    • B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
    • B29B7/22—Component parts, details or accessories; Auxiliary operations
    • B29B7/24—Component parts, details or accessories; Auxiliary operations for feeding
    • B29B7/246—Component parts, details or accessories; Auxiliary operations for feeding in mixers having more than one rotor and a casing closely surrounding the rotors, e.g. with feeding plungers
    • 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
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/52—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices with rollers or the like, e.g. calenders
    • B29B7/56—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices with rollers or the like, e.g. calenders with co-operating rollers, e.g. with repeated action, i.e. the material leaving a set of rollers being reconducted to the same set or being conducted to a next set
    • B29B7/566—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices with rollers or the like, e.g. calenders with co-operating rollers, e.g. with repeated action, i.e. the material leaving a set of rollers being reconducted to the same set or being conducted to a next set provided with means to take material away from a set of rollers and to reconduct it to the same set; provided with endless belts, e.g. which can be in or out of cooperation with at least one of the rollers
    • 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
    • B29B7/60—Component parts, details or accessories; Auxiliary operations for feeding, e.g. end guides for the incoming material
    • B29B7/606—Component parts, details or accessories; Auxiliary operations for feeding, e.g. end guides for the incoming material specially adapted for feeding calenders or the like
    • 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
    • B29B7/7461—Combinations of dissimilar mixers
    • 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
    • B29B7/748—Plants
    • 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
    • B29B7/7485—Systems, i.e. flow charts or diagrams; Plants with consecutive mixers, e.g. with premixing some of the components
    • 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
    • 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
    • B29B7/94—Liquid charges
    • 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
    • B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
    • B29B7/06—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices
    • B29B7/10—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary
    • B29B7/18—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/183—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft having a casing closely surrounding the rotors, e.g. of Banbury type
    • 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
    • B29B7/584—Component parts, details or accessories; Auxiliary operations for mixers with rollers, e.g. wedges, guides, pressing means, thermal conditioning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2021/00—Use of unspecified rubbers as moulding material

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)

Abstract

There is provided a preferred process for continuous mill mixing which comprises: (i) blending a gas-phase produced elastomer and one or more other compounding ingredients in a dry blender (distributive mixing), (ii) feeding the blend to an open roll mill for compounding into sheets or strips (dispersive mixing). A vulcanizing system can be introduced in either the dry blending (i) or mill mixing compounding (ii) step, but is preferably introduced during dry blending.

Description

The elastomeric method that the compound gas phase of mill mixing is produced
Invention field
The present invention relates to the mill mixing crumb rubber, particularly the elastomeric method of gas phase production.More specifically, the present invention relates to use dry-mixed machine and roll-type mill continuous mixing, the synthetic rubber, particularly EPM that the production gas phase is produced and the method for EPDM synthetic rubber compound.
Background of invention
Up to date, commercial synthetic rubber is to adopt emulsion, solution and suspension/slurry method to produce always.The synthetic rubber of producing with these methods is that the form with condensing blob of viscose (condensed bales) provides.They are to provide to push uncompacted frangible blob of viscose form, spend additionally still that granulation provides with particle form in water, depend on the composition of synthetic rubber blob of viscose sometimes.In order to obtain chip, particle or pulverous rubber, must grind or grind with the method for physics blob of viscose densification with micron mill, also must add anti-acidblocking agent to alleviate sticking problem.Is that a kind of cost is very high, the rapid method of the catabiotic again multistep of labour intensive with condensing blob of viscose as elastomeric batching.Need firm mixing facilities, for example adopt intermittently banbury batching.When packing big blob of viscose and food ingredient into, be quite uneven beginning, and the danger with poor reproducibility.The difference of blob of viscose density also can cause mixing fluctuation on FCL or whole supporting plate.
The mixing operating process of commercial rubber at present, generally comprise a banbury with two tangential engagements or intermeshing rotor, flat mill and/or intermittently mill with sizing material mixer, make by mixing sizing material even, and before cooling off in the equipment intermittence, compound is cut into slices or the feed bar.Adopt another kind of scheme, can adopt extruder and the discharging of running roller grain silk mould.
, the blob of viscose of densification is pulverized for example in the blend step of carbon black filler, white filler, process oil, activator and processing aid at rubber and food ingredient by rotor.Carry out the distribution and the dispersion of formula components then.
The shearing force that produces between rotor tip and mixer wall can not only be guaranteed the fine dispersion of compound, but also makes time and spinner velocity and do not wish that the heat that produces is related.
In order to guarantee the fine dispersion of compound, can not make the overheated danger that causes the compound scorching of curing agent again, particularly higher to hardness or sizing material that the compound Mooney is high intermittently mixingly need divide two sections often and carries out.The compound of soft need prolong mixing time and carry out multistage mixing, with the dispersion of guaranteeing that polymer is good.
When each mixing EO, the compound of making needs carry out the homogenising step of 5min at least in the mill at intermittence in batches, mixing sizing material is cooled off, then to wave the mode lay-up on supporting plate in the cooling bath of equipment at intermittence.
In single mixing, curing agent needs before discharging in the about 105 ℃ of addings of temperature.Otherwise they are added in the intermittently mill, by sizing material mixer about 5min that fully distributes.See Fig. 1.
In two-stage mixing,, curing agent is directly added in the banbury first section mixing film being added again in the banbury behind the The pre-heat treatment 2min.
Can find out at an easy rate that the above-mentioned business method that compound conventional synthetic rubber uses needs lot of energy or shearing force in mixing and refining step.Therefore need to feel for a long time that a kind of method-cost of simplifying greatly is low, the labour is few and method more efficiently, preferably mix continuously and/or refine compound elastomeric method, particularly do not need to buy the process equipment of new costliness.
Recent findings, many synthetic rubber that can only be obtained by emulsion, solution and suspension method can adopt gas phase process to prepare in fluidized-bed reactor now in the past.Find that surprisingly the synthetic rubber cost that gas phase is produced is low, the labour is few and have the performance of continuous mixing and refining, need not adopt other process equipment.
Summary of the invention
The purpose of this invention is to provide a kind of elastomeric mill mixing method, this method is quick, simple, dustless, the labour is not intensive, use little energy (being that shearing force is less) and do not buy the expensive device of producing compound synthetic rubber product and goods in addition.
In view of the above, the invention provides a kind of compounding process, is exactly synthetic rubber with granular production comprising (i) with at least a coming out from fluidized-bed reactor of mill mixing (a), therefore do not need after reactor, to adopt the method for physics that synthetic rubber is processed into particle, (b) one or more adding ingredients, with optional (c) vulcanizing agent with (ii) unload mixture from described mill.
In preferred embodiments, the invention provides a kind of intermittence or continuous mill mixing method, this method comprises the synthetic rubber that (i) produces at least a gas phase, one or more food ingredients that randomly comprise vulcanizing system (curing agent) add in the high-speed mixer, this mixer is a kind of fluid mixer that mixes at normal temperatures, and the vulcanizing system when making synthetic rubber, food ingredient and employing vulcanizing system is evenly distributed in the dry mixture; Then (ii) equally distributed dry mixture is added in the roll-type mill, make the compound of dispersion; (iii), from the roll-type mill, draw off the compound dicing or the bar that disperse.Can be randomly sheet or the bar of step in be (iii) added in the roller of the second bench roller formula mill again, this machine is equipped with the sizing material mixer, to obtain continuous operation mode and to strengthen mixing peptizaiton and cooling capacity.In preferred embodiments, in doing mixed step (i), add vulcanizing system.
The accompanying drawing summary
The conventional mixing sketch that Fig. 1 is up to now to be adopted wherein uses the interstation banbury of having a rest, and an interstation have a rest mill and the dispersion mill that the sizing material mixer is installed when adopting the synthetic rubber blob of viscose, are adopted this method commercial always.
Fig. 2 is combination process and the apparatus sketch that the present invention adopts the mill continuous mixing.In Fig. 2: 1=liquid feeder (for example pump); The 2=feeder for solid materials; 3=vacuum gas induction system, the 4=funnel; The 5=dry-mixed machine; The 6=dry mixture; The mill of 7=roll-type; The sheet of 8=compound or bar; 9=is equipped with the mill of sizing material mixer; The 10=device for discharging; 11=finished product synthetic rubber compound.
Detailed Description Of The Invention
When producing with phase fluidised bed processes, synthetic rubber be granular, can be free-pouring, Do not need to adopt again physics fragmentation, efflorescence or smash to pieces and make uniform powder. In the present invention can Adopt with the gas phase process preparation granular, can free-pouring synthetic rubber, comprise for example second Alkene and C3-C 12The copolymer of alpha-olefin particularly comprises the copolymer of ethene and propylene, ethene, at least a C3-C 12Alpha-olefin (particularly propylene) and three of alkadienes (preferably unconjugated) Polymers. This class alkadienes is disclosed, and is for example at United States Patent (USP) 5,317, disclosed in 036. Particularly preferred ethene-alpha-olefin-dience rubber is that some adopt C3-C 6Alpha-olefin (spy Be not as alpha-olefin with propylene or butylene) and this class rubber of alkadienes, wherein alkadienes choosing From ethylidene norbornene, comprise the methyl octadiene (1-methyl isophthalic acid for example, the 6-octadiene and-7-methyl isophthalic acid, 6-octadiene) interior octadiene, hexadiene, dicyclopentadiene and Mixture.
The synthetic rubber that other gas phase that can adopt is in the present invention produced comprises for example poly-isoamyl Diene, polybutadiene, butadiene and styrene copolymerized polymer, isobutene and isoprene are altogether The copolymer of poly-polymer, polychloroprene, butadiene and isoprene and styrene, butadiene Trimer, polyisoprene, polybutadiene, polychloroprene, poly-(styrene with isoprene-butadiene) rubber is preferred.
In the synthetic rubber that the gas phase of enumerating is in the above produced, polyisoprene, polybutadiene, poly-(styrene-butadiene), ethylene-propylene copolymer, ethylene-propylene-alkadienes trimer (for example ethylene-propylene-ethylidene norbornene and ethylene-propylene-1-or 7-methyl-1,6-octadiene) be particularly preferred. Should be appreciated that the method according to this invention is mixing and multiple The synthetic rubber that closes, if they are different aspect certain of molecular structure basically, it Chemically also not necessarily different. For example, they can be basically different at two The identical synthetic rubber of molecular weight ranges, perhaps they comprise the amount of the corresponding monomer that forms them Or ratio is different basically.
Above-mentioned synthetic rubber polymer is with for example at nearest patent such as United States Patent (USP) 4,994,534; 5,304,588; 5,317,036; With 5,453, the gas phase process of lecturing in 471 utilizes fluidized-bed reactor to produce.This gas-phase polymerization can be by comprising conventional condensation mode (United States Patent (USP) 4,543,399 of inducing the condensation mode; 4,588,790; 5,352,749; With 5,462,999) and liquid monomer mode (United States Patent (USP) 5,453,471; WO 96/04322 and WO96/04323) technical process carry out.Synthetic rubber generally is softening at polymeric articles or more than the temperature that is clamminess in optional gas-phase fluidized-bed reactor, preferably in the presence of inert particle material, adopt the general polymerization catalyst that adopts of production polymeric articles to produce, inert particle material is selected from carbon black, silica, clay, stone and composition thereof.In inert particle material, carbon black, silica and composition thereof are preferred, and carbon black is most preferred.Calculate based on the weight of synthetic rubber polymer finished product, the inert particle material amount that adopts in gas-phase polymerization is about 0.3% to about 80% (weight), and preferred about 5% to about 75% (weight), most preferably 5%-50% (weight).
The synthetic rubber of producing with gas-phase polymerization is that granular energy is free-pouring, and its particle mean size is about 0.01mm about 3mm extremely, preferably about 0.02mm to 1.5mm, most preferably from about 0.05mm to 1.0mm.When producing with gas phase process, elastomeric particle has core-shell structurre.Promptly inert particle material is introduced in the finished product of synthetic rubber polymer, most inert particle material is concentrated in the shell, and most synthetic rubber polymer is concentrated on the core of particle.The applicant believes that elastomeric core-shell structurre that gas phase is produced is in the mixed refining process and playing sizable effect aspect the serviceability of final products.
Core-the shell structurre of the synthetic rubber particle that gas phase is produced can make the speed of rotor improve, the time of mixing and refining is shortened, even in the more compound of filler, because wettability was poor when accidental and condensing blob of viscose met, do not have the danger that not scattered polymer blocks and the mixed little filler of opening are rolled into a ball.Not the synthetic rubber of pulverizing the briquetting form when married operation begins, but the synthetic rubber that the compacting gas phase is produced.The applicant thinks that this is because its particle size is little and/or it has the cause of core-shell structurre.
In addition, can be slightly (be lower than 49% of the synthetic rubber total amount that adopts in the compound, preferably be lower than 25%) adopt the synthetic rubber of producing with the solution or the suspension method of non-gas phase.The preferred most of or whole synthetic rubber that adopt of the present invention are all produced with gas phase, because this synthetic rubber has the above-mentioned uncommon character of the particle of gas phase production, make it possible to the method according to this invention and mix.For example, liquid component such as oils are absorbed in the gas phase tartan, form single dried solid phase.On the contrary, but do not absorb oils in routine (blob of viscose form) synthetic rubber that the employing suspension and the solution methods of efflorescence are produced, oil remains the liquid in the two-phase mixture, and the synthetic rubber of blob of viscose form then is still the solid in the two-phase mixture.In the method for the invention, the whole synthetic rubber that adopted are most preferably by gas phase polymerization process production, because this can strengthen and simplify compounding process widely.
Other food ingredient.Except the synthetic rubber that gas phase is produced, other raw material of Cai Yonging or food ingredient comprise that filler (particularly carbon black and white filler), oil or plasticizer and vulcanizing system, other additive can comprise antioxidant, antiozonant, activator, plasticizer, thermoplastic polymer, adhesion promotor, homogenizing agent, peptizer, pigment, fire retardant and bactericide etc. in the methods of the invention.
When adopting, filler is selected from silicate of carbon black, silica, atomite, aluminium, magnesium, calcium, sodium and potassium and composition thereof; Carbonate of calcium, magnesium and composition thereof; The oxide of silicon, calcium, zinc, iron, titanium and aluminium; Calcium, barium and plumbous sulfate; Gibbsite; Magnesium hydroxide, P-F, polystyrene and poly-(Alpha-Methyl) styrene resin, natural fiber, synthetic fibers and composition thereof.The silane of organosilan, vinyl three-'beta '-methoxy Ethoxysilane and the γ-isobutene oxygen base propyl group-trimethoxy silanes of sulfuration more than resembling etc.
The plasticizer that can adopt is selected from oil in the method for the invention; Polyalkylbenzene oil; The organic acid monoesters; The organic acid diester; The ethylene glycol diester; Trihemellitic acid three alkane esters; Trialkyl, tri-alkoxy alkyl, alkyl diaryl and triaryl phosphate; Chlorocosanes, vegetable oil, ester and epoxidised derivative thereof; With its mixture.
Antioxidant that can adopt and antiozonant are selected from the two thiophenols of hindered phenol, bis-phenol and benzene; The quinhydrones that replaces; Three (alkyl phenyl) phosphite ester; The dialkyl group thiodipropionate; Nonox; The diphenylamines that replaces; The p-phenylenediamine (PPD) that dialkyl group, alkylaryl and diaryl replace; The p-phenylenediamine (PPD) that dialkyl group, alkylaryl and diaryl replace; The EEDQ of monomer and polymerization; 2-(4-hydroxyl-3,5-Te-Ding is for aniline)-4, two (the octylsulfo)-1,3,5-triazines of 6-; Six hydrogen-1,3,5-three-§-(3,5-two-tertiary butyl-4-hydroxyphenyl) propionyl-in addition-triazine; 2,4,6-three (just-1,4-dimethyl amyl group-p-phenylenediamine (PPD) base)-1,3,5-triazines; Three-(3,5-two-tertiary butyl-4-acrinyl) isocyanuric acid esters; Aminodithioformic acid dibutyl ester nickel; 2-sulfydryl tolyl imidazoles and zinc salt thereof; Pertroleum wax; With its mixture.
When adopting, activator is selected from metal oxide; Aliphatic acid and slaine thereof; Two-, three-and polyethylene glycol; Triethanolamine; With its mixture.
The promoter that Cai Yongs is selected from sulfenamide, thiazole, dithiocarbamate, phosphorodithioate, thiuram, guanidine, xanthate, thiocarbamide, cyano group diamines, caprolactam and composition thereof in the methods of the invention.
The tackifier of Shi Yonging are selected from resin in the method for the invention; Resin acid; Hydrocarbon resin; Fragrance indene resin, phenolic aldehyde methylene donor resin; Thermosetting phenolic resin; Resorcinol-formaldehyde resin; Alkylphenol-formaldehyde resin, for example octyl phenol formaldehyde resin; Coumarone-indene resin; Pine tar; With its mixture.The preferred in the present invention tackifier that use are low-melting tackifier, are being liquid more than 20 ℃, and general fusing point is at 30 °-80 ℃, and making has instantaneous viscosity to bending.These tackifier can increase the belt speed of mill.Can use these tackifier to replace part oil in the prescription, to improve to the viscosity of bending with to the adhesive force of finished product.
The example of the thermoplastic polymer that comprises often in prescription described herein is polyethylene ex hoc genus anne copolymer, for example the copolymer of butylene, propylene, hexene, octene, 4-methyl-1-pentene; Poly function class (functional grades).For example maleate, acrylic acid and methacrylate, acrylonitrile, vinyl acetate and derivative, for example chlorination and polyethylene sulfonation and copolymer; Polypropylene ex hoc genus anne copolymer; Polyacrylic function class, for example maleate, acrylic acid and methacrylate; The modification class (modifiedgrades) of polypropylene and copolymer; The polymer that contains ionic bond; Polyvinyl chloride, its same analog copolymer, function class and modification class; The polymer of acetal, it is with analog copolymer and modification class; The olefin polymer of fluoridizing; Polyvinylidene fluoride, polyvinyl fluoride; Polyamide and modification class thereof; Poly-imines, polyacrylate; Merlon, it is with analog copolymer and modification class; Polyethers; Polyether sulfone; Polypropylene sulfone; Polyketone; Polyimide; Poly-(4-methyl-1-pentene); Polyhenylene and modification class; Polysulfones; The modification class that polyureas alkane is similar with it; The modification class that polyester is similar with it; Polystyrene; Copolymer that it is similar and modification class; Polybutene; Acrylonitrile polymer, polyacrylate and its mixture etc.Wherein polyethylene and its same analog copolymer, the copolymer of butylene, propylene, hexene, octene, 4-methyl-1-pentene for example, poly function class, for example maleate, acrylic acid and methacrylate, acrylonitrile, vinyl acetate and derivative, for example chlorination and polyethylene sulfonation and copolymer; Polypropylene and its same analog copolymer; Polypropylene function class, for example the modification class of maleate, acrylic acid and methacrylate, polypropylene and copolymer; Poly-(vinyl chloride) and its same analog copolymer, function class and modification class; Polyamide and its modification class; The modification class of polyester and common class; Polystyrene, it is with analog copolymer and modification class; The modification class that polyureas alkane is similar with it; The polyester modification class similar with it is preferred.
Sulfuration (slaking) system.The vulcanizing agent that uses for the present invention comprises the compound of sulfur-bearing, for example elementary sulfur, 4,4 '-dithio morpholine, thiuram disulphide and polysulfide, alkyl phenol disulphide and 2-morpholino-two sulfo-benzothiazole; Peroxide, for example two-t-butyl peroxide, tertiary butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-two-(tertiary butyl peroxide) hexane, two-(tertiary butyl peroxy isopropyl base) benzene, tertiary butyl peroxy benzoate and 1,1-two-(tertiary butyl peroxide)-3, the 5-trimethyl-cyclohexane; Collaborative reagent (co-agents) is triallylcyanurate, ethylene glycol dimethacrylate, trimethylol-propane trimethacrylate etc. for example; Metal oxide, for example zinc, magnesium and plumbous oxide; Dinitro compound, para-quinone dioxime and right for example, right '-the dibenzoyl quininie dioxime; With the phenolic resins that comprises methylol or halogenated methyl functional group.Should be appreciated that the mixture that can adopt two kinds or multiple vulcanizing agent in the method for the invention.Any applicability depends on selected synthetic rubber basically in these vulcanizing agents that can use for the present invention or the sulfur agent mixture, and for cooperating the technical staff in field, this is well-known.For the preferred synthetic rubber of the present invention, sulfur-containing compound and peroxide are preferred vulcanizing agents, and sulfur-containing compound is most preferred.100 parts of calculating of synthetic rubber amine in the composition, the consumption of vulcanizing agent can be about 1-10 part (weight).
Mixing program the present invention adopts continuous mill mixing shown in Figure 2, comprising the liquid component by one or more liquid charge pump (1) metering and adding compound or mixture, by one or more batcher (2) metering and adding solid constituent.Solid constituent randomly is transported to funnel (4) by vacuum gas induction system (3) from dispenser.These compositions are put into dry-mixed machine (5) from funnel (4), and synthetic rubber and other required composition that gas phase is produced mix therein, and single composition is evenly distributed in the mixture (6).Synthetic rubber and other required composition preferably begin to mix under the crosslinked temperature to being lower than vulcanizing system in room temperature.
Secondly mixture (6) being added to mill (7) from dry-mixed machine (5) disperses.These compositions scatter in mill equably, and compound composition (8) is made band, sheet or bar.Though can add vulcanizing system in the mill mixing step, preferably it done mixed step adding with other composition.In two roller mills (7), the synthetic rubber composition that preferably includes vulcanizing system is made sheet or band on roller, adopt slit roll to downcut bar (8) from the roll-type mill.Unload the part (8) of downcutting by delivery device (10) from mill, send to the back and further process from film, for example mixing, compressing tablet, molding and/or extrude (11).Adopting another kind of scheme, is that slitting or section (8) are added in second two roller mill (9) that the sizing material mixer is installed again, carries out once more mixing (distributing and dispersion) fully up hill and dale, and obtains continuous mode of operation.See Fig. 2 (9).After unloading film (11) from the roll-type mill, can further in the back first being processed and/or afterwards that it is folding.Other well-known back further processes, and for example can comprise:
A) air cooling adhesive tape and online adding rotation aging machine (rotocure machine) are right
Film carries out continuous ripening;
B) air cooling adhesive tape and online adding flexible pipe extruder;
C) air cooled adhesive tape and film are added comminutor, be extruder or injection-molded preparation
The feed particle.
D) air cooled film is added in the calender, make cladding material and coat coiled material.
The high-speed mixer program.By automatic Weighing, the synthetic rubber that gas phase is produced adds in (at a high speed) dry-mixed machine, to improve the uniformity and the accuracy of compounding process.Eliminate the variation that mixes the inhomogeneous blob of viscose weight that causes.The variation of blob of viscose weight is not only relevant with blob of viscose weight, but also relevant with the accuracy and the frequency of cutting blob of viscose for the required polymer weight of satisfied each batching.The synthetic rubber that adopts gas phase to produce has been got rid of these variablees from compounding process.
Dry mixture according to this method preparation is can be free-pouring, and still can flow freely at least one week, generally the longlyest surpasses six months, depends on the composition of prescription.Dry mixture is preferably by metering these compositions to be added preparation in the high-speed mixer (being also referred to as dry-mixed machine or fluid mixer), and for example Henschel  mixer and Papenmeier  are desirable.Other mixer that is fit to this method can comprise for example Littleford  and L  dige .These compositions can comprise for example carbon black filler; Plasticizer, for example paraffin oil; The synthetic rubber that gas phase is produced, for example EPDM or EPM; Desirable any other optional member (for example pigment, dyestuff, bactericide etc.) and optional slaking (sulfuration) system.
Start the high-speed mixer that mixed composition is housed, under normal temperature (about 20 °-30 ℃),, preferably move about 15s-60s, preferably about 25s-45s at about 450-600rpm at about 300-650rpm.Behind about 30s, the temperature of mixture reaches in the high-speed mixer about 30 ℃.Spinner velocity is increased to about 750-2500rpm, and preferably about 900-1500rpm keeps about 1-2min, preferred about 1 1/2min.When mixture being discharged into the storage funnel, its temperature reaches about 40 ℃.For can free-pouring dried batching, total incorporation time be up to about 5min, preferably about 3min, the about 300-2500rpm of the speed of rotor during this period.Mixture from the optional storage feed bin that is transported to of high-speed mixer, and is entered the inlet duct of air transport device by means of charging device (for example globe valve), or be transported to the roll-type mill by other device.
The mill mixing program preferably can free-pouring dried batching add the mill of at least one bench roller formula from storing funnel in a continuous manner with intermittent mode.At least two mills of preferred in the method for the invention employing, wherein one at sizing material mixer of top installation.Suitable roll-type mill can comprise the mill that for example has good water cooling ability, preferred roller rotating speed and the adjustable mill of installing space.Sizing material mixes function and improves mixing ability, and it can not only cool off or control the temperature of rubber composite and can also improve mixing dispersion and the distribution effect.When adopting second mill, with its uniformity and plasticity that forms continuous mode of operation and in given mixing time, improve compound.Sizing material mixer on second mill top is made up of two spacing deflection rollers identical with mixing roller basically, and they are configured on the mill framework on roller gap and two deflector roll tops that can move forward and backward abreast.
After reaching enough degree of scatter in first mill, rubber just is imported in second mill.After band forms, adhesive tape is cut at once, upwards draw the deflection roller of crossing the sizing material mixer to introduce the gap of this roller from rear side adhesive tape.The deflection roller that is driven guarantees the conveying of adhesive tape.Make adhesive tape distortion and generation evenly with mixing fully by moving forward and backward of deflector roll, do not need operating personnel to do any back work.
Simple rotating drum cutter width on request downcuts film, and deflector roll is delivered to next procedure with adhesive tape, and next procedure may be extruder, calender etc., proceeds the production of final articles for use again.
Preferably in do mixing operation, add sulfuration or slaking system, if or do not comprise this system therein, so just this system is added in out and refines the beginning (ii) of roller procedure of processing.
The friction ratio of roll-type mill is about 0.6: 1-2: 1, preferred about 1.15: 1-1.35: 1.Initial temperature is about 30 °-70 ℃.Temperature about 50 °-70 ℃ can guarantee before roller strap and slaking system (for example promoter) disperse faster.The about 55-85 of temperature of mill finished product compound ℃, back one temperature is corresponding to about 70 ℃ initial temperature, i.e. the composite temperature that mill is made is compared with high about 15 ℃ of beginning temperature.The speed of roller is about 15-22rpm, preferably about 16-20rpm.
When mill mixing, the starting mill does not have roll gap, in case the composition of dry mixture falls down by the gap, and obtains closely knit adhesive tape as quickly as possible.At about 50 °-70 ℃, adopt the dry mixture aliquot or the material amount of appointment, compound is made strip material on the preliminary roller moving faster.In about 3min at the most, preferably in about 2-3min,, make smooth solid preceding roller strap at about 55 °-75 ℃.Disperse to accelerate in order making, when mill mixing processing beginning, to cut band very little, fold, and reinforced once more.In 4-6min, under 60 °-80 ℃, this batch of material is sent into the sizing material mixer then.According to the composition of prescription, under about 60 °-85 ℃, behind about 7-10min, preferably behind about 8-9min, lay down compound.
The granular synthetic rubber that adopts gas phase to produce can provide composition mixing faster and disperse preferably, thereby has shortened mixing time, needs less mixing energy and lower discharge temp.The granular free-pouring form of energy of synthetic rubber that gas phase is produced, industrial automatic gauge and reinforced aspect, technical process is simplified significantly.
Now be incorporated herein all patents of quoting as a reference.
Provide following embodiment just for the present invention is described, rather than as restriction of the present invention.Except as otherwise noted, all consumptions all are percetages by weight.
Embodiment
Carry out three experiments with following method, factory's mill mixing is compound, and the mixing operation of two laboratory mills.
Original formulation is as at table 1, and is listed in 5 and 8.
Table 1 is a kind of typical formulation for covering materials, Shore A hardness 65.
Table 5 is a kind of typical flexible pipe prescriptions, rubber ratio height, Shore A hardness 75.
Table 8 is a kind of typical general purpose section bar prescriptions, proportion of filler height, Shore A hardness 70.
Whole compositions are put into L  dige high-speed mixer, and the theoretical capacity of mixer is 75l, power 30kW under rotating speed 500rpm, power 36kW under rotating speed 1000rpm.The about 0.06-0.08mm of resin particle particle mean size that gas phase is produced.Because in fact dried mixing method is an isothermal, so when having curing agent to exist, the temperature that the temperature of these compositions of maintenance works far below curing agent in mixer.
The food ingredient mixture of the abundant distribution that obtains added in the roll-type mill continuously disperse,, make the film of 3mm under the following conditions,, make the film of 2mm for laboratory mill operation for factory's mill experiment.By the check film strip following character evaluation by the good compound of mill mixing.
Table 1: to the formulation for covering materials of high-speed mixer
The EPDM* 122 that gas phase is produced
Zinc oxide 5
Stearic acid 1
FEF?N-550 1 50
GPF?N-660 2 58
Paraffin oil, Sunpar 2,280 75
Escorez?5320 3 15
Sulphur 1.3
CBS 4 2
MBTS 5 1
Amount to 330.3
The hydrocarbon content 30 of rubber
* the MEGA 6322 that obtains from Union Carbide Corporation, C 2=65%; Ethylidene norbornene (ENB)=2%, carbon black (CB)=22Phr, granular.
1 extrudes furnace black soon
2 general purpose furnace blacks
The aliphatic hydrocarbon resin of 3 hydrogenation
4N-cyclohexyl-2-[4-morpholinodithio base sulfenamide
5 benzothiazole based bisulfides
The gathering that the Mooney viscosity of raw polymer is not assembled itself
ML?1+4-125℃ 95 86
The wet strength of raw polymer
Hygrometric state modulus 50%, MPa 1.5
Hygrometric state modulus 100%, MPa 1.7
Hygrometric state modulus 300%, MPa 2.4
Hygrometric state tensile strength, MPa 7.3
Hygrometric state percentage elongation % 1025 before the fracture
Table 2: the preparation of dry mixture * *
L  dige type high-velocity fluid mixer, capacity 75 l
Time RPM temperature program(me)
00 23 ℃ become carbon black, oil, rubber with other
Divide the mixing roll of packing into
30 " 500 23 ℃ initial
1 ' 30 " 1,000 30 ℃ of raising speed operations 1 ' 30 "
3 ' 00 " 40 ℃ are discharged into the storage funnel
The * dry mixture is can be free-pouring, and the back inspection still can flow freely in a week.
Table 3: factory's mill mixing condition
Mill: size 1500 * 600mm
The sizing material mixer is installed on top
Friction ratio 1.15 to 1
About 50 ℃ of initial temperature
60 °-75 ℃ of the temperature of finished product compound
The thickness 3mm of film or adhesive tape
Table 4: factory's mill mixing program
The time-temperature program
00 30-50 ℃-mill roller does not have the gap makes film thick
Degree is 3mm
-once add the 20kg dry mixture
-compound is wrapped on the preliminary roller
2 ' 00 " 40-60 ℃-make smooth solid preceding roller strap
-it can be disperseed, cut very carefully
5 ' 00 " 50-70 ℃-deliver on the sizing material mixer in batches
8 ' 00 " 60-75 ℃-draw off
Table 5: to the cooling tube prescription (rubber ratio height) of high-speed mixer
The EPDM* 119 that gas phase is produced
Zinc oxide 5
Stearic acid 1
FEF?N-550 101
Paraffin oil, Sunpar 2,280 60
Sulphur (95%) 0.5
ZDBC 1 2
ZDMC 2 2
DTDM 3 0.6
Amount to 291.1
The hydrocarbon content 34 of rubber
* MEGA 7265 C that obtain from Union Carbide Corporation 2=70%; Ethylidene norbornene (ENB)=4.5%, carbon black (CB)=19 phr, granular
1 zinc dibutyl dithiocarbamate
2 PZs
34,4 '-the sulfo-dimorpholine
The gathering that the Mooney viscosity of raw polymer is not assembled itself
ML?1+4-125℃ 90 79
The wet strength of raw polymer
Hygrometric state modulus 50%, MPa 2.5
Wet 1 morphotype amount 100%, MPa 3.3
Hygrometric state modulus 300%, MPa 5.8
Hygrometric state tensile strength, MPa 11.3
Hygrometric state percentage elongation % 625 before the fracture
Table 6: laboratory mill mixing condition/rubber ratio height
Mill: size 320 * 150mm
Friction ratio 1.25 to 1
About 70 ℃ of initial temperature
73 °-75 ℃ of the temperature of finished product compound
The thickness 2mm of film or adhesive tape
Table 7: laboratory mill mixing program
The time-temperature program
00 70 ℃-mill roller does not have the gap, makes film
Thickness is 2mm
-once add the 400kg dry mixture
1 ' 30 " 70 ℃-compound wraps on the preliminary roller
3 ' 00 " 75 ℃-compound fully mixing (not cutting)
Unload compound from mill
Table 8: to the general service section bar prescription (proportion of filler height) of high-speed mixer
The EPDM* 119 that gas phase is produced
Zinc oxide 5
Stearic acid 1
FEF?N-550 151
Paraffin oil, Sunpar 2,280 120
Sulphur (95%) 0.5
ZDBC 2
ZDMC 2
DTDM 0.6
Amount to 401.1
The hydrocarbon content of rubber, % 25
* MEGA 7265 C that obtain from Union Carbide Corporation 2=70%; Ethylidene norbornene (ENB)=4.5%, carbon black (CB)=19 phr, granular
The gathering that the Mooney viscosity of raw polymer is not assembled itself
M?1+4-125℃ 90 79
The wet strength of raw polymer
Hygrometric state modulus 50%, MPa 2.5
Hygrometric state modulus 100%, MPa 3.3
Hygrometric state modulus 300%, MPa 5.8
Hygrometric state tensile strength, MPa 11.3
Hygrometric state percentage elongation before the fracture, % 625
Table 9: laboratory mill mixing condition/general purpose section bar/proportion of filler height
Mill: size 320 * 150mm
Friction ratio 1.25 to 1
50 ℃ of initial temperatures
53 °-55 ℃ of the temperature of finished product compound
The thickness 2mm of film or adhesive tape
Table 10: laboratory mill mixing program/general purpose section bar/proportion of filler height
The time-temperature program
00 50 ℃-mill roller does not have the gap, makes film
Thickness is 2mm
-once add the 400kg dry mixture
45 " 52 ℃-compound wraps on the preliminary roller
2 ' 15 " 55 ℃-compound fully mixing (not cutting)
Unload compound from mill
The result.The Shore A hardness of cladding material compound is 65.Doing earlier and mix, carry out the mill mixing of plant layout then, is a dustless operation.In the refining step, doing the loose free-pouring composition of energy of batching, with dry mixture composition minimum in the mill dish in mill roller gap by after once, form film in moment immediately.In the roll-type mill, after compound begins to leave preliminary roller and removes the back roller, in about 2min, just at rotating speed closely knit compound band appears faster on the preliminary roller, and operation also is like this on the contrary.Those skilled in the art will readily appreciate that, in the procedure of processing afterwards, for example mixing at sizing material, adhesive tape added second mill or air cooled adhesive tape added in the charging box and/or the calender of then processing and extruder online reinforced in, preliminary roller processing is important.
Average dispersion (fully mixing) time is about 5min.Sizing material mixes about 3min of (thoroughly mixing) time.The even peptizaiton of resulting all mixing compositions that comprise curing agent is equally matched with the banburying that the synthetic rubber of blob of viscose form up to now adopts.Whole operations of this method do not have the scorching phenomenon.The present invention is that downstream processing (for example extrude, calendering and molding) for next step is got ready with the compound of mill mixing in about 8min altogether.The physical property of the compound of the inventive method refining is equally matched or better with the physical property that the conventional banburying that synthetic rubber to the blob of viscose form adopts obtains.
With mill mixing Shore A hardness is that 75 typical cooling tube prescription (rubber ratio height) and Shore hardness are that the laboratory scale of 70 typical general purpose section bar prescription (proportion of filler height) experiment showed, that the dry mixture of the EPDM that produces based on gas phase disperses soon.The particle mean size of particle is 0.6-0.8mm, and these particles are partly used 15-25phr carbon black " wetting ", depend on the composition of polymer.The employing gas phase process can be produced this uncommon structure (core-shell) and make it take place to interact fully, and does not cause shearing, heat and over time mixing.Because carbon black in the skin of polymer beads, has the effect of " planting brilliant " so expect the surface of wetting in advance EPDM particle.In addition, when adopting this uncommon core-shell particle in prescription, the total amount of the loose carbon black filler that prescription needs is less, thereby this has quickened the mixing of these compositions again.Infer that also the carbon black that is enriched in the granular resin particle shell can give polymer beads a kind of polarity, thereby loose carbon black in the easier attraction prescription, mixing process strengthened.This form impels the whole distribution of formula components to accelerate, and will the danger of composition segregation reduce to minimum in the dry mixture storage process that is preparing before the mill mixing.
Low and the oil/filler of rubber content sees Table 8 than some prescriptions of high (proportion of filler height), adds 50 ℃ of preferred initial temperatures in man-hour with mill, to obtain the low temperature wet strength, prevents expansion (bagging).
Yet the prescription that rubber content is high (rubber ratio height) sees Table 5, process with mill under the initial temperature that Ying Zaiyue is 70 ℃, so that make full use of the thermal softening effect of ethene composition, along with the increase of viscosity own, obtain non-solid compound, help mill to make band quickly.

Claims (10)

1. compounding process, this method comprise that with at least a coming out from reactor of mill mixing be exactly synthetic rubber, one or more adding ingredients and optional vulcanizing agent with granular production, and draw off mixture from mill.
2. the compounding process of claim 1, this method comprises that synthetic rubber, one or more food ingredients and optional vulcanizing system that (i) produces at least a gas phase add in the high-speed mixer, mix at normal temperatures, synthetic rubber, food ingredient and the vulcanizing system when adopting vulcanizing system are evenly distributed in the dry mixture; (ii) equally distributed dry mixture is sent in the roll-type mill then, made the compound of dispersion; (iii) the compound that disperses is cut into slices or bar, draw off from the roll-type mill.
3. the compounding process of claim 2 wherein adds vulcanizing system in doing mixed step (i).
4. the compounding process of claim 2, wherein roll-type mill mixing step (ii) begin to add vulcanizing system.
5. the compounding process of claim 2, wherein the synthetic rubber produced of gas phase is selected from polyisoprene, polybutadiene, polychloroprene, poly-(styrene-butadiene) rubber, ethylene-propylene rubber, ethylene-propylene dience rubber and composition thereof; Food ingredient is selected from oil or plasticizer, carbon black, white filler and composition thereof; Vulcanizing system is selected from compound, per-compound of sulfur-bearing and composition thereof; One or more optional promoter and optional anticorrosive and activator.
6. the compounding process of claim 2, wherein the gas phase elastomeric particle mean size of producing is about 0.01mm about 3mm extremely.
7. the compounding process of claim 2, wherein this method is a kind of continuous method.
8. the compounding process of claim 3, wherein synthetic rubber, food ingredient and vulcanizing system mix 2-5min at normal temperatures in high-speed mixer, spinner velocity is 300-2500rpm, compound is delivered in the roll-type mill then, and imposing a condition of mill is as follows:
About 30 °-70 ℃ of temperature
Friction ratio about 1.35: 1-1.15: 1
The about 2-6mm of roll spacing
The about 15-22rpm of roller rotating speed
About 5min to 15min of the holdup time of mill.
9. the compounding process of claim 2 wherein adds dry mixture in the roll-type mill by the weight metering proportioner, also to wherein adding low-melting tackifier, increases the speed of mill adhesive tape.
10. the compounding process of claim 2 wherein is added to step section or slitting (iii) in second roll-type mill that the sizing material mixer is installed.
CN98806830A 1997-05-02 1998-05-01 Mill mixing process for compounding gas-phase produced elastomers Pending CN1261843A (en)

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CN106217672A (en) * 2016-08-16 2016-12-14 海宁海橡鞋材有限公司 The mixing equipment of sheet imitated by a kind of footwear material

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HUP0003390A2 (en) 2001-06-28
AU7174698A (en) 1998-11-27
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KR20010012161A (en) 2001-02-15
CA2288889A1 (en) 1998-11-12
EP0979161A1 (en) 2000-02-16
WO1998050210A1 (en) 1998-11-12
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TR199902687T2 (en) 2000-06-21
ZA983741B (en) 1998-11-24

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