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CN1189514A - Process for preparing elastomeric compounds from granular elastomers and polymers and articles manufacturing therefrom - Google Patents

Process for preparing elastomeric compounds from granular elastomers and polymers and articles manufacturing therefrom Download PDF

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Publication number
CN1189514A
CN1189514A CN96123319A CN96123319A CN1189514A CN 1189514 A CN1189514 A CN 1189514A CN 96123319 A CN96123319 A CN 96123319A CN 96123319 A CN96123319 A CN 96123319A CN 1189514 A CN1189514 A CN 1189514A
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CN
China
Prior art keywords
multipolymer
modification product
relevant
polymkeric substance
mixing device
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN96123319A
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Chinese (zh)
Inventor
R·J·N·伯尼尔
E·T·伊塔利尔安德
A·U·佩利斯
B·R·罗森布拉特
L·S·斯卡罗拉
A·森
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Union Carbide Chemicals and Plastics Technology LLC
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Union Carbide Chemicals and Plastics Technology LLC
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Priority to CN96123319A priority Critical patent/CN1189514A/en
Publication of CN1189514A publication Critical patent/CN1189514A/en
Pending legal-status Critical Current

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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
    • B29B7/74—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
    • B29B7/02—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
    • B29B7/30—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
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • B29B7/482—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws provided with screw parts in addition to other mixing parts, e.g. paddles, gears, discs
    • B29B7/483—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws provided with screw parts in addition to other mixing parts, e.g. paddles, gears, discs the other mixing parts being discs perpendicular to the screw axis
    • 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
    • B29B7/7485—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
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/94—Liquid charges

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The present invention provides a continuous process for compounding one or more polymers and finished articles thereof. The process comprises continuously feeding at least one granular elastomer optionally with one or more thermoplastic polymers having average particle sizes of about 5mm or smaller and with optionally one or more additives to a continuous mixer where the components are masticated and melted into a compound and pumping said compound through an orifice or die.

Description

By the method for granular elastomer and polymer manufacture elastomeric compounds and by the goods of its manufacturing
The present invention relates to prepare by granular elastomer and other continuation method of the compound formed of elastomerics and thermoplastic polymer arbitrarily.The invention still further relates to the goods of producing by the compound of preparation by this method.
Elastomerics, particularly with the elastomerics of packetized form, needing progressively, the course of processing enters end article.The discontinuity of process is the good mutual dissemination of pulverizing the packing part or be pressed into the spherical various compositions that reach elastomerics and use among a small circle in the prescription of compound owing to needing.The existing blending means general using that elastomerics becomes the product of making by filling a prescription fully has single or for example tangential (Banbury mixer) mixing tank of two stage mixing step batch mixers or batch mixer.In one step, be lower than 115 ℃ stacking a temperature, interior, for example rubber, carbon black, white filler, softening agent and other solids or fluid additive join in the mixing tank all mixing elements together with solidifying agent.For two stage mixing steps, in the fs, for example carbon black filler, softening agent and other solids or fluid additive add and form uniform melting mixing and dispersive composition in the mixing tank various compositions.Under about 140 ℃ to 160 ℃ or higher storage temperature, mix for the composition that comprises thermoplastic polymer.Then the blended batch of material is discharged on two roller mills, or in the extrusion machine and make tabular, sheet or granular.In subordinate phase, compound is delivered in second mixing tank.For vulcanizable composition, avoid their activation to cause too early crosslinked of elastic composition thereby in this stage, under the storage temperature that keeps below 115 ℃, add solidifying agent.For comprising thermoplastic polymer or requiring the higher processing temperature of composition needs of solid cure.This compound is dumped into is shaped to the intermediates form on the processing units for future use or be shaped to the final form of end article.
The continuous equipment complex of the tradition of the typical heat plastic working that this area is familiar with is twin-screw extruder (Werner ﹠amp for example; Pfleiderer, Berstorff, or the like) and continuous mixing device (Farrel, KobeSteel, Japan Steel, or the like) can be used to replace batch mixer sometimes.Yet these devices need to use carries the unrestricted flow composition continuously, and the packing rubber of traditional form is not suitable for this purposes.Equally, because their limited availability and grinding and elastomerics keep the expense of free-flowing when selecting desired performance, ban use of traditional continuous mixing device for traditional rubber of powder-form.
All these traditional complex methods have mixing process and the relevant shortcoming of operational example as handling, mixing and store the complicacy of starting material and work in-process and middle formulation product.These methods are effort and big energy-consuming and need a large amount of investments on processing unitss, have therefore increased the cost of the finished product greatly.
In view of the situation of present this area production of articles, its at least a elastomerics is combined into final compound, and a kind of with traditional method is compared and reduced labor force and cost of energy and be applicable to that the method for the industrialness product of entire area obviously is useful.
The invention provides a kind of continuation method of compound one or more polymkeric substance, comprising: (i) with at least a granular elastomer with any one or multiple thermoplastic polymer and with any one or multiple additives to feeding in the continuous mixing device; (ii) when said granular elastomer and said any thermoplastic polymer and said any additive were present in the said continuous mixing device, mastication formed compound; (iii) the said compound following current of pumping is arrived said continuous mixing device afterbody by mould.
In addition, also provide the method for compound one or more polymkeric substance continuously, comprising: (i) in mixing vessel, at least a granular elastomer is mixed to form mixture with any one or multiple additives with any one or multiple thermoplastic polymer; (ii) continuously this mixture is fed in the continuous mixing device together with this any thermoplastic polymer and additive; (iii) the said mixture of mastication forms compound; (iv) the said compound following current of pumping is by the afterbody of mould to said continuous mixing device.Use granular, goods that the unrestricted flow polymkeric substance is made and the resin that in gas phase polymerization, produces that improvement and advantages different end-uses and performance are arranged according to this method.
Fig. 1 is continuously rubber combined sketch.In the figure, component of the present invention and step have been represented.Feeder (a) feeding solids component by gravity or volume design adds liquid component with volume pump (b).This mixture is admitted in the premixed device, and this premixed device can be for example Littleford of successive type High-speed steel type mixing tank (c) or batch mixer be Henschel for example Mixing tank, in this case, can be at Henschel The mixture that is metered into continuous mixing device of an additional feeder of suit after the mixing tank.By nozzle (d) sprinkling oil and make its atomizing.After mixing 1 to 5 minute, mixture is sent in the continuous mixing device (e).As required, additional oil is for example located to be sprayed in the continuous mixing device at (f).As required, temperature-control device (g) is used for cylindrical shell (i) and rotator (j).This mixture of mastication and melting mixing, and by discharge port (k) eliminating volatile matter.By moulding mould (l) blended extruded polymer forming shape or granular.Finish sulfuration by heating means (m) heating or radiation forming mould.On the other hand, the sulfuration admixture can directly spray in the continuous mixing device (e).
Nearest patent is U.S. Patent number 4994534 for example; 5304588; 5317036 and 5453471 disclose the production of elastomeric polymer in the gas phase of sulfuration bed bioreactor.According to traditional, comprise and induce concentrated pattern (U.S. Patent number 4543399; 4588790; 5352749 and 5462999) and liquid monomer pattern (U.S. Patent number 5453471; PCT95/09826 and PCT95/09827) spissated method carry out gas phase polymerization.The elastomerics of being produced by these methods is unrestricted flow and has mean particle size and approximately reach 5mm, and preferably approximately reaches 2mm or littler and most preferably about 1mm or littler granular.These elastomeric polymers are usually and preferably when the sticking temperature of the polymkeric substance that uses one or more inert particle material produce or softening temperature or polymerization when above.The inert particle material is referred to as vulcanization aid sometimes, and is open and comprise carbon black, silica, clay, talcum and composition thereof in U.S. Patent number 4994534.In these materials, preferred carbon black, silica and composition thereof, carbon black is most preferred inert particulate materials.
Granular, the free-pouring polymkeric substance of producing in gas phase when being higher than the softening temperature of polymeric articles under the condition that inert particulate materials exists is unique and is different from by powdery that industry solution/batch polymerization reaction is produced, granular, chip or spherical rubber, the gas phase polymer product has the form of center housing, wherein inert particulate materials mixes in the polymkeric substance, and a large amount of inert particulate materials concentrate on the granular form of the unrestricted flow with wide region comonomer composition and molecular weight is provided on the housing.On the contrary, even filler is added in traditional fragmental material of foregoing description, it also only provides physical mixture and dedusting.Completely contradict with non-gas phase rubber, for example the same with use ground tire, the gas phase that crumb rubber of the present invention (for example granular EPDM, EPM and BR product) is produced can become the untreated rubber component in the ordinary rubber compound fully but also can vulcanize or the peroxide cure effect.
As follows according to granular, the free-pouring elastomeric illustration that the present invention makes in gas phase process that can be processed:
IR (polyisoprene)
BR (polyhutadiene)
SBR (divinyl and styrene copolymerized polymkeric substance)
Nitrile (polymkeric substance of divinyl and acrylonitrile compolymer)
Butyl (polymkeric substance of iso-butylene and isoprene copolymer)
EPM (polymkeric substance of ethene and copolymerization of propylene)
EPDM (ethene and propylene and diene such as hexadiene, Dicyclopentadiene (DCPD) or ethylidene norborneol)
Ethene and C 3-C 12The multipolymer of alpha-olefins
Ethene, alpha-olefins (C 3-C 12) and diene (preferably unconjugated) terpolymer
Neoprene (chloroprene rubber)
Silicone (polyxylene siloxanes)
The multipolymer of ethene and vinyltrimethoxy silane
The multipolymer of ethene and one or more vinyl cyanide, maleic acid ester, vinyl-acetic ester, vinylformic acid and methacrylic ester or the like
The multipolymer of divinyl and isoprene
Polystyrene
The ter-polymers of vinylbenzene, divinyl and isoprene
Chlorobutyl rubber (fluorinated copolymers of iso-butylene and isoprene)
Brombutyl rubber (brominated copolymer of iso-butylene and isoprene)
The brominated copolymer of iso-butylene and p-methylstyrene
Chlorination and chlorine-sulfonated polyethylene
In these materials, preferred polyisoprene, chloroprene, poly-(styrene butadiene) rubber, ethylene-propylene rubber (EPM) and ethylene-propylene elastoprene (EPDM).Also can compound continuously quadripolymer according to method described herein according to WO96/11960 and WO96/12744.
Implementing method of the present invention comprises at least a granular elastomer is sent into continuous mixing device with the various thermoplasticity and the admixture material of the prescription of forming final composition.This mixing tank is a processing units, and mastication and break-up shot gonosome and admixture form compound therein.Though almost any processing units can this composition of mastication, preferably continuous mixing device such as Farrel ' s FCM Or the like, or twin screw recombiner or extrusion machine such as Werner and Pfleiderer ' sZSk Series or the like, planetary or Berstorff Mixing tank, or on cylindrical shell with or without the single-screw extrusion machine of bolt as by Davis Standard Provide, or axially reciprocal rotary screw such as Buss-Condux Type.General and preferred extrusion machine has and comprises the two rotators of a single rotator, or single and cylindrical shell of two rotator blended.Especially, this cylindrical shell has one or more spouts and any one or a plurality of relief outlet of arranging along its length direction.Can be separately or add various elastomericss, thermoplastic polymer and admixture together by relief outlet.When using one or more rotators, the preferred use is no more than two.Then, the compound by orifice plate or this mastication of mould pumping.Usually, orifice plate is that a kind of being used for is shaped to intermediate shape to compound for future use or be shaped to the mould of end article form.Continuous mixing device is usually designed to the direct pumping of a compound and passes through mould.On the other hand, it also can be by sending into single-screw extrusion machine, two or twin-screw extruder to the compound of mastication continuously, or the continuous mixing device of Melting pump is additionally finished.Certainly granular elastomer and the feeding of other thermoplastic materials of admixture and/or composition can be along mixing tank, pumping extrusion machine arbitrarily, on the unlikely position of Melting pump, by on one or more positions of mixing tank or add this material along extrusion machine by opening, discharge or relief outlet and act on simultaneously.
In another scheme of the present invention, at least a granular elastomer is sent into mixing tank continuously with the part or all of additive of one or more granular thermoplastic polymers and composition.The size of particles of these polymkeric substance is approximately 5mm or littler, preferred 2mm or littler and 1mm or littler most preferably.Usually, thermoplastic polymer it is characterized in that not relying on by some admixtures for example the corsslinking molecular net under most of elastomeric situations maintain the ability of the final service performance of dress of usefulness.
The example of thermoplastic polymer is polyethylene and relevant multipolymer thereof for example butylene, propylene, hexene, octene, 4 methyl 1 pentene copolymer; Poly functionalized products is for example chlorination and sulfonated polyethylene and multipolymer of maleic acid ester, vinylformic acid and methacrylic ester, vinyl cyanide, vinyl-acetic ester and derivative for example; Polypropylene and relevant multipolymer thereof; Polyacrylic functionalized products is maleic acid ester, vinylformic acid and methacrylic ester for example; The modification product of polypropylene and multipolymer; Ionomer; Polyvinyl chloride and relevant multipolymer thereof, functionalized and modification product acetal copolymer and related copolymers and modification product; Fluoridize the olefin polymerization thing; Poly-difluoroethylene; Fluorinated ethylene propylene; Polymeric amide and modification product thereof; Polyimide; Polyarylate; Polycarbonate and relevant multipolymer and modification product thereof; Polyethers; Polyethersulfone; Polyaryl sulfone; Polyketone; Polyetheramides; Poly-(4-ethyl-1-amylene); Polyphenylene and modification product; Polysulfones; Polyurethane and relevant modification product thereof; Polyester and relevant modification product thereof; Polystyrene and relevant multipolymer and modification product thereof; Polybutene; The polymkeric substance of vinyl cyanide, polyarylate, and composition thereof or the like.In the middle of these materials, preferably polyethylene and relevant multipolymer thereof be polyethylene for example chlorination and the sulfurized polyethylene and the multipolymer of maleic acid ester, vinylformic acid and methacrylic ester, vinyl cyanide, vinyl-acetic ester and derivative for example of butylene, propylene, hexene, octene, 4 methyl 1 pentene copolymer, functionalized products for example; Polypropylene and relevant multipolymer thereof, polyacrylic functionalized products be the modification product of maleic acid ester, vinylformic acid and methacrylic ester, polypropylene and multipolymer for example; Poly-(vinylchlorid) and relevant multipolymer, functionalized and modification product thereof; Polymeric amide and modification product thereof; Polyester and relevant modification product thereof; Polystyrene and relevant multipolymer and modification product thereof; Polyurethane and relevant modification product thereof; Polyester and relevant modification product thereof are preferred.
If certainly in fact they are different aspect some of molecular structure, the method according to this invention blended elastomerics is not distinct on chemical property.For example, they in fact can be identical elastomerics or their the corresponding amount of monomer of composition or the ratio difference that are in fact comprised in the differing molecular magnitude at two kinds.Effective equally when using thermoplastic polymer.
Another scheme of the present invention is mixed mutually with any one or multiple polymers by at least a granular elastomer and is formed.Preferably, mixture also comprises some or all of other composite partss or admixture except comprising polymkeric substance.The method of the physical mixed granular solids that some are traditional is for example rotated in cylinder or is stirred, and can be used for preparing this mixture.With the operation of pattern in batches or continuously mixing vessel.Then, this mixture is sent into continuous mixing device continuously, is compound at this this mixture mastication.Certainly, this mixture is made up of the component of two kinds of compositions at least.Being not included in admixture in the mixture (promptly feeds the position of mixture) with polymkeric substance in identical position or is sent in the mixing tank continuously by opening or relief outlet in other the suitable position along mixing tank, pumping screw rod or Melting pump.
The composition of indication or admixture are to be selected from filler, softening agent, antioxidant and antiozonidate, activator, promotor, tackifier, levelling agent, peptizer, pigment, fire retardant, processing material for example vulcanized vegetable oil (Fatice) and sterilant arbitrarily in the present invention.
The filler of Shi Yonging comprises carbon black in the present invention; Silicate of aluminium, magnesium, calcium, sodium, potassium and composition thereof; Carbonate of calcium, magnesium and composition thereof; The oxide compound of silicon, calcium, zinc, iron, titanium and aluminium; Calcium, barium and plumbous vitriol; Alumina trihydrate; Magnesium hydroxide; P-F; Polystyrene; With poly-(α methyl) styrene resin; Natural fiber; Synthon; Or the like.
The softening agent of Shi Yonging comprises oil for example ASTM D2226 aromatic oil, naphthenic oil and paraffin oil in the present invention; Polyoxyethylene alkylphenyl oil; The organic acid monoesters is the oleic acid ester and the stearate of alkyl and alkoxyalkyl for example; The organic acid dibasic acid esters is phthalic ester, terephthalate, sebate, adipic acid ester and the glutarate of dialkyl group, dialkoxy alkyl and alkylaryl for example; Diethylene glycol dilaurate for example three-, four-and polyethylene glycol two alkanoatess; Three benzene hexacarboxylic acid trialkyl esters; Trialkyl, tri-alkoxy alkyl, alkyl diaryl and triarylated phosphoric acid ester; Chlorinated paraffinic oil; Coumarone-indene resin; Stockholm tar; Vegetables oil is Viscotrol C, oil slick, rapeseed oil and soya-bean oil and ester and epoxidised derivative thereof or the like for example.
Antioxidant of Shi Yonging and antiozonidate comprise hindered phenol, bis-phenol and thiobisphenol in the present invention; Replace Resorcinol; Three (alkyl phenyl) sulphite; The dialkyl group thiodipropionate; Phenyl naphthyl amines; Substituted diphenylamine; Dialkyl group, alkaryl and diaryl replace p-phenylenediamine; Monomer and polymerization dihydroquinoline; 2-(4-hydroxyl-3,5-t-butylaniline)-4, two (octylsulfo)-1,3 of 6-, the 5-triazine, hexahydro--1,3,5-three-β-(3,5-two-t-butyl-4-hydroxyphenyl) propionyl-sym-triazine, 2,4,6-three (n-1,4-dimethyl amyl group-p-phenylenediamine)-1,3, the 5-triazine, three-(3,5-two-t-butyl-4-hydroxyl-phenmethyl) chlorinated isocyanurates, dibutyl dithio first propylhomoserin nickel, 2-mereaptol phenmethyl imidazoles and its zinc salt, oil is cured or the like.
Other any admixtures that the present invention uses comprise activator, and (metal oxide is zinc, calcium, magnesium, cadmium and plumbous oxide compound for example; Lipid acid is stearic acid, lauric acid, oleic acid, mountain Yu's acid and palmitinic acid and their zinc, copper, cadmium and lead salt for example; Two-, three-and polyethylene glycol; Trolamine); Promotor (sulfinyl amine is the benzothiazole sulfinyl amine for example, comprises two-benzothiazole sulfinyl amine and thiocarbamyl sulfinyl amine, thiazole, dithio carbamate, phosphorodithioate, thiuram, guanidine, xanthate, thiocarbamide and their mixture thereof); Tackifier (rosin and sylvic acid, hydrocarbon resin, fragrant indene resin, phenolic aldehyde methylene donor resin and thermosetting phenolic resin, resorcinol formaldehyde resin and alkyl phenolic resin be the octyl phenol urea formaldehyde for example); Levelling agent, softening agent, pigment, fire retardant, sterilant, functionalized polymeric (Malaysia EPM, EPDM, polyethylene and polypropylene) or the like.The total amount of preferred admixture changes in the scope of 40 to 800 parts (weight) based on 100 parts of elastomericss in the composition.
The compound that the vulcanizing agent that uses among the present invention comprises sulfur-bearing is elementary sulfur for example, 4,4 '-dithio morpholine, two-and many sulfuration tetraalkyl thiurams, curing alkylphenol and 2-morpholide-dithio benzothiazoles; Superoxide is two-tert-butyl peroxide for example, tert butyl isopropyl benzene peroxide, the diisopropylbenzyl superoxide, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, two-(t-butyl peroxy sec.-propyl) benzene, t-butyl peroxy benzoic ether and 1,1-two-(t-butyl peroxy)-3,3, the 5-trimethyl-cyclohexane; Metal oxide is zinc, magnesium and plumbous oxide compound for example; The dinitroso compound is para-quinone dioxime and p for example, p '-dibenzoyl quininie dioxime; With the resol that comprises hydroxymethyl or monochloromethyl functional group.Certainly can use the mixture of two or more vulcanizing agents in the method for the invention.The suitability of the mixture of any vulcanizing agent of Shi Yonging or vulcanizing agent depends on elastomeric selection largely in the present invention, and this technician for chemical field knows.For preferred elastomer of the present invention, the compound of sulfur-bearing and superoxide are preferred vulcanizing agents, and the compound of sulfur-bearing is most preferred.The quantity of vulcanizing agent can change in the scope of 1 to 10 part (weight) based on 100 parts of elastomericss in the composition.
The curing temperature and the time of using are typical.Employed temperature is approximately 250 °F-400 °F, and the time is approximately 1-60 minute.Final composition polymer product of producing by the present invention in continuous mixing device camber sulfuration or at least a composition (granular elastomer, thermoplastic polymer or admixture) that comprises composite prod.
The present invention is specially adapted to produce for example roof membrane of sulfurized EPDM goods, sealing and wind erosion bar, the sebific duct and the inner tube of a tyre, and moldings.Usually be referred to as aspect the thermoplastic elastomer of TPE in preparation, the dispersity of rubber phase is crucial for the performance of resultant composition in thermoplastic matrix here, and the present invention has very big advantage.The embodiment of TPE is impact-resistant modified polypropene and multipolymer, impact-resistant modified polyester, impact-resistant modified polyamine and impact-resistant modified polyurethane class.Same the present invention also can prepare the solid cure thermoplastic elastomer that its characteristics are the vulcanized rubber phase.The solid cure thermoplastics is referred to as the embodiment of TPV usually, is for example Santoprene of EPDM and polypropylene Mixture, EPDM and polyethylene be Sarlink for example Mixture, or disperse phase is that vulcanized rubber and external phase are the mixtures of other combinations of thermoplastics.
The present invention also is applicable to the manufacturing of the sidewall of being made up of EPDM and one or more height unsaturated elastic body (for example BR, SBR and IR) mixture.Granular mixing in the inventive method or premix elastomerics are that the granular mixing or the premix elastomerics that enter in the energy collecting mastication process of energy-intensive are decentralized very highly mutually than the elastomeric advantage of tradition packing.Therefore, if elastomerics enters the mastication process with traditional packetized form, compare with it so need be quite few mastication just can reach the desired high dispersingization of optimum performance.Like this, compare, at short notice with less polymer degradation, can be mixed into highly mutual dispersive elastomerics to gas phase, unrestricted flow, granular, mixing or premix elastomerics with tradition packing elastomerics.
Can be according to the elastomer compounds of the special preparation of method of the present invention preparation by the mould extrusion production goods rectangular sizing material of tree lace for example, the tyre bead filler component of sidewall and Pneumatic tyre, or be used for producing the thin plate of storage gas back boxing.Can be pressed into textiles or steel wire fiber by wheel according to elastomer compounds of other special preparations of the present invention preparation and produce the endless belt component that the line of cover tire is strengthened thin plate and tire.
Here all patents of quoting are introduced for your guidance hereby.
The present invention is described for the embodiment appear and is not limitation of the present invention.Except as otherwise noted, quantity is meant weight percentage.EXAMPLE Example 1
This embodiment illustrates preferred being fit to the EPDM of granular form and admixture and the continuous compound processing units of filler.At 50hp Henschel Except oil, mix the component of the compound prescription of table 1 expression in the FM 200C mixing tank.When mixing element, heated oil also is sprayed into pre-mixing in the mixing tank.Resulting pre-composition is sent in the various equipment complex described below continuously.Though prepare pre-composition with batch mode, but the further automatization of feeding procedure is possible and easily shown in Fig. 1 diagram, solids component granular elastomer for example wherein, thermoplastic resin arbitrarily, filler and admixture are sent among the mixing tank C continuously by gravimetric feeder A.In particular cases this, list the liquid ingredient in the compound prescription in, for example oil mixes in the mixing tank by nozzle D via pump B.Any second nozzle F can be used to send into liquid ingredient directly in recombiner along separate routes.
The compound premixing thing is proved to be at single-screw extrusion machine Werner continuously And Pfleiderer Twin screw rotates inner engagement extrusion machine and Pomini jointly Twin screw, non-inner engagement is possible in the counter-rotating mixing tank.The screw-type of every kind of machine is provided in table 2.Illustrate that the useful important parameter of the present invention is final storage temperature and dispersive quality.The outlet temperature of compound need be for fear of the too early activation of solidifying agent like this and the dispersity of composition is to reach the key of solidifying physical property.As shown in table 2, finish drilling in this condition and to make compound equipment, when disperse to be better than or equal in the compound of same batch mixing, to obtain the time, under this condition, produce the useful compound of making end article.The table 1 compound formulas component % purposes supplier EPDM granular Carbide of 38.5 gas phase Union60Mooney (ML1+4@125C) EPDM rubber UNIPOL TM33%C32%ENBN-650 carbon black 31.O filler ColumbianSUNPAR-2280 27.5 handling oil R.E CarrollKADOX-902 zinc oxide 1.4 activator R.E Carroll stearic acid 0.3 activator HarwickTBBS 0.7 captax onsantoTMTD 0.3 promoter Vanderbilt sulphur 0.3 vulcanizing agent adds up to 100.0 table 2 tables of equipment screw rods1The twin screw rotation 2The two spiral shells of ZSK-53 32451b/ hour 50lb/ hour 40lb/ hour speed of rotation 10rpm 40rpm of bar counter-rotating LCM-50 rate of feeding 54rpm barrel zone temperature------80 ℃ of 118 ℃ of squeeze 77amps--------88 ℃ 111 ℃ 115 ℃ of----combined temps 1. single-screw extrusion machine:
Feeding part: 7.94 " OD, 8 " pitch, 3.375L/D, the compression screw thread root diameter afterbody by the pressure zone is from 7 " dropping to 3.5 ".
Press member: 1L/D
Metering section: 4.49 " OD, 4.5 " pitch, 4.5l/d, 0.493 " groove depth. 2. twin-screw rotates ZSK-53 3-LOBE extruder jointly: the nominal screw diameter: the 53mm screw part is described: #OF pitch (mm) length (mm) unit type 1 45 45 SPACER1 90SK 45 CONVEYING UNDERCUT FLIGHT2 60 180 CONVEYING2 45 30 CONVEYING1 5 * 11 RHKB 60 KNEADING BLOCK; RIGHT HAND2 5 * 5 RHKB 30 KNEADING BLOCK; RIGHT HAND1 5 * 5 LHKB 30 KNEADING BLOCK, LEFT HAND1 90 30 CONVEYING1 3/1 30 TRANSITION2 60SF 6 SINGLE FLIGHT CONVEYING3. twin screw counter-rotating LCM-50: nominal thread diameter: 50mm embodiment 2
It is in order to make them have more weather resistance that elastomerics usually is combined into firm thermoplastics.These mixtures are because the elastomerics that has as discontinuous disperse phase generally is rich in thermoplasticity.The composition that table 2 provides is represented the prescription of a typical class material, and it is represented as thermoplastic olefin or TPO.This class material use usually polypropylene as firm thermoplasticity and with ethylene-propylene rubber as elastomerics.Under continuous-mode operation, carry out compound, preferred twin-screw extruder or equivalent.Note because the continuous character of equipment, be used to produce TPO industrial elastomeric or with the balling-up form exist or with polypropylene refining glue.In this embodiment, we select the DFDB-1085 of balled form as object of reference.This low-density ethylene-butene copolymer is to have the thermoplastic resin identical with elastomer performance.This product can obtain from Union Carbide.
Five kinds of granular elastomers are denoted as product A-D and I, with typical TPO method for making, compare with industrial impact modifying agent DFDB-1085.The composition of having represented granular elastomer at table 3.At BerStorff In the 25mm twin-screw extruder every kind of elastomer composite is become the 12MFR homopolymer polypropylene.Processing condition are listed table 4 in.As shown in table 4, have identical performance with the industrial impact modifying agent object of reference granular elastomer of comparing.The composition of table 3-granular elastomer
Product A Product B Products C Product D Product I
C2＝，wt％ C3＝，wt％ ENB，wt％ CB，wt％ ML(1+4) 100℃ 78 22 0 3 ????66 ????32 ????2 ????26 ????55 ????74 ????22 ????4 ????11 ????55 ????67 ????20 ????4 ????22 ????55 ????70 ????24 ????6 ????18 ????40
Screw arrangement is as follows:
9 * C/3 * KB/B/5 * P/LGM/4 * P/2 * SGM/c/2 * S/C screw rod parameter code: C=transport portion, KB=mixing zone, the B=ring that foams, P=pressure, LGM=master wheel mixing tank, SGM=pinion(gear) mixing tank, S=pad table 4-test design and result
Prescription Unit
1 ?2 ??3 ????4 ????5 ????6 ????7
The single polymers product A product B products C product D product I VLDPE (DFDB-1085) of PP wt％ wt％ wt％ wt％ wt％ wt％ wt％ 100 ?85.7 14.3 ??81 ??19 ????84.3 ????15.7 ????82 ????18 ????83 ????17 ????86 ????14
Processing condition
1 humidity province, humidity province, 2 humidity provinces, 3 humidity provinces, 4 mould temperature melt temperature pressure RPM °F °F °F °F °F °F ??psi ??360 ??350 ??380 ??370 ??360 ??405 ??200 ??100 ??360 ??350 ??365 ??370 ??370 ??404 ??300 ??100 ??360 ??350 ??365 ??370 ??370 ??409 ??620 ??100 ????360 ????350 ????365 ????370 ????370 ????410 ????570 ????100 ????360 ????350 ????365 ????370 ????370 ????409 ????510 ????100 ????360 ????350 ????365 ????370 ????370 ????408 ????530 ????100 ????360 ????350 ????370 ????370 ????370 ????405 ????210 ????100
Product performance
MFR230 ℃, 0 ℃ of N. cantilever-20 of 23 ℃ of N. cantilevers of 44psi modulus in flexure N. cantilever ℃ g/dmin kpsi ftlb/in ftlb/in ftlb/in ?8.6 ?171 .8 .4 .4 ????10.9 ????161 ????.9 ????.6 ????.4 ????9.1 ????162 ????.8 ????.5 ????.4 ????10.4 ????159 ????1 ????.6 ????.3 ????10.4 ????161 ????1 ????.7 ????.4 ????10.4 ????164 ????.9 ????.4 ????.4
Embodiment 3
The mixture of elastomerics and the elastomeric thermoplastics of enrichment is referred to as thermoplastic elastomer (TPE) usually.The set of TPE family is that elastomerics is at present crosslinked composition.These mixture of polymers are referred to as efficient vulcanizing agent.They provide and the closely similar performance of traditional cross-linked elastomer, and have the advantage of reprocessing.Present fabrication scheme is the masterbatch method of using when carrying elastomerics continuously.In this embodiment, we compare granular and former batch of elastomeric use in making the efficient vulcanizing agent of typical heat plasticity.
Three kinds of granular elastomers are denoted as product A-C in table 5, compare with polypropylene/ethylene-acrylic rubber former batch (33: 67).The composition of having represented every kind of prescription in the table 6.All composite partss are admitted to the inlet of extrusion machine except vulcanization activator.By the inlet of second on machine barrel 1/3rd length, add vulcanization activator along first inlet.Venting port is positioned near the discharge volatile matter of discharge port.At Berstorff Compound this compound in the 25mm twin-screw extruder.Though less labor force and the energy of cost in preparation process, the composite prod performance that has a granular elastomer is compared with commercial available elastomerics has identical performance.The composition of table 5-granular elastomer
Product A Product B Products C
C2＝，wt％ C3＝，wt％ ENB，wt％ CB.wt％ Gum?ML(1+4)125℃ 70 26 4.5 20 65 ????65 ????31 ????4.5 ????22 ????70 ????65 ????33 ????2 ????25 ????65
Table 6-test design
Prescription Unit ??1 ????2 ????3 ????4
Former batch of kaolin oil of PP homopolymers product A product B products C EPR ZnO TiO2 paraffin phenolic aldehyde sulfuration resin stannous chloride ????phr ????phr ????phr ????phr ????phr ????phr ????phr ????phr ????phr ????phr ????phr ????phr ????77 ????100 ????37 ????130 ????2 ????5 ????5 ????10 ????1.7 ????77 ????120 ????37 ????130 ????2 ????5 ????5 ????10 ????17 ????77 ????122 ????37 ????130 ????2 ????5 ????5 ????10 ????1.7 ????77 ????125 ????37 ????130 ????2 ????5 ????5 ????10 ????1.7

Claims (9)

1. the continuation method of compound one or more polymkeric substance, it comprises: (i) at least a granular elastomer is joined in the continuous mixing device with any one or multiple thermoplastic polymer and any one or multiple admixture; In the time of (ii) in appearing at said continuous mixing device, said granular elastomer forms compound with said any thermoplastic polymer and said admixture mastication; (iii) pass through the said compound of mould pumping along said continuous mixing device.
2. the process of claim 1 wherein that granular elastomer is selected from down group:
Ethylene-propylene copolymer;
Ethylene-propylene diene termonomer;
Ethene and multipolymer with alhpa olefin of 3 to 12 carbon atoms;
Ethene has the alhpa olefin of 3 to 12 carbon atoms and the ter-polymers of diene;
Polyisoprene;
Polyhutadiene;
Divinyl and styrene copolymerized polymkeric substance;
Vinyl cyanide, divinyl and cinnamic polymkeric substance;
The polymkeric substance of divinyl and acrylonitrile compolymer;
The polymkeric substance of iso-butylene and isoprene copolymer;
Chloroprene rubber;
Polydimethylsiloxane;
The multipolymer of ethene and vinyltrimethoxy silane;
The multipolymer of ethene and one or more vinyl cyanide, maleic acid ester, vinyl-acetic ester, vinylformic acid and methacrylic ester;
The multipolymer of divinyl and isoprene;
The ter-polymers of vinylbenzene, divinyl and isoprene;
Chlorobutyl rubber (fluorinated copolymers of iso-butylene and isoprene);
Brombutyl rubber (brominated copolymer of iso-butylene and isoprene); With
The brominated copolymer of iso-butylene and p-methylstyrene; With
Wherein thermoplastic polymer is selected from polyethylene and relevant multipolymer thereof for example butylene, propylene, hexene, octene, 4 methyl 1 pentene copolymer; Poly functionalized products is for example chlorination and sulfonated polyethylene and multipolymer of maleic acid ester, vinylformic acid and methacrylic ester, vinyl cyanide, vinyl-acetic ester and derivative for example; Polypropylene and relevant multipolymer thereof; Polyacrylic functionalized products is maleic acid ester, vinylformic acid and methacrylic ester for example; The modification product of polypropylene and multipolymer; Ionomer; Polyvinyl chloride and relevant multipolymer thereof, functionalized and modification product; Acetal copolymer and related copolymers thereof and modification product; Fluoridize the olefin polymerization thing; Poly-difluoroethylene; Fluorinated ethylene propylene; Polymeric amide and modification product thereof; Polyimide; Polyarylate; Polycarbonate and relevant multipolymer and modification product thereof; Polyethers; Polyethersulfone; Polyaryl sulfone; Polyketone; Polyetheramides; Poly-(4-ethyl-1-amylene); Polyphenylene and modification product; Polysulfones; Polyurethane and relevant modification product thereof; Polyester and relevant modification product thereof; Polystyrene and relevant multipolymer and modification product thereof; Polybutene; The polymkeric substance of vinyl cyanide, polyarylate, and composition thereof.
3. the method for claim 2, wherein under any condition that the inert particle material that is selected from carbon black, silica, clay, talcum and composition thereof exists, granular elastomer is polymerization in gas phase; In the barrel liner harness one or more rotators are arranged in the wherein said continuous mixing device, said machine barrel has one or more spouts and any one or multiple discharge port and at least a kapillary mould or pass mould along its length direction and is connected on the said machine barrel; Be connected on Melting pump or the single-screw extrusion machine with said continuous mixing device.
4. the process of claim 1 wherein the efficient sulfuration of in continuous mixing device, finishing the elasticity phase.
5. the continuation method of compound one or more polymkeric substance, it comprises: at least a granular elastomer and any one or multiple thermoplastic polymer and any one or multiple admixture are mixed mutually to form mixture; (ii) when needs add in the continuous mixing device, said mixture is fed together with any thermoplastic polymer and admixture; (iii) the said mixture of mastication forms compound; (iv) said compound is by the afterbody of mould pumping following current to said continuous mixing device.
6. the method for claim 5, wherein granular elastomer is selected from down group:
Ethylene-propylene copolymer;
Ethylene-propylene diene termonomer;
Ethene and have 3 multipolymers to the alhpa olefin of twelve carbon atom;
Ethene has 3 to the alhpa olefin of twelve carbon atom and the ter-polymers of diene;
Polyisoprene;
Polyhutadiene;
Divinyl and styrene copolymerized polymkeric substance;
Vinyl cyanide, divinyl and cinnamic polymkeric substance;
The polymkeric substance of divinyl and acrylonitrile compolymer;
The polymkeric substance of iso-butylene and isoprene copolymer;
Chloroprene rubber;
Polydimethylsiloxane;
The multipolymer of ethene and vinyltrimethoxy silane;
The multipolymer of ethene and one or more vinyl cyanide, maleic acid ester, vinyl-acetic ester, vinylformic acid and methacrylic ester;
The multipolymer of divinyl and isoprene;
The ter-polymers of vinylbenzene, divinyl and isoprene;
Chlorobutyl rubber (fluorinated copolymers of iso-butylene and isoprene);
Brombutyl rubber (brominated copolymer of iso-butylene and isoprene); With
The brominated copolymer of iso-butylene and p-methylstyrene; With
Wherein thermoplastic polymer is selected from polyethylene and relevant multipolymer thereof for example butylene, propylene, hexene, octene, 4 methyl 1 pentene copolymer; Poly functionalized products is for example chlorination and sulfonated polyethylene and multipolymer of maleic acid ester, vinylformic acid and methacrylic ester, vinyl cyanide, vinyl-acetic ester and derivative for example; Polypropylene and relevant multipolymer thereof; Polyacrylic functionalized products is maleic acid ester, vinylformic acid and methacrylic ester for example; The modification product of polypropylene and multipolymer; Ionomer; Polyvinyl chloride and relevant multipolymer thereof, functionalized and modification product; Acetal copolymer and related copolymers thereof and modification product; Fluoridize the olefin polymerization thing; Poly-difluoroethylene; Fluorinated ethylene propylene; Polymeric amide and modification product thereof; Polyimide; Polyarylate; Polycarbonate and relevant multipolymer and modification product thereof; Polyethers; Polyethersulfone; Polyaryl sulfone; Polyketone; Polyetheramides; Poly-(4-ethyl-1-amylene); Polyphenylene and modification product; Polysulfones; Polyurethane and relevant modification product thereof; Polyester and relevant modification product thereof; Polystyrene and relevant multipolymer and modification product thereof; Polybutene; The polymkeric substance of vinyl cyanide, polyarylate, and composition thereof.
7. the method for claim 6, wherein under any condition that the inert particle material that is selected from carbon black, silica, clay, talcum and composition thereof exists, granular elastomer is polymerization in gas phase; In the barrel liner harness one or more rotators are arranged in the wherein said continuous mixing device, said machine barrel has one or more spouts and any one or multiple discharge port and at least a kapillary mould or pass mould along its length direction and is connected on the said machine barrel; Be connected on Melting pump or the single-screw extrusion machine with said continuous mixing device.
8. the method for claim 5 is wherein finished the efficient sulfuration of elasticity phase in continuous mixing device.
9. according to the goods of claim 1,4, the preparation of 5 or 8 method.
CN96123319A 1995-11-22 1996-11-21 Process for preparing elastomeric compounds from granular elastomers and polymers and articles manufacturing therefrom Pending CN1189514A (en)

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US007,442 1995-11-22
US745,006 1996-11-07
CN96123319A CN1189514A (en) 1995-11-22 1996-11-21 Process for preparing elastomeric compounds from granular elastomers and polymers and articles manufacturing therefrom

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1308357C (en) * 2002-01-15 2007-04-04 高级弹性体系统两合公司 Thermoplastic elastomer and process for making the same
CN103159883A (en) * 2011-12-09 2013-06-19 中国石油化工股份有限公司 Material pre-mixing method for preparing isoprene rubber and preparation method for isoprene rubber
CN111704772A (en) * 2020-04-30 2020-09-25 浙江信汇新材料股份有限公司 Granular butyl rubber composition with anti-sticking effect and preparation method and application thereof
CN113185934A (en) * 2021-05-10 2021-07-30 四川远星橡胶有限责任公司 Self-repairing adhesive composition and preparation method and use method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1308357C (en) * 2002-01-15 2007-04-04 高级弹性体系统两合公司 Thermoplastic elastomer and process for making the same
US7696276B2 (en) 2002-01-15 2010-04-13 Exxonmobil Chemical Patents Inc. Thermoplastic elastomers and process for making the same
CN103159883A (en) * 2011-12-09 2013-06-19 中国石油化工股份有限公司 Material pre-mixing method for preparing isoprene rubber and preparation method for isoprene rubber
CN103159883B (en) * 2011-12-09 2015-10-21 中国石油化工股份有限公司 For the preparation of the material method for pre mixing of polyisoprene rubber and the preparation method of polyisoprene rubber
CN111704772A (en) * 2020-04-30 2020-09-25 浙江信汇新材料股份有限公司 Granular butyl rubber composition with anti-sticking effect and preparation method and application thereof
CN113185934A (en) * 2021-05-10 2021-07-30 四川远星橡胶有限责任公司 Self-repairing adhesive composition and preparation method and use method thereof

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