CN102782035A - Compositions with compatibilized silica, nitrile rubber, styrene butadiene rubber, elastomeric compounds, and/or recycled materials - Google Patents

Abstract

A process for forming a compatibilized silica and nitrile polymer blend in latex form is described herein. The process can include treating a silica with a coupling agent to form a compatibilized silica slurry. The process can include blending the compatibilized silica slurry into a styrene butadiene polymer latex and an acrylonitrile butadiene polymer latex. The process can include blending silica styrene butadiene polymer latex with silica acrylonitrile butadiene polymer latex. A polymer composition of a compatibilized silica in blends of acrylonitrile butadiene polymer and styrene butadiene polymer and a recycled elastomeric composition are described herein. The recycled elastomeric composition can also include a compatibilized silica with a coupling agent, a crumb rubber, a carbon black, a filler, and an extender oil.; Articles comprising the recycled elastomeric composition are disclosed herein.

Description

The compsn that contains increase-volume silicon-dioxide, paracril, styrene-butadiene rubber(SBR), elastomer compounds and/or twice-laid stuff

The cross reference of related application

The application requires the right of priority and the interests of following patented claim: the U.S. Provisional Patent Application sequence number 61/292 that on January 7th, 2010 submitted to; The patent application number 12/984 that submit to 910 and 2011 year January 4; 267, the two all is entitled as " PROCESS FOR MAKING COMPATIBILIZED SILICA AND NITRILE POLYMER COMPOSITIONS "; The U.S. Provisional Patent Application sequence number 61/292 that on January 7th, 2010 submitted to; The patent application number 12/984 that submit to 917 and 2011 year January 4; 280, the two all is entitled as " COMPATIBILIZED SILICA IN NITRILE RUBBER AND BLENDS OF NITRILE RUBBER AND STYRENE BUTADIENE RUBBER COMPOSITIONS "; With the U.S. Provisional Patent Application sequence number of submitting on January 7th, 2,010 61/292; The U.S. Patent Application Serial Number 12/984 that submit to 923 and 2011 year January 4; 295, the two all is entitled as " ELASTOMERIC COMPOUNDS CONTAINING RECYCLED MATERIALS AND SILICA ".These reference papers are incorporated this paper in full into.

Technical field

This embodiment relate in general to the latex form increase-volume silicon-dioxide and nitrile polymer blend, with the vinyl cyanide styrene butadiene ter-polymers latex of increase-volume silicon-dioxide blend, with acrylonitrile butadiene polymkeric substance and styrene butadiene latex polymer blend, chemically-resistant and antibiont infringement or the polymer compsn of harm and the regenerated elastic body compsn that contains micelle, increase-volume silicon-dioxide and carbon black of increase-volume silicon-dioxide blend.

Background technology

Need at present a kind of the latex stage with silicon-dioxide and other strengthening agent; For example carbon black is evenly introduced in the polymkeric substance so that simple and lower-cost production technology to be provided; This technology need not used complicated auxiliary process; Can not cause latex to condense too early, wherein can be in the course of processing basic homodisperse and compatible of silicon-dioxide with polymeric matrix yet.

Need utilize coupling agent to handle the precipitator method or fumed silica (fumed silica), make the compatible wet processing of polymer phase in silicon-dioxide and polymer latex Ruzhong thus.

The compsn that needs its uniform filling to disperse, be prone to preparation, contain the UV stablizer, density is high, in light weight and can resists chemical warfare is used for antibiont war with the protection user.

Need a kind of through not using former hydrocarbon ils (usually from offshore deep-sea oil well and expensive); Thereby it is energy-conservation in process of production, production cost is low, the regenerated elastic nanocrystal composition that reduces transportation cost and have " green " characteristic (for example recyclable and regenerated rubber is to reduce the rubber amount of landfill).

This embodiment can satisfy these demands.

Description of drawings

Detailed description in conjunction with following accompanying drawing can be understood the present invention better, and accompanying drawing is following:

Fig. 1 is the diagram of an embodiment of working method.

Fig. 2 is an embodiment diagram of method that forms the blend of vinyl cyanide and styrene butadiene ter-polymers latex and increase-volume silicon-dioxide.

Fig. 3 is an embodiment diagram of method that forms the blend of acrylonitrile butadiene polymkeric substance and styrene butadiene latex polymer and the blend of increase-volume silicon-dioxide.

Fig. 4 is an embodiment diagram that in the latex blends of acrylonitrile butadiene polymkeric substance and styrene butadiene polymkeric substance, forms the method for increase-volume silicon-dioxide.

Fig. 5 is an embodiment diagram of method that forms increase-volume silicon-dioxide and the nitrile polymer blend of latex form.

The cited accompanying drawing of following reference is described this embodiment in detail.

Embodiment

Before illustrated in detail present method, compsn and goods, should be appreciated that this method, compsn and goods are not limited to particular, and this method, compsn and goods can be implemented in many ways or carry out.

One or more embodiments relate to the continuous flow mode of utilizing; From the zero-pressure to low pressure; From envrionment temperature to hyperenvironment temperature slightly; Use the emulsion polymerization elastomeric polymer composition that form, that contain scrap rubber grain and silicon-dioxide of acvator, radical initiator, water and terminator, and relate to the goods of processing by this elastomeric polymer composition.

The said elastomeric polymer composition that contains scrap rubber grain and silicon-dioxide can contain the synthetic elastomer polymkeric substance of 18wt% ~ 93wt%, in the gross weight of said compsn.

The synthetic elastomer polymkeric substance can comprise the liquid 1,3-butadiene monomer of 60wt% ~ 82wt%, in the gross weight of said elastomeric polymer composition.

The said elastomeric polymer composition that contains scrap rubber grain and silicon-dioxide can contain the styrene monomer of 18wt% ~ 40wt%, in the gross weight of said elastomeric polymer composition.

Said elastomeric polymer composition with scrap rubber grain and silicon-dioxide can contain the increase-volume silicon-dioxide of 5wt% ~ 80wt%, in the gross weight of said elastomeric polymer composition.Increase-volume silicon-dioxide can contain the organo-silicon coupling agent of 1wt% at least, and it combines with the said increase-volume silica sphere of about 20wt%.

Said elastomeric polymer composition with scrap rubber grain and silicon-dioxide can contain the regeneration scrap rubber grain of 1wt% ~ 50wt%, in the gross weight of said compsn.

Said elastomeric polymer composition with scrap rubber grain and silicon-dioxide can contain the carbon black of 1wt% ~ 40wt%, in the gross weight of said compsn, or the carbon black of 1wt% ~ 10wt%, in the gross weight of said compsn.

Said elastomeric polymer composition with scrap rubber grain and silicon-dioxide wherein can contain the rubber grain of recovery.In one or more embodiment, the scrap rubber particle of at least 50 volume % can be less than #10 order U.S. series screen cloth, or the scrap rubber particle of at least 50 volume % can be less than #200 order U.S. series screen cloth.Said elastomeric polymer composition with scrap rubber grain and silicon-dioxide can comprise 100% from the scrap rubber grain that reclaims tire.The rubber grain that reclaims can be introduced this scrap rubber grain in said elastomeric polymer composition or the rubber combination after sieving again.

Prepare with emulsion polymerization in the process of elastomeric polymer composition, the synthetic elastomer polymkeric substance can be latex or dried particulate form.

Said elastomeric polymer composition with scrap rubber grain and silicon-dioxide can comprise the filler of 0.1wt% ~ 50wt%, in the gross weight of said compsn.

The filler that is used for method described herein, compsn and goods can be the Pericarppium arachidis hypogaeae, talcum, the carbon of pulverizing, bagasse, ash content, perlite, clay, lime carbonate, biomass or its combination of pulverizing of the walnut shell pulverized, cellulose materials, ensilage, zeyssatite, pulverizing.

Said elastomeric polymer composition with scrap rubber grain and silicon-dioxide can comprise the extending oil of 1wt% ~ 40wt%, in the gross weight of said compsn.

The extending oil that is used for method described herein, compsn and goods can be synthetic oil, perfume oil, NO, alkyl oil, polycyclic aromatic hydrocarbons is oily or its combination.

Said elastomeric polymer composition with scrap rubber grain and silicon-dioxide can comprise thermoplastic polymer, thermoplastic elastomer, TPV or its arbitrary combination of 25wt% at the most, in the gross weight of said compsn.

Said elastomeric polymer composition with scrap rubber grain and silicon-dioxide can be a cross-linked polymer.Said elastomeric polymer composition with scrap rubber grain and silicon-dioxide can be used for making various types of goods.

Can comprise by the goods of method and composition manufacturing described herein: car mat, tire, belt, cylinder, overshoes, cable jacket, edge, roof, flexible pipe, shock eliminator peculiar to vessel, industrial belt, non-doughnut, mining belt, bearing, conduit, gasket stamping machine roller, O shape ring, footwear, garden hoses, pipeline, dock side buffer, non-latex glove, gas mask, the pneumatic tyre that on bike, automobile or aircraft, uses etc.

The goods that one or more embodiments relate to regenerated elastic body compsn and processed by this regenerated elastic body compsn.

The tree elastomer that is used for method described herein, compsn and goods can be any TR 301, like rubber.The synthetic elastomer polymkeric substance that is used for method described herein, compsn and goods can be a styrene-butadiene rubber(SBR).

Said synthetic elastomer polymkeric substance can comprise the liquid 1 of 60wt% ~ 82wt%; The increase-volume silicon-dioxide of the vinylbenzene of 3-divinyl, 18wt% ~ 40wt%, 5wt% ~ 80wt%, it contains the coupling agent that is bonded to this increase-volume silica sphere, the scrap rubber grain of 1wt% ~ 50wt% and the carbon black of 1wt% ~ 40wt% of 1wt% at least.

Said synthetic elastomer polymkeric substance can prepare like divinyl, isoprene, chloroprene, pentadiene and dimethylbutadiene through polymerization and/or copolymerization conjugate diene monomer.Said synthetic elastomer polymkeric substance can comprise the combination of vinyl monomer and conjugated diolefine and vinyl monomer.

The pinane hydrogen peroxide can be used for letex polymerization.

The suitable vinyl monomer that is used for method described herein, compsn and goods can comprise: vinylbenzene, alpha-methyl styrene, alkyl-substituted styrene, Vinyl toluene, Vinylstyrene, vinyl cyanide, vinylchlorid, methacrylonitrile, iso-butylene, maleic anhydride, propenoate and acid, methacrylic ester, vinyl ether and vinyl pyridine.

Said synthetic elastomer polymkeric substance can comprise the blend of SBR styrene butadiene rubbers (SBR), paracril (NBR), acrylonitrile-butadiene-styrene (ABS) polymkeric substance (ABS), polyhutadiene, SE (PVC), PS, PVA, divinyl-vinylpyridine polymer, TR 301, sovprene, X 050, styrene-acrylonitrile copolymer (SAN) or paracril and SE.

The regenerated elastic body polymkeric substance of gained can be processed by blend, and it can comprise thermoplastic polymer, thermoplastic elastomer, TPV or its combination of 25wt% at the most.Thermoplastic polymer can be a thermoplastic polyolefin blend.Thermoplastic elastomer can be a styrene-butadiene block copolymer.TPV can be the cross-linked ethylene propylene diene material in the polypropylene-base.

Silicon-dioxide can account for the 5wt% ~ 80wt% of total composition of said regenerated elastic body polymkeric substance.

Can carry out the letex polymerization blend through the time of using Banbury mixer in 800 pounds ~ 1200 pounds speed ranges, to mix 90 seconds ~ 30 minutes.

Silicon-dioxide is except the polymer blending of having put down in writing with this paper, and what said increase-volume silicon-dioxide can also be with polyolefine, poly-alpha olefins, polyester, polymeric amide, polycarbonate, ppe, polyepoxides, polyacrylic ester and propenoate and vinyl monomer is copolymer blended.

Polyolefine can be by straight chain, side chain or ring-type α-monoolefine, vinylidene alkene and non-conjugated two and alkatrienes; Comprise 1; 4-pentadiene, 1; 4-hexadiene, 1,5-hexadiene, Dicyclopentadiene (DCPD), 1, the homopolymer of preparation such as 5-cyclooctadiene, sarohornene, norbornadiene, alkylidene group norbornylene, vinyl norbornene, multipolymer, cross-linking copolymer and the combination of other comonomer.

The example of this polymkeric substance comprises Vilaterm, Vestolen PP 7052, ethylene-propylene copolymer, ethylene-alpha-olefin-nonconjugated diene terpolymers (EPDM), chlorinatedpolyethylene, polybutylenes, polynorbornene and poly-alpha olefins resin.

In one or more embodiment, can be used in method as herein described, compsn and the goods in order to make increase-volume silicon-dioxide, the coupling agent in the used water solution is handled silicon-dioxide, to form the slurry with other component blend.

Silicon-dioxide can be processed like the precipitator method or fumed silica by various commercially available soft silicas, and it has fine particle diameter and high surface area.The size of silica dioxide granule can change in the scope than broad, as is 7nm ~ 60nm, can come filled polymer usefulness according to this silicon-dioxide, end-use such as still makes to strengthen that polymkeric substance is used and decides.

Fine silicon-dioxide thereby can form water slurry, but and handle with the coupling agent of chemically bonded to silica sphere.Coupling agent known in the art can be used for the wetting ability packing material like spun glass or silicon-dioxide, is coupled to hydrophobic material, like the natural and synthetic elastomer polymkeric substance as rubber or thermoplastic material.Coupling agent capable of using is accomplished at least 20% bonding.

Become known for silica-bound can be used as coupling agent to natural with the silicoorganic compound synthetic elastomer polymkeric substance.Organosilicon can be derived from organosilane.

In some embodiments, can 1-3 organic group be directly connected on the Siliciumatom so that its with to add the natural of silicon-dioxide or synthetic elastomer polymer-compatible.

In the process of sulfurized natural rubber or synthetic elastomer polymkeric substance, but coupling agent chemically bonded to tree elastomer, synthetic elastomer polymkeric substance or its combination.

Coupling agent can have the ability of carrying out chemical reaction with silica sphere, so that coupling agent is bonded on it.Coupling agent can be maybe to comprise two (trialkoxysilyl alkyl) polysulfide.Two (trialkoxysilyl alkyl) polysulfide can have 2-8 sulphur atom, and wherein alkyl can be the C1-C18 alkyl, and alkoxyl group can be the C1-C8 alkoxyl group.

The amount of used coupling agent can basis and the amount of the silicon-dioxide of natural or synthetic elastomer polymer blending, and changes in the scope than broad according to the molecular weight of coupling agent.Can use 1-25 weight part coupling agent/100 weight part silicon-dioxide, for example 1-15 weight part coupling agent/100 weight part silicon-dioxide.Can be according to being deposited in the consumption that organosilyl AW percentage ratio on the silica sphere limits coupling agent.Coupling agent with the process of silica sphere reaction and self condensation in can its many weight of loss.

In order to realize that the silicon-dioxide more than the 90wt% is introduced in the letex polymerization polymkeric substance; Organosilyl weight percentage on silica sphere can be 0.50 to 10.0; Like this, the organosilicon from silane of minimum 0.5-5g can be bonded on the 100g silicon-dioxide that charges in the slurry.

For increase consistency in do mixing or with the extra chemical reaction of natural or synthetic elastomer polymkeric substance, can be on silica sphere bonding greater than the organosilicon residue of 1wt%.For example, can be on silica sphere the organosilicon of bonding 10wt%-20wt%.

The synthetic elastomer polymkeric substance can have or comprise the divinyl of the about 92wt% of about 55wt%-, for example liquid 1,3-butadiene (CH ₂=CHCH=CH ₂).The synthetic elastomer polymkeric substance can comprise the vinylbenzene of the about 45wt% of about 8-.In embodiments, the synthetic elastomer polymkeric substance can be latex or dried particulate form.

Term used herein " latex " is meant stabilising dispersions or the emulsion of polymer micropellet in medium.Exemplary medium can comprise water or other fluid.Latex can be natural or synthetic.

In one embodiment, elastic composition can comprise the increase-volume silicon-dioxide of the about 80wt% of about 5wt%-.

In some embodiments, increase-volume silicon-dioxide contains the coupling agent on this increase-volume silica sphere that is bonded to of 1wt% at least.In some embodiments, the amount of coupling agent can be the about 50wt% of about 1wt%-.

Regenerated elastic body compsn can comprise the scrap rubber grain of the about 50wt% of about 1wt%-.

Term used herein " scrap rubber grain " is meant through damaged tire or other rubber are broken into single-size; To wherein inherent supporting material simultaneously; Like the inertia pollutent of steel and fiber and any other type, remove together and the material that obtains like dust, glass or rock.The scrap rubber grain can comprise the rubber grain of recovery.Reclaiming rubber can be regenerated rubber, and it derives from synthetic and/or tree elastomer or plastics.In some embodiments, the scrap rubber grain can be processed by 100% recovery tire.Can, the scrap rubber grain make at least a portion that reclaims rubber grain before being introduced rubber combination through U.S.'s series screen cloth as described herein.For example, the recovery rubber grain of 10%-50% can be through the screen cloth of #200 order or other order number.

The embodiment of elastic composition can comprise the carbon black of 1wt%-40wt%.Carbon black can be that the simple substance carbon of the agglomerate particles coacervate form of the subsphaeroidal colloidal solid that basically obtained by the partial combustion thermolysis of hydrocarbon and this colloidal-sized constitutes.Can use two kinds of dissimilar carbon blacks.

Elastic composition can comprise filler, for example as herein described those.Some embodiments of elastic composition can comprise the filler of the about 50wt% of about 0.1wt%-.

Method described herein, compsn and goods can comprise " other material ", like ultraviolet ray (UV) stablizer, extending oil or inhibitor.Said composition can comprise about 0.1wt%-3wt%'s " other material ", in the gross weight of compsn.

Ultraviolet ray (UV) stablizer can be hindered amine, benzotriazole, triazine or its combination.Inhibitor can be phenol antioxidant, phosphite, bis-phenol, amine inhibitor or its combination.For example, elastic composition can comprise the extending oil of the about 40wt% of about 0.01wt%-.Extending oil can be used as softening agent and can be used for enhancement process.

Some embodiments can comprise the goods by this rubber combination preparation, goods for example as herein described.

One or more embodiments are from comprising the increase-volume silicon-dioxide that contains the about 90wt% of 6wt%-that has an appointment, coupling agent, the styrene butadiene polymkeric substance and the polymer compsn of the acrylonitrile butadiene polymkeric substance of 10wt% at least of 10wt% at least of 1wt% at least, until the goods that obtain by its manufacturing.

Polymer compsn also is called as blend polymer in this article, can have the intensity that is used for tire, shellproof clothes and personnel's shielding, keeps flexible, weather resistance simultaneously and can bear the temperature that is low to moderate-35 degrees centigrade and indeformable.This blend polymer can have the filler of holding and chip-proof ability.

In some embodiments, polymer compsn can comprise that minimum is the letex polymerization acrylonitrile-butadiene copolymers of 10wt% at least, and its surplus is an increase-volume silicon-dioxide.Divinyl can be the liquid 1,3-butadiene.

Increase-volume silicon-dioxide can have and is bonded to its surperficial organo-silicon coupling agent, and per unit weight silicon-dioxide has the organosilicon of the about 10wt% of about 2wt%-, thereby forms increase-volume silicon-dioxide.

In embodiments, polymer compsn can be a blend polymer.Polymkeric substance can be: polyolefine, poly-alpha olefins, polyester, polymeric amide, polycarbonate, ppe, polyacrylic ester, urethane, ethene; The ter-polymers of propylene and non-conjugated diene, fluorinated elastomer, chlorination elastomer, TR 301, polyhutadiene, gather isobutyl diene, sovprene, SE, styrene-butadiene rubber(SBR), paracril, polyepoxide, ethene interpretation, butadiene-styrene block copolymer, above cross-linked polymer, the homopolymer of styrene isoprene and the multipolymer of segmented copolymer, propenoate and vinyl monomer of listed polymkeric substance, or its combination.

Also can comprise polyvinyl chloride polymer with the polymer compsn with increase-volume silicon-dioxide of acrylonitrile butadiene polymer blending.The polyvinyl chloride polymer of the about 50wt% of about 20wt%-can use with the acrylonitrile butadiene polymkeric substance of 10wt% at least.Polymer compsn can comprise that minimum is the acrylonitrile/butadiene polymkeric substance of the 15:50 of 10wt% at least, and its surplus is made up of increase-volume silicon-dioxide.

One or more embodiment relate to the goods that formed or processed by polymer compsn as herein described.Said goods can be any goods as herein described or similar articles.Formed goods can be anti-biological and chemical war components, as the protective clothing of gas mask, soldier's boots, anti-arc lightning and the clothes of protection carnivore.

Organosilicon can be used as average tetramer structure and exists, by ²⁹Si CPMAS NMR measures it and has the T more than 0.75 ³/ T ²Ratio.Term " T ²" and " T ³" be meant two (T ²) and three (T ³) silicon that connects of doubly Si-O-key." Si CPMAS NMR " is meant silicon cross polarization magic-angle-spinning nuclear magnetic resonance (silicon cross polarization magic angle spinning nuclear magnetic resonance), and subscript 29 is meant the nucleidic mass of the silicon isotope of being analyzed.

Coupling agent can the about 25wt% of about 1wt%-organosilyl amount be bonded to silica sphere, in the weight of silicon-dioxide.

With ²⁹Si CPMAS NMR measures, and increase-volume silicon-dioxide can have the T more than 0.9 ³/ T ²Ratio.

It is the nitrile polymer of 10-100 and the vinyl cyanide compsn of 10wt%-50wt% that the increase-volume silicon-dioxide of latex form and nitrile polymer blend can have mooney viscosity (ML1+4,100 ℃).

The process of preparation polymer compsn can be carried out when polymkeric substance is the latex form.The so-called emulsion polymerization latex of this paper is meant the reaction mixture before the agglomeration phase in the emulsion polymerization process.

In one or more embodiment, filler can in polymer compsn, be added, like carbon black.Polymer compsn can comprise the carbon black of about 1wt%-50wt%, and carbon black can be two kinds of different sooty mixtures.Like this, the silica carbon black-compsn can reach the even high capacity introducing and the degree of quantitatively introducing of total filler.

Polymer compsn can comprise other polymkeric substance with the latex prepare, comprises conjugated diene polymer, based on the combination of polymer of vinyl monomer, conjugated diene and vinyl monomer.Suitable vinyl monomer can comprise and is used for those vinyl monomers described in method as herein described, compsn and the goods.

Polymer compsn can comprise the blend of tree elastomer, styrene-butadiene rubber(SBR) (SBR), paracril (NBR), acrylonitrile butadiene styrene polymer (ABS), polyhutadiene, SE (PVC), PS, PVA, divinyl vinylpyridine polymer, TR 301, sovprene, X 050, styrene acrylonitrile copolymer (SAN), paracril and SE etc.Polymer compsn can have at least a multipolymer, homopolymer, cross-linked polymer, partial cross-linked polymkeric substance or its combination.

Polymer compsn can be through preparing to form the increase-volume silica slurry with coupling agent treatment silicon-dioxide in aqeous suspension.The increase-volume silica slurry can have aqueous solution part and increase-volume silicon-dioxide.

Increase-volume silicon-dioxide can contain and accounts for organosilicon silica weight 2wt%-25wt%, that be bonded to this silica sphere.Increase-volume silicon-dioxide can have the median size of 1 nanometer (nm)-15 micron.The silicon-dioxide of non-reunion can have the median size of 1 nanometer-15 micron.Silicon-dioxide can be fumed silica, and for example pyrolytic silicon dioxide, soft silica are like zeyssatite, faujusite or its combination.

Can white rouge formed water slurry and handles with coupling agent solution, but the coupling agent chemically bonded be to silica sphere.Various coupling agent known in the art can be used as hydrophilic filler, like spun glass, silicon-dioxide etc., is coupled to hydrophobic material, like the coupling agent as the natural and synthetic polymer of rubber or thermoplastic material.As everyone knows, silicoorganic compound can be used for silica-bound on natural and synthetic polymer.

One or more embodiment relate to the method that forms the blend polymer with increase-volume silicon-dioxide, and relate to goods and the compsn that is formed by said method.

In the first embodiment, this method can comprise handles silicon-dioxide to form the increase-volume silica slurry, produces the silicon-dioxide styrene butadiene latex polymer that contains silicon-dioxide acrylonitrile butadiene polymkeric substance then.

In the first embodiment, can produce the increase-volume silicon-dioxide of latex form and the blend of nitrile polymer.Formed increase-volume silicon-dioxide and nitrile polymer blend can have the mooney viscosity (ML1+4,100 ℃) of 10-100 and the vinyl cyanide compsn of 10wt%-50wt%.

First embodiment can comprise the method when polymkeric substance is the latex form.

This method can be configured to be applicable to natural rubber latex and polymeric latex.

This method can adopt letex polymerization, and promptly polymkeric substance can aggregate into the latex in the reaction mixture before agglomeration phase." latex " used herein or " latex form " is meant the hydro-colloid/emulsion of rubber grain.

Each embodiment as herein described can be carried out with the form of polymer latex, wherein can add other component such as filler, inhibitor, UV stabilizer and carbon black.These technologies can form the even high capacity of total filler and introduce and silicon-dioxide-carbon black compsn of quantitatively introducing.

This method can be applied to other polymkeric substance with the latex prepare, comprises conjugated diolefin polymer, based on the combination of polymer of vinyl monomer, conjugated diene and vinyl monomer.The spendable suitable vinyl monomer of this paper can comprise any vinyl monomer as herein described and similar monomer.

For example, polymkeric substance can be the blend of tree elastomer, styrene-butadiene rubber(SBR) (SBR), paracril (NBR), acrylonitrile butadiene styrene polymer (ABS), polyhutadiene, SE (PVC), PS, PVA, divinyl vinylpyridine polymer, TR 301, sovprene, X 050, styrene acrylonitrile copolymer (SAN), paracril and SE etc.

In order to form the blend of glue lactous increase-volume silicon-dioxide and nitrile polymer, can use tensio-active agent, like the soap class.Can use initiator, like the pinane hydrogen peroxide.Can use acvator, like ferrous sulfate.Said soap class can obtain from MeadWestvaco, and can replenish caustic alkali such as sodium hydroxide.The soap class can directly be added in the raw material of vinylbenzene, divinyl and acrylonitrile monemer.Divinyl can be the liquid 1,3-butadiene.

Emulsion polymerization in disclosed all methods of this paper can carry out under 1 degree centigrade-30 degrees centigrade temperature.The transformation efficiency of the disclosed letex polymerization of this paper can be 59% to 80%.

This paper so-called " natural polymer " is meant the polymkeric substance that the rubber that obtained by plant origin etc. is processed.Term used herein " synthetic polymer " is meant the polymkeric substance and the analogue thereof of the fossil fuel-derived with rubber property or rubber elastomer characteristics.Can use natural and mixture synthetic polymer.

Polymer latex can be that solid content is the emulsion of 5wt% to 75wt%.

The process that formation has a blend polymer of increase-volume silicon-dioxide can be included in the aqeous suspension with coupling agent treatment silicon-dioxide to form the increase-volume silica slurry.

Aqeous suspension can comprise water, soap, emulsifying agent, tensio-active agent or thickening material, includes but not limited to viscosity modifier, like starch or CMC 99.5.

Silicon-dioxide can be handled with coupling agent, as is bonded to the organosilicon of silica sphere, and wherein organosilicon accounts for the 1wt%-25wt% of silica weight.

Fig. 1 illustrates first embodiment of present method.

Step 100 can be included in the aqeous suspension and form the increase-volume silica slurry with coupling agent treatment silicon-dioxide, and then forms the increase-volume silicon-dioxide of latex form and the blend of nitrile polymer.

Coupling agent can be can with silica sphere generation chemical reaction and the organosilicon of Cheng Jian above that.

Step 102 can comprise at least a portion of increase-volume silicon-dioxide and styrene butadiene latex polymer blend to form the silicon-dioxide styrene butadiene latex polymer.

Step 104 can comprise at least a portion of increase-volume silicon-dioxide and the blend of acrylonitrile butadiene polymer latex to form silicon-dioxide acrylonitrile butadiene polymer latex.

Step 106 can comprise silicon-dioxide styrene butadiene latex polymer and the blend of silicon-dioxide acrylonitrile butadiene polymer latex with the increase-volume silicon-dioxide that forms the latex form and the blend of nitrile polymer.

Silicoorganic compound can have 1-3 and the direct-connected facile hydrolysis group of Siliciumatom and at least one and the direct-connected organic group of Siliciumatom.The organic group that is directly connected to Siliciumatom can have at least one functional group.This functional group can be in the polymer cure process can with the functional group of polymer chemistry reaction.

This functional group can select according to the specific preparation method of specific polymkeric substance and elastomer compounds.For example; If embodiment comprises the styrene-butadiene rubber(SBR) with silicon-dioxide; Then it can be cured through crosslinking reaction; This crosslinking reaction can relate to sulfocompound, has at least one silicoorganic compound that contain the organic group of sulfydryl, polysulfide, thiocyanogen (SCN), halogen and/or amido functional group, just can make coupling agent with these.Correspondingly, at least one organic group of silicoorganic compound can have ethylenically unsaturated group or epoxide group, makes silica-filled polymkeric substance can carry out the curing reaction of peroxy type.

The representative of hydrolysable group commonly used comprises in this coupling agent: halogen, hydrogen, hydroxyl, lower alkoxy such as methoxyl group, oxyethyl group, propoxy-etc.

For example; Be prepared as in the embodiment that contains styrene-butadiene rubber(SBR) at polymer compsn; styrene-butadiene rubber(SBR) can be cured through the crosslinking reaction that relates to sulphur compound, coupling agent can be to have selected from mercapto, polysulfide, thiocyanogen (SCN) or the silicoorganic compound of at least one organic group of halogen and/or amido functional group.Correspondingly, at least one organic group of silicoorganic compound can have the unsaturated or epoxide group of olefinic, makes silica-filled polymkeric substance can carry out the curing reaction of peroxy type.

This method can be used the monomer that can become homopolymer, complete cross-linking copolymer, partial cross-linked polymkeric substance, multipolymer or their combination.

Formed styrene butadiene latex polymer, silicon-dioxide styrene butadiene latex polymer and/or acrylonitrile butadiene latex can also comprise TR 301.

It is 0.1 micron to 20 microns silicon-dioxide that this method can be used median size.

This method can be used the silicon-dioxide of fumed silica, soft silica or its combination and so on.

Step 108 can comprise the carbon black slurry is added at least a monomer of latex form.

This method can be used the component as coupling agent, and this component has following general structure:

" X " can be the functional group that is selected from amino, polyamino alkyl, sulfydryl, polysulfide base, epoxy group(ing), vinyl, acryloxy and methacryloxy." y " is equal to or greater than 0 integer." Z ₁", " Z ₂", " Z ₃" can be independently selected from respectively: hydrogen, C1-C18 alkyl, aryl, naphthenic base, alkoxy aryl, halogen-substituted alkyl." Z ₁", " Z ₂" and " Z ₃" between at least one can be alkoxyl group, hydrogen, halogen or hydroxyl.Other embodiment of method as herein described, compsn and goods also can comprise maybe can use the coupling agent with following general formula:

Coupling agent can be or comprise two (trialkoxysilyl alkyl) polysulfide; Or be selected from: trialkyl silane, dialkyl silane, trialkyl organoalkoxysilane, trialkyl halosilanes, dialkyl group organoalkoxysilane, dialkyl dialkoxy silicane, dialkyl group alkoxyl group halosilanes, trialkyl silanol, alkyltrialkoxysilaneand, alkyl-dialkoxysilanes, alkyl dialkoxy halosilanes and monoalkyl silane, wherein alkyl is C ₁-C ₁₈Straight chain, ring-type or branched-chain hydrocarbon or its combination.In one or more embodiment, one or two alkyl can be replaced by phenyl or benzyl, or phenyl, benzyl or alkoxyl group that one to two alkyl can be substituted alkyl replace.

Coupling agent can comprise two (trialkoxysilyl alkyl) polysulfide of 2-8 sulphur atom, and wherein alkyl can be C ₁-C ₁₈Alkyl, alkoxyl group can be C ₁-C ₈Alkoxyl group.

Silicon-dioxide can be nanometer grade silica, like polyhedral oligomeric silsesquioxane (POSS).

Coupling agent can be silane or other silicoorganic compound.Silicoorganic compound are the compounds that comprise carbon silicon key.

Step 110 can comprise condenses increase-volume silicon-dioxide and nitrile polymer blend after becoming the latex form.

Step 112 can comprise that the increase-volume silicon-dioxide of dry cohesion and nitrile polymer blend anhydrate to remove.

The increase-volume silica slurry can comprise the silicon-dioxide of 1wt%-40wt%.

This method can comprise that the silicon-dioxide of per 100 weight parts uses the coupling agent of 1-25 weight part.

The described method of Fig. 1 can comprise that the amount of the increase-volume silica slurry that uses is 5wt%-80wt%, with the solid weight meter in silicon-dioxide styrene butadiene latex polymer or silicon-dioxide acrylonitrile butadiene polymer latex Ruzhong.

Step 114 can be included at least a polymer latex Ruzhong and add extending oil, inhibitor or its combination.

One or more embodiments relate to compsn and the goods by the method manufacturing of Fig. 1.

Fig. 2 illustrates the process that forms the vinyl cyanide styrene butadiene ter-polymers latex with increase-volume silicon-dioxide.The described method of Fig. 2 can produce acrylonitrile butadiene polymer latex and styrene butadiene latex polymer.

Step 200 can comprise styrene butadiene latex polymer and the blend of acrylonitrile butadiene polymer latex to form acrylonitrile butadiene polymkeric substance and styrene butadiene latex polymer blend.

Step 202 can be included in the aqeous suspension and form the increase-volume silica slurry with coupling agent treatment silicon-dioxide.Coupling agent can be with the silica sphere chemical reaction so that coupling agent be bonded on it.

Step 204 can comprise increase-volume silica slurry and acrylonitrile butadiene polymkeric substance and the blend of styrene butadiene latex polymer blend, forms the vinyl cyanide styrene butadiene ter-polymers blend with increase-volume silicon-dioxide of latex form.

Step 206 can be with styrene butadiene latex polymer and the acrylonitrile butadiene polymer latex of 1wt%-30wt% and the increase-volume silica slurry blend of 1wt%-30wt% of 2wt%-80wt%.If with the solid weight meter in the latex, the amount of increase-volume silica slurry can be in the scope of about 5wt%-80wt%.

The said method of Fig. 2 can be used the polymkeric substance identical with method shown in Figure 1, and can be included in adding carbon black slurry at least a latex.

The available coupling agent can be silicoorganic compound in the method shown in Figure 2.Coupling agent can be two (trialkoxysilyl alkyl) polysulfide that contains 2-8 S atom, and wherein alkyl can be C ₁-C ₁₈Alkyl, alkoxyl group can be C ₁-C ₈Alkoxyl group.Silicoorganic compound can have 1-3 and the direct-connected facile hydrolysis group of Siliciumatom and at least one and the direct-connected organic group of Siliciumatom.The organic group that is directly connected to Siliciumatom can have at least one functional group.This functional group can be in the polymer cure process can with the functional group of polymer chemistry reaction.

Coupling agent can have general formula as described herein: amount of the coupling agent that uses in this method can be the coupling agent of the about 1-25 weight part of the silicon-dioxide of per 100 weight parts.

Method shown in Figure 2 can comprise the amount of the increase-volume silica slurry that uses about 5-80wt%, with the solid weight meter in silicon-dioxide styrene butadiene latex polymer or silicon-dioxide acrylonitrile butadiene polymer latex Ruzhong.

Step 208 can comprise the interpolation filler.Filler can be selected from: the walnut shell of zeyssatite, pulverizing, cellulose materials, the coal of the Pericarppium arachidis hypogaeae of pulverizing, talcum, pulverizing, bagasse, ash content, perlite, ensilage, clay, lime carbonate, biomass or its combination.

Step 210 can comprise inhibitor is added in the monomer of emulsion polymerization process.Inhibitor can be phenol antioxidant, phosphite, bis-phenol, amine inhibitor or its combination.

One or more embodiments relate to compsn and the goods by the method preparation of Fig. 2.

Fig. 3 illustrates three embodiment of formation with the blend method of the acrylonitrile butadiene polymkeric substance of emulsion polymerization preparation and styrene butadiene latex polymer and the blend of increase-volume silicon-dioxide.

Step 300 can be included in the aqeous suspension with coupling agent treatment silicon-dioxide to form the increase-volume silica slurry.Step 300 can be taked to carry out with the same way as described in Fig. 1 and 2 or any alternate manner as herein described.

Step 302 can comprise at least a portion of increase-volume silica slurry and styrene butadiene latex polymer blend, forms the silicon-dioxide styrene butadiene latex polymer.

Step 304 can comprise silicon-dioxide styrene butadiene latex polymer and the blend of acrylonitrile butadiene polymer latex, forms the blend of acrylonitrile butadiene polymkeric substance and styrene butadiene latex polymer and increase-volume silicon-dioxide.

One or more embodiments relate to compsn and the goods by the method preparation of Fig. 3.

Fig. 4 is illustrated in the 4th embodiment that forms the method for increase-volume silicon-dioxide in the latex blends of acrylonitrile butadiene polymkeric substance and styrene butadiene polymkeric substance.

Step 400 can be included in the aqeous suspension and form the increase-volume silica slurry with coupling agent treatment silicon-dioxide.Step 400 any coupling agent as herein described capable of using carries out, as at described in Fig. 1-3 those.

Step 402 can comprise at least a portion of increase-volume silica slurry and the blend of acrylonitrile butadiene polymer latex, forms silicon-dioxide acrylonitrile butadiene polymer latex.

Step 404 can comprise styrene butadiene latex polymer and the blend of silicon-dioxide acrylonitrile butadiene polymer latex, thereby in the latex blends of acrylonitrile butadiene polymkeric substance and styrene butadiene polymkeric substance, form increase-volume silicon-dioxide.

One or more embodiments relate to by the method for Fig. 4 prepared compsn and goods.

Fig. 5 illustrates the 5th embodiment of the method for the increase-volume silicon-dioxide that forms the latex form and nitrile polymer blend.

Step 500 can be included in the aqeous suspension with coupling agent treatment silicon-dioxide to form the increase-volume silica slurry.Step 500 any coupling agent as herein described capable of using carries out, as at described in Fig. 1-4 those.

Step 502 can comprise at least a portion and the styrene butadiene latex polymer blend of increase-volume silica slurry, forms the silicon-dioxide styrene butadiene latex polymer.

Step 504 step can comprise sneaks into the acrylonitrile butadiene polymer latex in the silicon-dioxide styrene butadiene latex polymer, forms the increase-volume silicon-dioxide and the nitrile polymer blend of latex form.

In one or more embodiment, the increase-volume silica slurry can comprise the silicon-dioxide of 1-30wt%.For example, the increase-volume silica slurry can comprise the silicon-dioxide of the about 15wt% of about 10-and the coupling agent of 20wt% at the most.

Coupling agent can be silane or other silicoorganic compound.Silicoorganic compound are the compounds that contain carbon-silicon key.

The silicon-dioxide of non-reunion can have the median size of about 0.1 nanometer to 200 nanometer.In one or more embodiment, nano level silicon-dioxide can be used as the silicon-dioxide in this paper method, like polyhedral oligomeric silsesquioxane (POSS).Silicon-dioxide can be for example pyrolytic silicon dioxide, soft silica such as zeyssatite, faujusite or its combination of fumed silica.Silicon-dioxide can be to form water slurry and with the white rouge of coupling agent treatment.

Coupling agent can chemically bonded at least 30% silica sphere.Coupling agent can have with silica sphere generation chemical reaction coupling agent is bonded to the ability on it.Coupling agent can be through covalent bonding to silica sphere.Coupling agent can be well known in the prior art, be used for wetting ability packing material such as spun glass or silicon-dioxide are coupled to hydrophobic material like all cpds such as natural and synthetic elastomer polymkeric substance as rubber or thermoplastic material.The amount of coupling agent can be the coupling agent of about 25 weight parts of the about 1-of silicon-dioxide of per 100 weight parts.

In some embodiments, this method can be applied to styrene-butadiene rubber(SBR) so that the silicon dioxide compositions that can be cured through the sulphur compound crosslinking reaction to be provided.Therefore, coupling agent can be silicoorganic compound, and it has at least one and has sulfydryl, polysulfide, thiocyanogen (SCN), the organic group of halogen and/or amido functional group.At least one organic group of silicoorganic compound can have the unsaturated or epoxide group of olefinic, makes silica-filled polymkeric substance can carry out the curing reaction of peroxy type.

In one or more embodiments, one or two alkyl can be replaced by phenyl or benzyl, or phenyl, benzyl or alkoxyl group that one to two alkyl can be substituted alkyl replace.

In case take place the cohesion back and in case at polymkeric substance with after the increase-volume silica slurry contacts, just can carry out the recovery of polymkeric substance.

In this process, temperature in the blend process and reaction times can change in relative broad range.In embodiments, TR is to about 125 ℃ from envrionment temperature.

Emulsion blending can utilize the impeller blend of pump then through using common groove, and speed is 10rpm ~ 80rpm, and the time length is 5 minutes to 1.5 hours.

In this process, being used to influence the time length of reacting between hydrolysis coupling agent and the silicon-dioxide can change in the limited field than broad, and this scope can be 4 h ~ 48 hours, depends on the temperature that is adopted.

In this process, part can be according to the use of used coupling agent, polymer latex characteristic, other filler such as carbon black and the end-use of polymkeric substance etc., and the silica volume that adds in one or more latex can change in wide scope.For example, the silica volume that adds in one or more latex can be about 1wt% ~ about 70wt%.

Silicon-dioxide can comprise untreated flaky silicon dioxide, and through pretreated silicon-dioxide.

In some embodiments, the increase-volume silica slurry can be about 5wt% ~ about 60wt% of the solid weight in the polymer latex.

Styrene butadiene latex polymer can be a mobile emulsion at normal temperatures, makes styrene butadiene latex polymer to pour into a mould.

The part of increase-volume silica slurry and styrene butadiene latex polymer can each personal common grooves that is pumped to, and carry out blend to be enough to making emulsion under service temperature, keep the speed of suspension to stir the mixture.For example, mixture can use the impeller of pump to stir under the speed of 5rpm-80rpm 5 minutes ~ 1.5 hours.

The silicon-dioxide styrene butadiene latex polymer can comprise the increase-volume silica slurry/styrene butadiene latex polymer of about 50:50 ratio.

The part of increase-volume silica slurry and acrylonitrile butadiene polymer latex can each personal common grooves that is pumped to, and carry out blend enough to make emulsion under service temperature, keep the speed of suspension to stir the mixture.For example, mixture can use the impeller of pump to stir under the speed of 5rpm-80rpm 5 minutes ~ 1.5 hours.

Formed silicon-dioxide acrylonitrile butadiene polymer latex can comprise the increase-volume silica slurry/acrylonitrile butadiene polymer latex of about 50:50 ratio.

In some embodiments, silicon-dioxide styrene butadiene latex polymer and silicon-dioxide acrylonitrile butadiene polymer latex can flow into common groove through making latex, and stir the mixture and carry out blend.For example, polymer latex can use the impeller of pump to stir under the speed of 5rpm-80rpm 5 minutes ~ 1.5 hours.

One or more embodiments of this method can comprise adds the carbon black slurry at least a polymer latex Ruzhong.The carbon black slurry can be or comprise the oven process carbon black that it can comprise high structure carbon black, low structure carbon black or acetylene carbon black.

The carbon black slurry can add through carbon black is flowed in one or more above-mentioned common grooves.

For example, the solid of the about 40wt% of about 5-can be added in one or more common grooves in the carbon black slurry.The addition of carbon black slurry in latex can be 1-80wt%.

Can the extending oil of the about 60wt% of about 0.1wt%-be added at least a polymer latex Ruzhong.Extending oil can be NO, alkyl oil, synthetic oil, perfume oil, rudimentary polycyclic aromatic hydrocarbons (PAH) oil or its combination.

Can the inhibitor of consumption for the about 0.05wt% of about 2-be added in the latex.Inhibitor can add at least a polymer latex or its combination.Inhibitor can be phenol antioxidant, phosphite, bis-phenol, amine inhibitor or its combination.

Can filler be added in a kind of or more blend as herein described.For example, can the filler of the about 50wt% of about 0.1-be added in a kind of or more blend as herein described.

In case take place the cohesion back and in case at polymkeric substance with after the increase-volume silica slurry contacts, can carry out the recovery of polymkeric substance.

Aqeous suspension can comprise water, soap, emulsifying agent, tensio-active agent, thickening material (comprising viscosity modifier such as starch or CMC 99.5).

Acvator, radical initiator and terminator can 0.1-5wt% amount in emulsion polymerization process, make up use.Acvator can be a superoxide.

In some embodiments, the curing bag that is used for crosslinked formed polymkeric substance can be used for emulsion polymerization process, for example zinc oxide, other organo-peroxide or propenoate.

In one or more embodiment, the increase-volume silica slurry can comprise the silicon-dioxide of 1-30wt%.For example, the increase-volume silica slurry can comprise the silicon-dioxide of about 10-15wt% and the coupling agent of 20wt% at the most.

Temperature in the blend process and reaction times can change in relative broad range.In some embodiments, TR is to about 125 ℃ from envrionment temperature.Blend can utilize the impeller stirring of pump to carry out.Influence the time of reacting between hydrolysis coupling agent and the silicon-dioxide, can in the limited field than broad, change, this scope can be 4 h ~ 48 hours, depends on the temperature that is adopted.

Part is according to the use of used coupling agent, polymer latex characteristic, other filler such as carbon black and the end-use of polymkeric substance, and the silica volume that adds in the latex can change in wide scope.For example, the silica volume that adds in one or more latex can be about 25wt% ~ about 80wt%.

In some embodiments, the increase-volume silica slurry can be about 5wt% ~ about 60wt% of the solid weight in the polymer latex.

This method can also comprise at least a portion of increase-volume silica slurry and styrene butadiene latex polymer blend, forms the silicon-dioxide styrene butadiene latex polymer that can flow at ambient temperature with pourable emulsion form.

The part of increase-volume silica slurry and styrene butadiene latex polymer can each personal common grooves that is pumped to, and carry out blend with this mixture of speed stirring that emulsion is kept suspend under service temperature.For example, can use the impeller of pump to stir the mixture.

This silicon-dioxide styrene butadiene latex polymer can comprise the increase-volume silica slurry/styrene butadiene latex polymer of about 25:75 ratio.

In one or more embodiment, at least a portion of increase-volume silica slurry can with the blend of acrylonitrile butadiene polymer latex, form silicon-dioxide acrylonitrile butadiene polymer latex.

The part of increase-volume silica slurry and acrylonitrile butadiene polymer latex can each personal common grooves that is pumped to, and carry out blend with this mixture of speed stirring that emulsion is kept suspend under service temperature.

Formed silicon-dioxide acrylonitrile butadiene polymer latex can comprise the increase-volume silica slurry/acrylonitrile butadiene polymer latex of about 25:75 ratio.

At least a polymkeric substance can be or comprise multipolymer, homopolymer, cross-linked polymer, partial cross-linked polymkeric substance or its combination.At least a polymkeric substance can be natural or synthetic polymer.

The acrylonitrile butadiene polymer latex can with TR 301 such as tree elastomer, viton, rubber latex blend, scrap rubber grain or its combined hybrid.

The part of styrene butadiene latex polymer can with the blend of silicon-dioxide acrylonitrile butadiene polymer latex, form increase-volume silicon-dioxide and nitrile polymer blend.

Silicon-dioxide styrene butadiene latex polymer and silicon-dioxide acrylonitrile butadiene polymer latex can be through making latex flow into common groove and stirring blend.Polymer latex can be blended into vinyl cyanide and cinnamic ratio is 3:1 ~ 8:1; The ratio of vinylbenzene and divinyl is 0.06:1 ~ 0.14:1; Divinyl and cinnamic ratio are 7:1 ~ 14:1; The ratio of vinyl cyanide and divinyl is 0.4:1 ~ 0.75:1, and the ratio of divinyl and vinyl cyanide is 1.3:1 ~ 2.5:1.

One or more embodiments of this method can comprise the carbon black slurry is added at least a latex.Said carbon black slurry can be or comprise the oven process carbon black that it can comprise high structure carbon black, low structure carbon black and acetylene carbon black.

The carbon black slurry can add through carbon black is flowed in the above-mentioned common groove.For example, the carbon black of the about 50wt% of about 1-slurry can be added in one or more common grooves.

Polymer compsn can comprise extending oil, inhibitor or its arbitrary combination, and they can add at least a latex.For example, can the extending oil of the about 60wt% of about 4-be added at least a polymer latex Ruzhong, can the inhibitor of the about 3wt% of about 0.1-be added at least a polymer latex or its combination.

Polymer compsn can comprise filler, and it can be added in any one or multiple these blends.For example, can the filler of the about 50wt% of about 0.1-be added in one or more these blends.

One or more embodiment can be included in the latex blends of acrylonitrile butadiene polymkeric substance and styrene butadiene polymkeric substance and sneak into increase-volume silicon-dioxide.

At least a portion of styrene butadiene latex polymer can with the blend of acrylonitrile butadiene polymer latex, form vinyl cyanide and the styrene butadiene latex polymer blend can flow at ambient temperature with pourable emulsion form.

Coupling agent can have with the silica sphere generation chemical reaction of 20wt% at least and with the form of covalent linkage coupling agent is bonded to it on and the ability of formation increase-volume silicon-dioxide

Vinyl cyanide and styrene butadiene latex polymer blend can with the blend of increase-volume silica slurry, be formed on the blend of sneaking into increase-volume silicon-dioxide in vinyl cyanide and the styrene butadiene latex polymer.

In one or more embodiment, the styrene polymer latex of the about 80wt% of about 2wt%-can with the increase-volume silica slurry blend of acrylonitrile butadiene latex and the about 30wt% of about 1wt%-of the about 30wt% of about 1wt%-.The amount of increase-volume silica slurry is about 5-80wt% of solid weight in the latex.

The embodiment that describes one or more part embodiments of the inventive method is described below, and it can be used for forming the affiliated compsn of this paper and one or more embodiments of goods.

The preparation of embodiment 1:SBR-silicon-dioxide-carbon black

A. the preparation of increase-volume silica slurry

In container, add 55.1g Silquest.RTM A-189 (OSi specification), 27g Virahol, 1.1g Glacial acetic acid min. 99.5 and 27g water and prepare silane-water solution, they can form the mixture of initial muddiness.

Like 50rmp, room temperature is as stirring under 72 Fahrenheit degrees, and is limpid up to mixture at a high speed for mixture that this is initially muddy.In one or more embodiment, this initial muddy mixture can be at a high speed as stirring under the high temperature of 50rmp and 60 ℃-66 ℃, and is limpid up to mixture.

High-speed stirring can about 10-20 minute, can add 28g water more afterwards, and this can cause mixture to become muddy.

Can continue stir about 15-20 minute, limpid once more up to mixture, and form solution.

Can in being equipped with another container of whisking appliance, add: 16 pounds of water and 4.05 pounds of fine particles, dried silicon-dioxide, HiSil.RTM 233 and stir abouts 15 minutes are so that silicon-dioxide is wetting and dispersion, to form silane-water solution.

Continue to stir down with the silane-water solution adding wherein, and adding 25% sodium hydroxide, it can be heated to 76 ℃.Therefore, the pH value can be brought up to 7.5-8.0.Temperature can keep about 4 hours down at 76 ℃, was cooled to then about 60 ℃.At this moment, can this increase-volume silica slurry be added to the latex stage of continuous emulsion polymerization process, but or intermittent feeding to revertex.

B. the blend of increase-volume silica slurry and styrene butadiene rubber latex

The increase-volume silica slurry can prepare like the said method of A part of above embodiment 1.

Can the increase-volume silica slurry be added in 35 pounds of SBR latex comprising 7 or 8 pound of 1502 type rubber and the stirred vessel of Santoflex.RTM as the mixture of the 6PPD of antioxidant solution that contains the Sinorgchem preparation, and this compound is remained on 66 ℃ or 60 ℃.

Can the thermal black slurry be added in this original mixture.For example, the deep fat emulsion of the thermal black of about 20 pounds N234 type carbon black that contains the 10wt% that has an appointment slurry and the about 3 pounds SundexRTM that contains 62.8wt% 8125.This compound can 66 ℃ with normal pressure down or 60 ℃ with normal pressure under stirring 30 minutes.

The slowly blend of above-mentioned latex, for example speed is 50rpm, joins that to contain the 45 pounds-Yue 50 pounds of water of having an appointment be in 4 the bigger stirred vessel of vitriolic with being enough to provide pH.In one or more embodiment, above-mentioned latex blends steam capable of using contain have an appointment 45 pounds-Yue 50 pounds of water be enough to provide pH be in 4 the bigger stirred vessel of vitriolic moment mix.

The pH that latex blends and vitriolic interpolation ratio can change with the cohesion slurries that keep gained remains in the scope of 4-5 in 38 fens clock times of adding blend.

Remix 38 minutes and use extra acid so that the product particle size growth as required, as rise to 1 millimeter to 30 millimeters particle diameter, and make the slurries that do not contain latex limpid, this point is well-known to those skilled in the art.

The wet compsn particle diameter that obtains through this cohesion or the size of chip are similar to the particle diameter that cohesion obtained or the size of chip when not containing silicon-dioxide.

Can confirm to add to that basic all solid and liquid all is absorbed and uniform distribution in the latex mixture to the range estimation of drying compsn and chemical analysis.Estimated like ash analysis, the specific absorption of silicon-dioxide can be about 96%-about 99% of its loading level.

Embodiment 2: styrene butadiene ribber-silicon-dioxide-carbon black preparation of compositions

A. the preparation of increase-volume silica slurry

In container, add 100g Silquest.RTM A-189,50g Virahol, 2g Glacial acetic acid min. 99.5 and 47g water and form the mixture of initial muddiness, thereby prepare silane-water solution.Should can up to limpid, for example continue about 22 minutes of about 12-in high speed and stirring at room by initial muddy mixture, and can add 50g water more afterwards, this can cause mixture to become muddy.Can continue stir about 12-about 22 minutes, limpid up to solution.

In being equipped with another container of whisking appliance, add: 15 pounds of water and 5 pounds of dried silicon-dioxide HiSil.RTM 233 of fine particle and stir about 20 minutes, so that silicon-dioxide is wetting and disperse.Continue to stir down wherein, add 25% sodium hydroxide simultaneously, make the pH value can bring up to 7.5-8.0 the silane-water solution adding.Blend can be heated to 64 ℃-77 ℃.Temperature can keep about 3.5 hours down at 64 ℃-77 ℃, was cooled to 60 ℃ then.At this moment, can the increase-volume silica slurry be added to the latex stage of continuous emulsion polymerization technique, but or intermittent feeding to revertex.

B. the blend of increase-volume silica slurry and styrene-butadiene rubber(SBR) (SBR) latex

Can the increase-volume silica slurry like the said preparation of A part of above-mentioned embodiment 2 be added and contain in the latex mixture described in embodiment 1.Final mixture can stir 35 minutes down at 60 degrees centigrade.

Can make above-mentioned latex blends cohesion, of embodiment 1.The wet composition grain of realizing through this cohesion or the size of powder can be similar to or be slightly larger than when not containing silicon-dioxide cohesion gained, for example 1 millimeter to 30 millimeters size.To the range estimation of drying compsn with chemical analysis can confirm to add to solids basic all in the latex mixture and liquid is absorbed and uniform distribution.Estimated like ash analysis, the specific absorption of silicon-dioxide can be about 96%-about 99% of its loading level.

The preparation of embodiment 3:SBR-silicon dioxide compositions

Can the increase-volume silica slurry like the said preparation of A part of above-mentioned embodiment 2 be charged in the latex mixture of SBR latex of Santoflex 134 of 1502 SBR that contain 20wt% that contain 40 pounds and 2wt%, it can remain under 60 degrees centigrade.

In this mixture, can charge into 3 pounds of deep fat emulsions that contain the Sundex 8125 of 60wt%.Subsequently, but mixture restir 38 minutes keeps 60 degrees centigrade temperature simultaneously, can this hot glue breast slowly be charged into another container that is used for condensing thereafter, thereby can form dehydration or exsiccant powder.

The particle diameter of dehydration powder can be similar to the not particle diameter of silica containing SBR, as 1 millimeter to 30 millimeters, because it flocks together.To the range estimation of drying compsn with chemical analysis can confirm to add to the basic all solids in the latex mixture and liquid is absorbed and uniform distribution.Estimated like ash analysis, the silicon-dioxide specific absorption can be about 96%-about 99% of its loading level.

Embodiment 4: the preparation of paracril (NBR)-silicon dioxide compositions

A. the preparation of increase-volume silica slurry

In container, add 20g Silquest.RTM A-189,15g Virahol, 0.7g Glacial acetic acid min. 99.5 and 10g water and form the mixture of initial muddiness, thereby prepare silane-water solution.Should can up to limpid, for example continue about 20 minutes of about 10-in high speed and stirring at room by initial muddy mixture, and can add 15g water more afterwards, this can cause mixture to become muddy.Can continue stir about 12-about 25 minutes, limpid up to solution.

In being equipped with another container of whisking appliance, add: 7 pounds of water and 2 pounds of dried silicon-dioxide HiSil.RTM 233 of fine particle and stir about 20 minutes, so that silicon-dioxide is wetting and disperse.Continuing to add silane-water solution under the stirring, add 25% sodium hydroxide simultaneously, make the pH value can bring up to 7.5-8.0.Blend can be heated to 70 ℃ and kept about 3.5 hours, is cooled to 60 ℃ then.At this moment, can the increase-volume silica slurry be added to the latex stage of continuous emulsion polymerization process, but or intermittent feeding to revertex.

B. the blend of increase-volume silica slurry and paracril (NBR) latex

Can the increase-volume silica slurry like the said preparation of A part of embodiment 4 be charged in the stirred vessel that contains following mixture: the emulsion of antioxidant of acrylonitrile butadiene polymkeric substance (NBR) latex of 30 pounds the Nysyn.RTM 40-5 rubber that contains 22wt% and the Agerite Geltrol (tm) (Vanderbilt Chemical) that 200g contains 16wt%, it can remain under 60 degrees centigrade.In this original mixture, can charge into 15 pounds of thermal black slurries that contain the N234 type carbon black of 7wt%.Final mixture can stir 35 minutes down at 60 degrees centigrade.

Can above-mentioned latex blends slowly be added and contain 30 pounds of water and the capacity vitriolic that is enough to obtain pH 4 more in the large container.Can described in previous embodiment, accomplish cohesion.The wet composition powder particle size that produces through this cohesion can be similar to the size of NBR cohesion gained when not containing silicon-dioxide, for example 1 millimeter to 30 millimeters.Basic all solids and the liquid that can confirm to add in the latex mixture to the range estimation and the chemical analysis of drying compsn all are absorbed and uniform distribution.Estimated like ash analysis, the silicon-dioxide specific absorption can be about 96%-about 99% of its loading level.

The goods of being processed by this material can comprise pneumatic tyre.The goods that formed by the disclosed blend polymer of this paper can be through injection moulding, extrude, pressing mold, cutting, rolling, rotational moulding or its combination are made.

Method as herein described can be included in cohesion polymer under 57 degrees centigrade-74 degrees centigrade the temperature.

Method as herein described can comprise that the polymkeric substance to cohesion filters, to remove unnecessary water, for example through using screen cloth, cellulose membrane strainer, French oil abrasion or expressed water from polymkeric substance.

Method as herein described can comprise utilizes heat, for example utilizes heated tray or fluidized-bed in drying oven heating, the drying oven to come dry isolating polymkeric substance.

Method as herein described can be continuous emulsion polymerization or interrupter method.

Embodiment 5: can handle ending or to stop polyreaction through short stopping from the latex of emulsion polymerization, and can further handle to remove unreacted monomer.Residual unreacted monomer can be removed through stripping.The latex of processing can be introduced the latex storage tank.Can the finished product latex from storage tank be pumped into charging stock tank as required and carry out blend, to realize the target molecular weight of product.Through the measurement mooney viscosity, but the indirect measurement molecular weight.

Latex can be constantly from nitrile rubber charging stock tank and/or butyronitrile and the pumping of styrene-butadiene latex charging stock tank, and can in pressure head jar (head tank), mix inhibitor and/or extending oil, and all components may be combined in together therein.Mixture can be pumped in the carbex jar (a carbex tank) etc. and with increase-volume silica slurry, carbon black slurry or its combined hybrid.

The carbex jar can overflow get into the first cohesion jar.If use clean or pure extending oil, rather than fat liquor, then mixture can be through a series of online static mixers to promote thoroughly mixing and to disperse.

The cohesion jar that mixture can flow into heating and stir wherein can add the dilute sulphuric acid flocculation agent.When carrying out paracril flow process (NBR), Tai-Ace S 150 and calcium chloride can be used as and helps flocculation agent.Can decide sour inlet amount according to a cohesion jar required pH value, and alum and calcium chloride can carry out charging according to flow control.All three kinds of flocculation agent can be used to destroy latex emulsion and cause micelle to form.The control of powder size can become the deciding factor of flocculation agent interpolation and can preferentially replace the prescription value.

The content of storage tank can thoroughly stir with the center at storage tank and produce vortex.Processing condition that adopt and add cohesion chemical as herein described and can make mixture coagulated form micelle to starch with water slurry or powder.

When under condition as herein described, condensing, latex, oil, increase-volume silica slurry, carbon black slurry, inhibitor and combination thereof can disperse equably.The powder slurry can overflow to the second cohesion jar from the first cohesion jar and be used for for cohesion extra dwell time being provided.

The soap conversion tank can provide the more residence time to accomplish agglomeration step.Can, realize material cohesion fully before leaving the soap conversion tank, to avoid the upstream device fouling.

Can in agglomeration process, use a spot of flocculant aid, to promote the slurries clarification and to accomplish cohesion.

Centrifuge dehydration unit or rotary dewaterer can be used for the moisture content machinery of coloured micelle is reduced to about 35wt%-40wt%, so that carry out more energy-conservation moisture eliminator operation.

The micelle slurry of leaving water cleaning of evaporator can get into rotary dewaterer and throw to cylinder screen.Water can pass cylinder screen, and can be removed by the bottom of gravity at rotary dewaterer.Micelle can rise path movement also through discharging the entering classifier in its vertical outlet along spiral.

Classifier can be the shaker conveyer that is equipped with the grid bar.The grid distance of grid bar can be used for regulating the powder size.Less powder can fall through the grid space, and oversize powder then is maintained at the top of grid bar and discharges through the side exit groove.

Acceptable powder can be discharged into the wet feed twist lock valve from classifier, supplies with the wet mash gas blower more thus.Wet feed twist lock valve can prevent that wet mash from blowing back from gas blower.

Micelle can be in rotary dewaterer fluidisation, it is undertaken by the air that makes progress from the rotary dehydration motor spindle.The upward movement of air can partly be supported micelle and micelle is suspended to form the ebullient material.

The dry powder grain can be disposed to the powder hopper through the opening of final drying compartment end.Discharging powder hopper can be with it to the charging of dry powder gas blower.The dry powder gas blower can be delivered to packing balance swirler-(baler scale cyclones) with dry powder.Micelle can be fed to the balance of each packing machine top with gravity, and wherein micelle can be compressed into the bale packing form.

Micelle also can be transferred to the pack operation room, and wherein micelle can be coated with separant, and is packaged as free-pouring powder.

Embodiment 6: the formation of elastic composition can comprise at first introduces last processing district with the synthetic elastomer polymkeric substance of 47wt%.The synthetic elastomer polymkeric substance can comprise the vinylbenzene of 70wt% and the divinyl of 30wt%.

Then, can add the increase-volume silicon-dioxide of 10wt%.Increase-volume silicon-dioxide can comprise the silicon-dioxide of 90wt% and the coupling agent of 10wt%.

In addition, can add the scrap rubber grain of 25wt% to last processing district

In addition, can add the carbon black of 8wt% and the extending oil of 10wt% to last processing district.

Last processing district can remain under 60 degrees centigrade the temperature and normal pressure.The component of compsn is 38 minutes time of reaction in the processing district in the end.

In emulsion polymerization process, can use soap class, water, acvator, radical initiator and terminator to form long chain polymerization.

Embodiment 7: can prepare solid content and be the scrap rubber grain slurry of 2%-15% and remain in the stirring heating storage tank.This scrap rubber grain slurry in the stirring heating storage tank be directed into the agglomeration step of production process.

Can handle ending or to stop polyreaction through short stopping from the latex of emulsion polymerization process, and can further handle to remove unreacted monomer.Residual unreacted monomer can be removed through stripping.Final latex can be introduced the latex storage tank.

Can final latex be pumped into charging stock tank from storage tank.Final latex can be as required in charging stock tank blend to reach the target molecular weight of product.Through the measurement mooney viscosity, but the indirect measurement molecular weight.

Latex can be constantly from nitrile rubber charging stock tank, butyronitrile and styrene-butadiene latex charging stock tank and/or the pumping of styrene-butadiene latex charging stock tank; And can in the pressure head jar, mix inhibitor and/or extending oil; All components may be combined in together therein, and formation can be pumped to the mixture in carbex jar etc.

Scrap rubber grain slurry can be pumped to according to the schedule speed of prescription in the carbex jar etc.Increase-volume silica slurry, carbon black slurry or its combination can be added in the carbex jar etc.

The carbex jar can overflow get into the first cohesion jar.If use clean or pure extending oil, rather than fat liquor, then mixture can be through a series of online static mixers to promote thoroughly mixing and to disperse.

The cohesion jar that mixture can flow into heating and stir wherein can add the dilute sulphuric acid flocculation agent.When carrying out paracril (NBR) technology, Tai-Ace S 150 and calcium chloride can be used as and helps flocculation agent.Can require according to pH value to decide sour inlet amount, and alum and calcium chloride can carry out charging according to flow control to the cohesion jar.All three kinds of flocculation agent can be used to destroy latex emulsion and cause the micelle of new cohesion to form.The control of the powder size of new cohesion can become the deciding factor of flocculation agent interpolation and can preferentially replace the prescription value.

The content of storage tank can thoroughly stir with the center at storage tank and produce vortex.Adopting certain processing condition and adding cohesion chemical as herein described to make mixture coagulated form fresh micelle and water slurry.

When under embodiment 2 described conditions, condensing, latex, oil, increase-volume silica slurry, carbon black slurry, inhibitor and combination thereof can disperse equably.Recovery powder that merges and slurries can overflow to the second cohesion jar with thinking that cohesion provides extra dwell time from the first cohesion jar.

The soap conversion tank can provide the more residence time to accomplish agglomeration step.Can, realize material cohesion fully before leaving the soap conversion tank, to avoid the upstream device fouling.Can in agglomeration process, use a spot of flocculant aid, to promote the slurries clarification and to accomplish cohesion.

Centrifuge dehydration unit or rotary dewaterer can be used for the moisture content machinery of coloured micelle is reduced to about 35wt%-40wt%, so that carry out more energy-conservation moisture eliminator operation.The micelle slurry of leaving water cleaning of evaporator can get into rotary dewaterer and can throw to cylinder screen.Water can pass cylinder screen, and can be removed with the bottom of gravity at rotary dewaterer.Micelle can rise path movement also through its vertical outlet discharge entering classifier along spiral.

Classifier can be the shaker conveyer that is equipped with the grid bar.The grid distance of grid bar can be used for regulating the powder size.Less powder can fall through the grid space, and oversize powder then is maintained at the top of grid bar and discharges through the side exit groove.

Acceptable powder can be discharged into the wet feed twist lock valve from classifier, and it gives wet mash gas blower feed again.Wet feed twist lock valve can prevent that wet mash from blowing back from gas blower.

Micelle can be in rotary dewaterer fluidisation, it is undertaken by the air that makes progress from the rotary dehydration motor spindle.The upward movement of air can partly be supported micelle and micelle is suspended to form the ebullient material.The dry powder grain can be disposed to the powder hopper through the opening of final drying compartment end.

Discharging powder hopper can be to the charging of dry powder gas blower.The dry powder gas blower can be delivered to packing balance device swirler-with dry powder.Micelle can be fed to the balance of each packing machine top by gravity, and wherein micelle can be compressed into the bale packing form.Micelle can also be transferred to the pack operation room, and wherein micelle can be coated with separant and be packaged as free-pouring powder.

Though these embodiments are that example is described with ben embodiment, it should be understood that within the scope of the appended claims, embodiment can be different from the specifically described mode of this paper and implement.

Claims (68)

1. the increase-volume silicon-dioxide and the nitrile polymer blend of a latex form that forms through following method, said method comprises:

In aqeous suspension with coupling agent treatment silicon-dioxide forming the increase-volume silica slurry, the surface generation chemical reaction of wherein said coupling agent and said silicon-dioxide is so that said coupling agent bonding on it;

With at least a portion and the styrene butadiene latex polymer blend of said increase-volume silica slurry, form the silicon-dioxide styrene butadiene latex polymer;

With at least a portion and the blend of acrylonitrile butadiene polymer latex of said increase-volume silica slurry, form silicon-dioxide acrylonitrile butadiene polymer latex; With

With said silicon-dioxide styrene butadiene latex polymer and the blend of said silicon-dioxide acrylonitrile butadiene polymer latex, form the increase-volume silicon-dioxide and the nitrile polymer blend of latex form.

2. increase-volume silicon-dioxide as claimed in claim 1 and nitrile polymer blend, wherein said coupling agent is silicoorganic compound.

3. increase-volume silicon-dioxide as claimed in claim 2 and nitrile polymer blend; Wherein said silicoorganic compound have 1-3 and the direct-connected facile hydrolysis group of Siliciumatom and at least one and the direct-connected organic group of said Siliciumatom; Wherein said at least one organic group has at least one functional group, and wherein said at least one functional group is the functional group that in solidification process, can chemical reaction take place with said styrene butadiene latex polymer, said acrylonitrile butadiene polymer latex or its combination.

4. increase-volume silicon-dioxide as claimed in claim 1 and nitrile polymer blend, the multipolymer of the first at least, homopolymer, cross-linked polymer, partial cross-linked polymkeric substance or its combination in wherein said polymer latex Ruzhong.

5. increase-volume silicon-dioxide as claimed in claim 1 and nitrile polymer blend, wherein said styrene butadiene latex polymer, said silicon-dioxide styrene butadiene latex polymer or said acrylonitrile butadiene polymer latex comprise TR 301.

6. increase-volume silicon-dioxide as claimed in claim 1 and nitrile polymer blend, the median size of wherein said silicon-dioxide are 0.1 micron-20 microns.

7. increase-volume silicon-dioxide as claimed in claim 1 and nitrile polymer blend, wherein said silicon-dioxide are fumed silica, soft silica or its combination.

8. increase-volume silicon-dioxide as claimed in claim 1 and nitrile polymer blend, wherein said method also comprise carbon black slurry are added in the one of which at least of said polymer latex.

9. increase-volume silicon-dioxide as claimed in claim 1 and nitrile polymer blend, wherein said coupling agent has general formula Wherein X is the functional group that is selected from amino, polyamino alkyl, sulfydryl, polysulfide base, epoxy group(ing), vinyl, acryloxy and methacryloxy, and wherein y is equal to or greater than 0 integer, Z ₁, Z ₂And Z ₃Can be independently selected from respectively: hydrogen, C ₁-C ₁₈Alkyl, aryl, naphthenic base, alkoxy aryl, halogen-substituted alkyl, and Z wherein ₁, Z ₂And Z ₃In at least one can be alkoxyl group, hydrogen, halogen or hydroxyl.

10. increase-volume silicon-dioxide as claimed in claim 1 and nitrile polymer blend, wherein said coupling agent are two (trialkoxysilyl alkyl) polysulfides that contains 2-8 sulphur atom, and wherein alkyl is C ₁-C ₁₈Alkyl, alkoxyl group are C ₁-C ₈Alkoxyl group.

11. increase-volume silicon-dioxide as claimed in claim 1 and nitrile polymer blend, wherein said method also comprise increase-volume silicon-dioxide and the cohesion of nitrile polymer blend that makes said latex form.

12. like the increase-volume silicon-dioxide and the nitrile polymer blend of claim 11, wherein said method comprises that also increase-volume silicon-dioxide and the nitrile polymer blend to the latex form of cohesion carries out drying to dewater.

13. like the increase-volume silicon-dioxide and the nitrile polymer blend of claim 11, wherein said increase-volume silica slurry contains the silicon-dioxide of 1wt%-40wt%.

14. like the increase-volume silicon-dioxide and the nitrile polymer blend of claim 13, wherein said coupling agent consumption is the said coupling agent that the said silicon-dioxide of per 100 weight parts adds the 1-25 weight part.

15. increase-volume silicon-dioxide and nitrile polymer blend like claim 13; The amount of wherein said increase-volume silica slurry is 5wt%-80wt%, with the solid weight meter in said silicon-dioxide styrene butadiene latex polymer or said silicon-dioxide acrylonitrile butadiene polymer latex Ruzhong.

16. increase-volume silicon-dioxide as claimed in claim 1 and nitrile polymer blend, wherein said method also comprise extending oil, inhibitor or its combination are added in the one of which at least of said polymer latex.

17. the vinyl cyanide styrene butadiene ter-polymers latex blends with increase-volume silicon-dioxide that forms through following method, wherein said method comprises:

With styrene butadiene latex polymer and the blend of acrylonitrile butadiene polymer latex, form styrene butadiene polymkeric substance and acrylonitrile butadiene polymer latex blend;

In aqeous suspension with coupling agent treatment silicon-dioxide forming the increase-volume silica slurry, the surface generation chemical reaction of wherein said coupling agent and said silicon-dioxide is so that said coupling agent bonding on it; With

With said increase-volume silicon-dioxide and said styrene butadiene polymkeric substance and the blend of acrylonitrile butadiene polymer latex blend, form the vinyl cyanide styrene butadiene ter-polymers latex blends with increase-volume silicon-dioxide of latex form.

18., wherein form styrene butadiene latex polymer and acrylonitrile butadiene polymer latex and comprise with following each thing blend like the vinyl cyanide styrene butadiene ter-polymers latex blends with increase-volume silicon-dioxide of claim 17:

The said styrene butadiene latex polymer of 2wt%-8wt%;

The said acrylonitrile butadiene polymer latex of 1wt%-30wt%;

The said increase-volume silica slurry of 1wt%-30wt%, wherein, as if the solid content meter with said styrene butadiene latex polymer and acrylonitrile butadiene polymer latex Ruzhong, the amount of said increase-volume silica slurry is 5wt%-80wt%.

19. like the vinyl cyanide styrene butadiene ter-polymers latex blends with increase-volume silicon-dioxide of claim 17, the multipolymer of the first at least, homopolymer, cross-linked polymer, partial cross-linked polymkeric substance or its combination in wherein said polymer latex Ruzhong.

20. like the vinyl cyanide styrene butadiene ter-polymers latex blends with increase-volume silicon-dioxide of claim 17, wherein said method also comprises adds the carbon black slurry in the one of which at least of said polymer latex to.

21. like the vinyl cyanide styrene butadiene ter-polymers latex blends with increase-volume silicon-dioxide of claim 17, wherein said coupling agent is silicoorganic compound.

22. vinyl cyanide styrene butadiene ter-polymers latex blends with increase-volume silicon-dioxide like claim 21; Wherein said silicoorganic compound have 1-3 and the direct-connected facile hydrolysis group of Siliciumatom and at least one and the direct-connected organic group of said Siliciumatom; Wherein said at least one organic group has at least one functional group, wherein said at least one functional group be in solidification process can with the functional group of said polymer latex generation chemical reaction.

23. like the vinyl cyanide styrene butadiene ter-polymers latex blends with increase-volume silicon-dioxide of claim 17, wherein said coupling agent has general formula

Wherein X is the functional group that is selected from amino, polyamino alkyl, sulfydryl, polysulfide base, epoxy group(ing), vinyl, acryloxy and methacryloxy, and wherein y is equal to or greater than 0 integer, Z ₁, Z ₂And Z ₃Can be independently selected from respectively: hydrogen, C ₁-C ₁₈Alkyl, aryl, naphthenic base, alkoxy aryl, halogen-substituted alkyl, and Z wherein ₁, Z ₂And Z ₃In at least one can be alkoxyl group, hydrogen, halogen or hydroxyl; Method as claimed in claim 17, wherein said coupling agent are two (trialkoxysilyl alkyl) polysulfides that contains 2-8 sulphur atom, and wherein alkyl is C ₁-C ₁₈Alkyl, alkoxyl group are C ₁-C ₈Alkoxyl group.

24. like the vinyl cyanide styrene butadiene ter-polymers latex blends with increase-volume silicon-dioxide of claim 17, wherein said coupling agent consumption is the said coupling agent that the said silicon-dioxide of per 100 weight parts adds the 1-25 weight part.

25. vinyl cyanide styrene butadiene ter-polymers latex blends with increase-volume silicon-dioxide like claim 17; The amount of wherein said increase-volume silica slurry is 5wt%-80wt%, with the solid weight meter in said silicon-dioxide styrene butadiene latex polymer or said silicon-dioxide acrylonitrile butadiene polymer latex Ruzhong.

26. vinyl cyanide styrene butadiene ter-polymers latex blends with increase-volume silicon-dioxide like claim 17; Wherein said method comprises that also interpolation is selected from following filler: the walnut shell of zeyssatite, pulverizing, cellulose materials, the carbon of the Pericarppium arachidis hypogaeae of pulverizing, talcum, pulverizing, bagasse, ash content, perlite, ensilage, clay, lime carbonate, biomass or its combination.

27. like the vinyl cyanide styrene butadiene ter-polymers latex blends with increase-volume silicon-dioxide of claim 17, wherein said method comprises that also interpolation is selected from following inhibitor: phenol antioxidant, phosphite, bis-phenol, amine or its combination.

28. acrylonitrile butadiene polymkeric substance with increase-volume silicon-dioxide and styrene butadiene latex polymer blend through a following method preparation, wherein said method comprises:

In aqeous suspension with coupling agent treatment silicon-dioxide forming the increase-volume silica slurry, the surface generation chemical reaction of wherein said coupling agent and said silicon-dioxide is so that said coupling agent bonding on it;

With at least a portion and the styrene butadiene latex polymer blend of said increase-volume silica slurry, form the silicon-dioxide styrene butadiene latex polymer; With

With said silicon-dioxide styrene butadiene latex polymer and the blend of acrylonitrile butadiene polymer latex, form acrylonitrile butadiene polymkeric substance and styrene butadiene latex polymer blend with increase-volume silicon-dioxide.

29. the increase-volume silicon-dioxide in acrylonitrile butadiene polymkeric substance and styrene butadiene latex polymer blend through following method preparation, said method comprises:

In aqeous suspension with coupling agent treatment silicon-dioxide forming the increase-volume silica slurry, the surface generation chemical reaction of wherein said coupling agent and said silicon-dioxide is so that said coupling agent bonding on it;

With at least a portion and the blend of acrylonitrile butadiene polymer latex of said increase-volume silica slurry, form silicon-dioxide acrylonitrile butadiene polymer latex; With

With styrene butadiene latex polymer and the blend of said silicon-dioxide acrylonitrile butadiene polymer latex, be formed on the increase-volume silicon-dioxide in acrylonitrile butadiene polymkeric substance and the styrene butadiene latex polymer blend.

30. an increase-volume silicon-dioxide and a nitrile polymer blend that utilizes the latex form of following method formation, wherein said method comprises:

In aqeous suspension with coupling agent treatment silicon-dioxide forming the increase-volume silica slurry, the surface generation chemical reaction of wherein said coupling agent and said silicon-dioxide so that said coupling agent be bonded on it;

With at least a portion and the styrene butadiene latex polymer blend of said increase-volume silica slurry, form the silicon-dioxide styrene butadiene latex polymer; With

With acrylonitrile butadiene polymer latex and the blend of said silicon-dioxide styrene butadiene latex polymer, form the increase-volume silicon-dioxide and the nitrile polymer blend of latex form.

31. the polymer compsn of the acrylonitrile butadiene polymkeric substance of increase-volume silicon-dioxide and letex polymerization and the styrene butadiene polymer blending of letex polymerization, said polymer compsn comprises:

In the total solid weight of said polymer compsn, the increase-volume silicon-dioxide of 6wt%-90wt%, in the weight of said increase-volume silicon-dioxide, wherein said increase-volume silicon-dioxide comprises the organo-silicon coupling agent of 1wt% at least;

The styrene butadiene polymkeric substance of the said letex polymerization of 10wt%-80wt%;

The acrylonitrile butadiene polymkeric substance of the said letex polymerization of 10wt%-80wt%; Wherein the acrylonitrile butadiene polymkeric substance of the said letex polymerization of 10wt% is acrylonitrile polymer and the liquid 1 of 15:50 by ratio at least; The 3-butadiene polymer constitutes; The HS bonding of said increase-volume silicon-dioxide and every kind of polymkeric substance is provided, and wherein divinyl and cinnamic ratio are 7:1-17:1, and the ratio of vinyl cyanide and divinyl is 0.4:1-0.75:1.

32. polymer compsn like claim 31; The increase-volume silicon-dioxide that also comprises 10wt%-50wt%; Wherein said organo-silicon coupling agent chemically bonded to the surface of said increase-volume silicon-dioxide, wherein said organosilicon exists as average tetramer structure, and it has 0.75 or above T ³/ T ²Ratio is measured through silicon cross polarization magic-angle-spinning nuclear magnetic resonance, and wherein said increase-volume silicon-dioxide has 0.9 or above T ³/ T ²Ratio.

33. like the polymer compsn of claim 32, wherein the amount of the said organo-silicon coupling agent of chemically bonded to said increase-volume silica sphere is counted 1-25wt% with the weight of said silicon-dioxide.

34. like the polymer compsn of claim 32, wherein said organo-silicon coupling agent derived from have with

35. the organosilane of following structure:

Wherein X is the functional group that is selected from amino, polyamino alkyl, sulfydryl, polysulfide base, thiocyanogen, epoxy group(ing), vinyl, halogen, acryloxy and methacryloxy, and wherein y is equal to or greater than 0 integer, Z ₁, Z ₂And Z ₃Can be independently selected from respectively: hydrogen, alkoxyl group, halogen or hydroxyl.

36. like the polymer compsn of claim 32, the acrylonitrile butadiene polymkeric substance of the styrene butadiene polymkeric substance of wherein said letex polymerization, said letex polymerization or its combination are formed by tree elastomer, viton, thermoplastic polymer or resinous polymer.

37. like the polymer compsn of claim 35, wherein said polymer compsn comprises and is selected from following member: the ter-polymers of conjugated diene polymer, combination, polyolefine, poly-alpha olefins, polyester, polymeric amide, polycarbonate, ppe, polyacrylic ester, urethane, ethylene, propylene and non-conjugated diene, fluoroelastomer, chlorine bomb gonosome, TR 301, polyhutadiene, the multipolymer that gathers isobutyl diene, sovprene, SE, paracril, polyepoxide, ethene interpretation, butadiene styrene block copolymerization thing, styrene isoprene segmented copolymer, propenoate-cross-linking monomer-vinyl monomer and combination thereof based on polymer of vinyl monomer, conjugated diene and vinyl monomer.

38. like the polymer compsn of claim 35, wherein at least a said polymkeric substance is multipolymer, homopolymer, cross-linked polymer, partial cross-linked polymkeric substance or its combination.

39. like the polymer compsn of claim 31, the median size of wherein said increase-volume silicon-dioxide is 1 nanometer-15 micron.

40. like the polymer compsn of claim 31, the silicon-dioxide that wherein is used to form said increase-volume silicon-dioxide is fumed silica, soft silica or its combination.

41., also comprise the carbon black of 1wt%-50wt% like the polymer compsn of claim 31.

42. polymer compsn like claim 31; The organosilicon of wherein said organo-silicon coupling agent has 1-3 and the direct-connected facile hydrolysis group of Siliciumatom and at least one and the direct-connected organic group of said Siliciumatom; Wherein said at least one organic group has at least one functional group, wherein said at least one functional group be in the solidification process of said polymer compsn can with the functional group of said polymer compsn generation chemical reaction.

43. like the polymer compsn of claim 42, wherein said coupling agent has general formula

Wherein X is the functional group that is selected from amino, polyamino alkyl, sulfydryl, polysulfide base, thiocyanogen, epoxy group(ing), vinyl, halogen, acryloxy and methacryloxy, and wherein y is equal to or greater than 0 integer, Z ₁, Z ₂And Z ₃Can be independently selected from respectively: hydrogen, alkoxyl group, halogen or hydroxyl.

44. like the polymer compsn of claim 42, wherein said coupling agent is two (trialkoxysilyl alkyl) polysulfide that contains 2-8 sulphur atom, wherein alkyl is C ₁-C ₁₈Alkyl, alkoxyl group are C ₁-C ₈Alkoxyl group.

45., also comprise its amount and be the extending oil of 4wt%-60wt%, inhibitor or its combination like the polymer compsn of claim 31.

46. like the polymer compsn of claim 45, wherein said extending oil is NO, alkyl oil, synthetic oil, perfume oil, rudimentary polycyclic aromatic hydrocarbons oil or its combination.

47. like the polymer compsn of claim 45, wherein said inhibitor is phenol antioxidant, phosphite, bis-phenol, amine inhibitor or its combination.

48. polymer compsn like claim 31; The filler that also comprises 0.1wt%-50wt%; Said filler is to be selected from following a member: the walnut shell of zeyssatite, pulverizing, cellulose materials, the carbon of the Pericarppium arachidis hypogaeae of pulverizing, talcum, pulverizing, bagasse, ash content, perlite, ensilage, clay, lime carbonate, biomass and combination thereof.

49. like the polymer compsn of claim 31, also comprising the combination total amount is acvator, radical polymerization inhibitor and the terminator of 0.1wt%-5wt%.

50. like the polymer compsn of claim 49, wherein said acvator is a superoxide.

51., also comprise the curing bag that utilizes zinc oxide, organo-peroxide or propenoate to come cross-linked polymer like the polymer compsn of claim 50.

52. the goods of processing by the polymer compsn of claim 51.

53. like the goods of claim 52, wherein said goods are car mat, tire, belt, cylinder, footwear, cable jacket, edge, roof, flexible pipe, shock eliminator peculiar to vessel, industrial belt, non-doughnut, mining belt, bearing, pipeline or pneumatic tyre.

54. like the goods of claim 53, wherein said goods through injection moulding, extrude, pressing mold, cutting, rolling, rotational moulding or its combination make.

55. elastomeric polymer composition of utilizing the continuous flow emulsion polymerization formation of acvator, radical initiator, water and terminator with scrap rubber grain and silicon-dioxide; Wherein said continuous flow emulsion polymerization under no pressure or low pressure and room temperature carry out to the temperature more than the room temperature, said compsn comprises:

In the gross weight of said compsn, the synthetic elastomer polymkeric substance of 18wt%-93wt%, wherein said synthetic elastomer polymkeric substance comprises:

In the gross weight of said compsn, the liquid 1,3-butadiene monomer of 60wt%-82wt%; Or

In the gross weight of said compsn, the styrene monomer of 18wt%-40wt%;

In the gross weight of said compsn, the increase-volume silicon-dioxide of 5wt%-80wt%, wherein said increase-volume silicon-dioxide has the organo-silicon coupling agent of 1wt% at least, and it is bonded on the surface of the said increase-volume silicon-dioxide of 20wt% at least;

In the gross weight of said compsn, the recovery scrap rubber grain of 1wt%-50wt%; With

In the gross weight of said compsn, the carbon black of 1wt%-40wt%.

56. like the elastomeric polymer composition with scrap rubber grain and silicon-dioxide of claim 55, wherein said recovery scrap rubber grain comprises the particle that reclaims rubber, wherein the said recovery rubber grain of at least 50 volume % is less than #10 order U.S. sieve series.

57. like the elastomeric polymer composition with scrap rubber grain and silicon-dioxide of claim 55, wherein said regeneration scrap rubber grain comprises the particle that reclaims rubber, wherein the said recovery rubber grain of at least 50 volume % is less than #200 order U.S. sieve series.

58. like the elastomeric polymer composition with scrap rubber grain and silicon-dioxide of claim 55, wherein said synthetic elastomer polymkeric substance is latex form or dried particle form.

59. like the elastomeric polymer composition with scrap rubber grain and silicon-dioxide of claim 55, wherein said regeneration scrap rubber grain is 100% from reclaiming tire.

60., also comprise the filler of 0.1wt%-50wt%, in the gross weight of said compsn like the elastomeric polymer composition with scrap rubber grain and silicon-dioxide of claim 55.

61. elastomeric polymer composition with scrap rubber grain and silicon-dioxide like claim 60; Wherein said filler is to be selected from following member: the walnut shell of pulverizing, cellulose materials, the carbon of the Pericarppium arachidis hypogaeae of ensilage, zeyssatite, pulverizing, talcum, pulverizing, the bagasse of pulverizing, ash content, perlite, clay, lime carbonate, biomass or its combination.

62., also comprise the extending oil of 1wt%-40wt%, in the gross weight of said compsn like the elastomeric polymer composition with scrap rubber grain and silicon-dioxide of claim 55.

63. like the elastomeric polymer composition with scrap rubber grain and silicon-dioxide of claim 62, wherein said extending oil is selected from: synthetic oil, perfume oil, NO, alkyl oil, polycyclic aromatic hydrocarbons is oily and combination.

64., also comprise thermoplastic polymer, thermoplastic elastomer, TPV or its arbitrary combination of 25wt% at the most, in the gross weight of said compsn like the elastomeric polymer composition with scrap rubber grain and silicon-dioxide of claim 55.

65. like the elastomeric polymer composition with scrap rubber grain and silicon-dioxide of claim 55, wherein said monomer is crosslinked.

66., also comprise the carbon black of 1wt%-10wt%, in the gross weight of said compsn like the elastomeric polymer composition with scrap rubber grain and silicon-dioxide of claim 55.

67. elastomeric polymer composition goods that comprise like the compsn of claim 55 with scrap rubber grain and silicon-dioxide.

68. like the elastomeric polymer composition goods with scrap rubber grain and silicon-dioxide of claim 67, wherein said goods are car mat, tire, belt, cylinder, footwear, cable jacket, edge, roof, flexible pipe, shock eliminator peculiar to vessel, industrial belt, non-doughnut, mining belt, bearing or pipeline.

Images