JP2013516540A - Composition comprising compatible silica, nitrile rubber, styrene butadiene rubber, elastomer compound, and / or recycled material - Google Patents

Abstract

A process for forming a compatible silica and nitrile polymer blend in latex form is disclosed herein. The process includes treating silica with a coupling agent to form a compatible silica slurry. The process includes mixing a compatible silica slurry into a styrene butadiene polymer latex and an acrylonitrile butadiene polymer latex. The process includes blending a silica styrene butadiene polymer latex with a silica acrylonitrile butadiene polymer latex. Polymeric compositions of compatible silica in blends of acrylonitrile butadiene polymer and styrene butadiene polymer and recycled elastomer compositions are described herein. The recycled elastomeric composition also includes compatible silica containing a coupling agent, crumb rubber, carbon black, filler, and extender oil. Articles comprising the recycled elastomer composition are disclosed herein.
[Selection] Figure 1

Description

Cross-reference of related applications

  This application is based on US Provisional Patent Application Nos. 61 / 292,910 and January 2011, both filed January 7, 2010, both entitled “Process for Making Compatible Silica and Nitrile Polymer Compositions”. US Patent Application No. 12 / 984,267, filed 4 days; January 7, 2010, both entitled "Compatibilized Silica in Nitrile Rubber and Blend of Nitrile Rubber and Styrene Butadiene Rubber Composition" US provisional patent application 61 / 292,917 and US application Ser. No. 12 / 984,280 filed Jan. 4, 2011; and both “recycled materials and elastomeric compounds comprising silica. United States provisional patent application 61 / 292,923, filed January 7, 2010, and United States filed January 4, 2011, entitled “ Priority and claims the benefit to Patent Application No. 12 / 984,295. These references are incorporated herein in their entirety.

  Embodiments of the present invention generally include a compatible silica and nitrile polymer blend in latex form, an acrylonitrile styrene butadiene terpolymer latex blend containing compatible silica, a blend of acrylonitrile butadiene polymer and styrene butadiene polymer latex blend containing compatible silica, The present invention relates to a polymer composition that counters both mechanical and biological invasion or danger, and a recycled elastomeric composition comprising rubber crumb, compatible silica and carbon black.

  Incorporation of silica and other reinforcing agents such as carbon black into a homogeneous polymer in the latex stage without the need for complex processing aids and without causing premature latex coagulation (where silica is There is a need to provide a simpler and less expensive technique for (which can be substantially uniformly dispersed in a polymer matrix and is compatible).

  There is a need for a wet process for the treatment with a coupling agent on precipitated silica or fumed silica, whereby the silica is compatible with the polymer phase of the polymer latex.

  A chemical weapon composition that has uniform filler dispersion, is easy to manufacture, contains UV stabilizers, has high density, is lightweight, and is used to combat biological weapons for user protection. There is a need to provide a polymer composition that can withstand.

  Save energy during production, reduce production costs, reduce transportation costs by not using expensive raw hydrocarbons that usually originate from offshore wells, and landfills such as rubber that is recovered and recycled There is a need for recycled elastomeric blends with “green” properties that reduce the amount of rubber in the environment.

  Embodiments of the present invention meet these needs.

  The detailed description will be better understood when taken in conjunction with the accompanying drawings, in which:

FIG. 1 is a diagram of one embodiment of a process. FIG. 2 is an illustration of one embodiment of a process for forming a blend of acrylonitrile and styrene butadiene terpolymer latex containing compatible silica. FIG. 3 is an illustration of one embodiment of a process for forming a blend of acrylonitrile butadiene polymer and styrene butadiene polymer latex comprising compatible silica. FIG. 4 is an illustration of one embodiment of a process for forming compatible silica in a latex blend of acrylonitrile butadiene polymer and styrene butadiene polymer. FIG. 5 is an illustration of one embodiment of a process for forming a compatible silica and nitrile polymer blend in latex form.

  Embodiments of the present invention are described in detail below with reference to the figures described.

  Before describing the processes, compositions and articles of the present invention in detail, the processes, compositions and articles are not limited to a particular embodiment, and the processes, compositions and articles are in various ways. It should be understood that it can be practiced or implemented.

  In one or more embodiments, a continuous flow is formed using emulsion polymerization with no pressure or low pressure, ambient temperature or slightly above ambient temperature, using an activator, free radical initiator, water and terminator. , An elastic polymer composition comprising crumb rubber and silica, and articles made from the elastic polymer composition.

  The elastic polymer composition comprising crumb rubber and silica can have 18% to 93% by weight of the synthetic elastic polymer based on the total weight of the composition.

  The synthetic elastic polymer may include 60% to 82% by weight of liquid 1,3-butadiene monomer, based on the total weight of the elastic polymer composition.

  The elastic polymer composition comprising crumb rubber and silica can have 18% to 40% by weight styrene monomer based on the total weight of the elastic polymer composition.

  The elastic polymer composition comprising crumb rubber and silica can have 5% to 80% by weight of compatible silica, based on the total weight of the elastic polymer composition. The compatible silica can have at least 1% by weight of an organosilicon coupling agent bonded to about 20% by weight of the surface of the compatible silica.

  The elastic polymer composition comprising crumb rubber and silica can have 1% to 50% by weight recycled crumb rubber based on the total weight of the composition.

  The elastic polymer composition comprising crumb rubber and silica comprises 1% to 40% by weight of carbon black based on the total weight of the composition or 1% to 10% by weight of carbon black based on the total weight of the composition. Can do.

  The elastic polymer composition comprising crumb rubber and silica can contain recycled rubber particles therein. In one or more embodiments, at least 50% by volume of crumb rubber particles may be smaller than US series sieve # 10 mesh, or at least 50% by volume of crumb rubber particles may be US standard series sieve # 200 mesh. Can be smaller. The elastic polymer composition containing crumb rubber and silica can contain crumb rubber that can be supplied 100% from recycled tires. The particles of reclaimed rubber can be passed through a sieve before the reclaimed rubber is incorporated into the elastic polymer composition or rubber composition.

  During the emulsion polymerization to produce the elastic polymer composition, the synthetic elastic polymer can be in the form of latex or dry particulates.

  The elastic polymer composition comprising crumb rubber and silica can further comprise 0.1 wt% to 50 wt% filler, based on the total weight of the composition.

  The fillers used in the processes, compositions and articles described herein include ground pecan shells, cellulosic materials, silage, diatomaceous earth, ground peanut shells, talc, ground coal, ground bagasse, ash, perlite, clay. , Calcium carbonate, biomass, and combinations thereof.

  The elastic polymer composition comprising crumb rubber and silica can comprise 1 wt% to 40 wt% of extender oil, based on the total weight of the composition.

  The extender oil used in the processes, compositions and articles described herein may be a synthetic oil, aromatic oil, naphthenic oil, hydrocarbon, polycyclic aromatic hydrocarbon oil, or combinations thereof.

  The elastic polymer composition comprising crumb rubber and silica can comprise up to 25% by weight of a thermoplastic polymer, thermoplastic elastomer, thermoplastic vulcanizate, or any combination thereof, based on the total weight of the composition.

  The elastic polymer composition comprising crumb rubber and silica may be a crosslinked polymer composition. Elastic polymer compositions comprising crumb rubber and silica can be used to make various types of articles.

  Articles that can be made from the processes and compositions described herein include floor mats, tires, belts, rollers, footwear, wire and cable jackets, roof trims, tubular hoses, marine impact bumpers. , Industrial belts, non-automotive tires, mining belts, bearings, conduits, gasket printer rollers, O-rings, shoes, garden hoses, pipes, side bumpers used for ship docking, non-latex gloves, gas masks , Pneumatic tires used in motorcycles, automobiles, airplanes, and the like.

  One or more embodiments relate to recycled elastomeric compositions and articles made from recycled elastomeric compositions.

  The natural rubber used in the processes, compositions and articles described herein can be any polyisoprene, such as rubber. The synthetic elastomeric polymer used in the processes, compositions and articles described herein may be a styrene butadiene rubber.

  The synthetic elastic polymer is 60% to 82% by weight liquid 1,3-butadiene, 18% to 40% by weight styrene, 5% compatible silica with at least 1% by weight coupling agent bound to the surface of the compatible silica. % To 80% by weight, crumb rubber 1% to 50% by weight, and carbon black 1% to 40% by weight.

  Synthetic elastic polymers can be prepared by polymerization or copolymerization of conjugated diene monomers such as butadiene, isoprene, chloroprene, pentadiene, and dimethylbutadiene. Synthetic elastomeric polymers can include vinyl monomers and combinations of common diene and vinyl monomers.

  Pinane hydroperoxide can be used in emulsion polymerization.

  Suitable vinyl monomers for use in the processes, compositions and articles described herein include: styrene, alpha methyl styrene, alkyl substituted styrene, vinyl toluene, divinyl benzene, acrylonitrile, vinyl chloride, It can include methacrylonitrile, isobutylene, maleic anhydride, acrylic esters and acrylic acids, methacrylic esters, vinyl ethers and vinyl pyridines.

  Synthetic elastic polymers are styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), acrylonitrile-butadiene-styrene polymer (ABS), polybutadiene, polyvinyl chloride (PVC), polystyrene, polyvinyl acetate, butadiene-vinylpyridine polymer , Polyisoprene, polychloroprene, neoprene, styrene-acrylonitrile copolymer (SAN) or blends of acrylonitrile-butadiene rubber and polyvinyl chloride.

  The resulting recycled elastic polymer can be made from a blend and can contain up to 25 wt% of a thermoplastic polymer, a thermoplastic elastomer, a thermoplastic vulcanizate, or a combination thereof. The thermoplastic polymer may be a thermoplastic polyolefin blend. The thermoplastic elastomer may be a styrene butadiene block copolymer. The thermoplastic vulcanizate can be a cross-linked ethylene propylene diene material in a polypropylene matrix.

  Silica can constitute 5% to 80% by weight of the total composition of the recycled elastic polymer.

  Emulsion polymerization blending can be performed using a Banbury mixer that mixes at a rate of 800 pounds to 1200 pounds for 90 seconds to 30 minutes.

  In addition to blending the silica already listed herein with the polymer, the compatible silica is a polyolefin, polyalphaolefin, polyester, polyamide, polycarbonate, polyphenylene oxide, polyepoxide, polyacrylate, and a copolymer of acrylate and vinyl monomer. Can be blended with.

  Polyolefins can be homopolymers, copolymers, cross-linked copolymers, and comonomer blends prepared from linear, branched or cyclic alpha monoolefins, vinylidene olefins, and unconjugated di- and triolefins, 1,4 -Pentadiene, 1,4-hexadiene, 1,5-hexadiene, dicyclopentadiene, 1,5-cyclooctadiene, octatriene, norbornadiene, alkylidene norbornene, vinyl norbornene and the like.

  Examples of such polymers include polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-α-olefin-nonconjugated diene terpolymers (EPDMs), chlorinated polyethylene, polybutylene, polybutene, polynobornene and alpha olefin resins.

  In one or more embodiments, the silica is treated with a coupling agent in an aqueous solution to produce compatible silica suitable for use in the processes, compositions, and articles described herein, and other components. A slurry for blending with can be formed.

  The silica is made of many commercially available amorphous silicas, such as precipitated silica or fumed silica, and may have a finely divided particle size and high surface area. The size of the silica particles can be varied within a relatively wide range, such as from 7 nm to 60 nm, depending on the end use of the silica filled polymer or silica reinforced polymer.

  Micronized silica can thus be formed into an aqueous slurry and treated with a coupling agent that can be chemically bonded to the silica surface. Coupling agents well known in the art are used to link hydrophilic filler materials such as glass fibers or silica with natural and synthetic elastic polymers useful as hydrophobic materials such as rubber or thermoplastic materials. be able to. At least 20% binding can be achieved with the coupling agent.

  Organosilicon compounds well known to bind silica to natural and synthetic elastic polymers can be used as coupling agents. The organosilicon may be derived from an organosilane.

  In embodiments, 1 to 3 organic groups can be directly bonded to a silicon atom that is miscible with a natural or synthetic elastic polymer to which silica is added.

  The coupling agent can be chemically combined with natural rubber, synthetic elastic polymer or a combination thereof during curing of the natural rubber or synthetic elastic polymer.

  The coupling agent can have the ability to chemically react with the surface of the silica to bind the coupling agent thereto. The coupling agent can include bis (trialkoxysilylalkyl) polysulfide. The bis (trialkoxysilylalkyl) polysulfide can have 2 to 8 sulfur atoms, where the alkyl group can be an alkyl group having 1 to 18 carbon atoms, and the alkoxy group has It may be 1 to 8 alkoxy groups.

  The amount of coupling agent used can vary within relatively wide limits depending on the amount of silica blended with the natural or synthetic elastic polymer and depending on the molecular weight of the coupling agent. 1 part to 25 parts of coupling agent can be used for 100 parts of silica, for example, 1 part to 15 parts of coupling agent can be used for 100 parts of silica. The amount of coupling agent used can be defined by the actual weight percentage of organosilicon present on the silica surface. Much of the weight of the coupling agent can be lost during the reaction with the silica surface and its own condensation.

  In order to achieve incorporation of 90% by weight or more of silica into the emulsion polymerized polymer, the weight percent of organosilicon on the silica surface may be between 0.50 and 10.0. Thus, a minimum of 0.5-5 g of silane-derived organosilicon can be bound to 100 g of silica filled in the slurry.

  For enhanced compatibility in the dry mix, or for additional chemical reactions with natural or synthetic elastic polymers, more than 1 wt.% Organosilicon residues per silica weight bind on the surface of the silica. For example, 10% to 20% by weight of organosilicon can be bound to the surface of silica.

The synthetic elastomeric polymer may have or include from about 55% to about 92% by weight of butadiene (eg, liquid 1,3-butadiene CH ₂ ═CHCH═CH ₂ ). The synthetic elastomeric polymer can contain about 8 to about 45 weight percent styrene. In embodiments, the synthetic elastomeric polymer can take the form of a latex or dry particulate.

  The term “latex” as used herein refers to a stable dispersion or emulsion of polymer microparticles in a medium. Illustrative media can include water or other liquids. The latex may be natural or synthetic.

  In one embodiment, the elastomeric composition can include about 5% to about 80% by weight of compatible silica.

  In embodiments, the compatible silica can include at least 1% by weight of a coupling agent that is bound to the surface of the compatible silica. In embodiments, the amount of coupling agent may be from about 1% to about 50% by weight coupling agent.

  The recycled elastomeric composition can include from about 1% to about 50% by weight crumb rubber.

  As used herein, the term “crumb rubber” refers to steels and fibers where waste tires or other rubber is removed along with any other type of inert impurities such as dust, glass or rock. A substance obtained by being reduced to a homogeneous granule together with a reinforcing material. Recycled rubber may be recycled rubber, which is obtained from synthetic and / or natural rubber or plastic. In an embodiment, the crumb rubber may be made from 100% recycled tires. As described herein prior to being incorporated into the rubber composition, at least a portion of the reclaimed rubber particles can be passed through a US standard series mesh screen. For example, 10% to 50% of the recycled rubber particles can be passed through a # 200 mesh or other mesh screen.

  Elastomer composition embodiments may include from about 1% to about 40% by weight carbon black. Carbon black can be a substance that is essentially elemental carbon in the form of approximately spherical colloidal particles and colloid-sized coalesced particle coagulum obtained by partial combustion of hydrocarbon pyrolysis. Two different types of carbon black can be used.

  The elastomeric composition can include a filler as described herein. Embodiments of the elastomer composition can include from about 0.1% to about 50% by weight filler.

  The compositions, articles and processes described herein can include “other materials” such as ultraviolet (UV) stabilizers, extender oils, antioxidants or antioxidants. The composition can include from about 0.1% to 3% by weight of “other materials” based on the total weight of the composition.

  The ultraviolet (UV) stabilizer may be a hindered amine, benzotriazole, triazine, or a combination thereof. The antioxidant may be a phenolic antioxidant, phosphite, bisphenol, an amine antioxidant, or a combination thereof. For example, the elastomeric composition can comprise from about 0.01% to about 40% by weight extender oil. Extender oil can act as a plasticizer and enhance processability.

  Embodiments can include articles made from the rubber composition, such as the articles described herein.

  One or more embodiments include a polymer composition having about 6% to 90% by weight compatible silica, at least 1% by weight coupling agent, at least 10% by weight styrene butadiene polymer, and at least 10% by weight acrylonitrile butadiene polymer. Articles manufactured therefrom can be included.

The polymer composition, also referred to herein as a polymer blend, is ballistic clothing for tires, personnel while maintaining flexibility, durability and withstanding low temperatures of -35 ° C without deformation. Excellent for use in and shield.
The polymer blend can have the ability to accept fillers without being disjointed.

  In embodiments, the polymer composition can include a minimum amount of at least 10% by weight of an emulsion polymerized acrylonitrile butadiene polymer and the remainder consisting of compatible silica. The butadiene can be liquid 1,3-butadiene.

  The compatible silica can include an organosilicon coupling agent bonded to its surface, from about 2% to about 10% by weight of organosilicon, based on the weight of the silica, thereby forming a compatible silica.

  In embodiments, the polymer composition may be a blend of polymers. The polymers include polyolefins, polyalphaolefins, polyesters, polyamides, polycarbonates, polyphenylene oxides, polyacrylates, polyurethanes, terpolymers with ethylene propylene and non-conjugated dienes, fluoroelastomers, chloroelastomers, polyisoprenes, polybutadienes, polyisobutylidenes. , Polychloroprene, polyvinyl chloride, styrene butadiene rubber, acrylonitrile butadiene rubber, polyepoxide, ethylene interpolymers, block copolymers of styrene butadiene, cross-linked polymers listed above, homopolymers and copolymers of styrene isoprene, copolymers of acrylates, vinyl monomers, or It can be a combination of these.

  A polymer composition comprising compatible silica in an acrylonitrile butadiene polymer blend can also include a polyvinyl chloride polymer. From about 20% to about 50% by weight of the polyvinyl chloride polymer can be used with at least 10% by weight of the acrylonitrile butadiene polymer. The polymer composition may include a minimum amount of at least 10% of 15:50 acrylonitrile to butadiene polymer, with a balance consisting of compatible silica.

  One or more embodiments relate to an article formed from or made of the polymer composition described herein. The article can be any article described herein or the like. The formed article is chemically resistant to biological and chemical weapon components for use as gas masks, soldier boots, protective clothing against arc flashing and protective clothing against carnivorous organic organisms. be able to.

Organosilicon can be present as an average tetrameric structure having a T ³ / T ² ratio of 0.75 or more as measured by ²⁹ Si CPMAS NMR. The terms “T ² ” and “T ³ ” refer to double (T2) and triple (T3) Si—O bonded silicon. “Si CPMAS NMR” refers to silicon cross-polarization magic angle rotational nuclear magnetic resonance, with superscript number 29 indicating the isotope atomic weight of the silicon being analyzed.

  The coupling agent can bind to the surface of the silica in an amount of about 1% to about 25% by weight of organosilicon based on the weight of the silica.

The compatible silica has a T ³ / T ² ratio of 0.9 or greater as measured by ²⁹ Si CPMAS NMR.

  The compatible silica and nitrile polymer blend in latex form can have a Mooney viscosity (ML 1 + 4, 100 ° C.), a nitrile polymer of 10 to 100 and an acrylonitrile composition of 10% to 50% by weight.

  The method for producing the polymer composition can be performed while the polymer is in the form of a latex. As used herein, emulsion polymerized latex refers to the reaction mixture prior to the coagulation stage in the emulsion polymerization process.

  In one or more embodiments, a filler such as carbon black can be added to the polymer composition. The polymer composition can comprise from about 1% to about 50% by weight of carbon black, which can be a mixture of two different carbon blacks. The silica-carbon black composition can achieve a uniform and high load of the total amount of the filler and quantitatively incorporate the filler.

  The polymer composition can include other polymers in latex form, including conjugated diene-based polymers, polymers based on vinyl monomers, and combinations of conjugated dienes with vinyl monomers. Suitable vinyl monomers can include those vinyl monomers described herein for use in the processes, compositions, and articles described herein.

  The polymer composition is natural rubber, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), acrylonitrile-butadiene-styrene polymer (ABS), polybutadiene, polyvinyl chloride (PVC), polystyrene, polyvinyl acetate, butadiene-vinyl. Pyridine polymers, polyisoprene, polychloroprene, neoprene, styrene-acrylonitrile copolymers (SAN) or blends of acrylonitrile-butadiene rubber and polyvinyl chloride can be included. The polymer composition can have at least one copolymer, homopolymer, crosslinked polymer, partially crosslinked polymer, or combinations thereof.

  The polymer composition can be made by treating silica with a coupling agent in an aqueous suspension to form a compatible silica slurry. The compatible silica slurry includes an aqueous portion and compatible silica.

  The compatible silica can have from 2% to 25% by weight of organosilicon bound to its surface based on the weight of silicon. The compatible silica can have an average particle size of 1 nanometer (nm) to 15 microns. Uncoagulated compatible silica can have an average particle size of 1 nanometer to 15 microns. The silica can be fumed silica such as calcined silica, amorphous silica such as diatomaceous earth, faujasite, or combinations thereof.

  Fine powdered silica can be formed into an aqueous slurry and treated with a solution of a coupling agent that can chemically bond to the silica surface. Various coupling agents known in the art as coupling agents for bonding hydrophilic filler materials such as glass fibers, silica and the like with natural and synthetic polymers useful as hydrophobic materials such as rubber or thermoplastic materials. Compounds can be used. Organosilicon compounds are well known for bonding silica to natural and synthetic polymers.

  One or more embodiments relate to a process for forming a polymer blend comprising compatible silica and articles and compositions formed from the process.

  In the first embodiment, the process can include treating the silica to form a compatible silica and then making a silica styrene butadiene polymer latex comprising a silica acrylonitrile butadiene polymer.

  In this first embodiment, a compatible silica and nitrile polymer blend in latex form can be made. The formed compatible silica and nitrile polymer blend can have a Mooney viscosity (ML 1 + 4, 100 ° C.) of 10 to 100 and an acrylonitrile composition of 10% to 50% by weight.

  The first embodiment can include a process that can be performed while the polymer is in the form of a latex.

  The process can be set up for application to natural rubber latex and polymerized latex.

  The process can be used for emulsion polymerization, i.e. the polymer can be polymerized into a latex in the reaction mixture prior to the coagulation stage. As used herein, the term “latex” or “latex form” refers to an aqueous colloid / emulsion of rubber particles.

  All of the various embodiments described herein can be performed with polymer latexes, to which other components such as fillers, antioxidants, UV stabilizers and carbon black can be added. These processes can form a silica-carbon black composition capable of achieving a uniform high loading of the total amount of filler and quantitative filler incorporation.

  The process is applicable to other polymers made in latex form, including conjugated diene polymers, polymers based on vinyl monomers, and combinations of conjugated dienes and vinyl monomers. Suitable vinyl monomers that can be used herein can include any of the vinyl monomers described herein.

  For example, the polymers are natural rubber, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), acrylonitrile-butadiene-styrene polymer (ABS), polybutadiene, polyvinyl chloride (PVC), polystyrene, polyvinyl acetate, butadiene-vinylpyridine. It may be a polymer, polyisoprene, polychloroprene, neoprene, styrene-acrylonitrile copolymer (SAN) or a blend of acrylonitrile-butadiene rubber and polyvinyl chloride.

  Surfactants such as soaps can be used to form compatible silica and nitrile polymer blends in the latex. Initiators such as pinane hydroperoxide can be used. An activator such as ferrous sulfate can be used. Soap is available from Meadwestvaco and can supplement caustic such as sodium hydroxide. Soap can be added directly to the styrene, butadiene, acrylonitrile monomer feed. Butadiene may be liquid 1,3-butadiene.

  Emulsion polymerization for all processes disclosed herein can occur at temperatures from 1 degree Celsius to 30 degrees Celsius. The conversion to emulsion polymerization disclosed herein is 59% to 80%.

  The term “natural polymer” as used herein refers to a polymer made from rubber obtained from plant sources and the like. As used herein, the term “synthetic polymer” refers to polymers derived from fossil fuels that have rubber or elastic properties. Mixtures of natural and synthetic polymers can be used.

  The polymer latex may be an emulsion containing from 5 wt% to 75 wt% solids.

  The process of forming a polymer blend comprising a compatible silica can include treating the silica with a coupling agent in an aqueous suspension to form a compatible silica slurry.

  The aqueous suspension may contain water, soap, emulsifier, surfactant, thickener (including but not limited to viscosity modifiers) such as starch and carboxymethylcellulose.

  Silica can be treated with a coupling agent, such as organosilicon bonded to the surface of the silica, including 1 to 25 weight percent per weight of silica.

  FIG. 1 shows a first embodiment of the process.

  Step 100 can include forming a compatible silica and nitrile polymer blend in latex form by treating the silica with a coupling agent in an aqueous suspension to form a compatible silica slurry.

  The coupling agent can be an organosilicon that can chemically react with the surface of the silicon to form a bond thereto.

  Step 102 can include blending at least a portion of the compatible silica slurry with a styrene butadiene polymer latex to form a silica styrene butadiene polymer latex.

  Step 104 can include blending at least a portion of the compatible silica slurry with the acrylonitrile butadiene polymer latex to form a silica acrylonitrile butadiene polymer latex.

  Step 106 can include blending the silica styrene butadiene polymer latex and the silica acrylonitrile butadiene polymer latex to form a compatible silica and nitrile polymer blend in latex form.

  The organosilicon compound can have 1 to 3 readily hydrolyzable groups bonded directly to the silicon atom and at least one organic group bonded directly to the silicon atom. The organic group directly bonded to the silicon atom contains at least one functional group. The functional group may be a functional group that can undergo a chemical reaction with the polymer during curing of the polymer.

  The functional groups can be selected based on the specific polymer and specific manufacture of the elastomeric blend. For example, when the embodiment includes a styrene butadiene rubber containing silica that can be cured by a crosslinking reaction that includes a sulfur compound, an organic group having a mercapto group, a polysulfide group, a thiocyanato group (-SCN), a halogen atom, and / or an amino functionality. An organosilicon compound having at least one of can be used as a coupling agent. Correspondingly, at least one group of the organosilicon compound can have an ethylenically unsaturated group or an epoxy group so that the silica-filled polymer can undergo a peroxy-type curing reaction.

  Typical examples of hydrolyzable groups commonly used in such coupling agents include: halogen atoms, hydrogen atoms, hydroxyl groups, lower alkoxy groups such as methoxy groups, ethoxy groups, propoxy groups, and similar groups.

  For example, in embodiments where the polymer composition is made from a styrene butadiene rubber that can be cured by a crosslinking reaction that includes a sulfur compound, the coupling agent can be a mercapto group, a polysulfide group, a thiocyanato group (—SCN), a halogen atom, and / or Alternatively, it can be an organosilicon compound having at least one organic group having amino functionality. Accordingly, at least one group of the organosilicon compound can have an ethylenically unsaturated group or an epoxy group so that the silica-filled polymer can undergo a peroxy-type curing reaction.

  The process can use monomers that become monomer homopolymers, fully cross-linked copolymers, partially cross-linked polymers, copolymers, or combinations thereof.

  The formed styrene butadiene polymer latex, silica styrene butadiene polymer latex, and / or acrylonitrile butadiene polymer latex can further comprise polyisoprene.

  The process can use silica with an average particle size of 0.1 microns to 20 microns.

  The process can use fumed silica, amorphous silica, or a combination thereof as silica.

  Step 108 can include adding the carbon black slurry to at least one of the monomers in latex form.

  Process as a coupling agent, general structure:

Can be used. “X” may be a functional group selected from the group consisting of an amino group, a polyaminoalkyl group, a mercapto group, a polysulfide group, an epoxy group, a vinyl group, an acryloxy group, and a methacryloxy group. “Y” can represent an integer of 0 or more. “Z ₁ ”, “Z ₂ ”, and “Z ₃ ” are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group, a cycloalkyl group, an arylalkoxy group, or a halo-substituted alkyl group. You can choose from the group At least one of “Z ₁ ”, “Z ₂ ”, and “Z ₃ ” represents an alkoxy group, a hydrogen atom, a halogen atom, or a hydroxyl group. Other embodiments of the processes, compositions and articles described herein have the general structural formula:

Can be included or used.

  Coupling agent is: bis (trialkoxysilylalkyl) polysulfide, or: trialkylsilane, dialkylsilane, trialkylalkoxysilane, trialkylhalosilane, dialkylalkoxysilane, dialkyldialkoxysilane, dialkylalkoxyhalosilane, trialkylsilanol , Alkyltrialkoxysilanes, alkyldialkoxysilanes, alkyldialkoxyhalosilanes, and monoalkylsilanes, or at the same time, wherein the alkyl group has 1 to 18 carbon atoms. Linear, cyclic, or branched hydrocarbons, or combinations thereof. In one or more embodiments, one or two alkyl groups can be substituted with a phenyl group or a benzyl group, or one or two alkyl groups can be substituted with a phenyl group, a benzyl group, or an alkoxy substituted alkyl group.

  The coupling agent may be a bis (trialkoxysilylalkyl) polysulfide containing 2 to 8 sulfur atoms, wherein the alkyl group may be an alkyl group having 1 to 18 carbon atoms and the alkoxy group is carbon. It may be an alkoxy group having 1 to 8 atoms.

  The silica may be nano-sized silica, such as polyhedral oligomeric silsesquioxane (POSS).

  The coupling agent may be silane or another organosilicon compound. An organosilicon compound is a compound containing a carbon-silicon bond.

  Step 110 can include coagulating the compatible silica and nitrile polymer blend after it is in latex form.

  Step 112 can include drying the coagulated compatible silica and nitrile polymer blend to remove some water.

  The compatible silica slurry can contain 1 wt% to 40 wt% silica.

  The process can use an amount of coupling agent that is 1 to 25 parts by weight of coupling agent per 100 parts by weight of silica.

  The process described in FIG. 1 uses an amount of compatible silica slurry that is between 5 wt% and 80 wt% based on the weight of solids in either silica styrene butadiene polymer latex or silica acrylonitrile butadiene polymer latex. Can be included.

  Step 114 can include adding an extender oil, an antioxidant, or a combination thereof to at least one of the polymer latexes.

  One or more embodiments can include a composition and an article made from the process of FIG.

  FIG. 2 shows a process for forming a blend of an acrylonitrile styrene butadiene terpolymer latex and a compatible silica. The process shown in FIG. 2 can produce acrylonitrile butadiene polymer latex and styrene butadiene polymer latex.

  Step 200 can include blending the styrene butadiene polymer latex with the acrylonitrile butadiene polymer latex to form an acrylonitrile tributadiene polymer and styrene butadiene polymer latex blend.

  Step 202 can include treating the silica with a coupling agent in an aqueous suspension to form a compatible silica slurry. The coupling agent can include chemically reacting with the surface of the silica to bind the coupling agent thereto.

  Step 204 can include blending the compatible silica slurry with an acrylonitrile butadiene polymer and styrene butadiene polymer latex blend to form an acrylonitrile styrene butadiene terpolymer latex blend containing the compatible silica in latex form.

  Step 206 may include blending 2% to 80% by weight styrene butadiene polymer latex with 1% to 30% by weight acrylonitrile butadiene polymer latex and 1% to 30% by weight compatible silica slurry. The amount of the compatible silica slurry can be about 5% to 80% by weight based on the weight of the latex solids.

  The process shown in FIG. 2 can use the same polymer as the process shown in FIG. 1 and can include adding a carbon black slurry to at least one of the latexes.

  The coupling agent that can be used in the process shown in FIG. 2 may be an organosilicon compound. The coupling agent may be a bis (trialkoxysilylalkyl) polysulfide containing 2 to 8 sulfur atoms, wherein the alkyl group represents an alkyl group having 1 to 18 carbon atoms, and the alkoxy group has 1 carbon atom. To 8 alkoxy groups. The organosilicon compound can have 1 to 3 readily hydrolyzable groups directly bonded to silicon and at least one organic group directly bonded to the silicon atom. The organic group directly bonded to the silicon atom contains at least one functional group. The functional group may be a functional group that can undergo a chemical reaction with the polymer during curing of the polymer.

  Coupling agents have the general structure described herein:

Can have. The amount of coupling agent used in the process can be from about 1 part to about 25 parts by weight of coupling agent per 100 parts by weight of silica.

  The process shown in FIG. 2 uses an amount of compatible silica slurry that is between about 5 wt% and 80 wt% based on the weight of solids in either silica styrene butadiene polymer latex or silica acrylonitrile butadiene polymer latex. Can be included.

  Step 208 can include adding a filler. The filler may be selected from the group consisting of diatomaceous earth, ground pecan shell, cellulosic material, ground peanut shell, talc, ground coal, bagasse, ash, perlite, silage, clay, calcium carbonate, biomass, and combinations thereof. it can.

  Step 210 can include adding an antioxidant to the monomer of the emulsion polymerization process. The antioxidant may be a phenolic antioxidant, phosphite, bisphenol, an amine antioxidant, or a combination thereof.

  One or more embodiments relate to compositions and articles made from the process of FIG.

  FIG. 3 shows a third embodiment, which is a process for forming a blend of acrylonitrile butadiene polymer and styrene butadiene polymer latex blends comprising compatible silica produced by an emulsion polymerization process.

  Step 300 can include treating the silica with a coupling agent in an aqueous suspension to form a compatible silica slurry. The procedure of step 300 can be performed in a manner similar to that described with respect to FIGS. 1 and 2, or other methods described herein.

  Step 302 can include blending at least a portion of the compatible silica slurry with a styrene butadiene polymer latex to form a silica styrene butadiene polymer latex.

  Step 304 can include blending the silica styrene butadiene polymer latex with the acrylonitrile butadiene polymer latex to form a blend of acrylonitrile butadiene polymer and styrene butadiene polymer latex containing compatible silica.

  One or more embodiments relate to compositions and articles made from the process of FIG.

  FIG. 4 shows a fourth embodiment which is a process of forming compatible silica in a latex blend of acrylonitrile butadiene polymer and styrene butadiene polymer.

  Step 400 can include treating the silica with a coupling agent in an aqueous suspension to form a compatible silica slurry. The procedure of step 400 is performed using any of the coupling agents described herein as described in FIGS.

  Step 402 can include blending at least a portion of the compatible silica slurry with the acrylonitrile butadiene polymer to form a silica acrylonitrile butadiene polymer latex.

  Step 404 can include blending the styrene butadiene polymer latex with a silica acrylonitrile butadiene polymer latex to form a compatible silica in the latex blend of acrylonitrile butadiene polymer and styrene butadiene polymer.

  One or more embodiments relate to compositions and articles made from the process of FIG.

  FIG. 5 shows a fifth embodiment of a process for forming a compatible silica and nitrile polymer blend in latex form.

  Step 500 can include treating the silica with a coupling agent in an aqueous suspension to form a compatible silica slurry. The procedure of step 500 is performed using any of the coupling agents described herein as described in FIGS.

  Step 502 can include blending at least a portion of the compatible silica slurry with a styrene butadiene polymer latex to form a silica styrene butadiene polymer latex.

  Step 504 can include blending the acrylonitrile butadiene polymer latex into the silica styrene butadiene polymer latex to form a compatible silica and nitrile polymer blend in latex form.

  In one or more embodiments, the compatible silica slurry can comprise 1 wt% to 30 wt% silica. For example, a compatible silica slurry can include from about 10% to about 15% silica by weight and up to 20% by weight coupling agent.

  The coupling agent may be silane or another organosilicon compound. An organosilicon compound is a compound containing a carbon-silicon bond.

  Uncoagulated silica can have an average particle size of about 0.1 nanometers to 200 nanometers. In one or more embodiments, the silica can be nano-sized silica, such as polyhedral oligomeric silsesquioxane (POSS). The silica can be fumed silica such as calcined silica, amorphous silica such as diatomaceous earth, faujasite, or combinations thereof. The silica can be finely divided silica that forms an aqueous slurry and can be treated with a solution of the coupling agent.

  The coupling agent can be chemically bonded to at least 30% by weight of the silica surface. The coupling agent can have the ability to chemically react with the silica surface to bind the coupling agent thereto. The coupling agent can be bonded to the surface of the silica by a covalent bond. Coupling agents are known in the art as coupling agents for bonding hydrophilic filler materials such as glass fibers, silica and the like with natural and synthetic polymers useful as hydrophobic materials such as rubber or thermoplastic materials. Various compounds can be used. Organosilicon compounds are well known for bonding silica to natural and synthetic polymers. The amount of coupling agent can be from about 1 part to about 25 parts by weight of coupling agent per 100 parts by weight of silica.

  In an embodiment, the process can be applied to styrene butadiene rubber to provide a silica composition that can be cured by a crosslinking reaction that includes a sulfur compound. The coupling agent can be an organosilicon compound having at least one of a mercapto group, a polysulfide group, a thiocyanato group (—SCN), a halogen atom and / or an organic group having amino functionality. At least one group of the organosilicon compound can have an ethylenically unsaturated group or an epoxy group so that the silica-filled polymer can undergo a peroxy-type curing reaction.

  In one or more embodiments, one or two alkyl groups can be substituted with a phenyl group or a benzyl group, or one or two alkyl groups can be substituted with a phenyl group, a benzyl group, or an alkoxy substituted alkyl group.

  The polymer solidifies once and can be recovered once the polymer is in contact with the compatible silica slurry.

  During the process, the temperature and reaction time during blending can be varied within wide limits. In embodiments, the temperature may range from ambient temperature up to about 125 degrees Celsius.

  Latex blending can be performed using a common tank and blending with a pump impeller at a speed of 10 to 80 rpm and a time of 5 minutes to 1.5 hours.

  During the process, the amount of time used to carry out the reaction of the hydrolyzed coupling agent and silica can vary with relatively wide limits, which can range from about 4 hours to about 48 hours.

  During the process, the amount of silica added to one or more latex (s) will depend, in part, on the coupling agent employed, the nature of the polymer latex, the use of other fillers such as carbon black and the end use the polymer will receive. It can be varied within a wide range. For example, the amount of silica added to one or more latex (s) may range from about 1% to about 70% by weight.

  Silica can include chip silica, which is untreated silica, as well as pretreated silica.

  In embodiments, the compatible silica slurry can be about 5% to about 60% by weight based on the weight of the solids of the polymer latex.

  The styrene butadiene polymer latex can be made into an emulsion that can flow at ambient temperature, allowing the styrene butadiene polymer latex to be poured.

  A portion of the compatible silica slurry and the styrene butadiene polymer latex are each pumped to a common tank and blended at the operating temperature by stirring the mixture at a rate sufficient to maintain the suspension emulsion. Can do. For example, the mixture can be agitated using a pump impeller at a speed of 5 to 80 rpm for 5 minutes to 1.5 hours.

  The silica styrene butadiene polymer latex can include a ratio of compatible silica slurry to styrene butadiene polymer latex of about 50:50.

  A portion of the compatible silica slurry and the acrylonitrile butadiene polymer latex are each pumped to a common tank and blended at the operating temperature by stirring the mixture at a rate sufficient to maintain the suspension emulsion. Can do. For example, the mixture can be agitated using a pump impeller at a speed of 5 to 80 rpm for 5 minutes to 1.5 hours.

  The formed silica acrylonitrile butadiene polymer latex can include a ratio of compatible silica slurry to acrylonitrile butadiene polymer latex of about 50:50.

  In embodiments, the silica styrene butadiene polymer latex along with the silica acrylonitrile butadiene polymer latex can be blended by flowing the latex into a common tank and stirring the mixture. For example, the polymer latex can be stirred using a pump impeller at a speed of 5 to 80 rpm for 5 minutes to 1.5 hours.

  One or more embodiments of the process can include adding a carbon black slurry to at least one of the polymer latexes. The carbon black slurry may be or may include furnace carbon black, low structure carbon black, or acetylene carbon black, which may include high structure carbon black.

  Carbon black can be added by flowing the carbon black slurry into one or more of the above common tanks.

  For example, a carbon black slurry having a solids content of about 5% to about 40% by weight can be added to one or more common tanks. The carbon black slurry can be added to the latex at 1 wt% to 80 wt%.

  About 0.1% to about 60% by weight of extender oil can be added to at least one of the polymer latexes. The extender oil can be a naphthenic oil, a hydrocarbon-based oil, a synthetic oil, an aromatic oil, a low polycyclic aromatic hydrocarbon oil (PAH), or a combination thereof.

  Antioxidants can be added to the latex in amounts of about 2% to about 0.05% by weight. Antioxidants can be added to at least one of the polymer latexes or combinations thereof. The antioxidant can be a phenolic antioxidant, phosphite, bisphenol, an amine antioxidant, or a combination thereof.

  Fillers can be added to any one or more of the blends described herein. For example, from about 0.1% to about 50% by weight filler can be added to one or more blends described herein.

  The polymer solidifies once and can be recovered once the polymer is in contact with the compatible silica slurry.

  The aqueous suspension can contain water, soap, emulsifier, surfactant, thickener (including viscosity modifier) such as starch and carboxymethylcellulose.

  Activators, free radical initiators, and terminators can be used in combination, from 0.1% to 5% by weight, in the emulsion polymerization process. The activator may be a peroxide.

  In embodiments, a curing package for crosslinking the formed polymer can be used with the emulsion polymerization process, such as zinc oxide, another organic peroxide or acrylate.

  In one or more embodiments, the compatible silica slurry can include 1 wt% to 30 wt% silica. For example, a compatible silica slurry can include from about 10% to about 15% silica by weight and up to 20% by weight coupling agent.

  The temperature and reaction time during blending can vary within wide limits. In embodiments, the temperature may range from ambient temperature up to about 125 degrees Celsius. Blending can be performed using impeller agitation. The amount of time used to react the hydrolyzed coupling agent with silica can vary within a relatively wide range of 4 to 48 hours depending on the temperature used.

  The amount of silica added to the latex can vary within wide limits to some extent depending on the coupling agent used, the nature of the polymer, the use of other fillers such as carbon black, and the end use the polymer receives. it can. For example, the amount of silica added to one or more latex (s) is in the range of about 25% to about 80% by weight.

  In embodiments, the compatible silica slurry can range from about 5% to about 60% based on the weight of solids in the polymer latex.

  The process can also include blending at least a portion of the compatible silica slurry with the styrene butadiene polymer latex to form a silica styrene butadiene polymer latex that can be made into an emulsion that can be flowed and poured at ambient temperature.

  A portion of the compatible silica slurry and the styrene butadiene polymer latex can be blended by pumping each to a common tank and stirring the mixture at operating temperature at a rate sufficient to maintain the emulsion in suspension. For example, impeller agitation can be used to agitate the mixture.

  The silica styrene butadiene polymer latex can include a ratio of compatible silica slurry to styrene butadiene polymer latex of about 25:75.

  In one or more embodiments, at least a portion of the compatible silica slurry can be mixed into the acrylonitrile butadiene polymer latex to form a silica acrylonitrile butadiene polymer latex.

  A portion of the compatible silica slurry and the acrylonitrile butadiene polymer latex can be blended by pumping each to a common tank and stirring the mixture at an operating temperature at a rate sufficient to maintain an emulsion of the suspension. .

  The formed silica acrylonitrile butadiene polymer latex can include a ratio of compatible silica slurry to acrylonitrile butadiene polymer latex of about 25:75.

  At least one of the polymers can include a copolymer, a homopolymer, a crosslinked polymer, a partially crosslinked polymer, or a combination thereof. At least one of the polymers can be a natural or synthetic polymer.

  The acrylonitrile butadiene polymer latex can be mixed with polyisoprene such as natural rubber, synthetic rubber, rubber latex blend, rubber crumb or combinations thereof.

  A portion of the silica styrene butadiene polymer latex can be blended with the silica acrylonitrile butadiene polymer latex to form a compatible silica and nitrile polymer blend.

  Silica styrene butadiene polymer latex can be blended with silica acrylonitrile butadiene polymer latex by flowing the latex into a common tank and stirring. The polymer latex has an acrylonitrile to styrene ratio of 3: 1 to 8: 1; a styrene to butadiene ratio of 0.06: 1 to 0.14: 1; a butadiene to styrene ratio of 7: 1 to 14: 1; 4: 1 to 0.75: 1; and a butadiene to acrylonitrile ratio of 1.3: 1 to 2.5: 1.

  One or more embodiments of the process can include adding a carbon black slurry to at least one of the polymer latexes. The carbon black slurry may be or may include furnace carbon black, low structure carbon black, or acetylene carbon black, which may include high structure carbon black.

  The carbon black slurry can be added by flowing carbon black into a common tank as described above. For example, about 1% to about 50% by weight of carbon black slurry can be added to one or more common tanks.

  The polymer composition can include extender oil, antioxidants, or any combination thereof, which can be added to at least one of the latexes. For example, from about 4% to about 60% by weight of extender oil can be added to at least one of the polymer latexes, and from about 0.1% to about 3% by weight of antioxidant to at least one of the polymer latexes or combinations thereof. Can be added.

  The polymer composition can include a filler, which can be added to any one or more of these blends. For example, from about 0.1% to about 50% by weight filler can be added to one or more blends.

  One or more embodiments can include compatible silica in a latex blend of acrylonitrile butadiene polymer and styrene butadiene polymer.

  At least a portion of the styrene butadiene polymer latex is blended with the acrylonitrile butadiene polymer latex to form an acrylonitrile and styrene butadiene polymer latex blend, which can be an emulsion that can be flowed and poured at ambient temperature.

  The coupling agent can have the ability to chemically react with at least 20% by weight of the surface of the silica to covalently bond the coupling agent thereto to form compatible silica.

  The acrylonitrile and styrene butadiene polymer latex blend can be blended with a compatible silica slurry to form a compatible silica in the acrylonitrile and styrene butadiene polymer latex blend.

  In one or more embodiments, the styrene polymer latex is about 2% to about 80% by weight, the acrylonitrile butadiene polymer latex is about 1% to about 30% by weight, and the compatible silica slurry is about 1% to about 30%. Can be blended with weight percent. The amount of the compatible silica slurry can be from about 5% to about 80% by weight based on the weight of solids in the latex.

  Examples are provided below that illustrate embodiments of one or more portions of the process that can be used to make one or more embodiments of the compositions and articles described herein.

  Example 1: Preparation of SBR-silica-carbon black

  A. Preparation of compatible silica slurry

  An aqueous solution of silane is placed in a container: Silquest. RTMA-189 (OSi Specialties) can be prepared by charging 55.1 g, 27 g isopropanol, 1.1 g glacial acetic acid and 27 g water, which can initially form a cloudy mixture.

  The initially cloudy mixture can be stirred at a high speed, eg, 50 rpm, at room temperature, eg, 72 ° F., until the mixture is clear. In one or more embodiments, the initially turbid mixture can be agitated at an elevated temperature, such as 50 rpm, 60 degrees Celsius to 66 degrees Celsius, until the mixture becomes clear.

  High speed agitation can be performed for about 10 to 20 minutes, after which an additional 28 g of water can be added, which makes the mixture cloudy.

  Stirring can be continued for about 15 to about 20 minutes until the mixture becomes clear again and a solution is formed.

  In a separate container equipped with a stirrer: 16 lbs of water, fine particles of dry silica HiSil. Charge 4.05 pounds of RTM 233 and stir for about 15 minutes to wet and disperse the silica to form an aqueous solution of silane.

  An aqueous solution of silane can be added with 25% sodium hydroxide with continued stirring and it can be heated to 76 degrees Celsius. So the pH can be increased to 7.5-8.0. The temperature can be maintained at 76 degrees Celsius for about 4 hours and then cooled to about 60 degrees Celsius. At this point, the compatible silica slurry can be added to the latex stage of the continuous emulsification process or can be fed batchwise to the concentrated polymer latex.

  B. Blend of compatible silica slurry and styrene butadiene rubber latex

  A compatible silica slurry can be prepared as described in Part A of Example 1 above.

  1502-type rubber 35 pounds of SBR containing 7 or 8 pounds of rubber, and Santoflex.com manufactured by Sinorgchem. As an antioxidant emulsion containing RTM 134, a compatible silica slurry can be loaded into a stirred vessel containing a mixture of 6 PPD and the mixture is kept at 66 degrees Celsius or 60 degrees Celsius.

  The hot carbon black slurry can be charged to the initial mixture. For example, 20 pounds of hot carbon black slurry containing about 10% by weight of N234 type carbon black and about 3 pounds of hot oil emulsion containing 62.8% by weight of Sundex ™ 8125. This mixture can be stirred for 30 minutes at 66 degrees Celsius, atmospheric pressure, or at 60 degrees Celsius, atmospheric pressure.

  The latex blend described above is slowly blended and added, for example at a rate of 50 rpm, to a large stirred vessel containing about 45 pounds to about 50 pounds of water and sufficient sulfuric acid to produce a pH of 4. In one or more embodiments, the latex blend described above can be instantaneously mixed in a container using about 45 pounds to about 50 pounds of water and steam containing sufficient sulfuric acid to produce a pH of 4. .

  The rate of addition of the latex blend and sulfuric acid can be varied to maintain the pH of the resulting coagulant serum in the pH range of 4-5 over the 38 minute period when the latex blend is added.

  As required by those skilled in the art to allow the product particle size to increase, for example, to crumb sizes of 1 to 30 millimeters, as well as to make the free latex serum clear. Thus, an additional 38 minutes of mixing time and an additional portion of acid can be used.

  The size of the wet composition particles or crumb achieved by this coagulation can be similar to the size obtained from coagulation without silica.

  Visual inspection and chemical analysis of the dried composition confirms that essentially all solid and liquid components added to the latex mixture have been absorbed and uniformly dispersed. Assessed by ash analysis. Silica absorption can be from about 96% to about 99% of the charge.

  Example 2: Preparation of styrene butadiene rubber-silica-carbon black composition

  A. Preparation of compatible silica slurry

  An aqueous solution of silane is placed in a container: Silquest. RTM. It can be prepared by charging 100 g of A-189, 50 g of isopropanol, 2 g of glacial acetic acid and 47 g of water to form a cloudy mixture. The initially cloudy mixture can be stirred at high speed and at room temperature until the mixture is clear, for example from about 12 minutes to about 22 minutes, after which an additional 50 g of water can be added, thereby rendering the mixture cloudy. Stirring can be continued for about 12 minutes to about 22 minutes until the solution is clear.

  In a separate container equipped with a stirrer: 15 pounds of water and fine particles of dry silica HiSil. Charge 5 pounds of RTM233 and stir for about 20 minutes to wet and disperse the silica. An aqueous solution of silane can be added to 25% sodium hydroxide with continued stirring, while the pH can be increased to 7.5-8.0. The blend can be heated to a temperature of 64 degrees Celsius to 77 degrees Celsius. The temperature is held at 64 degrees Celsius to 77 degrees Celsius for about 3.5 hours and then cooled to about 60 degrees Celsius. At this point, the compatible silica slurry can be added to the latex stage of the continuous emulsification process or can be fed batchwise to the concentrated polymer latex.

  B. Blend of compatible silica slurry and styrene butadiene rubber (SBR) latex

  The compatible silica slurry prepared as described in Part A of Example 2 above can be loaded into a stirred vessel containing a latex mixture as described in Example 1. The final composition mixture can be stirred for 35 minutes at 60 degrees Celsius.

  The latex blend described above can be coagulated as described in Example 1. The wet composition particles or crumb size achieved by this coagulation can be similar to the size obtained from silica-free coagulation, or slightly larger, for example 1-30 mm. Visual inspection and chemical analysis of the dried composition confirms that essentially all solid and liquid components added to the latex mixture have been absorbed and uniformly dispersed. Silica absorption, as assessed by ash analysis, can be from about 96% to about 99% of the charge.

  Example 3: Preparation of a composition of SBR silica

  A compatible silica slurry prepared as described in Part A of Example 2 above, contains 20% by weight of 1502-SBR and Santoflex. A stirred vessel containing a latex mixture made from 40 pounds of SBR latex containing 2% by weight of 134 can be charged and it can be kept at 60 degrees Celsius.

  This mixture can be charged with 3 pounds of hot oil emulsion containing 60% by weight of Sundex 8125. The mixture can be stirred for an additional 38 minutes while maintaining the temperature at 60 degrees Celsius, after which the hot latex can be slowly charged into another container for coagulation, which can form a dehydrated or dried crumb.

  When set, the dewatered crumb can be similar in particle size to that obtained from that of SBR without silica, for example 1 to 30 millimeters. Visual inspection and chemical analysis of the dried crumb confirms that essentially all the oil and silica components added to the latex have been absorbed and evenly dispersed. Silica absorption, as assessed by ash analysis, can be from about 96% to about 99% of the charge.

  Example 4: Preparation of Nitrile Butadiene Rubber (NBR) -Silica Composition

  A. Preparation of compatible silica slurry

  An aqueous solution of silane is placed in a container: Silquest. RTM. It can be prepared by charging 20 g of A-189, 15 g of isopropanol, 0.7 g of glacial acetic acid and 10 g of water, which can form the first cloudy mixture. The initial cloudy mixture can be stirred at high speed at room temperature for about 10 to 20 minutes until clear, after which an additional 15 g of water can be added, which makes the mixture cloudy. Stirring can be continued from about 12 minutes to about 25 minutes until the solution is clear.

  In a separate container equipped with a stirrer: 7 lbs of water, fine particles of dry silica Charge 2 pounds of RTM233 and stir for about 20 minutes to wet and disperse the silica. An aqueous solution of silane can be added with 25% sodium hydroxide while continuing to stir, so that the pH can be increased to 7.5-8.0. The blend can be heated to 70 degrees Celsius and maintained for about 3.5 hours, and then cooled to about 60 degrees Celsius. At this point, the compatible silica slurry can be added to the latex stage of the continuous emulsification process or can be fed batchwise to the concentrated polymer latex.

  B. Blend of compatible silica slurry and NBR latex

  A compatible silica slurry, which can be prepared as described in Part A of Example 4 above, is 30 pounds of acrylonitrile butadiene polymer (NBR) latex containing 22 wt% Nysyn ™ 40-5 rubber and registered trademark: Agerite Geltrol (Vanderbilt Chemical). A stirred vessel containing a mixture with 200 g of an antioxidant emulsion containing 16% by weight can be filled, which can be kept at 60 degrees Celsius. This initial mixture can be charged with 15 pounds of hot carbon black slurry containing about 7 wt% N234 type carbon black. This final mixture can be stirred for 35 minutes at 60 degrees Celsius.

  The latex blend described above can be slowly added to a large stirred vessel containing 30 pounds of water and enough sulfuric acid to give a pH of 4. Solidification can be completed as described in the previous examples. The size of the wet composition crumb achieved by this coagulation can be similar to that obtained from silica-free NBR coagulation, for example 1 to 30 millimeters. Visual inspection and chemical analysis of the dried composition confirms that essentially all solid and liquid components added to the latex mixture have been absorbed and uniformly dispersed. Silica absorption, as assessed by ash analysis, can be from about 96% to about 99% by weight of the charge.

  Articles made from this material can include pneumatic tires. Articles formed from the polymer blends described herein can be manufactured by injection molding, extrusion, press molding, cutting, milling, rotational molding, or combinations thereof.

  The process described herein can include coagulating the polymer at a temperature of 57 degrees Celsius to 74 degrees Celsius.

  The process described herein can include filtering the coagulated polymer using, for example, a screen, cellulose membrane filter, French oil mill to remove excess water, or by squeezing water from the polymer. .

  The process described herein can also include drying the separated polymer by using drying oven heat, a shelf using drying oven heat, or a fluidized bed.

  The processes described herein can be continuous emulsion polymerization or batch processing.

  Example 5: The latex from the emulsion polymerization process can be treated with a polymerization terminator to stop or stop the polymerization reaction and to remove unreacted monomers. The remaining unreacted monomer can be removed by steam stripping. The finished latex can be sent to a latex storage tank. The finished latex from the storage tank can be sent to the supply tank and blended as necessary to achieve the target molecular weight of the product. Molecular weight can be determined indirectly by measuring Mooney viscosity.

  Latex can be continuously fed from nitrile latex feed tanks and / or nitrile and styrene butadiene latex feed tanks and mixed with antioxidants and / or extender oil in a head tank where all of the components can be mixed together. Can do. The mixture can be poured into a carbex tank or the like and mixed with a compatible silica slurry, carbon black slurry, or a combination thereof.

  The carvex tank can overflow to the first coagulation tank. When using undiluted or pure extender oils for the oil emulsion, the mixture can be sent through a series of in-line static mixers to facilitate thorough mixing and dispersion.

  The mixture can flow into a heated and stirred coagulation tank to which dilute sulfuric acid coagulant can be added. Aluminum sulfate and calcium chloride can be used when nitrile (NBR) rubber is flowing as a coagulant. Both alum and calcium chloride can be supplied based on flow adjustment, whereas acid can be supplied based on pH adjustment of the coagulation tank. All three coagulants can serve to break the latex emulsion and form rubber crumbs. Adjustment of the crumb size can be a determinant of coagulant addition and can take precedent beyond prescription values.

  The tank contents can be thoroughly stirred so that a vortex is generated in the center of the tank. Similar to the addition of coagulant chemicals described herein, process conditions can coagulate the mixture to form a rubber crumb, an aqueous slurry, or a crumb slurry.

  When coagulated under the conditions described herein, the latex, oil, compatible silica slurry, carbon black slurry, antioxidant, and combinations thereof can be evenly dispersed. To provide additional residence time for coagulation, the crumb slurry can overflow from the first to the second coagulation tank.

  A soap conversion tank can be provided for more residence time to complete the coagulation stage. In order to avoid fouling of downstream equipment, complete solidification can be achieved before the material exits the soaping tank.

  A small amount of coagulant aid can be used during coagulation to facilitate clearing of the serum and completion of coagulation.

  Centrifugal dewatering units, or spin dryers, can be used to mechanically reduce the water content of colored rubber crumbs to about 35-40% by weight, allowing more energy efficient dryer operation.

  The rubber crumb slurry leaving the wash water tank can enter the spin dryer and be charged to the cylindrical screen. Water can pass through the cylindrical screen and can be removed by gravity at the bottom of the spin dryer. The rubber crumb travels upward in the spiral path and is discharged from the upper end through the outlet to the classifier.

  The classifier may be a vibrating conveyor with a grid bar. The grid spacing of the grid bars can be used to adjust the crumb size. Smaller crumbs can fall through the grid bar spacing, while oversized crumbs can remain on the grid bars and drain from the side exit chute.

  Acceptable crumb can be discharged from the classifier into a wet feed rotolock valve that feeds a wet feed crumb blower. The wet feed funnel lock valve can prevent blow back from the wet feed clam blower.

  The rubber crumb is fluidized in the spin dryer by air pointing upward from the bottom of the spin dryer. The upward movement of the air can partially support the crumb and form a floating and boiling material.

  Dry crumb can be discharged to the crumb hopper through an opening at the end of the last dryer section. The discharge crumb hopper can supply a dry crumb blower. The dry crumb blower can carry the dried crumb to a baler scale cyclones. The rubber crumb can be gravity fed onto the scale on each baler, where the rubber crumb can be compressed into a bale form.

  The rubber crumb can be converted into a bagging operation where it can be covered with partition material and packaging as a free flowing crumb.

  Example 6: Formation of an elastomeric composition can include initially introducing 47% by weight of a synthetic elastomeric polymer into the finishing process area. The synthetic elastic polymer can comprise 70% by weight butadiene and 30% by weight styrene.

  Next, 10% by weight of compatible silica can be added. The compatible silica can include 90% by weight silica and 10% by weight coupling agent.

  Furthermore, 25% by weight of crumb rubber can be added to the finishing process area.

  Furthermore, 8% carbon black and 10% extender oil can be added to the finishing process area.

  The finishing process area can be maintained at ambient pressure at a temperature of 60 degrees Celsius. The components of the composition can be allowed to react for 38 minutes in the finishing process area.

  Soap, water, activators, free radical initiators and terminators can be used to form long chain polymerizations in the emulsion polymerization process.

  Example 7: A crumb rubber slurry with a solid content of 2% to 15% can be prepared and held in a stirred and heated holding tank. The crumb rubber slurry in the stirred and heated holding tank can be introduced into the solidification step of the manufacturing process.

  The latex from the emulsion polymerization process can be treated with a polymerization terminator to stop or stop the polymerization reaction, and unreacted monomers can be removed. The remaining unreacted monomer can be removed by steam stripping. The finished latex can be sent to a latex storage tank.

  The finished latex can be poured from the storage tank into the supply tank and blended if necessary to achieve the target molecular weight of the product. Molecular weight can be determined indirectly by measuring the Mooney viscosity of the finished latex.

  Latex can be fed continuously from nitrile latex feed tanks, nitrile and styrene butadiene latex feed tanks and / or styrene butadiene feed tanks, and antioxidants and / or extenders in the head tank where all of the components are mixed together. It forms a mixture that can be mixed with oil and injected into a carvex tank or the like.

  The crumb rubber slurry can also be poured into a carvex tank or the like at a prescribed rate based on the prescription. A compatible silica slurry, carbon black slurry, or a combination thereof can be added to a carvex tank or the like.

  The carvex tank can overflow into the first coagulation tank. If an undiluted or pure extender oil is used for the oil emulsion, the mixture can be sent through a series of in-line static mixers to facilitate thorough mixing and dispersion.

  The mixture can flow into a heated and stirred coagulation tank to which dilute sulfuric acid coagulant can be added. Aluminum sulfate and calcium chloride can be used when nitrile (NBR) rubber is flowing as a coagulant. Both alum and calcium chloride can be supplied based on flow adjustment, whereas acid can be supplied based on pH adjustment of the coagulation tank. All three coagulants can serve to break the latex emulsion and form a newly coagulated rubber crumb. Adjusting the size of the newly coagulated crumb can be a determinant for coagulant addition and can take precedent beyond prescription values.

  The tank contents can be thoroughly stirred so that a vortex is generated in the center of the tank. Similar to the addition of coagulant chemicals described herein, process conditions can coagulate the mixture to form new rubber crumbs and aqueous slurries.

  When coagulated under the conditions described in Example 2, the latex, oil, compatible silica slurry, carbon black slurry, antioxidant, recycled crumb and combinations thereof can be evenly dispersed. The blended recycled crumb and slurry can overflow from the first to the second coagulation tank and provide additional residence time for coagulation.

  The soap tank can provide more residence time to complete the solidification stage. In order to avoid fouling of downstream equipment, complete solidification can be achieved before the material exits the soaping tank. A small amount of coagulant aid can be used during coagulation to facilitate clearing of the serum and completion of coagulation.

  Centrifugal dewatering units, or spin dryers, can be used to mechanically reduce the water content of colored rubber crumbs to about 35-40% by weight, allowing more energy efficient dryer operation. The rubber crumb slurry leaving the wash water tank can enter the spin dryer and be charged to the cylindrical screen. Water can pass through the cylindrical screen and can be removed by gravity at the bottom of the spin dryer. The rubber crumb travels upward in the spiral path, and is discharged from the outlet toward the classifier because it is at the upper end.

  The classifier may be a vibrating conveyor with a grid bar. The grid spacing of the grid bars can be used to adjust the crumb size. Smaller crumbs can fall through the grid bar spacing, while oversized crumbs can remain on the grid bars and drain from the side exit chute.

  An acceptable crumb can be discharged from the classifier into a wet feed funnel lock valve, which can supply a wet feed crumb blower. The wet feed funnel lock valve can prevent blow back from the wet feed clam blower.

  The rubber crumb is fluidized in the spin dryer by air pointing upward from the bottom of the spin dryer. The upward movement of the air can partially support the crumb and form a floating and boiling material. Dry crumb can be discharged to the crumb hopper through an opening at the end of the last dryer section.

  The discharge crumb hopper can supply a dry crumb blower. Dry crumb blowers can carry dry crumbs to baler scale cyclones. The rubber crumb can be gravity fed onto the scale on each baler, where the rubber crumb can be compressed into a bale form. The rubber crumb can be converted into a bagging operation where it can be covered with partition material and packaging as a free flowing crumb.

  While these embodiments have been described with emphasis on the present embodiments, the embodiments may be practiced other than as specifically described within the scope of the appended claims. It should be understood that there is sex.

Claims (68)

A compatible silica and nitrile polymer blend in latex form formed by the following process, the process:
Silica is treated with a coupling agent in an aqueous suspension to form a compatible silica slurry, where the coupling agent chemically reacts with the surface of the silica to bind the coupling agent thereto. Let;
Blending at least a portion of the compatible silica slurry with a styrene butadiene polymer latex to form a silica styrene butadiene polymer latex;
At least a portion of the compatible silica slurry is blended with an acrylonitrile butadiene polymer latex to form a silica acrylonitrile butadiene polymer latex; and the silica styrene butadiene polymer latex is blended with the silica acrylonitrile butadiene polymer latex to form a latex form. A polymer blend comprising forming a compatible silica and nitrile polymer blend.   The compatible silica and nitrile polymer blend according to claim 1, wherein the coupling agent is an organosilicon compound.   The organosilicon compound has 1 to 3 easily hydrolyzable groups directly bonded to the silicon atom and at least one organic group directly bonded to the silicon atom, wherein the at least one organic group is at least The phase of claim 2 having one functional group, wherein the at least one functional group is capable of undergoing a chemical reaction with a styrene butadiene polymer latex, an acrylonitrile butadiene polymer latex or a combination thereof during curing. Soluble silica and nitrile polymer blends.   The compatible silica and nitrile polymer blend of claim 1, wherein at least one of the polymer latexes is a copolymer, homopolymer, cross-linked polymer, partially cross-linked polymer, or combinations thereof.   The compatible silica and nitrile polymer blend of claim 1, wherein either the styrene butadiene polymer latex, the silica styrene butadiene polymer latex, or the acrylonitrile butadiene polymer latex comprises polyisoprene.   The compatible silica and nitrile polymer blend of claim 1 wherein the silica has an average particle size of 0.1 to 20 microns.   The compatible silica and nitrile polymer blend of claim 1, wherein the silica is fumed silica, amorphous silica, or a combination thereof.   The compatible silica and nitrile polymer blend of claim 1, wherein the process further comprises adding a carbon black slurry to at least one of the polymer latexes. Coupling agents have the general structural formula:
(Wherein X represents a functional group selected from the group consisting of an amino group, a polyaminoalkyl group, a mercapto group, a polysulfide group, an epoxy group, a vinyl group, an acryloxy group, and a methacryloxy group, and y is 0 or more. Z ₁ , Z ₂ , and Z ₃ each independently comprise a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group, a cycloalkyl group, an arylalkoxy group, and a halo-substituted alkyl group. The compatible silica and nitrile according to claim 1, which are selected from the group and represented by at least one of Z ₁ , Z ₂ or Z ₃ represents an alkoxy group, a hydrogen atom, a halogen atom or a hydroxyl group) Polymer blend.   The coupling agent comprises bis (trialkoxysilyl) containing 2 to 8 sulfur atoms and an alkyl group that is an alkyl group having 1 to 18 carbon atoms and an alkoxy group that is an alkoxy group having 1 to 8 carbon atoms. The compatible silica and nitrile polymer blend of claim 1 which is an (alkyl) polysulfide.   The compatible silica and nitrile polymer blend of claim 1, wherein the process further comprises coagulating the compatible silica and nitrile polymer blend in latex form.   The compatible silica and nitrile polymer blend of claim 11, wherein the process further comprises drying the compatible silica and nitrile polymer blend coagulated in latex form to remove water.   The compatibilized silica and nitrile polymer blend of claim 11 wherein the compatible silica slurry comprises 1 wt% to 40 wt% silica.   14. The compatibilized silica and nitrile polymer blend of claim 13, wherein the amount of coupling agent is from 1 to 25 parts by weight of coupling agent per 100 parts by weight of silica.   The compatible silica and nitrile of claim 13, wherein the amount of the compatible silica slurry is from 5 wt% to 80 wt%, based on the weight of solids of either the silica styrene butadiene polymer latex or the silica acrylonitrile butadiene polymer latex. Polymer blend.   The compatible silica and nitrile polymer blend of claim 1, wherein the process further comprises adding the extender oil, antioxidant, or combination thereof to at least one of the polymer latexes. An acrylonitrile styrene butadiene terpolymer latex blend comprising compatible silica formed by the following process, the process:
Blending a styrene butadiene polymer latex with an acrylonitrile butadiene polymer latex to form an acrylonitrile butadiene polymer and a styrene butadiene polymer latex blend;
In an aqueous suspension, silica is treated with a coupling agent to form a compatible silica slurry, where the coupling agent chemically reacts with the silica surface to bind the coupling agent to it; And blending said compatible silica slurry with said acrylonitrile butadiene polymer and styrene butadiene polymer latex blend;
A latex blend comprising forming an acrylonitrile styrene butadiene terpolymer latex blend comprising compatible silica in latex form. Forming an acrylonitrile butadiene polymer latex and a styrene butadiene polymer latex;
2% to 80% by weight of styrene butadiene polymer latex;
1% to 30% by weight of acrylonitrile butadiene polymer latex; and 1% to 30% by weight of compatible silica slurry (wherein the amount of the compatible silica slurry is the solid content in the styrene butadiene polymer latex and acrylonitrile butadiene polymer latex). 18. The acrylonitrile styrene butadiene terpolymer latex blend comprising the compatibilized silica of claim 17 comprising blending from 5% to 80% by weight based on the weight of.   The acrylonitrile styrene butadiene terpolymer latex blend comprising compatibilized silica according to claim 17, wherein at least one of the polymer latex is a copolymer, a homopolymer, a crosslinked polymer, a partially crosslinked polymer, or a combination thereof.   The acrylonitrile styrene butadiene terpolymer latex blend comprising compatibilized silica of claim 17 wherein the process further comprises adding a carbon black slurry to at least one of the polymer latexes.   18. The acrylonitrile styrene butadiene terpolymer latex blend containing compatibilized silica according to claim 17, wherein the coupling agent is an organosilicon compound.   The organosilicon compound has 1 to 3 easily hydrolyzable groups directly bonded to the silicon atom and at least one organic group directly bonded to the silicon atom, wherein the at least one organic group is at least one The acrylonitrile styrene butadiene terpolymer latex comprising compatibilized silica according to claim 21, wherein the acrylonitrile styrene butadiene terpolymer latex is a functional group, wherein the at least one functional group is a functional group capable of undergoing a chemical reaction with the polymer latex during curing. Coupling agent is a general structural formula:
(Wherein X represents a functional group selected from the group consisting of an amino group, a polyaminoalkyl group, a mercapto group, a polysulfide group, an epoxy group, a vinyl group, an acryloxy group, and a methacryloxy group, and y is 0 or more. Z ₁ , Z ₂ , and Z ₃ each independently comprise a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group, a cycloalkyl group, an arylalkoxy group, and a halo-substituted alkyl group. And wherein at least one of Z ₁ , Z ₂ , or Z ₃ represents an alkoxy group, a hydrogen atom, a halogen atom, or a hydroxyl group, and a cup during the process of claim 17 The ring agent is a bis (trialkoxysilylalkyl) polysulfide containing 2 to 8 sulfur atoms, 18. The acrylonitrile styrene butadiene terpolymer latex blend containing compatible silica according to claim 17, wherein the alkyl group represents an alkyl group having 1 to 18 carbon atoms, and the alkoxy group represents an alkoxy group having 1 to 8 carbon atoms.   18. The acrylonitrile styrene butadiene terpolymer latex blend containing compatible silica according to claim 17, wherein the amount of coupling agent is 1 to 25 parts by weight of coupling agent per 100 parts by weight of silica.   18. The acrylonitrile containing compatible silica according to claim 17, wherein the amount of the compatible silica slurry is 5% to 80% by weight, based on the weight of solids of either silica styrene butadiene polymer latex or silica acrylonitrile butadiene polymer latex. Styrene butadiene terpolymer latex blend.   The process further includes a filler from the group consisting of diatomaceous earth, ground pecan shell, cellulosic material, ground peanut shell, talc, ground coal, bagasse, ash, perlite, silage, clay, calcium carbonate, biomass, and combinations thereof. The acrylonitrile styrene butadiene terpolymer latex blend containing the compatible silica of claim 17 comprising adding.   18. The compatibility of claim 17, wherein the process further comprises adding an antioxidant, wherein the antioxidant is a phenolic antioxidant, phosphite, bisphenol, an amine antioxidant, or a combination thereof. Acrylonitrile styrene butadiene terpolymer latex blend containing silica. An acrylonitrile butadiene polymer and styrene butadiene polymer latex blend comprising compatible silica produced by the following method, the method comprising:
Treating the silica in an aqueous suspension with a coupling agent to form a compatible silica slurry, wherein the coupling agent chemically reacts with the silica surface to bind the coupling agent thereto;
At least a portion of the compatible silica slurry is blended with a styrene butadiene polymer latex to form a silica styrene butadiene polymer latex; and the silica styrene butadiene polymer latex is blended with an acrylonitrile butadiene polymer latex to include a compatible silica. A latex blend comprising forming a blend of an acrylonitrile butadiene polymer and a styrene butadiene polymer latex. A compatible silica in a latex blend of acrylonitrile butadiene polymer and styrene butadiene polymer produced by the following process, the process:
Treating the silica in an aqueous suspension with a coupling agent to form a compatible silica slurry, wherein the coupling agent chemically reacts with the silica surface to bind the coupling agent thereto;
At least a portion of the compatible silica slurry is blended with an acrylonitrile butadiene polymer latex to form a silica acrylonitrile butadiene polymer latex, and a styrene butadiene polymer latex is blended with the silica acrylonitrile butadiene polymer latex to produce acrylonitrile butadiene polymer and styrene. A compatible silica comprising forming a compatible silica in a latex blend of butadiene polymers. A compatible silica and nitrile polymer blend in latex form, manufactured using the following process, the process:
Treating the silica in an aqueous suspension with a coupling agent to form a compatible silica slurry, wherein the coupling agent chemically reacts with the silica surface to bind the coupling agent to it;
At least a portion of the compatible silica slurry is blended with a styrene butadiene polymer latex to form a silica styrene butadiene polymer latex, and an acrylonitrile butadiene polymer latex is incorporated into the silica styrene butadiene polymer latex to form a latex form phase. A blend comprising forming a soluble silica and nitrile polymer blend. A polymer composition of compatible silica in an emulsion polymerized acrylonitrile butadiene polymer and emulsion polymerized styrene butadiene polymer blend, the polymer composition comprising:
6% to 90% by weight of compatible silica, based on the total solids of the polymer composition, wherein the compatible silica comprises at least 1% by weight of an organosilicon coupling agent based on the weight of the compatible silica. ;
10% to 80% by weight of the emulsion polymerized styrene butadiene polymer; and 10% to 80% by weight of the emulsion polymerized acrylonitrile butadiene polymer, wherein at least 10% by weight of the emulsion polymerized acrylonitrile butadiene polymer is acrylonitrile polymer. Consisting of a 15:50 ratio of liquid to 1,3-butadiene polymer, providing high strength binding of compatible silica to each polymer, where butadiene to styrene is in a ratio of 7: 1 to 17: 1; And acrylonitrile to butadiene in a ratio of 0.4: 1 to 0.75: 1. Further comprising 10% to 50% by weight of compatible silica, wherein the organosilicon coupling agent is chemically bonded to the surface of the silica of the compatible silica, the organosilicon coupling agent being silicon cross-polarization magic. Claims exist as an average tetrameric structure with a T ³ / T ² ratio of 0.75 or higher as measured by angular rotation nuclear magnetic resonance, and the compatible silica has a T ³ / T ² ratio of 0.9 or higher; 31. The polymer composition according to 31.   The polymer composition of claim 32, wherein the organosilicon coupling agent is bound to the silica surface of the compatible silica in an amount of 1 to 25 wt% organosilicon coupling agent, based on the weight of the silica. The organic coupling agent has the following structure
35. The polymer composition of claim 32, derived from an organosilane having: In the formula, X represents a functional group selected from the group consisting of an amino group, a polyaminoalkyl group, a mercapto group, a polysulfide, a thiocyanato group, an epoxy group, a vinyl group, a halogen atom, an acryloxy group, and a methacryloxy group; Z _l , Z ₂ , and Z ₃ are each independently selected from the group consisting of a hydrogen atom, an alkoxy group, a halogen atom, and a hydroxyl group.   35. The polymer composition of claim 32, wherein the emulsion polymerized styrene butadiene polymer, emulsion polymerized acrylonitrile butadiene polymer, or combinations thereof are formed from natural rubber, synthetic polymer, thermoplastic polymer, or resin polymer.   Polymer composition: conjugated diene polymer, polymer based on vinyl monomer, combination of conjugated diene and vinyl monomer, polyolefin, polyalphaolefin, polyester, polyamide, polycarbonate, polyphenylene oxide, polyacrylate, polyurethane, non-conjugated with ethylene propylene Terpolymer with diene, fluoroelastomer, chloro-elastomer, polyisoprene, polybutadiene, polyisobutyldiene, polychloroprene, polyvinyl chloride polymer, acrylonitrile butadiene rubber, polyepoxide, ethylene interpolymer, block copolymer of styrene butadiene, block of styrene isoprene Copolymers, copolymers of acrylates, crosslinkable monomers, vinyl monomers and combinations thereof Including members of the group consisting allowed, claim 35 polymer composition.   36. The polymer composition of claim 35, wherein at least one of the polymers is a copolymer, a homopolymer, a crosslinked polymer, a partially crosslinked polymer, or a combination thereof.   32. The polymer composition of claim 31, wherein the compatible silica has an average particle size in the range of 1 nanometer to 15 microns.   32. The polymer composition of claim 31, wherein the silica used to form the compatible silica is fumed silica, amorphous silica, or a combination thereof.   32. The polymer composition of claim 31, further comprising 1% to 50% by weight of carbon black.   Organosilicon of the organosilicon coupling agent has 1 to 3 easily hydrolyzable groups directly bonded to the silicon atom of the organosilicon coupling agent and at least one organic group directly bonded to the silicon atom. Wherein the at least one organic group has at least one functional group, wherein the at least one functional group is a functional group capable of undergoing a chemical reaction with the polymer composition during curing of the polymer composition. 32. The polymer composition of claim 31. Organosilicon coupling agents have the general structural formula:
(Wherein X represents a functional group selected from the group consisting of an amino group, a polyaminoalkyl group, a mercapto group, a polysulfide group, a thiocyanato group, an epoxy group, a vinyl group, a halogen atom, an acryloxy group, and a methacryloxy group; y represents an integer of 0 or more, and Z ₁ , Z ₂ , and Z ₃ are each independently selected from the group consisting of a hydrogen atom, an alkoxy group, a halogen atom, or a hydroxyl group. 43. The polymer composition of claim 42.   The organosilicon coupling agent is a bis (trialkoxysilylalkyl) polysulfide containing 2 to 8 sulfur atoms, the alkyl group represents an alkyl group having 1 to 18 carbon atoms, and the alkoxy group has 1 to 8 carbon atoms. 43. A polymer composition according to claim 42, which represents an alkoxy group.   32. The polymer composition of claim 31, further comprising an extender oil, an antioxidant, or a combination thereof in an amount of 4% to 60% by weight.   46. The polymer composition of claim 45, wherein the extender oil is a naphthenic oil, a hydrocarbon-based oil, a synthetic oil, an aromatic oil, a low polycyclic aromatic hydrocarbon oil, or a combination thereof.   46. The polymer composition of claim 45, wherein the antioxidant is a phenolic antioxidant, phosphite, bis-phenol, an amine antioxidant, or a combination thereof.   Filler 0.1 which is a member of the group consisting of diatomaceous earth, ground pecan shell, cellulosic material, ground peanut shell, talc, ground coal, bagasse, ash, perlite, silage, clay, calcium carbonate, biomass, and combinations thereof 32. The polymer composition of claim 31, further comprising from 50% to 50% by weight.   32. The polymer composition of claim 31, further comprising an activator, free radical inhibitor, and terminator in an amount of 0.1% to 5% by weight in the combination.   50. The polymer composition of claim 49, wherein the activator is a peroxide.   51. The polymer composition of claim 50 further comprising a curing agent package for the crosslinked polymer using zinc oxide, organic peroxide, or acrylate.   52. An article made from the polymer composition of claim 51.   Articles are floor mats, tires, belts, rollers, footwear, wire and cable jackets, roof trims, tubular hoses, marine impact bumpers, industrial belts, non-automobile tires, mining belts, bearings, conduits or 53. The article of claim 52, which is a pneumatic tire.   54. The article of claim 53, wherein the article is manufactured by injection molding, extrusion, press molding, cutting, milling, rotational molding, or combinations thereof. An elastic polymer composition comprising crumb rubber and silica, formed using continuous flow emulsion polymerization with an activator, free radical initiator, water and terminator,
The continuous flow emulsion polymerization is carried out at no pressure or low pressure and above ambient temperature, the composition comprising 18% to 93% by weight of a synthetic elastic polymer based on the total weight of the composition;
Here, the synthetic elastomeric polymer is 60% to 82% by weight of liquid 1,3-butadiene monomer based on the total weight of the composition or 18% to 40% by weight of styrene monomer based on the total weight of the composition. Consists of;
5% to 80% by weight of compatible silica, based on the total weight of the composition, wherein the compatible silica is at least 1% by weight of the organosilicon coupling agent combined with at least 20% by weight of the surface of the compatible silica Having
A polymer composition comprising 1% to 50% by weight of recycled crumb rubber based on the total weight of the composition and 1% to 40% by weight of carbon black based on the total weight of the composition.   56. The elastic polymer composition comprising crumb rubber and silica according to claim 55, wherein the recycled crumb rubber comprises recycled rubber particles, and wherein at least 50% by volume of the recycled rubber particles are smaller than US standard series sieve # 10 mesh.   56. The elastic polymer composition comprising crumb rubber and silica according to claim 55, wherein the recycled crumb rubber comprises recycled rubber particles, and wherein at least 50% by volume of the recycled rubber particles are smaller than US standard series sieve # 200 mesh.   56. An elastic polymer composition comprising crumb rubber and silica according to claim 55, wherein the synthetic elastic polymer is in latex form or in dry particulate.   56. The elastic polymer composition comprising crumb rubber and silica according to claim 55, wherein the recycled crumb rubber is 100% derived from a recycled tire.   The elastic polymer composition comprising crumb rubber and silica according to claim 55, further comprising 0.1 wt% to 50 wt% filler, based on the total weight of the composition.   The filler is a member of the group consisting of ground pecan shell, cellulosic material, silage, diatomaceous earth, ground peanut shell, talc, ground coal, ground bagasse, ash, perlite, clay, calcium carbonate, biomass, and combinations thereof 61. An elastic polymer composition comprising the crumb rubber and silica of claim 60.   The elastic polymer composition comprising crumb rubber and silica according to claim 55, further comprising 1 wt% to 40 wt% of extender oil based on the total weight of the composition.   64. The elastic polymer composition comprising crumb rubber and silica according to claim 62, wherein the extender oil is selected from the group consisting of synthetic oils, aromatic oils, naphthenic oils, hydrocarbons, polycyclic aromatic hydrocarbon oils, or combinations thereof.   56. The elastic polymer composition comprising crumb rubber and silica according to claim 55, further comprising up to 25 wt% of a thermoplastic polymer, a thermoplastic elastomer, a thermoplastic vulcanizate, or any combination thereof, based on the total weight of the composition. object.   56. An elastic polymer composition comprising crumb rubber and silica according to claim 55, wherein the monomers are crosslinked.   56. The elastic polymer composition comprising crumb rubber and silica according to claim 55 comprising 1% to 10% by weight of carbon black, based on the total weight of the composition.   58. An article of elastic polymer composition comprising crumb rubber and silica, comprising the composition of claim 55.   Articles are floor mats, tires, belts, rollers, footwear, wire and cable jackets, roof trims, tubular hoses, marine impact bumpers, industrial belts, non-automobile tires, mining belts, bearings or conduits 68. An article of an elastic polymer composition comprising a crumb rubber and silica according to claim 67.