# US 10,308,807 B2 · Dissolvable rubber > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,308,807 B2 - Document ID: US10308807B2 - Status: Granted - Kind: B2 - Application number: 15/592,325 - Filed: 2017-05-11 - Published: 2017-12-07 - Granted: 2019-06-04 - Earliest claimed: 2016-06-01 - Assignees: Terves, LLC - Applicants: Terves Inc. - Inventors: Andrew J. Sherman; Brian Doud - Web page: https://patentgrep.com/patent/US10308807B2 ## CPC - C08L 75/04: Polyurethanes - C08L 9/02: Copolymers with acrylonitrile - C08L 17/00: Compositions of reclaimed rubber - C08L 29/04: Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids - C08L 67/04: Polyesters derived from hydroxycarboxylic acids, e.g. lactones (C08L67/06 takes precedence) - C08L 2207/02: Heterophasic composition - C08L 2207/04: Thermoplastic elastomer - C08L 2207/20: Recycled plastic - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) ## Abstract A degradable elastomeric material that is formed from a composite blend of elastomeric particles in a continuous degradable binder. The degradable binder is generally a water-soluble binder which has a temperature dependent solubility in water and brine systems. Such degradable elastomers are particularly useful in the fabrication of degradable oil tools, among other applications. ## Claims ### Claim 1 A degradable, elastomeric composite material comprised of a first material and a second material, said first material is a polymer that is dissolvable in a fluid, degradable in a fluid, or combinations thereof and constitutes about 5 vol. % to about 60 vol. % of said composite material, said second material is particles of elastomer that are evenly disbursed in said first material and constitutes about 5 vol. % to about 90 vol. % of said composite material, said particles of elastomer having a particle size of 30-1000 μm, said elastomer has a stretched length that is at least 20% greater than its relaxed unstretched length, said elastomer includes olefinic elastomer, ethylene elastomer, vulcanized elastomer and/or nitrile rubber, said second material having a different composition than said first material, said first material is a water-soluble and/or water-reactive polymer that has a solubility at below about 30° C. that is less than a solubility at about 70-130° C., said composite material formulated to have at least 10% dissolution or hydrolyzation in a 2-3 hour period at a temperature of at least 55° C. ### Claim 2 (depends on 1) The composite material as defined in claim 1, wherein said first material is a liquid-soluble polymer including one or more materials selected from the group consisting of poly(vinyl alcohol) (PVA), polyethylene glycol (PEG), polyglycolide (PGA), poly(lactic acid) (PLA), polysaccharides, collagen, polyvinyl pyrrolidone, hydroxyethyl acrylate or methacrylate, hydroxypropyl acrylate or methacrylate, acrylic or methacrylic acid, acrylic or methacrylic esters or vinyl pyridine, acrylamide, vinyl acetate, vinyl alcohol, and ethylene oxide. ### Claim 3 (depends on 1) The composite material as defined in claim 1, wherein said second material includes one or more materials selected from the group consisting of natural rubber, vulcanized rubber, silicone, polyurethane, synthetic rubber, polybutadiene, nitrile rubber (NBR), polyisobutylene, acrylate-butadiene rubber, and styrene butadiene rubber. ### Claim 4 (depends on 1) The composite material as defined in claim 1, further including one or more secondary components selected from the group consisting of plasticizer, compatibilizer, binder, polyester, filler, adhesion additions, reactive and/or swellable additive. ### Claim 5 (depends on 4) The composite material as defined in claim 4, wherein said secondary component is dissolvable or degradable by hydrolysis. ### Claim 6 (depends on 4) The composite material as defined in claim 4, wherein said secondary component forms a third phase in said composite material. ### Claim 7 (depends on 4) The composite material as defined in claim 4, wherein said secondary component includes a material that undergoes a volume change, gas-generating reaction, decomposition, reaction, and/or other force-generating interaction upon exposure to fluid about said composite material, said secondary components formulated to facilitate in a break-up and/or dispersion of said second material in said composite material. ### Claim 8 (depends on 4) The composite material as defined in claim 4, wherein said secondary component includes one or more components selected from the group consisting of manganese chloride tetrahydrate, magnesium chloride hexahydrate, and glycerol. ### Claim 9 (depends on 4) The composite material as defined in claim 4, wherein said secondary component includes one or more components selected from the group consisting of magnesium alloys, aluminum alloys, oxides, carbonates, nickel-containing alloys, and/or iron-based alloys. ### Claim 10 (depends on 4) The composite material as defined in claim 4, wherein said secondary component includes one or more components selected from the group consisting of calcium oxide, magnesium oxide, iron, silicon, zinc, aluminum, aluminum alloy, magnesium, and magnesium alloy. ### Claim 11 (depends on 7) The composite material as defined in claim 7, wherein said secondary component includes one or more components selected from the group consisting of carbon black, glass fiber, and fumed silica. ### Claim 12 (depends on 4) The composite material as defined in claim 4, wherein said secondary component includes a compatibilizer, adhesion addition, or combinations thereof. ### Claim 13 (depends on 4) The composite material as defined in claim 4, wherein said secondary component includes one or more components selected from the group consisting of polyvinylpyrrolidone (PVP), MnCl24H2O and MgCl26H2O to tie or bind together the continuous matrix and second material. ### Claim 14 (depends on 4) The composite material as defined in claim 4, wherein said secondary component includes plasticizer, said plasticizer constitutes about 1 vol. % to about 40 vol. % of said composite material. ### Claim 15 (depends on 4) The composite material as defined in claim 4, wherein said secondary component includes a material formulated to swell before dissolution of said first material, said secondary component including one or more materials selected from the group consisting of CaO, MgO, Fe, Mg, Li, Ca, Zn, montmorrilinate, clay, and polyacrylate. ### Claim 16 (depends on 1) The composite material as defined in claim 1, wherein said composite material derives at least about 80% of its hardness and mechanical response from said second material. ### Claim 17 (depends on 1) The composite material as defined in claim 1, further including a coating material, said coating material formulated to degrade. ### Claim 18 A degradable, elastomeric composite material consisting essentially of a continuous matrix having first and second phases, and at least one secondary component, said first phase of said continuous matrix including a first material, said second phase of said continuous matrix including a second material, said first material is a polymer that is dissolvable in a fluid, degradable in a fluid, or combinations thereof and constitutes about 5 vol. % to about 60 vol. % of said composite material, said second material includes particles of elastomer that are evenly disbursed in said first material and constitutes about 5 vol. % to about 90 vol. % of said composite material, said one or more optional secondary components constitute up to about 60 vol. % of said composite material, said particles of elastomer having a particle size of 30-1000 min, said elastomer has a stretched length that is at least 20% greater than its relaxed unstretched length, said elastomer includes olefinic elastomer, ethylene elastomer, vulcanized elastomer and/or nitrile rubber, said second material having a different composition than said first material, said first material is a water-soluble and/or water reactive polymer that has a solubility at below about 30° C. that is less than a solubility at about 70-130° C., said composite material formulated to have at least 10% dissolution or hydrolyzation in a 2-3 hour period at a temperature of at least 55° C., said at least one secondary component includes plasticizer, compatibilizer, binder, polyester, filler, adhesion addition, reactive and/or swellable additive, said at least one optional component having a different composition from said first and second materials. ### Claim 19 (depends on 18) The composite material as defined in claim 18, wherein said first material is a liquid-soluble polymer including one or more materials selected from the group consisting of poly(vinyl alcohol) (PVA), polyethylene glycol (PEG), polyglycolide (PGA), polylactic acid) (PLA), polysaccharides, collagen, polyvinyl pyrrolidone, hydroxyethyl acrylate or methacrylate, hydroxypropyl acrylate or methacrylate, acrylic or methacrylic acid, acrylic or methacrylic esters or vinyl pyridine, acrylamide, vinyl acetate, vinyl alcohol, and ethylene oxide; said second material includes one or more materials selected from the group consisting of natural rubber, vulcanized rubber, silicone, polyurethane, synthetic rubber, polybutadiene, nitrile rubber (NBR), polyisobutylene, acrylate-butadiene rubber, and styrene butadiene rubber. ### Claim 20 (depends on 19) The composite material as defined in claim 19, wherein said first material constitutes about 8 vol. % to about 45 vol. % of said composite material, said second material constitutes about 15 vol. % to about 80 vol. % of said composite material, said one or more optional secondary components constitute about 2 vol. % to about 40 vol. % of said composite material. ### Claim 21 (depends on 20) The composite material as defined in claim 20, wherein said first material constitutes about 20 vol. % to about 40 vol. % of said composite material, said second material constitutes about 15 vol. % to about 60 vol. % of said composite material, said one or more optional secondary components constitute about 3 vol. % to about 30 vol. % of said composite material. ### Claim 22 (depends on 21) The composite material as defined in claim 21, wherein said one or more optional secondary components has one or more properties selected from the group consisting of a) dissolvable by hydrolysis, b) degradable by hydrolysis, c) forms a third phase in said composite material, d) undergoes a volume change upon exposure to fluid about said composite material, e) undergoes a gas-generating reaction upon exposure to fluid about said composite material, f) undergoes a decomposition upon exposure to fluid about said composite material, g) undergoes a reaction upon exposure to fluid about said composite material, h) undergoes a force-generating interaction upon exposure to fluid about said composite material, i) formulated to facilitate in a break-up of said second material in said composite material, and j) formulated to facilitate in a dispersion of said second material in said composite material. ### Claim 23 (depends on 22) The composite material as defined in claim 22, wherein said secondary component includes one or more materials selected from the group consisting of manganese chloride tetrahydrate, magnesium chloride hexahydrate, glycerol, magnesium alloys, aluminum alloys, oxides, carbonates, nickel-containing alloys, iron-based alloy, calcium oxide, magnesium oxide, iron, silicon, zinc, aluminum, aluminum alloy, magnesium, magnesium alloy, carbon black, glass fiber, fumed silica, polyvinylpyrrolidone (PVP), MnCl24H2O and MgCl26H2O, lithium, calcium, montmorrilinate, clay, and polyacrylate. ### Claim 24 (depends on 23) The composite material as defined in claim 23, wherein said secondary component adds color to said composite material. ### Claim 25 (depends on 18) The composite material as defined in claim 18, wherein said composite material has a hardness of 70-99 shore A hardness. ### Claim 26 (depends on 23) The composite material as defined in claim 23, wherein said composite material has a hardness of 70-99 shore A hardness. ### Claim 27 (depends on 25) The composite material as defined in claim 25, wherein said composite material has a hardness of 82-92 shore A hardness. ### Claim 28 A degradable, elastomeric composite material comprised of a first material, a second material, and a secondary component, said first material is a polymer that is dissolvable in a fluid and/or degradable in a fluid, said first material constitutes about 5-60 vol. %© of said composite material, said second material is particles of elastomer that are evenly disbursed in said first material, said second material about 5-90 vol. % of said composite material, said secondary component constitutes 1-60 vol. % of said composite material, said particles of elastomer have a particle size of 30-1000 μm, said elastomer has a stretched length that is at least 20% greater than its relaxed unstretched length, said elastomer includes olefinic elastomer, ethylene elastomer, vulcanized elastomer and/or nitrile rubber, said first material includes 1) vinyl alcohol polymers; 2) copolymers of vinyl alcohol; 3) monomers of vinyl pyrrolidone, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylic acid, methacrylic acid, acrylic esters, acrylic vinyl pyridine, methacrylic esters, methacrylic vinyl pyridine, acrylamide, vinyl acetate, vinyl alcohol, ethylene oxide, and/or polyvinylpyrrolidone; 4) polyamides; 5) polyesters; and/or 6) polycarbonates, said first material is a water-soluble and/or water-reactive polymer that has a solubility and/or dissolution rate of less than 1% after five hours at a temperature of below about 30° C. and has a solubility and/or dissolution rate of at least 10% after three hours at a temperature of at least 55° C. in water and/or brine, said secondary component includes plasticizer, compatibilizer, binder, filler, adhesion additions, reactive and/or swellable additive, said secondary component having a different composition from said first and second material. ### Claim 29 (depends on 28) The composite material as defined in claim 28, wherein said first material includes polyvinyl alcohol), polyethylene glycol, polyglycolide, poly(lactic acid), polysaccharides, collagen, polyvinylpyrrolidone, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, vinyl pyridine, acrylamide, vinyl acetate, vinyl alcohol, and/or ethylene oxide. ### Claim 30 (depends on 28) The composite material as defined in claim 28, wherein said second material includes one or more materials selected from the group consisting of natural rubber, vulcanized rubber, silicone, polyurethane, synthetic rubber, polybutadiene, nitrile rubber (NBR), polyisobutylene, acrylate-butadiene rubber, and styrene butadiene rubber. ### Claim 31 (depends on 29) The composite material as defined in claim 29, wherein said second material includes one or more materials selected from the group consisting of natural rubber, vulcanized rubber, silicone, polyurethane, synthetic rubber, polybutadiene, nitrile rubber (NBR), polyisobutylene, acrylate-butadiene rubber, and styrene butadiene rubber. ### Claim 32 (depends on 28) The composite material as defined in claim 28, wherein said secondary component forms a third phase in said composite material. ### Claim 33 (depends on 31) The composite material as defined in claim 31, wherein said secondary component forms a third phase in said composite material. ### Claim 34 (depends on 28) The composite material as defined in claim 28, wherein said secondary component includes manganese chloride tetrahydrate, magnesium chloride hexahydrate, glycerol, magnesium alloys, aluminum alloys, oxides, carbonates, nickel-containing alloys, iron-based alloys, calcium oxide, magnesium oxide, iron, silicon, zinc, aluminum, aluminum alloy, magnesium, magnesium alloy, carbon black, glass fiber, fumed silica, polyvinylpyrrolidone (PVP), MnCl24H2O, MgCl26H2O, CaO, MgO, Li, Ca, montmorrilinate, clay, and/or polyacrylate. ### Claim 35 (depends on 33) The composite material as defined in claim 33, wherein said secondary component includes manganese chloride tetrahydrate, magnesium chloride hexahydrate, glycerol, magnesium alloys, aluminum alloys, oxides, carbonates, nickel-containing alloys, iron-based alloys, calcium oxide, magnesium oxide, iron, silicon, zinc, aluminum, aluminum alloy, magnesium, magnesium alloy, carbon black, glass fiber, fumed silica, polyvinylpyrrolidone (PVP), MnCl24H2O, MgCl26H2O, CaO, MgO, Li, Ca, montmorrilinate, clay, and/or polyacrylate. ### Claim 36 (depends on 28) The composite material as defined in claim 28, further including an outer polymer coating material, said outer polymer coating material formulated to degrade, said outer polymer coating material encapsulating said first and second materials. ### Claim 37 (depends on 35) The composite material as defined in claim 35, further including an outer polymer coating material, said outer polymer coating material formulated to degrade, said outer polymer coating material encapsulating said first and second materials.