# US 9,040,136 B2 · Flexible pipe > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,040,136 B2 - Document ID: US9040136B2 - Status: Granted - Kind: B2 - Application number: 12/531,135 - Filed: 2008-03-17 - Published: 2010-03-11 - Granted: 2015-05-26 - Earliest claimed: 2007-03-16 - Assignees: National Oilwell Varco Denmark I/S - Applicants: Inger-Margrete Procida - Inventors: Inger-Margrete Procida - Web page: https://patentgrep.com/patent/US9040136B2 ## CPC - B32B 1/08: Tubular products - B32B 27/12: next to a fibrous or filamentary layer - F16L 11/081: {comprising one or more layers of a helically wound cord or wire (in combination with braided layers F16L11/088)} - F16L 11/125: {non-inflammable or heat-resistant hoses} - Y10T 428/13: Hollow or container type article [e.g., tube, vase, etc.] - Y10T 428/1303: Paper containing [e.g., paperboard, cardboard, fiberboard, etc.] - Y10T 428/1352: Polymer or resin containing [i.e., natural or synthetic] - Y10T 428/1359: Three or more layers [continuous layer] - Y10T 428/139: Open-ended, self-supporting conduit, cylinder, or tube-type article - Y10T 428/1393: Multilayer [continuous layer] - B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM - F16L: PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract The invention relates to a flexible pipe comprising at least one polymer layer, and at least one armoring layer unbounded to said polymer layer, wherein at least one polymer layer is a cationic clay containing polymer layer of a polymer material comprising a polymer matrix and from about 0.1 to about 5% by weight of at least one cationic clay silicate. Preferred cationic clay silicates comprise kaolinite; smectite; Illite; chlorite; and synthetic cationic clays. The cationic clay silicate may e.g. be an organo-cationic clay. The cationic clay silicate may preferably be exfoliated and/or intercalated in the polymer matrix. The polymer layer may preferably comprise an inner liner, a thermally insulating layer, an anti-wear layer and/or an outer sheath or a sub-layer thereof. ## Claims ### Claim 1 An unbonded flexible pipe for use in offshore transportation of oil products and gas products, the flexible pipe comprising at least one polymer layer including an inner liner, and at least one armouring layer on an outer side of and unbonded to said inner liner, which is a cationic clay silicate containing polymer layer of a polymer material comprising a polymer matrix and from about 0.1 to about 4% by weight of at least one cationic clay silicate, wherein said at least one cationic clay silicate is in the form of platelets having a thickness of about 10 nm or less. ### Claim 2 (depends on 1) An unbonded flexible pipe as claimed in claim 1 wherein said at least one cationic clay silicate is selected from kaolinite; smectite; Illite; or chlorite. ### Claim 3 (depends on 1) An unbonded flexible pipe as claimed in claim 1 wherein said at least one cationic clay silicate is selected from alumino-silicate(s) or magnesium-silicate(s). ### Claim 4 (depends on 1) An unbonded flexible pipe as claimed in claim 1 wherein said at least one cationic clay silicate has an octahedral metal element crystal lattice structure. ### Claim 5 (depends on 1) An unbonded flexible pipe as claimed in claim 1 wherein said at least one cationic clay silicate is an organo-cationic clay. ### Claim 6 (depends on 5) An unbonded flexible pipe as claimed in claim 5 wherein said organo-cationic clay comprises an adsorbed monolayer of a quaternary amine. ### Claim 7 (depends on 5) An unbonded flexible pipe as claimed in claim 5 wherein said organo-cationic clay is surface modified cationic clay silicate according to the following formula quaternary amine+−CLAY, wherein the quaternary amine preferably is selected from ditallow dimethyl ammonium chloride, hexadecyl ammonium chloride, octadecyl ammonium chloride, di-methyl di-hydrogenated tallow ammonium chloride, dicocodimethyl ammonium chloride, acids thereof, or mixtures thereof. ### Claim 8 (depends on 1) An unbonded flexible pipe as claimed in claim 1 wherein said cationic clay silicate(s) is in the form of platelets having an aspect ratio of at least about 50. ### Claim 9 (depends on 1) An unbonded flexible pipe as claimed in claim 1 wherein said at least one cationic clay silicate is exfoliated in the polymer matrix. ### Claim 10 An unbonded flexible pipe as claimed in any one of the preceding claims wherein said at least one cationic clay silicate is intercalated in the polymer matrix. ### Claim 11 (depends on 1) An unbonded flexible pipe as claimed in claim 1 wherein said cationic clay silicate containing polymer layer(s) comprises at least about 50% by weight of one or more of the polymers polyolefins; polyamide; polyureas; polyesters; polyacetals; polyethers; polyoxides; polysulfides; polysulphones; polyacrylates; polyethylene terephthalate (PET); polyether-ether-ketones (PEEK); polyvinyls; polyacrylonitrils; polyetherketoneketone (PEKK); copolymers of the preceding and fluorous polymers. ### Claim 12 (depends on 1) An unbonded flexible pipe as claimed in claim 1 wherein the cationic clay silicate containing polymer matrix is cross-linked polyethylene (XLPE). ### Claim 13 (depends on 12) An unbonded flexible pipe as claimed in claim 12 wherein said XLPE is cross-linked by electromagnetic wave activation of a radical generator. ### Claim 14 An unbonded flexible pipe for use in offshore transportation of oil products and gas products, the flexible pipe comprising at least one polymer layer, and at least one armouring layer unbonded to said polymer layer, said flexible pipe comprises an inner liner which is a cationic clay silicate containing polymer layer of a polymer material comprising a polymer matrix and from about 0.1 to about 4% by weight of at least one cationic clay silicate, said inner liner providing the innermost barrier to a fluid to be transported in the pipe, wherein said at least one cationic clay silicate is in the form of platelets having a thickness of about 10 nm or less. ### Claim 15 (depends on 14) An unbonded flexible pipe as claimed in claim 14 wherein the inner liner has a thickness of at least about 4 mm. ### Claim 16 (depends on 1) An unbonded flexible pipe as claimed in claim 1 wherein said cationic clay silicate containing polymer layer(s) comprises an outer sheath preferably providing the outermost barrier to water when the pipe in applied in water. ### Claim 17 (depends on 1) An unbonded flexible pipe as claimed in claim 1 wherein said cationic clay silicate containing polymer layer(s) comprises an intermediate layer in the form of a thermally insulating layer. ### Claim 18 (depends on 1) An unbonded flexible pipe as claimed in claim 1 wherein said cationic clay silicate containing polymer layer(s) has a thickness of at least about 0.5 mm. ### Claim 19 (depends on 1) An unbonded flexible pipe as claimed in claim 1 wherein said cationic clay silicate containing polymer layer(s) is an extruded layer. ### Claim 20 (depends on 1) An unbonded flexible pipe as claimed in claim 1 wherein said cationic clay silicate containing polymer layer(s) is a wound layer. ### Claim 21 (depends on 1) An unbonded flexible pipe as claimed in claim 1 wherein said cationic clay silicate containing polymer layer(s) comprises a film layer having a thickness of up to about 0.5 mm. ### Claim 22 (depends on 21) An unbonded flexible pipe as claimed in claim 21 wherein the film layer is a wound film layer or a folded film layer. ### Claim 23 (depends on 21) An unbonded flexible pipe as claimed in claim 21 wherein the film layer is a layered material comprising at least one polymer sub-layer comprising cationic clay silicates. ### Claim 24 (depends on 21) An unbonded flexible pipe as claimed in claim 21 wherein the film layer has a thickness of about 25 μm or more. ### Claim 25 (depends on 21) An unbonded flexible pipe as claimed in claim 21 wherein the film layer is applied in direct contact to, and innermost to another polymer layer. ### Claim 26 (depends on 1) An unbonded flexible pipe as claimed in claim 1 wherein the cationic clay silicate containing polymer layer additionally comprises filler material(s), preferably selected from the group consisting of pigments, heat stabilisers, process stabilisers, metal deactivators, flame-retardants, reinforcement fillers and mixtures thereof. ### Claim 27 (depends on 1) An unbonded flexible pipe as claimed in claim 1 wherein said pipe comprises one or more innermost unbonded armouring layers (carcass). ### Claim 28 (depends on 1) An unbonded flexible pipe according to claim 1 wherein said pipe comprises more than one unbonded armouring layers (outer armouring layers) on the outer side of an inner liner. ### Claim 29 (depends on 1) A method of producing an unbonded flexible pipe of claim 1 wherein the cationic clay silicate containing polymer layer is produced by a method comprising compounding the cationic clay silicate into the polymer at a temperature of about the melting point to +20° C. for the polymer in question. ### Claim 30 (depends on 29) A method of claim 29 wherein the cationic clay silicate containing polymer layer is produced by a method comprising compounding the cationic clay silicate into the polymer at a temperature of about the melting point to +10° C. for the polymer in question.