# US 11,077,604 B2 · Polymeric tubes with controlled orientation > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,077,604 B2 - Document ID: US11077604B2 - Status: Granted - Kind: B2 - Application number: 16/148,826 - Filed: 2018-10-01 - Published: 2019-03-14 - Granted: 2021-08-03 - Earliest claimed: 2017-09-08 - Assignees: Zeus Industrial Products, Inc. - Applicants: Zeus Industrial Products, Inc. - Inventors: James M. Lindsey; John Richard Campanelli; Elizabeth A. Foley; Bruce L. Anneaux; Justin A. Marro - Web page: https://patentgrep.com/patent/US11077604B2 ## CPC - B32B 1/08: Tubular products - A61L 31/06: obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds {(A61L31/041 takes precedence)} - A61L 31/129: {containing macromolecular fillers} - A61L 31/14: Materials characterised by their function or physical properties {, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials} - A61L 31/148: {Materials at least partially resorbable by the body} - A61L 31/16: Biologically active materials, e.g. therapeutic substances {(A61L31/047 takes precedence)} - B29C 55/26: biaxial - B32B 27/36: comprising polyesters - B29K 2067/046: {PLA, i.e. polylactic acid or polylactide} - B29K 2995/0053: bi-axially - B29K 2995/006: Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible - B29L 2031/7534: {Cardiovascular protheses} - B32B 2307/514: Oriented - B32B 2307/7163: Biodegradable - Y10T 428/1328: Shrinkable or shrunk [e.g., due to heat, solvent, volatile agent, restraint removal, etc.] - Y10T 428/1352: Polymer or resin containing [i.e., natural or synthetic] - Y10T 428/139: Open-ended, self-supporting conduit, cylinder, or tube-type article - B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM - A61L: METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES (preservation of bodies or disinfecting characterised by the agents employed A01N; preserving, e.g. sterilising, food or foodstuffs A23; preparations for medical, dental or toiletry purposes A61K) - B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00) - B29K: INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR {MOULDS, } REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS - B29L: INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract Methods for preparing oriented polymer tubes, such as biodegradable polymer tubes suitable for in vivo use, are provided herein. The disclosed methods provide alternatives to the typical extrusion/expansion methods by which oriented polymeric tubes for such uses are commonly produced. Advantageously, the disclosed methods can provide more homogeneous molecular orientation of crystallizable polymers within the tube walls, which can endow such polymeric tubes with enhanced strength (e.g., resistance to compression) and toughness. ## Claims ### Claim 1 A method for producing a multilayered tube, comprising: stretching at least one polymeric material, which comprises at least one crystallizable biodegradable polymeric material and has a first dimension, wherein the stretching is performed in a manner that increases the first dimension and that results in a controlled level of orientation; forming a multilayered tube using the at least one polymeric material and at least one adhesive material layer or forming a multilayered tube using the at least one stretched polymeric material and at least one adhesive material layer, wherein the multilayer tube has an orientation profile that is substantially consistent throughout a wall of the multilayered tube. ### Claim 2 (depends on 1) The method of claim 1, wherein the stretching the at least one polymeric material comprises planar stretching. ### Claim 3 (depends on 1) The method of claim 1, wherein one or more of the at least one polymeric material is one or more of a polymer film, a polymer monofilament, a polymer tape, and a polymer rod. ### Claim 4 (depends on 1) The method of claim 1, wherein: the at least one polymeric material has a second dimension, and the stretching the at least one polymeric material comprises stretching the at least one polymeric material to increase the second dimension, such that the at least one stretched polymeric material comprises a biaxially stretched polymeric material. ### Claim 5 (depends on 1) The method of claim 1, wherein the at least one adhesive polymeric material layer is in contact with the at least one stretched polymeric material before, during, or after the stretching of the at least one polymeric material. ### Claim 6 (depends on 1) The method of claim 1, further comprising: obtaining the at least one polymeric material based at least in part on combining the at least one adhesive material layer with the at least one crystallizable biodegradable polymeric material. ### Claim 7 (depends on 6) The method of claim 6, wherein the at least one polymeric material is a composite polymeric material comprising the at least one crystallizable biodegradable polymeric material and the at least one adhesive material layer in layered form. ### Claim 8 (depends on 6) The method of claim 6, wherein the at least one adhesive material layer and the at least one crystallizable biodegradable polymeric material are combined before, during, or after the at least one polymeric material is stretched. ### Claim 9 (depends on 1) The method of claim 1, wherein the forming the tube comprises wrapping the at least one stretched polymeric material and the at least one adhesive material layer around a support. ### Claim 10 (depends on 9) The method of claim 9, wherein the support has one or more of a cylindrical shape, a round shape, a rectangular shape, a triangular shape, an elliptical shape, a polygonal shape, and a tubular form. ### Claim 11 (depends on 9) The method of claim 9, wherein the wrapping comprises wrapping the at least one stretched polymeric material and the at least one adhesive material layer around the support multiple times such that the multilayered tube comprises multiple layers of the at least one stretched polymeric material and multiple layers of the at least one adhesive material layer. ### Claim 12 (depends on 9) The method of claim 9, wherein: the at least one stretched polymeric material comprises a plurality of units of stretched polymeric material, the plurality of units of stretched polymeric material comprises different polymeric materials or a same polymeric material; and the forming the multilayered tube comprises arranging the plurality of units of stretched polymeric material in at least one of a stacked manner and a staggered manner, and wrapping the arranged plurality of units of stretched polymeric material on a bias angle. ### Claim 13 (depends on 9) The method of claim 9, wherein the support is a mandrel, and the method further comprises removing the multilayered tube from the mandrel. ### Claim 14 (depends on 9) The method of claim 9, wherein the support comprises a device. ### Claim 15 (depends on 14) The method of claim 14, further comprising forming a resulting composite based at least in part on the multilayered tube and the support, and the resulting composite is a medical device. ### Claim 16 (depends on 1) The method of claim 1, further comprising forming a medical device based at least in part on the multilayered tube. ### Claim 17 (depends on 16) The method of claim 16, wherein the forming the medical device comprises: cutting the multilayered tube into a stent. ### Claim 18 (depends on 17) The method of claim 17, further comprising applying one or more of a therapeutic, a covering, and a coating to the stent. ### Claim 19 (depends on 1) The method of claim 1, wherein the forming the tube comprises subjecting the at least one stretched polymeric material to at least one of heat and pressure. ### Claim 20 (depends on 1) The method of claim 1, wherein the forming the tube comprises: forming a layered structure, the forming the layered structure comprising: applying a shrink tube or shrink film around at least part of the at least one stretched polymeric material to give a layered structure, and subjecting the layered structure to at least one of heat and pressure. ### Claim 21 (depends on 1) The method of claim 1, wherein the forming the tube comprises: inserting at least part of the at least one stretched polymeric material in a mold; positioning the at least one stretched polymeric material over an expandable support; and subjecting the at least one stretched polymeric material to at least one of heat and pressure. ### Claim 22 (depends on 1) The method of claim 1, wherein one or more of the at least one crystallizable biodegradable polymeric material is selected from the group consisting of poly(L-lactide) (PLLA), poly(D-lactide) (PDLA), poly(ε-caprolactone) (PCL), polyglycolic acid (PGA), poly(para-dioxanone) (PDO), poly(hydroxybutyrate), poly(hydroxyvalerate), poly(tetramethyl carbonate), poly(ethylene oxide) (PEO), poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), and copolymers and derivatives and combinations thereof. ### Claim 23 (depends on 1) The method of claim 1, wherein the adhesive polymeric material is selected from the group consisting of poly(ε-caprolactone), poly(trimethylene carbonate), poly(D,L-lactide), poly(L-lactide)-co-ε-caprolactone), poly(L-lactide-co-trimethylene carbonate), poly(ε-caprolactone-co-trimethylene carbonate), poly(ethylene glycol), poly(L-lactide-co-poly(ethylene glycol)), and copolymers and derivatives and combinations thereof. ### Claim 24 (depends on 5) The method of claim 5, wherein the forming the tube comprises using the at least one stretched polymeric material and at least one adhesive polymeric material, and the at least one crystallizable biodegradable polymeric material and the at least one adhesive polymeric material comprise a same polymeric material. ### Claim 25 (depends on 1) The method of claim 1, wherein the at least one stretched polymeric material is stretched at least ten percent of a maximum stretch ratio respectively corresponding to the at least one polymeric material. ### Claim 26 (depends on 1) The method of claim 1, wherein the stretching the at least one polymeric material comprises controlling, during the stretching, one or more of a mechanical property, a thermodynamic property, a chemical property, an electrical property, and a degradation rate, of the at least one polymeric material. ### Claim 27 (depends on 1) The method of claim 1, wherein the at least one polymeric material is stretched between three hundred percent and one thousand percent of an original dimension of the at least one polymeric material. ### Claim 28 (depends on 1) The method of claim 1, further comprising stretching the multilayered tube. ### Claim 29 A method, comprising: obtaining at least one stretched polymeric material exhibiting at least partial molecular orientation, wherein: the at least one stretched polymeric material comprises at least one crystallizable biodegradable polymeric material, wherein the at least one stretched polymeric material has a first dimension, and wherein the at least one stretched polymeric material was prepared by stretching at least one polymeric material in a manner that increased the first dimension and that resulted in a controlled level of orientation; forming a multilayered tube using the at least one stretched polymeric material and at least one adhesive material layer, wherein the multilayer tube has an orientation profile that is substantially consistent throughout a wall of the multilayered tube. ### Claim 30 (depends on 29) The method of claim 29, further comprising stretching the multilayered tube.