IP Library Granted Patent US 11,999,130
Granted Patent B2
US 11,999,130 · App. 17/355,261 · Granted Jun 4, 2024

Polymeric tubes with controlled orientation

Inventors: James M. Lindsey (Lexington, SC); John Richard Campanelli (West Columbia, SC); Elizabeth A. Foley (Columbia, SC); Bruce L. Anneaux (Lexington, SC); Justin A. Marro (Orangeburg, SC)
Assignee: Zeus Company LLC
B32B1/08A61L31/06A61L31/129A61L31/14A61L31/148A61L31/16B29C55/26B32B27/36B29K2067/046B29K2995/0053B29K2995/006B29L2031/7534B32B2307/514B32B2307/7163Y10T428/1328Y10T428/1352Y10T428/139
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Quick Facts
Patent No.
US 11,999,130
App. No.
17/355,261
Granted
Jun 4, 2024
Kind
B2
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 (35)

1. A multilayered tube, comprising:

at least one stretched polymeric material layer comprising a polymer 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, derivatives and combinations thereof; and

at least one adhesive material layer comprising a polymer 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, derivatives and combinations thereof, wherein:

the at least one stretched polymeric material layer exhibits at least partial molecular orientation;

the at least one stretched polymeric material layer and the adhesive material layer are comprised in different layers of the tube;

the at least one adhesive material layer adheres adjacent layers of the at least one stretched polymeric material layer to itself or to other layers within the multilayered tube;

the multilayer tube has an orientation profile that is substantially consistent throughout a wall of the multilayered tube.

2. The multilayered tube of claim 1 , wherein the at least one stretched polymeric material layer is obtained based at least in part on stretching at least one polymeric material in a manner that increases the at least one polymeric material in a first direction.

3. The multilayered tube of claim 2 , wherein the stretching comprises a planar stretching.

4. The multilayered tube of claim 2 , wherein the at least one polymeric material is stretched at least ten percent of a maximum stretch ratio corresponding to the at least one polymeric material.

5. The multilayered tube of claim 2 , wherein the at least one polymeric material is stretched at least twenty percent of a maximum stretch ratio respectively corresponding to the at least one polymeric material.

6. The multilayered tube of claim 1 , wherein:

the at least one stretched polymeric material layer is obtained based at least in part on: stretching at least one polymeric material in a manner that increases the at least one polymeric material in a first direction; and

stretching the at least one polymeric material in a manner that increases the at least one polymeric material in a second direction.

7. The multilayered tube of claim 1 , wherein:

the at least one stretched polymeric material layer is obtained based at least in part on stretching at least one polymeric material in a manner that increases the at least one polymeric material in a first direction; and

the at least one adhesive polymeric material layer is in contact with the at least one stretched polymeric material layer before, during, or after the stretching of the at least one polymeric material layer.

8. The multilayered tube of claim 2 , wherein the at least one adhesive material layer and the at least one stretched polymeric material are combined before, during, or after the at least one polymeric material layer is stretched.

9. The multilayered tube of claim 1 , wherein the tube 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.

10. The multilayered tube of claim 1 , further comprising one or more of a therapeutic, a covering, and a coating.

11. The multilayered tube of claim 1 , wherein the tube exhibits:

a maximum stress value of about 20 MPa or greater measured based on a first compression cycle; and

the tube being deformed 17% or less in at least a first dimension after the first compression cycle.

12. The multilayered tube of claim 11 , wherein the first compression cycle comprises:

obtaining an initial distance between two parallel plates between which the tube is disposed, the two parallel plates contacting an outer surface of the tube in a manner in which the two parallel plates provide substantially no load on the tube;

compressing the plates to a distance that is 50% of the initial distance at a rate of 50% of the initial distance of the two parallel plates per minute, the compressing the plates causing the tube to deform in the first direction, the first direction being a direction in which the plates are compressed; and

releasing a compression of the plates on the tube at a rate of 50% of the initial distance of the two parallel plates per minute.

13. The multilayered tube of claim 12 , wherein a total energy value under an engineering stress-strain curve corresponding to the tube after the first compression is at least 138 kgf·mm/cm.

14. The multilayered tube of claim 1 , wherein the at least one stretched polymeric layer comprises polylactide.

15. The multilayered tube of claim 14 , wherein the polylactide is PLLA.

16. The multilayered tube of claim 14 , wherein the polylactide is PDLA.

17. The multilayered tube of claim 1 , wherein the at least one stretched polymeric material layer comprises polycaprolactone.

18. The multilayered tube of claim 1 , wherein the at least one stretched polymeric material layer comprises a copolymer of lactide and caprolactone.

19. The multilayered tube of claim 1 , wherein the at least one adhesive material layer comprises poly(D,L-lactide).

20. The multilayered tube of claim 1 , wherein the at least one adhesive material layer comprises poly(L-lactide)-co-ε-caprolactone).

Assignments (6)
CHANGE OF NAME Recorded Apr 9, 2024
From: ZEUS COMPANY INC.
To: ZEUS COMPANY LLC
Reel/Frame 067043/0815 →
SECURITY INTEREST Recorded Feb 28, 2024
From: ZEUS COMPANY LLC
To: GOLDMAN SACHS BDC, INC., AS AGENT
Reel/Frame 066702/0187 →
CHANGE OF NAME Recorded Feb 27, 2024
From: ZEUS COMPANY INC.
To: ZEUS COMPANY LLC
Reel/Frame 066696/0788 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 15, 2023
From: ANNEAUX, BRUCE L.
To: ZEUS INDUSTRIAL PRODUCTS, INC.
Reel/Frame 065880/0715 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 15, 2023
From: LINDSEY, JAMES M.; CAMPANELLI, JOHN RICHARD; FOLEY, ELIZABETH A.; MARRO, JUSTIN A.
To: ZEUS INDUSTRIAL PRODUCTS, INC.
Reel/Frame 065880/0777 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 25, 2022
From: ZEUS INDUSTRIAL PRODUCTS, INC.
To: ZEUS COMPANY INC.
Reel/Frame 058758/0410 →
Continuity (4)
Continuation 16148826 · Oct 1, 2018
Continuation In Part 16124398 · Sep 7, 2018
Provisional Application 62555796 · Sep 8, 2017
Related Publication 20220040905A1 · Feb 10, 2022