Continuous formation of tubes of poly-4-hydroxybutyrate and copolymers thereof
Methods have been discovered that make it possible to continuously extrude tubes of P4HB and copolymers thereof. These methods allow tubes of P4HB and copolymers thereof to be produced without radial deformation of the tubes despite the slow crystallization of the polymer and copolymers. The methods can produce tubes of P4HB and copolymers thereof with tightly defined outside and inside diameters which are required for medical application. These tubes are produced by radial expansion at temperatures above the melting temperature of P4HB and copolymers thereof, and using low tube cooling temperatures and prolonged cooling times. The tubes made from P4HB and copolymers thereof are flexible, and can be prepared with high elongation to break values.
1. A tube produced by a process comprising:
extruding molten poly-4-hydroxybutyrate thermoplastic polymer or copolymer thereof through an annular passageway formed between a die and a mandrel to form an extruded tube,
radially expanding the extruded tube at a temperature greater than the melt temperature of the polymer or copolymer to form a molten tube,
cooling the molten tube in a cold water bath, and drawing the thus cooled tube away from the extruder thereby forming the tube,
wherein the tube comprises an inner and outer diameter, and has a tensile strength greater than 50 MPa, but less than 2 GPa or an elongation to break of 30% to 1,100%.
2. The tube of claim 1 wherein the tube has an elongation to break of 30% to 1,100%.
3. The tube of claim 1 further comprising one or more of the following: medical marker, therapeutic agent, diagnostic agent, bioactive agent, antimicrobial, antibiotic, prophylactic agent, contrast agent, radiopaque marker, radioactive substance, hyaluronic acid or derivative thereof, collagen, and hydroxyapatite.
4. The tube of claim 1 wherein the outer diameter is 1 mm to 10 mm and the inner diameter is 0.5 mm to 9.5 mm.
5. The tube of claim 4 wherein the average outer and inner diameters of the tube varies less than ±0.003″ inches (±0.08 mm).
6. A process for forming the tube of claim 1 comprising:
extruding molten poly-4-hydroxybutyrate thermoplastic polymer or copolymer thereof through an annular passageway formed between a die and a mandrel to form an extruded tube,
radially expanding the extruded tube at a temperature greater than the melt temperature of the polymer or copolymer to form a molten tube,
cooling the molten tube in a cold water bath, and
drawing the thus cooled tube away from the extruder thereby forming the tube of claim 1 .
7. The process of claim 6 wherein (a) there is an air gap between the exit of the die and the surface of the water bath of 2-1000 mm; (b) the temperature of the cold water bath is from 1 to 25° C.; or (c) the cold water bath is longer than 2 feet (0.61 meters) and less than or equal to 24 feet (7.3 meters), and the tube is collected at a speed of 2 to 3 feet per minute (0.61 to 0.91 meters per minute).
8. The process of claim 7 wherein the temperature of the cold water bath is from 4 to 15° C.
9. The process of claim 8 wherein the molten tube is cooled in the water bath for 2 to 5 minutes.
10. The process of claim 8 wherein the molten tube is cooled in the water bath for 6 to 12 minutes.
11. The process of claim 7 wherein the cold water bath is 20 to 24 feet long (6.1 to 7.3 meters).
12. The process of claim 6 wherein: (a) the polymer or copolymer is dried to a moisture content of less than 300 ppm prior to extrusion; (b) the molten polymer or copolymer is heated to temperatures from 80° C. to 270° C.; or (c) pressurized air is introduced into the inner diameter of the extruded tube.
13. The process of claim 12 wherein the pressurized air has a pressure from 2 to 4 inches of water (498 to 995 Pa of water).
14. The process of claim 6 wherein there is an air gap between the exit of the die and the surface of the water bath of 10-20 mm.
15. The process of claim 6 wherein the temperature of the cold water bath is from 4 to 10° C.
16. The process of claim 6 wherein the extruded tube is radially expanded at 62° C. to 270° C.
17. The process of claim 6 wherein the polymer or copolymer further comprises one or more of the following: nucleant, plasticizer, dye, and ceramic.
18. The process of claim 6 wherein the tensile modulus of the tube is 60 to 700 MPa.
19. The process of claim 6 wherein the tube is an implantable device.