Thermoplastic polyurethane admixtures

• US 9,744,269 B2
• Filed: 11/20/2015
• Issued: 08/29/2017
• Est. Priority Date: 03/15/2013
• Status: Active Grant

• Current Assignee: AngioDynamics, Inc., Evonik Canada Inc. (Rag-Stiftung)
• Original Assignee: AngioDynamics, Inc., Interface Biologics, Inc.
• Inventors: Santerre, J. Paul, Ho, Jeannette, Piotrowicz, Alexandra, Esfand, Roseita, Lareau, Raymond, Bell, Benjamin
• Primary Examiner(s): Rodd, Christopher M
• Application Number:
  US14/947,026
• Publication Number:
  US 20160310641A1
• Time in Patent Office: 648 Days
• Field of Search: None
• CPC Class Codes: A61L 29/049 Mixtures of macromolecular compounds
• CPC Class Codes: A61L 29/06 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/2885 containing halogen atoms
• CPC Class Codes: C08G 18/4825 Polyethers containing two hydroxy groups C08G18/4833 - C08G18/5096 take precedence
• CPC Class Codes: C08G 18/485 containing mixed oxyethylene-oxypropylene or oxyethylene-higher oxyalkylene end groups
• CPC Class Codes: C08G 18/73 acyclic
• CPC Class Codes: C08G 18/831 by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides by aldehydes C08G18/84, by peroxides C08G18/86
• CPC Class Codes: C08L 75/04 Polyurethanes
• CPC Class Codes: C09D 175/04 Polyurethanes

Abstract

The invention relates to admixtures of thermoplastic polyurethane base polymers that resist surface dulling and fluorinated additives and their use in the manufacture of articles, such as medical devices. For example, the admixtures of the invention are useful in the manufacture of blood dwelling medical devices, such as catheters.

Claims

1. A medical device having a surface comprising an admixture comprising a thermoplastic polyurethane base polymer and a fluorinated additive mixture, wherein said fluorinated additive mixture comprises compounds of formula (I):

G-[B-A]_n-B-G 

 

(I),

and greater than 0% to 10% (w/w) trimer of formula (II);

G-B-G 

 

(II),

wherein

A is a soft segment comprising polypropylene oxide, polyethylene oxide, polytetramethylene oxide, hydrogenated polybutadiene (HLBH), poly (2,2 dimethyl-1,3-propylcarbonate) (PCN), polybutadiene (LBHP), diethyleneglycol-orthophthalicanhydride polyester (PDP), poly (hexamethyhlenecarbonate)diol, hydroxyl terminated polydimethylsiloxanes (PrO-PDMS-PrO) block copolymer, hydrogenated-hydroxyl terminated polyisoprene, poly(ethyleneglycol)-block-poly(propyleneglycol))-block-poly(ethylene glycol), 1,12-dodecanediol, hydrogenated polyisoprene (HHTPI), poly(hexamethylene carbonate), or poly(2-butyl-2-ethyl-1,3-propyl carbonate);

B is a hard segment comprising terminal urethane linkages;

G is an polyfluoroalkyl group; and

n is an integer from 1 to 15.

2. The medical device of claim 1, wherein said fluorinated additive mixture comprises between 0.1% and 5% (w/w) trimer of formula (II).

3. The medical device of claim 1, wherein said polyfluoroalkyl group is selected from radicals of the general formula CF₃(CF₂)_rCH₂CH₂—

wherein r is 2-20, and CF₃(CF₂)_s(CH₂CH₂O)_χ

wherein χ

is 1-10 and s is 1-20.

4. The medical device of claim 1, wherein said fluorinated additive mixture is formed by a process that comprises (i) reacting a diisocyanate corresponding to hard segment B with a diol corresponding to soft segment A to form a prepolymer, and (ii) reacting said prepolymer with a polyfluoroalkyl alcohol corresponding to polyfluoroalkyl group G to form a mixture of compounds of formula (I).

5. The medical device of claim 4, wherein said diisocyanate corresponding to hard segment B is selected from the group consisting of 2,4 toluene diisocyanate, 2,6 toluene diisocyanate, methylene bis(p-phenyl) diisocyanate, 1,5 naphthalene diisocyanate, 3,3′

bitoluene diisocyanate, methylene bis (p-cyclohexyl isocyanate), 1,6 hexane diisocyanate, 1,12 dodecane diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, lysine diisocyanate, and trimethyl-1,6 diisocyanatohexane.

6. The medical device of claim 4, wherein said diol corresponding to soft segment A is selected from polyalkylene oxide diols, polycarbonate diols, polyester diols, and lactone diols.

7. The medical device of claim 6, wherein said diol corresponding to soft segment A is selected from the group consisting of polyethylene oxide diol, polypropylene oxide diol, and polytetramethylene oxide diol.

8. The medical device of claim 4, wherein said diol corresponding to soft segment A has a theoretical molecular weight of from 400 to 3,000 Daltons.

9. The medical device of claim 4, wherein said diisocyanate corresponding to hard segment B is 1,6 hexane diisocyanate.

10. The medical device of claim 4, wherein said fluorinated additive mixture is formed by a process that comprises (i) reacting about 1 equivalent of said diol corresponding to soft segment A with about 1.4 to 1.8 equivalents of said diisocyanate corresponding to hard segment B to form a prepolymer and (ii) reacting said prepolymer with a polyfluoroalkyl alcohol corresponding to polyfluoroalkyl group G to form said fluorinated additive mixture.

11. The medical device of claim 4, wherein said fluorinated additive mixture is formed by a process that comprises (i) reacting 1 equivalent of polyethylene oxide diol, polypropylene oxide diol, and polytetramethylene oxide diol with about 1.4 to 1.8 equivalents of 1,6-hexamethylene diisocyanate to form a prepolymer;

and (ii) reacting said prepolymer with a polyfluoroalkyl alcohol corresponding to polyfluoroalkyl group G to form said fluorinated additive mixture.

12. The medical device of claim 4, wherein said fluorinated additive mixture is formed by a process that further comprises an extraction step for removing some of said trimer of formula (II).

13. The medical device of claim 4, wherein said polyfluoroalkyl alcohol corresponding to polyfluoroalkyl group G is selected from 1H,1H,2H,2H-perfluoro-1-decanol;

1H,1H,2H,2H-perfluoro-1-octanol;

1H,1H,5H-perfluoro-1-pentanol; and

1H,1H, perfluoro-1-butanol, and mixtures thereof.

14. The medical device of claim 1, wherein said fluorinated additive mixture has a polystyrene equivalent weight average molar mass, M_w, of from 2,000 to 26,000 g/mole.

15. The medical device of claim 1, wherein said fluorinated additive mixture has a polystyrene equivalent number average molar mass, M_n, of from 2,000 to 18,000 g/mole.

16. The medical device of claim 1, wherein said fluorinated additive mixture has a polystyrene equivalent molecular weight at highest peak, M_p, of from 2,000 to 26,000 g/mole.

17. The medical device of claim 1, wherein said fluorinated additive mixture has a polydispersity index of between 1.0 and 2.0.

18. The medical device of claim 1, wherein said fluorinated additive mixture has a weight average molar mass, M_w, of from 2,000 to 14,000 g/mole, a number average molar mass, M_n, of from 2,000 to 12,000 g/mole, and comprises between 0.3% and 3% (w/w) trimer of formula (II).

19. The medical device of claim 1, wherein said fluorinated additive mixture has a weight average molar mass, M_w, of from 14,000 to 26,000 g/mole, a number average molar mass, M_n, of from 10,000 to 16,000 g/mole, and comprises greater than 0% to 3% (w/w) trimer of formula (II).

20. The medical device of claim 1, wherein said thermoplastic polyurethane base polymer is a poly (carbonate urethane) base polymer.

21. The medical device of claim 20, wherein said poly (carbonate urethane) base polymer comprises poly(hexamethylene carbonate) and 4,4′

-methylene bis(cyclohexyl urethane).

22. The medical device of claim 1, wherein said thermoplastic polyurethane base polymer has a Shore durometer hardness of between 70 A and 95 A.

23. The medical device of claim 1, wherein said admixture comprises from 1% to 8% (w/w) fluorinated additive mixture.

24. The medical device of claim 23, wherein said admixture comprises greater than 0% to less than 1% (w/w) of trimer of formula (II).

25. The medical device of claim 24, wherein said admixture comprises greater than 0% to less than 0.3% (w/w) of trimer of formula (II).

26. The medical device of claim 1, wherein said medical device is a central venous catheter, dialysis catheter, implanted port, or peripherally inserted central catheter.