Thermoplastic Polyurethane Materials For Forming Medical Devices

Patent metadata

Field	Value
Publication number	US-2017107320-A1
Application number	US-201615291291-A
Country	US
Kind code	A1
Filing date	Oct 12, 2016
Priority date	Oct 14, 2015
Publication date	Apr 20, 2017
Grant date	—

Abstract

Principles and embodiments of the present invention relate generally to thermoplastic polyurethane materials having controlled and improved stiffness and/or flexibility, and methods to prepare them. The thermoplastic polyurethanes described herein having superior stiffness and softening properties may be fabricated into film, tubing, and other forms of medical devices. The thermoplastic polyurethanes comprise: an aromatic diisocyanate excluding non-aromatic diisocyanates; at least one polyglycol; and a chain extender comprising at least one side-chain branching diol and excluding linear diols.

First claim

What is claimed is:

1 . A thermoplastic polyurethane comprising a product from the reaction of:
an aromatic diisocyanate; at least one polyglycol; and a chain extender comprising at least one side-chain branching diol and excluding linear diols, and optionally, an amine-terminated polyether; with the proviso that the polyurethane does not contain any non-aromatic diisocyanates, and wherein the polyurethane has an isocyanate index in the range of 1 to 1.4.

2 . The thermoplastic polyurethane of claim 1 , wherein the side-chain branching diol has a structure according to Formula (IV):

wherein R 1 is a methyl group, and R 2 is a methyl group or hydrogen atom.

3 . The thermoplastic polyurethane of claim 2 , wherein the side-chain branching diol comprises 2,2-dimethyl-1,3-propanediol, 2-methyl-1,3-propanediol, or both in a weight ratio of from 0:100 to 100:0 of 2,2-dimethyl-1,3-propanediol to 2-methyl-1,3-propanediol.

4 . The thermoplastic polyurethane of claim 3 , wherein the side-chain branching diol consists essentially of a mixture of 2,2-dimethyl-1,3-propanediol and 2-methyl-1,3-propanediol in a weight ratio of from 10:90 to 90:10.

5 . The thermoplastic polyurethane of claim 1 , wherein the at least one polyglycol is selected from the group consisting of polyethylene oxide glycol (PEG), polypropylene oxide glycol (PPG), polytetramethylene ether glycol (PTMEG), polyester glycol, silicone glycol, polycarbonate glycol and combinations thereof.

6 . The thermoplastic polyurethane of claim 5 , wherein the at least one polyglycol is polytetramethylene ether glycol (PTMEG) having the formula: HO(CH 2 CH 2 CH 2 CH 2 —O—) n H, where n has an average value in the range of 3 to 40.

7 . The thermoplastic polyurethane of claim 6 , wherein the at least one polyglycol is a blend of at least two PTMEGs, a first PTMEG having a first nominal molecular weight in the range of 250 to less than 1000 daltons and a second PTMEG having a second nominal molecular weight in the range of 1000 to 2900 daltons.

8 . The thermoplastic polyurethane of claim 1 , wherein the at least one polyglycol is a blend of two or more PTMEG250, PTMEG650, PTMEG1000, PTMEG1450, PTMEG1800, PTMEG2000, and PTMEG2900.

9 . The thermoplastic polyurethane of claim 1 , wherein the aromatic diisocyanate is selected from the group consisting of diphenylmethane-4,4′-diisocyanate (MDI), 2,4-toluene diisocyanate, 2,6-toluene diisocyanate (TDI), 1,5-naphthalene diisocyanate (NDI), 3,3′-dimethyldiphenyl 4,4′-diisocyanate (TODI), 4,6′-xylylene diisocyanate (XDI), 3,3′-dimethyl-diphenylmethane 4,4′-diisocyanate (DMMDI), dianisidine diisocyanate (DADI), and combinations thereof.

10 . The thermoplastic polyurethane of claim 1 , wherein the aromatic diisocyanate is 4,4′-diphenylmethane diisocyanate, and has hard segment content in the range of 50% and 75% by weight.

11 . The thermoplastic polyurethane of claim 1 , which further comprises one or more of a radiopaque material, an antithrombogenic agent, an antimicrobial agent, a lubricant, or a colorant.

12 . The thermoplastic polyurethane of claim 1 , wherein the side-chain branching diol chain extender comprises about 5% to about 20% (w/w) of the polyurethane.

13 . The thermoplastic polyurethane of claim 1 comprising the amine-terminated polyether, which is one or more amine-terminated polyethers having repeating units of polyethylene oxide, polypropylene oxide, or polytetramethylene oxide and having a molecular weight in the range of about 400 to 8,000.

14 . A melt-processable thermoplastic polyurethane comprising the reaction product of:
an aromatic diisocyanate selected from the group consisting of 4,4′-diphenylmethane diisocyanate, 2,2′-dimethyl-4,4′-biphenyldiisocyanate, 3,3′-dimethyl-4,4′-biphenyl diisocyanate, and combinations thereof; at least one polyglycol selected from the group consisting of polyethylene oxide glycol (PEG), polypropylene oxide glycol (PPG), polytetramethylene ether glycol (PTMEG), and combinations thereof; and at least one chain extender selected from the group consisting of 2,2-dimethyl-1,3-propanediol, 2-methyl-1,3-propanediol, and combinations thereof; and optionally, an amine-terminated polyether.

15 . The melt-processable thermoplastic polyurethane of claim 14 comprising, in weight percentages based on the polyurethane:
about 40 to about 55% of the aromatic diisocyanate;
about 15 to about 59.9% of the at least one polyglycol; and
about 0.1 to about 25% of the at least one chain extender, and
optionally, 0 to about 30% of the amine-terminated polyether;
with the proviso that the amounts add to 100%.

16 . The melt-processable thermoplastic polyurethane of claim 14 , which further comprises one or more of a radiopaque material, an antithrombogenic agent, an antimicrobial agent, a lubricant, or a colorant.

17 . The melt-processable thermoplastic polyurethane of claim 14 , comprising a hard segment content in the range of 50% and 75% by weight.

18 . The melt-processable thermoplastic polyurethane of claim 15 comprising the aromatic diisocyanate in an amount in the range of about 46 to about 49% (w/w) and the chain extender in an amount in the range of about 12% to about 18% (w/w) of the polyurethane.

19 . A vascular access device comprising the melt-processable thermoplastic polyurethane of claim 14 .

20 . The vascular access device of claim 19 , wherein the vascular access device is selected from a group including a central venous catheter, a peripherally inserted central catheter, or peripheral intravenous cannula.

21 . A method of making a vascular access device comprising:
combining the following ingredients: an aromatic diisocyanate excluding non-aromatic diisocyanates; at least one polyglycol; and a chain extender comprising at least one side-chain branching diol and excluding linear diols; polymerizing the ingredients in a one-step bulk polymerization without a catalyst to form a thermoplastic polyurethane; curing the polyurethane; convening the polyurethane into chips suitable for melt forming; and melt forming the polyurethane into vascular access devices.

22 . The method of claim 21 , wherein the side-chain branching diol consists essentially of 2,2-dimethyl-1,3-propanediol, 2-methyl-1,3-propanediol, or both in a weight ratio of from 0:100 to 100:0 of 2,2-dimethyl-1,3-propanediol to 2-methyl-1,3-propanediol.

Assignees

• Becton Dickinson Co

Inventors

• Zhou Ming
• Hermel-Davidock Theresa

Classifications

• B29C48/10

  flexible, e.g. blown foils · CPC title

• C08G18/6681

  with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 · CPC title

• C08G18/7671

  containing only one alkylene bisphenyl group · CPC title

• B29B9/12

  characterised by structure or composition · CPC title

• B29B9/02

  by dividing preformed material · CPC title