Polyurethane based medical articles

Patent metadata

Field	Value
Publication number	US-12102736-B2
Application number	US-202217680646-A
Country	US
Kind code	B2
Filing date	Feb 25, 2022
Priority date	Feb 25, 2021
Publication date	Oct 1, 2024
Grant date	Oct 1, 2024

Abstract

Medical articles formed from a polyurethane-based resin including an ionically-charged modifier provide enhanced properties. The polyurethane-based resin is a reaction product of ingredients comprising: a diisocyanate; a diol chain extender; a polyglycol; and an ionically-charged modifier incorporated into a backbone, as a side chain, or both of the polyurethane-based resin. Embodiments include the ionically-charged modifier is a combination of anionic and cationic modifiers. Embodiments include the ionically-charged modifier is zwitterionic. Medical articles herein either have inherent antimicrobial and/or anti-fouling characteristics or can easily bond ionic active agents to provide desirable material properties, including antimicrobial, anti-fouling, and/or radiopacity.

First claim

What is claimed is:

1. A medical article formed from a polyurethane-based resin, which is a reaction product of ingredients comprising:
a diisocyanate;
a diol chain extender;
a polyglycol; and
a zwitterionic modifier or a combination of anionic and cationic modifiers incorporated into a backbone, as a side chain, or both of the polyurethane-based resin formed by the diisocyanate, the polyglycol, and the diol chain extender, wherein the zwitterionic modifier comprises at least one anionic functional moiety and at least one cationic functional moiety, the anionic functional moiety comprises —SO 3 − , or a combination of —COO − and —SO 3 − , and the cationic functional moiety comprises quaternary ammonium, and wherein the anionic modifier comprises —SO 3 − , or a combination of —COO and —SO 3 − , and the cationic modifier comprises quaternary ammonium;
the polyurethane-based resin having a hard segment content in a range of from greater than 60% to 75% by weight and a soft segment content of the resin is in a range of from 25% 25% to less than 40% by weight.

2. The medical article of claim 1 , which is effective to reduce thrombus formation and/or bacterial biofilm formation.

3. The medical article of claim 1 , wherein the anionic modifier comprises one or more of: bis-1,4-((2-hydroxypropoxy)-2-propoxy)-butane sulfonate sodium salt; 2,3-dihydroxypropane-1-sulfonate sodium salt; N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonate sodium salt; 2,2-bis(hydroxymethyl) propionic acid; 2,2-bis(hydroxymethyl) butyric acid (BHMBA); or combination thereof.

4. The medical article of claim 1 , wherein the cationic modifier comprises: bis(2-hydroxyethyl)dimethylammonium chloride (BHDAC).

5. The medical article of claim 1 , wherein the zwitterionic modifier comprises: N,N-bis(2-hydroxyethyl)-2-amino-ethanesulfonic acid, or a combination of N,N-bis(2-hydroxyethyl)-2-amino-ethanesulfonic acid and N, N-bis(2-hydroxyethyl)glycine.

6. The medical article of claim 1 , wherein the ingredients of the reaction product consist essentially of:
4,4′-diphenylmethane diisocyanate (MDI) as the diisocyanate;
1,4-butanediol as the diol chain extender;
a polytetramethylene ether glycol as the polyglycol;
bis(2-hydroxyethyl)dimethylammonium chloride (BHDAC) as the cationic modifier; and
bis-1,4-((2-hydroxypropoxy)-2-propoxy)-butane sulfonate sodium salt, or 2,2-bis(hydroxymethyl) butyric acid (BHMBA) and bis-1,4-((2-hydroxypropoxy)-2-propoxy)-butane sulfonate sodium salt as the anionic modifier.

7. The medical article of claim 1 , wherein the zwitterionic, cationic, or anionic modifier is present in an amount of greater than or equal to 0.01 weight percent of the overall composition of the polyurethane-based resin.

8. The medical article of claim 1 , wherein the zwitterionic, cationic, or anionic modifier is present in an amount of less than or equal to 75 weight percent of the overall composition of the polyurethane-based resin.

9. The medical article of claim 1 , wherein the diisocyanate is selected from the group consisting of: an aliphatic diisocyanate, alicyclic diisocyanate and an aromatic diisocyanate.

10. The medical article of claim 1 , wherein the diisocyanate is selected from the group consisting of: 4,4′-diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), methylene-bis(4-cyclohexylisocyanate) (HMDI), and combinations thereof.

11. The medical article of claim 1 , wherein the diol chain extender is selected from the group consisting of: ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, and alicyclic glycols having up to 10 carbon atoms.

12. The medical article of claim 1 , wherein the polyglycol is selected from the group consisting of: polyalkylene glycol, polyester glycol, polycarbonate glycol, and combinations thereof.

13. The medical article of claim 1 , wherein the polyglycol comprises the polyalkylene glycol.

14. The medical article of claim 13 , wherein the polyalkylene glycol comprises a polytetramethylene ether glycol.

15. The medical article of claim 1 , wherein the polyurethane-based resin is bound to an ionic agent through ionic bonding, which is effective to actively provide enhanced surface properties including antimicrobial and/or anti-fouling activity.

16. A method of infusion therapy comprising: infusing a material from a medical article according to claim 1 into a patient.

17. A medical article formed from a polyurethane-based resin, which is a reaction product of ingredients comprising:
a diisocyanate comprising 4,4′-diphenylmethane diisocyanate (MDI);
a diol chain extender comprising 1,4-butanediol;
a polyglycol comprising polytetramethylene ether glycol; and
a zwitterionic modifier or a combination of anionic and cationic modifiers incorporated into a backbone, as a side chain, or both of the polyurethane-based resin formed by the diisocyanate, the polyglycol, and the diol chain extender, the cationic modifier comprising bis(2-hydroxyethyl)dimethylammonium chloride (BHDAC), the anionic modifier comprising bis-1,4-((2-hydroxypropoxy)-2-propoxy)-butane sulfonate sodium salt, or 2,2-bis(hydroxymethyl) butyric acid (BHMBA) and bis-1,4-((2-hydroxypropoxy)-2-propoxy)-butane sulfonate sodium salt;
the polyurethane-based resin having a hard segment content in a range of from 25% to 75% by weight and a soft segment content of the resin is in a range of from 75% to 25% by weight.

18. A medical article formed from a polyurethane-based resin, which is a reaction product of ingredients comprising:
a diisocyanate comprising 4,4′-diphenylmethane diisocyanate (MDI);
a diol chain extender comprising 1,4-butanediol;
a polyglycol comprising a polytetramethylene ether glycol; and
a zwitterionic modifier or a combination of anionic and cationic modifiers incorporated into a backbone, as a side chain, or both of the polyurethane-based resin formed by the diisocyanate, the polyglycol, and the diol chain extender, the cationic modifier comprising bis(2-hydroxyethyl)dimethylammonium chloride (BHDAC), the anionic modifier comprising one or more of bis-1,4-((2-hydroxypropoxy)-2-propoxy)-butane sulfonate sodium salt, 2,3-dihydroxypropane-1-sulfonate sodium salt, N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonate sodium salt, 2,2-bis(hydroxymethyl) propionic acid, or 2,2-bis(hydroxymethyl) butyric acid (BHMBA), and the zwitterionic modifier comprising N, N-bis(2-hydroxyethyl)-2-amino-ethanesulfonic acid, or a combination of N,N-bis(2-hydroxyethyl)-2-amino-ethanesulfonic acid and N,N-bis(2-hydroxyethyl)glycine;
the polyurethane-based resin having a hard segment content in a range of from 25% to 75% by weight and a soft segment content of the resin is in a range of from 75% to 25% by weight.

Assignees

• Becton Dickinson Co

Inventors

• Bai He
• Weimer Marc W
• Freasier James

Classifications

• C08G18/3206

  aliphatic · CPC title

• C08G18/6692 Primary

  with compounds of group C08G18/34 · CPC title

• C08G18/6688

  with compounds of group C08G18/3271 · CPC title

• C08G18/7671

  containing only one alkylene bisphenyl group · CPC title

• C08G18/4854

  Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group · CPC title