Urethane bioimplant membrane

• US 4,127,124 A
• Filed: 05/12/1977
• Issued: 11/28/1978
• Est. Priority Date: 05/12/1977
• Status: Expired due to Term

• Current Assignee: Hampshire Chemical Corp. (Dow, Inc.)
• Original Assignee: WR Grace & Company
• Inventors: Clagett, Donald C., Scott, Peter H., Svetly, Michael J.
• Primary Examiner(s): Hoke, V. P.
• Application Number:
  US05/796,218
• Time in Patent Office: 565 Days
• Field of Search: 260/2.5 A, 260/2.5 BB, 260/2.5 AN, 260/2.5 AP, 260/2.5 AY, 260/2.5 AD, 260/77.5 AM, 260/77.5 AA, 260/75 TN, 428/315, 428/320, 428/322, 128/156, 3/1
• US Class Current: 523/113
• CPC Class Codes: A61L 15/425 Porous materials, e.g. foams or sponges
• CPC Class Codes: A61L 27/18 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 18/2815 Monohydroxy compounds
• CPC Class Codes: C08G 18/3206 aliphatic
• CPC Class Codes: C08L 75/00 Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
• CPC Class Codes: Y10S 521/905 Hydrophilic or hydrophobic cellular product
• CPC Class Codes: Y10S 623/92 Method or apparatus for preparing or treating prosthetic
• CPC Class Codes: Y10T 428/249978 Voids specified as micro

Abstract

Bioimplant three dimensional latice of hydrophilic polyurethane having a backbone of polyetherol or polyesterol, end-capped with aliphatic or aromatic diisocyanate, chain branched with polyol and bound into a latice by chain extension alkyl diols. The method of producing such a latice. An extension would be the use of the latice for other medical and veterinary purposes.

Claims

1. A method of implanting an unfoamed microporous hydrophilic bioimplant membrane within the living tissue in a mammal comprising the steps of producing a substantially unfoamed microporous hydrophilic bioimplant membrane by reacting a first component comprising isocyanate end-capped polyol chosen from the group consisting of polyetherol, polyesterol and mixtures thereof and having a reaction functionality of at least two with a second component comprising a C₂ to C₆ diol in an isocyanate monomer to diol molar ratio of 1 to 3.5 in a non-aqueous solvent reaction medium at a total solids concentration of less than 25%, volatilizing the solvent at a rate not causing the reaction product to foam whereby said unfoamed microporous hydrophilic bioimplant membrane is produced and placing the membrane so produced within the living tissue of a mammal.

2. The method of claim 1 wherein the membrane is implanted beneath the panniculus carnosus.

6. The method of claim 1 wherein said isocyanate is an aliphatic diisocyanate;

the diol is an alkyl diol, polyetherol oligomer or mixture of 2 or more of them;

the solvent is a 3 to 5 membered ketone or mixture thereof; and

the total solids concentration is 0.5 to 10%.

7. The method of claim 6 wherein said alphatic diisocyanate in the prepolymer is isophoronediisocyanate, the C₂ to C₆ diol is butane-1,4-diol, the solvent is acetone and the total solids concentration is 0.5 to 2%.

8. The method of claim 1 wherein a mono-alcohol chain stopper is included in the solvent reaction medium as a reactant.

9. The method of claim 1 wherein the isocyanate capped polyetherol or polyesterol is a diisocyanate end capped polyetherol and is dissolved in a non-aqueous solvent reaction medium to form a stock solution and said C₂ to C₆ diol is dissolved in a non-aqueous solvent reaction medium to form an activator solution and said reaction is brought about by combining said stock solution and said activator solution.

10. The method of claim 1 wherein said unfoamed microporous hydrophilic bioimplant membrane is free of silicon agents and chloroflurocarbons and has levels of free diisocyanate not exceeding 0.005 millimoles/gram and levels of free amines not exceeding 210 parts per million.

11. The method of claim 9 wherein said diisocyanate end-capped polyetherol has an average molecular weight of less than 1250, said diol is a C₂ to C₅ diol, the solvent is a 3 to 5 membered anhydrous ketone or mixture thereof, the total solids concentration is 0.5 to 10% and the molar ratio of isocyanate monomer to diol is 1.5 to 3.

12. The method of claim 11 wherein said diisocyanate end-capped polyetherol is polyoxyethylene polyol and said diisocyanate capped polyoxyethylene polyol was prepared with a stannous octoate catalyst and contains a 2,6-disubstituted hindered phenol as an antioxidant, said diol is butane-1,4-diol, said solvent is acetone, the total solids concentration is 0.5 to 2%, the molar ratio of isocyanate monomer to diol is about 2, and said unfoamed microporous hydrophilic membrane is free of silicon agents and chlorofluorocarbons and has levels of free diisocyanate not exceeding 0.005 millimoles/gram and levels of free amines not exceeding 210 parts per million.

3. A method of placing a hydrophilic biononirritating material within the living tissue in a mammal comprising producing a hydrophilic biononirritating material by reacting a first component comprising isocyanate end-capped polyol chosen from the group consisting of polyetherol, polyesterol and mixtures thereof and having a reaction functionality of at least two with a second component comprising a C₂ to C₆ diol in an isocyanate monomer to diol molar ratio of 1 to 3.5 in a non-aqueous solvent reaction medium at a total solids concentration of less than 25%, volatilizing the solvent whereby said hydrophilic biononirritating material is produced and placing the material within the living tissue of a mammal.

4. The method of claim 3 wherein the material is placed beneath the panniculus carnosus.

5. A method of producing a substantially unfoamed microporous hydrophilic bioimplant membrane comprising reacting a first component comprising isocyanate end-capped polyol chosen from the group consisting of polyetherol, polyesterol and mixtures thereof and having a reaction functionality of at least two with a second component comprising a C₂ to C₆ diol in an isocyanate monomer to diol molar ratio of 1 to 3.5 in a non-aqueous solvent reaction medium at a total solids concentration of less than 25% and volatilizing the solvent at a rate not causing the reaction product to foam and producing said unfoamed microporous hydrophilic bioimplant membrane.

13. A bioimplant member comprising a microporous molecular lattice of hydrophilic polyurethane, said polyurethane having a backbone chosen from the group consisting of polyetherols and polyesterols, or mixtures thereof, said backbone end-capped with isocyanate selected from the group consisting of aliphatic isocyanates and aromatic isocyanates, said urethane having chain branching centers of polyol, said branched urethane chains being bound by a C₂ to C₆ diol chain extension to form continuous three dimensional lattices and said urethane having a molar ratio of isocyanate to diol of from 1 to 3.5.

14. The member of claim 13 wherein some of the urethane chains are chain stopped with alcohol.

15. The member of claim 13 wherein said isocyanate is an aliphatic diisocyanate;

the diol is a C₂ to C₆ alkyl diol, polyetherol oligomer or mixture of 2 or more of them;

the solvent is a 3 to 5 membered ketone or mixture thereof; and

the total solids concentration is 0.5 to 10%.

16. The member of claim 13 wherein the isocyanate capped polyetherol or polyesterol is a diisocyanate end-capped polyetherol and said diol is a C₂ to C₆ alkyl diol.

17. The member of claim 13 wherein said microporous molecular lattice of hydrophilic polyurethane is free of silicon agents and chlorofluorocarbons and has levels of free diisocyanate not exceeding 0.005 millimoles/gram and levels of free amines not exceeding 210 parts per million.

18. The member of claim 16 wherein said diisocyanate end-capped polyetherol or polyesterol is an etherol having an average molecular weight of less than 1250, said diol is a C₂ to C₅ diol, and the molar ratio of isocyanate monomer to diol is 1 to 3.5.

19. The member of claim 18 wherein a mono-alcohol chain stopper is included.

20. The member of claim 19 wherein said etherol of said diisocyanate end-capped polyetherol is polyoxyethylene polyol and said diisocyanate capped polyoxyethylene polyol was prepared with a stannous octoate catalyst and contains a 2,6-disubstituted hindered phenol as an antioxidant, said diol is butane-1,4-diol, the molar ratio of isocyanate monomer to diol is 1.5 to 3, and said member is free of silicon agents and chlorofluorocarbons and has levels of free diisocyanate not exceeding .005 millimoles/gram and levels of free amines not exceeding 210 parts per million.

21. A method of producing a hydrophilic biononirritating material comprising reacting a first component comprising isocyanate end-capped polyol chosen from the group consisting of polyetherol, polyesterol and mixtures thereof and having a reaction functionality of at least two with a second component comprising a C₂ to C₆ diol in an isocyanate monomer to diol molar ratio of 1 to 3.5 in a non-aqueous solvent reaction medium at a total solids concentration of less than 25% and volatilizing the solvent and producing said hydrophilic biononirritating material.

22. The method of claim 21 wherein said isocyanate is an aliphatic diisocyanate;

the diol is an alkyl diol, polyetherol oligomer or mixture of 2 or more of them;

the solvent is a 3 to 5 membered ketone or mixtures thereof; and

the total solids concentration is 0.5 to 10%.

23. The method of claim 22 wherein said aliphatic diisocyanate is isophoronediisocyanate, the diol is butane-1, 4-diol, the solvent is acetone and the total solids concentration is 0.5 to 2%.

24. The method of claim 21 wherein a mono-alcohol chain stopper is included in the solvent reaction medium as a reactant.

25. The method of claim 21 wherein the isocyanate end-capped polyetherol or polyesterol is a diisocyanate end-capped polyetherol and is dissolved in a non-aqueous solvent reaction medium to form a stock solution and said C₂ to C₆ diol is dissolved in a non-aqueous solvent reaction medium to form an activator solution and said reaction is brought about by combining said stock solution and said activator solution.

26. The method of claim 21 wherein said hydrophilic biononirritating material is free of silicon agents and chlorofluorocarbons and has levels of free diisocyanate not exceeding 0.005 millimoles/gram and levels of free amines not exceeding 210 parts per million.

27. The method of claim 25 wherein said etherol of said diisocyanate end-capped polyetherol is polyoxyethylene polyol with an average molecular weight of less than 1250, and said diisocyanate end-capped polyoxyethylene polyol was prepared with a stannous octoate catalyst and contains a 2,6-disubstituted hindered phenol as an antioxidant, said diol is butane-1,4-diol, said solvent is acetone, the total solids concentration is 0.5 to 2%, the molar ratio of isocyanate monomer to diol is 1.5 to 3, and said hydrophilic biononirritating material is free of silicon agents and chlorofluorocarbons and has levels of free diisocyanate not exceeding .005 millimoles/gram and levels of free amines not exceeding 210 parts per million.

28. A substantially biononirritating material comprising a hydrophilic polyurethane, said polyurethane having a backbone chosen from the group consisting of polyetherols and polyesterols, or mixtures thereof, said backbone end-capped with isocyanate chosen from the group consisting of aliphatic isocyanates and aromatic isocyanates, said urethane having chain branching centers of polyol, said branched urethane chains being bound by a C₂ to C₆ diol chain extension to form continuous three dimensional lattices and said urethane having a molar ratio of isocyanate to diol of from 1 to 3.5.

29. The material of claim 28 wherein some of urethane chains are chain stopped with alcohol.

30. The material of claim 28 wherein said diisocyanate end-capped polyetherol or polyesterol is an etherol having an average molecular weight of less than 1250 and said diol is a C₂ to C₆ alkyl diol.

31. The material of claim 30 wherein a monoalcohol chain stopper is included in the solvent reaction medium as a reactant.

32. The material of claim 31 wherein said etherol of said diisocyanate end-capped polyetherol is polyoxyethylene polyol and said diisocyanate capped polyoxyethylene polyol was prepared with a stannous octoate catalyst and contains a 2,6-disubstituted hindered phenol as an antioxidant, said diol is butane-1,4-diol, the molar ratio of isocyanate monomer to diol is 1.5 to 3, and said material is free of silicon agents and chlorofluorocarbons and has levels of free diisocyanate not exceeding 0.005 millimoles/gram and levels of free amines not exceeding 210 parts per million.