Polyurethane or polyurethane-urea elastomeric compositions

• US 5,393,858 A
• Filed: 02/23/1993
• Issued: 02/28/1995
• Est. Priority Date: 06/26/1990
• Status: Expired due to Term

• Current Assignee: AorTech Biomaterials Pty Ltd
• Original Assignee: Commonwealth Scientific & Industrial Research Organisation (Commonwealth Of Australia As Represented By Department Of Industry, Innovation, Climate Change, Science, Research And Tertiary Education), Unisearch Limited (University Of New South Wales)
• Inventors: Rizzardo, Ezio, Schindhelm, Klaus H., Brandwood, Arthur, Gunatillake, Pathiraja, Meijs, Gordon F.
• Primary Examiner(s): WELSH JR, MAURICE
• Application Number:
  US07/962,799
• Time in Patent Office: 735 Days
• Field of Search: 528/61, 528/58, 528/76
• US Class Current: 528/61
• CPC Class Codes: A61L 17/04 Non-resorbable materials
• CPC Class Codes: A61L 27/18 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• 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 18/3206 aliphatic
• CPC Class Codes: C08G 18/3228 acyclic
• CPC Class Codes: C08G 18/4858 Polyethers containing oxyalkylene groups having more than four carbon atoms in the alkylene group
• CPC Class Codes: C08G 18/765 alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring
• CPC Class Codes: C08L 75/04 Polyurethanes

Abstract

A polyurethane or polyurethane-urea elastomeric composition, characterized in that the composition is a reaction product of:

(A) a soft segment macrodiol which is either:

(i) a homopolymer represented by formula I,

HO--[(CH.sub.2).sub.n O].sub.m --H                         I

wherein n represents an integer greater than 5 and less than 13, m is a number such that the number average molecular weight of the compound of formula I falls in the range from 218 to 5000 and optionally at least one hydrogen atom represented in formula I is substituted by a C₁ to C₃ alkyl group or a halogen atom;

(ii) a copolymer containing at least 25% by mass of repeating units --(CH₂)_n O-- wherein n is as defined in formula I above; or

(iii) mixture of macrodiols comprising greater than 10% of a macrodiol as defined in formula I above;

(B ) an aliphatic or aromatic diisocyanate known in the art of polyurethane manufacture; and

(C) optionally a chain extender.

A biomaterial and a medical device which are composed wholly or partly of the polyurethane or polyurethane-urea elastomeric composition are also described.

Claims

1. A degradation resistant material which comprises a polyurethaneor polyurethane-urea elastomeric composition which comprises a reaction product of:

(A) a soft segment macrodiol which is either;

(i) a homopolymer represented by formula I,

space="preserve" listing-type="equation">HO--[(CH.sub.2).sub.n O].sub.m --H I

wherein n represents an integer greater than 5 and less than 13, m is a number such that the number average molecular weight of the compound of formula I falls in the range from 218 to 5000 and optionally at least one hydrogen atom represented in formula I is substituted by a C₁ to C₃ alkyl group or a halogen atom;

(ii) a copolymer containing at least 25% by mass of repeating units --(CH₂)_n O-- wherein n is as defined in formula I above;

or

(iii) a mixture of macrodiols comprising greater than 10% of a macrodiol as defined in formula I above, with the proviso that the mixture of macrodiols does not include polyethylene glycol and/or polypropylene glycol;

(B) an aliphatic or aromatic diisocyanate; and

(C) optionally a chain extender.

2. A degradation resistant material according to claim 1, wherein the homopolymer (i) comprises a range of molecular weights such that the number average molecular weight falls between 218 and 5000.

3. A degradation resistant material according to claim 1, wherein the aliphatic or aromatic diisocyanate (B) is selected from the group consisting of:

4,4'"'"'-diphenylmethane diisocyanate (MDI);

methylene bis(cyclohexyl) diisocyanate (H₁₂ MDI);

p-phenylene diisocyanate (p-PDI);

trans-cyclohexane-1,4-diisocyanate (CHDI);

1,6-diisocyanatohexane (DICH);

2,4-toluene diisocyanate (2,4-TDI);

meta-tetramethylxylene (m-TMXDI); and

para-tetramethylxylene diisocyanate (p-TMXDI).

4. A degradation resistant material according to claim 1, wherein the chain extender (C) is selected from the group consisting of:

1,4-butanediol (BDO);

1,6-hexanediol (HDO);

1,2-ethylene diamine (EDA);

1,6-hexanediamine (HDA); and

1,2-propanediamine (1,2-PDA).

5. A degradation resistant material according to claim 1, wherein the composition further comprises one or more of a cross-linking agent, a catalyst, an antioxidant, a stabilizer and a processing aid.

6. A material having improved durability in hostile environments which comprises a polyurethane or polyurethane-urea elastomeric composition as defined in claim 1.

7. A device or article which comprises a polyurethane or polyurethane-urea elastomeric composition as defined in claim 1.

8. A degradation resistant material according to claim 1, wherein the soft segment macrodiol is a homopolymer represented by formula I,

9. A degradation resistant material according to claim 1 wherein the soft segment macrodiol is a copolymer containing at least 25% by mass of repeating units --(CH₂)_n O-- wherein n greater than 5 and less than 13.

10. A degradation resistant material according to claim 8 wherein n is 6, 8 or 10.

11. A degradation resistant material which comprises a polyurethane or polyurethane-urea elastomeric composition which comprises a reaction product of:

(A) a soft segment macrodiol which is either;

(i) a homopolymer represented by formula I,

space="preserve" listing-type="equation">HO--[(CH.sub.2).sub.n O].sub.m --H I

wherein n represents an integer greater than 5 and less than 13, m is a number such that the number average molecular weight of the compound of formula I falls in the range from 218 to 5000 and at least one hydrogen atom represented in formula I is substituted by a halogen atom;

(ii) a copolymer containing at least 25% by mass of repeating units --(CH₂)_n O-- wherein n is as defined in formula I above;

or

(iii) a mixture of macrodiols comprising greater than 10% of a macrodiol as defined in formula I above;

(B) an aliphatic or aromatic diisocyanate; and

(C) optionally a chain extender.

12. A degradation resistant material according to claim 11 wherein the halogen atom is fluorine.

13. An in vivo degradation resistant material which comprises a polyurethane or polyurethane-urea elastomeric composition which comprises a reaction product of:

(A) a soft segment macrodiol which is either;

(i) a homopolymer represented by formula I,

space="preserve" listing-type="equation">HO--[(CH.sub.2).sub.n O].sub.m --H I

wherein n represents an integer greater than 5 and less than 13, m is a number such that the number average molecular weight of the compound of formula I falls in the range from 218 to 5000 and optionally at least one hydrogen atom represented in formula 1 is substituted by a C₁ to C₃ alkyl group or a halogen atom;

(ii) a copolymer containing at least 25% by mass of repeating units --(CH₂)_n O-- wherein n is as defined in formula I above;

or

(iii) a mixture of macrodiols comprising greater than 10% of a macrodiol as defined in formula I above;

(B) an aliphatic or aromatic diisocyanate; and

(C) optionally a chain extender.

14. A biomaterial which comprises a polyurethane or polyurethane-urea elastomeric composition as defined in claim 13.

15. Artificial leather, shoe soles or cable sheathing which comprises a polyurethane or polyurethane-urea elastomeric composition as defined in claim 13.

16. A medical device article or implant which comprises a polyurethane or polyurethane-urea elastomeric composition as defined in claim 13.

17. A medical device, article or implant according to claim 16 which is a pacemaker lead, a catheter, an implantable prosthesis, a cardiac assist device, a heart valve, a suture, a vascular graft, an extra-corporeal device or an artificial heart.

18. A medical device, article or implant according to claim 16 which is a pacemaker lead or a defibrillator lead.

19. A polyurethane or polyurethane urea elastomeric composition as defined in claim 13.