Polymeric hybrid precursors, polymeric hybrid precursor composite matrices, medical devices, and methods

• US 20070149743A1
• Filed: 12/23/2005
• Published: 06/28/2007
• Est. Priority Date: 12/23/2005
• Status: Active Grant

• Current Assignee: Boston Scientific Scimed (Boston Scientific Corporation)
• Original Assignee: Boston Scientific Scimed (Boston Scientific Corporation)
• Inventors: Schewe, Scott, Warner, Robert, Atanasoska, Liliana, Zoromski, Michele
• Granted Patent: US 7,674,864 B2
• Time in Patent Office: Days
• US Class Current: 528/26
• CPC Class Codes: A61L 27/48 with macromolecular fillers
• CPC Class Codes: C08G 18/4854 Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
• CPC Class Codes: C08G 18/718 containing silicon
• CPC Class Codes: C08G 2270/00 Compositions for creating interpenetrating networks
• CPC Class Codes: C08G 77/458 containing polyurethane sequences
• CPC Class Codes: C08L 77/00 Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: C08L 83/14 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms C08L83/10 takes precedence
• CPC Class Codes: C08L 83/16 in which all the silicon atoms are connected by linkages other than oxygen atoms
• CPC Class Codes: Y10S 528/901 Room temperature curable silicon-containing polymer

Abstract

Polymeric hybrid precursors, mixtures of polymeric hybrid precursors and polymers, and polymer composite matrices prepared from the mixture of the polymeric hybrid precursors and the polymer. The mixture of the polymeric hybrid precursors and the polymer can undergo a process to form the polymer composite matrix having a cross-linked network of a silasesquioxane based polymer formed from the polymeric hybrid precursors that interpenetrates the polymer. The polymeric hybrid precursors include chemical linkage moieties that are capable of forming non-covalent bonds with portions of the polymer. The polymer composite matrices are useful as biomaterials in medical devices.

Claims

1. A method of preparing a polymeric hybrid precursor, comprising:

providing at least one compound of the formula (Formula II) RO_f—

(C═

O)_i—

[(R₁)_m—

O_x]_q(C═

O)_n—

O_e—

R where i, n, x, e and f are each independently 0 or 1, each R is independently H, an amine, an isocyanate, or an organic group, R₁ is an organic group, m is 1 to 18; and

q is 1 to 200;

providing at least one alkoxy silane containing compound of the formula (Formula III) (R₂O)₃Si(R₃—

A), where;

R₂ and R₃ are each independently an organic group;

A is independently a hydroxyl, an isocyanate, an amine, or an epoxy compound; and

reacting the at least one compound of Formula III with the at least one compound of Formula II to form the polymeric hybrid precursor of the formula;

(Formula I) (R₂O)₃—

Si—

R₃—

NH—

(C═

O)—

[(R₁)_m]_q—

(C═

O)—

NH—

R₃—

Si—

(OR₂)₃ when A is an amine;

f, i, n and e are 1;

x is 0, and R is H;

(Formula I) (R₂O)₃—

Si—

R₃—

O—

(C═

O)—

[(R₁)_m—

O_x]_q—

(C═

O)—

R₃—

Si—

(OR₂)₃ when A is a hydroxyl;

f, i, n, and e are 1, and R is H;

(Formula I) (R₂O)₃—

Si—

R₃—

(NR₄)—

(C═

O)—

(NH)—

[(R₁)_m—

O_x]_q—

(NR₄)—

(C═

O)—

(NH)—

R₃—

Si—

(OR₂)₃ when A is —

(NR₄)H;

f, i, n and e are 0;

R₄ is an organic group or H, and R is an isocyanate; and

(Formula I) [(R₂O)₃—

Si—

R₃—

O—

CH₂—

(CHOH)—

CH₂—

]₂—

N—

[(R₁)_m—

O_x]_q—

N—

[CH₂—

(CHOH)—

CH₂—

O—

R₃—

Si—

(OR₂)₃]₂, when A is an epoxy compound;

f, i, n, and e are 0; and

R is an amine.

2. The method of claim 1, where each R, R₂ and R4 is independently a (C1-C18)alkyl group and each R₁ and R₃ is independently a (C1-C18)alkylene group.

3. The method of claim 1, where m and q are 1;

x is 0, and R₁ is selected from the group consisting of polypropylene, polyurethane, fluorpolymer, polyester, polyethylene, polyvinyl chloride, polyamide, and polyimide.

4. A polymeric hybrid precursor formed from the method of claim 1.

5. A method of preparing a polymer composite matrix, comprising:

providing at least one polymeric hybrid precursor of the formula (Formula I);

[(R₂O)₃—

Si—

R₃]_z—

Y—

[(R₁)_m—

O_x]_q—

Y′

—

[R₃—

Si—

(OR₂)₃]_z

where x and z are each independently 0 or 1;

m is 1 to 18; and

q is 1 to 200;

R₁, R₂ and R₃ are each independently an organic group; and

Y and Y′

are selected together from the group consisting of;

—

NH—

(C═

O)—

for Y and —

(C═

O)—

NH—

for Y′

, where x=0 and z=1;

—

O—

(C═

O)—

for Y and —

(C═

O)—

for Y′

, where z=1;

—

(NR₄)—

(C═

O)—

(NH)—

for Y and Y′

, where z=1, and R₄ is an organic group or H; and

—

N—

[CH₂—

(CHOH)—

CH₂—

O—

R₃—

Si—

(OR₂)₃]₂ for Y and Y′

, where z=0; and

forming a mixture of the at least one compound of Formula I with a polymer having a functional group that can chemically bond with the group Y.

6. The method of claim 5, where R₂ is a (C1-C18)alkyl group, and each R₁ and R₃ is independently a (C1-C18)alkylene group.

7. The method of claim 5, where m and q are 1;

x is 0, and R₁ is selected from the group consisting of polypropylene, polyurethane, fluorpolymer, polyester, polyethylene, polyvinyl chloride, polyamide, and polyimide.

8. The method of claim 5, where the functional group of the polymer is a chemical linkage moiety capable of forming a non-covalent bond with the group Y.

9. The method of claim 5, where forming a mixture of the at least one compound of Formula I with a polymer includes mixing the at least one compound of Formula I and the polymer to disperse the at least one compound of Formula I in the polymer.

10. The method of claim 9, including processing the mixture of at least one compound of Formula I and the polymer into a desired shape.

11. The method of claim 10, including forming a cross-linked network that includes at least one compound of Formula I through the polymer using a sol-gel process.

12. A polymeric hybrid precursor comprising a compound of the formula [(R₂O)₃—

Si—

R₃]_z—

Y—

[(R₁)_m—

O_x]_q—

Y′

—

[R₃—

Si—

(OR₂)₃]_z, where x and z are each independently 0 or 1;

m is 1 to 18; and

q is 1 to 200;

R₁, R₂ and R₃ are each independently an organic group; and

Y and Y′

are selected together from the group consisting of;

—

NH—

(C═

O)—

for Y and —

C═

O)—

NH—

for Y′

, where x=0 and z=1;

—

O—

(C═

O)—

for Y and —

C═

O)—

for Y′

, where z=1;

—

(NR₄)—

(C═

O)—

(NH)—

for Y and Y′

, where z=1; and

—

N—

[CH₂—

(CHOH)—

CH₂—

O—

R₃—

Si—

(OR₂)₃]₂ for Y and Y′

, where z=0.

13. The polymeric hybrid precursor of claim 12, where the compound of the formula [(R₂O)₃—

Si—

R₃]_z—

Y—

[(R₁)_m—

O_x]_q—

Y′

—

[R₃—

Si—

(OR₂)₃]_z is derived from at least one compound of the formula (Formula II) RO_f—

(C═

O)_i—

[(R₁)_m—

O_x]_q(C═

O)_n—

O_e—

R and at least one alkoxy silane containing compound of the formula (Formula III) (R₂O)₃Si(R₃—

A), where i, n, x, e and f are each independently 0 or 1;

each R is independently H, an amine, an isocyanate, or an organic group;

each R₁, R₂, and R₃ is independently an organic group, m is 1 to 18; and

q is 1 to 200; and

A is independently, a hydroxyl, an isocyanate, an amine, or an epoxy compound.

14. The polymeric hybrid precursor of claim 12, where R₂ is a (C1-C8)alkyl group and each R₁ and R₃ is independently a (C1-C8)alkylene group.

15. The polymeric hybrid precursor of claim 12, where the compound of the formula [(R₂O)₃—

Si—

R₃]_z—

Y—

[(R₁)_m—

O_x]_q—

Y′

—

[R₃—

Si—

(OR₂)₃]_z can melt without significant thermal degradation.

16. The polymeric hybrid precursor of claim 12, where the polymeric hybrid precursor can be mixed in a polymer to form a mixture, where the polymeric hybrid precursor includes chemical linkage moieties that can non-covalently bond with portions of the polymer.

17. The polymeric hybrid precursor of claim 16, where the polymeric hybrid precursor mixed in the polymer can be shaped through a molding process selected from the group of blow molding, injection molding, extrusion, casting, coating and fiber spinning.

18. The polymeric hybrid precursor of claim 12, where the compound of the formula [(R₂O)₃—

Si—

R₃]_z—

Y—

[(R₁)_m—

O_x]_q—

Y′

—

[R₃—

Si—

(OR₂)₃]_z can form a cross-linked network that interpenetrates the polymer using a sol-gel process.

19. A medical device prepared from the polymeric hybrid precursor of claim 12.

20. A polymer composite matrix, comprising:

a cross-linked network of a silasesquioxane based polymer formed through a sol-gel process, the silasesquioxane based polymer having chemical linkage moieties that can chemically bond with portions of a polymer, where the polymer and the cross-linked network of the silasesquioxane based polymer form the polymer composite matrix.

21. The polymer of claim 20, where the chemical linkage moieties of the silasesquioxane based polymer are capable of forming a non-covalent bond with the portions of the polymer.

22. The polymer of claim 20, where the chemical linkage moieties of the silasesquioxane based polymer are capable of forming a covalent bond with the portions of the polymer.

23. The polymer of claim 22, where the silasesquioxane based polymer of the cross-linked network is formed using at least one polymeric hybrid precursor of the formula (Formula I) [(R₂O)₃—

Si—

R₃]_z—

Y—

[(R₁)_m—

O_x]_q—

Y—

[R₃—

Si—

(OR₂)₃]_z in the sol-gel process, where m is 1 to 18 and q is 1 to 200;

R₁, R₂ and R₃ are each independently an organic group;

x and z are each independently 0 or 1; and

Y and Y′

are selected together from the group consisting of;

—

NH—

(C═

O)—

O—

for Y and —

C═

O)—

NH—

for Y′

where z=1;

—

NH—

(C═

O) for Y and —

(C═

O)—

NH—

for Y′

where x=0 and z=1;

—

O—

(C═

O)—

for Y and —

(C═

O)—

for Y′

where z=1;

—

(NR₄)—

(C═

O)—

(NH)—

for Y and Y′

, where z=1, and R₄ is an organic group or H; and

—

N—

[CH₂—

(CHOH)—

CH₂—

O—

R₃—

Si—

(OR₂)₃]₂ for Y and Y′

, where z=0,

where Y is a chemical linkage moiety that can chemically bond with portions of the polymer.

24. The polymer of claim 23, where R₂ is a (C1-C8) alkyl group, and each R₁ and R₃ is independently a (C1-C8) alkylene group.

25. The polymer of claim 20, where the portions of the polymer that can chemically bond with chemical linkage moieties of the silasesquioxane based polymer are selected from the group of a urethane linkage, an ester linkage, an amide linkage, an imide linkage, a urea linkage, and a combination thereof.

26. The polymer of claim 20, where the polymer is selected from the group polyamide, polyurethane, polyurea, polyurethane-urea, and polyester.

27. A biomaterial comprising the polymer of claim 20.

28. A medical device comprising the polymer of claim 20.