Biomaterial compositions
Biomaterial compositions comprising organosilicon monomers (such as silorane monomers) and chemical curing systems or dual chemical/light curing systems, in conjunction with optional tetraoxaspiro[5.5]undecanes (“TOSUs”) and/or fillers. The present invention is directed to biomaterial compositions, as well as methods for manufacturing the same, and methods of using the compositions. The biomaterial composition comprises one or more organosilicon monomers (such as a silorane) and a chemical curing system or dual chemicaVlight curing system for polymerizing the 10 monomer(s). The compositions may include one or more tetraoxaspiro[5.5]undecanes “TOSUs”) and/or fillers. Accelerators (such as photoacids), photosensitizers, and/or electron donors may also be included in the composition as appropriate.
1. A biomaterial composition comprising:
a polymerizable silorane monomer, and
a curing system selected from the group consisting of a chemical curing system and a dual chemical/light curing system,
wherein the curing system comprises a rhodium-based or platinum-based organometallic catalyst, and wherein said silorane monomer comprises a mixture of 2,4,6,8-tetramethyl-2,4,6,8-tetrakis-[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]-1,3,5,7-tetraoxa-2,4,6,8-tetrasilacyclooxtane (CYGEP) and methylbis[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]phenylsilane (PHEPSI).
2. The biomaterial composition of claim 1 wherein said curing system comprises an organometallic catalyst selected from the group consisting of Lamoreaux's catalyst, Wilkinson's catalysts, Speier's catalyst, and Karstedt's catalyst, or mixtures thereof.
3. The biomaterial composition of claim 1 wherein said chemical curing system further comprises a photoacid.
4. The biomaterial composition of claim 3 , wherein said photoacid is a phenyliodonium compound.
5. The biomaterial composition of claim 4 wherein said photoacid is selected from the group consisting of (4-n-octyloxyphenyl)phenyliodonium hexafluoroantimonate, [4-(2-hydroxy-tetradecyloxyphenyl)]phenyliodonium hexafluoroantimonate, [4-1-methylethyl)-phenyl](4-methylphenyl)iodonium tetrakis(pentafluorophenyl)borate(1-), and combinations thereof.
6. The biomaterial composition of claim 1 wherein said curing system is a dual chemical/light curing system, wherein said dual chemical/light curing system additionally comprises an acid selected from the group consisting of a Bronsted acid, Lewis acid, and a superacid, and mixtures thereof.
7. The biomaterial composition of claim 1 wherein said curing system is a dual chemical/light curing system additionally comprises an acid selected from the group consisting of acetic acid, phosphoric acid, sulfuric acid, hydrobromic acid, hydroiodic acid, trichloroacetic acid, trifluoroacetic acid, p-toluenesulfonic acid, boron trifluoride, aluminium chloride, tin (IV) chloride, titanium chloride, pentafluoroproprionic acid, triflic acid, hexafluorophosphoric acid, ethyl triflate, potassium t-butoxide, and mixtures thereof.
8. The biomaterial composition of claim 7 wherein said dual chemical/light curing system further comprises a photosensitizer.
9. The biomaterial composition of claim 8 wherein said photosensitizer is a diketone.
10. The biomaterial composition of claim 7 wherein said dual chemical/light curing system further comprises an electron donor compound in which said electron donor is a substituted amine.
11. The biomaterial composition of claim 7 wherein said dual chemical/light curing system comprises acetic acid, p-(octyloxyphenyl)phenyliodonium hexafluoroantimonate, and camphorquinone.
12. The biomaterial composition of claim 11 further comprising a filler.
13. The biomaterial composition of claim 12 further comprising a tetraoxaspiro[5.5]undecane.
14. The biomaterial composition of claim 1 wherein said curing system is a dual chemical/light curing system, wherein said dual chemical/light curing system comprises a rhodium or platinum-based organometallic catalyst and a light initiation system having a photoacid, photosensitizer, and an electron donor.
15. The biomaterial composition of claim 14 wherein
said organometallic catalyst is selected from the group consisting of Lamoreaux's catalyst, Wilkinson's catalysts, Speier's catalyst, and Karstedt's catalyst;
said photoacid is a phenyliodonium compound;
said photosensitizer is a diketone; and
said electron donor is a substituted amine.
16. The biomaterial composition of claim 14 wherein
said organometallic catalyst comprises Lamoreaux's catalyst;
said photoacid comprises p-(octyloxyphenyl)phenyliodonium hexafluoroantimonate;
said photosensitizer comprises camphorquinone; and
said electron donor comprises ethyl p-dimethylaminobenzoate.
17. The biomaterial composition of claim 16 further comprising a filler.
18. The biomaterial composition of claim 17 further comprising a tetraoxaspiro[5.5]undecane.
19. The biomaterial composition of claim 1 further comprising one or more tetraoxaspiro[5.5]undecanes.
20. The biomaterial composition of claim 19 , wherein said tetraoxaspiro[5.5]undecane is selected from the group consisting of a 2,4,8,10-tetraoxaspiro[5.5]undecane or a 1,5,7,11- tetraoxaspiro[5.5]undecane.
21. The biomaterial composition of claim 19 wherein said tetraoxaspiro[5.5]undecane is selected from Formulas A1 and A2
wherein R 1 and R 3 are independently is alkyl, aryl, aralkyl, or hydrogen; and
wherein R 2 and R 4 are independently alkenoxy, alkenoxyalkyl, or silicon-containing moiety selected from alkylsilyl, arylsilyl, arylalkylsilyl, alloxysilyl, aryloxysilyl, arylalkoxysilyl, alkylsiloxy, arylsiloxy, arylalkylsiloxy, alkoxysiloxy, aryloxysiloxy, arylalkoxysiloxy, alkylsilylalkyl, arylsilylalkyl, arylalkysilylalkyl, alkoxysilylalkyl, aryloxysilylalkyl, arylalkoxysilylalkyl, alkylsiloxyalkyl, arylsiloxyalkyl, arylalkylsiloxyalkyl, alkoxysiloxyalkyl, aryloxysiloxyalkyl, arylalkoxysiloxyalkyl, alkylsilylalkoxy, arylsilylalkoxy, arylalkylsilylalkoxy, alkoxysilylalkoxy, aryloxysilylalkoxy arylalkyloxysilylalkoxy, alkylsiloxyalkoxy, arylsiloxyalkoxy, arylalkylsiloxyalkoxy, alkoxysiloxyalkoxy, aryloxysiloxyalkoxy, and arylalkoxysiloxyalkoxy.
22. The biomaterial composition of claim 19 , wherein said tetraoxaspiro[5,5]undecane is selected from the group consisting of 3,9-diethyl-3,9-bis(allyloxymethyl)-1,5,7,11-tetraoxaspiro[5.5]undecane (DEBAOM-1,5,7,11-TOSU); 3,9-bis(3-trimethylsilylpropyl)-1,5,7,11-tetraoxaspiro[5.5]undecane (BTMSP- 1,5,7,11-TOSU); 3,9-bis(allyloxymethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (BAOM-2,4,8,10-TOSU); 3,9-bis(2-trimethylsilylethyl)-2,3,8,10-tetraoxaspiro[5.5]undecane (BTMSE-2,4,8,10-TOSU); 5,5-diethyl-19-oxadispiro[1,3-dioxane-2,2′-1,3-dioxane-5′,4″-bicyclo[4.1.0]heptane ](DECHE-1,5,7,11-TOSU); 3,9-diethyl-3,9-bis(3-trimethylsilylpropyloxymethyl)-1,5,7,11-tetraoxaspiro[5.5]-undecane (DEBTMSPOM-1,5,7,11-TOSU); (9-allyloxymethyl-9-ethyl-1,5,7,11-tetraoxaspero[5.5]undec-3-ylmethyl)-dimethylphenyl-silane (AOME-TOSU-MDMPS); and
methyl[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]-pheynl[3-(3,9,9-triethyl-1,5,7,11-tetraoxaspiro[5.5]undec-3-ylmethoxy)propyl]silane (MOB-HEP-TETOSU-MOPS).
23. The biomaterial composition of claim 1 further comprising a filler.
24. The biomaterial composition of claim 1 further comprising a pre-polymerized polymer derived from said polymerizable silorane monomer.
25. The biomaterial composition of claim 1 comprising about 30 to 60 wt % silorane monomers; about 1 to 50 wt % of a pre-polymerized polymer derived from the silorane monomers; and about 0.05 to 5 wt % of the chemical curing system or dual chemical/light curing system, and wherein said curing system comprises acetic acid or Lamoreaux's catalyst.
26. The biomaterial composition of claim 25 further comprising about 5 to 50 wt % of a filler.
27. The biomaterial composition of claim 1 wherein said composition after polymerization exhibits a peak exotherm below about 30 ° C.
28. The biomaterial composition of claim 1 wherein said composition after polymerization exhibits a flexural strength of about 22 to 50 MPa.
29. The biomaterial composition of claim 1 wherein said composition after polymerization exhibits a flexural modulus about 1.5 to 3.5 GPa.
30. The biomaterial composition of claim 1 further comprising a heat-sensitive antimicrobial or growth factor that is stable at about 25 to 30 ° C.
31. The biomaterial composition of claim 1 further comprising a growth factor selected from the group consisting of TGFβ1, TGFβ2, TGFβ3, BMP-2, BMP-3, BMP-4, BMP-5, BMP-6, BMP-7, BMP-8, BMP-9, CDMP-1, CDMP-2, or CDMP-3.