Polylactide and apatite compositions and methods of making the same
A method is provided for synthesizing PLA/apatite composites with improved mechanical strength. In one aspect, a calcium-phosphate/phosphonate hybrid shell is developed to incorporate more reactive hydroxyl groups onto hydroxyapatite (HA) particles. PLA is covalently bonded to HA calcium phosphate hybrid shell, creating a strong interphase between HA and PLA, thus significantly improve the mechanical strength in comparison to that of non-modified HA.
1. A polylactide/calcium phosphate containing material prepared by a process comprising the steps of:
combining a calcium phosphate containing material selected from the group consisting of an apatite material having a general formula of Ca 10 (PO 4 ) 6 X 2 , where X=—OH or F, monocalcium phosphate, dicalcium phosphate, tricalcium phosphate, amorphous calcium phosphate, tetracalcium phosphate, fluoroapatite, and octacalcium phosphate with an organic material having phosphonic acid functionality to form an intermediate calcium phosphate and phosphonic acid containing material; and
combining a lactide material having a general formula of —(OCHRCO) n —where R=H or C1-C10 alkyl, and n=2, or dimer thereof, or trimer thereof, or mixtures thereof, with the intermediate calcium phosphate and phosphonic acid containing material and using surface initiated polymerization of lactide onto the intermediate calcium phosphate and phosphonic acid containing material via —OH or —NH 2 groups on a surface of the intermediate calcium phosphate and phosphonic acid containing material to form the polylactide/calcium phosphate containing material.
2. The polylactide/calcium phosphate containing material of claim 1 wherein the polylactide/calcium phosphate containing material has a diametral tensile strength that is at least 1.5 times the diametral tensile strength of a polylactide/calcium phosphate containing material prepared without combining a calcium phosphate containing material with the organic material having phosphonic acid functionality.
3. The polylactide/calcium phosphate containing material of claim 1 further comprising combining the polylactide/calcium phosphate containing material with additional polylactide to form a composite polylactide/calcium phosphate containing material.
4. The polylactide/calcium phosphate containing material of claim 1 wherein combining the calcium phosphate containing material with the organic material having phosphonic acid functionality introduces —OH or —NH 2 groups on the surface of the calcium phosphate containing material to form the intermediate calcium phosphate and phosphonic acid containing material.
5. The polylactide/calcium phosphate containing material of claim 1 further comprising separating unreacted organic material having phosphonic acid functionality from the intermediate calcium phosphate and phosphonic acid containing material.
6. The polylactide/calcium phosphate containing material of claim 1 further comprising separating unreacted lactide material from the polylactide/calcium phosphate containing material.
7. The polylactide/calcium phosphate containing material of claim 1 wherein combining the calcium phosphate containing material with the organic material having phosphonic acid functionality includes combining N-(2-hydroxyethyl) iminobis(methylphosphonic) acid or hydroxyethylphophonic acid or an organic phosphonic acid containing hydroxyl or amino group with the calcium phosphate containing material.
8. The polylactide/calcium phosphate containing material of claim 7 wherein the calcium phosphate containing material is suspended in an aqueous solution of N-(2-hydroxyethyl) iminobis(methylphosphonic) acid or hydroxyethylphophonic acid or an organic phosphonic acid containing hydroxyl or amino group.
9. The polylactide/calcium phosphate containing material of claim 7 wherein hydroxyapatite is precipitated in the presence of N-(2-hydroxyethyl) iminobis(methylphosphonic) acid or hydroxyethylphophonic acid or an organic phosphonic acid containing hydroxyl or amino group.
10. A polylactide/apatite composition comprising:
an apatite and phosphonic acid containing substrate having lactide coupled to at least a portion of the apatite and phosphonic acid containing substrate through —OH or —NH 2 groups on the substrate having lactide functionality,
wherein the apatite and phosphonic acid containing substrate comprises a calcium-phosphate/phosphonate hybrid shell including a Ca—PO 3 H 2 link.
11. The polylactide/apatite composition of claim 10 further comprising a plurality of polylactide/apatite molecules joined to one another via lactide containing compounds thereby forming a polylactide/apatite composite.
12. The polylactide/apatite composition of claim 11 wherein the polylactide/apatite composite has a diametral tensile strength that is at least 1.5 times the diametral tensile strength of a polylactide/apatite material that does not contain phosphonic acid functionality.
13. A biodegradable polymeric material/calcium phosphate containing composition prepared by a process comprising the steps of:
combining a calcium phosphate containing material selected from the group consisting of a phosphate having a general formula of Ca 10 (PO 4 ) 6 X 2 , where X=—OH or F, monocalcium phosphate, dicalcium phosphate, tricalcium phosphate, amorphous calcium phosphate, tetracalcium phosphate, fluoroapatite, and octacalcium phosphate with an organic material having phosphonic acid functionality to form an intermediate calcium phosphate and phosphonic acid containing material;
combining a lactide material having a general formula of —(OCHRCO) n —, where R=H or C1-C10 alkyl, and n=2, or dimer thereof, or trimer thereof, or mixtures thereof, with the intermediate calcium phosphate and phosphonic acid containing material and using surface initiated polymerization of lactide onto the intermediate calcium phosphate and phosphonic acid containing material via —OH or —NH 2 groups on a surface of the intermediate calcium phosphate and phosphonic acid containing material to form the polylactide/calcium phosphate containing material, and
combining a biodegradable polymeric material selected from the group consisting of polylactide, polyhydroxybutyrate, poly(hydroxyvalerate), polyphosphazene, polyester, polyurethane and cellulose, starch, gelatin, chitosan, peptide and derivatives thereof with the polylactide/calcium phosphate containing material to form the biodegradable polymeric material/calcium phosphate containing composition.
14. A polylactide/calcium phosphate containing material prepared by a process comprising the steps of:
combining a calcium phosphate containing material selected from the group consisting of an apatite material having a general formula of Ca 10 (PO 4 ) 6 X 2 , where X=—OH or F, monocalcium phosphate, dicalcium phosphate, tricalcium phosphate, amorphous calcium phosphate, tetracalcium phosphate, fluoroapatite, and octacalcium phosphate with an organic material having phosphonic acid functionality and co-precipitating in the presence of a calcium source to form an intermediate calcium phosphate and phosphonic acid containing material; and
combining a lactide material having a general formula of —(OCHRCO) n —, where R=H or C1-C10 alkyl, and n=2,or dimer thereof, or trimer thereof, or mixtures thereof, with the intermediate calcium phosphate and phosphonic acid containing material to form the polylactide/calcium phosphate containing material.