Three-dimensional printed hydroxyapatite composite scaffolds for bone regeneration, precursor compositions and methods of printing

A precursor composition comprising a non-aqueous slurry comprising a mixture of:

• a solid phase comprising a mixture of tetracalcium phosphate (TTCP) and dicalcium phosphate anhydrous (DCPA), and
• a non-aqueous liquid phase comprising a polymer and a non-aqueous solvent in which the polymer is soluble,
• wherein
• i) the non-aqueous solvent is selected from the group consisting of ethanol and tetrahydrofuran,
• ii) optionally the liquid phase further comprises at least one additional non-aqueous solvent selected from the group consisting of acetic acid, acetone, methanol, 2-propanol, butanol, 2-butoxyethanol, benzyl alcohol, 1-methoxy-2-propanol, butyl glycol, n-butyl acetate, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone (NMP), carbon tetrachloride, benzene, toluene, cyclohexanone, 2-nitropropane, 2-butanone, acetonitrile, dichloromethane, chloroform, and ethyl acetate, and
• iii) the polymer is selected from the group consisting of poly(ethylene glycol), polyvinyl pyrrolidone (PVP), poly(methyl methacrylate) (PMMA), polyoxazoline, polyphosphoesters (PPE), dextran, polyvinyl butyral (PVB), polycaprolactone (PCL), and poly lactic-co-glycolic acid (PLGA).