Polylactide and calcium phosphate compositions and methods of making the same

Patent metadata

Field	Value
Publication number	US-9399708-B2
Application number	US-201314391054-A
Country	US
Kind code	B2
Filing date	Mar 8, 2013
Priority date	Apr 12, 2012
Publication date	Jul 26, 2016
Grant date	Jul 26, 2016

Abstract

A method is provided for synthesizing polylactide/calcium phosphate composites. In one aspect, an intermediate silanized calcium phosphate material calcium-phosphate/phosphonate is developed to improve the tensile strength of the composite.

First claim

What is claimed is:

1. A method for preparing a polylactide/calcium phosphate containing material comprising the steps of:
combining a calcium phosphate material having a general formula of Ca p (PO 4 ) q X z , where p=1-10, q=1-10 and z=1-5 and where X may be O, CO 3 , F, Cl, Br with a silane material haying a general formula of (R 1 O)(R 2 O)(R 3 O)Si—R 4 —Y, where Y can be OH, NH2, SH, Cl; R 1 , R 2 , R 3 can be the same or different C1-C10 alkyl, R 4 is C1-C20 alkyl, to form an intermediate silanized calcium phosphate material; and
combining polymer selected from the group consisting of a lactide material haying a general formula of —(OCR 1 R 2 CO) n — or —(R 3 COO) n —, where R 1 , R 2 , R 3 can be any of H, alkyl less than C10, polyglycolide, polylactide-co-glycolide, polycaprolactone and mixtures thereof with the intermediate silanized calcium phosphate material to form the polylactide/calcium phosphate material initiated.

2. The method of claim 1 wherein the step of combining the calcium phosphate material with a silane material reacts hydroxyl groups on the surface of the calcium phosphate material through alkoxy groups of the silane material to form the intermediate silanized calcium phosphate material.

3. The method of claim 1 wherein the step of combining the calcium phosphate material with the silane material creates a P—O—Si structure in the intermediate silanized calcium phosphate material.

4. The method of claim 1 wherein the calcium phosphate material surface is protonated.

5. A method for preparing a polylactide/calcium phosphate containing material comprising the steps of:
combining a calcium phosphate material having a general formula of Ca p (PO 4 ) q X z , where p=1-10, q=1-10 and z=1-5 and where X may be OH, O, CO 3 , F, Cl, Br with a silane material having a general formula of (R 1 O)(R 2 O)(R 3 O)Si—R 4 —Y, where Y can be OH, NH2, SH, Cl; R 1 , R 2 , R 3 can be the same or different C1-C10 alkyl, R 4 is C1-C20 alkyl, to form an intermediate silanized calcium phosphate material;
combining polymer selected from the group consisting of a lactide material having a general formula of —(OCR 1 R 2 CO) n — or —(R 3 COO) n —, where R 1 , R 2 , R 3 can be any of H, alkyl less than C10, polyglycolide, polylactide-co-glycolide, polycaprolactone and mixtures thereof with the intermediate silanized calcium phosphate material to form the polylactide/calcium phosphate material initiated; and
wherein combining calcium phosphate material with a silane material includes combining pyromellitic dianhydride with the calcium phosphate material.

6. The method of claim 1 wherein the calcium phosphate material is suspended in an anhydrous solvent.

7. A method for preparing a polylactide/calcium phosphate containing material comprising the steps of:
combining a calcium phosphate material having a general formula of Ca p (PO 4 ) q X z , where p=1-10, q=1-10 and z=1-5 and where X may be OH, O, CO 3 , F, Cl, Br with a silane material having a general formula of (R 1 O)(R 2 O)(R 3 O)Si—R 4 —Y, where Y can be OH, NH2, SH, Cl; R 1 , R 2 , R 3 can be the same or different C1-C10 alkyl, R 4 is C1-C20 alkyl, to form an intermediate silanized calcium phosphate material;
combining polymer selected from the group consisting of a lactide material having a general formula of —(OCR 1 R 2 CO) n — or —(R 3 COO) n —, where R 1 , R 2 , R 3 can be any of H, alkyl less than C10, polyglycolide, polylactide-co-glycolide, polycaprolactone and mixtures thereof with the intermediate silanized calcium phosphate material to form the polylactide/calcium phosphate material initiated; and
wherein the silane material includes N-(2-aminoethyl)-3-aminoproplytrimethoxysilane.

8. The method of claim 1 wherein the intermediate silanized calcium phosphate is filtered and washed with anhydrous solvent for removal of non-bounded coupling agent.

9. The method of claim 1 wherein the calcium phosphate material is tetracalcium phosphate.

10. A method for preparing a polylactide/calcium phosphate containing material comprising the steps of:
combining a calcium phosphate material having a general formula of Ca p (PO 4 ) q X z , where p=1-10, q=1-10 and z=1-5 and where X may be O, CO 3 , F, Cl, Br with a silane material haying a general formula of (R 1 O)(R 2 O)(R 3 O)Si—R 4 —Y, where Y can be OH, NH2, SH, Cl; R 1 , R 2 , R 3 can be the same or different C1-C10 alkyl, R 4 is C1-C20 alkyl, to form an intermediate silanized calcium phosphate material; and
combining polymer selected from the group consisting of a biodegradable polymer selected from the group consisting of polyhydroxybutyrate, poly(hydroxyvalerate, poly(carbonates), polyphosphazene, polyanhydrides, polyurethane, polyesters cellulose, starch, gelatin, chitosan, peptides and mixtures thereof with the intermediate silanized calcium phosphate material to form the polylactide/calcium phosphate material.

11. A method for preparing a polylactide/calcium phosphate containing material comprising the steps of:
combining a calcium phosphate material selected from the group consisting of tricalcium phosphate, tetracalcium phosphate, monocalcium phosphate, dicalcium phosphate, amorphous calcium phosphate, octacalcium phosphate with a silane material having a general formula of (R 1 O)(R 2 O)(R 3 O)Si—R 4 —Y, where Y can be OH, NH2, SH, Cl; R 1 , R 2 , R 3 can be the same or different from alkyl (C1-C10), R 4 is alkyl (C1-C20), to form an intermediate silanized calcium phosphate material; and
combining polymer selected from the group consisting of a lactide material having a general formula of —(OCR 1 R 2 CO) n — or —(R 3 COO) n —, where R 1 , R 2 , R 3 can be any of H, alkyl less than C10, polyglycolide, polylactide-co-glycolide, polycaprolactone and mixtures thereof with the intermediate silanized calcium phosphate material to form the polylactide/calcium phosphate material initiated.

Assignees

• Wang Tongxin
• Mitchell James W
• Univ Howard

Inventors

• Wang Tongxin
• Mitchell James W

Classifications

• A61L27/12

  Phosphorus-containing materials, e.g. apatite · CPC title

• A61L27/18

  obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds · CPC title

• C08K3/32 Primary

  Phosphorus-containing compounds · CPC title

• A61L2430/02

  for reconstruction of bones; weight-bearing implants · CPC title

• C08K2003/325

  Calcium, strontium or barium phosphate · CPC title