Method for producing an implant using a calcium carbonate-containing composite powder comprising microstructured particles

Patent metadata

Field	Value
Publication number	US-11318229-B2
Application number	US-201716331575-A
Country	US
Kind code	B2
Filing date	Aug 17, 2017
Priority date	Sep 8, 2016
Publication date	May 3, 2022
Grant date	May 3, 2022

Abstract

The invention relates to a method for producing an implant which contains a composite powder comprising microstructured particles, obtainable by a method in which large polymer particles are bonded to small spherical calcium carbonate particles. Said calcium carbonate particles can be obtained by a method with the following steps: a) providing a calcium hydroxide suspension, b) introducing carbon dioxide or a carbon dioxide-containing gas mixture into the suspension from step a), and c) separating the calcium carbonate particles formed, while adding 0.3 wt.-% to 0.7 wt.-% of at least one amino trialkylene phosphonic acid.

First claim

The invention claimed is:

1. A method for producing an implant using a composite powder having microstructured particles, the method comprising:
bonding large particles to small particles,
wherein the large particles comprise at least one polymer and have an average particle diameter in the range from 0.1 μm to 10 mm,
wherein the small particles:
are arranged on the surface of the large particles or are distributed non-homogeneously within the large particles, and

comprise spherical precipitated calcium carbonate particles having an average diameter in the range from 0.05 μm to 50.0 μm,
wherein the spherical precipitated calcium carbonate particles are obtained by:
providing a calcium hydroxide suspension,
introducing carbon dioxide or a gas mixture containing carbon dioxide into the calcium hydroxide suspension,
separating the spherical precipitated calcium carbonate particles formed, and
adding 0.3% by weight to 0.7% by weight of at least one aminotrialkylene phosphonic acid; and

forming the implant by selective laser sintering of a composition comprising the composite powder,
wherein the microstructured particles of the composite powder have an average particle size of d 50 within the range from 10 μm to less than 200 μm.

2. The method according to claim 1 , further comprising adding at least one of: aminotrimethylene phosphonic acid, aminotriethylene phosphonic acid, aminotripropylene phosphonic acid or aminotributylene phosphonic acid obtain the spherical precipitated calcium carbonate particles.

3. The method according to claim 1 , wherein introducing the carbon dioxide or the gas mixture containing carbon dioxide is performed until the reaction mixture has a pH value of less than 9.

4. The method according to claim 1 , wherein the reaction of the calcium hydroxide suspension with the carbon dioxide or the gas mixture containing carbon dioxide is carried out at a temperature of less than 25° C.

5. The method according to claim 1 , wherein at least one of:
the carbon dioxide or the gas mixture containing carbon dioxide is introduced into the calcium hydroxide suspension with a gas flow rate in the range from 0.02 l CO 2 /(h*g Ca(OH) 2 ) to 2.0 l CO 2 /(h*g Ca(OH) 2 ),
the spherical calcium carbonate particles have a mean diameter greater than 3.0 μm,
the spherical calcium carbonate particles have an average diameter of less than 30.0 μm,
the spherical calcium carbonate particles have a size distribution in which at least 90.0% by weight of all calcium carbonate particles have a particle diameter in the range from mean particle diameter −30% to mean particle diameter+30%, or
the spherical calcium carbonate particles have a form factor of greater than 0.90, defined as the quotient of minimum particle diameter and maximum particle diameter.

6. The method according to claim 1 , wherein the large particles comprise at least one thermoplastic polymer.

7. The method according to claim 1 , wherein the large particles comprise at least one resorbable polymer.

8. The method according to claim 7 , wherein the resorbable polymer has an inherent viscosity, measured in chloroform at 25° C. with 0.1% polymer concentration, in the range from 0.3 dl/g to 8.0 dl/g.

9. The method according to claim 1 , wherein at least one of:
the large particles comprise poly-D-, poly-L- or poly-D,L-lactic acid,
the large particles comprise at least one resorbable polyester having a number average molecular weight in the range from 500 g/mol to 1,000,000 g/mol,
the large particles comprise at least one polyimide,
the large particles comprise at least one polyurethane,
the proportion by weight of the spherical precipitated calcium carbonate particles, based on the total weight of the composite powder, is at least 0.1% by weight, or
the composite powder, based on the total weight of the composite powder, comprises 40.0 wt. % to 80.0 wt. % PLLA and 20.0 wt. % to 60.0 wt. % of the spherical precipitated calcium carbonate particles.

10. A method for forming an implant having spherical calcium carbonate particles, the method comprising:
providing a calcium hydroxide suspension;
introducing carbon dioxide or a gas mixture containing carbon dioxide into the calcium hydroxide suspension;
separating the spherical calcium carbonate particles formed;
adding 0.3% by weight to 0.7% by weight of at least one aminotrialkylene phosphonic acid; and
forming the implant by selective laser sintering of a composition comprising the spherical calcium carbonate particles,
wherein the spherical calcium carbonate particles of the composition have an average particle size d 50 within the range from 10 μm to less than 200 μm.

11. The method according to claim 10 , wherein the spherical calcium carbonate particles are used as an additive for the implant which implant is prepared for in medical technology.

12. The method according to claim 2 , wherein introducing the carbon dioxide or the gas mixture containing carbon dioxide is performed until the reaction mixture has a pH value of less than 9.

13. The method according to claim 2 , wherein the reaction of the calcium hydroxide suspension with the carbon dioxide or the gas mixture containing carbon dioxide is carried out at a temperature of less than 25° C.

14. The method according to claim 3 , wherein the reaction of the calcium hydroxide suspension with the carbon dioxide or the gas mixture containing carbon dioxide is carried out at a temperature of less than 25° C.

15. The method according to claim 2 , wherein at least one of:
the carbon dioxide or the gas mixture containing carbon dioxide is introduced into the calcium hydroxide suspension with a gas flow rate in the range from 0.02 l CO 2 /(h*g Ca(OH) 2 ) to 2.0 l CO 2 /(h*g Ca(OH) 2 ),
the spherical calcium carbonate particles have a mean diameter greater than 3.0 μm,
the spherical calcium carbonate particles have an average diameter of less than 30.0 μm,
the spherical calcium carbonate particles have a size distribution in which at least 90.0% by weight of all calcium carbonate particles have a particle diameter in the range from mean particle diameter −30% to mean particle diameter+30%, or
the spherical calcium carbonate particles have a form factor of greater than 0.90, defined as the quotient of minimum particle diameter and maximum particle diameter.

16. The method according to claim 3 , wherein at least one of:
the carbon dioxide or the gas mixture containing carbon dioxide is introduced into the calcium hydroxide suspension with a gas flow rate in the range from 0.02 l CO 2 /(h*g Ca(OH) 2 ) to 2.0 l CO 2 /(h*g Ca(OH) 2 ),
the spherical calcium carbonate particles have a mean diameter greater than 3.0 μm,
the spherical calcium carbonate particles have an average diameter of less than 30.0 μm,
the spherical calcium carbonate particles have a size distribution in which at least 90.0% by weight of all calcium carbonate particles have a particle diameter in the range from mean particle diameter −30% to mean particle diameter+30%, or
the spherical calcium carbonate particles have a form factor of greater than 0.90, defined as the quotient of minimum particle diameter and maximum particle diameter.

17. The method according to claim 4 , wherein at least one of:
the carbon dioxide or the gas mixture containing carbon dioxide is introduced into the calcium hydroxide suspension with a gas flow rate in the range from 0.02 l CO 2 /(h*g Ca(OH) 2 ) to 2.0 l CO 2 /(h*g Ca(OH) 2 ),
the spherical calcium carbonate particles have a mean diameter greater than 3.0 μm,
the spherica

Assignees

• Karl Leibinger Medizintechnik Gmbh & Co Kg

Inventors

• Reinauer Frank
• Luger Siegmund
• Vucak Marijan

Classifications

• B33Y70/10

  Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials · CPC title

• C08J3/203

  Solid polymers with solid and/or liquid additives · CPC title

• B01J2/00

  Processes or devices for granulating materials {, e.g. fertilisers} in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic · CPC title

• C08K7/18

  inorganic · CPC title

• C08J2367/04

  Polyesters derived from hydroxy carboxylic acids, e.g. lactones (C08J2367/06 takes precedence) · CPC title