Molded foam body having anisotropic shape memory properties, method for manufacturing same and article comprising the molded foam body

• US 20120308804A1
• Filed: 11/23/2010
• Published: 12/06/2012
• Est. Priority Date: 12/22/2009
• Status: Abandoned Application

• Current Assignee: Helmholtz-Zentrum Geesthacht Zentrum FüR Material- und Kã¼Stenforschung GmbH
• Original Assignee: Helmholtz-Zentrum Geesthacht Zentrum Fur Material-Und Kustenforschung GmbH
• Inventors: Lendlein, Andreas, Madbouly, Samy, Kratz, Karl, Lützow, Karola, Klein, Andreas
• Application Number:
  US13/516,736
• Publication Number:
  US 20120308804A1
• Time in Patent Office: Days
• US Class Current: 428/221
• CPC Class Codes: A61L 2400/16 Materials with shape-memory or superelastic properties
• CPC Class Codes: A61L 27/50 Materials characterised by their function or physical properties , e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
• CPC Class Codes: A61L 27/56 Porous materials, e.g. foams or sponges
• CPC Class Codes: B01J 3/008 Processes carried out under supercritical conditions
• CPC Class Codes: B29C 44/00 Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
• CPC Class Codes: B29C 44/348 by regulating the temperature and/or the pressure, e.g. suppression of foaming until the pressure is rapidly decreased
• CPC Class Codes: B29C 44/352 Means for giving the foam different characteristics in different directions
• CPC Class Codes: C08G 18/4266 prepared from hydroxycarboxylic acids and/or lactones
• CPC Class Codes: C08G 18/4269 Lactones
• CPC Class Codes: C08G 18/4277 Caprolactone and/or substituted caprolactone
• CPC Class Codes: C08G 18/73 acyclic
• CPC Class Codes: C08G 2101/00 Manufacture of cellular products
• CPC Class Codes: C08G 2280/00 Compositions for creating shape memory
• CPC Class Codes: C08J 2375/04 Polyurethanes
• CPC Class Codes: C08J 9/122 Hydrogen, oxygen, CO2, nitrogen or noble gases
• CPC Class Codes: Y10T 428/249921 Web or sheet containing structurally defined element or component

Abstract

The invention relates to a molded foam body having anisotropic shape memory properties, to a method for manufacturing such a molded foam body and to an article, which contains or is composed of such a molded foam body.

The molded foam body according to the invention comprises at least one shape memory polymer, which forms a foam structure having asymmetric pores oriented substantially in a common, first spatial direction (L). Said molded foam body is manufactured by foaming the polymer by means of the release of a gaseous propellant under conditions that promote the release and the escape of the propellant from the polymer substantially in a main flow direction. Following thermomechanical programming, such a shape memory foam exhibits a direction-dependent level of recovery and recovery forces when reheated.

Claims

1. A molded foam body having anisotropic, thermally inducible shape memory properties, comprising at least one shape memory polymer which, after a mechanical or thermomechanical programming, is able to execute at least one shape transition temperature-induced from a temporary shape to a permanent shape, characterized in that the unprogrammed shape memory polymer exhibits a foam structure having asymmetric pores, oriented substantially in a common, first spatial direction, wherein a ratio of an average pore dimension in the first spatial direction to an average pore dimension in a second spatial direction extending orthogonally thereto is at least 2.

2. The molded foam body according to claim 1, wherein a ratio of an average pore dimension in the first spatial direction to an average pore dimension in a second spatial direction extending orthogonally thereto is at least 3, preferably at least 4, especially preferably at least 5.

3. The molded foam body according to claim 1, wherein a density of the molded foam body is located within the range of 0.01 to 0.30 g/cm³, particularly 0.02 to 0.20 g/cm³, preferably 0.07 to 0.13 g/cm³.

4. The molded foam body according to claim 1, wherein the shape memory polymer is a physically or covalently crosslinked polymer network which exhibits at least one switching segment that is selected from the group consisting of polyesters, especially poly(ε

-caprolactone);

polyethers, polyurethanes, especially polyurethane;

polyimides, polyetherimides, polyacrylates, polymethacrylates, polyvinyls, polystyrenes, polyoxymethyls, poly(para-dioxanone).

5. The molded foam body according to claim 1, wherein the shape memory polymer includes hydrolytically cleavable groups which are especially selected from the group consisting of glycolides, lactides, diglycolides, dilactides, polyanhydrides and polyorthoesters.

6. An article comprising or consisting of a molded foam body according to claim 1.

7. The article according to claim 6, wherein the article is an object for use in the medical, pharmaceutical or biochemical field.

8. A method for manufacturing a molded foam body having anisotropic, thermally inducible shape memory properties according to claim 1 having the steps

a) manufacture of a substantially homogeneous mixture of a melt of a shape memory polymer which, after a programming, temperature-induced, is able to execute at least one shape transition from a temporary shape to a permanent shape, and of a propellant or a chemical precursor of such, the propellant or the precursor being present in a first state;

and

b) transfer and release of the propellant into a second, gaseous state in such a way that the shape memory polymer and the propellant separate, wherein process parameters of the release and a geometry of a process container, in which the release of the propellant takes place, are selected in such a way that the released gaseous propellant substantially escapes from the shape memory polymer along a predetermined main flow direction, so that the shape memory polymer forms a foam structure having asymmetric pores, oriented substantially in a common, first longitudinal spatial direction corresponding to the main flow direction, wherein the geometry of the process container is selected so that this is open on one or both sides in the longitudinal spatial direction and is closed in the other spatial directions and so that the mixture of the shape memory polymer and the propellant occupies a column in the process container, which column in the longitudinal direction has a greater extent than in a transverse direction extending orthogonally thereto.

9. The method according to claim 8, wherein in a further step (c) the molded foam body is deformed for its thermomechanical programming at a material temperature above a switching temperature of the shape memory polymer using a deformation constraint and is cooled while maintaining the deformation constraint at a temperature below the switching temperature.

10. The method according to claim 8, wherein, as the propellant, a physical propellant is used which under the temperature and the pressure of step (a) exists in a liquid, solid or supercritical state, and its release in step (b) is effected by the temperature and/or the pressure being altered such that the propellant passes over into the gaseous state.

11. The method according to claim 10, that as the propellant carbon dioxide is used which is present in step (a) in a supercritical state and by reducing the pressure in step (b) passes over into the gaseous state.

12. The method according to claim 10, wherein in step (b) the propellant is released by reducing the pressure, wherein the pressure is reduced especially at a rate of at least 10 bar/s, preferably of at least 15 bar/s, especially preferably of at least 20 bar/s.

13. The method according to claim 8, wherein in step (a) a propellant existing in a liquid or supercritical state is used, in which a further substance, especially a pharmaceutical active substance, is dissolved.