IP Library Granted Patent US 11,618,980
Granted Patent B2
US 11,618,980 · App. 16/623,256 · Granted Apr 4, 2023

Surface-functionalised polymeric object and method of its production

Inventors: Andreas Lendlein (Berlin, DE); Axel Thomas Neffe (Berlin, DE); Paul Jakob Hommes-Schattmann (Berlin, DE); Quanchao Zhang (Jiangxi, CN)
Assignee: HELMHOLTZ-ZENTRUM HEREON GMBH
D01F8/14C08J7/0427D01D5/003D01D5/0053C08J2367/04C08J2467/04
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Quick Facts
Patent No.
US 11,618,980
App. No.
16/623,256
Granted
Apr 4, 2023
Kind
B2
Abstract

The invention provides a surface-functionalised polymeric object ( 10 ), comprising: a bulk material ( 11 ) comprising a copolymer containing constitution units derived from a first comonomer and constitution units derived from a second comonomer, the first comonomer being selected from L-lactide and D-lactide and forming sequences of oligo(L-lactide) or oligo(D-lactide) in the copolymer the copolymer having a substantially random, partially blocky structure with a dyad ratio of (lactide-lactide)-dyads to (lactide-second comonomer)-dyads of at least 2.0:1; and a surface layer ( 12 ) disposed on a surface of the bulk material ( 11 ), the surface layer ( 12 ) comprising a functionalising species and at least one chain of poly(D-lactide) or of poly(L-lactide) covalently bound to the functionalising species, and at least one chain being different from the oligo(L-lactide) sequences or oligo(D-lactide) sequences contained in the copolymer; wherein the surface layer ( 12 ) is attached to the bulk material ( 11 ) via stereocomplexes formed between the poly(D-lactide) chain(s) of the functionalising species and the oligo(L-lactide) sequences contained in the copolymer or via stereocomplexes formed between the poly(L-lactide) chain(s) of the functionalising species and the oligo(D-lactide) sequences contained in the copolymer, respectively. The surface-functionalised polymeric object can be produced in a one-step procedure by coaxial electrospinning.

Claims (19)

1. A surface-functionalised polymeric object ( 10 ), comprising:

a bulk material ( 11 ) comprising a copolymer containing constitution units derived from a first comonomer and constitution units derived from a second comonomer, the first comonomer being L-lactide or D-lactide and forming sequences of oligo(L-lactide) or oligo(D-lactide) in the copolymer, the copolymer having a substantially random, partially blocky structure with a dyad ratio of (lactide-lactide)-dyads to (lactide-second comonomer)-dyads of at least 2.0:1; and

a surface layer ( 12 ) disposed on a surface of the bulk material ( 11 ), the surface layer ( 12 ) comprising a functionalising species and at least one chain of poly(D-lactide) or of poly(L-lactide) covalently bound to the functionalising species, the at least one chain being poly(D-lactide) when oligo(L-lactide) segments are present in the copolymer and being poly(L-lactide) when oligo(D-lactide) segments are resent in the copolymer wherein the surface layer ( 12 ) is attached to the bulk material ( 11 ) via stereocomplexes formed between the poly(D-lactide) chain(s) of the functionalising species and the oligo(L-lactide) sequences contained in the copolymer or via stereocomplexes formed between the poly(L-lactide) chain(s) of the functionalising species and the oligo(D-lactide) sequences contained in the copolymer, respectively.

2. The surface-functionalised polymeric object according to claim 1 , wherein the functionalising species of the surface layer ( 12 ) is a macro-molecule, comprising synthetic polymers and biopolymers; such as proteins, polysaccharides, glycoproteins, proteoglycans, nucleic acids; or a low-molecular weight molecule, comprising synthetic molecules or biomolecules.

3. The surface-functionalised polymeric object according to claim 1 , wherein the functionalising species has 2 or more chains of poly(D-lactide) or of poly(L-lactide) covalently bound to it.

4. The surface-functionalised polymeric object according to claim 1 , wherein the copolymer of the bulk material ( 11 ) has a dyad ratio of (lactide-lactide)-dyads to (lactide-second comonomer)-dyads of at least 2.5:1.

5. The surface-functionalised polymeric object according to claim 1 , wherein a weight content of L-lactide or D-lactide in the copolymer is in the range 55 to 90 wt %, based on the total weight of the copolymer.

6. The surface-functionalised polymeric object according to claim 1 , wherein the copolymer of the bulk material ( 11 ) is selected from poly[(L-lactide)-co-(e-caprolactone)] and poly[(D-lactide)-co-(e-caprolactone)].

7. The surface-functionalised polymeric object according to claim 1 , wherein the copolymer has a weight average molecular weight M w of at least 80 kDa.

8. The surface-functionalised polymeric object according to claim 1 , wherein the bulk material ( 11 ) comprises a blend comprising the copolymer and a second polymer component different from the copolymer and selected from poly(L-lactide), poly(D-lactide), poly[(L-lactide)-co-(e-caprolactone)] and poly[(D-lactide)-co-(e-caprolactone)], wherein the copolymer and the second polymer are selected such that the resulting polymer blend comprises a combination of constitution units derived from L-lactide and constitution units derived from D-lactide.

9. The surface-functionalised polymeric object according to claim 8 , wherein the blend comprises or consists of 80 to 99 wt % of the copolymer and 1 to 20 wt % of the second polymer.

10. The surface-functionalised polymeric object according to claim 8 , wherein the second polymer has a weight average molecular weight M w in the range of 2 to 20 kDa.

11. The surface-functionalised polymeric object according to claim 8 , wherein the polymer blend has an elongation at break in the range of 400 to 1000% at 25° C. and/or has an elastic modulus in the range of 25 to 150 MPa at 25° C.

12. The surface-functionalised polymeric object according to claim 1 , wherein the bulk material ( 11 ) has the form of fibers coated with the surface layer ( 12 ).

13. The surface-functionalised polymeric object according to claim 12 , wherein the fibers have an average fiber diameter in the range of 0.5 to 10 μm.

14. The method of producing a surface-functionalised polymeric object according to claim 1 , comprising:

providing a first solution of the copolymer derived from a first comonomer and a second comonomer, the first comonomer being selected from L-lactide and D-lactide and forming sequences of oligo(L-lactide) or oligo(D-lactide) in the copolymer;

providing a second solution of the functionalising species having at least one chain of poly(D-lactide) or of poly(L-lactide) covalently bound to it; and

subjecting the first and second solution to coaxial electrospinning to produce fibers having a core ( 11 ) of the copolymer and a surface layer ( 12 ) of the functionalising species.

Assignments (2)
CHANGE OF NAME Recorded Aug 29, 2022
From: HELMHOLTZ-ZENTRUM GEESTHACHT ZENTRUM FUER MATERIAL-UND KUESTENFORSCHUNG GMBH
To: HELMHOLTZ-ZENTRUM HEREON GMBH
Reel/Frame 061355/0188 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 16, 2019
From: LENDLEIN, ANDREAS; NEFFE, AXEL THOMAS; HOMMES-SCHATTMANN, PAUL JAKOB; ZHANG, QUANCHAO
To: HELMHOLTZ-ZENTRUM GEESTHACHT ZENTRUM FUER MATERIAL-UND KUESTENFORSCHUNG GMBH
Reel/Frame 051297/0298 →
Priority Claims (1)
EP 17193860 · Sep 28, 2017 · regional
Continuity (1)
Related Publication 20200172688A1 · Jun 4, 2020