Triblock copolymers based on ε-caprolactone and trimethylene carbonate for the 3D printing of tissue engineering scaffolds.
BACKGROUND
Biodegradable PCL-b-PTMC-b-PCL triblock copolymers based on trimethylene carbonate (TMC) and ε-caprolactone (CL) were prepared and used in the 3D printing of tissue engineering scaffolds. Triblock copolymers of various molecular weights containing equal amounts of TMC and CL were prepared. These block copolymers combine the low glass transition temperature of amorphous PTMC (approximately -20°C) and the semi-crystallinity of PCL (glass transition approximately -60°C and melting temperature approximately 60°C).


METHODS
PCL-b-PTMC-b-PCL triblock copolymers were synthesized by sequential ring opening polymerization (ROP) of TMC and ε-CL. From these materials, films were prepared by solvent casting and porous structures were prepared by extrusion-based 3D printing.


RESULTS
Films prepared from a polymer with a relatively high molecular weight of 62 kg/mol had a melting temperature of 58°C and showed tough and resilient behavior, with values of the elastic modulus, tensile strength and elongation at break of approximately 120 MPa, 16 MPa and 620%, respectively. Porous structures were prepared by 3D printing. Ethylene carbonate was used as a crystalizable and water-extractable solvent to prepare structures with microporous strands. Solutions, containing 25 wt% of the triblock copolymer, were extruded at 50°C then cooled at different temperatures. Slow cooling at room temperature resulted in pores with widths of 18 ± 6 μm and lengths of 221 ± 77 μm, rapid cooling with dry ice resulted in pores with widths of 13 ± 3 μm and lengths of 58 ± 12 μm. These PCL-b-PTMC-b-PCL triblock copolymers processed into porous structures at relatively low temperatures may find wide application as designed degradable tissue engineering scaffolds.


CONCLUSIONS
In this preliminary study we prepared biodegradable triblock copolymers based on 1,3-trimethylene carbonate and ε-caprolactone and assessed their physical characteristics. Furthermore, we evaluated their potential as melt-processable thermoplastic elastomeric biomaterials in 3D printing of tissue engineering scaffolds.
Department of Biomaterials Science and Technology, MIRA Institute for Biomedical Engineering and Technical Medicine, University of Twente, Enschede - The Netherlands.
Aysun
A
Güney
Department of Orthopedics, University Medical Center Utrecht, Utrecht - The Netherlands.|Faculty of Veterinary Sciences, University of Utrecht, Utrecht - The Netherlands.
Jos
J
Malda
Department of Orthopedics, University Medical Center Utrecht, Utrecht - The Netherlands.|Faculty of Veterinary Sciences, University of Utrecht, Utrecht - The Netherlands.
Wouter J A
WJA
Dhert
Department of Biomaterials Science and Technology, MIRA Institute for Biomedical Engineering and Technical Medicine, University of Twente, Enschede - The Netherlands.|Department of Biomedical Engineering, W.J. Kolff Institute, University Medical Center Groningen, University of Groningen, Groningen - The Netherlands.
Dirk W
DW
Grijpma
D001672:Biocompatible Materials; D002208:Caproates / Q000737:chemistry*; D004146:Dioxanes / Q000737:chemistry*; D020724:Elastomers; D007783:Lactones / Q000737:chemistry*; D011108:Polymers / Q000138:chemical synthesis; D066330:Printing, Three-Dimensional; D023822:Tissue Engineering; D054457:Tissue Scaffolds
D001672:Biocompatible Materials; D002208:Caproates; D004146:Dioxanes; D020724:Elastomers; D007783:Lactones; D011108:Polymers; C443643:trimethylene carbonate; C121056:caprolactone