Block Copolymers of Poly(ω-Pentadecalactone) in Segmented Polyurethanes: Novel Biodegradable Shape Memory Polyurethanes

Czifrák, Katalin; Lakatos, Csilla; Kordován, Marcell Árpád; Nagy, Lajos; Daróczi, Lajos; Zsuga, Miklós; Kéki, Sándor

doi:10.3390/polym12091928

Cited by 11 publications

(6 citation statements)

References 36 publications

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“…However, the ultimate tensile stress values do not rise and fall in proportion to each other, indicating a complex physical state of the resin during the stretching process. This may be attributed to strain-induced crystallization within the polymer during elongation, thereby affecting the mechanical properties …”

Section: Results and Discussionmentioning

confidence: 99%

“…Within the library of semicrystalline polymers, poly(ε-caprolactone) (PCL), poly(ω-pentadecalactone) (PPDL), as well as their copolymers are among the most popular semi-crystalline materials for shape memory copolymer systems due to their high crystallinity, low toxicity, highly tunable mechanical properties, and excellent biodegradability. ,,, However, most reports focus on the principles of implementing two-way shape memory materials, and manufacturing methods to achieve such are often neglected. The incorporation of PCL and PPDL in similar systems for two-way shape memory actuation have previously been attempted, but these were mostly achieved by casting and molding methods, which may be unsuitable for advanced manufacturing methods requiring high resolution and precision. − The incorporation of high T m switching segments such as PCL and PPDL in photopolymerization-based 3D-printing resins for 4D printing has been scarce and challenging due to their physical states at room temperature and high viscosities when codissolved with other monomers.…”

Section: Introductionmentioning

confidence: 99%

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4D Printing of Single-Network Shape Memory Polyurethanes with Two-Way Actuation Properties

Jiang

Leng

Yan

et al. 2022

ACS Appl. Polym. Mater.

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Two-way shape memory polymers (SMPs) have received much attention due to their ability to enable stimuli-responsive reversible structures without requiring repeated human intervention, which may be useful for application in many fields where multiple actuation cycles are desired. However, many layered or composite SMP systems are not integrated structures and suffer from several disadvantages, such as poor interlayer adhesion with limited actuation repeatability. In addition, twoway SMPs are limited by their manufacturing method to producing userdefined, complex, high-precision devices and parts. In this work, we developed a 3D-printable resin comprising two polyurethane-based oligomers with distinctly different transition temperatures�polypentadecalactone diacrylate (PPDLDA) and polycaprolactone diacrylate (PCLDA)�together with other monomers to fabricate single-network two-way shape memory smart materials by digital light projection 3D printing. The chemical, mechanical, and thermal properties of printed products can be easily tuned by facile manipulation of monomer and oligomer compositions. The PCLDA and PPDLDA switching segments were found to exhibit high mean shape fixity ratios (R f ) of >97% and high shape recovery ratios (R r ) of >89%. The strategy for achieving 3D-printable single-network two-way SMPs presented herein holds promise for applications in soft robotics, medicine, and so forth.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

4D Printing of Single-Network Shape Memory Polyurethanes with Two-Way Actuation Properties

Jiang

Leng

Yan

et al. 2022

ACS Appl. Polym. Mater.

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“…The hard segments provide the elasticity of the matrix that is required for shape recovery thanks to the presence of physical cross-links of hydrogen bonds. Improvement and modification of the adaptive properties of TPUs can be achieved either by changing the ratio of soft [10][11][12] and hard segments [1,13,14] or by introducing nanoscale fillers, such as silicon [2] or carbon nanoparticles [15][16][17]. In the last decade, researchers have been particularly attracted to nanoscale particles from natural sources to reinforce polymers or give them new functional properties.…”

Section: Introductionmentioning

confidence: 99%

Nanocellulose-Based Thermoplastic Polyurethane Biocomposites with Shape Memory Effect

Gorbunova

Grunin²,

Morris

et al. 2023

J. Compos. Sci.

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In 2020, we published a review on the study of semi-crystalline thermoplastic polyurethane elastomers and composites based on the shape memory effect. The shape recovery ability of such polymers is determined by their sensitivity to temperature, moisture, and magnetic or electric fields, which in turn are dependent on the chemical properties and composition of the matrix and the nanofiller. Nanocellulose is a type of nanomaterial with high strength, high specific surface area and high surface energy. Additionally, it is nontoxic, biocompatible, environmentally friendly, and can be extracted from biomass resources. Thanks to these properties, nanocellulose can be used to enhance the mechanical properties of polymer matrices with shape memory effect and as a switching element of shape memory. This review discusses the methods for producing and properties of nanocellulose-based thermo-, moisture-, and pH-sensitive polyurethane composites. The synergistic effect of nanocellulose and carbon nanofillers and possible applications of nanocellulose-based thermoplastic polyurethane biocomposites with shape memory effect are discussed. A brief description of nanocellulose terminology is also given, along with the structure of shape memory thermoplastic polyurethanes. There is significant interest in such materials for three primary reasons: the possibility of creating a new generation of biomaterials, improving the environmental friendliness of existing materials, and exploiting the natural renewability of cellulose sources.

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“…Polyurethanes find application in various long-term implantable devices, such as scaffolds, cardiac valves, and ocular implants [ 4 ], as well as in commercial products intended for removal after use, such as wound dressings [ 5 , 6 ]. For all mentioned applications, especially when a certain level of elasticity is required, segmented polyurethanes, consisting of soft and hard segments, are commonly chosen materials [ 7 ]. The soft segment is an alternating flexible component or macrodiol, whereas the hard segment is a stiff component generated from diisocyanate and a chain extender.…”

Section: Introductionmentioning

confidence: 99%

The Influence of Soft Segment Structure on the Properties of Polyurethanes

Ristić,

Cakić,

Vukić

et al. 2023

Polymers

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A series of polyurethanes (PU) were synthesised via one-step polymerisation without a chain extender, using toluene diisocyanate as well as a variety of soft segments composed of different macrodiols. Poly(D,L-lactide) (PDLLA) and polycaprolactone diol (PCL) were synthesised as a polyester type polyols to obtain soft segments. The process of varying the molar ratio of newly synthesised PDLLA in soft segments has been confirmed as a powerful tool for fine-tuning the final properties of PU. Fourier-transformed infrared spectroscopy was used for evaluation of molecular structures of synthesised PDLLA polyol and final PU. Nuclear magnetic resonance spectrometry was used to confirm the presumed structure of PU. The influence of soft segment composition on polyurethane thermal characteristics was examined using thermogravimetric analysis and differential scanning calorimetry. The composition of soft segments had little impact on the thermal stability of PU materials, which is explained by the comparable structures of both polyester polyols. Wide-angle X-ray scattering was utilised to evaluate the effect of amorphous PDLLA on the degree of crystallinity of PCL in soft PU segments. It was discovered that not only did the PDLLA ratio in the soft segment have a substantial influence on the degree of microphase separation in the soft and hard segments, but it also influenced the crystallisation behaviour of the materials. Furthermore, the restriction of crystallisation of the PCL soft segment has been verified to be dependent on the hard segment concentration and the ratio of PDLLA/PCL polyols. The sample with pure PCL as the polyol component achieved the highest degree of crystallinity (34.8%). The results demonstrated that the composition of soft segments directly affected the properties of obtained polyurethane films. These results can be utilised to easily achieve a desirable set of properties required for application in biomaterials.

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Block Copolymers of Poly(ω-Pentadecalactone) in Segmented Polyurethanes: Novel Biodegradable Shape Memory Polyurethanes

Cited by 11 publications

References 36 publications

4D Printing of Single-Network Shape Memory Polyurethanes with Two-Way Actuation Properties

4D Printing of Single-Network Shape Memory Polyurethanes with Two-Way Actuation Properties

Nanocellulose-Based Thermoplastic Polyurethane Biocomposites with Shape Memory Effect

The Influence of Soft Segment Structure on the Properties of Polyurethanes

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