Injectable and photocurable macromonomers synthesized using a novel heterometallic magnesium-titanium metal-organic catalyst

Michalkiewicz

Fray

2023

Preprint

In this study, the synthesis and physico-chemical properties of sustainable poly(butylene succinate-dilinoleic succinate) (PBS-DLS) copolymers modified with hydrophilic poly(ethylene glycol)(PEG) are discussed in context of structure-properties relationship of polymeric materials and their processibility. The copolymers of variable segmental composition and containing green monomers such as succinic acid and dilinoleic diol, were successfully synthesized by non-solvent two-step transesterification and polycondensation reaction. Synthesized polymers were collected as crystallized filaments directly from the reactor. These filaments were used without any postprocessing for 3D printing. Characterization of chemical structure confirmed the presence of functional ester and ether groups. Crystallized copolymers revealed spherulitic morphology and phase transitions which were dependent from the segmental composition. Interestingly, incorporation of 5 wt% PEG into copolymers containing higher hard segments content (70 wt%) disturbed the banded spherulitic morphology of copolymers, contributed to the increase of elasticity up to 830%, and reduced the water contact angle in comparison to copolymers containing 60 wt% of PBS hard segments. The mechanical properties and printability of the copolymers depended also on their segmental composition, where higher hard segment content (70 wt%) facilitated better printability compared to polymers containing 60 wt% of PBS hard segments. Additionally, we demonstrate that new copolymers were suitable for electrospinning yielding nanofibers of average fiber diameters between 400 and 600 nm. The obtained results showed excellent processability, rubber-like elasticity and improved hydrophilicity of new polymers thus indicating that segmental composition can be important design parameter in preparation of new green copolymers for advanced processing by 3D printing and electrospinning.

Section: Chemical Structure Of Copolymers By Nmr and Ir Spectroscopymentioning

confidence: 99%

Investigation of structure-properties relationship of modified green PBS-DLS copolymers and their processability by 3D printing

Michalkiewicz

Fray

2023

Preprint

“…In addition of using monomers from renewable sources, the environmental friendly synthesis process also utilized a non-toxic magnesium/titanium butoxide catalyst. [34] To investigate the influence of the DLS soft segment content on the material properties, copolymers with different ratios of hard to soft segments (70-30 and 60-40 wt%) were produced. Moreover, the effect of addition of 5 wt% PEG of M n =6000 g/mol on copolymer's properties was also investigated.…”

Section: Chemical Structure Of Copolymers By Nmr and Ir Spectroscopymentioning

confidence: 99%

Investigation of the structure-properties relationship of modified green PBS-DLS copolymers and their processability by 3D printing and electrospinning

Żwir

Wiśniewska

et al. 2023

Preprint

In this study, the synthesis and physico-chemical properties of poly(butylene succinate-dilinoleic succinate) (PBS-DLS) copolymers modified with hydrophilic poly(ethylene glycol)(PEG) differing in segmental composition are discussed in order to determine their structure-properties relationship and translate it to their processability. The copolymers, containing bio-based monomers such as succinic acid and dilinoleic diol, were successfully synthesized by two-step transesterification and polycondensation, and collected directly from the reactor as crystallized filaments suitable for 3D printing. Chemical characterization indicated the formation of expected functional ester groups and incorporation of PEG into polymer chain. Crystallized copolymers revealed spherulitic morphology and phase transitions which were dependent from the segmental composition. Interestingly, incorporation of 5 wt% PEG into copolymers containing higher hard segments content (70 wt%) disturbed the banded spherulitic morphology of copolymers, contributed to the increase of elasticity up to 830%, and reduced the water contact angle indicating improvement of copolymers hydrophilicity. We examined the role of segmental composition on 3D printing and demonstrate that copolymers can also be turned into 400 to 600 nm nanofibers via electrospinning. Further, all copolymers showed excellent cell proliferation thus confirming the suitability of these materials for biomedical applications.

“…In addition of using monomers from renewable sources, the environmental friendly synthesis process also utilized a non-toxic magnesium/titanium butoxide catalyst. 21 To investigate the influence of the DLS soft segment content on the material properties, copolymers with different ratios of hard to soft segments (70-30 and 60-40 wt%) were produced. Moreover, the effect of addition of 5 wt% PEG of Mn=6000 g/mol on copolymer's properties was also investigated.…”

Section: Chemical Structure Of Copolymers By Nmr and Ir Spectroscopymentioning

confidence: 99%

The effect of segmental composition of bio-based PBS-DLS-PEG copolymers on their physico-chemical properties and processability by 3D printing and electrospinning

Michalkiewicz

Fray

2022

Preprint

In this study, the synthesis and physico-chemical properties of poly(butylene succinate-dilinoleic succinate-ethylene glycol succinate) (PBS-DLS-PEG) copolymers differing in segmental composition are discussed in order to determine their structure-properties relationship and translate it to their electrospinability and 3-D printability. The copolymers, containing sustainable monomers such as succinic acid and dilinoleic diol, were successfully synthesized by two-step transesterification and polycondensation, and collected directly from the reactor as crystallized filaments suitable for 3D printing. Chemical characterization indicated the formation of expected functional ester groups. Crystallized copolymers revealed spherulitic morphology and phase transitions typical for thermoplastic elastomers. Interestingly, incorporation of 5 wt% PEG into copolymers containing higher hard segments content (70 wt%) disturbed the banded spherulitic morphology of copolymers, contributed to the increase of elasticity up to 830%, and reduced the water contact angle indicating improvement of copolymers hydrophilicity. The mechanical properties and printability of the copolymers depended on their segmental composition, with higher hard segment content facilitating good printability. In solution processing, the copolymers turned into nanofibers via electrospinning with average fiber diameters between 400 and 600 nm. The obtained results showed excellent melt and solution processability, rubber-like elasticity and tailored physical characteristics dependent from segmental composition of the new sustainable PBS-DLS-PEG copolymers.