Developing non-isocyanate urethane-methacrylate photo-monomers for 3D printing application

Singh, Neelima; Bakhshi, Hadi; Meyer, Wolfdietrich

doi:10.1039/d0ra06388f

Cited by 15 publications

(20 citation statements)

References 45 publications

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“…At 5°C, UrA displayed a shorter t GP (4.4 s) and lower DBC GP (11.9%) and DBC total (78.7%) values, which was attributed to the crystallization of UrA molecules with a melting point ( T m ) of 5 °C, leading to lower molecular mobility within the photo-curing mixture. This observation is in agreement with a previous report on crystalizable monomers [ 7 ].…”

Section: Resultssupporting

confidence: 94%

“…Photo-DSC analyses have been widely utilized to evaluate the photo-activity of 3D-printing photo-inks [ 7 , 16 , 17 ]. Primarily, the photopolymerization kinetics of difunctional UrDMA and monofunctional UrA were studied separately in the isothermal mode at different temperatures, i.e., at 5, 25, 45, 65, or 85 °C ( Figure 2 a and Figure 3 a).…”

Section: Resultsmentioning

confidence: 99%

“…The R p (1/s) and DBC (%) values as a function of time were calculated from the photo-DSC data using Equations (1)–(3) [ 7 ]:

where ΔH theor (J/g) is the theoretical total heat released during the complete polymerization of the monomers within the sample, f is the mass fraction of each monomer within the sample, n is the number of double bonds in each monomer, ΔH 0 (J/mol) is the standard heat of polymerization for either methacrylate (54.8 kJ/mol [ 19 , 20 ]) or acrylate (86.2 kJ/mol [ 20 , 21 ]), M w (g/mol) is the molecular weight of each monomer, dH p /dt (J/s·g or W/g) is the normalized heat flow per second, and ΔH p (J/g) is the heat generated from the start of photo-curing up to a certain time that is obtained from the integration of the thermograms.…”

Section: Methodsmentioning

confidence: 99%

“…Under irradiation, liquid photo-ink consisting of mono- and multifunctional monomers and a photoinitiator undergoes a photopolymerization reaction and transforms into a solid polymeric network within a very short time. Recently, urethane-acrylates have been used to formulate 3D-printing photo-inks [ 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 ]. The intermolecular hydrogen bonding between the urethane groups allows the pre-association of urethane-acrylate molecules and, consequently, 3–6 times faster photo-curing in comparison to their corresponding nonhydrogen-bonding acrylates [ 11 , 12 ].…”

Section: Introductionmentioning

confidence: 99%

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Photo-Curing Kinetics of 3D-Printing Photo-Inks Based on Urethane-Acrylates

et al. 2022

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In this study, photo-curing kinetics for urethane-acrylate-based photo-inks for 3D printing were evaluated using a photo-differential scanning calorimetry analysis. Initially, the photopolymerization kinetics of di- and monofunctional monomers were separately studied at different temperatures (5–85 °C). Later, the photo-curing kinetics and mechanical properties of photo-inks based on different monomer mixtures (40/60–20/80) were evaluated. The results showed that urethane-dimethacrylate (UrDMA) and urethane-acrylate (UrA) had no light absorption in the region of 280–700 nm, making them a proper crosslinker and a reactive diluent, respectively, for the formulation of 3D-printing photo-inks. The kinetics investigations showed a temperature dependency for the photo-curing of UrDMA, where a higher photopolymerization rate (Rp,max: from 5.25 × 10−2 to 8.42 × 10−2 1/s) and double-bound conversion (DBCtotal: from 63.8% to 92.2%) were observed at elevated temperatures (5–85 °C), while the photo-curing of UrA was independent of the temperature (25–85 °C). Enhancing the UrA content from 60% to 80% in the UrDMA/UrA mixtures initially increased and later decreased the photopolymerization rate and conversion, where the mixtures of 30/70 and 25/75 presented the highest values. Meanwhile, increasing the UrA content led to lower glass transition temperatures (Tg) and mechanical strength for the photo-cured samples, where the mixture of 30/70 presented the highest maximum elongation (εmax: 73%).

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Section: Resultssupporting

confidence: 94%

Section: Resultsmentioning

confidence: 99%

“…The R p (1/s) and DBC (%) values as a function of time were calculated from the photo-DSC data using Equations (1)–(3) [ 7 ]:

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Photo-Curing Kinetics of 3D-Printing Photo-Inks Based on Urethane-Acrylates

et al. 2022

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“…15 Bakhshi et al prepared cross-linked poly(urethane-methacrylate)s based on aliphatic diamines, five-membered cyclic carbonates, and methacrylic anhydride. 16 Li et al proposed the synthesis of non-isocyanate poly(ether-urethane)s via co-polycondensation of isophorone bis(2-hydroxyethyl carbamate) with poly(ethylene glycol)s having various molar masses at 170 °C. 17 Deng et al presented a similar synthetic way toward poly(ether-urethane)s via melt polycondensation of hexamethylene bis(2-hydroxyethyl carbamate) and ethylene glycol oligomers.…”

Section: ■ Introductionmentioning

confidence: 99%

Environmentally Friendly Synthesis of Urea-Free Poly(carbonate-urethane) Elastomers

2022

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This work presents an eco-friendly synthetic pathway toward non-isocyanate poly(carbonate-urethane)s (NIPCUs) obtained from carbon dioxide and its simple derivativesorganic carbonates. Bis(hydroxyalkyl carbamate)s synthesized from ethylene carbonate and appropriate α,ω-diamines were used as polyurethane hard segment precursors while oligocarbonate diols as soft segment ones. The structures and properties of the obtained NIPCUs were explored by means of 1H NMR, 13C NMR, and FT-IR spectroscopies, MALDI-ToF mass spectrometry, DSC, and mechanical testing. Based on spectroscopic data as well as model reactions, it was demonstrated that the formation of the urea bonds was suppressed due to the presence of carbonate moieties. The reaction of urea bonds with carbonate residues led to urethane group formation. In addition, the influence of the polyurethane structure on the mechanical and thermal properties of the obtained polymers was studied. The obtained NIPCUs exhibited mechanical properties comparable to conventional polyurethane elastomers (e.g., a tensile strength of 32 MPa and an elongation at break of 800%). The described synthetic route is an straightforward way toward the replacement of conventional polyurethanes with environmentally friendly ones.

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3D/4D Printing of Polyurethanes by Vat Photopolymerization

Mauriello

Maury

Guillaneuf

et al. 2023

Adv Materials Technologies

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Vat photopolymerization relies on the light‐induced polymerization of liquid photopolymer to produce the targeted structure. Among all the polymers prepared by vat photopolymerization, due to their numerous properties polyurethanes have recently gained great attention in the industrial and academic fields. In this review article, recent progress in printing techniques, resin compositions, and applications related to 3D/4D printing by vat photopolymerization of polyurethanes are highlighted.

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Developing non-isocyanate urethane-methacrylate photo-monomers for 3D printing application

Abstract: Synthesis of urethane-methacrylate photo-monomers via a non-isocyanate route for 3D printing of flexible biomedical materials.

Cited by 15 publications

References 45 publications

Photo-Curing Kinetics of 3D-Printing Photo-Inks Based on Urethane-Acrylates

Photo-Curing Kinetics of 3D-Printing Photo-Inks Based on Urethane-Acrylates

Environmentally Friendly Synthesis of Urea-Free Poly(carbonate-urethane) Elastomers

3D/4D Printing of Polyurethanes by Vat Photopolymerization

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