Cooligomers from morpholine-2,5-dione and para-dioxanone and catalyst complex SnOct2/2-hydroxyethyl sulfide

Complexes from catalysts and initiator can be used to insert a specific number of additional chemical functional groups in (co)polymers prepared by ring-opening polymerization (ROP) of lactones. We report on the synthesis of cooligomers from sec-butyl-morpholine-2,5-dione (SBMD) and para-dioxanone (PDX) by ROP with varied feed ratios in the bulk using the catalyst complex SnOct2/2-hydroxyethyl sulfide. Mn of the cooligomers (determined by GPC) decreased with decreasing SBMD feed ratio from 4200 ± 420 to 800 ± 80 g mol−1. When the feed ratio was reduced from 80 to 50 mol% the molar ratio of SBMD of the cooligomers (determined by 1H-NMR) remained nearly unchanged between 81 and 86 mol% and was attributed to a higher reactivity of SBMD. This assumption was confirmed by fractionation of GPC, in which an increase of SBMD with increasing molecular weight was observed. The catalyst/initiator system provides a high potential to create orthogonal building blocks by cleavage of the sulfide bond. Graphic abstract

A Critical Review for Synergic Kinetics and Strategies for Enhanced Photopolymerizations for 3D-Printing and Additive Manufacturing

The synergic features and enhancing strategies for various photopolymerization systems are reviewed by kinetic schemes and the associated measurements. The important topics include (i) photo crosslinking of corneas for the treatment of corneal diseases using UVA-light (365 nm) light and riboflavin as the photosensitizer; (ii) synergic effects by a dual-function enhancer in a three-initiator system; (iii) synergic effects by a three-initiator C/B/A system, with electron-transfer and oxygen-mediated energy-transfer pathways; (iv) copper-complex (G1) photoredox catalyst in G1/Iod/NVK systems for free radical (FRP) and cationic photopolymerization (CP); (v) radical-mediated thiol-ene (TE) photopolymerizations; (vi) superbase photogenerator based-catalyzed thiol−acrylate Michael (TM) addition reaction; and the combined system of TE and TM using dual wavelength; (vii) dual-wavelength (UV and blue) controlled photopolymerization confinement (PC); (viii) dual-wavelength (UV and red) selectively controlled 3D printing; and (ix) three-wavelength selectively controlled in 3D printing and additive manufacturing (AM). With minimum mathematics, we present (for the first time) the synergic features and enhancing strategies for various systems of multi-components, initiators, monomers, and under one-, two-, and three-wavelength light. Therefore, this review provides not only the bridging between modeling and measurements, but also guidance for further experimental studies and new applications in 3D printings and additive manufacturing (AM), based on the innovative concepts (kinetics/schemes).

Application of Bacterial Cellulose in the Textile and Shoe Industry: Development of Biocomposites

Several studies report the potential of bacterial cellulose (BC) in the fashion and leather industries. This work aimed at the development of BC-based composites containing emulsified acrylated epoxidized soybean oil (AESO) that are polymerized with the redox initiator system hydrogen peroxide (H2O2) and L-ascorbic acid and ferrous sulfate as a catalyst. BC was fermented under static culture. The polymerization of the emulsified organic droplets was tested before and after their incorporation into BC by exhaustion. The composites were then finished with an antimicrobial agent (benzalkonium chloride) and dyed. The obtained composites were characterized in terms of wettability, water vapor permeability (WVP), mechanical, thermal and antimicrobial properties. When AESO emulsion was polymerized prior to the exhaustion process, the obtained composites showed higher WVP, tensile strength and thermal stability. Meanwhile, post-exhaustion polymerized AESO conferred the composite higher hydrophobicity and elongation. The composites finished with the antimicrobial agent showed activity against S. aureus. Finally, intense colors were obtained more uniformly when they were incorporated simultaneously with the emulsified AESO with all the dyes tested.

New Star-Shaped Polyether-Pentols (PEPOs) for Fabrication of Crosslinked Polyurethanes—Synthesis and Characterization

Polyether-pentols (PEPOs) were synthesized from glycidyl ethers and butylene oxide with the application of tripotassium salts of 2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol (HMCH) activated 18C6 for ring-opening polymerization (ROP). The construction of the applied initiator system reflects the ability of crown ether to influence the degree of ion-pair separation with an increased activating effect. As a result formation of bi- or trimodal polymers was observed with molar masses in the range of (Mn = 1200–6000). The observed multi-fraction composition is prescribed to the formation of ionic aggregates with different reactivities during polymerization. The mechanism of the studied processes is discussed. The obtained PEPOs served for a crosslinked PUR synthesis, for which the hydrogen bond index for coupling of hard segments was calculated. Additionally, the range of phase separation was calculated that was higher for PUR-containing aromatic rings as the substituent.

Adhesive Resins with High Shelf-Life Stability Based on Tetra Unsaturated Monomers with Tertiary Amines Moieties

This work reports the use of two monomers with two tertiary amines and four methacrylic (TTME) or acrylic (TTAC) terminal groups as co-initiators in the formulation of experimental resin adhesive systems. Both monomers were characterized by FT-IR and 1H NMR spectroscopies. The control adhesive was formulated with BisGMA, TEGDMA, HEMA, and the binary system CQ-EDAB as a photo-initiator system. For the experimental adhesives, the EDAB was completely replaced for the TTME or the TTAC monomers. The adhesives formulated with TTME or TTAC monomers achieved double bond conversion values close to 75%. Regarding the polymerization rate, materials formulated with TTME or TTAC achieved lower values than the material formulated with EDAB, giving them high shelf-life stability. The degree of conversion after shelf simulation was only reduced for the EDAB material. Ultimate tensile strength, translucency parameter, and micro-tensile bond strength to dentin were similar for control and experimental adhesive resins. Due to their characteristics, TTME and TTAC monomers are potentially useful in the formulation of photopolymerizable resins for dental use with high shelf-life stability.

SYNTHETIC POLYAMPHOLYTE HYDROGELS BASED ON VARIOUS ALIPHATIC DIAMINS FOR REMOVING DYES FROM AQUEOUS SOLUTIONS

Были исследованы полиамфолитные гидрогели, полученные на основе частично гидролизованного полиакриламида и алифатических диаминов (этилендиамина, 1,3-диаминопропана и 1,4-диаминобутана) без использования инициирующей системы и сшивающего агента. Использованные азотсодержащие мономеры, обладая высокой химической активностью, осуществляют химическую сшивку получаемых полиамфолитных гидрогелей. Было установлено, что полиамфолиты, полученные из сильного основания и слабой кислоты, теряют свою чувствительность к рН и ионной силе из-за несбалансированности заряженных функциональных групп, что расширяет области применения полиамфолитных гидрогелей в различных областях промышленности, где в течение процесса значения рН и содержание электролитов могут меняться. Полученные полиамфолитные гидрогели на основе различных алифатических диаминов могут быть использованы в качестве сорбционных материалов для удаления окрашенных примесей и могут применяться в широком диапазоне значений рН. Polyampholytic hydrogels based on partially hydrolyzed polyacrylamide and aliphatic diamines (ethylenediamine, 1,3-diaminopropane, and 1,4-diaminobutane) without using an initiator system and a crosslinking agent was studied. The used nitrogen-containing monomers, possessing high chemical activity, carry out chemical crosslinking of the obtained polyampholytic hydrogels. It was found that polyampholytes obtained from a strong base and a weak acid lose their sensitivity to pH and ionic strength due to the imbalance of charged functional groups, which expands the scope of application of polyampholyte hydrogels in various industries, where during the process the pH values and electrolyte content can change. The obtained polyampholytic hydrogels based on various aliphatic diamines can be used as sorption materials to remove colored impurities and can be used in a wide range of pH values.

Surface and mechanical properties of adhesives with calcium phosphates challenged to different storage media

Aim: To evaluate the behavior of experimental dental adhesiveswith hydroxyapatite (HAp), alpha-tricalcium phosphate (α-TCP)or octacalcium phosphate (OCP) after storing them in threedifferent media: dry storage, distilled water, or lactic acid.Methods: An experimental adhesive resin was formulated withbisphenol A glycol dimethacrylate, 2-hydroxyethyl methacrylate,and photoiniciator/co-initiator system. HAp (GHAp), α-TCP(Gα-TCP), or OCP (GOCP) were added to the adhesive resin at 2wt.%, and one group remained without calcium phosphates tobe used as a control (GCtrl). The adhesives were evaluated forsurface roughness, scanning electron microscopy (SEM), andultimate tensile strength (UTS) after storing in distilled water(pH=5.8), lactic acid (pH=4) or dry medium. Results: The initialsurface roughness was not different among groups (p>0.05).GHAp showed increased values after immersion in water(p<0.05) or lactic acid (p<0.05). SEM analysis showed a surfacevariation of the filled adhesives, mainly for Gα-TCP and GHAp. GHApshowed the highest UTS in dry medium (p<0.05), and its valuedecreased after lactic acid storage (p<0.05). Conclusions:The findings of this study showed that HAp, OCP, and α-TCPaffected the physical behavior of the experimental adhesiveresins in different ways. HAp was the calcium phosphatethat most adversely affected the surface roughness and themechanical property of the material, mainly when exposed toan acid medium.

The Role of the Initiator System in the Synthesis of Acidic Multifunctional Nanoparticles Designed for Molecular Imprinting of Proteins

Multifunctional nanoparticles have been shown earlier to bind certain proteins with high affinity and the binding affinity could be enhanced by molecular imprinting of the target protein. In this work different initiator systems were used and compared during the synthesis of poly (N-isopropylacrylamide-co-acrylic acid-co-N-tert-butylacrylamide) nanoparticles with respect to their future applicability in molecular imprinting of lysozyme. The decomposition of ammonium persulfate initiator was initiated either thermally at 60 °C or by using redox activators, namely tetramethylethylenediamine or sodium bisulfite at low temperatures. Morphology differences in the resulting nanoparticles have been revealed using scanning electron microscopy and dynamic light scattering. During polymerization the conversion of each monomer was followed in time. Striking differences were demonstrated in the incorporation rate of acrylic acid between the tetramethylethylenediamine catalyzed initiation and the other systems. This led to a completely different nanoparticle microstructure the consequence of which was the distinctly lower lysozyme binding affinity. On the contrary, the use of sodium bisulfite activation resulted in similar nanoparticle structural homogeneity and protein binding affinity as the thermal initiation.