New BODIPY Dyes Based on Benzoxazole as Photosensitizers in Radical Polymerization of Acrylate Monomers

A series of 2-phenacylbenzoxazole difluoroboranes named BODIPY dyes (1–8) was designed and applied as photosensitizers (PS) for radical photopolymerization of acrylate monomer. The light absorption within the ultraviolet-visible (UV–Vis) range (λmax = 350–410 nm; εmax = 23,000–42,500 M−1cm−1), that is strongly influenced by the substituents on the C3 and C4 atoms of phenyl ring, matched the emission of the Omnicure S2000 light within 320–500 nm. The photosensitizer possess fluorescence quantum yield from about 0.005 to 0.99. The 2-phenacylbenzoxazole difluoroboranes, together with borate salt (Bor), iodonium salt (Iod) or pyridinium salt (Pyr) acting as co-initiators, can generate active radicals upon the irradiation with a High Pressure Mercury Lamp which initiates a high-performance UV–Vis light-induced radical polymerization at 320–500 nm. The polymers obtained are characterized by strong photoluminescence. It was found that the type of radical generator (co-initiator) has a significant effect on the kinetic of radical polymerization of acrylate monomer. Moreover, the chemical structure of the BODIPY dyes does not influence the photoinitiating ability of the photoinitiator. The concentration of the photoinitiating system affects the photoinitiating performance. These 2-phenacylbenzoxazole difluoroborane-based photoinitiating systems have promising applications in UV–Vis-light induced polymerization.

Photocurable Coatings Based on Bio-Renewable Oligomers and Monomers

Due to long-term problems related to environmental protection, economic aspects, and waste management in the chemical industry, it is justified to develop renewable polymers as an alternative to synthetic polymers. Two kinds of acrylic bio-renewable components were used for the modification of acrylated epoxidized soybean oil (AESO). The bio-based compositions used as photocurable binders to obtain the photocurable coatings with satisfactory properties and high bio content were then prepared. The kinetic of curing reaction of the oligomers and monomers towards radical photopolymerization and the properties of the cured coatings were fully investigated; the results are discussed in relation with the compounds’ structures. Important information about how to design and obtain renewable photocurable coatings with satisfactory properties was provided in this study. In this study, AESO resin was modified with renewable oligomer or (math)acrylate monomer to increase the reactivity and reduce the viscosity of the photoreactive system in order to obtain renewable and viable alternatives to petroleum-based polymeric materials with perfect film-forming properties. It turned out that both photopolymerization rate and hardness of cured coatings were increased significantly with the addition of modifiers; the use of a thiol modifier and change of the photoinitiator concentration allowed to improve the adhesion, hardness, and control of the photo-curing process.

Evaluation of Reactive Diluent Impact on Stability of Systems Viscosity in UV-Curable Compositions

This study investigated the impact of various reactive diluents on viscosity of uncured mixture at 50 °C over a 12-week period. This criterion is important to predict the shelf life of uncured composition. Studied mono-functional acrylate monomers were: hydroxypropyl methacrylate (HPMA), hydroxyethyl methacrylate (HEMA), tetrahydrofurfuryl acrylate (THFA), isobornyl methacrylate (IBOMA), isobornyl acrylate (IBOA), 2-(2-Ethoxyethoxy)ethyl acrylate (EOEOEA), acryloyl morpholine (ACMO), glacial methacrylic acid (GMAA) and phosphate acrylate monomer (PAM); and various solvents: isopropanol(IP) ethyl acetate (EA), butyl acetate (BA). There was found the difference of effect on the systems viscosity in time between the mono-functional monomers and solvents. HPMA and IPA showed the most stable viscosity values in time.

Synthesis of poly (n-butyl acrylate) with tempo by nitroxide mediated polymerization method

It has been observed that acrylate monomers are very difficult to polymerize with the low cost nitroxide catalyst 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO). Therefore, costly acyclic nitroxides such as N-tert-butyl-N-(1-diethylphosphono-2,2-dimethyl)-N-oxyl, (SG1), 2,2,5-Trimethyl-4-phenyl-3-azahexane-3-nitroxide (TIPNO) and TIPNO derivatives have to be used for the polymerization of the acrylic acid derivatives. There are very few reports on the use of TEMPO-derivatives toward the polymerization of n-butyl acrylate. Generally different reducing agents viz. glucose, ascorbic acid, hydroxyacetone etc. have been used to destroy excess TEMPO during the polymerization reaction. The acrylate polymerizations fail in the presence of TEMPO due to the strong C–O bond formed between the acrylate chain end and nitroxide. To the best of our knowledge, no literature report is available on the use of TEMPO without reducing agent or high temperature initiators, toward the polymerization of n-butyl acrylate. The present study has been carried out with a view to re-examine the application of low cost nitroxide TEMPO, so that it can be utilized towards the polymerization of acrylate monomers (e.g. n-butyl acrylate). We have been able to polymerize n-butyl acrylate using the nitroxide TEMPO as initiator (via a macroinitiator). In this synthesis, a polystyrene macroinitiator was synthesized in the first step from TEMPO, after this TEMPO end-capped styrene macroinitiator (PSt-TEMPO) is used to polymerize n-butyl acrylate monomer. The amount of macroinitiator taken was varied from 0.05% to 50% by weight of n-butyl acrylate monomer. The polymerization was carried out at 120°C by bulk polymerization method. The experimental findings showed a gradual increase in molecular weight of the polymer formed and decrease in the polydispersity index (PDI) with increase in amount of PSt-TEMPO macroinitiator taken. In all experiments conversion was more than 80%. These results indicate that the polymerization takes place through controlled polymerization process. Effect of different solvents on polymerization has also been investigated. In the following experiments TEMPO capped styrene has been used as macroinitiator leading to the successful synthesis of poly n-Butyl acrylate. It has been found that styrene macroinitiator is highly efficient for the nitroxide mediated polymerization, even in very small concentration for the synthesis of poly n-butyl acrylate. High concentration of macroinitiator results in the formation of block copolymers of polystyrene and poly ( n-butyl acrylate) viz. polystyrene-block-poly-( n-butyl acrylate). The use of TEMPO toward controlled polymerization is of much importance, because it is the nitroxide commercially available at the lowest cost.

Synthesis of macro-RAFT agent containing M13-10 and its application in surface sizing agent

A novel macro-RAFT emulsifier was synthesized with S, S’-bis(α, α’-dimethyl-α”-acetic acid)-trithiocarbonate (BDATT), M13-10 (self-made emulsifier) and acrylate monomer, which was further used to prepare surface sizing agent. On the other hand, M13-10 was synthesized with iso-tridecanol polyoxyethylene ether, sodium methoxide and sulfamic acid as the starting materials. The hydrophilicity of macro-RAFT emulsifier and the performance of surface sizing agent were affected by BDATT used as the chain transfer agent and M13-10 as the hydrophilic monomer. So, the CMC and HLB of the emulsifier prepared with different M13-10 content and BDATT content, were compared, as well as the particle size of the prepared surface sizing agent, and the cobb, bursting resistance, tensile resistance, folding endurance and roughness of paper sized. The results reveal that surface sizing agent with macro-RAFT emulsifier of which the amount of M13-10 is 7 w% and the amount of BDATT is 2.5 w% demonstrates the best sizing effect on paper with the contact angle of 119°, the surface water absorption (cobb) of 48.8 g/m2, the bursting strength of 285 kPa, the folding endurance of 19 and the tensile strength of 59.6 kN/m.

In Situ Compatibilization of Isotactic Polypropylene and High-Density Polyethylene by a Melt Cobranching Reaction

Incompatible polypropylene (PP) and polyethylene (PE) are difficult to separate in mixed recycling streams such as waste plastic packaging, which makes these polyolefin mixtures unsuitable for high-quality products. In this work, based on the free radical branching reaction, a co-branching reaction of isotactic polypropylene (iPP) and high-density polyethylene (HDPE) blends was carried out in the presence of the peroxide, free radical regulator and multifunctional acrylate monomer, and a star-like long-chain branching (LCB) copolymer was acquired. The effect of in situ compatibilization on the structure and mechanical properties of iPP/HDPE was investigated, and the compatibilization mechanism was discussed. Results showed that the mechanical properties of the modified blends were largely improved, and efficient in-situ compatibilization of iPP and HDPE could be taken place in a wide process window. Moreover, the size of the dispersed phase in the modified blend was clearly decreased, and the interfacial thickness increased. Compared with the pure iPP/HDPE blend, the initial crystallization temperature of iPP in the modified iPP/HDPE blend was increased, and long branched chains of the LCB copolymer were physically entangled with the chemical identical homopolymers or even participate in the crystallization of iPP and HDPE. Thanks to the in situ compatibilization strategy, the compatibility of iPP/HDPE was significantly improved.

Optical Nanocomposites Containing Low Refractive Index MgF2 Nanoparticles

Nanoparticles composed of magnesium fluoride were successfully introduced into polymer matrices used for the fabrication of planar optical waveguides. Optical layers without visible scattering were successfully prepared. The transparent nanocomposites were formulated by direct mixing of modified MgF2 nanoparticles with fluorinated co-polymer matrix or acrylate monomer mixture with a help of additional solvent. An addition of MgF2 nanoparticles results in decrease of refractive index and thermo-optic coefficient of the polymer but increases substantially the optical propagation losses for planar waveguide at 1547 nm.

Synthesis of Silica-Supported Hydroxamic Ligand for Removal of Metals Ions from Water

Mesoporous silica supported adsorbents have been used towards metal ion removal from water due to their thermally stability and good sorption capacity. Thus, mesoporous silica-based methyl acrylate monomer (Silica-APTES-DPNO) was converted into hydroxamic acid (SBHA) by using oximation reaction and all products are analyzed by by FT-IR. The SBHA showed satisfactory binding properties with copper, cobalt, nickel and lead are 242, 206, 195 and 516 mg g−1, respectively, with the batch adsorption system was set to pH 6. The kinetics of metal ions binding obeyed the pseudo-1st-order process up to 60 min. In this study also consider the Langmuir and Freundlich isotherm to find out the sorption behavior. The isotherm study demonstrated the well fit with Freundlich isotherm (R2 > 0.99). Thus, adsorption take place as a multilayer system, therefore, SBHA material is useful for the metal ions removal from water.