Benzyl methacrylate (BzMA) is widely used in nanoimprinting lithography, paint applications, inkjet inks, transparent adhesives, orthodontic adhesive compositions, and also as stationary phases in liquid chromatography. However, as far as we know, no study to date has investigated the application of benzyl methacrylate as “hard” monomer in both emulsion polymerization and acrylate PSAs. The aim of the present work was to investigate systematically the effect of cyclic methacrylate monomer BzMA on the comprehensive properties of the acrylate latex PSA. Statistical copolymers of benzyl methacrylate and diethylaminoethyl methacrylate: monomer reactivity ratios and thermal properties: The synthesis of poly(benzyl methacrylate) (PBzMA) and poly(diethylaminoethyl methacrylate) (PDEAEMA) statistical copolymers via free radical polymerization.

An oil-absorbing resin with a simple polymerization system with benzyl methacrylate

Oil-absorbing resins, as ideal oil-absorbent materials, are extensively used for oily wastewater remediation, and display high oil absorbency and good oil/water selectivity, oil retention and reusability. To overcome the defect of low oil absorbency, a series of studies were conducted, such as introducing monomers with long side chains. To boost oil absorbency, in this study benzyl methacrylate (BZMA) with benzene ring groups was introduced as a functional monomer, which can contribute to the formation of a structure that both has a rigid backbone and is easily extended. It is predicted that benzyl methacrylate, as a functional monomer of copolymerization, is qualified to provide more space volume, enhance mechanical strength and decrease the entanglement of long-chain alkyl groups to stretch easily. These results reflected that BZMA, as a functional monomer, was successfully introduced into the copolymerization system and reacted with SMA and BA to synthesize the terpolymer PAMs.[1]

Apparently, oil absorbency increased after adding benzyl methacrylate as a functional monomer. It can be speculated that the benzene ring, as a large and rigid group, occupied a certain network volume and supported the internal skeleton structure of the resin because of its steric effect. However, the curve of oil absorbency declined with the continuous addition of BZMA after reaching a peak. The excess amount of benzyl methacrylate quickly boosted the content of benzene rings between crosslinked points, which led to excessive rigidity so that the effective structure volume was occupied by large benzene rings. On the other hand, it was difficult to cause swelling because of the surplus of hard monomers, so the oil absorbability decreased rapidly. Oil-absorbing resins (PAMs) were successfully synthesized by introducing commercially available benzyl methacrylate as a functional monomer via an uncomplicated polymerization process. According to the test of the optimizing synthesis parameters, the best performance was observed when the ratio of the monomers was ω (SMA : BA : BZMA) = 1 : 0.2 : 0.2, and the concentrations of BPO, PVA and MBA were 0.5 ωt%, 0.5 ωt% and 0.5 ωt%, respectively.

Preparation and Evaluation of Benzyl Methacrylate Monoliths

Capillary liquid chromatography has been one of the most important developments in separation and analysis technology in the few last years. Capillary liquid chromatography offers several advantages over conventional normal scales. The advantages include increased chromatographic resolution, higher efficiency, lower consumption of samples and solvents, the ability to analyze and isolate rare compounds of interest, greater mass sensitivity and ease of online connection to a mass spectrometer. In this study, more than 30 monolithic columns (including preliminary and reproducibility experiments) were thermally prepared by one-step in situ copolymerization of benzyl methacrylate (BMA) and ethylene dimethacrylate (EDMA) in the presence of a suitable porogen mixture (1-propanol, 1,4-butanediol and water) and 2,2'-azobisisobutyronitrile (AIBN). According to preliminary studies, the benzyl methacrylate monomer (percentage v/v) in the polymerization mixture was set in the range of 10–30%, whereas the EDMA crosslinker (percentage v/v) was set in the range of 10–25%. On the other hand, the AIBN initiator content was varied between 2 and 20 mg/mL.[2]

Varying the ratio of each component of the polymerization mixture generates monolithic columns with different physical properties and chromatographic behavior. All column preparations were controlled by varying six factors (percentage v/v): concentration of monomer (Benzyl methacrylate), concentration of crosslinker (EDMA), concentration of each solvent in porogenic mixture (1-propanol, 1,4-butanediol and water) and concentration of AIBN initiator. The Benzyl methacrylate monomer has benzyl groups, which are supposed to provide π–π interactions between the stationary phase and aromatic analytes such as polycyclic aromatic hydrocarbons and phenol compounds. Some of the prepared capillary columns were successfully applied for the separation of a mixture of aromatic hydrocarbons using different experimental conditions.  The results indicated that both peak shape and resolution of the three aromatics were improved by adding tetrahydrofuran to the mobile phase.

Benzyl Methacrylate-Based Matrix Enhanced Eu3+ Narrow-Band Emission

Lanthanide-chelate (LC) emissions have widely attracted intensive research because of their unique optical emissions spanning a wide wavelength range from ultraviolet (UV)-visible to near-infrared regions. Many studies have tried to reduce such optical losses of the ECs by accessing coordinated or anionic ligands (most of which are β-diketones) of ternary europium, such as pyridylcyclotetramine-based, Eu(tta)3dpbt, and coumarin-based europium. We chose a host-guest approach to develop polymer-chromophore systems. Poly-benzyl methacrylate matrix is amorphous, has low reflectance, as well as metal/ion chelating stability, and is a class of optically transparent, UV-curable polymers. The structural properties and photophysical behaviors of composites of a europium complex bound to PBMA were extensively demonstrated. Poly-benzyl methacrylate and the europium/PBMA composite displayed excellent optical transmittance (>88%) and lower reflectance (<8.2% for PBMA and <7.9% for the europium/PBMA composite in the visible region with maximal values of 7.6% for PBMA and 5.6% for the europium/PBMA composite), indicating that the europium/PBMA composite system can be regarded as a high-transmittance material in the range of visible to near-IR radiation.[3]

References

[1]Zhou Y, Zhang M, Liu Y, Xu B, Qiu H, Che X, Lan G. An oil-absorbing resin with a simple polymerization system with benzyl methacrylate as a functional monomer. R Soc Open Sci. 2023 Oct 11;10(10):230343. doi: 10.1098/rsos.230343. PMID: 37830033; PMCID: PMC10565408.

[2]Aqel, Ahmad et al. “Preparation and evaluation of benzyl methacrylate monoliths for capillary chromatography.” Journal of chromatographic science vol. 52,3 (2014): 201-10. doi:10.1093/chromsci/bmt011

[3]Lee JF, Chen HL, Lee GS, Tseng SC, Lin MH, Liau WB. Photosensized controlling benzyl methacrylate-based matrix enhanced Eu(3+) narrow-band emission for fluorescence applications. Int J Mol Sci. 2012;13(3):3718-3737. doi: 10.3390/ijms13033718. Epub 2012 Mar 21. PMID: 22489178; PMCID: PMC3317738.