Polymerizable Groups Research Articles

Synthesis of Eugenol–Lauryl Methacrylate Copolymers via Cationic Polymerization

Eugenol is one of the most abundant natural resources in Indonesia. The recently bio-based polymer resin is created based on eugenol because eugenol is functionalized with the polymerizable group. In order to improve the functional properties of eugenol, in this research Eugenol–Lauryl Methacrylate copolymers (co-poly(Eg-LMA)) were synthesized by cationic polymerization using H2SO4 as an initiator under the nitrogen atmosphere. Structure identification of the copolymer showed the absorption of the vinyl group from the monomers disappear at the analysis through FTIR at the wave number 1637-1639 and 985-995 cm-1 and also 1H-NMR on the chemical shift 5,97 and 5,08 ppm. The resulting copolymers obtained brown powder in 32.03 % yieldsand melting point at 96 – 97 °C. Solubility test of the co-poly(Eg-LMA) showed that the polymer couldnot soluble in water but soluble in chloroform, diethyl ether, and benzene. Average molecular weight of co-poly(Eg-LMA) Led Ostwald viscometry was obtained 42020 with the degree of polymerization by 200.

Characterization and Polymerization of Epoxidized Methacrylated Castor Oil

In this study, synthesis and polymerization of epoxidized methacrylated castor oil (EMETCO) is demonstrated. EMETCO is synthesized in two steps. Castor oil (CO) is methacrylated with methacryloyl chloride at the first step. Then the methacrylated castor oil (METCO) is epoxidized by Prilezhaev reaction. Structure of EMETCO is determined by1H NMR and IR techniques. EMETCO was copolymerized with acrylic acid (AA), styrene (ST), and methacrylic acid (MA). Thermal and mechanical properties of the synthesized polymers are evaluated. Among the polymers synthesized EMETCO‐ST‐MA polymer gives the highest storage modulus at 2.25 GPa. On the other hand, EMETCO‐AA copolymer exhibited the lowest storage modulus at 350 MPa. Moreover, EMETCO‐ST copolymer shows the lowest 5% weight loss temperature while EMETCO‐MA exhibited the highest 5% weight loss temperature at 280 °C.Practical Applications: Epoxidized Methacrylated Castor Oil is a bio‐based epoxy acrylate monomer. The low viscosity and two different functional groups make this material suitable for many polymerization reactions and applications. This compound would be used as a replacement materials for many industrial monomers such as styrene, acrylated epoxidized soybean oil, or prepolymers in the future.EMETCO is a castor oil based epoxy acrylate monomer. It is a hybrid material that contains different types of polymerizable groups. Synthesis of the monomer is not complicated and completed in two steps. Methacrylation of castor oil occurs at the first step and epoxidation follows that reaction. The resultant compounds is a transparent oil.

Synthesis of Polymeric Nanocomposite Hydrogels Containing the Pendant ZnS Nanoparticles: Approach to Higher Refractive Index Optical Polymeric Nanocomposites

Nanocomposites have attracted more attention due to their extensive applications. However, it is still a huge technological challenge in fabrication of transparent hybrid materials because of nanoparticle aggregation resulting from their high specific surface energies. In this paper polymerizable molecule was controlled chemically grafted onto ZnS nanoparticles to obtain polymerizable-group-capped nanoparticles that can copolymerize with a mixture of acrylic monomers of N,N-dimethylacrylamide (DMA) and 2-hydroxyethyl methacrylate (HEMA) or glycidyl methacrylate (GMA) or methyl methacrylate (MMA) to prepare transparent high refractive index (RI) nanocomposite hydrogels. The dispersion homogeneity of the nanoparticles in the nanocomposites was studied by dynamic mechanical thermal analysis (DTMA), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and energy dispersive X-ray mapping analysis (EDX). Moreover, the nanocomposites were characterized by transmittance, mechanical properties, and refractive index (RI). The results showed that grafted amount of polymerizable group on the nanoparticle surface influences the cross-link density and microphase structure of the resultant nanocomposites, leading to different transmittance and mechanical properties. The RI of hydrated and dry nanocomposites can be regulated to a peak value of 1.652 and 1.751, respectively, by a simple adjustment of ZnS content in the nanocomposites. Our approach was also proved to be effective in preparing DMA-free transparent nanocomposites with high RI of 1.824 by copolymerizing between polymerizable-group-capped ZnS and single monomer of HEMA or GMA or MMA.

Stimuli responsive microgels decorated with oligoglycidol macromonomers: Synthesis, characterization and properties in aqueous solution

In this work we focused on synthesis and characterization of aqueous poly(N-vinylcaprolactam) (PVCL) microgels decorated with oligoglycidol-macromonomers. Oligoglycidol macromonomers with styrene or acrylate polymerisable group and tunable length of the oligoglycidol chain (6, 12 and 50 glycidol units) were synthesized. The microgels were synthesized by aqueous precipitation copolymerization of N-vinylcaprolactam and oligoglycidol macromonomers in presence of crosslinking agent. The length of the oligoglycidol chain and the concentration of macromonomer in the reaction mixture were varied to investigate a direct influence on the polymerization rate and microgel properties. Synthesized microgels exhibit radii from 50 to 350 nm and show temperature-responsive properties. We demonstrate that oligoglycidol macromonomers are localized predominantly on the microgel surface. This ensures excellent colloidal stabilisation of oligoglycidol-decorated microgels in aqueous solutions and functionalization of microgels with hydroxyl groups, which can be potentially used for further post-modification reactions.

Enzymatic synthesis and structural characterization of methacryloyl‐D‐fructose‐ and methacryloyl‐D‐glucose‐based monomers and poly(methacryloyl‐D‐fructose)‐based hydrogels

AbstractBACKGROUNDCarbohydrates are important renewable raw materials and their modification by enzymatic reactions with polymerizable groups is of great importance due the possibility of production of polymers with properties for biomedical applications. In this study, D‐fructose‐ and D‐glucose‐based monomers were prepared by enzymatic reactions and structurally characterized. Moreover, hydrogels based on poly(methacryloyl‐D‐fructose) were also prepared and characterized.RESULTSThe conversions of 99% and 34% for D‐fructose and D‐glucose, respectively, were achieved using 2,2,2‐trifluoroethyl methacrylate as the methacrylic donor and commercial lipase Novozyme® 435 (EC 3.1.1.3) as enzymatic catalyst in t‐butanol. The molar ratios of D‐fructose and D‐glucose mono‐ and dimethacrylate were 57/43 and 87/13, respectively. These monomers are an isomeric mixture related to the tautomeric equilibrium of the carbohydrates in solution. Methacryloyl‐D‐fructose was polymerized in the presence of a controlled amount of ethyleneglycol dimethacrylate as crosslinker achieving hydrogels with different crosslinking densities which are mechanically stable when subject to compression–decompression cycles and have a high water swelling capability.CONCLUSIONThe combination of 2,2,2‐trifluoroethylmethacrylate and Novozym® 435 in a heterogeneous media lead to the continuous carbohydrate solubilization and reaction with the formation of carbohydrates‐based monomers. The control of the monomer functionality enables the synthesis of hydrogels with different crosslinking densities that tune their properties. © 2017 Society of Chemical Industry

Preparation of Polyurethane Acrylate Coated Carbon Nanotube Nanocomposites by Emulsion Polymerization

The aim of this work was to prepare strong and conductive polyurethane acrylate nanocomposites. First, urethane prepolymers with different molecular weights and hydrophilicities were synthetized. Then, their corresponding polyurethane acrylate nanocomposites were prepared by ultrasonically-assisted emulsion polymerization in the presence of various ratios of urethane prepolymers and acrylate monomers. Thermogravimetric analysis (TGA) and tensile results showed that thermal stability and mechanical properties of polyurethane acrylate samples are significantly dependent on the molecular weight and hydrophilicity of the urethane prepolymer as well as the content of acrylate monomers. Polyurethane acrylate sample (i.e., PUAc-2B50) with optimum mechanical properties and thermal stability were chosen as matrix to prepare nanocomposites in the presence of nanotubes grafted with polymerizable acrylate groups (G-MWNTs). Transmission electron microscope (TEM) revealed that the surface of nanotubes is uniformly coated with polymer nanoparticles. The nanocomposites containing 3 wt% G-MWNTs demonstrated a great modulus up to 374 MPa and excellent strength up to 18.74 MPa. Meanwhile, they indicated remarkable high electrical and thermal conductivities; as the electrical conductivity of the nanocomposites increased by more than twelve orders of magnitude, and thermal conductivity reached to 12.5 times of the neat matrix. The developed nanocomposites hold high potential for diverse applications, such as printable electronic devices, nano-sensors, and heat/electrical induced shape memory polymers.

Dual-responsive hydrogels based on maleilated curdlan-graft-poly(N-isopropylacrylamide)

ABSTRACTThe esterification reaction between curdlan and maleic anhydride was performed to provide polymerizable double bonds and pH-sensitive carboxylic groups for the curdlan chains. The new derivative was used as macromolecular cross-linker in the polymerization of N-isopropylacrylamide, when thermo and pH-sensitive networks were obtained in the form of microparticles. The loading and releasing profiles of a model macromolecular drug, lysozyme, were evaluated. The protein release rate was influenced by the pH and temperature. The pulsatile release of the lysozyme was also observed, the pulse being the swelling of the microparticles due to the decrease of the temperature under the volume phase transition temperature.

Bioinspired Catecholic Primers for Rigid and Ductile Dental Resin Composites.

In the construction of dental restorative polymer composite materials, surface priming on mineral fillers is essential to improve the mechanical performance of the composites. Here we present bioinspired catechol-functionalized primers for a tougher dental resin composite containing glass fillers. The catecholic primers with different polymerizable end groups were designed and then coated on glass surfaces using a simple drop-casting or dip-coating process. The surface binding ability and possible cross-linking (coupling or chemical bridging between the glass substrate and the dental resin) of the catecholic bifunctional primers were evaluated using atomic force microscopy, contact angle measurements, and the knife shear bonding test and compared to a state-of-the-art silane-based coupling agent. Various mechanical tests including shrinkage and compression tests of the dental resin composites were also conducted. Compression tests of the composites containing the catecholic primed fillers exhibited enhanced mechanical properties, owing to the bidentate hydrogen bonding of catechol moieties to the oxide mineral surface. Furthermore, the superior biocompatibility of the primed surface was confirmed via cell attachment assay, thus providing applicability of catecholic primers for practical dental and biomedical applications.

Functional Organo-Nano Particles by RAFT Copolymerisation

A significant impact of this work on the use of polymers is expected because the developed organo-nano particles (ONP) mixed into standard polymers will make them unique and traceable. The doping of polymers with non migrating ONP was demonstrated and applications for the recycling of plastics were discussed. Thus, perylene derivatives were linked to polymerisable vinyl groups and copolymerized under RAFT conditions (Reversible Addition Fragmentation chain Transfer) with styrene and methylmethacrylate, respectively, to obtain fluorescent ONP with sizes of 40 nm or even less and narrow distributions of molecular weight in most cases with polydispersities PD of 1.1 and lower.

Hyperbranched Aliphatic Polyester via Cross-Metathesis Polymerization: Synthesis and Postpolymerization Modification.

A novel postpolymerization modification methodology is demonstrated to achieve selective functionalization of hyperbranched polymer (HBP). Terminal and internal acrylates of HBP derived from cross-metathesis polymerization (CMP) are functionalized in a chemoselective fashion using the thiol-Michael chemistries. Model reactions between different thiols (benzyl mercaptan and methyl thioglycolate) and acrylates (n-hexyl acrylate and ethyl trans-2-decenoate) by using dimethylphenylphosphine or amylamine as the catalyst are investigated to optimize the modification protocol for HBP. High-molecular-weight HBP P0 is generated through CMP of AB2 monomer 2, a compound containing one α-olefin and two acrylate metathetically polymerizable groups. CMP kinetics is monitored by NMR and gel permeation chromatography (GPC). Accordingly, microstructural analysis is conducted in detail, and CMP procedure is optimized. Postpolymerization modification of HBP P0 is performed via two distinguished strategies, namely one-step complete modification and sequential modification, to generate terminally and/or internally functionalized HBPs P1-P3 in a chemoselective fashion by using phosphine-initiated and/or base-catalyzed thiol-Michael chemistries. Finally, thermal stability and glass transition behaviors of HBPs P0-P3 are studied by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC), respectively.

In-situ cross interface linking of PIM-1 polymer and UiO-66-NH2 for outstanding gas separation and physical aging control

Typical preparation of mixed matrix membranes (MMM), where the pre-synthesized polymer and filler are simply mixed together in a suitable solvent before casting, often suffer from poor polymer-filler adhesion. This study introduces a novel generation of MMM where the fillers are covalently linked with the polymer matrix, hence generating defect-free membranes. To do so, a metal-organic framework (MOF) bearing polymerizable groups (UiO-66-NH2) was in-situ linked with a polymer of intrinsic microporosity (PIM-1) during the polymer synthesis. The PIM-MOF chemical cross interface linking was confirmed by combined analytical technics including 1H-NMR, 13C-MAS NMR, FTIR, SEM, XRD and contact angle. Compared with traditional non-crosslinked MMMs, the in-situ derived MMMs showed a significantly higher permeability and ideal selectivity for all the gases tested (CO2, CH4, N2 and O2). These improvements are highly related to the degree of cross interface linking between PIM-1 and UiO-66-NH2. For the same filler loading of 20 wt.%, the CO2/CH4 selectivity increases from 19.1 to 31.9 as the in-situ polymerization time is extended from 12 to 72 h. The physical aging was also effectively controlled for the in-situ crosslinked MMMs where gas permeability remained up to 80% of its initial value after 400 days of storage at ambient conditions.

Nonconventional Fluorescent Polynorbornenes Bearing Aminosuccinimide Side Groups

AbstractIn this contribution, a new class of fluorescent polynorbornenes containing side chains that homogeneously decorated with aminosuccinimide side groups as nonconventional chromophores is introduced. First of all, monomers M1–M3 are synthesized in an efficient and straightforward fashion by means of Michael addition between three kinds of alkyl amines and monomer precursor 1, a compound containing norbornene (polymerizable group) and maleimide (Michael acceptor) groups. Subsequently, ring‐opening metathesis polymerization of M1–M3 is conducted to generate polymers P1–P3 with high molecular weights (Mn values exceeding 9800) and narrow molecular weight distributions (Ð values no more than 1.20), respectively. Quantitative conversion of monomers and microstructural integrity of polymers are verified in all cases. Finally, thermal stability, glass transition behavior, wettability, and optical properties of polymers P1–P3 are investigated. In particular, this new class of fluorescent polymeric materials exhibits blue emission (470–478 nm) under UV irradiation with large Stokes shifts (over 110 nm).

Direct 3D Printing of Catalytically Active Structures

3D printing of materials with active functional groups can provide custom-designed structures that promote chemical conversions. Herein, catalytically active architectures were produced by photopolymerizing bifunctional molecules using a commercial stereolithographic 3D printer. Functionalities in the monomers included a polymerizable vinyl group to assemble the 3D structures and a secondary group to provide them with active sites. The 3D-printed architectures containing accessible carboxylic acid, amine, and copper carboxylate functionalities were catalytically active for the Mannich, aldol, and Huisgen cycloaddition reactions, respectively. The functional groups in the 3D-printed structures were also amenable to postprinting chemical modification. As proof of principle, chemically active cuvette adaptors were 3D printed and used to measure in situ the kinetics of a heterogeneously catalyzed Mannich reaction in a conventional solution spectrophotometer. In addition, 3D-printed millifluidic devices with c...

Modulating Wettability of Layered Materials by Controlling Ligand Polar Headgroup Dynamics.

Integrating functionalized 2D materials into multilayer device architectures increasingly requires understanding the behavior of noncovalently adsorbed ligands during solution processing. Here, we demonstrate that the headgroup dynamics of polymerized monolayers of functional alkanes can be controlled to modify surface wetting and environmental interactions. We find that headgroup dynamics are sensitive to the position of the polymerizable diyne group; thus, the polymerization process, typically used to stabilize the noncovalent monolayer, can also be used to selectively destabilize chain-chain interactions near the headgroups, making the headgroups more solvent-accessible and increasing surface hydrophilicity. Conversely, interactions with divalent ions can be used to tether headgroups in-plane, decreasing surface hydrophilicity. Together, these results suggest a strategy for the rational design of 2D chemical interfaces in which the polymerization step reconfigures the monolayer to promote the desired environmental interactions.

Synthesis of imine-ester-linked benzothiazole mesogen containing liquid crystalline monomers with different terminal substituents

ABSTRACTA series of imine-ester-linked benzothiazole mesogen-based liquid crystalline (LC) monomers (M1–M4) having polymerizable methacrylate functional group as the terminal were designed and synthesized. These monomers were differentiated from each other by varying the terminal substituents (-H, -CH3, -OCH3, and -OCH2CH3) at the sixth position on the benzothiazole moiety. The chemical structures of the synthesized monomers were characterized and confirmed by spectroscopic techniques such as FTIR, 1H NMR, and 13C NMR. Thermogravimetric analysis (TGA) was used to study the thermal properties of the investigated monomers. The ethoxy substituted monomer (M4) showed higher thermal stability compared with the other monomers. The mesomorphic behavior of all the monomers was studied using differential scanning calorimetry (DSC) and polarized optical microscopy (POM). DSC and POM studies revealed that the monomer (M1) having no substituent at the sixth position on the benzothiazole ring exhibited both smectic and nematic mesophases, whereas -CH3-, -OCH3-, and -OCH2CH3-substituted compounds revealed only nematic mesophase.

Prediction of the char formation of polybenzoxazines: The effect of heterogeneities in the crosslinked network to the prediction accuracy in quantitative structure-properties relationship (QSPR) model

Molecular Operating Environment (MOE) software has great potential when combined with the Quantitative Structure-Property Relationship (QSPR) approach, and was proven to be useful to make good prediction models for series of polybenzoxazines [1–3]. However, the effect of heterogeneities in the crosslinked network to the prediction accuracy is yet to be tested. It was found that polybenzoxazines with polymerisable functional group (e.g. acetylene-based benzoxazines) form up to 40% higher char yield compared to their analogue polybenzoxazines due to the contribution of the polymerisable functional group (e.g. ethynyl triple bond) in the cross-linked network. In order to investigate the effect of the inconsistent cross-linking network, a data set consisting of thirty-three benzoxazines containing various structures of benzoxazines was subdivided into two smaller data sets based on their functional group, either benzoxazines with polymerisable functional group (acetylene-based benzoxazines set (Ace-M)) or non-polymerisable functional group (aniline-based benzoxazines (Ani-M)). Char yield predictions for the polybenzoxazines for these data sets (Ace-M and Ani-M) were compared with the larger thirty-three polybenzoxazines data set (GM) to investigate the effect of the inconsistency in crosslink network on the quality of prediction afforded by the model. Prediction performed by Ace-M and Ani-M were found to be more accurate when compared with the GM with total prediction error of 3.15% from both models compared to the GM (4.81%). Ace-M and Ani-M are each better at predicting the char yields of similar polybenzoxazines (i.e. one model is specific for a polymerisable functional group; the other for non-polymerisable functional group), but GM is more practical as it has greater ‘general’ utility and is applicable to numerous structures. The error shown by GM is considerably small and therefore it is still a good option for prediction and should not be underestimated.

Synthesis of Multiwalled Carbon Nanotubes–Poly(Methacrylic Acid) Nanohybrid Systems: Characterization, Thermal Properties, and In Vitro Release Studies of Naproxen as a Model Drug

ABSTRACTNanohybrid systems based on carbon nanotubes and pH-sensitive poly(methacrylic acid) were prepared through attaching polymer chains onto carbon nanotubes. First, polymerizable groups were attached onto carbon nanotube walls, then the polymerizable groups were copolymerized with different ratios of methacrylic acid. Obtained systems were studied and characterized through Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, and transmission electron microscopy. A model drug (naproxen) was entrapped into the prepared materials and in vitro release studies were performed in pH 1 (simulated gastric fluids) and pH 7.4 (simulated intestinal fluids). It was noticed that release in simulated intestinal fluids was faster than simulated gastric fluids, therefore the prepared nanohybrid systems can be considered as appropriate carriers for colon-specific drug delivery.

Polymerizable Ionic Liquid Crystals Comprising Polyoxometalate Clusters toward Inorganic-Organic Hybrid Solid Electrolytes.

Solid electrolytes are crucial materials for lithium-ion or fuel-cell battery technology due to their structural stability and easiness for handling. Emergence of high conductivity in solid electrolytes requires precise control of the composition and structure. A promising strategy toward highly-conductive solid electrolytes is employing a thermally-stable inorganic component and a structurally-flexible organic moiety to construct inorganic-organic hybrid materials. Ionic liquids as the organic component will be advantageous for the emergence of high conductivity, and polyoxometalate, such as heteropolyacids, are well-known as inorganic proton conductors. Here, newly-designed ionic liquid imidazolium cations, having a polymerizable methacryl group (denoted as MAImC1), were successfully hybridized with heteropolyanions of [PW12O40]3− (PW12) to form inorganic-organic hybrid monomers of MAImC1-PW12. The synthetic procedure of MAImC1-PW12 was a simple ion-exchange reaction, being generally applicable to several polyoxometalates, in principle. MAImC1-PW12 was obtained as single crystals, and its molecular and crystal structures were clearly revealed. Additionally, the hybrid monomer of MAImC1-PW12 was polymerized by a radical polymerization using AIBN as an initiator. Some of the resulting inorganic-organic hybrid polymers exhibited conductivity of 10−4 S·cm−1 order under humidified conditions at 313 K.

Polypropylene thermosets by VBTEMPO-mediated radical crosslinking

New chemistry for preparing polypropylene (PP) thermosets is described, wherein radical degradation suffered during conventional peroxide treatment is overcome using a nitroxyl additive that bears a polymerizable functional group. A small amount of 4-vinylbenzoic-2,2,6,6-tetramethylpiperidin-N-oxyl (VBTEMPO) is used to trap peroxide-derived, alkyl radical intermediates during the early stages of the modification process, yielding a macromonomer derivative that crosslinks in the post-quenching phase through side-chain oligomerization. This process produces thermosets of a PP homopolymer with gel contents in excess of 90%, while providing the induction period needed to shape the formulation before the melt viscosity increases. Furthermore, a preliminary accelerated oxidation study suggests that the polymer-bound N-alkoxyamine functionality generated by this process can confer oxidative stability to the thermoset product.

Coordination-Supported Imidazolate Networks: Water- and Heat-Stable Mesoporous Polymers for Catalysis.

The poor water stability of most porous coordination polymers (PCPs) or metal-organic frameworks (MOFs) is widely recognized as a barrier hampering their practical applications. Here, a facile and scalable route to prepare metal-containing polymers with a good stability in boiling water (100 °C, 24 h) and air (up to 390 °C) is presented. The bifunctional 1-vinylimidazole (VIm) with a coordinating site and a polymerizable organic group is introduced as the building block. This core strategy includes the synthesis of a rigid monomer with four VIm branches through a coordination process at room temperature, followed by a radical polymerization. We refer to this material as coordination-supported imidazolate networks (CINs). Interestingly, CINs are composed of rich mesopores from 2-15 nm, as characterized by low-energy (60 kV) STEM-HAADF images. In particular, the stable CINs illustrate a high turnover frequency (TOF) of 779 h-1 in the catalytic oxidation of phenol with H2 O as the green solvent.