Acryloyloxy)-2-hydroxypropyl Methacrylate Research Articles

A benzenesulfonic acid-modified organic polymer monolithic column with reversed-phase/hydrophilic bifunctional selectivity for capillary electrochromatography

Here, a styrene-based polymer monolithic column poly(VBS-co-TAT-co-AHM) with reversed-phase/hydrophilic interaction liquid chromatography (RPLC/HILIC) bifunctional separation mode was successfully prepared for capillary electrochromatography by the in situ polymerization of sodium p-styrene sulfonate (VBS) with cross-linkers 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHM) and 1,3,5-triacryloylhexahydro-1,3,5-triazine (TAT). The preparation conditions of the monolith were optimized. The morphology and formation of the poly(VBS-co-TAT-co-AHM) monolith were confirmed by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR). The separation performances of the monolith were evaluated systematically. It should be noted that the incorporation of VBS functional monomer can provide π−π interactions, hydrophilic interactions, and ion-exchange interactions. Hence, the prepared poly(VBS-co-TAT-co-AHM) monolith can achieve efficient separation of thiourea compounds, benzene series, phenol compounds, aniline compounds and sulfonamides in RPLC or HILIC separation mode. The largest theoretical plate number for N,N′-dimethylthiourea reached 1.7 × 105 plates/m. In addition, the poly(VBS-co-TAT-co-AHM) monolithic column showed excellent reproducibility and stability. This novel monolithic column has great application value and potential in capillary electrochromatography (CEC).

The effect of heterobifunctional crosslinkers on HEMA hydrogel modulus and toughness.

The use of hydrogels in load bearing applications is often limited by insufficient toughness. 2-Hydroxyethyl methacrylate (HEMA) based hydrogels are appealing for translational work, as they are affordable and the use of HEMA is FDA approved. Furthermore, HEMA is photopolymerizable, providing spatiotemporal control over mechanical properties. We evaluated the ability of vinyl methacrylate (VM), allyl methacrylate (AM), and 3-(Acryloyloxy)-2-hydroxypropyl methacrylate (AHPM) to tune hydrogel toughness and Young’s modulus. The crosslinkers were selected due to their heterobifunctionality (vinyl and methacrylate) and similar size and structure to EGDMA, which was shown previously to increase toughness as compared to longer crosslinkers. Vinyl methacrylate incorporation into HEMA hydrogels gave rise to hydrogels with Young’s moduli spanning ranges for ligament to cartilage, with a peak toughness of 519 ± 70 kJ/m3 under physiological conditions. We report toughness (work of extension) as a function of modulus and equilibrium water content for all formulations. The hydrogels exhibited 80%-100% cell viability, which suggests they could be used in tissue engineering applications.

Spectroscopic analysis of methacrylate groups introduced on silica particle surfaces by the aza-Michael addition reaction

We modified silica nanoparticles with a N′-(3-trimethoxysilylpropyl)diethylenetriamine (TPDT) silane coupling agent, which has one primary and two secondary amino groups in each molecule, to introduce amino groups on silica surfaces. After surface modification of silica, we used an acrylate group containing 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHM) to introduce free radical polymerizable methacrylate groups by the aza-Michael addition reaction. Fourier transform infrared spectroscopy (FTIR), elemental analysis (EA), liquid state 1H and 13C nuclear magnetic resonance spectroscopy (NMR) and solid state cross polarization magic angle spinning (CP/MAS) 29Si NMR were used to investigate the effects of various reaction conditions on the degree of reaction between the N-H groups of the TPDT-modified silica surface and the acrylate groups of AHM. We found that approximately 48% of the N-H groups of the TPDT-modified silica surface reacted with the acrylate groups of AHM, compared with approximately 83% of the N-H groups of pure TPDT reacting with the acrylate groups of AHM at the same reaction conditions. This lower degree of the aza-Michael addition reaction between the N-H groups of the TPDT grafted on the solid silica particle versus the N-H groups of pure TPDT, both with acrylate groups of liquid AHM, may be caused by the lower mobility of the N-H groups of the grafted TPDT on the solid silica particle and the higher steric hindrance caused by the solid silica particle.

Dual antimicrobial effects induced by hydrogel incorporated with UV-curable quaternary ammonium polyethyleneimine and AgNO3

This study presents a simple method for fabricating a highly potent dual effect antibacterial hydrogel consisting of a UV-curable cationic polyethyleneimine (QUV-PEI) and embedded silver nitrate (AgNO3). In the first part of this study, polyethyleneimine (PEI) was reacted with 3-(acryloyloxy)-2-hydroxypropyl methacrylate (ACOM) to introduce methacryl functionality onto the backbone. UV-curable PEI was further quaternized by N-methylation with methyl iodate. Hydrogels based on QUV-PEI and AgNO3were found to have impressive biocidal properties. The antibacterial properties were assessed by spraying aqueous suspensions of bacterial cells on the surface, followed by air drying and counting the number of remaining viable cells (i.e. capable of growing into colonies). In a manner depending on the QUV-PEI content in the gel formulation, up to 99±1% of Escherichia coli and Staphylococcus aureus cells sprayed on the resulting hydrogel surfaces were killed. The inclusion of AgNO3 in the QUV-PEI based hydrogel not only enhanced the antimicrobial property against adherent bacteria but also led to the inhibition of bacterial growth in suspended culture via the long-term release of Ag/Ag+ to the surrounding media. Cytotoxicity studies on human umbilical vein endothelial cells and MTS cell lines were also performed with hydrogels. These findings confirm that hydrogels are potentially useful as antimicrobial agents in a wide variety of applications.

Mechanical Properties of UV-cured Urethane Acrylate Nanocomposite with Methacrylate-grafted Silica Nanoparticles

In this study, we prepared silica nanoparticles with methacrylate groups on their surface by two-step modification process. Silica particles were first silanized with (3-trimethoxysilylpropyl)diethylenetriamine (TPDT), after that Michael addition reaction was performed between N-H groups on the TPDT modified silica surface with acrylate groups of 3-(acryloyloxy)-2-hydroxypropylmethacrylate (AHM). We also used pristine silica and 3-methacryloxypropyltrimethoxysilane (MPTMS) modified silica as fillers to make nanocomposites with urethane acrylate resin. We studied effects of above mentioned silica types on the mechanical properties of UV-cured nanocomposites. We found Young’s modulus values of UV cured resin, nanocomposites with 0.5 wt% pristine silica, with 0.5 wt% MPTMS modified silica and with 0.5 wt% TPDT/AHM modified silica were 386.6, 433.6, 462.4 and 517.6 MPa, respectively. The highest modulus was found in the nanocomposite of 0.5 wt% TPDT/AHM modified silica.

2차 아미노기가 결합된 실리카 나노 입자 표면에 3-(Acryloyloxy)-2-hydroxypropyl Methacrylate의 마이클 부가 반응에 대한 분광학적 분석

본 연구에서는 나노크기의 실리카 입자를 2차 아미노기를 가지는 dipodal 형태의 실란커플링제인 bis[3-(trimethoxysilyl)propyl]ethylenediamine(BTPED)으로 표면 개질한 후, 실리카에 도입되는 2차 아미노기인 N-H기와 마이클 부가 반응이 가능한 acrylate기를 가지는 3-(acryloyloxy)-2-hydroxypropyl methacrylate(AHM)로 표면 처리를 하여 중합 반응성 methacrylate기를 도입하는 연구를 수행하였다. 1 분자에 2차 아미노기를 2개 가지는 BTPED와 마이클 부가 반응성이 있는 acrylate기와 부가 반응성이 없는 methacrylate기를 각각 1개씩 가지는 AHM을 사용하여 BTPED와 AHM의 투입량 및 개질 반응 시간의 변화가 실리카 표면의 methacrylate기 도입에 미치는 영향을 Fourier transform infrared spectroscopy(FTIR), elemental analysis(EA)와 액체 및 고체 상태 cross polarization magic angle spinning(CP/MAS) nuclear magnetic resonance spectroscopy(NMR)법을 사용하여 분석하였다. 실리카 표면에 BTPED 를 도입하는 반응은 1시간 내에, BTPED로 개질된 실리카의 N-H기에 대한 AHM의 acrylate기와의 마이클 부가 반응에 따른 methacrylate기 도입은 2시간 내에 반응이 각각 완결됨을 확인하였다. 또한 BTPED로 개질된 실리카에 대하여 투입되는 AHM의 몰 비가 증가할수록 N-H기와 acrylate기의 마이클 부가 반응으로 인한 methacrylate기의 도입이 증가하였으며 이는 AHM을 도입했을 때 나타나는 FTIR 스펙트럼의 C=O 피크 면적 변화로 확인하였다. 위의 결과를 EA 및 고체 상태 <TEX>$^{13}C$</TEX> 및 <TEX>$^{29}Si$</TEX> NMR 분석으로도 확인하였다. In this study, we modified silica nanoparticles with bis[3-(trimethoxysilyl)propyl]ethylenediamine (BTPED) silane coupling agent, which has two secondary amino groups in a molecule, to introduce amino groups on the silica surface. After modification of silica, we used acrylate group containing 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHM) to introduce polymerizable methacrylate groups by Michael addition reaction. We used Fourier transform infrared spectroscopy (FTIR), elemental analysis (EA) and liquid and solid state cross polarization magic angle spinning (CP/MAS) nuclear magnetic resonance spectroscopy (NMR) to understand the reactions between N-H groups of BTPED modified silica surface and acrylate groups of AHM monomer. We confirmed Michael addition reaction between BTPED modified silica and AHM completed in 2 hr reaction time. We also found increased methacrylate group introduction with increase of mol ratio of the acrylate group of AHM to N-H group of BTPED modified silica by increase of C=O peak area of measured FTIR spectra. These results were also supported by EA and solid state <TEX>$^{13}C$</TEX> and <TEX>$^{29}Si$</TEX> NMR results.

PEGylated dendrimer polystyrene support: synthesis, characterisation and evaluation of biologically active peptides

Poly(N,N-bisethylamine) dendrimers with high content of poly(ethylene glycol) were synthesized on 3-(Acryloyloxy)-2-hydroxypropylmethacrylate-crosslinked polystyrene (PS-AHMA) resin and tested in various conditions of solid phase peptide synthesis. The dendritic templates were generated to the second generation on cross-linker active site of 3-(Acryloyloxy)-2-hydroxypropylmethacrylate (AHMA). First generation dendrimer was designed by series of four-stage reactions, such as Schiff base incorporation, acidolytic cleavage, diazotization and thionyl chloride treatment and same synthetic routes were followed for second generation also. Poly(ethylene glycol) (PEG1000) has been grafted to second-generation dendrimer and used to check various physico-chemical parameters in Fmoc/Boc peptide synthetic conditions. The utility of PEGylated dendrimer support was demonstrated by synthesizing biologically potent linear as well as disulfide-bonded peptide by Fmoc method.

2차 아미노기를 갖는 실리카 나노입자와 (메타)아크릴레이트 단량체와의 마이클 부가반응에 대한 분광학적 분석

In this study, we modified silica nanoparticles with bis[3-(trimethoxysilyl)propyl]amine (BTMA) silane coupling agent to introduce secondary amino groups on the silica surface. After modification of silica, we investigated effects of different types of (meth)acrylate group containing monomers on the Michael addition reaction to introduce reactive (meth)acrylate groups on the BTMA modified silica surface. We used two kinds of (meth)acrylate monomers, trimethylolpropane ethoxylate triacrylate (TMPET) which has three identical acrylate groups, and 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHM) which has one acrylate and one methacrylate group. We used fourier transform infrared spectroscopy (FTIR), elemental analysis (EA) and solid state cross-polarization magic angle spinning (CP/MAS) nuclear magnetic resonance spectroscopy (NMR) to understand reactions between NH groups on the silica surface with (meth)acrylate groups of TMPET and AHM monomers. We found almost complete Michael addition reaction between all three acrylate groups of TMPET with NH groups on the BTMA modified silica. But, for the AHM treatment of BTMA modified silica, we found Michael addition reaction occurred only between acrylate groups of AHM and NH groups of silica surface, not between methacrylate groups of AHM and NH groups of BTMA modified silica surface.

Synthesis of Sterically-Stabilized Polystyrene Latexes Using Well-Defined Thermoresponsive Poly(N-isopropylacrylamide) Macromonomers

A series of well-defined thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) macromonomers was prepared by reversible addition–fragmentation chain transfer (RAFT) polymerization followed by aminolysis and nucleophilic Michael addition. 2-(Dodecylthiocarbonothioylthio)-2-methylpropanoic-2-phenoxyethyl ester (CTA) was used as the RAFT chain transfer agent to prepare six PNIPAM-CTA precursors with target degrees of polymerization of 20, 30, 40, 50, 60, and 75. These NIPAM polymerizations were conducted in 1,4-dioxane and proceeded with good control and low polydispersities (Mw/Mn < 1.10) up to more than 90% conversion. The PNIPAM trithiocarbonate end-groups were then converted to methacrylate end-groups by combining (i) aminolysis and (ii) nucleophilic Michael addition using the bifunctional reagent, 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHPMA), in a one-pot reaction. The resulting PNIPAM macromonomers were evaluated as reactive steric stabilizers for latex syntheses. Near-monodisperse submicrometer-sized latexes were obtained by alcoholic dispersion polymerization of styrene in methanol, as judged by scanning electron microscopy (SEM) and dynamic light scattering (DLS). In contrast, a latex synthesized in the presence of a PNIPAM-CTA had a bimodal size distribution, while thiol-capped PNIPAM chains produced ill-defined nonspherical particles and styrene polymerization conducted in the absence of any stabilizer led to macroscopic precipitation. These control experiments confirm that using the methacrylate-capped macromonomers is essential for successful latex syntheses. 1H NMR analysis confirm the presence of PNIPAM chains in the latex particles and XPS measurements indicate that the stabilizer is located on the particle surface, as expected. The well-known thermo-responsive nature of the stabilizer was successfully transferred to these latexes, which exhibit reversible flocculation upon heating above the LCST of the PNIPAM chains.

Synthesis and polymerizations of six aminophosphonate-containing methacrylates

Two different groups of novel aminophosphonate-containing methacrylates were synthesized. The route to the first group involves reactions of ethyl α-bromomethacryate (EBBr) and t-butyl α-bromomethacryate (TBBr) with diethyl aminomethylphosphonate and diethyl 2-aminoethylphosphonate. Bulk and solution polymerizations at 60–80 °C with 2,2′-azobis(isobutyronitrile) (AIBN) gave crosslinked or soluble polymers depending on monomer structure and polymerization conditions. Increasing bulkiness from ethyl to t-butyl decreases the polymerization rate, correlated well with the chemical shift differences of double bond carbons and consistent with the lower molecular weights of t-butyl ester polymers (Mn = 1800–7900 vs. 50,000–72,000). The route to the second group involves the Michael addition reaction between diethyl aminomethylphosphonate and diethyl 2-aminoethylphosphonate with 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHM) to give secondary amines. The photopolymerization using differential scanning calorimeter showed that these monomers have similar or higher reactivities than AHM, even though AHM has two double bonds. The high rates of polymerization of these monomers were attributed to both hydrogen bonding interactions due to additional NH groups as well as chain transfer reactions. All the homopolymers obtained produced char (17–35%) on combustion. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.

Polymerization of methacryl and triethoxysilane functionalized stearate ester: Titanium dioxide composite films and their photocatalytic degradations

AbstractStearoyl chloride was reacted with 3‐(acryloyloxy)‐2‐hydroxypropyl methacrylate (AHM). Then the resulting product (SAHM) was reacted with 3‐amino propyl ethoxysilane (APTES) by Michael addition on the acrylate. The product (SAHMA) is a specialized coupling agent containing an oleophilic 18 carbon alkyl chain, a radically polymerizable methacrylate and an alkoxysilane group capable of coupling to inorganic surfaces, analyzed by FT‐IR, NMR, and UV techniques. Photopolymerization and free radical homo and copolymerization of SAHMA with styrene were examined. SAHMA was coupled to powdered titanium dioxide (P25‐Degussa) and polymerized. TiO2 filled materials were analyzed by SEM, UV and TGA techniques. Glass transiton temperatures (Tg) of the polymers were determined by differential scanning calorimeter (DSC). Interfacial compatibility between SAHMA and TiO2 was demonstrated by FT‐IR spectroscopy. The photocatalytic degradation of the TiO2‐SAHMA polymer films was also investigated under medium pressure mercury lamp illumination in air. SAHMA based film containing 2 wt % TiO2 showed the highest degradation and the highest loss in weight. The weight of the polymer was reduced by 25% of its initial value after irradiation for 40 h. To examine the surface morphology of the irradiated polymer films, SEM analysis was carried out and cavities were detected around TiO2 particles. The photocatalytic and thermomechanical properties of SAHMA and styrene (STY) based copolymers were also investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007

A novel photoinimer for the polymerization of acrylates and methacrylates

AbstractA new class of multifunctional photoinitiating system based on 3‐(acryloyloxy)‐2‐hydroxypropyl methacrylate (AHM), N,N,N′‐trimethylethylenediamine (TMED) and 3‐benzoylbenzoyl chloride present in the same molecule has been synthesized and characterized by 1H and 13C NMR spectroscopy. This self‐contained photoinitiator‐monomer (photoinimer) was used to efficiently initiate polymerization of acrylates and methacrylates. Both rate of polymerization and percentage conversion increased with increase in initiator concentration. An increment in rate of polymerization observed when the benzophenone moiety was directly attached to the parent molecule (obtained from the Michael addition reaction between AHM and TMED) appears to be due to proximity effect: chemical bonding provides a high local concentration of both components of the photo‐activated system involving benzophenone and a hydrogen atom source from an electron‐rich tertiary amine. For the three initiating systems investigated, lowering the initiator concentration plays an important role; i.e., the polymerization rate for the chemically linked system was about two times faster than the mixed initiating system. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5661–5670, 2005

Synthesis and photopolymerizations of phosphate-containing acrylate/(di)methacrylate monomers from 3-(acryloyloxy)-2-hydroxypropyl methacrylate

Novel phosphorus-containing acrylate/(di)methacrylate monomers based on 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHM) were prepared by two different methods. The first method involved reaction of AHM with diethylchlorophosphate to produce a phosphate-containing acrylate/methacrylate monomer followed by Michael addition of this monomer with dihexyl amine. In the second method, a hydroxyl-containing dimethacrylate monomer was prepared via Michael addition of hydroxyl amine to AHM followed by its reaction with diethylchlorophosphate. The photopolymerization kinetics of the synthesized monomers were investigated using a differential scanning calorimeter. It was shown that changing the monomer structure allows control of polymerization reactivity and new phosphorus-containing polymers can be obtained.

Synthesis and antibacterial activities of new quaternary ammonium monomers

New monomers and polymers with amine and quaternary ammonium groups on the side chain were synthesized. The first series of monomers were the derivatives of 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHM). Hydroxylated secondary and tertiary amine derivatives were prepared by reaction of AHM with various amines. One of the amine monomers was quaternized with bromohexane to give a quaternary ammonium monomer. A second series of amine and quaternary ammonium monomers were based on acrylamide and methacrylamide derivatives. New acrylamide/methacrylamide monomers with tertiary amine groups were synthesized and quaternized with various alkyl halides. All monomers were homo-polymerized and co-polymerized with 2-hydroxyethylmethacrylate (HEMA). The synthesized monomers and polymers were tested for antibacterial activities against Staphylococcus aureus and Escherichia coli bacteria. Amine monomers, their homo-polymers and co-polymers did not show any antibacterial activities. It was also found that the antibacterial activity of the quaternized methacrylamide-3-(aminomethyl) pyridine (METH-PYR) monomers increased as the alkyl chain length on nitrogen increased.

Synthesis of New Hydroxylated Monomers Based on Methacrylate, Dimethacrylate, and Tetramethacrylate Michael Adducts and Photopolymerization Kinetics of Bulk Cross-Linkers

A series of new hydroxylated monomers was synthesized from the Michael addition reaction between ethanolamine, diethylene glycol amine, triethylene glycol amine, tetradecylamine, and adamantanamine with 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHM). Selective formation of secondary amine (mono adduct) or tertiary amine (bis adduct) products was obtained by controlling the stoichiometry of the reactants and reaction temperature. The Michael addition reactions were highly exothermic and carried out without the need of catalyst. The use of solvent, however, was required in some systems. The tetramethacrylate monomer was synthesized via the Michael addition reaction of 1,6-hexanediamine (HDA) to AHM. The photopolymerization kinetics of the synthesized monomers were investigated using differential scanning calorimeter. The rates of polymerization for the hydroxylated dimethacrylate systems were significantly higher than that of a typical dimethacrylate monomer (HDDMA) and approached that of the diacrylate...

Synthesis and photopolymerizations of new hydroxyl-containing dimethacrylate crosslinkers

Abstract Two new hydroxyl-containing di(meth)acrylate monomers were synthesized from the reaction of methyl α-chloromethylacrylate (MCMA) and of ethyl α-chloromethylacrylate (ECMA) with glycerol. The monomers were obtained as mixtures of two isomers in different ratios and in combination with the analogous trimethacrylate monomers. Each monomer was isolated by column chromatography. The photopolymerization of these isomer mixtures and the trimethacrylate monomers was investigated individually by photodifferential scanning calorimetry (photoDSC) at room temperature using 2,2′-dimethoxy-2-phenyl-acetophenone (DMPA) as a photoinitiator. The effect of hydrogen bonding on the rates of polymerizations and conversions was examined. The results obtained for the synthesized monomers were compared to the values obtained for commercial monomers. It was observed that the hydroxyl-containing dimethacrylates polymerize much faster and to considerably higher conversion than the trimethacrylate monomers. The maximum rates of polymerization of the hydroxyl-containing monomers were higher than that of the hexanediol dimethacrylate (HDDMA), comparable to glycerol dimethacrylate and lower than hexanediol diacrylate (HDDA) and 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHM).