Synthesis of well‐defined comb‐like amphiphilic copolymers with protonizable units in the pendent chains: 1. Preparation of narrow polydispersity copolymers of methyl methacrylate and 2‐hydroxyethyl methacrylate by atom‐transfer radical polymerization

Well‐defined methyl methacrylate (MMA) and 2‐(trimethylsiloxy)ethyl methacrylate (Pro‐HEMA) copolymers were prepared by atom‐transfer radical polymerization(ATRP), using CuCl/2,2′‐bipyridine as catalytic system and p‐toluenesulfonyl chloride as initiator. ATRP process of MMA and Pro‐HEMA was monitored by ¹H NMR, and the kinetic curves of the MMA/Pro‐HEMA copolymerization were plotted in terms of the ¹H NMR data. At low content of Pro‐HEMA in the feed composition, the copolymerization can be well controlled with the molecular weight, polydispersity and the monomer distribution in the copolymer chain. With the increase of Pro‐HEMA content in the feed mixture, the composition of the final copolymer deviates from the composition of the feed mixture gradually, and gradient copolymers of MMA/Pro‐HEMA can be obtained. Through the hydrolysis process, well‐defined copolymers of MMA/HEMA were obtained from poly(MMA/Pro‐HEMA). Copyright © 2003 Society of Chemical Industry     

Synthesis and polymerization of some iodine-containing monomers for biomedical applications

Triiodophenol and iothalamic acid (5-acetamido-2,4,6-triio-N-methyl isophthalamic acid) were converted to their acrylic derivatives by esterfication with methacryloyl chloride and 2-hydroxyethyl methacrylate (HEMA), respectively. The monomers due to presence of heavy iodine atoms were expected to be radiopaque in nature. The monomers were characterized using TLC, IR, and ¹H-NMR spectroscopy. Both monomers were highly resistant to homopolymerization and copolymerization with other acrylic monomers such as methyl methacrylate (MMA) or HEMA by initiators such as 2,2′-azobis isobutyronitriie (AIBN) or benzoyl peroxide (BPO) yielding only polymers of low molecular weight. The polymers obtained were charactrized by gel permeation chromatography (GPC) and differential thermal analysis (DTA). The resistance to polymerization is presumably due to the presence of bulky iodine atoms in the monomers sterically hindering the propagation step. The decomposition temperatures of the homopolymers and copolymers were close to 300°. Copolymers of HEMA with both radiopaque monomers incorporated to the extent of 25 wt % in the feed, however, produced polymers with good radiopacity. Copolymers with HEMA were also prepared in the form of microspheres by a solvent evaporation method with the aim of using them as particles in therapeutic embolization. While the polymer based on triiodophenol was found to cause extensive blood haemolysis in in vitro tests, polymer based on iothalamic acid was found to be nonhemolytic in character suggesting that copolymers based on iothalamic acid would be suitable for implantation in the living tissue.     

Microbial screening of copolymers of 2,4‐dichlorophenyl methacrylate with N‐vinylpyrrolidone: synthesis and characterization

Copolymers of 2,4‐dichlorophenyl methacrylate and hydrophilic monomer (N‐vinylpyrrolidone) were synthesized with different feed ratios using dimethylformamide as solvent and 2,2′‐azobisisobutyronitrile as initiator at 70 °C. The copolymers were characterized by IR spectrometry. Copolymer compositions were determined by UV spectrometry. The monomer reactivity ratios were determined by applying the conventional linearization method of Fineman‐Ross. Gel permeation chromatography was employed for determining molecular weights and polydispersity indexes. Thermogravimetric analyses of polymers were carried out in nitrogen atmosphere. Homo‐ and copolymers were tested for their antimicrobial properties against selected microorganisms. © 2003 Society of Chemical Industry     

Methyl Methacrylate-8-Quinolinyl Acrylate Copolymers-I: Synthesis and Characterization

Abstract

The monomer, 8-quinolinyl acrylate (8-QA) was synthesized and characterized by IR and ¹H-NMR spectroscopy, high performance liquid chromatography (HPLC) and elemental analysis. The homopolymer, poly (8-QA) and its copolymers with methyl methacrylate (MMA) in different monomer feed ratio were prepared by free radical polymerization using dimethyl formamide (DMF) as a solvent and 2,2′-azobis-isobutyronitrile (AIBN) as an initiator. The resulting polymers were characterized by IR spectroscopy, UV-visible spectrophotometry, gel permeation chromatography (GPC), solution viscosity and thermal analysis (TG and DSC). It was observed from the GPC results that as the 8-QA content in the copolymer increases, the molecular weight decreases whereas polydispersity increases with increasing 8-QA content in the copolymers. It was also observed from the TG data that the initial decomposition temperature (IDT) of the copolymers decreases with increasing 8-QA content in the copolymers.     

Synthesis and characterization of high molecular weight side chain liquid crystalline/photoactive polymers

Various liquid crystalline and photoactive azobenzene monomers were synthesized and attached to copoly(methyl methacrylate‐glycidyl methacrylate) [copoly (MMA‐GMA)] to get high molecular weight side chain liquid crystalline (LC)/photoactive copolymers. Further, spacers are generated in situ and reactive groups are obtained after the modification. All monomers and polymers were thoroughly characterized by FTIR, ¹H and ¹³C NMR, UV‐VIS spectrophotometry, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, and polarized optical microscopy. All side chain LC polymers showed higher thermal stability than that of copoly(MMA‐GMA). Three LC and one azo monomer exhibited characteristic nematic mesophase where as one LC monomer has shown nematic and sanded smectic‐A texture. The rate of trans‐cis isomerization of polymer was lower than that of the monomer and both monomers and polymers showed slow back isomerization. Present approach offers convenient way to synthesize high/desired molecular weight photoactive LC polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis,polymerization, and copolymerization of aliphatic vinyl azide

The synthesis and characterization of a fully aliphatic polymeric azide by polymerization of its vinyl monomer 1,3‐diazidoisopropyl methacrylate (DAIPM) is reported. DAIPM was prepared by azidation of epichlorohydrin followed by coupling with methacrylic acid. Homopolymer and copolymers with methyl methacrylate were prepared and characterized by IR, GPC, TGA, DTA, and elemental analyses. These polymers are freely soluble in organic solvents like dichloromethane, tetrahydrofuran, dimethyl formamide, acetone, and so forth and do not crosslink on storing. The polymers show decreased thermal stability with an increase in azide content and undergo exothermic decomposition on heating. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1852–1857, 2003     

Synthesis,characterization, and antimicrobial activity of acrylic copolymers

2,4‐Dichlorophenyl methacrylate (2,4‐DMA) and vinyl acetate (VAc) were copolymerized with different feed ratios using dimethyl formamide (DMF) as a solvent and 2,2′‐azobisisobutyronitrile (AIBN) as an initiator at 70°C. The copolymers were characterized by infrared (IR) spectroscopy. Copolymer compositions were determined by ultraviolet (UV) spectroscopy. The monomer reactivity ratios were evaluated by the Fineman–Ross method. Average molecular weight and polydispersity index were determined by gel permeation chromatography (GPC), and the intrinsic viscosities of polymers were also discussed. Thermogravimetric analyses of polymers were carried out under a nitrogen atmosphere. The homo‐ and copolymers were tested for their antimicrobial activity against selected microorganisms. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 895–900, 2003     

Synthesis and characterization of oil sorbers based on docosanyl acrylate and methacrylates copolymers

Docosanyl acrylate (DCA) monomer was copolymerized with different monomer feed ratios of cinnamoyloxy ethyl methacrylate (CEMA) or methyl methacrylate (MMA) monomer to produce different compositions for DCA/CEMA or DCA/MMA copolymer with low conversions.¹H NMR spectroscopy was used to confirm the copolymer structure. DCA was crosslinked with different mol % of CEMA or MMA using dibenzoyl peroxide as initiator and various weight percentages of either 1,1,1‐trimethylolpropane triacrylates or 1,1,1‐trimethylolpropane trimethacrylates crosslinkers. The effects of monomer feed composition, crosslinker concentration, and the hydrophobicity of the copolymer units on swelling properties of the crosslinked polymers were studied through the oil absorbency tests. The network parameters, such as polymer solvent interaction (χ), effective crosslink density (υ_e), equilibrium modulus of elasticity (G_T), and average molecular weight between crosslinks (M_c), were determined and correlated with the structure of the synthesized copolymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of defined polyhedral oligosilsesquioxane‐containing diblock and triblock methacrylate copolymers by atom transfer radical polymerization

Defined diblock and triblock copolymers composed of methyl methacrylate‐co‐glycidyl methacrylate block and 3‐{3,5,7,9,11,13,15‐hepta(2‐methylpropyl)‐pentacyclo[9.5.1.1^3,9.1^5,15.1^7,13]‐octasiloxan‐1‐yl}propyl methacrylate block(s), i.e., P(MMA‐co‐GMA)‐b‐PiBuPOSSMA and PiBuPOSSMA‐b‐P(MMA‐co‐GMA)‐b‐PiBuPOSSMA, were synthesized by atom transfer radical polymerization (ATRP). First, monofunctional and bifunctional P(MMA‐co‐GMA) copolymers were synthesized by ATRP. Subsequently, these copolymers were successfully used as macroinitiators for ATRP of POSS‐containing methacrylate monomer. The process showed high initiation efficiency of macroinitiators and led to products with low dispersity. The synthesized block copolymers were characterized by size exclusion chromatography, ¹H‐NMR spectroscopy and their glass transition temperatures were determined by differential scanning calorimetry. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of well‐defined comb‐like amphiphilic copolymers with protonizable units in the pendent chains: 2. Poly(2‐(dimethylamino)ethyl methacrylate) grafted poly(methyl methacrylate‐co‐2‐hydroxyethyl methacrylate) copolymers and their association behavior in aqueous solution

Narrow‐distribution, well‐defined comb‐like amphiphilic copolymers are reported in this work. The copolymers are composed of poly(methyl methacrylate‐co‐2‐hydroxyethyl methacrylate) (P(MMA‐co‐HEMA)) as the backbones and poly(2‐(dimethylamino)ethyl methacrylate) (PDMAEMA) as the grafted chains, with the copolymer backbones being synthesized via atom‐transfer radical polymerization (ATRP) and the grafted chains by oxyanionic polymerization. The copolymers were characterized by gel permeation chromatography (GPC), Fourier‐transform infrared (FT‐IR) spectroscopy and ¹H NMR spectroscopy. The aggregation behavior in aqueous solutions of the comb‐like amphiphilic copolymers was also investigated. ¹H NMR spectroscopic and surface tension measurements all indicated that the copolymers could form micelles in aqueous solutions and they possessed high surface activity. The results of dynamic light scattering (DLS) and scanning electron microscopy (SEM) investigations showed that the hydrodynamic diameters of the comb‐like amphiphilic copolymer aggregates increased with dilution. Because of the protonizable properties of the graft chains, the surface activity properties and micellar state can be easily modulated by variations in pH. Copyright © 2004 Society of Chemical Industry     

Synthesis and antimicrobial activity of metronidazole containing polymer and copolymers

Homopolymer and copolymers containing metronidazole (MTZ) drug were synthesized. Acryloyl chloride was reacted with MTZ (drug) to produce monomer containing MTZ, and then the monomer was copolymerized with various amounts of methyl methacrylate. The produced monomer, homopolymer, and copolymers were characterized by elemental analysis, IR, and ¹H‐NMR. The antimicrobial activities of the synthesized polymers were tested against Kelpsilic as fungal organisms, and Escherichia coli, Bacillus subitilus, and Pesudomonus areuginosa as bacteria organisms. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Acrylic Homo- and Co-polymers Based on 2, 4-dichlorophenyl Methacrylate and 8-quinolinyl Methacrylate

The monomer 2, 4-dichlorophenyl methacrylate (2,4-DMA) was synthesized from 2, 4-dichlorophenol and characterized by conventional methods. The homopolymers of 2,4-dichlorophenyl methacrylate and its copolymers with 8-quinolinyl methacrylate (8-QMA) in different feed ratio were prepared by free radical polymerization using dimethyl formamide (DMF) as a solvent and 2,2-azobis iso butyronitrile (AIBN) as an initiator. The resulting polymers were characterized by using IR spectroscopy. Reactivity ratios of monomer were evaluated using UV-spectroscopy. Average molecular weights and polydispersity were determined by gel permeation chromatography (GPC). Solution viscosity was also obtained. The thermal analysis was carried out using TGA and DSC. The homo- and co-polymers were also tested for their antimicrobial properties against selected microorganism. The metal ion uptake capacity of synthesized copolymers was estimated by batch equilibration method using different metal ion solution under different experimental conditions. It is observed that due to the presence of pendant ester bound quinoline group, the copolymers are capable of adsorbing cations from their aqueous solution.     

Synthesis of superabsorbent copolymers as water manageable materials

Strongly water‐absorbing polymers based on the monomers acrylamide, potassium acrylate and magnesium methacrylate were prepared by copolymerization using ammonium persulfate as initiator and N,N‐methylene‐bisacrylamide (MBA) as crosslinking agent. The copolymers are synthesized by varying monomer, crosslinker and initiator concentrations. The experimental results shows that superabsorbents (SAPs) have good absorbency both in water and NaCl solutions. The copolymers are characterized by IR spectroscopy. Water retention in soil is enhanced by use of these superabsorbents. The SAPs use for the growth of sunflower plants is also investigated. The water retention capacity of the SAPs was carried out at 60 °C and 100 °C. Copyright © 2003 Society of Chemical Industry     

Simultaneous interpenetrating polymer networks based on bromoacrylated castor oil polyurethane

In the first part of this study, simultaneous addition of bromine and acrylate to the double bonds of castor oil was achieved. In the second part of the study, bromoacrylated castor oil (BACO) was reacted with toluenediisocyanate (TDI), to form a prepolyurethane (BACOP). The prepolyurethanes were reacted with styrene (STY), 2‐hydroxyethyl methacrylate (HEMA), methyl methacrylate (MMA), and 3‐(acryloxy)‐2‐hydroxy propyl methacrylate (AHPMA) free radically, using the acrylate functional group to prepare the simultaneous interpenetrating polymer networks (SINs). 2,2′‐Azobis (isobutyronitrile) (AIBN) was used as the initiator and diethylene glycol dimethacrylate (DEGDMA) was used as the crosslinker. BACO and BACOP were characterized by IR, ¹H‐NMR, and ¹³C‐NMR techniques. Synthesized polymers were characterized by their resistance to chemical reagents, thermogravimetric analysis, and dynamic mechanical thermal analyzer (DMTA). All the polymers decomposed with 6–10% weight loss in a temperature range of 25–240°C. MMA‐type SIN showed the highest T_g (126°C), while STY‐type SINs showed the highest storage modulus (8.6 × 10⁹ Pa) at room temperature, with respect to other synthesized SINs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2947–2955, 2006     

Frontal copolymerization of 2‐hydroxyethyl methacrylate and ethylene glycol dimethacrylate without porogen: comparison with suspension polymerization

Networked, crosslinked poly[(2‐hydroxyethyl methacrylate)‐co‐(ethylene glycol dimethacrylate)] (HEMA‐EGDM) was synthesized by frontal polymerization (FP) using azobisisobutyronitrile as initiator. HEMA‐EGDM copolymers of similar composition were also synthesized by suspension polymerization. The two sets of copolymers were characterized for functional groups (IR), pore volume (mercury intrusion porosimetry), surface area (nitrogen adsorption) and morphology (scanning electron microscopy). FP‐generated polymeric network structures had higher internal pore volumes and surface areas but their surface morphologies were inferior to those of copolymers synthesized by suspension polymerization. Copyright © 2004 Society of Chemical Industry     

Synthesis of graft copolymers of binary vinyl monomer mixtures onto acetylated Saccharum spontaneum L and characterization

Methylmethacrylate (MMA) + acrylamide (AAm), MMA + acrylonitrile (AN), and MMA + acrylic acid (AA) binary vinyl monomer mixtures were graft copolymerization onto acetylated Saccharum spontaneum L, was carried out and maximum graft yield (185.6 %) was found with MMA+AAm binary mixture. Synthesized graft co‐polymers were characterized with FT‐IR spectrophotometry, scanning electron microscopy (SEM), thermal analysis TGA/DTA/DTG, and X‐ray diffraction (XRD) techniques. Thermal stability of Ss‐g‐poly(MMA + AAm) was found to be more than that of natural, acetylated S. spontaneum fiber and other graft copolymers. Although on grafting, percentage crystallinity and crystallinity index were found to decrease but graft copolymers were found to exhibit more moisture, chemical, and thermal resistance. Also, it can be observed that the surface of the grafted fibers is highly rough in comparison with the ungrafted fiber. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Differential microemulsion polymerization as a new root for entrapment of drugs

Nanosized particles derived from poly(methyl methacrylate) as well as copolymer of methyl methacrylate (MMA) and 2‐hydroxyethyl methacrylate (HEMA) were synthesized by differential microemulsion technique in the presence of ammonium persulfate as water‐soluble initiator. The polymerization was stabilized by adding biologically safe emulsifiers namely the sodium dodecyl sulfate (SDS) or polyvinyl pyrrolidone (PVP) either alone or in conjunction with polyethylene glycol. The turbidity measurements, surface tension, ζ potential, and morphological characterizations of the obtained nanosized poly MMA and its copolymer with HEMA in different monomer feed compositions were investigated. It is found that increasing HEMA content leads to increase in the particle size, turbidity measurements but the negatively charged ζ potential decreased. However, when SDS is used, the surface tension of the prepared lattices increased, whereas it is decreased by using PVP. Kinetic studies of (MMA/HEMA) in ratio of 95/5 wt % in the presence of SDS or PVP revealed that the emulsifier concentration has a considerable effect on the rate of polymerization and the power of the emulsifier. The entrapment of drug was investigated using two active molecules different in water solubility (sodium warfarin and ibuprofen). It is noted that entrapment efficiency is independent of HEMA content in the monomer feed composition but dependent on type of drug and the amount of drug introduced. Hence, higher entrapment efficiency was attained for sodium warfarin (more hydrophilic) than that of ibuprofen (more hydrophobic) and they were 95.5 and 85%, respectively. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparations and oil absorptivities of poly(stearyl methacrylate-co-cinnamoyloxyethyl methacrylate) and PET nonwoven fiber photocrosslinked with it

Cinnamoyloxyethyl methacrylate (CEMA) was synthesized by the reaction of cinnamoyl chloride (CMC) and 2-hydroxyethyl methacrylate (HEMA). Its copolymers with stearyl methacrylate (SMA) were synthesized using benzoyl peroxide (BPO) as an initiator. The synthesized copolymers, poly(SMA-co-CEMA)s (PSCMAs), were photocrosslinked by UV light irradiation. The structures of the products were confirmed by IR and NMR spectroscopies. The thermal properties of the synthesized polymers were determined by DSC. The crystalline melting temperature of crosslinked PSCMA was decreased with increasing CEMA content in the feed. The oil absorptivities of the synthesized polymers were evaluated by the ASTM method (F726-81). The highest oil absorptivity of crosslinked PSCMA on poly(ethylene terephthalate) (PET) nonwoven fiber (NWF) was 610% in 10% crude oil diluted with toluene when the mol percentage of CEMA to SMA in the feed was 7.5. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2349–2357, 1999     

Synthesis of methacrylate copolymers and their effects as pour point depressants for lubricant oil

In this study, polymethacrylate polymers were synthesized by free‐radical polymerization for use as pour point depressants in lubricant oil, and their low‐temperature properties were investigated. Four methacrylate monomers were synthesized by the esterification of methyl methacrylate (MMA) with four kinds of fatty alcohols. The purification step was performed to prepare the pure monomers. Two polymerization experiments were carried out with four kinds of methacrylate monomers obtained previously and MMA. Copolymers, which were made from one kind of monomer and MMA, and terpolymers, which were made from two kinds of monomers and MMA, were prepared. The molecular structures of the synthesized methacrylate monomers and polymethacrylate polymers were verified by ¹H‐NMR, and the molecular weight data were obtained by gel permeation chromatography. The pour points of the base oils containing 0.1 wt % polymethacrylate polymers were measured according to ASTM D 97‐93. The pour points of most base oils containing each polymer decreased compared to that of the pure base oil. Particularly, poly(dodecyl methacrylate‐co‐hexadecyl methacrylate‐co‐methyl methacrylate), made of dodecyl methacrylate, hexadecyl methacrylate, and MMA at a molar ratio of 3.5 : 3.5 : 3, showed the best low‐temperature properties. This terpolymer dropped the pour point of the base oil by as much as 23°C, and its yield was 93.5%. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Micropatterning of polymethacrylates by single‐ or two‐photon irradiation using π‐conjugated o‐nitrobenzyl ester phototrigger as side chains

A new single‐/two‐photon sensitive monomer, (E)‐5‐(4‐ethoxystyryl)?2‐nitrobenzyl methacrylate (ENbMA), was synthesized and copolymerized with methyl methacrylate (MMA) to form a series of photosensitive copolymers P(ENbMA–MMA)s that were well characterized by ¹H NMR and GPC. The photochemical and photophysical properties of both photosensitive monomer and copolymers upon visible light irradiation were studied by UV–Vis, FTIR, and HPLC spectra, which confirmed that 5‐(4‐ethoxystyryl)‐2‐nitrobenzyl ester can be photolyzed effectively with generation of the corresponding 5‐(4‐ethoxystyryl)‐2‐nitrosobenzaldehyde and carboxylic acid groups. The successful photocleavage endowed the optimized copolymers with excellent micropatterning property due to the effective generation of alkaline‐soluble carboxylic acid groups. Moreover, the high two‐photon absorption cross‐sections (over 20 GM at 800 nm) and the comparable photolysis upon two‐photon NIR light irradiation of the chromophores provided the copolymers with significant application in two‐photon microfabrication. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4099–4106, 2013