Synthesis,Antimicrobial Activity and Semi-conducting Properties of Novel 2-(4-Chloro-1-Naphtyloxy)-2-Oxoethyl Methacrylate with 2-(Diethylamino)Ethyl Methacrylate Copolymers

The free-radical initiated copolymerization of 2-(4-chloro-1-naphtyloxy)-2-oxoethyl methacrylate (ClNOEMA) with 2-(diethylamino) ethyl methacrylate (DEAEMA) was carried out in 1,4-dioxane solution at 70 ± 1°C using 2,2′-azobisisobutyronitrile (AIBN) as an initiator with different monomer-to-monomer ratios (ranging from 0.15 to 0.85) in the feed. The copolymer composition obtained by elemental analysis led to the determination of reactivity ratios employing Fineman-Ross (F-R) and Kelen-Tüdös (KT) linearization methods. These parameters were also estimated using a non-linear computational fitting procedure, known as reactivity ratios error in variable model (RREVM). The prepared homo and copolymers were tested for their antimicrobial activity against bacteria and yeast. These copolymers have been converted into novel salts by reaction with the iodemethane (CH₃I). The copolymers and the corresponding salts have been characterized fully by a range of spectroscopic analysis techniques. The electrical conductivity dependence of temperature of the polymers were measured and the polymers exhibit the semi-conducting behavior, confirming that the electrical conductivity increases with increasing temperature. The poly(CINOEMA-co-DEAEMA) polymer doped by CH₃I for 15 min shows the highest conductivity. The optical band gap, activation energy and room temperature conductivity values of these polymers were obtained. These electronic parameters suggest that the poly(CINOEMA-co-DEAEMA)s doped by CH₃I for 15 min is an organic semiconductor with the thermally activated conduction mechanism.     

The Microstructure of Poly(Isobutylene-co-p-Methylstyrene) by NMR Spectroscopy

Abstract

The microstructure of isobutylene-para-methylstyrene (IB-pMeSt) copolymers was studied by NMR spectroscopy. ¹H- and ¹³C-NMR spectra were used to obtain overall copolymer compositions. ¹³C-NMR signals were assigned in terms of triad monomer sequences, and triad distributions were obtained over a wide copolymer composition range. According to statistical tests, the IB-pMeSt copolymerization cannot be described by zero- (Bernoullian) or first-order Markov models because reactivity ratios r _IB and r _pMeSt were found to change with the monomer feed composition. Additional insight into the microstructure of IB-pMeSt copolymers was gained by calculating sequence numbers, run numbers, and sequence lengths from triad distributions. Further, the Kelen-Tüdös plot showed a distinct curvature indicating that the Kelen-Tüdös method, applied over the entire monomer feed composition range, cannot give meaningful reactivity ratios for this monomer pair. Evidently the simple two-parameter Mayo-Lewis model is inadequate to describe the IB-pMeSt copolymerization system.     

Phenylalanine-Tethered pH-Responsive Poly(2-Hydroxyethyl Methacrylate)

A series of pH-responsive random copolymers comprised of 2-hydroxyethyl methacrylate (HEMA) and tert-butyl carbamate (Boc)-protected phenylalanine methacryloyloxyethyl ester (Boc-Phe-EMA) were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization in N,N′-dimethylformamide (DMF) at 70 °C. The synthesized copolymers were comprehensively characterized using a combination of techniques, including ¹H NMR, FT-IR spectroscopy and size exclusion chromatography (SEC). Reactivity of each monomers towards controlled radical polymerization was evaluated by determining the reactivity ratios by virtue of extended Kelen-Tüdös method at high conversions revealed the higher reactivity of non-modified HEMA (r_HEMA=1.03) in contrast to Boc-Phe-EMA (r_Boc-Phe-EMA=0.48). Furthermore, the expulsion of the Boc-groups resulted copolymers with ionizable pendant primary ammonium and hydroxyl groups. To understand the glass transition behaviours of homo- and co-polymers, differential scanning calorimetric (DSC) measurements were carried out. The effect of HEMA content on the pH-sensitivity of the copolymers in aqueous medium was investigated through turbidity measurements. Finally, the counteranion exchange from trifluoroacetate to chloride provided copolymers with enhanced water solubility and unaltered phase transition pH.     

PHOTOPOLYMERS: SYNTHESIS AND CHARACTERIZATION OF POLY(4-CINNA-MOYLPHENYL METHACRYLATE) WITH GLYCIDYL METHACRYLATE

Copolymers of 4-cinnmoylphenyl methacrylate (CPMA) with glycidyl methacrylate were synthesized in methyl ethyl ketone solution using benzoyl peroxide as initiator at 70 ± 1°C. They were characterized by UV, IR, ¹H-NMR, and ¹³C-NMR spectra. Their compositions were determined by ¹H-NMR technique. The monomer reactivity ratios were determined by the Fineman-Ross and Kelen-Tüdös methods. The molecular weights ([Mbar]_w and [Mbar]_n) of the polymers were determined by GPC technique. Thermogravimetric analysis of the copolymers were carried out in air. The T_g of the polymers were determined by differential scanning calorimetry. The photocrosslinking properties of the homo and copolymers were also discussed.     

Synthesis,Characterization, and Reactivity Ratios of Phenyl Methacrylate-N-vinyl-2-pyrrolidone Copolymers

Free radical solution copolymerization of phenyl methacrylate and N-vinyl-2-pyrrolidone was carried out using benzoyl peroxide in 2-butanone solution at 70°C. The composition of the copolymer was determined using ¹H-NMR spectra by comparing the intensities of aromatic protons to that of total protons. The results were used to calculaie the copolymerization reactivity ratios by both the Fineman-Ross (F-R) and Kelen-Tüdös (K-T) methods. The reactivity ratios are r ₁ = 4.49 ± 1.27 and r ₂ = 0.05 ± 0.09 as determined by the K-T method. These values are in good agreement with those determined by the F-R method. The FT-infrared and ¹³C-NMR spectra of the copolymer are discussed.     

Synthesis and characterization of trans-1,4-butadiene/isoprene copolymers: Determination of monomer reactivity ratios and temperature dependence

A series of trans-1,4-butadiene/isoprene copolymers were prepared using the catalyst system TiCl4/MgCl2-Al(iBu)3 with bulk precipitation technology at different temperatures. Monomers reactivity ratios were calculated based on the Kelen-Tüds(K-T) method and the Mao-Huglin(M-H) method. The influence of temperature on copolymer composition and polymerization rate was discussed in detail. The increase of reaction temperature brought the decrease of butadiene reactivity ratio rBd and supplied an effective adjustment on copolymers' composition distribution.     

Copolymers of 3-Methoxy-4-Acryloyloxy-Benzal Phenylimine with Methyl Methacrylate: Synthesis,Characterization and Monomer Reactivity Ratios

Abstract

Copolymers of 3-methoxy-4-acryloyloxybenzal phenylimine and methyl methacrylate with different feed ratios are synthesized in ethyl methyl ketone using benzoyl peroxide as a free radical initiator at 70 ± 1°CC. The polymers were characterized by IR and ¹H-NMR spectroscopic techniques. Copolymer compositions were determined by ^lH-NMR analysis of the polymers. The monomer reactivity ratios were determined by the application of conventional linearization methods such as Fineman-Rose and Kelen-Tüdös. The molecular weights M_n and M_w of the polymers and the poly-dispersity index were determined by gel permeation chroma-tography. The intrinsic viscosities and the thermal properties of the homo-and copolymers are also discussed.     

New Methacrylate Copolymers Based on the Benzofurane Ring: Synthesis,Characterization, Monomer Reactivity Ratios and Biological Activity

The free radical copolymerization of (5-bromo-1-Benzofuran-2-yl)(phenyl)-O-methacrylketoxime (BPMKO) with 2-(4-acetylphenoxy)-2-oxoethyl-2-methylacrylate(AOEMA) has been carried out in 1, 4-dioxane at 65°C ± 1 and was analyzed by Fourier transform infrared, ¹H-NMR, ¹³C-NMR and gel permeation chromatography. Elemental analysis was used to determine the molar fractions of BPMKO and AOEMA in the copolymers. The monomer–reactivity ratios were calculated according to the general copolymerization equation using Kelen-Tüdõs and Finemann-Ross linearization methods. The reactivity ratios indicated a tendency toward random copolymerization. The polydispersity indices of the polymers were determined by gel permeation chromatography and suggested a strong tendency for chain termination by disproportionation. The thermal behaviors of copolymers with various compositions were investigated by differential scanning calorimetry and thermogravimetric analysis. The glass-transition temperature of the copolymers increased with increasing BPMKO content in the copolymers. All the products showed moderate activity against different strains of bacteria and fungi.     

Organotin polymers—II.Copolymerization parameters for tributyltin methacrylate with methyl acrylate,ethyl acrylate,butyl acrylate and acrylonitrile

Copolymerizations of tributyltin methacrylate (M₁) with methyl acrylate, ethyl acrylate, n-butyl acrylate and acrylonitrile were carried out in solution at 70° using azobisisobutyronitrile as initiator. Copolymer compositions were determined by tin analysis; monomer reactivity ratios were calculated by Fineman-Ross and Kelen-Tüdös methods. The reactivities of acrylic esters decrease as the alkyl group becomes bulkier. Azeotropic copolymers could be formed from tributyltin methacrylate with butyl acrylate and with acrylonitrile. The structures of M₁ and its azeotropic copolymers have been investigated by infrared spectroscopy.     

Copolymers of 7-Methoxy-2-Acetyl Benzofuryl Methylmethacrylate With Styrene: Synthesis,Characterization, Reactivity Ratios and Determination of Kinetic Parameters With Thermogravimetric Analysis

The 7-methoxy-2-acetyl benzofuryl methylmethacrylate (MABMM) monomer was synthesized by reacting 7-methoxy-2-bromo acetyl benzofurane with sodium methacrylate in acetonitrile solvent at 70°C in the presence of triethylbenzylammoniumchloride (TEBAC). The monomer was characterized by FTIR, ¹H-and ¹³C-NMR spectral studies. Reactivity ratios for the copolymers 7-methoxy-2-acetyl benzofuryl methylmethacrylate (MABMM)-co- styrene (ST) are reported. Copolymers were prepared by free radical polymerization using 2,2′-azobisisobutyronitrile (AIBN) as an initiator at 70°C in 1,4-dioxane solution. FTIR, ¹H-and ¹³C-NMR spectral studies and gel permeation chromatography (GPC) were used the copolymer characterization. The monomer compositions in the copolymer were determined by elementel analyses and the reactivity ratios (ri) were calculated applying diverse linear methods, namely Finemann-Ross (FR) and Kelen-Tüdös (KT) and the nonlinear error invariable model method of a computer program RREVM. By using the latter pr°Cedure, the values of the reactivity ratios were estimated as 2.74 and 0.69 for the system MABMM (1) and ST (2), respectively. These values suggest the formation of nearly-alternating copolymers in the systems. Molecular weights were determined by gel permeation chromatography (GPC). The polydispersity indices of the polymers determined using suggest a strong tendency for chain termination by disproportionation. The glass transition temperature of the polymers were investigated by Shimadzu DSC-60 and the apparent thermal decomposition activation energies (E_d) were calculated by the Ozawa method using the Perkin-Elmer TGA thermobalance, respectively. Tg increases when the concentration of polar monomer (MABMM) in the copolymer increases. It was observed that thermal stabilities of copolymers increased with increasing of MABMM content in copolymers.     

MONOMER REACTIVITY RATIO AND THERMAL PERFORMANCE OFα-METHYL STYRENE AND GLYCIDYL METHACRYLATE COPOLYMERS

<正>Synthesis and characterization of the copolymers(PAG) ofα-methyl styrene(AMS) and glycidyl methacrylate (GMA) are presented.The copolymers of PAG were characterized by gel permeation chromatography(GPC),Fourier transform infrared spectroscopy(FTIR),nuclear magnetic resonance(~1H-NMR) and thermogravimetery(TG).Based on the copolymer compositions determined by ~1H-NMR,the reactivity ratios of AMS and GMA were found to be 0.105±0.012 and 0.883±0.046 respectively by Kelen-Tüds method.TG revealed that thermal stability of the copolymers decreased with increasing the AMS content in the copolymers,which indicated that the degradation was mainly caused by the chain scission of AMS-containing structures.Under heating,the copolymers depolymerize at their weak bonds and form chain radicals, which could further initiate other chemical reactions.     

Copolymerization of styrene and acrylonitrile with functional silanes

Styrene has been copolymerized to high conversions with vinylmethyl diacetoxysilane (VMDAS) and vinylmethyldiethoxysilane (VMDES) in bulk and in toluene at 60 using azobisisobutyronitrile (AIBN) as initiator. Acrylonitrile has also been copolymerized with VMDAS at 50 in bulk using AIBN. The compositions of the copolymers were determined from the silicon contents; reactivity ratios were calculated by the Kelen-Tüdös method. The reactivity ratio r₁ (styrene) is higher for styrene-VMDES than for styrene-VMDAS, indicating higher reactivity of VMDAS towards polystyryl radical. VMDAS was found to be more reactive towards the polyacrylonitrile than towards the polystyrene radical. The influences of the silicon comonomer on properties such as intrinsic viscosity, solubility, molecular weight distribution and thermal behaviour were also studied.     

Novel Copolymer of Diisopropyl Fumarate and Benzyl Acrylate Synthesized Under Microwave Energy and Quasielastic Light Scattering Measurements

Microwave assisted free radical copolymerization of diisopropyl fumarate (DIPF) and benzyl acrylate (BzA) with different copolymer compositions was performed using benzoyl peroxide as initiator. The effect of the reaction conditions on the macromolecular characteristics, monomer reactivity ratio and copolymer properties were studied. The monomer conversion and average molecular weights increase with the content of BzA units in the copolymer. The copolymers were characterized by IR, ¹H and ¹³C-NMR spectroscopies and the molecular weights were analyzed with size exclusion chromatography (SEC). The reactivity ratios obtained from an extended Kelen-Tüdös method under microwave irradiations are a factor which is double than those obtained by thermal copolymerization. The product r₁r₂ = 0.152 suggests a preference of both propagating macroradicals toward consecutive homopolymerization. The hydrodynamic and polydispersity size were measured in ethylacetate, tetrahydrofuran and methylethylketone with a quasi-elastic light scattering (QELS) technique showing that the quality of the solvents increases in the order: EA < THF < MEK.     

Novel Copolymers of N‐(4‐Bromophenyl)‐2‐Methacrylamide with 2‐Acrylamido‐2‐Methyl‐1‐Propanesulfonic Acid

The new acrylamide monomer, N‐(4‐Bromophenyl)‐2‐methacrylamide (BrPMAAm) has been synthesized by reacting 4‐Bromoaniline with methacryloyl chloride in the presence of triethylamine(NR₃) at 0–5°C. The radical‐initiated copolymerization of (BrPMAAm), with 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (AMPS) has been carried out in dimethylformamide (DMF) solution at 70±1°C using 2,2′‐azobisisobutyronitrile (AIBN) as an initiator with different monomer‐to‐monomer ratios in the feed. The copolymers were characterized by FTIR, ¹H‐ and ¹³C‐NMR spectroscopy. The copolymer composition was evaluated by nitrogen content (N for AMPS‐units) in polymers led to the determination of reactivity ratios. The monomer reactivity ratios for BrPMAAm (M₁)‐AMPS (M₂) pair were computed using the Fineman‐Ross (F‐R), Kelen‐Tüdös (KT) and Extended Kelen‐Tüdös (EKT) methods. These parameters were also estimated using a non‐linear computational fitting procedure, known as reactivity ratios error in variable model (RREVM). The mean sequence lengths determination indicated that the copolymer was statistically in nature. By TGA and DSC analyses, the thermal properties of the polymers have been studied. The antimicrobial effects of polymers were also tested on various bacteria, and yeast.     

Synthesis and Characterization of New Schiff Bases 2-(2-(2-(Aryl)Methyleneamino)Phenylthio) Ethylthio)-N-((aryl)Methylene)Benzeneamine

A series of Schiff bases containing four to six coordination sites N₂S₂ X₂(X = O,N) 2-(2-(2-(aryl)methyleneamino)phenylthio)ethylthio)-N-((aryl)methylene)benzeneamine (2c–f) were prepared from the reaction of 1,2-di(2-aminophenylthio)ethane (1) with aromatic aldehydes. All compounds were characterized by means IR, mass, ¹H and ¹³C NMR spectroscopy, and elemental analysis, and in the case of 2b with a single crystal X-ray diffraction. The X-ray crystal structure of 2b showed that the resonance occurs between aromatic rings, through the C=N bonds of the molecule.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Copolymers of 2‐(3‐(6‐tetralino)‐3‐methyl‐1‐cyclobutyl)‐2‐Hydroxyethyl Methacrylate with Acrylonitrile and 4‐Vinylpyridine: Synthesis,Characterization, and Monomer Reactivity Ratios

The copolymerization of 2‐(3‐(6‐tetralino)‐3‐methyl‐1‐cyclobutyl)‐2‐hydroxyethyl methacrylate (TCHEMA), monomer with acrylonitrile and 4‐vinylpyridine were carried out in 1,4‐dioxane solution at 65°C using AIBN as an initiator. The copolymers were characterized by FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopic techniques. Thermal properties of the polymers were also studied by thermogravimetric analysis and differential scanning calorimetry. The copolymer compositions were determined by elemental analysis. The monomer reactivity ratios were calculated by the Fineman‐Ross and Kelen‐Tüdös method. Also, the apparent thermal decomposition activation energies were calculated by the Ozawa method with a Shimadzu TGA 50 thermogravimetric analysis thermobalance.     

Synthesis and characterization of novel polymer-drug conjugate based on the anhydride containing copolymer as a potential method for drug carrier

5-Fluorouracil (5FU) is in clinical use as an antitumor agent for the treatment of several types of solid tumors and cancers. However, development of drug resistance within the tumor cells and side effects has been a major limitation for the clinical use of 5FU. Preparation polymer-5FU conjugation is a promising potential antitumor drug and alternative pathway that could be used to treatment of cancer. For this purpose, water soluble poly(maleic anhydride-alt-N-vinyl pyrrolidone)[Poly(MA-alt-NVP)] is synthesized via charge transfer complex (CTC) copolymerization with benzoyl peroxide as an initiator at 80°C under nitrogen atmosphere. CTC mechanism is formed between through MA and NVP by determined using Uv-vis spectroscopy. Molar absorption coefficient (?^AD) and equilibrium constant (K^AD) of the complex are determined by Scott equation. The results obtained from indicate that copolymerization of MA:NVP system is preceded via alternating mechanism. The compositions of synthesized copolymers are also investigated by elemental analysis and the reactivity ratios of these monomers are calculated by using the elemental analysis data through Kelen-Tüdös, Mayo-Lewis, Fineman-Ross and Inverted Fineman-Ross equations. For preparation of polymer-drug conjugate, chemical modification is employed between the copolymer and 5FU. Polymer-drug conjugate and conjugation mechanism are enlightened by ATR-FTIR, NMR, HR-Raman and XRD methods.     

Copolymerization of methacrylonitrile with p-methylstyrene

Methacrylonitrile was copolymerized with p-methylstyrene in methyl ethyl ketone at 80°C initiated by azobisisobutyronitrile. Monomer reactivity ratios of methacrylonitrile and p-methylstyrene were found to be 0.205 and 0.377, respectively, using the Kelen-Tüdos method. Triad fractions and monomer sequence lengths of three copolymers were determined from ¹³C-NMR spectra and were found to be in good agreement with those calculated from reactivity ratios. © 1994 John Wiley & Sons, Inc.     

Complex-radical terpolymerization of phenanthrene,maleic anhydride,and trans-stilbene

The radical terpolymerization of the donor-acceptor-donor monomer system, phenanthrene (P)—maleic anhydride (M)—trans-stilbene (S), was studied. These monomers are known to be nonhomopolymerizable. The terpolymerization was carried out in p-dioxane and/or toluene at 70°C in the presence of benzoyl peroxide used as the initiator. P and S were found to form charge transfer complexes (CTC) with M in p-dioxane at 35°C. The results obtained are discussed in terms of the free monomer and complex propagation models. It is shown that terpolymerization is carried out at a stage close to binary copolymerization of two complexomers. The reactivity ratio of P … M and S … M complexes was estimated by the Kelen-Tüdös method. Absorbance ratios at 1770 cm^?1 (v_C=0 of anhydride group), 764 cm^?1 (δ_CH in monosubstituted benzene of S), and 820 cm^?1 (δ_CH in disubstituted benzene of P) as a function of terpolymer composition were established. P—M—S terpolymers are shown to have high thermal stabilities. © 1995 John Wiley & Sons, Inc.     

Copolymerization of N-Vinylcarbazole with 2-Dimethylaminoethyl Methacrylate

The thermal copolymerization of N-vinylcarbazole (VCz) with 2-dimethylaminoethyl methacrylate (DMAEM) initiated by α,α′-azobisisobutyronitrile (AIBN) in solution in tetrahydrofuran at 60°C has been studied. Different compositions of copolymer were prepared and characterized by UV, IR, and ¹H-NMR spectroscopy, viscosity measurements, and thermal studies. The estimation of the composition of VCz and DMAEM in the copolymer was carried out by UV spectroscopy. The reactivity ratio of VCz (r ₁) and DMAEM (r ₂) was determined by the methods of Mayo and Lewis, Kelen and Tüdös, and Tidwell and Mortimer.