Monomer Reactivity Ratios R1 Research Articles

Synthesis and evaluation of new cationic polymeric surfactant based on N-phthalimidomethyl methacrylate

In our previous work N-phthalimidomethyl methacrylate (NPMMA) monomer was prepared through the reaction of N-hydroxymethyl phthalimide with methacrylic acid in the presence of N, N-dicyclohexylcarbodiimide (DCCI) as a condensing agent. Then a new series of copolymers containing imidazole have been synthesized through the reaction of NPMMA monomer with 1-vinylimidazole (VIM) in the presence of benzoyl peroxide as initiator. The copolymer composition was determined by 1H NMR spectroscopy and the values of monomer reactivity ratio (r1= 0.756, r2= 1.033, and r1r2= 0.781) were calculated through Fineman Ross and Kelen-Tudos methods. Conversion of copolymers to surfactants was achieved through quaternization of the imidazole nitrogen with dimethyl sulphate. The chemical structure of the produced monomer, copolymers, co-polymeric surfactants was confirmed by spectroscopic tools. The surface properties included surface tension, foaming power, emulsion stability, critical micelle concentration (CMC) have been measured in aqueous medium by traditional procedures. Also the different air/ water interface parameters including effectiveness (πcmc), efficiency (Pc20), maximum surface excess (Γmax) and minimum surface area (Amin) were also recorded. Moreover, the biodegradability for these cationic surfactants has been investigated and their D % was ranged from 67 to 100 %.

Copolymerization of N-Tert-Butylacrylamide (NTB) and 7-Methacryloyloxy-4-Methyl coumarin (MAMC): Synthesis and characterization

Copolymers of various feed ratio of N-tert-butylacrylamide (NTB) and 7-methacryloyloxy-4-methyl coumarin (MAMC) were prepared by free radical solution polymerization in DMF at 70 °C using AIBN as an initiator. Synthesised copolymers were characterized and copolymer compositions were obtained by 1H NMR analysis data. By using Fineman-Ross, Kelen-Tudos and extended Kelen-Tudos methods, monomer reactivity ratios (r1 and r2) were calculated. Mean sequence lengths of the copolymers were estimated from monomer reactivity ratio (r1 and r2) values. Thermal characterizations of the copolymers were carried out using thermogravimetric analysis. The antimicrobial effects of obtained copolymers were also tested on various bacteria, and fungi.

Accurate density functional theory (DFT) protocol for screening and designing chain transfer and branching agents for LDPE systems

This work emphasizes the importance of considering multiple reaction pathways when estimating the rate parameters for free radical polymerization using DFT.

Synthesis and Free Radical Copolymerization of a Vinyl Monomer from Soybean Oil

A one-step method that converts soybean oil into (acryloylamino)ethyl soyate, a new vinyl monomer of free radical polymerization, was developed. The synthesized monomer combines a vinyl double bond (acryloyl functional group) and nonconjugated (isolated) double bonds of fatty acids. The double bond of the acryloyl group is reactive in a free radical chain polymerization that yields linear macromolecules containing isolated double bonds in side chains. Monomer reactivity ratios (r1, r2) in copolymerization of the new soybean oil-based acrylic monomer (SBA) with styrene, methyl methacrylate, and vinyl acetate, as well as the Q–e parameters of the SBA, were determined. The obtained results indicate that copolymerization can be described with the classical Mayo–Lewis equation. In terms of polymerizability, the SBA can be classified as an acrylic monomer. The double bonds of the fatty acid chains remain mainly unaffected during the free radical polymerization. The remaining unsaturated fragments in the side ch...

Synthesis and Characterization of Homo- and Copolymers of N-4-Azodiphenyl Maleimide with Methyl Methacrylate and Styrene

The synthesis and free radical homopolymerization of N-4-azodiphenylmaleimide (ADPMI) and copolymerization of methyl methacrylate (MMA) and styrene (ST) with ADPMI using an AIBN initiator were performed in THF solvent at 70°C. A series of copolymers, ADPMI-MMA and ADPMI-ST, were prepared using different feed ratios of comonomers. The polymer samples have been characterized by solubility tests, intrinsic viscosity measurements, FT-IR, 1H-NMR spectral analysis, and thermo-gravimetric analysis. The values of monomer reactivity ratios r1 and r2 determined by Fineman-Ross and Kelen-Tudos methods are 0.16 and 0.63, and 0.26 and 0.25 in ADPMI/MMA and ADPMI/ST systems, respectively. Alfrey-Price Q-e values for ADPMI are Q = 2.27 and e = 1.92, and 0.41 and 1.949 for ADPMI/MMA and ADPMI/ST systems, respectively. It was found that the initial and final decomposition temperatures increased with the increase of ADPMI content in the copolymer samples.

Electropolymerization kinetics of a binary mixture of o‐phenylenediamine and 2‐aminobenzothiazole and characterization of the obtained polymer films

AbstractPoly(o‐phenylenediamine‐co‐2‐aminobenzothiazole), P(oPD‐co‐2ABT), has been synthesized electrochemically from an aqueous acid medium. The initial rate of electrocopolymerization reaction on platinum electrode is small, and the rate law is Rate = KE [Na2SO4]0.48 [HCl]1.09 [M]2.08. The apparent activation energy (Ea) is found to be 57.44 kJ mol−1. The polymer films obtained have been characterized by cyclic voltammetry, X‐ray diffraction, elemental analysis, TGA, scanning electron microscopy, and IR‐spectroscopy. The mechanism of the electrochemical polymerization reaction has been discussed. The monomer reactivity ratios (r1 and r2) were calculated using Fineman‐Röss method. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

A New Acrylamide-Based Peroxide Monomer: Synthesis and Copolymerization with Octyl Methacrylate

N-[(tert-Butylperoxy)methyl]acrylamide (tBPMAAm), a new peroxide monomer containing a primary-tertiary peroxide group, was synthesized and employed for radical copolymerization with octyl methacrylate (OMA) to yield a novel functional polyperoxide (FPP). Copolymerization kinetics were analyzed to find tBPMAAm and OMA monomer reactivity ratios (r1, r2) and Q − e values. Kinetic characteristics provide a way to control FPP composition and its reactivity in radical processes. It is expected that the developed functional polyperoxide containing long alkyl fragments provides an affinity to polymeric surface. At the same time, since the peroxide groups readily decompose at elevated temperatures, the FPP can be used as a macroinitiator of radical polymerization. As a result, we expect that in the future the FPP will be applied as an efficient modifier of the polymeric surface.

Cyclohexyl Methacrylate with Tetra (Ethylene Glycol) Dimethacrylate in Tertahydrofuran Radical Copolymerization

Free-radical copolymerization of cyclohexyl methacrylate (CHMA) and tetra (ethylene glycol) dimethacrylate (TtEGDMA) were carried out at 60 °C in tetrahydrofuran solution in presence of 2,2-azobisisobutyronitrile. The random copolymers were prepared with nominal crosslinking ratios, X of 1, 5 and 10% mol TtEGDMA / mol CHMA. The copolymers were characterized by 13C NMR spectroscopy. The copolymers was characterized by 13C RMN analysis and determined the copolymers composition. The monomer reactivity ratios r1 (TtEGDMA) and r2 (CHMA) were determined with the linearized copolymerization equations of the Fineman–Ross methods (r1 = 1.77 and r2 = 0.48) and Kelen–Tüdös (r1 = 1.81 and r2 = 0.46). Parameters of Alfrey-Price Q1 = - 1.10 (specific activity) and e1= - 0.64 (polarity) for TtEGDMA.

Electropolymerization kinetics of a binary mixture of pyrrole and o‐aminobenzoic acid and characterization of the obtained polymer films

AbstractPoly (pyrrol‐co‐o‐aminobenzoic acid) has been synthesized electrochemically from an aqueous acid medium. The initial rate of electrocopolymerization reaction on platinum electrode is small and the rate law is: Rate = K2 [D]1.02[HCl] 1.44[M]2.00. The apparent activation energy (Ea) is found to be 90.11 kJ mol−1. The polymer films obtained have been characterized by cyclic voltammetry, X‐ray diffraction, elemental analysis, thermogravimetric analysis, scanning electron microscopy, 1H NMR, and IR‐spectroscopy. The mechanism of the electrochemical polymerization reaction has been discussed. The monomer reactivity ratios (r1 and r2) were calculated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Bioengineering functional copolymers: synthesis and characterization of poly(N-isopropyl acrylamide-co-3,4-2H-dihydropyran)s

Novel bioengineering copolymers were synthesized by radical copolymerization of N-isopropylacrylamide (NIPA) and 3,4-2H-dihydropyran (DHP) with 2,2′-azobisisobutyronitrile as an initiator in acetone solution at 70 °C under nitrogen atmosphere. Structure, tacticity and compositons of the copolymers prepared in a wide range of monomer feed were confirmed by FTIR, 1H{13C} NMR-DEPT and elemental analyses. The monomer reactivity ratios (r1 and r2) were detected using known two methods: r1 (NIPA) = 1.25 and r2 = 0.035 (DHP), and r1 (NIPA) = 0.97 and r2 = 0.022 (DHP) by Kelen-Tudos and Jaacks methods, respectively. It was demonstrated that the studied monomer pair has a tendency to form H-bonding beween amide/ether groups through −NH...O< complexation which played an important role in the stereoselective chain growth, and significant decrease of allyl degradative chain transfer reactions. This phenomenon is also confirmed by the observed relatively high molecular weights of copolymers (Mv). The synthesized water-soluble stimuli-responsive poly(NIPA-co-DHP)s exhibit thermal stability, higher glass-transition temperature, polyelectrolyte, pH- and temperature-sensitive behavior and can be attributed to the class of bioengineering functional copolymers useful for various bio- and gene-engineering, and drug delivery applications.

Electrocopolymerization of a Binary Mixture of 2-chloroaniline and 2-amino-4-(4-methoxyphenyl) thiazole

Electropolymerization of a binary mixture of 2-chloroaniline and 2-amino-4-(4-methoxyphenyl) thiazole on platinum electrode in acid medium was carried out under varying reaction conditions as temperature, current density, hydrochloric acid, and monomer concentrations with duration time. The initial rate of the electrocopolymerization reaction was small and the rate law was RP = K2[D]0.92[HCl]0.98[M]1.93. The apparent activation energy (Ea) was found to be 57.34 kJ mol−1. The obtained copolymer films were characterized by 1HNMR, elemental analysis, GPC, IR, UV-visible, and cyclic voltammetry compared with those of the two homopolymers. The mechanism of the electrocopolymerization reaction had been also discussed. The monomer reactivity ratio (r1 and r2) was calculated. The thermogravimetric analysis (TGA) was used to confirm the proposed structure and determination of the number of water molecules in the copolymeric chain unit. X-ray and scanning electron microscopic analysis were used to investigate the surface morphology.

Preparation, characterization, and thermal properties of hydrophilic copolymers: p‐chlorophenylmaleimides with hydroxylethyl methacrylate and β‐methyl itaconate

AbstractThis work describes the synthesis, characterization, and thermal behavior of copolymers of p‐chlorophenylmaleimide (Cl‐PhMI) with β‐methyl itaconate (β‐MHI) and 2‐hydroxyethyl methacrylate (HEMA). Copolymerization was carried out with a radical initiator by varying the feed mole fraction of Cl‐PhMI from 0.25 to 0.75. The copolymer composition was determined from the N/C ratio based on elemental analysis data and with 1H NMR spectroscopy for poly(Cl‐PhMI‐co‐HEMA) using a proton signal attributed to the CH3 of HEMA (δ = 0.7–1.4 ppm) and the area of aromatic ring protons (δ = 7.2–7.8 ppm), where the proton/area relationship confirmed the copolymer compositions calculated by elemental analysis. The monomer reactivity ratios r1 and r2 were determined using the Kelen–Tüdös method. These values demonstrated that copolymerization produced random copolymers with an alternation tendency. The molecular weight and polydispersity were also determined. The thermal behavior can be correlated with the copolymer composition. An increase of the thermal decomposition temperature occurred when the content of Cl‐PhMI increased. The glass transition temperature and thermal stability of poly(β‐MHI) or poly(HEMA) increased with an increasing amount of Cl‐PhMI in the polymer backbone. Copyright © 2007 Society of Chemical Industry

Free Radical Copolymerization of Methyl Methacrylate and Styrene with N-(4-Carboxyphenyl)maleimide

The free radical copolymerization of methyl methacrylate (MMA) or styrene (St) with N-(4-carboxyphenyl)maleimide (CPMI) was carried with AIBN as an initiator in THF solvent at 80°C. A series of copolymers of MMA and St with CPMI were prepared using different feed ratios of comonomers. The values of monomer reactivity ratios (r1, r2) determined by Fineman-Ross and Kelen-Tudos methods are 0.26 and 2.51 in the CPMI/MMA system and 0.08 and 0.22 in the CPMI/St system. Alfrey–Price Q-e values for CPMI were calculated as Q = 1.05 and e = 0.41 in the CPMI/MMA system and Q = 1.21 and e = 0.91 in the CPMI/St system. The polymer samples have been characterized by solubility tests, intrinsic viscosity measurements, FT-IR and 1H-NMR spectral analysis, and thermo-gravimetric analysis. It was found that the initial and final decomposition temperatures increased with increasing the amount of CPMI in the copolymer. The integral procedural decomposition temperature and energy of activation of thermal degradation have also been reported.

Copolymerization of Methyl Methacrylate, Ethyl Acrylate, and Butyl Acrylate with N-2-Anisylmaleimide and Characterization of the Copolymers

The free radical copolymerizations of methyl methacrylate (MMA), ethyl acrylate (EA), and butyl acrylate (BA) with N-2-Anisylmaleimide (AMI), initiated by AIBN, were performed in THF solvent at 65°C. A series of copolymers of AMI-MMA, AMI-EA, and AMI-BA were prepared using different feed ratios of comonomers. The polymer samples have been characterized by solubility tests, intrinsic viscosity measurements, FT-IR, and 1H-NMR spectral analysis, and thermo-gravimetric analysis. The values of monomer reactivity ratios r1 and r2 determined by Fineman-Ross and Kelen-Tudos methods are 0.43 and 0.42 in AMI/MMA, 0.72 and 0.62 in AMI/EA and 0.76 and 0.72 in AMI/BA systems. Alfrey-Price Q-e values for AMI are Q = 3.13 and e = 1.71 in AMI/MMA, Q = 1.10 and e = 1.46 in AMI/EA and Q = 1.02 and e = 1.63 in AMI/BA systems. It was found that the initial and final decomposition temperature increased with increasing the component of AMI in the copolymer.

Synthesis and Radical Copolymerization of Ethyl Acrylate and Butyl Acrylate with N-[4-N'-(Phenylamino-carbonyl) phenyl] maleimide

Radical copolymerization of ethyl acrylate (EA) and butyl acrylate (BA) with 4-maleimidobenzanilide (MB), that is N-[4-N′-(phenylaminocarbonyl)phenyl]maleimide, initiated by AIBN was performed in THF solvent at 65°C. Nine copolymer samples of each type were prepared using different feed ratios of comonomers. All the polymer samples have been characterized by solubility test, intrinsic viscosity measurements, FT-IR and 1H-NMR spectral analysis, and thermo-gravimetric analysis. The values of monomer reactivity ratios r1 and r2 are 1.13 and 0.48 in MB/EA system and 0.45 and 0.52 MB/BA system. Alfrey-Price Q-e values for MB were Q = 1.31 and e = 1.33 in MB/EA and Q = 2.04 and e = 2.06 in MB/BA systems. The initial decomposition temperature of copolymer samples were in the range 310 to 365°C.

Electrocopolymerization of a binary mixture of pyrrole and 2‐amino‐4‐phenylthiazole: Kinetic studies, copolymer structure, and applications as corrosion protection for mild steel in acid medium

AbstractElectrochemical copolymerization of a binary mixture of pyrrole and 2‐amino‐4‐phenylthiazole on platinum electrode in acid medium was carried out. The kinetic parameters were calculated using ex situ microgravimetric and electrochemical data. The experimentally obtained kinetic equations were RP,W = kW [acid]1.16 [monomer]1.85 from microgravimetric data and RP,E = kE [acid]1.1 [monomer]1.9 from the values of the anodic current density using cyclic voltammetry technique. The apparent activation energy was calculated by the two techniques and is found to be 32.55 and 29.6 kJ/mol from microgravimetric and electrochemical data respectively. The monomer reactivity ratios (r1 and r2) were calculated according to Fineman–Ross method and the copolymer structure was determined from the obtained data, which is found to be a block copolymer structure. The applications of the prepared copolymer as corrosion protection of mild steel in acid medium are studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 4047–4058, 2007

Some monomer reactivity ratios of styrene and (meth)acrylates in the presence of TEMPO

AbstractThe living free‐radical copolymerizations of styrene (St) with the polar monomers (methyl methacrylate (MMA), ethyl methacrylate (EMA), butyl methacrylate (BMA), methyl acrylate (MA), ethyl acrylate (EA), butyl acrylate (BA), 2‐hydroxyethyl acrylate (HEA), and vinyl acetate (VAc)) mediated by TEMPO and BPO as initiator at 125°C had been analyzed by 1H NMR and gel permeation chromatography (GPC). The data from GPC showed that the polydispersities of the resulted copolymers were below 1.5, and the rate of polymerization increased, while the polydispersity declined with increase in St molar fraction in the feed. Monomer reactivity ratios had been determined by expanded Kelen–Tüdos method. rSt = 1.32, rMA = 0.14; rSt = 1.17, rEA = 0.23; rSt = 0.83, rBA = 0.20; rSt = 0.74, rMMA = 0.25; rSt = 0.76, rEMA = 0.30; rSt = 1.27, rBMA = 0.59; rSt = 1.67, rVAc = 1.05; and rSt = 0.28, rHEA = 0.43. In the copolymerization of St with acrylates the monomer reactivity ratio r1 (St) decreases and in the copolymerization of St with methacrylates the monomer reactivity ratio r1 (St) increases while the length of the substituted group increases. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3531–3535, 2006

Instantaneous Copolymer Composition in High Conversion Copolymerization of Acrylonitrile and Methyl Acrylate Assessed by in Situ 13C NMR Measurements of Individual Monomer Reaction Rates

The copolymerization of acrylonitrile with methyl acrylate initiated by azobis(isobutyronitrile) in dimethyl sulfoxide at 60 °C has been investigated to high conversion using in situ 13C NMR spectroscopy. The focus has been on the relative rates of individual monomer consumption as a function of time up to as high a conversion as experimentally feasible. It has been found that the relative rates of monomer consumption, i.e., the instantaneous copolymer composition, cannot be described by the low conversion values of the monomer reactivity ratios r1 and r2. These findings are discussed within the framework of possible effects of monomer diffusion rates and explicit penultimate unit effects in connection with monomer composition drift.

Synthesis of novel polymethacrylate bearing an (S)-(+)-1-cyclohexylethyl urea group in the side chain and its chiral recognition ability

A new chiral methacrylate, (S)-(+)-1-cyclohexylethyl-(2-methacryloyloxyethyl)urea (CEMOU), was synthesized from 2-methacryloyloxyethyl isocyanate (MOI) and (S)-(+)-cyclohexylethylamine. Radical homopolymerization of CEMOU was performed in several solvents to obtain the corresponding chiral polymers having hydrogen bonds based on urea moieties. Specific optical rotations of poly(CEMOU) were slightly changed by the measurement temperature, which may be attributed in part to a change of conformation caused by hydrophobic interaction between the cyclohexyl groups. From the results of radical copolymerization of CEMOU (M1) with styrene (ST, M2) or methyl methacrylate (MMA, M2), monomer reactivity ratios (r1, r2) and Alfrey–Price Q–e values were determined: r1 = 0.89, r2 = 0.12, Q1 = 2.45, e1 = 0.68 for the CEMOU–ST system; r1 = 0.48, r2 = 0.18, Q1 = 8.39, e1 = 1.97 for the CEMOU–MMA system. The chiroptical property of the poly(CEMOU-co-ST) was slightly influenced by the co-units. Poly(CEMOU)-bonded silica gel as the chiral stationary phase (CSP) was prepared for high-performance liquid chromatography (HPLC). The CSP resolved trans-2-dibenzyl-4,5-di(o-hydroxyphenyl)-1,3-dioxolane in normal phase such as n-hexane/2-propanol by HPLC. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1018–1025, 2003

Synthesis and Polymerization of Novel Quinone Methide Ketals

Novel quinone methide ketals, 8-[ 1'-cyano-1'-(ethoxycarbonyl)methylene]-l,4-dioxaspiro[4.5]deca-6,9-diene (1a) and 8-(1',l'-dicyanomethy1ene)-1,4-dioxaspiro[4.5]deca-6,9-diene (1b), were synthesized, and their polymerization behavior was investigated. Polymerizations of 1a and 1b initiated with BPO and BF3·Et2O gave corresponding novel ring-opening polymers, but no polymerization with BuLi. Copolymerization of 1a with St in the presence of AIBN at 60 °C gave the monomer reactivity ratios r1(1a) = 0.50 ± 0.1 and r2(St) = 0.1 ± 0.02, and Q and e values of 1a were 2.46 and +0.93, indicating that 1a is a highly conjugative, electron-accepting monomer. Homopolymers of 1a and 1b had better thermal stability than that of 7-cyano-7-(ethoxycarbonyl)- 1,4-benzoquinone methide.