Spontaneous copolymerization of 1-(2-hydroxyethyl)aziridine with N-phenylmaleimide and p-methoxyphenylmaleimide

Summary The copolymerization of 1-(2-hydroxyethyl)aziridine as nucleophilic monomer with N-phenylmaleimide and p-methoxyphenylmaleimide as electrophilic monomer in the absence of an initiator in solution was investigated. Copolymerizations under different experimental conditions were carried out. The copolymers were characterized by FT-IR and ¹H-NMR spectroscopy. The copolymer compositions were determined by elemental analysis and ¹H-NMR spectroscopy. Almost all products are statistical copolymers.     

Copolymerization without initiator of 1-(2-hydroxyethyl)aziridine and acrylamide

Summary 1-(2-Hydroxyethyl)aziridine as nucleophilic monomer was copolymerized in the absence of an initiator under various experimental conditions with acrylamide as electrophilic monomer. All copolymers were characterized by elemental analysis, IR, and ¹H-NMR spectroscopy. The viscosity measurements showed that the copolymers behave as polyelectrolytes. The copolymer composition was determined from elemental analysis and ¹H-NMR spectra.     

Free Radical Solution Copolymerization of n-Octylacrylamide and Maleic Anhydride in a Non Polar Solvent; Synthesis and Characterization of a Difunctional Copolymer

Summary A novel difunctional random copolymer of maleic anhydride (MA) and n-octylacrylamide (acrylamide-n-octyl, AAO) with both anhydride and acrylamide moieties was synthesized. The copolymer had a molecular weight by SEC of between 950 and 1900 and a polydispersity of between 1.0 and 4.0. The performance of initiators azo-isobutyronitrile (AIBN) and benzoyl peroxide (BPO) at varying concentrations in solvent o-xylene were compared at four different initial MA:AAO ratios (7:3, 5:5, 6:4 and 4:6). The molecular weight of the synthesized copolymers at 7.5 mol % initiator concentration increased proportionally with the conversion at a 5:5 monomer ratio, whereas copolymerization at other initiator concentration and monomer ratios revealed a non-linear behavior. Characterization of monomer and copolymer on the basis of ¹H-NMR and ¹³C-NMR is also reported.     

“Spontaneous Copolymerization of p-Chlorophenylmaleimide with 2-Methylaziridine”

Abstract

p-Chlorophenylmaleimide as an electrophilic monomer was copolymerized in the absence of initiator with 2-methylaziridine as nuclephilic monomer. The copolymers were characterized by elemental analysis, FT-IR, and ¹H-NMR spectroscopy. The copolymer compositions were determined by chloro elemental analysis and ¹H-NMR spectroscopy. 2-Methylaziridine is more reactive than p-chlorophenylmaleimide yielding statistical copolymers. Mn, determined by vapor pressure osmometry, varied between 3.000 and 6.700 g/mol.     

Poly[N-(hydroxyethyl)ethyleneimine-co-phenyl succinic anhydride] Synthesis and structure

Summary Five copolymers from N-(hydroxyethyl)ethyleneimine as nucleophilic monomer and phenylsuccinic anhydride (PhSAn) as electrophilic monomer, were synthesized according to the spontaneous copolymerization concept. These copolymers were characterized by elemental analysis, FT-IR, ¹H-NMR, and ¹³C-NMR spectroscopy. The copolymer composition determined from the ¹H-NMR spectra showed that the copolymers are not alternating. According to all the data, it was suggested a copolymer structure which includes ester and anhydride bonds. The molecular weights determined by vapor pressure osmometry ranged between 5.100 and 6.100 g/mol. Received: 12 February 1999/Revised version: 5 October 1999/Accepted: 5 October 1999     

Reversible addition fragmentation chain transfer copolymerization: influence of the RAFT process on the copolymer composition

Reversible addition fragmentation chain transfer (RAFT) mediated and conventional copolymerizations at low monomer conversions have been carried out for the systems methyl methacrylate (MMA)-styrene, methyl acrylate (MA)-styrene and methyl methacrylate-butyl acrylate (BA). The polymer samples have been analyzed via ¹H-NMR spectroscopy to obtain the copolymer composition and the terminal model reactivity ratios. In the RAFT mediated copolymerizations, the polymer mole fraction of the monomer with the larger reactivity ratio is increased compared to the conventional copolymerization. Simulations have been carried out using the program package PREDICI^® to examine possible explanations for the experimental findings. The simulations demonstrate that the RAFT process itself may alter the macroradical populations and the copolymer composition by offering additional reaction pathways. Further, the rate coefficients for the initiation reaction and the pre-equilibrium play an important role in determining the copolymer composition. The rate coefficients governing the main equilibrium of the RAFT process have only a minor impact on the copolymer composition.     

Novel non-alternating copolymers synthesized by spontaneous copolymerization of p-chlorophenylmaleimide with 2-methyl-2-oxazoline

Summary The copolymerization of p-chlorophenylmaleimide (1) as electrophilic monomer with 2-methyl-2-oxazoline (2) as nucleophilic monomer without initiator in solution under different experimental conditions was investigated. Copolymers were characterized by FT-IR and ¹H-NMR spectroscopy. The copolymer composition was determined from ¹H-NMR spectra. Molecular weights ranged between 1700 and 5400 g/mol by vapor pressure osmometry. Received: 27 September 1998/Revised version: 27 January 1999/Accepted: 28 January 1999     

Spontaneous copolymerization of N-(2-hydroxyethyl)ethyleneimine with isatoic anhydride

The polymerization of isatoic anhydride (electrophilic monomer) with N-(2-hydroxyethyl)ethyleneimine (nucleophilic monomer) was studied in the absence of added initiator at different feed monomer concentrations, temperature, and time of copolymerization. The copolymers were characterized by FT-IR, ¹H-NMR and ¹³C-NMR spectroscopy, and TGA. Based on spectroscopic data and copolymer composition, a copolymer structure was suggested. Received: 25 April 1997/Revised: 11 August 1997/Accepted: 14 August 1997     

Copolymerization of 4-cyanophenyl methacrylate with methyl methacrylate: Synthesis,characterization and determination of monomer reactivity ratios

Summary A novel methacrylic monomer, 4-cyanophenyl methacrylate (CPM) was synthesized by reacting 4-cyanophenol dissolved in methyl ethyl ketone (MEK) with methacryloyl chloride in the presence of triethylamine as a catalyst. Copolymers of CPM with methyl methacrylate(MMA) at different composition was prepared by free radical solution polymerization at 70±1 °C using benzoyl peroxide as initiator. The copolymers were characterized by FT-IR, ¹H-NMR and ¹³C-NMR spectroscopic techniques. The solubility of the polymers was tested in various polar and non polar solvents. The molecular weight and polydispersity indices of the copolymers were determined using gel permeation chromatography. The glass transition temperature of the copolymers increases with increase in mole fraction of MMA content. The thermal stability of the copolymer increases with increases in mole fraction of CPM content in the copolymer. The copolymer composition was determined by using ¹H-NMR spectroscopy. The monomer reactivity ratios estimated by the application of linearization methods such as Fineman-Ross (r₁=2.524±0.038, r₂=0.502±0.015), Kelen-Tudos (r₁=2.562±0.173, r₂=0.487±0.005) and extended Kelen-Tudos methods (r₁=2.735±0.128, r₂=0.4915±0.007).     

Synthesis and elastomer behavior of a novel polymer electrolyte of acrylic ester–salt copolymer

This paper studied the synthesis of a novel elastomeric copolymer electrolyte in an aqueous phase. The monomer, sodium allyl sulfonate (SAS), was dissolved in continuous aqueous phase and the second monomer, methyl acrylate (MA), was supplied from MA micelles as dispersed phase. The copolymerization of the two monomers took place in continuous aqueous phase. Confirmed by FTIR and ¹H‐NMR, a binary copolymer electrolyte of MA and SAS, poly(MA‐co‐SAS), was obtained. The glass transition temperature of the copolymer was indicated as 20.4°C by DSC thermogram, thus, it behaves an elastomer in normal ambient temperature. The mechanical properties of the composite films consisting of both poly(MA‐co‐SAS) and Cu²⁺ ions or reduced copper were affected by the content of ions and reduced copper. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2796–2802, 2006     

Preparation and Properties of Polyether Scale Inhibitor Containing Fluorescent Groups

Water soluble fluorescent monomer, 8-allyloxy-1,3,6-pyrenetrisulfonic acid trisodium salt (AP), was synthesized from 8-hydroxy-1,3,6-pyrenetrisulfonic acid trisodium salt and allyl chloride. AP-tagged copolymer maleic anhydride (MA)–ammonium allyl polyethoxy sulfate (APES)-AP, which is a calcium phosphate inhibitor, was prepared and the structures of AP and MA-APES-AP were characterized by FTIR and ¹H-NMR. The influence of the mole ratio of MA:APES on a calcium phosphate inhibitor of MA-APES-AP was discussed. Fluorescent properties and scale inhibition performance of MA-APES-AP were also studied. The results indicate that monomer ratio has great impact on the performance of MA-APES-AP. Fluorescent intensity increases with the concentration of MA-APES-AP, with a correlation coefficient (r) of 0.9934 and MA-APES-AP limit of detection of 1.72 mg · L^?1. Calcium phosphate inhibition performance test results show that calcium phosphate inhibition of MA-APES-AP reaches 98.78 percent when the dosage is 12 mg · L^?1 at 80^°C.     

Controlled/living free-radical copolymerization of allyl glycidyl ether with methyl acrylate under Co γ-ray irradiation

An investigation on the copolymerization of allyl glycidyl ether (AGE), an epoxy-functional monomer, with methyl acrylate (MA) was performed in the presence of benzyl 1H-imidazole-1-carbodithioate (BICDT) under ⁶⁰Co γ-ray irradiation. The polymerizations revealed good characteristics of RAFT process. The content of AGE incorporation into the copolymer increased with higher monomer conversion and higher molar fraction of the AGE in the monomer feed. However, the polymerization could slow down when the fraction of AGE increased in the monomer feed, which might be attributed to the low activity of AGE. Taking advantage of RAFT process, functional block copolymer poly(AGE/MA)-block-poly(styrene) was prepared in the presence of poly(styrene) macroRAFT agent, and the copolymer was characterized by ¹H NMR spectra and GPC.     

A novel benzoxazine monomer with methacrylate functionality and its thermally curable (co)polymers

Benzoxazine monomer with methacrylate functionality, namely 2-(2-(2H-benzo[e][1,3]oxazin-3(4H)-yl)ethoxy) ethyl methacrylate (BEM) was synthesized by simple esterification reaction of hydroxyl containing benzoxazine (B–OH) with methacryloyl chloride, and characterized. BEM was then copolymerized with styrene in 1:4 mol ratio by free radical polymerization using 2,2′-azobis(isobutyronitrile) (AIBN) as initiator. The structure, chemical composition, and molecular weight characteristics of the resulting copolymer were confirmed by FT-IR, ¹H-NMR spectroscopy, and GPC, respectively. The curing behavior and thermal properties of both monomer and copolymer were also studied by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA).     

Linear-dendritic block copolymers as a green scale inhibitor for calcium carbonate in cooling water systems

Water-soluble monomer APEG-PG-(OH)n were produced and the Structure of APEG-PG-(OH)5 were identified by ¹H-NMR. APEG-PG-(OH)n were copolymerized with maleic anhydride (MA) to synthesize no phosphate and nitrogen free calcium carbonate inhibitor MA/APEG-PG-(OH)n. The structure and thermal property of MA/APEG-PG-(OH)5 were characterized and measured by ¹H-NMR, GPC and TGA. The observation shows that the dosage and n value of MA/APEG-PG-(OH)n plays an important role on CaCO₃ inhibition. MA/APEG-PG-(OH)5 displays superior ability to inhibit the precipitation of calcium carbonate, with approximately 97% inhibition at a level of 8 mg/L. The effect on formation of CaCO₃ was investigated with combination of SEM and XRD analysis.     

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.     

Atom transfer radical homo‐ and copolymerization of styrene and methyl acrylate initiated with trichloromethyl‐ terminated poly(vinyl acetate) macroinitiator: A kinetic study

Atom transfer radical bulk copolymerization of styrene (St) and methyl acrylate (MA) initiated with trichloromethyl‐terminated poly(vinyl acetate) macroinitiator was performed in the presence of CuCl/PMDETA as a catalyst system at 90°C. Linear dependence of ln[M]₀/[M] versus time data along with narrow polydispersity of molecular weight distribution revealed that all the homo‐ and copolymerization reactions proceed according to the controlled/living characteristic. To obtain more reliable monomer reactivity ratios, the cumulative average copolymer composition at moderate to high conversion was determined by ¹H‐NMR spectroscopy. Reactivity ratios of St and MA were calculated by the extended Kelen‐Tudos (KT) and Mao‐Huglin (MH) methods to be r_St = 1.018 ± 0.060, r_MA = 0.177 ± 0.025 and r_St = 1.016 ± 0.053, r_MA = 0.179 ± 0.023, respectively, which are in a good agreement with those reported for the conventional free‐radical copolymerization of St and MA. Good agreement between the theoretical and experimental composition drifts in the comonomer mixture and copolymer as a function of the overall monomer conversion were observed, indicating that the reactivity ratios calculated by copolymer composition at the moderate to high conversion are accurate. Instantaneous copolymer composition curve and number‐average sequence length of comonomers in the copolymer indicated that the copolymerization system tends to produce a random copolymer. However, MA‐centered triad distribution results indicate that the spontaneous gradient copolymers can also be obtained when the mole fraction of MA in the initial comonomer mixture is high enough. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Water-soluble Copolymers of N-vinylpyrrolidone and Vinyl Acetate: Synthesis, Characterization, and Monomer Reactivity at High Conversions

Homogeneous copolymers of N-vinylpyrrolidone (VP) and vinyl acetate (VA) which form clear aqueous solutions were prepared by free radical polymerization in a solution of isopropanol alcohol, using 2,2-azobisisobutyronitrile as an initiator. They were characterized by FTIR, ¹H-NMR, and element analysis studies. The reactivity ratios of the monomer were computed by the Extended Kelen–Tüdós method at high conversions, using data from both ¹H-NMR and elemental analysis studies. The reactivity ratios of VP and VA in a homogenous copolymer were observed to be very different from that of a heterogeneous copolymer. Additional information was obtained by finding out the sequence length distribution for copolymers.     

Synthesis,Characterization, Reactivity Ratio and Photo Crosslinking Properties of the Copolymer of 4-Cinnamoyl Phenyl Methacrylate with Butyl Methacrylate

Copolymers of 4-cinnamoyl phenyl methacrylate (4-CPMA) and n-butyl methacrylate (BMA) were prepared in a methyl ethyl ketone (MEK) solution with benzoyl peroxide (BPO) as an initiator at 70°C. They were characterized with UV, IR, ¹H-NMR, ¹³C-NMR, TGA, DSC and gel permeation chromatography. Copolymers were prepared by using different feed ratio of monomers. The monomer reactivity ratios determined by the method of Kelen-Tudos (K-T) were r₁ (CPMA) = 2.32, r₂ (BMA) = 0.56. The glass transition temperature of the copolymer shows a single Tg indicating the formation of random copolymer for all of the monomer feed composition. Thermogravimetric analysis in air has shown that the initial decomposition temperature of the copolymer was above 220°C. The photocrosslinking properties of the copolymer were examined by UV irradiation with polymer film.     

Synthesis and performance evaluation of carboxyl-rich low phosphorus copolymer scale inhibitor

A novel low phosphorus terpolymer scale inhibitor P(IA-MA-SHP) was prepared by aqueous free radical polymerization using itaconic acid (IA), maleic acid (MA), and sodium hypophosphite (SHP) as raw materials. It was mainly used as an efficient scale inhibitor to inhibit CaCO₃. The structures of the copolymers were characterized by Fourier transform infrared, ¹H-NMR, and ¹³C-NMR, and the thermal properties, and scale sample crystal structure morphology of the copolymers were analyzed by thermogravimetric analysis, x-ray diffraction (XRD), and scanning electron microscope (SEM). The effects of dosage, monomer ratio, temperature, and reaction time on the scale inhibition effect were investigated, and the optimal synthesis conditions were determined. The results show that: when the monomer ratio is n(IA):n(MA) = 1.0:1.0, the mass fraction of SHP is 10%, the amount of ammonium persulfate initiator is 12%, the reaction temperature is 90°C, and the reaction time is 4 h, when the dosage of the agent is 20 mg L⁻¹, the scale inhibition rate of CaCO₃ is 94.30%, while it also has a favorable inhibitory effect on CaSO₄. The results of SEM and XRD show that the copolymer scale inhibitor can distort the lattice and has a favorable adsorption and dispersion effect. In addition, it has a positive effect on controlling the scale.     

Silicone/polypropylene oxide-polyethylene oxide copolymer/clay composites (i) - curing behavior,intermolecular interaction and thermomechanical properties

The copolymerization of 2-(3-mesityl-3-methylcyclobutyl)-2-ketoethyl methacrylate monomer with acrylonitrile and styrene were carried out in 1,4-dioxane solution at 60^○C using AIBN as an initiator. The copolymers were characterized by Fourier transform infrared, 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 and ¹H-NMR technique. The monomer reactivity ratios were calculated by the application of conventional linearization methods as a result of Fineman–Ross and Kelen–Tüdös to less than 1 for both monomers.