Synthesis, characterization, and reactivity ratio studies on new sulfide copolymers containing ethylbenzene units

Soluble new sulfide copolymers were synthesized readily by the polycondensation of ethylene dibromide (EDB) (or methylene dibromide (MDB)) with styrene dibromide (SDB) and sodium sulfide (Na₂S) in the presence of phase transfer catalyst. The copolymers were characterized by using Fourier transform-infrared, ¹H NMR, ¹³C NMR, gel permeation chromatography, and thermogravimetric analysis (TGA) techniques. The copolymer composition obtained from the ¹H NMR spectra led to the determination of reactivity ratios. The analysis of reactivity ratios revealed that both EDB and MDB are more reactive than SDB towards Na₂S, and copolymers formed are random in nature. Furthermore, it also gave an insight on the microstructure of the copolymers that both poly (ethylene sulfide-co-styrene sulfide) (p(ES-co-SS)), and poly(methylene sulfide-co-styrene sulfide) (p(MS-co-SS)) copolymers have more of blocky structure with increase in the concentration of ethylene sulfide (ES) or methylene sulfide (MS) units in the respective copolymers. The TGA was used to find out the thermal stability of these polymers. The XRD data indicated an increase in the amorphous content of the copolymers with an increase in the concentration of styrene sulfide (SS) units and thereby resulting in most of these copolymers being soluble in common organic solvents. The solubility and molecular weight of the polymers formed were dependent on the concentration of SDB taken in the feed.     

Compositional analysis of biodegradable polyphosphoester copolymers using nmr spectroscopic methods

The chemical composition and quantitative molar ratios among all components of biodegradable polyphosphoester copolymers of DL ‐lactide and ethylphosphate were determined by a comprehensive set of NMR spectroscopic methods. The polyphosphoester copolymers studied were synthesized using condensation polymerization of oligomeric DL ‐lactide prepolymers and ethyl dichlorophosphate. Conclusive identification of the chemical shift patterns of all functional groups in the copolymers required additional NMR methods such as ³¹P‐NMR and two‐dimensional ¹H–¹H COSY NMR, in addition to the synthesis and comparative NMR analysis of model compounds possessing identical phosphoester linkages in the polyphosphoester copolymers. For the polymers synthesized using the bulk polycondensation process, ¹H–¹H COSY NMR analysis revealed the presence of a small amount of side products that were undetected by ¹H‐NMR alone. These side reactions most likely occurred between the pendant ethoxy group of the phosphoesters and the hydrogen chloride gas generated in the bulk polycondensation process. ³¹P‐NMR spectra of the copolymers revealed a consistent triple‐peak pattern characteristic of phosphoesters linked to a racemic mixture of D,L ‐lactides. These results offered new insight into the side reactions occurring in bulk polymerization of polyphosphoesters and provided a powerful tool of characterizing complex biodegradable polymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 4021–4031, 2003     

Synthesis and characterization of copolymers of bromoacrylated methyl oleate

In this study, methyl oleate was bromoacrylated in the presence of N‐bromosuccinimide and acrylic acid in one step. Homopolymers and copolymers of bromoacrylated methyl oleate (BAMO) were synthesized by free radical bulk polymerization and photopolymerization techniques. Azobisisobutyronitrile (AIBN) and 2,2‐dimethoxy‐2‐phenyl‐acetophenone were used as initiators. The new monomer BAMO was characterized by FTIR, GC‐MS, ¹H, and ¹³C‐NMR spectroscopy. Styrene (STY), methylmethacrylate (MMA), and vinyl acetate (VA) were used for copolymerization. The polymers synthesized were characterized by FTIR, ¹H‐NMR, ¹³C‐NMR, and differential scanning calorimetry (DSC). Molecular weight and polydispersities of the copolymers were determined by GPC analysis. Ten different feed ratios of the monomers STY and BAMO were used for the calculation of reactivity ratios. The reactivity ratios were determined by the Fineman–Ross and Kelen–Tudos methods using ¹H‐NMR spectroscopic data. The reactivity ratios were found to be r_sty = 0.891 (Fineman–Ross method), 0.859 (Kelen–Tudos method); r_bamo = 0.671 (Fineman–Ross method), 0.524 (Kelen–Tudos method). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2475–2488, 2004     

Electroactive Nanofibers of Poly (2-hydroxyethyl methacrylate-graft-aniline) Copolymers and Their Blends with Polycaprolactone

Copolymers of poly (2-hydroxyethyl methacrylate)-graft-polyaniline (PHEMA-g-PANI) were synthesized by atom-transfer radical polymerization (ATRP) of 2-hydroxyethyl methacrylate using polyaniline macro-initiators. The macro-initiators were synthesized by the reaction of amine nitrogens of polyaniline with chloroacetyl choloride. The obtained polymers were characterized by FT-IR and ¹H NMR spectroscopies. Uniform nanofibers consisting of blends of PHEMA-g-PANI copolymers and polycaprolactone (PCL) were prepared using an electrospinning technique. SEM was used to investigate the morphology of nanofibers produced from PHEMA-g-PANI copolymers and PCL blends. The cyclic voltammetry measurement of blends confirmed the preparation of electroactive nanofibers.     

SYNTHESIS,CHARACTERIZATION, AND THERMAL STABILITY OF HOMOPOLYMER AND COPOLYMER OF SOME 3-ARYL-2-HYDROXYPROPYL METHACRYLATES

Three new hydroxypropyl methacrylates having three different aryl rings were synthesized by addition of 2,3-epoxypropyl aromatic hydrocarbon to methacrylic acid. The monomers prepared are 3-phenyl-2-hydroxypropyl methacrylate, 3-tolyl-2-hydroxypropyl methacrylate, (THPMA), and 3-naphtyl-2-hydroxypropyl methacrylate. The homopolymers of these monomers and two different copolymers, [poly(THPMA-co-BMA)], were obtained from polymerization at 60°C in 1,4-dioxane solution using AIBN as initiator. All the monomers and the polymers were characterized by FT-IR and ¹H and ¹³C NMR techniques. Solubility parameters of the polymers and average molecular weight of poly(THPMA) were determined. Thermal stabilities of the polymers were given as comparing with each other by using TGA curves. Thermal degradation of poly(THPMA60%-co-BMA40%) was studied in detail.     

Preparation,Characterization and Biodegradable Characteristics of Poly(D,L-lactide-co-1,3-trimethylene carbonate)

Poly(D ,L -lactide-co-1,3-trimethylene carbonate) (PLCA) has been synthesized by ring-opening polymerization of 1,3-trimethylene carbonate (CA) and D ,L -lactide (LA) using stannous octoate as catalyst. The copolymers were characterized by ¹H nuclear magnetic resonance (NMR), ¹³C NMR and differential scanning calorimetry. Water content and static contact angle of distilled water on the polymer surface were used to evaluate hydrophobicity of the polymers. It was found that the hydrophobicity increased with increasing CA fractions in the copolymers. Biodegradation experiments were conducted in vitro and in vivo. The results indicated that the biodegradation behaviour changed from surface to bulk degradation when the LA content exceeded 30mol% in the copolymers. These properties of PLCA may be useful in protein delivery systems. © of SCI.     

Functional copolymers of p‐cumyl phenyl methacrylate and glycidyl methacrylate: Synthesis,characterization, and reactivity ratios

Free‐radical polymerization of p‐cumyl phenyl methacrylate (CPMA) was performed in benzene using bezoyl peroxide as an initiator at 80°C. The effect of time on the molecular weight was studied. Functional copolymers of CPMA and glycidyl methacrylate (GMA) with different feed ratios were synthesized by free‐radical polymerization in methyl ethyl ketone at 70°C, and they were characterized by FTIR and ¹H‐NMR spectroscopy. The molecular weights and polydispersity indexes of the polymers and copolymers were determined by gel permeation chromatography. The copolymer composition was determined by ¹H‐NMR. The glass‐transition temperature of the polymer and the copolymers was determined by differential scanning calorimetry. The reactivity ratios of the monomers were determined by the Fineman–Ross and Kelen–Tudos methods. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 336–347, 2005     

Synthesis, Characterization and Reactivity Ratios of Phenylethyl Acrylate/Methacrylate Copolymers

2-Phenylethyl acrylate (PEA) and 2-Phenylethyl methacrylate (PEMA) were synthesized by reacting 2-Phenyl ethanol with acryloyl and methacryloyl chloride respectively. Homopolymers and copolymers were prepared by free radical polymerization technique using benzoylperoxide as initiator. Copolymers of PEA and PEMA with methyl acrylate (MA) and N-vinyl pyrollidone (NVP) of different compositions were prepared. The monomers and polymers were characterized by IR and NMR techniques. Thermal stability of the polymers were determined by TG analysis. The composition of the copolymer was determined using ¹H-NMR analysis. The reactivity ratios of the monomers were determined by the application of Finemann–Ross and Kelen–Tudos methods. The prepared copolymers were tested on leather for their pressure sensitive adhesive property.     

Synthesis and characterization of novel fluorine‐containing methacrylate copolymers: Reactivity ratios,thermal properties,and antimicrobial activity

The free‐radical‐initiated copolymerization of 2‐(4‐acetylphenoxy)‐2‐oxoethyl‐2‐methylacrylate (AOEMA) and 2‐(4‐benzoylphenoxy)‐2‐oxoethyl‐2‐methylacrylate (BOEMA) with 2‐[(4‐fluorophenyoxy]‐2‐oxoethyl‐2‐methylacrylate (FPEMA) were carried out in 1,4‐dioxane solution at 65°C using 2,2′‐azobisisobutyronitrile as an initiator with different monomer‐to‐monomer ratios in the feed. The monomers and copolymers were characterized by FTIR and ¹H‐ and ¹³C‐NMR spectral studies. ¹H‐NMR analysis was used to determine the molar fractions of AOEMA, BOEMA, and FPEMA in the copolymers. The reactivity ratios of the monomers were determined by the application of Fineman‐Ross and Kelen‐Tudos methods. The analysis of reactivity ratios revealed that BOEMA and AOEMA are less reactive than FPEMA, and copolymers formed are statistically in nature. The molecular weights (M _w and M _n) and polydispersity index of the polymers were determined using gel permeation chromatography. Thermogravimetric analysis of the polymers reveals that the thermal stability of the copolymers increases with an increase in the mole fraction of FPEMA in the copolymers. Glass transition temperatures of the copolymers were found to decrease with an increase in the mole fraction of FPEMA in the copolymers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of novel functionalized methacrylate copolymers and their copolymerization kinetics,thermal stability,and biocidal properties

In the first step of this study, 2-[(methoxy-1,3-benzothiazole-2-yl)amino]-2-oxoethyl methacrylate (MBAOM) monomer was synthesized and characterized. Then, a series copolymers were obtained by free-radical copolymerization method of MBAOM and glycidyl methacrylate, which is a commercial monomer at 65°C in 1,4-dioxane solvent. Structural characterizations of synthesized monomer and copolymers were carried out using Fourier transform infrared spectrophotometer and nuclear magnetic resonance spectroscopy (¹H and ¹³C-NMR) instruments. The composition of the copolymers was estimated by elemental analysis. The thermal behaviors of all the polymers have been investigated using the differential scanning calorimetry and the thermogravimetric analysis. A kinetic study of the thermal decomposition of copolymers was investigated using thermogravimetric analyzer with non-isothermal methods selected for analyzing solid-state kinetics data. The activation energy (E_a) values were calculated via Kissinger and Ozawa models in a period of α = 0.10–0.80. Photostability of the copolymers was investigated. Also, the biological activity of the copolymers against different bacterial and fungal species has been investigated.     

Syntheses,antitumour activities and antiangiogenesis of 1,2,3‐tris(ethoxycarbonyl)‐2‐propyl acrylate and its polymers

A new monomer, 1,2,3‐tris(ethoxycarbonyl)‐2‐propyl acrylate (TPA), was synthesized by reaction of acryloyl chloride and triethyl citrate. The homopolymer of TPA and its copolymers with acrylic acid (AA), vinyl acetate (VAc) and maleic anhydride (MAH) were prepared by polymerization using lauroyl peroxide (LPO) at 70 °C for 24 h. The structures of TPA and its polymers were identified by FTIR, ¹H NMR, ¹³C NMR spectroscopies, and elemental analysis. The number average molecular weights and polydispersity indices of the synthesized polymers determined by GPC were in the range 4200–23 000 g mol^?1 and 1.1–2.1, respectively. The IC₅₀ values of the synthesized samples against cancer cell lines were greater than those of 5‐fluorouracil (5‐FU). The percentage inhibition values of SV40 DNA replication were 82.2 for TPA, 34.3 for poly (TPA), 81.9 for poly(TPA‐co‐AA), 82.0 for poly(TPA‐co‐VAc), 35.6 for poly(TPA‐co‐MAH) and 12.7 for 5‐FU. The inhibitions of SV40 DNA replication and antiangiogenesis for the synthesized TPA and its polymers are much greater than those of the control. © 2001 Society of Chemical Industry     

Poly(2‐) and (3‐aminobenzoic acids) and their copolymers with aniline: Synthesis,characterization, and properties

Poly(2‐aminobenzoic acid) and poly(3‐aminobenzoic acid) were synthesized by chemical polymerization of the respective monomers with aqueous 1M hydrochloric acid and 0.49M sodium hydroxide, using ammonium persulfate as an oxidizing agent. In addition, polymerization in an acid medium was carried out in the presence of metal ions, such as Cu(II), Ni(II), and Co(II). Poly(2‐aminobenzoic acid‐co‐aniline) and poly(3‐aminobenzoic acid‐co‐aniline) were synthesized by chemical copolymerization of aniline with 2‐ and 3‐aminobenzoic acids, respectively, in aqueous 1M hydrochloric acid. The copolymers were synthesized at several mole fractions of aniline in the feed and characterized by UV–visible and FTIR spectroscopy, the thermal stability, and the electrical conductivity. Metal ions, such as Cu(II), Ni(II), and Co(II), were incorporated into homo‐ and copolymers by the batch method. The percentage of metal ions in the polymers was higher in the copolymers than in the homopolymers. The thermal stability of the copolymers increased as the feed mole fraction of aniline decreased and varied with the incorporation of metal ions in the polymers. The electrical conductivity of the homo‐ and copolymers was measured, which ranged between 10^?3 and 10^?10 S cm^?1. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2641–2648, 2003     

Hyperbranched polymer based on triphenylamine and pyridine: Fluorescent chemosensors for palladium ions

Two new hyperbranched fluorescent conjugated polymers containing pyridine units were synthesized via Heck coupling reaction and Sonogashira coupling reaction, respectively, and characterized by ¹H NMR, ¹³C NMR, FTIR, and GPC. The copolymers are readily soluble in common organic solvents such as chloroform, THF, and DMF. Thermal analysis revealed that the copolymers had good thermal stability. The fluorescence quenching behaviors of the hyperbranched copolymers by metal ions were studied. It was found that the fluorescence of the copolymers can be effectively quenched by Pd²⁺. Moreover, the two hyperbranched copolymers exhibited different quenching efficiency, which may be related to difference in the hindrance for the chelation of pyridine unit with metal ions of the two polymers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of statistical copolymers of styrene and 4‐(1‐hydroxyalkyl)styrene

A family of new polymers based on poly(4‐(1‐hydroxyalkyl)styrene), and its copolymers with styrene were synthesized and thoroughly characterized by ¹H‐NMR, ¹³C‐NMR, FTIR, and UV spectroscopies. The chemical modification reactions of polystyrene (PS) was used as a novel method of performing the synthesis of poly(4‐(1‐hydroxyethyl‐co‐styrene)), poly(4‐(1‐hydroxypropyl‐co‐styrene)), poly(4‐(1‐hydroxybutyl‐co‐styrene)), and poly(4‐(1‐hydroxyphenylmethyl‐co‐styrene)). The novelty of this method lies in the incorporation of the desired mol % of the functional groups in polystyrene chain, to obtain random copolymers of desired composition. In preliminary testing/evaluation studies the utility and versatility of the new copolymers, which have the potential to be negative‐tone photoresist materials, were studied. Thus a few photoresist formulations based on poly(styrene‐co‐4‐(1‐hydroxyalkylstyrene)) were developed with 5 wt % of a photoacid generator. These studies suggested that the new copolymers synthesized by a simple and alternate method could have the same potential as a photoresist material when compared with the polymers synthesized by the polymerization of the corresponding functional monomer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1902–1914, 2004     

Synthesis and characterization of poly(o‐ and m‐amino benzyl amine) and the copolymers with aniline. Study with Cu(II)

Poly(o‐amino benzyl amine), poly(m‐amino benzyl amine), and the copolymers with aniline were synthesized in 10^?4M HCl by using ammonium persulfate as oxidizing agent. The copolymers were synthesized at various feed mole fractions of comonomer diamine and characterized by elemental analysis, FTIR, ¹H‐NMR spectroscopy, and electrical conductivity. The polymerization yield depended on the substituent position in the aromatic ring. Copper ion was incorporated in the polymers and the amount depended on the side groups position in the aromatic ring. The thermal stability increased when copper ions and aniline units were incorporated in the polymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 31–36, 2004     

Copolymers of aniline and o‐methoxyaniline: Synthesis and characterization

High‐conversion (HC) copolymers of aniline and o‐methoxyaniline (o‐anizidine) were synthesized for the first time by chemical oxidative copolymerization by using various polymerization techniques (simultaneous or consecutive introduction of comonomers into the polymerizing system). Low‐conversion (LC) copolymers have also been synthesized for comparison. The polymers obtained were characterized by using ¹H‐NMR, infrared, and electronic absorption spectroscopy; differential scanning calorimetry; and electrical conductivity measurements. Solubility characteristics and composition of different fractions of the copolymers were also determined. It was shown that, in contrast to the LC copolymers, HC copolymers reveal relatively poor solubility. Electrical conductivity of copolymers and also of o‐methoxyaniline homopolymer is lower as compared to polyaniline, which correlates with notable hypsochromic (blue) shift of the bands in electronic absorption spectra. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1822–1828, 2005     

Synthesis,characterization and polychelatogenic properties of poly[(2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid)‐co‐(methacrylic acid)]

Poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid), poly(methacrylic acid), and five copolymers of poly[(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid)‐co‐(methacrylic acid)] were synthesized by radical polymerization and obtained in yields >97%. The polymers were characterized by FT‐IR, [¹H]NMR, and [¹³C]NMR and studied by means of the Liquid‐phase Polymer‐based Retention (LPR) technique. The metal ion retention ability of the copolymers for Cu(II), Cd(II), Co(II), Hg(II), Ni(II), Zn(II), Cr(III) and Ag(I) was investigated at different pH values because of their environmental and analytical interest. The retention profiles of the copolymers were compared with those of the corresponding homopolymers and retention of metal ions was found to increase with increasing pH. © 2001 Society of Chemical Industry     

A novel hydrophobically associating polyampholytes of poly(AM/AA/AMQC12): preparation,characterization, and solution properties

A novel hydrophobically associating polyampholytes of poly(AM/AA/AMQC12) were synthesized by the free radical copolymerization of acrylamide (AM), acrylic acid (AA), and dimethyldodecyl(2-acrylamidoethyl)ammonium bromide (AMQC12) in water without any surfactants (named AAQ series). The structures of polymers were confirmed by ¹H NMR and ¹³C NMR. The molecular weight and polydispersity were obtained using gel permeation chromatography (GPC). The hydrophobically associated properties of polymer solution were characterized by rheology, steady-state fluorescence probe, and ¹H NMR relaxation time (T ₂). Isoelectric points (IEPs) of polymer solution were determined by the effect of pH on viscosity below critical association concentrations (cac), and the reduced viscosities of samples at IEPs were increased in the presence of NaCl. Moreover, the steady-shear viscosity of sample at IEP was also greatly enhanced in NaCl solutions when the polymer concentration is above the cac. Meantime, the storage modulus and the loss modulus of copolymers showed that the sample behaved as gel in salt media.     

Copolymers of aniline and o‐methoxyaniline: Synthesis and characterization

High‐conversion (HC) copolymers of aniline and o‐methoxyaniline (o‐anizidine) were synthesized for the first time by chemical oxidative copolymerization using various polymerization techniques (simultaneous or consecutive introduction of comonomers into the polymerizing system). Low‐conversion (LC) copolymers have also been synthesized for comparison. The polymers obtained were characterized using ¹H‐NMR, infrared, and electronic absorption spectroscopy, differential scanning calorimetry, and electrical conductivity measurements. Solubility characteristics and composition of different fractions of the copolymers were also determined. It was shown that in contrast to the LC copolymers, HC copolymers reveal relatively poor solubility. Electrical conductivity of copolymers and also of o‐methoxyaniline homopolymer is lower compared to polyaniline, which correlates with notable hypsochromic (blue) shift of the bands in electronic absorption spectra. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 75–81, 2006     

One‐step synthesis of star‐block copolymers via simultaneous free radical polymerization of styrene and ring opening polymerization of ε‐caprolacton using tetrafunctional iniferter

Star‐block copolymers comprised of poly(styrene) (S) core and four poly(ε‐caprolacton) (ε‐CL) arms were synthesized by the combination of free radical polymerization (FRP) of S and ring opening polymerization (ROP) of ε‐CL in one‐step in the presence of tetrafunctional ineferter. The block copolymers were characterized by ¹H‐NMR and FTIR spectroscopy, gel permeation chromatography (GPC), and fractional precipitation method. ¹H ‐NMR and FTIR spectroscopy and GPC studies of the obtained polymers indicate that star‐block copolymers easily formed as result of combination FRP and ROP in one‐step. The γ values (solvent/precipitant volume ratio) were observed between 1.04–2.72 (mL/mL) from fractional measurements. The results show that when the initial S feed increased, the molecular weights of the star‐block copolymers also increased and the polydispersities of the polymers decreased. M_w/M_n values of the products were measured between 1.4 and 2.86 from GPC. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010