Homopolymer of 4-chloro-3-methyl Phenyl Methacrylate and its Copolymers with Butyl Methacrylate: Synthesis, Characterization, Reactivity Ratios and Antimicrobial Activity

The methacrylate monomer 4-chloro-3‐methyl phenyl methacrylate (CMPM) was synthesized by reacting 4-chloro-3‐methyl phenol with methacryloyl chloride. The homopolymer and various copolymers of CMPM with n-butyl methacrylate were synthesized by free-radical polymerization in toluene at 70°C using 2,2′-azobis(isobutyronitrile) as the initiator. The CMPM monomer was characterized by Fourier transform IR and ¹H-NMR studies. The copolymers were characterized by IR spectroscopy. The molecular weights (M _n and M _w) and the polydispersity index were obtained from gel permeation chromatography. The solubility and intrinsic viscosity of the homopolymer and the copolymers are also discussed here. The copolymer composition obtained from UV spectra led to the determination of reactivity ratios employing Fineman-Ross and Kelen-Tudos linearization methods. Thermogravimetric analyses of the homopolymer and the copolymers were carried out under a nitrogen atmosphere. The homopolymer and the copolymers prepared were tested for their antimicrobial activity against bacteria, fungi and yeasts.     

Graft copolymers of poly(methyl methacrylate) and polyamide-6 via in situ anionic polymerization of ε-caprolactam and their properties

Graft copolymers of poly(methyl methacrylate) and polyamide-6 (PMMA-g–PA6) were investigated via in situ anionic polymerization of ε-caprolactam, using PMMA precursors with N-carbamated caprolactam pendants (PMMA–CCL) as macroactivators and sodium caprolactamate as catalyst. Three grades of PMMA–CCLs obtained by free radical copolymerization were used for synthesizing the PMMA-g–PA6 copolymers with different PMMA content. The resulting graft copolymer was characterized by Fourier-transform infrared spectroscopy and selective extraction. Scanning electron microscopy is used to clarify the phase morphology of obtained polymer by fracture surface. The thermal property, crystallinity and dimensional stability of graft copolymer were studied using differential scanning calorimetry, X-ray diffraction and water absorption measurement. The results show the T_g of graft copolymer is higher than that of neat PA6, but the onset and peak points of graft copolymer melting point are shifted to lower temperature. The percentage crystallinity and water absorption of PMMA-g–PA6 copolymer decrease with increasing PMMA content, but the crystal structure of PA6 is scarcely affected by the presence of PMMA. Graft copolymers have improved dimensional stabilities relative to neat PA6. Upon the incorporation of 19.9 wt% PMMA into PA6, the water absorption of PMMA-g–PA6 copolymer has been reduced from 4.8 for neat PA6 to 2.1%.     

Synthesis and characterization of poly(thiophen‐3‐yl acetic acid 4‐pyrrol‐1‐yl phenyl ester‐co‐N‐methylpyrrole) and its application in an electrochromic device

Copolymer of thiophen‐3‐yl acetic acid 4‐pyrrol‐1‐yl phenyl ester (TAPE) with N‐methylpyrrole (NMPy) was synthesized by potentiostatic electrochemical polymerization in acetonitrile–tetrabutylammonium tetrafluoroborate solvent–electrolyte couple. The chemical structures were confirmed via Fourier transform infrared spectroscopy (FTIR), cyclic voltammetry (CV), and UV–vis spectroscopy. Electrochromic and spectroelectrochemical properties of poly(TAPE‐co‐NMPy) [P(TAPE‐co‐NMPy)] were investigated. Results showed that the copolymer revealed color change between light yellow and green upon doping and dedoping of the copolymer, with a moderate switching time. Furthermore, as an application, dual‐type absorptive/transmissive polymer electrochromic device (ECD) based on poly(TAPE‐co‐NMPy) and poly(3,4‐ethylene dioxythiophene) (PEDOT) have been assembled, where spectroelectrochemistry, switching ability, stability, and optical memory of the ECD were investigated. Results showed that the device exhibited good optical memory and stability with moderate switching time. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1988–1994, 2006     

Chemoenzymatic synthesis of Y-shaped diblock copolymer

Y-shaped diblock copolymer polycaprolactone-block-(polystyrene)₂ [PCL-b-(PSt)₂] was synthesized successfully by the combination of enzymatic ring-opening polymerization (eROP) and atom transfer radical polymerization (ATRP). CH₃O-terminated PCL was synthesized firstly by eROP of ε-caprolactone (ε-CL) in the presence of biocatalyst Novozyme 435 and initiator CH₃OH, subsequently the resulting PCL was converted to macroinitiator by the esterification of it with 2,2-dichloro acetyl chloride (DCAC). PCL-b-(PSt)₂ diblock copolymers were synthesized in an ATRP of the styrene with CuCl/2,2′-bipyridine as the catalyst system. The kinetic analysis of ATRP indicated a controlled/‘living’ radical polymerization. The structure and composition of obtained polymers were characterized with NMR, GPC and FTIR. The thermal behavior was characterized by differential scanning calorimetry (DSC).     

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

A novel acrylic monomer, 4-cyanophenyl acrylate (CPA) was synthesized by reacting 4-cyanophenol dissolved in methyl ethyl ketone with acryloyl chloride in the presence of triethylamine as a catalyst. Copolymers of CPA with methyl methacrylate (MMA) at different composition was prepared by free radical solution polymerization at 70 ± 1 °C using benzoyl peroxide as an initiator. The copolymers were characterized by FT-IR, ¹H-NMR and ¹³C-NMR spectroscopic techniques. The solubility tests were checked in various polar and non polar solvents. The molecular weight and polydispersity indices of the copolymers were estimated by using gel permeation chromatography. The glass transition temperature of the copolymers increases with increases MMA content. The thermal stability of the copolymer increases with increases in mole fraction of CPA content in the copolymer. The copolymer composition was determined by using ¹H-NMR spectra. The monomer reactivity ratios determined by the application of linearization methods such Fineman–Ross (r ₁ = 0.535, r ₂ = 0. 0.632), Kelen–Tudos (r ₁ = 0.422, r ₂ = 0.665) and extended Kelen–Tudos methods (r ₁ = 0.506, r ₂ = 0. 0.695).     

Synthesis, characterization, and antibacterial activity of metal nanoparticles embedded into amphiphilic comb-type graft copolymers

The synthesis, spectroscopic characterization, and antimicrobial efficiency of gold and silver nanoparticles embedded in novel amphiphilic comb-type graft copolymers having good film-forming properties have been described. Amphiphilic comb-type graft copolymers were synthesized by the reaction of chlorinated polypropylene (PP) (M _w = 140,000 Da) with polyethylene glycol (PEG) (M _n  = 2,000 Da) at different molar ratios. Metal nanoparticles embedded graft copolymers were prepared by reducing solutions of the salts of silver or gold and the copolymer in tetrahydrofuran. The optical properties of the metal nanoparticle embedded copolymers were determined by using UV–visible spectroscopy. Surface plasmon resonance (SPR) of the gold and silver nanoparticle embedded copolymers in toluene was observed at a maximum wavelength (λ_max) of 428 and 551 nm in the UV–VIS absorption spectra, respectively. The average particle diameters of the gold and silver nanoparticles were found to be 50 nm from the high resolution scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Amphiphilic polymer films containing silver and gold nanoparticles were found to be highly antimicrobial by virtue of their antiseptic properties to Escherichia coli and Staphylococcus aureus.     

Synthesis and characterization of the novel inimer-containing fluorene units and preparation of blue light-emitting polymers

The novel inimer-containing fluorene units was successfully synthesized and characterized. Hyperbranched homopolymer and copolymers with methyl methacrylate (MMA) were prepared by the novel inimer via atom transfer radical polymerization where CuBr/1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA) were used as catalyst. The copolymerization of inimer and MMA was performed under different ratio of the initial inimer/MMA and the inimer acted as not only the branched point (BP) but also the functional groups which emit blue light. The number-average molecular weight (M _n) and polydispersity index (PDI) of polymers are in the ranges (3.6–18.4) × 10³ and (1.3–2.8), respectively. Thermal gravimetric analysis (TGA) results showed all polymers had good thermal stabilities. The number of the inimers acted as branched point in the copolymer backbone is estimated by ¹H NMR spectra and UV–Vis absorption spectra.     

Evaluation of Antibacterial Activity and Characterization of Synthesized Biodegradable Copolymers

Green copolymer Poly(MA-CA) was developed by the thermal condensation polymerization of monomers such as DL-Malic acid (MA) and Citric acid (CA). The copolymer of Poly(MA-CA) was synthesized by varying the ratio of MA and CA monomers with 1:0, 1:3, 1:1, 3:1 and 0:1, and their antibacterial properties were studied with respect to their activity on Gram-positive and Gram-negative bacteria by the bacterial count method. Furthermore, the biocidal activity of the plain monomers was also investigated and compared to those of the copolymers. Synthesized copolymers show good antibacterial effects towards both Gram-positive and Gram-negative bacteria. The antimicrobial properties of the copolymers and the monomers were studied by varying the ratio of polymers, effect of polymer concentration and effect of pH. Results indicated that the antibacterial activity of the copolymers increased with MA content and polymer dose. At low content of MA (wt.%), the copolymers poly(MA-CA)(1:3) possessed a higher effect on Gram-positive bacteria Bacillus cereus and Micrococcus luteus than Gram-negative bacteria Salmonella and Shigella. The other copolymers with the ratio of 1:1 and 3:1 including MA homopolymer possesses 100% inhibition of both Gram-positive and Gram-negative bacteria under the conditions studied. The developed polymers were extensively characterized by Fourier transform infrared spectroscopy analysis, thermal gravimetric analysis, X-ray diffraction analysis and scanning electron microscope-energy dispersive spectroscopy to understand their physicochemical properties.     

Synthesis of two‐end‐functionalized copolymer of styrene and methyl methacrylate via living radical polymerization

The random copolymers (HO‐P(St‐r‐MMA)‐COOH) of styrene (St) and methyl methacrylate (MMA) with hydroxyl group at one end and carboxyl group at another end were synthesized by nitroxide‐mediated living radical polymerization initiated by 4,4′‐azobis(4‐cyanovaleric acid) (ACVA) and 4‐hydroxyl‐2,2,6,6–tetramethylpiperidineoxyl (TEMPO‐OH). The experimental results have shown that all synthesized copolymers have narrow molecular weight distribution. The conversion of monomers and the molecular weight of copolymer increase with polymerization time. Thus, a copolymerization mechanism containing living radical polymerization is suggested. The use of this method permits the copolymer with two functional chain ends and controllable molecular weight as well as low molecular weight distribution. X‐ray photoelectron spectroscopy result shows that the synthesized copolymers can be tethered on the surface of silicon wafer through the reaction between the hydroxyl end of the copolymer and native oxide layer on the wafer. In addition, an organic/inorganic hybrid surface has achieved by treating copolymer tethered Si‐substrates with SiCl₄ vapor. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3118–3122, 2006     

Novel branched poly(l-lactide) with poly(glycerol-co-sebacate) core

A series of biodegradable poly (glycerol-sebacate-l-lactide) (PGSLA) copolymers, with variable PLLA length, were synthesized and characterized. The copolymers comprised PGS backbone chain with a nominal molecular weight of 2,800 g/mol. The length of each PLLA side chain covered the 800–14,000 range, while the length of the PLLA was easily controlled by the feed molar ratio of the l-lactide to the PGS. The structure of the copolymer was studied by nuclear magnetic resonance spectroscopy and gel permeation chromatography. Differential scanning calorimetric measurements and thermal gravimetric analysis had been performed to indicate the glass transition temperature (T _g), melting point (T _m), and the degree of crystallinity (χ _c). It was also found that the onset decomposition temperature (T _d) of the copolymers was lower than those of the linear polylactide (LPLLA). After solution casting and solvent evaporation, porous structures were found in the copolymer films by scanning electron microscope (SEM). Water contact angle results showed that the hydrophilicity of the copolymers was much higher than that of linear PLLA. In vivo, PGSLA copolymer demonstrated a favorable tissue response profile compared to PGS/LPLLA blend. There was also significantly less inflammation and fibrosis during degradation. PGSLA might therefore serve as an excellent candidate material for medical applications, given its minimal in vivo tissue response.     

Fast physical drying, high water and salt resistant coatings from non-drying vegetable oil

This paper reports fast physical drying, high water and salt resistances of coating materials from non-drying palm oleic acid. Short oil-length alkyd was synthesized and copolymerized with methyl methacrylate. Three copolymers of the alkyd and methyl methacrylate with different alkyd/MMA ratios were prepared via free radical polymerization. The copolymers were characterized by FTIR and H NMR spectroscopy, and glass transition temperatures (T_g) were measured by DSC. The decreasing amount of alkyd was noticed to increasing conversion and T_g. The overall thermal stability has increased with higher amount of alkyd in the copolymer. Moreover, incorporation of alkyd has improved the adhesion and film hardness of the coatings.     

Synthesis and characterization of thiophene functionalized polystyrene copolymers and their electrochemical properties

Thiophene functionalized polystyrene samples (TFPS) were synthesized by atom transfer radical polymerization (ATRP) of styrene, followed by Suzuki coupling with 3‐thiophene (Th) boronic acid. Conducting graft polymer of TFPS with thiophene was achieved at 1.5 V in tetrabutylammonium tetrafluoroborate/dichloromethane (TBAFB/DM) by electrochemical methods. Spectroelectrochemical analysis of the resulting copolymers [P(TFPS‐co‐Th)] reflected electronic transitions at 449, 721 and 880 nm, revealing π ? π* transition, polaron and bipolaron band formation, respectively. We also successfully established the utilization of dual type complementary colored polymer electrochromic devices using P(TFPS‐co‐Th)/poly(3,4‐ethylenedioxythiophene (PEDOT) in sandwich configuration. The switching ability, stability and optical memory of the electrochromic device were investigated by UV–visible spectrophotometry and cyclic voltammetry. Device switches between brown and blue color with a switching time of 1.3 s were prepared with optical contrast (%ΔT) of 25 %. Copyright © 2005 Society of Chemical Industry     

Electrochromic properties and electrochromic device application of copolymer of N‐(4‐(3‐thienyl methylene)‐oxycarbonylphenyl)maleimide with thiophene

A new copolymer of N‐(4‐(3‐thienyl methylene)‐oxycarbonylphenyl)maleimide (MBThi) with thiophene [P(MBThi‐co‐Th)] was synthesized electrochemically in the presence of tetrabutylammonium tetrafluoroborate as the supporting electrolyte, in acetonitrile/borontrifluoride ethylether solvent mixture (80 : 20, v/v). Spectroelectrochemical analysis of the resulting copolymer reflected electronic transitions at 440, 730, and ～1000 nm, revealing π–π* transition, polaron, and bipolaron band formation, respectively. Switching ability was evaluated by a kinetic study via measuring the transmittance (%T) at the maximum contrast. Dual‐type polymer electrochromic devices (ECDs) based on P(MBThi‐co‐Th) and poly(ethylene dioxythiophene) (PEDOT) were constructed. Spectroelectrochemistry, switching ability, and stability of the devices were investigated by UV–vis spectroscopy and cyclic voltammetry. These devices exhibit low switching voltages (between 0.0 and +2.0 V) and short switching times with reasonable switching stability under atmospheric conditions. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 4500–4505, 2006     

Synthesis and characterization of the novel block copolymer poly(ε‐caprolactone)‐b‐poly(4‐vinyl pyridine) by the combination of coordination and controlled free‐radical polymerizations

A novel block copolymer, poly(ε‐caprolactone)‐b‐poly(4‐vinyl pyridine), was synthesized with a bifunctional initiator strategy. Poly(ε‐caprolactone) prepolymer with a 2,2,6,6‐tetramethylpiperidinyloxy (TEMPO) end group (PCL_T) was first obtained by coordination polymerization, which showed a controlled mechanism in the process. By means of ultraviolet spectroscopy and electron spin resonance spectroscopy, the TEMPO moiety was determined to be intact in the polymerization. The copolymers were then obtained by the controlled radical polymerization of 4‐vinyl pyridine in the presence of PCL_T. The desired block copolymers were characterized by gel permeation chromatography, Fourier transform infrared spectroscopy, and NMR spectroscopy in detail. Also, the effects of the molecular weight and concentration of PCL_T on the copolymerization were investigated. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2280–2285, 2004     

A comparison of composition and sequence distribution of p(AM-MADQUAT) prepared by solution and inverse microemulsion polymerization

Acrylamide (AM)/2-(methacryloyloxy)ethyltrimethylammonium chloride (MADQUAT) copolymers were prepared by solution and inverse microemulsion polymerization using ammonium persulfate ((NH₄)₂S₂O₈)/sodium hydrosulfite (NaHSO₃) as redox initiator at 30 °C. The comonomer reactivity ratios, determined using the Kelen–Tudos (KT) method, were r _A = 0.30, r _M = 1.31 in solution and r _A = 0.63, r _M = 1.13 in the inverse microemulsion, respectively. The copolymer microstructure was deduced from the run number and the heterogeneity, based on reactivity ratios. It was found that copolymerization in the inverse microemulsion resulted in close to ideal copolymerization, giving almost random copolymers; copolymerization in solution resulted in some alternating copolymers. The copolymer compositions indicated that high-conversion samples obtained from the inverse microemulsion are much more homogeneous in composition compared with those obtained in solution. It was found that the composition distribution of the copolymer prepared by inverse microemulsion polymerization remained at approximately the feed ratio. The sequence distribution of the copolymer was predicted by first-order Markov statistical and Bernoulli statistical models, respectively. The results showed that the sequence distribution of the copolymer prepared by inverse microemulsion polymerization was almost random, which led to a wider cationic charge distribution and a microstructure that was coincident with the feed ratio.     

Chemozymatic synthesis and characterization of H-shaped triblock copolymer

The synthesis of well-defined H-shaped block copolymer based on the enzymatic ring-opening polymerization (eROP) and atom transfer radical polymerization (ATRP) is described. The dihydroxyl polycaprolactone (PCL) was synthesized by the eROP of ε-caprolactone (ε-CL) in the presence biocatalyst Novozyme 435 and initiator ethylene glycol. Subsequently, the resulting PCL was converted to tetrafunctional macroinitiator by the esterification with 2,2-dichloro acetyl chloride (DCAC). The H-shaped block copolymer was then synthesized by the ATRP of styrene. The polymers were characterized by NMR and GPC. Linear first-order kinetics, linearly increasing molecular weight with conversion, and low polydispersities observed from the ATRP of St showed that the polymerization was well controlled. (PSt)₂-b-PCL-b-(PSt)₂ block copolymers with varying molecular weight and controllable composition were obtained.     

Synthesis and characterization of biodegradable polymers composed of 3,4-dihydroxycinnamic acid and poly(ethylene glycol)

A novel series of biodegradable copolymers were synthesized by the thermal polycondensation of 3,4-dihydroxycinnamic acid (DHCA) and poly(ethylene glycol) (PEG). The copolymers were characterized by ¹H-NMR, Fourier transform infrared spectroscopy, and gel permeation chromatography. It was found that the incorporation of PEG reduced the glass-transition temperature (T_g) of the copolymers, and T_g decreased with increasing amount of PEG in the compositions. The fluorescence spectroscopy revealed that the homopolymer and copolymers of DHCA gave a higher fluorescence emission intensity than that of DHCA monomer, of which the strongest fluorescence emission peak occurred in the copolymers containing a small amount of PEG. X-ray diffraction spectra demonstrated that poly(3,4-dihydroxycinnamic acid) and copolymer were amorphous; this indicated the facile biodegradability of the copolymers. Furthermore, copolymer micelles formed by self-assembly were investigated. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Electrochromic properties of a copolymer of 1‐4‐di[2,5‐di(2‐thienyl)‐1H‐1‐pyrrolyl]benzene with EDOT

Homopolymer of 1‐4‐di[2,5‐di(2‐thienyl)‐1H‐1‐pyrrolyl]benzene and its copolymer with 3,4‐ethylenedioxythiophene (EDOT) were electrochemically synthesized and characterized. Resulting homopolymer and copolymer films have distinct electrochromic properties. At the neutral state, homopolymer has λ_max due to the π‐π* transition as 410 nm and E_g was calculated as 2.03 eV. The resultant copolymer revealed multichromism through the entire visible region, displaying red‐violet, brownish yellow green, and blue colors with the variation of the applied potential. For the copolymer, λ_max and E_g were found to be 450 nm and 1.66 eV, respectively. Double potential step chronoamperometry experiment shows that homopolymer and copolymer films have good stability, fast switching times, and high optical contrast in NIR region as 41 and 30%, respectively. Copolymerization with EDOT not only decreases the band gap, E_g, but also enhances the electrochromic properties. Hence, electrochemical copolymerization is considered to be a powerful tool to improve the electrochromic properties of N‐substituted 2,5‐di(2‐thienylpyrrole) derivatives. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of poly(ɛ-caprolactone-b-isobutylene) diblock copolymer and poly(ɛ-caprolactone-b-isobutylene-b-ɛ-caprolactone) triblock copolymer

Summary Poly(isobutylene-b-ɛ-caprolactone) diblock and poly(ɛ-caprolactone-b-isobutylene-b-ɛ-caprolactone) triblock copolymers have been prepared and characterized. The synthesis involved the living cationic polymerization of IB, followed by capping with 1,1-diphenylethylene or 1,1-p-ditolylethylene and end-quenching with 1-methoxy-1-trimethylsiloxy-2-methyl-propene to yield methoxycarbonyl functional PIB. Hydroxyl end-functional PIB polymers were quantitatively obtained by the subsequent reduction of methoxycarbonyl end-functional PIB with LiAlH₄. The structure of hydroxyl end-functional PIBs was confirmed by ¹H NMR and IR spectroscopy. Poly(ɛ-caprolactone-b-isobutylene) diblock copolymers and poly(ɛ-caprolactone-b-isobutylene-b-ɛ-caprolactone) triblock copolymers were synthesized by the living cationic ring-opening polymerization of ɛ-caprolactone with hydroxyl end-functional PIB as macroinitiator in the presence of HCl•Et₂O via the “activated monomer mechanism”. The block copolymers exhibited close to theoretical M_ns and narrow molecular weight distributions. Received: 30 January 2002/Revised version: 19 February 2002/ Accepted: 19 February 2002     

Investigation of the electroactivity,conductivity, and morphology of poly(pyrrole‐co‐N‐alkyl pyrrole) prepared via electrochemical nanopolymerization and chemical polymerization

The copolymerization of pyrrole (Py) with N‐ethyl pyrrole, N‐butyl pyrrole, and N‐octyl pyrrole (NOPy) was carried out by electrochemical and chemical oxidation. In the electrochemical method, copolymer thin films with different feed ratios of monomers were synthesized by the cyclic voltammetry method in a lithium perchlorate (LiClO₄)/acetonitrile (CH₃CN) electrolyte on the surface of a glassy carbon working electrode. The deposition conditions on the glassy carbon, the influence of the molar ratios of the monomers on the formation of the copolymers, and the electroactivity of the copolymers were investigated with cyclic voltammetry. Nanoparticles made of a conjugate of the copolymers with different feed ratios of monomers were prepared by chemical polymerization (conventional and interfacial methods) in the presence of iron(III) chloride hexahydrate (FeCl₃·6H₂O) as the oxidant. Nanostructural copolymers with higher conductivities were synthesized by simple tuning of the preparation conditions in a two‐phase medium. Fourier transform infrared spectroscopy, scanning electron microscopy, and four‐probe conductivity measurement techniques were applied for the characterization of the obtained copolymers. The conductivity of the obtained copolymer by an interfacial method with chloroform as the organic phase was 20 times higher than the copolymer obtained via an interfacial method with toluene as the organic phase and 700 times higher than the copolymer prepared by the conventional method (for a molar ratio of 70 : 30 Py : NOPy). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012