Copolymerization of N‐(4‐carboxyphenyl) itaconimide or N‐(4‐carboxyphenyl) itaconamic acid with methyl methacrylate

This paper describes the synthesis and characterization of N‐(4‐carboxyphenyl) itaconamic acid (CPA) and N‐(4‐carboxyphenyl) itaconimide (CPI) obtained by reacting itaconic anhydride with p‐aminobenzoic acid. Structural and thermal characterization of CPA and CPI was done using ¹H‐NMR, FTIR, and differential scanning calorimetry (DSC). Copolymerization of CPA or CPI with methyl methacrylate (MMA) in solution was carried out at 60 °C using azobisisobutyronitrile as an initiator and dimethyl acetamide or THF as solvent. Feed compositions having varying mole fractions of CPA or CPI ranging from 0.05–0.20 or 0.1–0.5 were taken to prepare copolymers. Copolymerizations were terminated at low percentage conversion. Structural characterization of copolymers was done by ¹H‐NMR and elemental analysis. Copolymer composition was determined using percentage nitrogen content. The reactivity ratios were r₁ (MMA) = 0.68 ± 0.06 and r₂ (CPI) = 0.46 ± 0.06. The intrinsic viscosity [η] was determined using an Ubbelohde suspension level viscometer. [η] decreased with increasing mole fraction of N‐(p‐carboxyphenyl) itaconimide or N‐(p‐carboxyphenyl) itaconamic acid in copolymers. Glass transition temperature and thermal stability of the copolymers were determined using DSC and thermogravimetric analysis, respectively. The glass transition temperature (T_g) as determined from DSC scans increased with increasing amounts of CPA or CPI in copolymers. A significant improvement in the char yield was observed upon copolymerization. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1909–1915, 2005     

Copolymerization and thermal behavior of methyl methacrylate with N‐(phenyl/p‐tolyl) itaconimides

This study describes the synthesis, characterization, and thermal behavior of copolymers of methyl methacrylate (MMA) and N‐p‐tolyl itaconimide (PTI)/N‐phenyl itaconimide (I). Homopolymerization and copolymerization of N‐(phenyl/p‐tolyl) itaconimide with MMA was carried out by use of various mole fractions of N‐aryl itaconimide in the initial feed from 0.1 to 0.5, using azobisisobutyronitrile as an initiator and tetrahydrofuran as the solvent. The copolymer composition was determined by ¹H‐NMR spectroscopy using the proton resonance signals attributed to –OCH₃ of MMA (δ = 3.5–3.8 ppm) and the aromatic protons (δ = 7.0–7.5 ppm) of N‐aryl itaconimide. The reactivity ratios of the monomers were found to be r₁ (PTI) = 1.33 ± 0.05/r₂ (MMA) = 0.24 ± 0.03 and r₁ (I) = 1.465 ± 0.035/r₂ (MMA) = 0.385 ± 0.005. The molecular weight of the copolymers decreased with increasing mole fraction of N‐aryl itaconimide in the copolymers. Glass‐transition temperature (T_g) and thermal stability of PMMA increased with increasing amounts of itaconimides in the polymer backbone. A significant increase in the percentage char yield at 700°C was observed on incorporation of a low mole fraction of N‐aryl itaconimides. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1195–1202, 2003     

Studies on the copolymerization of methyl methacrylate with N‐(o/m/p‐chlorophenyl) itaconimides

The article describes the synthesis and characterization of N‐aryl itaconimide monomers such as: N‐(p‐chlorophenyl) itaconimide (PI)/N‐(m‐chlorophenyl) itaconimide (MI)/N‐(o‐chlorophenyl) itaconimide (OI) and its copolymerization behavior with MMA. The homopolymers and copolymers of N‐aryl itaconimides and methyl methacrylate (MMA, M₂) were synthesized by varying the mol fraction of N‐aryl itaconimides in the initial feed from 0.1 to 0.5 using azobisisobutyronitrile (AIBN) as an initiator and tetrahydrofuran (THF) as the solvent. Copolymer composition was determined using ¹H‐NMR spectroscopy [by taking the ratio of intensities of signals due to ? OCH₃ of MMA (δ = 3.59 ppm) and the aromatic proton (δ = 7.2–7.5 ppm) of N‐aryl itaconimides] and percent nitrogen content. The reactivity ratios were found to be r₁ = 1.33 and r₂ = 0.36 (PI‐MMA) r₁ = 1.15 and r₂ = 0.32 (MI‐MMA) and r₁ = 0.81 and r₂ = 0.35 (OI‐MMA). Molecular weight as determined using high‐performance liquid chromatography decreased with increasing mol fraction of itaconimides in copolymers. All the polymers had a polydisperstivity index in the range of 1.5–2.6.Thermal characterization was done using differential scanning calorimetry and dynamic thermogravimetry in nitrogen atmosphere. Incorporation of these N‐aryl itaconimides in PMMA backbone resulted in an improvement in glass transition temperature (T_g) and thermal stability. Percent char increased with the increase of PI/MI/OI content in the copolymers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2078–2086, 2001     

Copolymerization of N‐aryl substituted itaconimide with methyl methacrylate: Effect of substituents on monomer reactivity ratio and thermal behavior

The article describes the synthesis and characterization of N‐(4‐methoxy‐3‐chlorophenyl) itaconimide (MCPI) and N‐(2‐methoxy‐5‐chlorophenyl) itaconimide (OMCPI) obtained by reacting itaconic anhydride with 4‐methoxy‐3‐chloroanisidine and 2‐methoxy‐5‐chloroanisidine, respectively. Structural and thermal characterization of MCPI and OMCPI monomers was done by using ¹H NMR, FTIR, and differential scanning calorimetry (DSC). Copolymerization of MCPI or OMCPI with methyl methacrylate (MMA) in solution was carried out at 60°C using AIBN as an initiator and THF as solvent. Feed compositions having varying mole fractions of MCPI and OMCPI ranging from 0.1 to 0.5 were taken to prepare copolymers. Copolymerizations were terminated at low percentage conversion. Structural characterization of copolymers was done by FTIR, ¹H NMR, and elemental analysis and percent nitrogen content was used to calculate the copolymer composition. The monomer reactivity ratios for MMA–MCPI copolymers were found to be r₁ (MMA) = 0.32 ± 0.03 and r₂ (MCPI) = 1.54 ± 0.05 and that for MMA–OMCPI copolymers were r₁ (MMA) = 0.15 ± 0.02 and r₂ (OMCPI) = 1.23 ± 0.18. The intrinsic viscosity [η] of the copolymers decreased with increasing mole fraction of MCPI/or OMCPI. The glass transition temperature as determined from DSC scans was found to increase with increasing amounts of OMPCI in copolymers. A significant improvement in the char yield as determined by thermogravimetry was observed upon copolymerization. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2391–2398, 2006     

Studies on the copolymerization of methyl methacrylate and N-aryl maleimides

This article describes the synthesis and characterization of copolymers of methyl methacrylate (MMA) and N-4-chlorophenyl maleimide (PC)/N-3-chlorophenyl maleimide (MC). The copolymers were synthesized by varying the mole fraction of N-aryl maleimides from 0.1 to 0.5 in the initial feed using azobisisobutyronitrile (AIBN) as an initiator and tetrahydrofuran (THF) as the solvent. The copolymer composition was determined from the ¹H-NMR spectra by taking the ratio of proton resonance signals due to methoxy protons (δ = 3.59 ppm) of MMA and aromatic protons (δ = 7.2–7.4 ppm) of N-aryl maleimides. The reactivity ratios for MMA–PC and MMA–MC copolymers were found to be 0.952 (r₁), 0.029 (r₂) and 0.833 (r₁) and 0.033 (r₂), respectively. Thermal characterization of the copolymers was done using differential scanning calorimetry (DSC) and dynamic thermo-gravimetry. Initial decomposition temperature and glass transition temperature increased with increasing mole fraction of N-aryl maleimide content in the copolymers. © 1996 John Wiley & Sons, Inc.     

Synthesis and thermal self-crosslinking reaction of copolymers from 2,3-epoxypropyl methacrylate and p-substituted phenyl methacrylates

Copolymers of 2,3-expoxypropyl (glycidyl) methacrylate (GMA) with various phenyl methacrylates such as 4-nitrophenyl methacrylate (NPMA), 4-chlorophenyl methacrylate (CPMA), or phenyl methacrylate (PMA), and other monomers such as methyl methacrylate (MMA), ethyl acrylate (EA), or styrene (ST) were synthesized by radical copolymerization, and then thermal self-crosslinking reactions of the obtained copolymers were carried out using various catalysts such as quarternary ammonium salts, tert-amines, or the crown ether/potassium salt systems at 100–150°C. Although the copolymer of GMA–NPMA–MMA does not produce any gel products without catalyst upon heating at 110°C for 5 h, this copolymer gives gel products in 82% yield using 10 mol% of tetrabutylammonium bromide as a catalyst under the same conditions. The rate of gel production of the copolymer of NPMA is faster than those of copolymers of CPMA and PMA. The rate of the gel production of the copolymer of GMA–NPMA–EA is also faster than those of copolymers of MMA and ST. Furthermore, it was found that the rate of gel production of the copolymer was strongly affected by the kind of catalyst, the catalyst concentration, and the reaction temperature.     

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     

Morphologies and dynamic mechanical properties of core‐shell emulsifier‐free latexes and their copolymers for P(BA/MMA)/P(MMA/BA) and P(BA/MMA)/PSt systems in the presence of AHPS

Different poly(methyl methacrylate/n‐butyl acrylate)/poly(n‐butyl acrylate/methyl methacrylate) [P(BA/MMA)/P(MMA/BA)] and poly(n‐butyl acrylate/methyl methacrylate)/polystyrene [P(BA/MMA)/PSt] core‐shell structured latexes were prepared by emulsifier‐free emulsion polymerization in the presence of hydrophilic monomer 3‐allyloxy‐2‐hydroxyl‐propanesulfonic salt (AHPS). The particle morphologies of the final latexes and dynamic mechanical properties of the copolymers from final latexes were investigated in detail. With the addition of AHPS, a latex of stable and high‐solid content (60 wt %) was prepared. The diameters of the latex particles are ～0.26 μm for the P(BA/MMA)/P(MMA/BA) system and 0.22–0.24 μm for the P(BA/MMA)/PSt system. All copolymers from the final latexes are two‐phase structure polymers, shown as two glass transition temperatures (T_gs) on dynamic mechanical analysis spectra. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3078–3084, 2002     

Controllable radical copolymerization of styrene and methyl methacrylate using 1,1,2,2‐tetraphenyl‐1,2‐bis(trimethylsilyloxy) ethane as initiator

Copolymerization of styrene (St) and methyl methacrylate (MMA) was carried out using 1,1,2,2‐tetraphenyl‐1,2‐bis (trimethylsilyloxy) ethane (TPSE) as initiator; the copolymerization proceeded via a “living” radical mechanism and the polymer molecular weight (M_w) increased with the conversion and polymerization time. The reactivity ratios for TPSE and azobisisobutyronitrile (AIBN) systems calculated by Finemann–Ross method were r_St = 0.216 ± 0.003, r_MMA= 0.403 ± 0.01 for the former and r_St= 0.52 ± 0.01, r_MMA= 0.46 ± 0.01 for the latter, respectively, and the difference between them and the effect of polymerization conditions on copolymerization are discussed. Thermal analysis proved that the copolymers obtained by TPSE system showed higher sequence regularity than that obtained by the AIBN system, and the sequence regularity increased with the content of styrene in copolymer chain segment. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1474–1482, 2001     

Transparent poly(methyl methacrylate‐co‐butyl acrylate) nanofibers

Nanofibers of n‐Butyl Acrylate/Methyl Methacrylate copolymer [P(BA‐co‐MMA)] were produced by electrospinning in this study. P(BA‐co‐MMA) was synthesized by emulsion polymerization. The structural and thermal properties of copolymers and electrospun P(BA‐co‐MMA) nanofibers were analyzed using Fourier transform infrared spectroscopy–Attenuated total reflectance (FTIR–ATR), Nuclear magnetic spectroscopy (NMR), and Differential scanning calorimetry (DSC). FTIR–ATR spectra and NMR spectrum revealed that BA and MMA had effectively participated in polymerization. The morphology of the resulting nanofibers was investigated by scanning electron microscopy, indicating that the diameters of P(BA‐co‐MMA) nanofibers were strongly dependent on the polymer solution dielectric constant, and concentration of solution and flow rate. Homogeneous electrospun P(BA‐co‐MMA) fibers as small as 390 ± 30 nm were successfully produced. The dielectric properties of polymer solution strongly affected the diameter and morphology of electrospun polymer fibers. The bending instability of the electrospinning jet increased with higher dielectric constant. The charges inside the polymer jet tended to repel each other so as to stretch and reduce the diameter of the polymer fibers by the presence of high dielectric environment of the solvent. The extent to which the choice of solvent affects the nanofiber characteristics were well illustrated in the electrospinning of [P(BA‐co‐MMA)] from solvents and mixed solvents. Nanofiber mats showed relatively high hydrophobicity with intrinsic water contact angle up to 120°. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4264–4272, 2013     

Studies on the microstructure of vinyl/N‐phenylmaleimide copolymers by NMR and their applications

The micro‐ and stereostructures and sequence distribution of methyl methacrylate (MMA)/N‐phenylmaleimide (PMI) and styrene (St)–PMI copolymers were studied in detail with NMR spectroscopy. The MMA–PMI copolymer was in a random sequence distribution and the St–PMI copolymer was alternating in structure. Some micro‐ and stereoinformation of the MMA–PMI copolymers could be obtained from ¹H‐NMR spectra. The average number sequence length obtained from the copolymer triad by ¹³C‐NMR spectra was in agreement with that calculated from the reactivity ratios measured by an elemental analyzer. From the triad fraction of the copolymer measured by ¹³C‐NMR, the copolymer chain of MMA–PMI was proved to be a one‐order Markov chain. More suitable propagation reactions were proposed from the deviation of sequence distribution of the St–PMI copolymer. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2581–2587, 2000     

Synthesis and characterization of diblock,triblock, and multiblock copolymers containing poly(3‐hydroxy butyrate) units

A poly[(R,S)‐3‐hydroxybutyrate] macroinitiator (PHB‐MI) was obtained through the condensation reaction of poly[(R,S)‐3‐hydroxybutyrate] (PHB) oligomers containing dihydroxyl end functionalities with 4,4′‐azobis(4‐cyanopentanoyl chloride). The PHB‐MI obtained in this way had hydroxyl groups at two end of the polymer chain and an internal azo group. The synthesis of ABA‐type PHB‐b‐PMMA block copolymers [where A is poly(methyl methacrylate) (PMMA) and B is PHB] via PHB‐MI was accomplished in two steps. First, multiblock active copolymers with azo groups (PMMA‐PHB‐MI) were prepared through the redox free‐radical polymerization of methyl methacrylate (MMA) with a PHB‐MI/Ce(IV) redox system in aqueous nitric acid at 40°C. Second, PMMA‐PHB‐MI was used in the thermal polymerization of MMA at 60°C to obtain PHB‐b‐PMMA. When styrene (S) was used instead of MMA in the second step, ABCBA‐type PMMA‐b‐PHB‐b‐PS multiblock copolymers [where C is polystyrene (PS)] were obtained. In addition, the direct thermal polymerization of the monomers (MMA or S) via PHB‐MI provided AB‐type diblocks copolymers with MMA and BCB‐type triblock copolymers with S. The macroinitiators and block copolymers were characterized with ultraviolet–visible spectroscopy, nuclear magnetic resonance spectroscopy, gel permeation chromatography, cryoscopic measurements, and thermogravimetric analysis. The increases in the intrinsic viscosity and fractional precipitation confirmed that a block copolymer had been obtained. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1789–1796, 2004     

Starch‐g‐polycaprolactone copolymerization using diisocyanate intermediates and thermal characteristics of the copolymers

Starch‐g‐polycaprolactone copolymers were prepared by two‐step reactions. The diisocyanate‐terminated polycaprolactone (NCO–PCL) was prepared by introducing NCO on both hydroxyl ends of PCL using diisocyanates (DI) at a molar ratio between PCL and DI of 2:3. Then, the NCO–PCL was grafted onto corn starch at a weight ratio between starch and NCO–PCL of 2:1. The chemical structure of NCO–PCL and the starch‐g‐PCL copolymers were confirmed by using FTIR and ¹³C‐NMR spectrometers, and then the thermal characteristics of the copolymers were investigated by DSC and TGA. By introducing NCO to PCL (M_n : 1250), the melting temperature (T_m ) was reduced from 58 to 45°C. In addition, by grafting the NCO–PCL (35–38%) prepared with 2,4‐tolylene diisocyanate (TDI) or 4,4‐diphenylmethane diisocyanate (MDI) onto starch, the glass transition temperatures (T_g 's) of the copolymers were both 238°C. With hexamethylene diisocyanate (HDI), however, T_g was found to be 195°C. The initial thermal degradation temperature of the starch‐g‐PCL copolymers were higher than that of unreacted starch (320 versus 290°C) when MDI was used, whereas the copolymers prepared with TDI or HDI underwent little change. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 986–993, 2000     

Novel amphiphilic polymer gel electrolytes based on (PEG‐b‐GMA)‐co‐MMA

Amphiphilic conetwork–structured copolymers containing different lengths of ethylene oxide (EO) chains as ionophilic units and methyl methacrylate (MMA) chains as ionophobic units were prepared by free radical copolymerization and characterized by FTIR and thermal analysis. Polymer gel electrolytes based on the copolymers complexed with liquid lithium electrolytes (dimethyl carbonate (DMC) : diethyl carbonate (DEC) : ethylene carbonate (EC) = 1 : 1 : 1 (W/W/W), LiPF₆ 1.0M) were characterized by differential scanning calorimetry and impedance spectroscopy. A maximum ion conductivity of 4.27 × 10^?4 S/cm at 25^oC was found for the polymer electrolyte based on (PEG2000‐b‐GMA)‐co‐MMA with long EO groups. Moreover, the effect of temperature on conductivity of the amphiphilic polymer electrolytes obeys the Arrhenius equation. The good room temperature conductivity of the polymer electrolytes is proposed to relate to the enhancement in the amorphous domain of the copolymers due to their amphiphilic conetwork structure. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and properties of chitosan‐graft‐poly(methyl methacrylate) nanoparticles using potassium diperiodatocuprate (III) as an initiator

Graft copolymer nanoparticles prepared from chitosan (CS) and methyl methacrylate (MMA) monomer were synthesized in aqueous solution by using potassium diperiodatocuprate [Cu(III)] as an initiator and characterized in terms of particle size, zeta potential, transmission electron microscopy (TEM), Fourier transform infrared spectroscopy, thermal stability, and X‐ray diffraction spectrometry. The results indicated that CS was covalently linked to poly(methyl methacrylate) (PMMA), and the resulting copolymers formed nanoparticles. These nanoparticles [prepared at 35°C, in a weight ratio of MMA/CS of 5 : 1 and with a Cu(III) concentration of 1.5 × 10⁻³ mol/L] were 54–350 nm in size, with a mean hydrodynamic diameter of 183 ± 3 nm and were highly uniform in particle‐size distribution, with a rather spherical shape and an obvious positive charge surface. The effect of reaction conditions such as Cu(III) concentration, reaction temperature, and the weight ratio of MMA/CS on the mean particle size was also investigated. Insulin‐loaded nanoparticles were prepared, and their maximal association efficiency was up to 85.41%. The experiment of release in vitro showed that the nanoparticles gave an initial burst release followed by a slowly sustained one. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Copolymers of a new methacrylate monomer bearing oxime ester and ether with methyl methacrylate: Synthesis,characterization, monomer reactivity ratios,and biological activity

The free‐radical copolymerization of 2‐metil‐1‐{[(1‐{4‐[(4‐nitrobenzil)oksi]fenil}etilidene)amino]oksi}prop‐2‐en‐1‐on (NBOEMA) with methyl methacrylate (MMA) was carried out in 1,4‐dioxane at 65 ± 1°C. The copolymers were analyzed by Fourier transform infrared spectroscopy, ¹H‐NMR, ¹³C‐NMR, and gel permeation chromatography (GPC). Elemental analysis was used to determine the molar fractions of NBOEMA and MMA in the copolymers and for the characterization of the compounds. The monomer reactivity ratios were calculated according to the general copolymerization equation with the Kelen–Tudos and Fineman–Ross linearization methods. The polydispersity indices of the polymers, determined with GPC, suggested a strong tendency for chain termination by disproportionation. The thermal behaviors of the copolymers with various compositions were investigated by differential scanning calorimetry and thermogravimetric analysis. The glass‐transition temperature of the copolymers increased with increasing NBOEMA content in the copolymers. Also, the apparent thermal decomposition activation energies were calculated by the Ozawa method with a Shimadzu TGA 60H thermogravimetric analysis thermobalance. All of the products showed moderate activity against different strains of bacteria and fungi. The photochemical properties of the polymers were investigated by UV spectroscopy. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of novel copolymers with the trimethylsilyl group for deep‐UV photoresists

N‐(4‐Acetoxyphenyl) maleimide (APMI) and three kinds of comonomers bearing a trimethylsilyl group were copolymerized at 60°C in the presence of azobisisobutyronitrile (AIBN) as an initiator in 1,4‐dioxane to obtain the three IP, IIP, and IIIP copolymers. These copolymers were removed from the acetoxy group in a transesterification process into new IVP, VP, and VIP copolymers with a pendant hydroxyl group. Two modified processes were adopted to prepare photoresists using these copolymers. The first process involved mixing the dissolution inhibitor, o‐nitrobenzyl cholate, with the new copolymers. Second, o‐nitrobenzyl cholate was introduced into the copolymers using 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) in dimethylformamide (DMF). The cyclic maleimide structure is responsible for the high thermal stability of these copolymers. After irradiation using deep–UV light and development with aqueous Na₂CO₃ (0.01 wt %), the developed patterns showed positive images and exhibited good adhesion to the silicon wafer without using any adhesion promoter. The resolution of these resists was at least 0.8 μm and an oxygen‐plasma etching rate was 1/5.3 to that of hard‐baked HPR‐204. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2791–2798, 2002; DOI 10.1002/app.10255     

PMMA‐multigraft copolymers derived from linseed oil,soybean oil,and linoleic acid: Protein adsorption and bacterial adherence

Synthesis of Poly(methyl methacrylate), PMMA‐multigraft copolymers derived from linseed oil, soybean oil, and linoleic acid PMMA‐g‐polymeric oil/oily acid‐g‐poly(3‐hydroxy alkanoate) (PHA), and their protein adsorption and bacterial adherence have been described. Polymeric oil/oily acid peroxides [polymeric soybean oil peroxide (PSB), polymeric linseed oil peroxide (PLO), and polymeric linoleic acid peroxide (PLina)] initiated the copolymerization of MMA and unsaturated PHA‐soya to yield PMMA–PLO–PHA, PMMA–PSB–PHA, and PMMA–PLina–PHA multigraft copolymers. PMMA–PLina–PHA multigraft copolymers were completely soluble while PMMA–PSB–PHA and PMMA–PLO–PHA multigraft copolymers were partially crosslinked. Crosslinked parts of the PLO‐ and PSB‐multigraft copolymers were isolated by the sol gel analysis and characterized by swelling measurements in CHCl₃. Soluble part of the PLO‐ and PSB‐multigraft copolymers and completely soluble PLina‐multigraft copolymers were obtained and characterized by spectroscopic, thermal, gel permeation chromatography (GPC), and scanning electron microscopy (SEM) techniques. In the mechanical properties of the PHA–PLina–PMMA, the elongation at break is reduced up to ～ 9%, more or less preserving the high stress values at its break point (48%) when compared to PLina‐g‐PMMA. The solvent casting film surfaces were studied by means of adsorption of blood proteins and bacterial adhesion. Insertion of the PHA into the multigraft copolymers caused the dramatic increase in bacterial adhesion on the polymer surfaces. PHA insertion into the graft copolymers also increased the protein adsorption. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis of well‐defined comb‐like amphiphilic copolymers with protonizable units in the pendent chains: 1. Preparation of narrow polydispersity copolymers of methyl methacrylate and 2‐hydroxyethyl methacrylate by atom‐transfer radical polymerization

Well‐defined methyl methacrylate (MMA) and 2‐(trimethylsiloxy)ethyl methacrylate (Pro‐HEMA) copolymers were prepared by atom‐transfer radical polymerization(ATRP), using CuCl/2,2′‐bipyridine as catalytic system and p‐toluenesulfonyl chloride as initiator. ATRP process of MMA and Pro‐HEMA was monitored by ¹H NMR, and the kinetic curves of the MMA/Pro‐HEMA copolymerization were plotted in terms of the ¹H NMR data. At low content of Pro‐HEMA in the feed composition, the copolymerization can be well controlled with the molecular weight, polydispersity and the monomer distribution in the copolymer chain. With the increase of Pro‐HEMA content in the feed mixture, the composition of the final copolymer deviates from the composition of the feed mixture gradually, and gradient copolymers of MMA/Pro‐HEMA can be obtained. Through the hydrolysis process, well‐defined copolymers of MMA/HEMA were obtained from poly(MMA/Pro‐HEMA). Copyright © 2003 Society of Chemical Industry     

Synthesis and polymerization of a new iodine‐containing monomer

A new iodine‐containing methacrylate monomer, 3,4,5‐triiodobenzoyloxyethyl methacrylate (TIBEM), was synthesized by coupling 2‐hydroxyethyl methacrylate (HEMA) with 3,4,5‐triiodobenzoic acid. The monomer was characterized by ¹H nuclear magnetic resonance, infrared (IR), and ultraviolet spectra. Homopolymerization and copolymerization of the monomer with methyl methacrylate (MMA) were carried out using 2,2′‐azobis isobutyronitrile as the initiator. A terpolymer of TIBEM, MMA, and HEMA was also synthesized. The copolymers were characterized by IR, gel permeation chromatography, differential thermal analysis, and thermogravimetric analysis (TGA). High molecular weight polymers were produced with MMA at different feed compositions of TIBEM. The polymers were found to be freely soluble in common solvents for acrylic polymers. TGA showed little decomposition of the copolymer below 280°C. Copolymers showed good radiopacity at 25 wt % of TIBEM in the feed. These copolymers could find applications in medical and dental areas where radiopacity is a desirable feature of the implants. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2580–2584, 2003