Synthesis and characterization of poly(ethylene oxide)‐based glycopolymers and their biocompatibility with osteoblast cells

Poly(ethylene oxide)‐block‐poly(methacryl‐d ‐glucopyranoside) (PEO‐GP) and poly(methacryl‐d ‐glucopyranoside) (H‐GP) glycopolymers were synthesized by deacetylation of acetylated polymers which were synthesized via atom transfer radical polymerization. The synthesized glycopolymers were characterized using ¹H NMR, ¹³C NMR and Fourier transform infrared (FTIR) spectroscopies, gel permeation chromatography (GPC), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The deacetylated polymers exhibited onset decomposition temperatures about 60 °C lower compared to the polymers having acetyl pendants. The glass transition temperature (T_g) of the acetylated homopolymer was 133 °C and that of the PEO‐based block copolymer was 124 °C. The deacetylated polymers H‐GP and PEO‐GP exhibited T_g values of about ?30 °C. Biocompatibility of the H‐GP and PEO‐GP glycopolymers was obtained by studying osteoblast cell adhesion, viability and proliferation in vitro. The cell viability showed an increase with increasing concentration of H‐GP from 0.1 to 1 µmol L^?1 and then decreased with further increase in its concentration (10–1000 µmol L^?1). PEO‐GP did not show a significant variation in cell viability on variation of its concentration from 0.1 to 1000 µmol L^?1. The significant improvement in biocompatibility with osteoblast cells in the presence of PEO‐GP was considered as due to the covalently bonded PEO segment of the methacrylate glycopolymer block. © 2014 Society of Chemical Industry     

Ethylene polymerization with hybrid nickel diimine/Cp2TiCl2 catalyst: a new method to prepare blends of linear and branched polyethylene

Blends of linear polyethylene (LPE) and branched polyethylene (BPE) display very good mechanic properties that can be beneficial for various applications such as shear thinning and melt elasticity. LPE, BPE and amorphous polyethylene can be produced using nickel diimine (DMN) catalyst under various polymerization conditions, while LPE can be obtained using metallocene catalyst. Thus, LPE/BPE blends can be achieved by in situ polymerization using a hybrid DMN/metallocene catalyst. A novel hybrid catalyst made of DMN and Cp₂TiCl₂ was designed and used for ethylene polymerization. A synergistic effect of the two active sites in the hybrid DMN/metallocene catalyst was observed. Blends of linear and low branched polyethylene were synthesized when polymerization was conducted at low temperature (0 °C), while blends of linear and highly branched polyethylene were obtained at high temperature (50 °C). However, the miscibility of the polymers obtained at 50 °C was dramatically reduced as compared to those obtained at 0 °C. Mesoporous particles (MCM‐41) consisting of aluminosilicate with cylindrical pores were used to support the hybrid catalyst, in which MCM‐41 provides sufficient nanoscale pores to facilitate the polymerization in well‐controlled confined spaces. Blends of LPE and BPE were synthesized by in situ polymerization without adding comonomer and characterized. The miscibility of the polymer blends can be improved by supporting the hybrid catalyst on MCM‐41. Copyright © 2009 Society of Chemical Industry     

Thermal and electrical properties of copoly(1,3,4‐oxadiazole‐ethers) containing fluorene groups

A series of aromatic copolyethers containing 1,3,4‐oxadiazole rings and fluorene groups was prepared by nucleophilic substitution polymerization technique of 9,9‐bis(4‐hydroxyphenyl)fluorene, 1 , or of different amounts of 1 and an aromatic bisphenol, such as 4,4′‐isopropylidenediphenol or phenolphthalein, with 2,5‐bis(p‐fluorophenyl)‐1,3,4‐oxadiazole. The polymers were easily soluble in polar solvents like N‐methylpyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide, and chloroform and can be cast from solutions into thin flexible films. They showed high thermal stability, with decomposition temperature being above 425°C. The polymers exhibited a glass‐transition temperature in the range of 195–295°C, with a reasonable interval between glass‐transition and decomposition temperature. Electrical insulating properties of some polymer films were evaluated on the basis of dielectric constant and dielectric loss and their variation with frequency and temperature. The values of the dielectric constant at 10 kHz and 20°C were in the range of 3.16–3.25. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Polyimides derived from 1,4‐bis [3‐oxy‐(N‐aminophthalimide)] benzene

A novel diamine, 1,4‐bis [3‐oxy‐(N‐aminophthalimide)] benzene (BOAPIB), was synthesized from 1,4‐bis [3‐oxy‐(N‐phenylphthalimide)] benzene and hydrazine. Its structure was determined via IR, ¹H NMR, and elemental analysis. A series of five‐member ring, hydrazine‐based polyimides were prepared from this diamine and various aromatic dianhydrides via one‐step polycondensation in p‐chlorophenol. The inherent viscosities of these polyimides were in the range of 0.17–0.61 dL/g. These polymers were soluble in polar aprotic solvents and phenols at room temperature. Thermogravimetric analysis (TGA) showed that the 5% weight‐loss temperatures of the polyimides were near 450°C in air and 500°C in nitrogen. Dynamic mechanical thermal analysis (DMTA) indicated that the glass‐transition temperatures (T_gs) of these polymers were in the range of 265–360°C. The wide‐angle X‐ray diffraction showed that all the polyimides were amorphous. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of temperature,solvent, Lewis acid and additives on the polymerization of tert‐butyl vinyl ether using Lewis acid‐induced N‐methyleneamines as cationic initiators

N‐Methyleneamines, formed by treating 1,3,5‐trimethylhexahydro‐1,3,5‐triazines with Lewis acids, have been shown to be capable initiators in the cationic polymerization of tert‐butyl vinyl ether, yielding polymers with amine functionality at the chain ends. Previous work was limited to titanium(IV) chloride (TiCl₄) as the Lewis acid in dichloromethane solvent at 0 °C (with resulting polymers possessing relatively broad polydispersity index (PDI) values near 2), while this contribution details the effect of reaction parameters on the polymeric products; specifically, the role of temperature, solvent, Lewis acid and additives. Ultimately, performing the polymerization at ?78 °C in dichloromethane with TiCl₄ as the Lewis acid and tetra‐n‐butylammonium chloride (nBu₄NCl) as the additive afforded the best control over the system, with polymers formed possessing low PDI values (<1.2). Dramatic changes in number‐average molecular weight and PDI were observed in polymers formed by initiating systems of Lewis acid‐induced N‐methyleneamines, with temperature, solvent, Lewis acid and additives all playing a role. By varying single parameters, optimization of the system was achieved. Copyright © 2009 Society of Chemical Industry     

Lanthanide(II) amide complexes: Efficient initiators for the living polymerization of methyl methacrylate

Lanthanide(II) complexes supported by amido ligands, [(C₆H₅)(Me₃Si)N]₂Ln(DME)₂ [Ln = Sm ( 1 ) or Yb ( 2 ); DME = 1,2‐dimethoxyethane] and [(C₆H₃? ⁱPr₂‐2,6)(Me₃Si)N]₂Ln(THF)₂ [Ln = Sm ( 3 ) or Yb ( 4 ); THF = tetrahydrofuran], were found to initiate the polymerization of methyl methacrylate (MMA) as efficient single‐component initiators (in toluene for 3 and 4 and in toluene with a small amount of THF for 1 and 2 ) to produce syndiotactic polymers. The catalytic behavior was highly dependent on both the amido ligand and the polymerization temperature. Initiators 3 and 4 initiated MMA polymerization over a wide range of temperatures (20°C to ?40°C), whereas the polymerization with 1 and 2 proceeded smoothly only at low temperatures (≤0°C). The kinetic behavior and some features of the polymerizations of MMA initiated by 3 and 4 were studied at ?40°C. The polymerization rate was first‐order with the monomer concentration. The molar masses of the polymers increased linearly with the increase in the polymer yields, whereas the molar mass distributions remained narrow and unchanged throughout the polymerization; this indicated that these systems had living character. A polymerization mechanism initiated by bimetallic bisenolate formed in situ was proposed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Fast responsive and strong swelling hydrogels based on N‐isopropylacrylamide with sodium acrylate

Poly(N‐isopropylacrylamide‐co‐sodium acrylate) gels with N,N‐methylene bisacrylamde (BIS) as crosslinker were prepared by free radical polymerization method at the temperature of 35°C, which was just around the lower critical solution temperature (LSCT) of the hydrogels. The gels synthesized at 35°C demonstrated strong swellability and fast responseability when compared with the gels synthesized at the temperature of 0 and 18°C (below the LCST) and 50 and 80°C (above the LSCT). The response rate and swelling behavior of poly(N‐isopropylacrylamide‐co‐sodium acrylate) gels was investigated and characterized by the temperature‐dependent swelling ratio and swelling and deswelling kinetics. The swelling behavior of the gels indicated that the synthesis temperature was the main factor when the swellability concerned and also had effect on the responseability of the resulting hydrogels. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Investigation of liquid crystalline and photocrosslinkable poly[4‐x‐phenyl‐4′‐(m‐methacryloyloxyalkyloxy)cinnamate]s

Three series of liquid‐crystalline‐cum‐photocrosslinkable polymers were synthesized from 4‐x‐phenyl‐4′‐(m‐methacryloyloxyalkyloxy)cinnamates (x = ? H, ? OCH₃ and ? CN; m = 6, 8 and 10) by free radical solution polymerization using azobisisobutyronitrile as an initiator in tetrahydrofuran at 60 °C. All the monomers and polymers were characterized using intrinsic viscosity, and FTIR, ¹H NMR and ¹³C NMR spectroscopy. The liquid crystalline behavior of these polymers was examined using a hot stage optical polarizing microscope. All the polymers exhibited liquid crystalline behavior. The hexamethylene spacer‐containing polymers exhibited grainy textures; in contrast, the octamethylene and decamethylene spacer‐containing polymers showed nematic textures. Differential scanning calorimetry data confirmed the liquid crystalline property of the polymers. Thermogravimetric analysis revealed that all the polymers were stable between 236 and 344 °C in nitrogen atmosphere and underwent degradation thereafter. As the methylene chain length increases in the polymer side‐chain, the thermal stability and char yield of the polymers decrease. The photocrosslinking property of the polymers was investigated using the technique of exposing the polymer solution to UV light and using UV spectroscopy. The crosslinking reaction proceeds via 2π–2π cycloaddition reactions of the ? CH?CH? of the pendant cinnamate ester. The polymers containing electron‐releasing substituents (? OCH₃) showed faster crosslinking than the unsubstituted polymers and those containing electron‐withdrawing substituents (? CN). Copyright © 2007 Society of Chemical Industry     

Synthesis and characterization of novel poly(phenylene sulfide) containing a chromophore in the main chain

A kind of novel poly(phenylene sulfide)s (PPSs) containing a chromophore group were synthesized by the reaction of dihalogenated monomer and sodium sulfide (Na₂S.xH₂O) via nucleophilic substitution polymerization under high pressure. The polymers were characterized by Fourier transform infrared spectroscopy, ultraviolet spectroscopy, fluorescence spectroscopy, XRD, DSC, TGA, mechanical testing and dissolvability experiments. The intrinsic viscosity of the polymers obtained with optimum synthesis conditions was 0.22 ? 0.38 dl g^?1 (measured in 1‐chloronaphthalene at 208 °C). These polymers were found to have good thermal performance with a glass transition temperature (T_g) of 90.5 ? 94.6 °C and initial degradation temperature (T_d) of 475–489 °C, showing improved thermal properties compared with homo‐PPS. At the same time the resultant resins had a high tensile strength of 67.5 ? 74.1 MPa and compressive strength of 70.7 ? 85.4 MPa. Additionally, these polymers exhibited a weak UV ? visible reflectivity minimum at 450–570 nm, and the fluorescence spectra of the polymers showed maximum emission around nearly 370 nm. Also they showed excellent chemical resistance and another special property ? bright shiny colors changed into different colors in acid solution. © 2014 Society of Chemical Industry     

Synthesis and characterization of hydrophilic copolymers of maleimide derivatives with 2‐hydroxyethyl methacrylate: electrochemical and thermal behavior

BACKGROUND: The high‐technology industries have been the driving force in the development of new synthetic polymers that combine thermal stability with specific functional properties. In this study p‐chlorophenylmaleimide, p‐hydroxyphenylmaleimide and p‐nitrophenylmaleimide (R‐PhMI) with 2‐hydroxyethyl methacrylate (HEMA) were synthesized by free radical polymerization to obtain hydrophilic polymers, in order to study the effect of the p‐chloroaryl, p‐hydroxyaryl or p‐nitroaryl group on the copolymer composition, electrochemical behavior and thermal properties. RESULTS: The thermal behavior was correlated with the copolymer composition and functional groups, maleimide derivatives, on the copolymers. Thermal decomposition temperature (TDT) and glass transition temperature (T_g) were influenced by the functional groups of R‐PhMI moiety on the copolymer. The polymers showed an electrochemically irreversible reduction process under the conditions tested. CONCLUSION: Poly[(p‐chloromaleimide)‐co‐(2‐hydroxyethyl methacrylate)] copolymer shows a higher TDT than poly[(p‐hydroxymaleimide)‐co‐(2‐hydroxyethyl methacrylate)] or poly[(p‐nitromaleimide)‐co‐(2‐hydroxyethyl methacrylate)] (NPHE). T_g decreases in going from nitro to hydroxyl to chloro groups. The NPHE copolymer shows a lower stability, losing weight at 200 °C. The NPHE copolymer shows a well‐defined reduction wave which is similar to those of the other copolymers and it also shows an additional quasi‐reversible reduction wave corresponding to the nitrobenzene group. Copyright © 2009 Society of Chemical Industry     

A novel amide and imide copolymer as matrix resin for UV photoresist

A novel amide and imide copolymer, poly(N‐phenylmethacrylamide‐co‐N‐(p‐hydroxyphenyl)maleimide) was synthesized for the matrix resin of ultraviolet (UV) photoresist. Elemental analysis and self‐polymerization experiment verified that this copolymer was very close to 1:1 (molar ratio) in composition and was predominately alternating. It was able to dissolve in various organic solvents and form uniform curing film when spin‐coating. Its differential scanning calorimetry and thermogravimetry analysis test showed good thermal stability and its glass transition temperature (T_g) was about 280°C. Photolithographic experiment indicated that the UV photoresist formulated with this copolymer as matrix resin was achieved the resolution of about 5 μm, the contrast of 3.001, and the sensitivity of 32 mJ/cm². With good plasma etching resistance, the photoresist studied was able to bear 250°C for 30 min without thermal deformation during the thermal resistance test. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

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 evaluation of antifouling polymers of 4‐acryloyloxybenzaldehyde with methyl methacrylate

In recent years, antifouling (AF) polymers are widely used in marine paints to protect the ship hulls from biofouling. The AF polymer coatings have better leaching characteristics and long lasting efficiency than other conventional formulations. In this study, an attempt has been made to prepare new p‐acryloyloxybenzaldehyde(AcBA) polymers to assess their AF efficiency against marine microfoulers. The monomer, AcBA was prepared by the esterification reaction between p‐hydroxybenzaldehyde (HBA) and acryloyl chloride (Ac) in presence of triethylamine (TEA) in MEK at 0°C. The reaction was monitored by TLC and the prepared monomer was characterized by UV, IR, ¹H‐NMR and GC‐MS. The homo‐[poly(AcBA)] and co‐polymers [poly(AcBA‐co‐MMA)] were prepared by solution polymerization using BPO as initiator. To find out the AF activity of prepared polymers, representatives of marine microfoulers, shipfouling bacteria (Bacillus macroides and Pseudomonas aeruginosa) and microalgae (Amphora coffeaeformis and Navicula incerta) were screened. The contact toxicity and diatom attachment assays were conducted with prepared polymers and microfouling formation on coatings was also investigated using a tubular biofilm reactor. AF potential of these polymers coating is demonstrated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and chemical properties of dielectric polyphenylenes with nitro group

Polyphenylenes consisting of nitrophenylene and didodecyloxy‐p‐phenylene units have been synthesized by Pd‐catalyzed organometallic polycondensation. The polymers showed good solubility and had number–average molecular weights (M_n) of 13,000–37,000. Their spin‐coated films showed fairly high dielectric constants (ε) of 3.75–6.36. The polymers were electrochemically active with electrochemical reduction peaks in the range of ?1.72 to ?1.99 V versus Ag⁺/Ag in an acetonitrile solution of [NEt₄]BF₄ (0.10M). The polymer composed of 2,3′‐dinitrobiphenyl and didodecyloxy‐p‐phenylene units showed thermotropic liquid crystalline phase at about 240°C. Cast films of the polymer had a birefringent phase at room temperature, suggesting self‐assembly of the polymer in the solid. XRD studies revealed that the polymers assumed an ordered structure assisted by aggregation of the long alkoxy side chains in the solid. The polymer main chain in the cast film is considered to be aligned parallel with respect to the surface of substrates. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

New polymer syntheses,Part 43: Novel polyamides‐based diarylidenecyclopentanone: Synthesis,characterization, and corrosion inhibition behavior

A new interesting class of polyamides containing diarylidenecyclopentanone moiety III_a–f was synthesized by polycondensation reaction of the new diamino arylidene monomer I with different aliphatic and aromatic diacid chlorides (including adipoyl, sebacoyl, oxaloyl, terephthaloyl, isophthaloyl, biphenyldicarbonyl) and LiCl anhydrous as a catalyst at room temperature in NMP. The model compound II was synthesized by the interaction of one mole of diarylidenecyclopentanone monomer I with two moles of benzoyl chloride in NMP/LiCl at room temperature. The structure of the model compound was confirmed by correct elemental and spectral analyses. The resulting polymers were characterized by elemental and spectral analyses, beside solubility and viscometry measurements. The thermal properties of those polymers were evaluated by TGA, DTG, and DTA measurements and correlated to their structural units. X‐ray analysis showed that polymers having high degree of crystallinity in the region 2θ = 5 ? 60°. In addition, the UV‐visible spectra of some selected polymers were measured in DMSO solution and showed absorption bands in the range 260 ? 475 nm, due to n ? π* and π ? π* transition. On the other hand, the corrosion inhibition behavior of selected examples of polyamides was carried out on carbon–steel in 0.5M H₂SO₄ at 40°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Novel thermally resistant polysilphenylenesiloxanes with a high content of vinyl substituents

Polysilphenylenesiloxanes containing various amounts of vinyl substituents (ranging from partial (25 %) to complete (100 %)) on the silicon atoms were synthesized. ²⁹Si NMR spectroscopy revealed that they had a well defined structure, as designed. Unlike the known crystalline poly(tetramethyl‐p‐silphenylenesiloxane), all polymers containing vinyl side groups were amorphous and showed low T_gs, ranging from ?52 to ?32 °C (from differential scanning calorimetry (DSC)). Dynamic and isothermal thermogravimetric (TG) analyses indicated that they all possessed a greatly improved thermal stability up to 500 °C, and have ultra‐high residual yields at 1000 °C under both inert and oxidative conditions. Polysilphenylenesiloxanes containing a high percentage of vulcanizable vinyl substituents should be excellent candidates for high‐temperature polymers and have potential applications such as heat‐resistant or flame‐retardant materials. Copyright © 2004 Society of Chemical Industry     

Synthesis and characterization of some aromatic polyimides

The diamine 2‐methyl‐1,3‐bis(4‐aminophenyloxy)benzene was prepared via a nucleophilic substitution reaction and was characterized with Fourier transform infrared, elemental analysis, and ¹H‐ and ¹³C‐NMR spectroscopy. The prepared diamine was also characterized with single‐crystal analysis. The geometric parameters of C₁₉H₁₈N₂O₂ were in the usual ranges. The dihedral angles between the central phenyl ring and the two terminal aromatic rings were 88.9 and 91.6°. The crystal structure was stabilized by N? H···N hydrogen bonds. The diamine was then polymerized with 3,3′,4,4′‐benzophenone tetracarboxylic acid dianhydride, 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, 3,4,9,10‐perylenetetracarboxylic acid dianhydride, and pyromellitic dianhydride by either a one‐step solution polymerization reaction or a two‐step procedure. These polymers had inherent viscosities ranging from 0.61 to 0.85 dL/gm. Some of the polymers were soluble in most common organic solvents even at room temperature, and some were soluble on heating. The degradation temperatures of the resultant polymers fell in the range of 260–500°C in nitrogen (with only 10% weight loss). The specific heat capacity at 200°C ranged from 1.0 to 2.21 J g^?1 K^?1. The temperatures at which the maximum degradation of the polymer occurred ranged from 510 to 610°C. The glass‐transition temperatures of the polyimides ranged from 182 to 191°C. The activation energy and enthalpy of the polyimides ranged from 44.44 to 73.91 kJ/mol and from 42.58 to 72.08 kJ/mol K, respectively. The moisture absorption was found in the range of 0.23–0.71%. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Improved dispersion of clay platelets in poly(butylene terephthalate) nanocomposite by ring‐opening polymerization of cyclic oligomers: Effect of the processing conditions and comparison with nanocomposites obtained by melt intercalation

Poly(butylene terephthalate) nanocomposites with organically modified montmorillonites have been prepared by in‐situ ring opening polymerization of PBT cyclic oligomers. High molecular weight polymers can be obtained by choosing the proper polymerization conditions and catalyst in very short polymerization time (10 min) and low temperature (205°C). A better dispersion of the clay and a consistently higher M_w have been obtained by this method respect to the standard melt intercalation approach, leading to improved thermo‐mechanical properties of the nanocomposite. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis,curing behavior and thermal properties of silicon‐containing hybrid polymers with Si−C≡C units

Three novel kinds of linear silicon‐containing hybrid polymers with Si?C≡C units were synthesized by polycondensation reactions using the Grignard reagent method. All the polymers were thermosetting, highly heat‐resistant, moldable and easily soluble in common organic solvents. The structure, curing behavior, thermal and oxidative properties were characterized using Fourier transform infrared spectroscopy, ¹H NMR, ¹³C NMR, gel permeation chromatography, differential scanning calorimetry and thermogravimetric analysis. The results obtained can provide theoretical guidance for determining the curing of the resin system. In addition, the cured polymers exhibit excellent thermal and oxidative stabilities with temperatures of 5% weight loss (T_d5) above 480 °C and 450 °C in nitrogen and air respectively; the residues at 1000 °C were above 70.0% and 45.0% respectively. The thermal and oxidative stabilities of the polymers are attributed to a crosslinking reaction between the Si?H and C≡C bonds or C≡C bonds. These polymers have the potential for use as high‐temperature‐resistant resins and ceramic precursors. © 2013 Society of Chemical Industry     

Synthesis of poly(methyl methacrylate) nanoparticles initiated by azobisisobutyronitrile using a differential microemulsion polymerization technique

Nanosized poly(methyl methacrylate) (PMMA) particles with a high molecular weight of 10⁶ g mol^?1 and a polydispersity index of about 1–2 were synthesized, for which 2,2′‐azobisisobutyronitrile was used as the initiator and a differential microemulsion polymerization technique was employed. The kinetics of the polymerization, the glass transition temperature, tacticity, the particle size distribution, and the morphology of the nanosized PMMA synthesized were investigated. The dependence of the number of the polymer particles (N_p) and the number of the micelles (N_m) on the concentration of the surfactant was discussed. The molecular weight distribution was found to be nearly constant over the polymerization time, which was attributed to the significance of micellar polymerization. The resultant nanosized PMMA has a rich syndiotactic configuration (53–57% rr triads) with a glass transition temperature of about 125°C. A beneficial operation condition was discovered where the conversion reached a maximum at a high monomer‐to‐water ratio. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009