Aerobic oxidative polymerization of 2,6‐dimethylphenol in water with a highly efficient copper(II)– poly(N‐vinylimidazole) complex catalyst

A Cu(II)–poly(N‐vinylimidazole) (PVI) complex was prepared and used to catalyze the oxidative polymerization of 2,6‐dimethylphenol (DMP) to form poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) in water. The stoichiometric ratio between imidazole groups in PVI and copper ions was found to be 4 when continuous variation analysis was applied. Compared with a conventional Cu(II)–low‐molecular‐weight ligand complex, a high catalytic efficiency was observed in the polymerization of DMP catalyzed by the Cu(II)–PVI complex. The influence of the Cu(II)–PVI complex concentration and imidazole/Cu(II) molar ratio on the oxidative polymerization of DMP was studied. Both the yield and molecular weight of PPO increased significantly with the catalyst concentration and decreased with the imidazole/Cu(II) molar ratio. The molecular weight of PVI also played an important role in the improvement of the catalytic efficiency. The high catalytic efficiency of the Cu(II)–PVI complex may have been due to the concentration effect of the catalyst and substrate. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Nickel(II) complexes bearing the bis(β‐ketoamino) ligand for the copolymerization of norbornene with a higher 1‐alkene

A novel bis(β‐ketoamino)Ni(II) complex catalyst, Ni{CF₃C(O)CHC[N(naphthyl)]CH₃}₂, was synthesized, and the structure was solved by a single‐crystal X‐ray refraction technique. The copolymerization of norbornene with higher 1‐alkene was carried out in toluene with catalytic systems based on nickel(II) complexes, Ni{RC(O)CHC[N(naphthyl)]CH₃}₂(R?CH₃, CF₃) and B(C₆F₅)₃, and high activity was exhibited by both catalytic systems. The effects of the catalyst structure and comonomer feed content on the polymerization activity and the incorporation rates were investigated. The reactivity ratios were determined to be r_1‐octene = 0.009 and r_norbornene = 13.461 by the Kelen–Tüdõs method for the Ni{CH₃C(O)CHC[N(naphthyl)]CH₃}₂/B(C₆F₅)₃ system. The achieved copolymers were confirmed to be vinyl‐addition copolymers through the analysis of ¹H‐NMR and ¹³C‐NMR. The thermogravimetric analysis results showed that the copolymers exhibited good thermal stability (decomposition temperature, T_dec > 400°C), and the glass‐transition temperature of the copolymers were observed between 215 and 275°C. The copolymers were confirmed to be noncrystalline by wide‐angle X‐ray diffraction analysis and showed good solubility in common organic solvents. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation,characterization, and metal ion retention capacity of Co(II) and Ni(II) from poly(p‐HO‐ and p‐Cl‐phenylmaleimide‐co‐2‐hydroxypropylmethacrylate) using the ultra filtration technique

p‐Chlorophenylmaleimide and p‐hydroxyphenylmaleimide with 2‐hydroxypropyl methacrylate were synthesized by radical polymerization, and the metal ion retention capacity and thermal behavior of the copolymers were evaluated. The copolymers were obtained by solution radical polymerization with a 0.50 : 0.50 feed monomer ratio. The maximum retention capacity (MRC) for the removal of two metal ions, Co(II) and Ni(II) in aqueous phase were determined using the liquid‐phase polymer based retention technique. Inorganic ion interactions with the hydrophilic polymer were determined as a function of pH. The metal ion retention capacity does not depend strongly on the pH. Metal ion retention increased with an increase of pH for a copolymer composition 0.50 : 0.50. At different pH, the MRC of the poly(p‐chlorophenylmaleimide‐co‐2‐hydroxypropylmethacrylate) for Co(II) and Ni(II) ions varied from 44.1 to 48.6 mg/g and from 41.5 mg/g to 46.0 mg/g, respectively; while the MRC of poly(p‐hydroxyphenylmaleimide‐co‐2‐hydroxypropyl methacrylate) for Co(II) and Ni(II) ions varied from 28.4 to 35.6 mg/g and from 27.2 to 30.8 mg/g, respectively. The copolymers and copolymer–metal complexes were characterized by elemental analysis, FT‐IR, ¹H NMR spectroscopy, and thermal behavior. The thermal behavior of the copolymer and polymer–metal complexes were studied using differential scanning calorimetry and thermogravimetry techniques under nitrogen atmosphere. The thermal decomposition temperature and T_g were influenced by the binding‐metal ion on the copolymer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis,characterization, and metal complexation of poly(N‐phenylmaleimide‐co‐acrylic acid) and poly(N‐phenylmaleimide‐co‐acrylamide) as polychelatogens in aqueous solution

We carried out the free‐radical copolymerization of N‐phenylmaleimide with acrylic acid and acrylamide with an equimolar feed monomer ratio. We carried out the synthesis of the copolymers in dioxane at 70°C with benzoyl peroxide as the initiator and a total monomer concentration of 2.5M. The copolymer compositions were obtained by elemental analysis and ¹H‐NMR spectroscopy. The hydrophilic polymers were characterized by elemental analysis, Fourier transform infrared spectroscopy, ¹H‐NMR spectroscopy, and thermal analysis. Additionally, viscosimetric measurements of the copolymers were performed. Hydrophilic poly(N‐phenylmaleimide‐co‐acrylic acid) and poly(N‐phenylmaleimide‐co‐acrylamide) were used for the separation of a series of metal ions in the aqueous phase with the liquid‐phase polymer‐based retention method in the heterogeneous phase. The method is based on the retention of inorganic ions by the polymer in conjunction with membrane filtration and subsequent separation of low‐molecular‐mass species from the formed polymer/metal‐ion complex. The polymer could bind several metal ions, such as Cr(III), Co (II), Zn(II), Ni(II), Cu(II), Cd(II), and Fe(III) inorganic ions, in aqueous solution at pH values of 3, 5, and 7. The interaction of the inorganic ions with the hydrophilic polymer was determined as a function of pH and a filtration factor. Hydrophilic polymeric reagents with strong metal‐complexing properties were synthesized and used to separate those complexed from noncomplexed ions in the heterogeneous phase. The polymers exhibited a high retention capability at pH values of 5 and 7. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Study of complexes of poly(vinyl pyrrolidone) with copper and cobalt on solid state

A polymer–metal complex is a metal complex containing a polymer ligand, showing a remarkably specific structure in which central metal ions are surrounded by a colossal polymer chain. Based on this polymeric ligand, the polymer–metal complex has interesting and important characteristics, especially catalytic activities. This activity is different from that of the corresponding ordinary metal complex of low molecular weight. In this work we studied the synthesis and characterization, in the solid state, of different poly(vinyl pyrrolidone)–cobalt (PVP/Co) and –copper (PVP/Cu) complexes. We used differential thermal analysis and FTIR as the experimental techniques. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1512–1518, 2004     

Rhodium(I) complex catalyst immobilized on terpolymers of N‐vinylpyrrolidinone and 1‐vinylimidazole

The hydrosilylation of cyclohexanone and acetone with triethysilane and diphenysilane catalyzed by polymer‐supported Rh(I) complex has been investigated. Two terpolymers of styrene, divinylbenzene, and 1‐vinylimidazole (S/DVB/VI) or N‐vinylpyrrolidinone (S/DVB/NVP) were used as the catalysts supports. Physical characterization of these materials has involved the measurements of the structural parameters in the dry and swollen states by DSC, the nitrogen BET adsorption method and inverse steric exclusion chromatography ISEC. From these results it can be concluded that the original polymer structure has been changed during the complex attachment giving rise to materials of higher porosity. X‐ray photoelectron spectroscopy XPS, IR, and AAS spectroscopy were used to characterization of heterogeneous complexes before and after use. The effect of the morphology of the support on the catalytic properties of the polymer‐supported Rh(I) species was tested in the hydrosilylation of ketones and correlated with the reaction mechanism. It was demonstrated that the high selectivity of homogeneous rhodium complex toward the silyl ethers can be partially reversed to the dehydrogenative silylation products by a proper choice of polymer support with favorable microporous structure. Recycling tests demonstrated high stability of the supported catalysts during prolonged use. The constant selectivity of the supported catalysts demonstrated during recycling experiments showed that they could be useful for practical application. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Self‐assembled poly(styrene‐co‐N‐isopropylacrylamide) film induced by capillary force

The monodisperse poly(styrene‐co‐N‐isopropylacrylamide) (poly(St‐co‐NIPAAm)) particles prepared by emulsifier‐free emulsion polymerization with microwave irradiation were induced by capillary forces to self‐assemble, and formed the two‐dimensional films on the clean glassware wafer substrates. The morphologies of the two‐dimensional films were characterized by scanning electron microscopy (SEM) and atom force microscopy (AFM). The results showed that monodisperse poly(St‐co‐NIPAAm) particles could form ordered two‐dimensional films by capillary forces. With NIPAAm concentration increasing, there gradually appeared surface undulations or surface defective region on the two‐dimensional films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3514–3519, 2006     

Synthesis and characterization of chelating resins with amino moieties and application on removal of copper(II) from EDTA complexes

Strong‐field ligands (amino moieties) are introduced into a hydrogel resin to obtain a chelating resin via inversion suspension polymerization. The characteristics of chelating copolymers are measured by using Fourier transform IR spectroscopy (FTIR), elemental analysis (EA), and scanning electron microscopy (SEM). After chelating copolymers adsorb cupric ions, the absorption peak of stretch N? H is shifted to higher frequency because of a coordination reaction from the FTIR spectra. Furthermore, the mechanism of metal complex adsorption on the chelating copolymer is that the strong‐field chelating ligand decomposes the bonding of the metal complexes and recoordinates the cupric ion to a chelating polymer, which is examined via FTIR, SEM with EA, and ionic chromatography analysis. The maximum adsorption capacity of cupric ions is 1.08 mmol/g and the adsorption capacity increases with the increase of the pH of the solution. The stability constant of the Cu chelating copolymer is 10^18.72, and it can have competition adsorption with EDTA in aqueous solution. These amino chelating copolymers can be used not only to recover metal ions but also to move anion pollution in wastewater. It is interesting that parts of the cupric ions adsorbed on the chelating copolymer are reduced into cupreous ions and/or copper atoms after electron spectroscopy for chemical analysis measurement. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2457–2468, 2005     

Synthesis and characterization of superhydrophobic wood surfaces

Superhydrophobic films were developed on wood substrates with a wet chemical approach. Growth of zinc oxide (ZnO) nanorods was found differentially in the cross‐sectional walls and inner lumenal surfaces. The surface roughness of the prepared films on the inner lumenal surface conformed to the Cassie–Baxter wetting model, whereas the roughness across the microsurface of the cell wall was in conformity with the hydrophobic porous wetting model. The space between the ZnO nanorods and the microstructure of the wood surface constituted the nanoscale and microscale roughness of the ZnO nanofilm, respectively. The water contact angle of the prepared wood surfaces was up to 153.5°. In the prepared films, monolayers of stearic acid molecules were self‐assembled on the ZnO nanorods, which in turn, were attached to the wood surface via dimeric bonds. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Metal‐ion‐retention properties of the poly(2‐acrylamido‐2‐methyl‐1‐propanosulfonic acid‐co‐4‐vinyl pyridine) resin

The water‐insoluble resin poly(2‐acrylamido‐2‐methyl‐1‐propanosulfonic acid‐co‐4‐vinyl pyridine), through a radical polymerization solution, was synthesized with ammonium persulfate as an initiator and N,N‐methylene bisacrylamide as a crosslinking reagent. The metal‐ion‐retention properties were studied by batch and column equilibrium procedures for the following metal ions: Hg(II), Cu(II), Cd(II), Zn(II), Pb(II), and Cr(III). These properties were investigated under competitive and noncompetitive conditions. The effects of the pH, maximum retention capacity, and regeneration capacity were studied. The resin showed a high retention ability for Hg(II) ions at pH 2.0. The retention of Hg(II) ions from a mixture of ions was greater than 90%. The resin showed a high selectivity for Hg(II) with respect to other metal ions. The Hg(II)‐loaded resin was able to be recovered with 4M HClO₄. The retention capacity was kept after four cycles of adsorption and desorption. The retention properties for Hg(II) were very similar with the batch and column methods. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3556–3562, 2003     

Conductivity of layer and matrix polyaniline–silver–copper composites by plasma

This work presents a study on the formation of polymer–metal composites by means of plasma, combining silver and copper alloys with semiconducting polymer films. The objective is to improve the electric conductivity of polyanilines by forming layer and matrix composites. In this way, it is possible to increase the superficial and/or volumetric conductivity of the polymers. Electronic variables as the electronic density and energy along the reactor and their influence on the chemical composition, deposition rate, and the morphology of plasma polymer–metal composites are taken into consideration in the course of this study, as the shower of the most energetic particles in the plasma can produce multiple bonds between the metals and the polymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1031–1036, 2004     

Synthesis,characterization, and ligating behavior of poly[N,N‐p‐phenylene bisacryl (methacryl)amide]

Monomers of diacylated amine were synthesized by the reaction of acryloyl chloride or methacryloyl chloride with p‐phenylenediamine. Heating DMF solution of these monomers at 75°C in the presence of AIBN as an initiator gave the corresponding polymer. The solid metallopolymer complexes with different metal salts were isolated either by the in situ addition of the monomer, metal salt, and initiator at 75°C or by the reaction of the isolated polymer with the metal salt at 150°C. The monomers, polymers, and their metallopolymer compounds were characterized using elemental analysis, IR, NMR (¹H and ¹³C), and MS spectral measurements in addition to thermal analysis. The IR data showed that the coordinating atoms of the polymer are dependent on the reaction temperature. The ion selectivity of the isolated polymers toward different metal ions either for a single metal ion or in a mixture as aqueous solutions are studied by the batch techniques. Energy dispersive spectroscopy (EDS) measurements showed that both polymers are more selective to Hg²⁺ and Pb²⁺. The morphology of the polymers and their metallopolymer complexes at different temperature was also studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2412–2422, 2006     

Influence of the matrix porosity on the synthesis and adsorption behavior of dithiocarbamate styrenic resins toward zinc(II) and cadmium(II) ions

The dependence of the adsorption behavior toward Zn²⁺ and Cd²⁺ on the synthesis conditions of dithiocarbamate styrenic resins was investigated. We synthesized styrene–divinylbenzene copolymers with different kinds of porous structures by varying the divinylbenzene (DVB)‐to‐styrene ratio and the dilution degree of the monomers with n‐heptane. The porous structure of these materials was characterized. The introduction of the dithiocarbamate moiety on the copolymers followed a synthetic pathway based on the nitration reaction, reduction of the nitro group to the amino one, and finally, the addition of the amino group to CS₂. All of the synthesis steps were monitored by Fourier transform infrared spectroscopy. Only the addition reaction to CS₂ was greatly influenced by the copolymer porosity. The effect of the dilution degree on the reaction extension was more pronounced than the effect of the DVB content. The more porous materials with higher dithiocarbamate contents adsorbed a higher amount of ions in a faster way, with Zn²⁺ being preferable over Cd²⁺ ions. The difference between the Zn²⁺ and Cd²⁺ adsorption rates was enhanced with the copolymer porosity, and also enhanced was the difference between the amounts of ions adsorbed by the copolymer; this suggested that the selectivity toward these ions could be controlled by the copolymer porous structure. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and adsorption properties of chitosan–poly(acrylic acid) nanoparticles for the removal of nickel ions

Chitosan (CS) nanoparticles with different mean sizes ranging from 100 to 195 nm were prepared by ionic gelation of CS and poly(acrylic acid) (PAA). Variations in the final solution pH value and CS : PAA volume ratio were examined systematically for their effects on nanoparticle size, intensity of surface charge, and tendency toward particle aggregation. The sorption capacity and sorption isotherms of the CS–PAA nanoparticles for nickel ions were evaluated. The parameters for the adsorption of nickel ions by the CS–PAA nanoparticles were also investigated. The CS–PAA nanoparticles could sorb nickel ions effectively. The sorption rate for nickel ions was affected significantly by the initial concentration of the solution, sorbent amount, particle size, and pH value of the solution. The samples of nanoparticles were well correlated with Langmuir's isotherm model, and the adsorption kinetics of nickel correlated well with the pseudo‐second‐order model. The maximum capacity for nickel sorption deduced from the use of the Langmuir isotherm equation was 435 mg/g, which was significantly higher than that of the micrometer‐sized CS. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Synthesis and characterization of water‐soluble oligosalicylaldehyde‐sulfanilic acid and its Cu(II), Co(II), Pb(II) complexes

This work presents the synthesis and characterization of a new water‐soluble oligophenol derivative, 4‐(2‐hydroxybenzylideneamino)benzenesulfanilic acid (OSAL‐SA) and its metal complexes. The chemical structure of the water‐soluble polymer was characterized by nuclear magnetic resonance (¹H NMR) and Fourier transform infrared (FTIR) spectroscopies and thermogravimetric analyses (TGAs). Pb(II), Cu(II), Co(II) complexes of the polymer were also synthesized in methanol. Characterizations of water insoluble polymer‐metal complexes were performed by FTIR, flame atomic absorption spectroscopy, and TGA. The conductivity measurements of OSAL‐SA and polymer–metal complexes were carried out by the four‐probe technique. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Self‐assembled structures in polystyrene‐block‐polyisoprene‐blend‐polystyrene and polystyrene‐block‐poly(methyl methacrylate)‐blend‐polystyrene or ‐blend‐poly(methyl methacrylate) in the strong segregation regime

This study deals with the investigation of microphase‐separated morphology and phase behaviour in blends of polystyrene‐block‐polyisoprene with homopolystyrene and blends of polystyrene‐block‐poly(methyl methacrylate) with homopoly(methyl methacrylate) or homopolystyrene in the strong segregation regime using small‐angle X‐ray scattering and transmission electron microscopy as a function of composition, molecular weight of homopolymers, r_M and temperature. Parameter r_M = M_H/M_C (where M_H is the molecular weight of homopolymer and M_C that of the corresponding block copolymer) was selected to encompass behaviour of the chains denoted as a ‘wet brush’ (i.e. r_M < 1). The relative domain spacing D/D_o increases in the regime 0 < r_M?1 with increasing concentration of homopolymer w_P and increasing r_M but depends on the specific implemented morphology. We tested a new approximate D/D_o versus w_P relation in the strong segregation regime using block copolymers of high molecular weights. It is shown that the parameters r_M and χ^3/2N determine the slope of the D/D_o versus w_P relation in the strong segregation regime and the new approximation generally matches the experimental data better than the approximations used so far. Copyright © 2010 Society of Chemical Industry     

Amphiphilic block copolymer poly(lactic acid)‐block‐(glycidylazide polymer)‐block‐polystyrene: synthesis and self‐assembly

The triblock energetic copolymer poly(lactic acid)‐block‐(glycidylazide polymer)‐block‐polystyrene (PLA‐b‐GAP‐b‐PS) was synthesized successfully through atom‐transfer radical polymerization (ATRP) of styrene and ring‐opening polymerization of d,l ‐lactide. The energetic macroinitiator GAP‐Br, which was made from reacting equimolar GAP with α‐bromoisobutyryl bromide, firstly triggered the ATRP of styrene with its bromide group, and then the hydroxyl group on the GAP end of the resulting diblock copolymer participated in the polymerization of lactide in the presence of stannous octoate. The triblock copolymer PLA‐b‐GAP‐b‐PS had a narrow distribution of molecular weight. In the copolymer, the PS block was solvophilic in toluene and improved the stability of the structure, the PLA block was solvophobic in toluene and served as the sacrificial component for the preparation of porous materials, and GAP was the basic and energetic material. The three blocks of the copolymer were fundamentally thermodynamically immiscible, which led to the self‐assembly of the block copolymer in solution. Further studies showed that the concentration and solubility of the copolymer and the polarity of the solvent affected the morphology and size of the micelles generated from the self‐assembly of PLA‐b‐GAP‐b‐PS. The micelles generated in organic solvents at 10 mg mL^?1 copolymer concentration were spherical but became irregular when water was used as a co‐solvent. The spherical micelles self‐assembled in toluene had three distinct layers, with the diameter of the micelles increasing from 60 to 250 nm as the concentration of the copolymer increased from 5 to 15 mg L^?1. © 2017 Society of Chemical Industry     

Self‐assembled micelles prepared from poly(ɛ‐caprolactone)–poly(ethylene glycol) and poly(ɛ‐caprolactone/glycolide)–poly(ethylene glycol) block copolymers for sustained drug delivery

A series of poly(?‐caprolactone)–poly(ethylene glycol) (PCL‐PEG) and poly(?‐caprolactone/glycolide)–poly(ethylene glycol) [P(CL/GA)‐PEG] diblock copolymers were prepared by ring‐opening polymerization of ?‐caprolactone or a mixture of ?‐caprolactone and glycolide using monomethoxy PEG (mPEG) as macroinitiator and Sn(Oct)₂ as catalyst. The resulting copolymers were characterized using ¹H‐NMR, gel permeation chromatography, differential scanning calorimetry, and wide‐angle X‐ray diffraction. Copolymer micelles were prepared using the nanoprecipitation method. The morphology of the micelles was spherical or worm‐like as revealed by transmission electron microscopy, depending on the copolymer composition and the length of the hydrophobic block. Introduction of the glycolide component, even in small amounts (CL/GA = 10), disrupted the chain structure and led to the formation of spherical micelles. Interestingly, the micelle size decreased with the encapsulation of paclitaxel. Micelles prepared from mPEG5000‐derived copolymers exhibited better drug loading properties and slower drug release than those from mPEG2000‐derived copolymers. Drug release was faster for copolymers with shorter PCL blocks than for those with longer PCL chains. The introduction of glycolide moieties enhanced drug release, but the overall release rate did not exceed 10% in 30 days. In contrast, drug release was enhanced in acidic media. Therefore, these bioresorbable micelles and especially P(CL/GA)‐PEG micelles with excellent stability, high drug loading content, and prolonged drug release could be promising for applications as drug carriers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45732.     

Effect of the nature of crosslinking agent on the unusual metal ion specificity and selectivity of N,N‐bis(2‐aminoethyl)polyacrylamide

Metal ion desorbed crosslinked N,N‐bis(2‐aminoethyl)polyacrylamides showed enhanced specificity for the desorbed metal ion, and these polymers selectively rebind the desorbed metal ion from a mixture of metal ions. For this, polyacrylamide with 8 mol % divinylbenzene (DVB) and N,N′‐methylene‐bisacrylamide (NNMBA) crosslinking were prepared by solution polymerization. Diethylenetriamino functions were incorporated into the polymers by polymer analogous reactions. The complexing ability of the amino polymers were investigated toward various transition metal ions like Co(II), Ni(II), Cu(II), and Zn(II). Polymeric ligand and metal complexes were characterized by various spectral methods. The removal of the metal ion from the polymer matrix resulted in a memory for the desorbed metal ion. On rebinding, these polymers specifically rebind the desorbed metal ion and from a mixture of metal ions, it showed selectivity to the desorbed metal ion. Thus, the Cu(II) desorbed polymer specifically and selectively rebind Cu(II) ion from a mixture of Cu(II) and other metal ion. This selectivity is higher in the rigid DVB‐crosslinked system, resulting from the high rigidity of the crosslinked matrix compared to the semirigid NNMBA‐crosslinked system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of unsaturated poly(ε‐caprolactone) with a new titanium alkoxide initiator

Titanium alkoxides are widely used in the ring‐opening polymerization of ε‐caprolactone. In this study, functional poly(ε‐caprolactone) was synthesized with a new titanium initiator by a two‐step procedure: First, the titanium initiator, with an unsaturated group, was prepared by a classical organic reaction between 2‐hydroxyethylmethacrylate or 2‐allyloxyethanol with titanium tetrapropoxide; then, we initiated the polymerization of the ε‐caprolactone monomer in a glass reactor or twin‐screw extruder. By means of NMR spectroscopy, the structures of the initiators and polymers were determined. When 2‐hydroxyethylmethacrylate was used, there was a side reaction (transesterification) during the preparation of the initiator, and so it was impossible to obtain the expected product. With 2‐allyloxyethanol, the designed titanium initiator was synthesized with high purity, and the allyl moiety remained intact after the polymerization of ε‐caprolactone. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008