Synthesis and characterization of well‐defined poly(2‐hydroxyethyl methacrylate‐co‐styrene)‐graft‐poly(ε‐caprolactone) by sequential controlled polymerization

A new graft copolymer, poly(2‐hydroxyethyl methacrylate‐co‐styrene) ‐graft‐poly(?‐caprolactone), was prepared by combination of reversible addition‐fragmentation chain transfer polymerization (RAFT) with coordination‐insertion ring‐opening polymerization (ROP). The copolymerization of styrene (St) and 2‐hydroxyethyl methacrylate (HEMA) was carried out at 60 °C in the presence of 2‐phenylprop‐2‐yl dithiobenzoate (PPDTB) using AIBN as initiator. The molecular weight of poly (2‐hydroxyethyl methacrylate‐co‐styrene) [poly(HEMA‐co‐St)] increased with the monomer conversion, and the molecular weight distribution was in the range of 1.09 ～ 1.39. The ring‐opening polymerization (ROP) of ?‐caprolactone was then initiated by the hydroxyl groups of the poly(HEMA‐co‐St) precursors in the presence of stannous octoate (Sn(Oct)₂). GPC and ¹H‐NMR data demonstrated the polymerization courses are under control, and nearly all hydroxyl groups took part in the initiation. The efficiency of grafting was very high. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5523–5529, 2004     

Poly(styrene‐b‐isobutylene) multiarm star‐block copolymers

Multiarm star‐branched polymers based on poly(styrene‐b‐isobutylene) (PS‐PIB) block copolymer arms were synthesized under controlled/living cationic polymerization conditions using the 2‐chloro‐2‐propylbenzene (CCl)/TiCl₄/pyridine (Py) initiating system and divinylbenzene (DVB) as gel‐core‐forming comonomer. To optimize the timing of isobutylene (IB) addition to living PS⊕, the kinetics of styrene (St) polymerization at −80°C were measured in both 60 : 40 (v : v) methyl cyclohexane (MCHx) : MeCl and 60 : 40 hexane : MeCl cosolvents. For either cosolvent system, it was found that the polymerizations followed first‐order kinetics with respect to the monomer and the number of actively growing chains remained invariant. The rate of polymerization was slower in MCHx : MeCl (k_app = 2.5 × 10⁻³ s⁻¹) compared with hexane : MeCl (k_app = 5.6 × 10⁻³ s⁻¹) ([CCl]_o = [TiCl₄]/15 = 3.64 × 10⁻³M; [Py] = 4 × 10⁻³M; [St]_o = 0.35M). Intermolecular alkylation reactions were observed at [St]_o = 0.93M but could be suppressed by avoiding very high St conversion and by setting [St]_o ≤ 0.35M. For St polymerization, k_app = 1.1 × 10⁻³ s⁻¹ ([CCl]_o = [TiCl₄]/15 = 1.82 × 10⁻³M; [Py] = 4 × 10⁻³M; [St]_o = 0.35M); this was significantly higher than that observed for IB polymerization (k_app = 3.0 × 10⁻⁴ s⁻¹; [CCl]_o = [Py] = [TiCl₄]/15 = 1.86 × 10⁻³M; [IB]_o = 1.0M). Blocking efficiencies were higher in hexane : MeCl compared with MCHx : MeCl cosolvent system. Star formation was faster with PS‐PIB arms compared with PIB homopolymer arms under similar conditions. Using [DVB] = 5.6 × 10⁻²M = 10 times chain end concentration, 92% of PS‐PIB arms (M_n,PS = 2600 and M_n,PIB = 13,400 g/mol) were linked within 1 h at −80°C with negligible star–star coupling. It was difficult to achieve complete linking of all the arms prior to the onset of star–star coupling. Apparently, the presence of the St block allows the PS‐PIB block copolymer arms to be incorporated into growing star polymers by an additional mechanism, namely, electrophilic aromatic substitution (EAS), which leads to increased rates of star formation and greater tendency toward star–star coupling. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1629–1641, 1999     

Radical ring‐opening copolymerization behavior of vinyloxirane: Synthesis of copolymer from 2‐isopropenyl‐3‐phenyloxirane and styrene and its functionalization

The radical ring‐opening copolymerization of 2‐isopropenyl‐3‐phenyloxirane (1) with styrene (St) was examined to obtain the copolymer [copoly(1‐St)] with a vinyl ether moiety in the main chain. The copolymers were obtained in moderate yields by copolymerization in various feed ratios of 1 and St over 120 °C; the number‐average molecular weights (M_n) were estimated to be 1800–4200 by gel permeation chromatography analysis. The ratio of the vinyl ether and St units of copoly(1‐St) was estimated with the ¹H NMR spectra and varied from 1/7 to 1/14 according to the initial feed ratio of 1 and St. The haloalkoxylation of copoly(1‐St) with ethylene glycol in the presence of N‐chlorosuccinimide produced a new copolymer with alcohol groups and chlorine atoms in the side group in a high yield. The M_n value of the haloalkoxylated polymer was almost the same as that of the starting copoly(1‐St). The incorporated halogen was determined by elemental analysis. The analytical result indicated that over 88% of the vinyl ether groups participated in the haloalkoxylation. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3729–3735, 2000     

The preparation of amphiphilic core‐shell nanospheres by using water‐soluble macrophotoinitiator

The amphiphilic poly(AM‐co‐SA)‐ITXH macrophotoinitiator was synthesized by precipitation photopolymerization under UV irradiation with isopropylthioxanthone (ITX) as free radical photoinitiator. A novel method has been developed to prepare amphiphilic core‐shell polymer nanospheres via photopolymerization of methyl methacrylate (MMA) in aqueous media, with amphiphilic copolymer macrophotoinitiator poly(AM‐co‐SA)‐ITXH. During polymerization, the amphiphilic macroradicals underwent in situ self‐assembly to form polymeric micelles, which promoted the emulsion polymerization of the monomer. Thus, amphiphilic core‐shell nanospheres ranging from 70 to 140 nm in diameter were produced in the absence of surfactant. The conversion of the monomer, number average molecular weights (M_n), and particle size were found to be highly dependent on the macrophotoinitiator and monomer concentration. The macrophotoinitiator and amphiphilic particles were characterized by FTIR, UV‐vis, ¹H NMR, TEM, DSC, and contact angle measurements. The results showed the particles had well‐defined amphiphilic core‐shell structure. This new method is scientifically and technologically significant because it provides a commercially viable route to a wide variety of novel amphiphilic core‐shell nanospheres. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 936–942, 2010     

Polar,functionalized diene‐based materials. V. Free‐radical polymerization of 2‐[(N‐benzyl‐n‐methylamino)methyl]‐1,3‐butadiene and copolymerization with styrene

2‐[(N‐Benzyl‐N‐methylamino)methyl]‐1,3‐butadiene (BMAMBD), the first asymmetric tertiary amino‐containing diene‐based monomer, was synthesized by sulfone chemistry and a nickel‐catalyzed Grignard coupling reaction in high purity and good yield. The bulk and solution free‐radical polymerizations of this monomer were studied. Traditional bulk free‐radical polymerization kinetics were observed, giving polymers with 〈M_n〉 values of 21 × 10³ to 48 × 10³ g/mol (where M_n is the number‐average molecular weight) and polydispersity indices near 1.5. In solution polymerization, polymers with higher molecular weights were obtained in cyclohexane than in tetrahydrofuran (THF) because of the higher chain transfer to the solvent. The chain‐transfer constants calculated for cyclohexane and THF were 1.97 × 10^?3 and 5.77 × 10^?3, respectively. To further tailor polymer properties, we also completed copolymerization studies with styrene. Kinetic studies showed that BMAMBD incorporated into the polymer chain at a faster rate than styrene. With the Mayo–Lewis equation, the monomer reactivity ratios of BMAMBD and styrene at 75 °C were determined to be 2.6 ± 0.3 and 0.28 ± 0.02, respectively. Altering the composition of BMAMBD in the copolymer from 17 to 93% caused the glass‐transition temperature of the resulting copolymer to decrease from 64 to ?7 °C. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3227–3238, 2001     

Synthesis and characterization of amphiphilic copolymer of linear poly(ethylene oxide) linked with [poly(styrene‐co‐2‐hydroxyethyl methacrylate)‐graft‐poly(ε‐caprolactone)] using sequential controlled polymerization

A well‐defined amphiphilic copolymer of ‐poly(ethylene oxide) (PEO) linked with comb‐shaped [poly(styrene‐co‐2‐hydeoxyethyl methacrylate)‐graft‐poly(ε‐caprolactone)] (PEO‐b‐P(St‐co‐HEMA)‐g‐PCL) was successfully synthesized by combination of reversible addition‐fragmentation chain transfer polymerization (RAFT) with ring‐opening anionic polymerization and coordination–insertion ring‐opening polymerization (ROP). The α‐methoxy poly(ethylene oxide) (mPEO) with ω,3‐benzylsulfanylthiocarbonylsufanylpropionic acid (BSPA) end group (mPEO‐BSPA) was prepared by the reaction of mPEO with 3‐benzylsulfanylthiocarbonylsufanyl propionic acid chloride (BSPAC), and the reaction efficiency was close to 100%; then the mPEO‐BSPA was used as a macro‐RAFT agent for the copolymerization of styrene (St) and 2‐hydroxyethyl methacrylate (HEMA) using 2,2‐azobisisobutyronitrile as initiator. The molecular weight of copolymer PEO‐b‐P(St‐co‐HEMA) increased with the monomer conversion, but the molecular weight distribution was a little wide. The influence of molecular weight of macro‐RAFT agent on the polymerization procedure was discussed. The ROP of ε‐caprolactone was then completed by initiation of hydroxyl groups of the PEO‐b‐P(St‐co‐HEMA) precursors in the presence of stannous octoate (Sn(Oct)₂). Thus, the amphiphilic copolymer of linear PEO linked with comb‐like P(St‐co‐HEMA)‐g‐PCL was obtained. The final and intermediate products were characterized in detail by NMR, GPC, and UV. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 467–476, 2006     

Synthesis of a new monomer N′‐(β‐methacryloyloxyethyl)‐2‐pyrimidyl‐(p‐benzyloxycarbonyl)aminobenzenesulfonamide and its copolymerization with N‐phenyl maleimide

The new monomer N′‐(β‐methacryloyloxyethyl)‐2‐pyrimidyl‐(p‐benzyloxy‐ carbonyl)aminobenzenesulfonamide (MPBAS) (M₁) is synthesized using sulfadiazine as parent compound. It could be homopolymerized and copolymerized with N‐phenyl maleimide (NPMI) (M₂) by radical mechanism using AIBN as initiator at 60 °C in dimethylformamide. The new monomer MPBAS and polymers were identified by IR, element analysis and ¹H NMR in detail. The monomer reactivity ratios in copolymerization were determined by YBR method, and r₁ (MPBAS) = 2.39 ± 0.05, r₂ (NPMI) = 0.33 ± 0.02. In the presence of ammonium formate, benzyloxycarbonyl groups could be broken fluently from MPBAS segments of copolymer by catalytic transfer hydrogenation, and the copolymer with sulfadiazine side groups are recovered. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2548–2554, 2000     

Synthesis,characterization and release profiles of nanoparticles self‐assembled from poly (PEGMA‐co‐MMA‐co‐acryloyl‐β‐CD) copolymers

A novel amphiphilic copolymer was synthesized from poly (ethylene glycol) methyl ether methacrylate (PEGMA950), methyl methacrylate (MMA) and acryloyl‐β‐cyclodextrin (acryloyl‐β‐CD) using the composites of (NH₄)₂S₂O₈/NaHSO₃ as the oxidation–reduction initiators. The successful fabrication of poly(PEGMA‐co‐MMA‐co‐acryloyl‐β‐CD) copolymers was confirmed by Fourier transform infrared spectrometer (FTIR), ¹H‐nuclear magnetic resonance (¹H NMR) spectra. The amphiphilic copolymer could self‐assemble into nanoparticles (NPs), and their morphology and particle size distribution were characterized with transmission electron microscopy (TEM), atomic force microscope (AFM) and dynamic light scattering (DLS) methods. Ibuprofen (IBU) was encapsulated in the novel NPs, and the release profiles of IBU were investigated. FTIR and ¹H NMR spectra illustrated that the poly(PEGMA‐co‐MMA‐co‐acryloyl‐β‐CD) copolymers were synthesized without any residual monomers and initiators. TEM and AFM photographs suggested that the obtained NPs were spherical, and the DLS results indicated that the diameter of blank NPs was 157.3 ± 32.7 nm. The IBU release profile showed that the IBU‐loaded NPs had certain pH responsibility. Copyright © 2014 John Wiley & Sons, Ltd.     

Radical copolymerization of vinylidene fluoride with 1‐bromo‐2,2‐difluoroethylene

The radical copolymerization of vinylidene fluoride (VDF) and 1‐bromo‐2,2‐difluoroethylene (BDFE) in 1,1,1,3,3‐pentafluorobutane solution at different monomer molar ratios (ranging from 96/4 to 25/75 mol %) and initiated by tert‐butylperoxypivalate (TBPPI, mainly) is presented. Poly(VDF‐co‐BDFE) copolymers of various aspects (from white powders to yellow viscous liquids) were produced depending on the copolymer compositions. The microstructures of the obtained copolymers were characterized by ¹⁹F and ¹H NMR spectroscopy and by elementary analysis and these techniques enabled one to assess the contents of both comonomers in the produced copolymers. VDF was shown to be more incorporated in the copolymer than BDFE. From the extended Kelen and Tudos method, the kinetics of the radical copolymerization led to the determination of the reactivity ratios, r_i, of both comonomers (r_VDF = 1.20 ± 0.50 and r_{BDFE =} 0.40 ± 0.15 at 75 °C) showing that VDF is more reactive than BDFE. Alfrey‐Price's Q and e values of BDFE monomer were calculated to be 0.009 (from Q_VDF = 0.008) or 0.019 (from Q_VDF = 0.015) and +1.22 (vs. e_VDF = 0.40) or +1.37 (vs. e_VDF = 0.50), respectively, indicating that BDFE is an electron‐accepting monomer. Statistic cooligomers were produced with molar masses ranging from 1,800 to 5,500 g/mol (assessed by GPC with polystyrene standards). A further evidence of the successful copolymerization was shown by the selective reduction of bromine atoms in poly(VDF‐co‐BDFE) cooligomers that led to analog PVDF. The thermal properties of the poly(VDF‐co‐BDFE) cooligomers were also determined and those containing a high VDF amount exhibited a high thermal stability. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3964–3976, 2010.     

Fluorescence studies of the self‐organization of a cholesterol‐bearing polymethacrylate in n‐hexane solution

A copolymer of cholesteryl 6‐(methacryloyloxy)hexanoate and a small amount of (1‐pyrenylmethyl) 6‐(methacryloyloxy)hexanoate (Py‐C₅‐MA) was prepared by free radical copolymerization. A copolymer of 1‐eicosanylmethacrylate and a small amount of Py‐C₅‐MA was also prepared as a reference copolymer. A wide‐angle X‐ray diffraction pattern for an n‐hexane solution of the cholesterol(Chol)‐containing copolymer showed a peak corresponding to a spacing of 5.3 Å. In n‐hexane, the hydrodynamic radius (R_h) for the Chol‐containing copolymer (M_w = 7.8 × 10⁴) was 8.1 nm, while that of the eicosanyl‐containing copolymer (M_w = 4.9 × 10⁴) was 9.6 nm, R_h for the former being smaller than that for the latter, although M_w for the former was higher than that of the latter. ¹H‐NMR spectra of the Chol‐containing polymer in n‐hexane‐d₁₄ indicated a strong restriction of local motions of pendant Chol groups. Fluorescence spectra of the Chol‐containing copolymer in n‐hexane indicated that each pyrene group was isolated from others. In n‐hexane/benzene mixed solutions of the Chol‐containing polymer, the ratio of the intensity of the excimer relative to the monomer emission decreased with increasing the ratio of n‐hexane in the mixed solvent. Electron transfer from N,N‐dimethylaniline to singlet‐excited pyrene chromophores was suppressed in the Chol‐containing copolymer in n‐hexane. The pyrene chromophores exhibited a long triplet lifetime in n‐hexane. These observations led us to conclude that Chol groups formed stacks in n‐hexane, and that the pyrene chromophores were trapped in the Chol stacks, leading to the “protection” of pyrene from the bulk phase. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 47–58, 1999     

Preparation and characterization of poly(2‐hydroxyethylme thacrylate)‐b‐P(N‐phenylmaleimide)‐ZnO and poly(2‐hydroxy ethylmethacrylate)‐b‐P(styrene)‐ ZnO micro/nanostructures: micro/nanocomposite particles with core‐shell morphology

The present work reports the incorporation of the ZnO doped diblock copolymer matrix and its conversion into a self‐assembled structure. The diblock P(HEMA)₈₀‐b‐P(N‐PhMI)₂₀ and P(HEMA)₉₀‐b‐P(St)₁₀ copolymers consist of a majority (HEMA) and minority (N‐PhMI or St) block. The copolymers were synthesized with a block repeat unit ratio by atom‐transfer radical polymerization (ATRP) using a poly(2‐hydroxyethylmethacrylate)‐Cl/CuBr/bipyridine initiating system. The P(HEMA)‐Cl was prepared by reverse ATRP¹. The average theoretical number molecular weight (M_n,th) was calculated from the feed capacity. The composite of the inorganic nanoparticles was achieved at room temperature in the liquid phase, using ZnCl₂ precursor dopant and wet chemical processing to convert to ZnO nanoparticle films. Thermal characterization was performed using differential scanning calorimetry (DSC) and thermogravimetry (TG). The proton/area relationship confirmed the block copolymer compositions calculated by elemental analysis, consisting of a majority and minority blocks. Morphology properties of the polymer samples were investigated by scanning electron microscopy (SEM). The microphotographs of the film's surfaces show that the film's upper surfaces were generally smooth with ordered structure morphology. FT‐IR spectroscopy confirmed the association of the ZnCl₂ precursor with the majority block and the formation of ZnO, the white SEM showed the morphology of ZnO nanoparticles' films when the surface relief changes principally due to surface loss rather than its orientation. Copyright © 2009 John Wiley & Sons, Ltd.     

Preparation of monodisperse nanoparticles containing poly(propylene imine)(NH2)32‐polystyrene

Polypropylenimine dendrimer (DAB‐Am‐32, generation 4.0) was converted into a macroinitiator DAB‐Am‐32‐Cl via reaction with 2‐chloropropionyl chloride. Monodisperse nanoparticles containing poly(propylene imine)(NH₂)₃₂‐polystyrene were prepared by emulsion atom transfer radical polymerization (ATRP) of styrene (St), using the DAB‐Am‐32‐Cl/CuCl/bpy as initiating system. The structure of macroinitiator was characterized by FTIR spectrum, ¹H NMR, and ¹³C NMR. The structure of poly(propylene imine)(NH₂)₃₂‐polystyrene was characterized by FT‐IR spectrum and ¹H NMR; the molecular weight and molecular weight distribution of poly(propylene imine)(NH₂)₃₂‐polystyrene were characterized by gel permeation chromatograph (GPC). The morphology, size and size distribution of the nanoparticles were characterized by photon correlation spectroscopy (PCS), transmission electron microscopy (TEM), and atomic force microscopy (AFM). The effects of monomer/macroinitiator ratio and surfactant concentration on the size and size distribution of the nanoparticles were investigated. It was found that the diameters of the nanoparticles were smaller than 100 nm (30–80 nm) and monodisperse; moreover, the particle size could be controlled by monomer/macroinitiator ratios and surfactant concentration. With the increasing of the ratio of St/DAB‐Am‐32‐Cl, the number‐average diameter (D_n), weight‐average diameter (D_w) were both increased gradually. With enhancing the surfactant concentration, the measured D_h of the nanoparticles decreased, while the polydispersity increased. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2892–2904, 2009     

Atom transfer radical copolymerization of styrene and N‐cyclohexylmaleimide

Atom transfer radical copolymerization of Styrene (St) and N‐cyclohexylmaleimide (NCMI) with the CuBr/bipyridine catalyst in anisole, initiated by 1‐phenylethyl bromide (1‐PEBr) or tetra‐(bromomethyl)benzene (TBMB), afforded well‐defined copolymers with predetermined molecular weights and low polydispersities, M_w/M_n < 1.5. The influences of several factors, such as temperature, solvent, and monomer ratio, on the copolymerization with the CuBr/bpy catalyst system were subsequently investigated. The apparent enthalpy of activation for the overall copolymerization was measured to be 28.2 kJ/mol. The monomer reactivity ratios were evaluated to be r_NCMI = 0.046 and r_St = 0.127. Using TBMB as the initiator produced four‐armed star copolymer. The copolymerization of styrene and NCMI with TBMB/CuBr/bpy in PhOCH₃ at 110 °C was found to provide good control of molecular weights and polydispersities and the similar copolymerization in cyclohexanone displayed poor control. The glass transition temperature of the resultant copolymer increases with increasing f_NCMI, which indicates that the heat resistance of the copolymer has been improved by increasing NCMI. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1203–1209, 2000     

Synthesis of well‐defined naphthalene and photo‐labile group‐labeled polystyrene via ATRP

The atom transfer radical polymerizations of styrene were successfully carried out in bulk and solution, respectively, at 115 °C, with a novel photoiniferter reagent, (1‐naphthyl)methyl N,N‐diethyldithiocarbamate (NMDC), as an initiator in the presence of copper (I) bromide and N,N,N′,N″,N″‐pentamethyldiethylenetriamine. The results showed that NMDC was an effective initiator with high initiation efficiency for ATRP of St. The polymerization rate was first‐order with respect to the monomer concentration and the molecular weights of the obtained polystyrene (PS) increased linearly with the monomer conversion, with very narrow molecular weight distributions (M_w/M_n = 1.07–1.29). The functionalized naphthalene‐labeled PS bearing N,N‐(diethylamino)dithiocarbamoyl group which was confirmed by ¹H NMR analysis, and chain extension of the PS exhibited fluorescence and ultraviolet absorption in chloroform (CHCl₃). © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 510–518, 2006     

Copolymers of 2,5‐bis[(4‐methoxyphenyl) oxycarbonyl]styrene with styrene and methyl methacrylate: Synthesis,monomer reactivity ratios,thermal properties,and liquid crystalline behavior

Copolymers of a liquid crystalline monomer, 2,5‐bis[(4‐methoxyphenyl)oxycarbonyl]styrene (MPCS), with St and MMA were prepared by free radical polymerization at low conversion in chlorobenzene with 2,2′‐azobisisobutyronitrile (AIBN) as initiator. The copolymers of poly(MPCS‐co‐St) and poly(MPCS‐co‐MMA) were characterized by ¹H NMR and GPC. The monomer reactivity ratios were determined by using the extended Kelen–Tudos (EKT) method. Structural parameters of the copolymers were obtained from the possibility statistics and monomer reactivity ratios. The influence of MPCS content in copolymers on the glass transition temperatures of copolymers was investigated by DSC. The thermal stabilities of the two copolymer systems increased with an increase of the molar fraction of MPCS in the copolymers. The liquid crystalline behavior of the copolymers was also investigated using DSC and POM. The results revealed that the copolymers with high MPCS molar contents exhibited liquid crystalline behaviors. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2666–2674, 2005     

Homo‐ and copolymerization of norbornene and 5‐norbornene‐2‐yl acetate with bis‐(β‐ketonaphthylamino)palladium(II)/B(C6F5)3 catalytic system

The polymerization of norbornene with bis(β‐ketonaphthylamino) palladium(II), Pd{CH₃C(O)CHC[N(naphthyl)]CH₃}₂, in combination with tris(pentafluorophenyl)borane (B(C₆F₅)₃), was investigated by varying the B:Pd(II) molar ratio, monomer concentration, reaction temperature, and time. The catalytic activity was found to reach 2.8 × 10⁴ gPolymer/(molPd^?h) and the obtained polynorbornene (PNBE) was confirmed to be vinyl addition polymer and showed good thermo‐stability (T_dec > 350°C), but exhibited poor solubility in organic solvents due to the relative higher stereo regularity. Pd{CH₃C(O)CHC[N(naphthyl)]CH₃}₂/B(C₆F₅)₃ system is also an active catalyst for copolymerization of norbornene and 5‐norbornene‐2‐yl acetate (NBE‐OCOCH₃) in toluene with moderate yields (in 9.2–36.5% yields) and produces the addition‐type copolymer with relatively high molecular weights (0.96 × 10⁴–2.13 × 10⁴ g/mol). The incorporation of functional group in the copolymer can be controlled up to 0.9–23.5 mol% by varying the NBE‐OCOCH₃ monomer feed ratios from 10 to 90%. The copolymers are proved to be noncrystalline and show good solubility in common organic solvents and excellent thermal stability up to 350°C. Copyright © 2011 John Wiley & Sons, Ltd.     

Effect of lithium perchlorate on the spontaneous copolymerization of 4‐vinylpyridine with various electron‐rich vinyl monomers

The spontaneous copolymerization of 4‐vinylpyridine (4‐VP) activated with lithium perchlorate (LiClO₄) with various electron rich monomers (p‐methoxystyrene, MeOSt; p‐methylstyrene, MeSt; styrene, St) was investigated in various solvent systems at 75°C. Increasing the LiClO₄ concentration and the nucleophilicity of the electron rich monomer increased the copolymer yields. Both ¹H‐NMR and elemental analysis confirmed the almost 1:1 copolymer structure for VP/MeOSt system which possessed high molecular weight and narrow polydispersity (PDI). Compared to 4‐VP activated with zinc chloride, LiClO₄ systems showed slightly lower yields and much narrower PDI. We also investigated the spontaneous copolymerization of 4‐VP activated with various protic acids in the reaction with various electron rich comonomers. However, generally protic salt forms showed less solubility in organic solvents and showed low molecular weight polymer products with low yields. The proposed initiation mechanism exhibits the formation of a σ‐bond between the β‐carbons of the two donor‐acceptor monomers, creating the 1,4‐tetramethylene biradical intermediate initiating the copolymerization. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1709–1716, 1999     

Kinetic Study of Radical Polymerization VI. Copolymer Composition and Kinetic Parameters for Coplymerization of Styrene‐Itaconic Acid by On‐Line 1H‐NMR

Free radical solution copolymerization of styrene (St) and itaconic acid (IA) in dimethylsulfoxide‐d₆ (DMSO‐d₆) as the solvent and the use of 2,2′‐azobisisobutyronitrile (AIBN) as the initiator at 78°C was investigated by an on‐line ¹H‐NMR spectroscopy technique. Individual monomer conversion vs. reaction time, which was calculated from the ¹H‐NMR spectra data, was used to study the drift in monomer mixture composition vs. conversion. It was found that in general, both monomers were incorporated almost equally into the copolymer. However, when the mole fraction of IA was low, the tendency of IA toward incorporation into the copolymer chain was somewhat higher than St and by increasing the mole fraction of IA in the reaction mixture, the inverse tendency was observed. Overall monomer conversion as a function of time was calculated from individual monomer conversion data and used for the estimation of k_p /k_t ^0.5 for various monomer mixture compositions. This ratio was decreased with increasing the amount of IA in the initial feed, indicating a decrease in the rate of copolymerization. Changes in the copolymer composition vs. overall monomer conversion were investigated experimentally from the NMR spectra. This was in good agreement with the changes in monomer mixture composition vs. reaction progress. Plotting the copolymer composition vs. initial monomer feed showed tendency of the system toward alternating copolymerization.     

Synthesis of tetrazole‐containing azo polymers with properties of photo‐induced birefringence and surface‐relief‐gratings via RAFT polymerization

A novel optically active monomer, 6‐{4‐[4‐(1‐phenyl‐1H‐tetrazol‐5‐yloxy)‐phenylazo] ‐phenoxy}‐hexyl methacrylate (PTPPHMA) bearing tetrazole and azobenzol moieties, was synthesized and polymerized by reversible addition‐fragmentation chain transfer (RAFT) polymerization using 2‐cyanoprop‐2‐yl dithiobenzoate (CPDB) as the RAFT agent and 2, 2′‐azobis(isobutyronitrile) (AIBN) as the initiator. Well‐defined optically active photochromic polyPTPPHMA(PPTPPHMA) was obtained. “Living”/controlled characteristics were observed in the polymerization: well‐controlled molecular weights (M_ns), narrow molecular weight distributions (M_w/M_n) of the polymers and successful chain‐extension of PPTPPHMA with styrene (St) as the second monomer. The photochemical interconversion between trans and cis isomers of PPTPPHMA in N,N′‐dimethyl formamide (DMF) solution was explored under irradiation of ultraviolet light. The photoinduced birefringence on the thin films of PPTPPHMA was investigated. A maximum birefringence of 0.1 was obtained, and no significant change of profiles of the birefringence after several cycles of writing/erasing/rewriting sequences was observed. The surface‐relief‐gratings (SRGs) were induced on the polymer films by interference of Kr⁺ laser beams at 413.1 nm with 35 mW/cm² intensity, the diffraction efficiencies from SRGs were measured to be in the range of 2.0–2.5%. The atomic force microscopy (AFM) results showed the gratings produced on the surfaces of the polymer film. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 682–691, 2008