A copolymer of poly[2,2′‐(m‐phenylene)‐5,5′‐ bibenzimidazole] and poly(2,5‐benzimidazole) for high‐temperature proton‐conducting membranes

A novel copolymer of polybenzimidazoles was prepared by copolymerization of 3,3′‐diaminobenzidine tetrahydrochloride, 3,4‐diaminobenzoic acid and isophthalic acid in polyphosphoric acid at 200 °C. The polymerization could be performed within 90–110 min with the assistance of microwave irradiation. The solubility of the copolymer obtained in N,N‐dimethylacetamide (DMAc) was improved compared with those of poly[2,2′‐(m‐phenylene)‐5,5′‐bibenzimidazole] and poly(2,5‐benzimidazole). Thus copolymer membranes could be readily prepared by dissolving the copolymer powders in DMAc with refluxing under ambient pressure. The decomposition temperature of the copolymer was about 520 °C in air according to thermogravimetric analysis data. The proton conductivity and mechanical strength of the phosphoric acid‐doped copolymer membranes were investigated at elevated temperatures. A conductivity of 0.09 S cm^?1 at 180 °C and a tensile stress at break of 5.9 MPa at 120 °C were achieved for the acid‐doped copolymer membranes by doping acids in a 75 wt% H₃PO₄ solution. Copyright © 2010 Society of Chemical Industry     

Microwave‐assisted one‐pot copolymerization of cyclic monomers and ethyl diazoacetate

The present contribution describes an innovation in the copolymerization of cyclic monomers, ε‐caprolactam (ε‐CL) and 2,2‐dimethyltrimethylene carbonate (DTC), with ethyl diazoacetate (EDA). The characterizations of the obtained copolymers, poly(EA‐ran‐EDA‐ran‐ε‐CL) and poly(EA‐ran‐EDA‐ran‐DTC) (where EA refers to the ethyl acetate group from EDA after nitrogen release), were performed using ¹H NMR and ¹³C NMR spectroscopies and size exclusion chromatography. Under optimized conditions, the copolymer of ε‐CL with EDA possessing a number‐average molar mass (M_n) of 1300 g mol^?1 and dispersity of 2.12 as well as that of DTC with EDA with M_n of 8000 g mol^?1 and dispersity of 1.47 were obtained. The incorporation of the azo group in the obtained copolymers was determined from the results of elemental analysis (3.30–10.22% nitrogen) and Fourier transform infrared spectroscopy. Furthermore, the thermal properties of the obtained copolymers were examined using differential scanning calorimetry. X‐ray diffraction results showed that the synthesized copolymers were amorphous. © 2014 Society of Chemical Industry     

Synthesis of vinyl end‐capped polydimethylsiloxane by ring opening polymerization of octamethylcyclotetrasiloxane (D4) catalyzed by rare earth solid super acid SO42‐/TiO2/Ln3+

Rare earth solid super acids SO₄^2?/TiO₂/Ln³⁺ have been successfully developed to synthesize vinyl end‐capped polydimethylsiloxane by ring opening polymerization of octamethylcyclotetrasiloxane (D4) end‐capped with 1,1,3,3‐tetramethyl‐1,3‐divinyldisiloxane. The features of ring opening polymerization reactions have been investigated in detail. The preferable conditions for the ring opening polymerization of D4 are as follows: [Nd³⁺] = 0.07 mol L^?1 and [SO₄^2?] = 1.85 mol L^?1 in the immersing solution; the amount of SO₄^2?/TiO₂/Nd³⁺ calcined at 500 °C was 5 wt% of the amount of D4; polymerization at 80 °C for 1 h. The average molecular weights of the products obtained using various rare earth catalysts were in order Nd > La > Sm > Gd, which shows that the light rare earths were more favorable for higher molecular weight products than the heavy ones. According to the polymerization features, a cationic equilibrium reaction mechanism is proposed. © 2013 Society of Chemical Industry     

The effect of dimethylsulfoxide on the dissociation process of physical complexes of polyacrylonitrile in N,N‐dimethylformamide

The physical properties and gelation behavior of polyacrylonitrile (PAN ) solutions were investigated in mixed solvents of N ,N ‐dimethylformamide (DMF ) and dimethylsulfoxide (DMSO ). For the individual solubility parameters, DMSO had the polar term closer to PAN than DMF . Small‐angle X‐ray scattering profiles and Fourier transform infrared spectra of 20 wt% PAN solutions confirmed that the internal structure and intermolecular complexes between nitrile groups were broken up by the DMSO molecules. The slope of Cole–Cole plot, a measure of the solution heterogeneity, increased with the mole fraction of DMSO (X _DMSO) via three distinct zones. The homogenization was particularly noticeable in Zone 1 (0.0 < X _DMSO < 0.4) and Zone 3 (0.7 < X _DMSO < 1.0). The Huggins constant and UV‐visible absorption at 268 nm of dilute solutions decreased sharply above X _DMSO of 0.7 in Zone 3. This indicated a marked increase of PAN solubility by dissociating the intramolecular complexes between nitrile groups. In Zone 1, the storage modulus of 20 wt% PAN solutions decreased but loss modulus remained almost constant with X _DMSO at lower frequency below 1 rad s^?1, indicating the weakening of the true entanglement points of the intermolecular complexes. The mechanism indicated that the intermolecular complexes between nitrile groups were dissociated by DMSO earlier than the intramolecular ones. © 2017 Society of Chemical Industry     

Ring opening polymerization of ε‐caprolactone initiated by decamolybdate anion: Determination of kinetic and thermodynamic parameters by DSC and 1H‐NMR

The aim of this work is the kinetic and thermodynamic study (by differential scanning calorimetry (DSC) and proton nuclear magnetic resonance (¹H‐NMR)) of the polymerization of ε‐caprolactone initiated by ammonium decamolybdate. By means of isothermal kinetics, enthalpies of reaction in the range 150–160°C, as well as constant rates of polymerization (using an nth‐order kinetics function model), were determined. From an Arrhenius plot, activation energy (E_a = 85.3 kJ/mol) and preexponential factor (A = 1.78 × 10⁸ min^?1) were estimated. Using dynamic methods, crystallization and melting temperatures for the polymer obtained in situ were derived. Kinetic data for polymerization (obtained by ¹H‐NMR) were fitted to 13 different model reaction functions. It was found that power law equations represent better the conversion versus time plots for this system. On the basis of experimental facts, a coordination‐insertion mechanism involving molybdenum(V) species is proposed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polymerization of 1,3‐dienes containing functional groups: 8. Free‐radical polymerization of 2‐triethoxysilyl‐ 1,3‐butadiene

The presence of a bulky substituent at the 2‐position of 1,3‐butadiene derivatives is known to affect the polymerization behavior and microstructure of the resulting polymers. Free‐radical polymerization of 2‐triethoxysilyl‐1,3‐butadiene ( 1 ) was carried out under various conditions, and its polymerization behavior was compared with that of 2‐triethoxymethyl‐ and other silyl‐substituted butadienes. A sticky polymer of high 1,4‐structure ( ) was obtained in moderate yield by 2,2′‐azobisisobutyronitrile (AIBN)‐initiated polymerization. A smaller amount of Diels–Alder dimer was formed compared with the case of other silyl‐substituted butadienes. The rate of polymerization (R_p) was found to be R_p = k[AIBN]^0.5[ 1 ]^1.2, and the overall activation energy for polymerization was determined to be 117 kJ mol^?1. The monomer reactivity ratios in copolymerization with styrene were r ₁ = 2.65 and r_st = 0.26. The glass transition temperature of the polymer of 1 was found to be ?78 °C. Free‐radical polymerization of 1 proceeded smoothly to give the corresponding 1,4‐polydiene. The 1,4‐E content of the polymer was less compared with that of poly(2‐triethoxymethyl‐1,3‐butadiene) and poly(2‐triisopropoxysilyl‐1,3‐butadiene) prepared under similar conditions. Copyright © 2010 Society of Chemical Industry     

Real‐time monitoring of ring‐opening polymerization of tetrahydrofuran via in situ Fourier Transform Infrared Spectroscopy

The polymerization of tetrahydrofuran (THF) was carried out in CH₂Cl₂ by using phosphotungstic heteropolyacid as initiator and epichlorohydrin as promoter. This cationic ring‐opening polymerization process was monitored by in situ mid‐infrared spectroscopy system (ReactIR) to further study the thermodynamics and kinetics of THF polymerization. It was observed that the sharp infrared peak of C? O? C stretching vibrations will shift from about 1068 to 1109 cm^?1 in THF ring‐opening step. The changes in absorbance intensity of the two characteristic peaks were used for determining instantaneous concentration of linear polymer and ring monomer. The experimental results demonstrated that the kinetics of THF polymerization proved to be typically first‐order. Thermodynamic parameters were determined from the temperature dependence of the monomer equilibrium concentration [M]_e over the range from ?5 to 25°C. The values of k_app were obtained via the plots of ln{([M]₀?[M]_e)/([M]_t?[M]_e)} vs reaction time, for polymerization under specific conditions. The apparent activation energy (E_a) and frequency (A) were determined from the Arrhenius plot of k_app vs. T^?1. Besides, the in situ kinetic investigation revealed that more chain‐transfer occurred at higher temperatures, leading to a reduction in propagation species concentration and a deviation from first‐order propagation at the later stage of polymerization. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40503.     

Effects of ethyl acetate on the soap‐free emulsion polymerization of 4‐vinylpyridine and styrene

The properties and morphologies of poly(4‐vinylpyridine‐co‐styrene) [P(4VP/St)] lattices, prepared by soap‐free emulsion polymerization using the water‐soluble initiator 2,2′‐azobis(2‐amidinopropane) · 2HCl (V50), were greatly affected by the addition of ethyl acetate (EA). The properties and morphologies of the resultant lattices were characterized by measuring the zeta potential, viscosity average molecular weight, particle size and distribution, glass‐transition temperature (T_g), and photographs taken by SEM and TEM. The effects of two kinds of monomer feeding modes, that is, the batch and semicontinuous emulsion copolymerization, were also investigated. For batch emulsion copolymerization, by charging EA, the core–shell morphology resulting from the disparate reactivity ratios of the 4VP(1)/St(2) copolymerization system (r₁ = 1.04, r₂ = ?0.73) disappeared. Instead, first a bimodal particle size distribution, with an apparently asymmetric composition structure, and then spherical microspheres were obtained as the amount of EA charged increased from 2 to 10 wt %. The particle size increased twofold by the addition of EA. The zeta potential of particles increased from +64.4 to more than +100 mV, and viscosity average molecular weight decreased from 9.70 to 0.97 × 10⁵ g/mol, as EA increased from 0 to 8 wt %. With the semicontinuous copolymerization, raspberry‐like particles were obtained by charging 10 wt % EA, whereas a sandwich‐like morphology was obtained without EA. The DSC curves showed one T_g for all the lattices prepared with charging EA, but two T_g's for the latex prepared without using EA, regardless of the monomer feeding modes. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1988–2001, 2001     

Polymerization of methyl methacrylate in micellar phase: A kinetic study

Polymerization of methyl methacrylate (MMA) using Ce(IV) as initiator in aqueous nitric acid solution in the presence of sodium lauryl sulphate (NaLS) has been studied kinetically at a temperature range of 25–35°C. The rate of polymerization (R_p) increases with increasing concentration of NaLS, and it was also proportional to [MMA]²; but, in the presence of NaLS, the change of R_p with respect to [Ce(IV)] and [H⁺] were not linear and similarly the rate of Ce(IV) disappearance was not proportional to its original concentration. The overall activation energy of the polymerization process in presence of 0.01M NaLS was found to decrease by ～ 7.0 kcal mol^?1. The monomer–micelle association constant has been calculated to be 5.135 × 10⁴ mol^?1 L. The polymer obtained in surfactant medium is sparingly soluble in benzene and DMSO. From infrared spectra clear evidence of vinyl polymerization was obtained.     

Synthesis and characterization of AB‐type copolymers poly(L‐lactide)‐block‐poly(methyl methacrylate) via a convenient route combining ROP and ATRP from a dual initiator

Diblock copolymers of poly(L ‐lactide)‐block‐poly(methyl methacrylate) (PLLA‐b‐PMMA) were synthesized through a sequential two‐step strategy, which combines ring‐opening polymerization (ROP) and atom transfer radical polymerization (ATRP), using a bifunctional initiator, 2,2,2‐trichloroethanol. The trichloro‐terminated poly(L ‐lactide) (PLLA‐Cl) with high molecular weight (M_n,GPC = 1–12 × 10⁴ g/mol) was presynthesized through bulk ROP of L ‐lactide (L ‐LA), initiated by the hydroxyl group of the double‐headed initiator, with tin(II) octoate (Sn(Oct)₂) as catalyst. The second segment of the block copolymer was synthesized by the ATRP of methyl methacrylate (MMA), with PLLA‐Cl as macroinitiator and CuCl/N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as catalyst, and dimethyl sulfoxide (DMSO) was chosen as reaction medium due to the poor solubility of the macroinitiator in conventional solvents at the reaction temperature. The trichloroethoxyl terminal group of the macroinitiator was confirmed by Fourier transform infrared spectroscopy (FTIR) and ¹H‐NMR spectroscopy. The comprehensive results from GPC, FTIR, ¹H‐NMR analysis indicate that diblock copolymers PLLA‐b‐PMMA (M_n,GPC = 5–13 × 10⁴ g/mol) with desired molecular composition were obtained by changing the molar ratio of monomer/initiator. DSC, XRD, and TG analyses establish that the crystallization of copolymers is inhibited with the introduction of PMMA segment, which will be beneficial to ameliorating the brittleness, and furthermore, to improving the thermal performance. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

An activated neodymium‐based catalyst for styrene polymerization

Coordination polymerization of styrene with a ternary catalyst system composed of catalyst neodymium tricarboxylate (Nd), co‐catalyst Al(i‐Bu)₃ (Al) and chlorinating agent trichloroethane (Cl) was carried out in cyclohexane. The effects of the catalyst system preparation procedure and of the reaction conditions on catalytic activity, molecular weight and molecular weight distribution of the resultant polymers were investigated. The catalytic activity depended mainly on the molar ratios of Al/Nd and of Cl/Nd and on the ageing temperature and polymerization temperature. High polymerization conversion and high catalytic activity could be obtained at high Al/Nd ratios and/or at high ageing temperature. The catalyst system exhibited high activity of 8.32 × 10⁴ g polystyrene (mol Nd h)^?1 at 50 °C. The molecular weight of the polymers obtained reached high weight‐average (M_w) values (M_w = 4.35 × 10⁵ g mol^?1) when Al/Nd = 8, but relatively low values (6000–11 000 g mol^?1) at high Al/Nd ratios. Copyright © 2005 Society of Chemical Industry     

Ultrafast preparation of branched poly(methyl Acrylate) through single electron transfer living radical polymerization at room temperature

Ultrafast preparation of branched poly(methyl acrylate) (BPMA) with high‐molecular weight through single electron transfer living radical polymerization (SET‐LRP) of inimer at 25°C has been attempted, atom transfer radical polymerization (ATRP) at 60°C was also carried out for comparison. Gas chromatography, proton nuclear magnetic resonance, and triple detection size exclusion chromatography were used to analyze these polymerizations. As expected, SET‐LRP system showed much faster polymerization rate than ATRP system, the calculated apparent propagation rate constants (k_p^app) are 3.69 × 10^?2 min^?1 and 6.23 × 10^?3 min^?1 for SET‐LRP and ATRP system, respectively. BPMA with high‐molecular weight (M_w._MALLS = 86,400 g mol^?1) compared with that in ATRP (M_w.MALLS = 61,400 g mol^?1) has been prepared. POLYM. ENG. SCI., 54:1579–1584, 2014. © 2013 Society of Plastics Engineers     

Preparation of high molecular weight poly(vinyl alcohol) with high yield using low‐temperature solution polymerization of vinyl acetate

Vinyl acetate (VAc) was solution‐polymerized in tertiary butyl alcohol (TBA) and in dimethyl sulfoxide (DMSO) having low chain transfer constant at 30, 40, and 50°C, using a low temperature initiator, 2,2′‐azobis(2,4‐dimethylvaleronitrile) (ADMVN). The effects of polymerization temperature and initiator concentration were investigated in terms of polymerization behavior and molecular structures of poly(vinyl acetate) (PVAc) and corresponding poly(vinyl alcohol) (PVA) obtained by saponification with sodium hydroxide. The polymerization rates of VAc in TBA and in DMSO were proportional to the 0.49 and 0.72 powers of ADMVN concentration, respectively. For the same polymerization conditions, TBA was absolutely superior to DMSO in increasing the molecular weight of PVA. In contrast, TBA was inferior to DMSO in causing conversion to polymer, indicating that the initiation rate of VAc in TBA was lower than that in DMSO. These effects could be explained by a kinetic order of ADMVN concentration calculated using initial rate method and by an activation energy difference of polymerization obtained from the Arrhenius plot. Low‐temperature solution polymerization of VAc in TBA or DMSO by adopting ADMVN proved successful in obtaining PVA of high molecular weight (number–average degree of polymerization (P_n): 4100–6100) and of high yield (ultimate conversion of VAc into PVAc: 55–80%) with diminishing heat generated during polymerization. In the case of bulk polymerization of VAc at the same conditions, maximum P_n and conversion of 5200–6200 and 20–30% was obtained, respectively. The P_n and lightness were higher, and the degree of branching was lower with PVA prepared from PVAc polymerized at lower temperatures in TBA. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1003–1012, 2001     

Ceric ion‐induced graft copolymerization of acrylamide on cationic guar gum at low temperature

The solution polymerization of acrylamide (AM) on cationic guar gum (CGG) under nitrogen atmosphere using ceric ammonium sulfate (CAS) as the initiator has been realized. The effects of monomer concentration and reaction temperature on grafting conversion, grafting ratio, and grafting efficiency (GE) have been studied. The optimal conditions such as 1.3 mol of AM monomer and 2.2 × 10^?4 mol of CAS have been adopted to produce grafted copolymer (CGG1‐g‐PAM) of high GE of more than 95% at 10°C. The rates of polymerization (R_p) and rates of graft copolymerization (R_g) are enhanced with increase in temperature (<35°C).The R_p is enhanced from 0.43 × 10^?4 mol L^?1 s^?1 for GG‐g‐PAM to 2.53 × 10^?4 mol L^?1 s^?1 for CGG1‐g‐PAM (CGG1, degree of substitute (DS) = 0.007), and R_g from 0.42 × 10^?4 to 2.00 × 10^?4 mol L^?1 s^?1 at 10°C. The apparent activation energy is decreased from 32.27 kJ mol^?1 for GG‐g‐PAM to 8.09 kJ mol^?1 for CGG1‐g‐PAM, which indicates CGG has higher reactivity than unmodified GG ranging from 10 to 50°C. Increase of DS of CGG will lead to slow improvement of the polymerization rates and a hypothetical mechanism is put forward. The grafted copolymer has been characterized by infrared spectroscopy, thermal analysis, and scanning electron microscopy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3715–3722, 2007     

Electroactive polythiophene/polystyrene bottlebrushes as morphology compatibilizers in photovoltaic systems

Poly(3‐thiophene ethanol) (P3ThEt)‐graft‐polystyrene (PSt) bottlebrushes were synthesized and applied in active layers of poly(3‐hexylthiophene) (P3HT):phenyl‐C71‐butyric acid methyl ester (PC71BM) solar cells as morphology compatibilizers. In the presence of 15 wt% of P3ThEt‐graft‐PSt bottlebrush compatibilizers, the P3HT crystallite dimensions (D₍₁₀₀₎ = 45.67 nm and D₍₀₂₀₎ = 30.12 nm) and R_mean (38.96 nm) of PCBM clusters were the largest and the layer spacings were all the smallest (d₍₁₀₀₎ = 1.054 nm, d₍₀₂₀₎ = 0.301 nm and d_(PCBM) = 0.406 nm). These dimensional properties led to better hole (1.9 × 10^?3 cm² V^?1 s^?1) and electron (1.2 × 10^?2 cm² V^?1 s^?1) mobilities. The content of bottlebrushes was optimized at 15 wt%, and thereby the best photovoltaic results including the maximum cell efficiency of 5.37% were obtained for this turning point (12.75 mA cm^?2, 61%, 0.69 V). On exceeding the optimum weight percentage, all photovoltaic parameters decreased markedly and reached even less than that of pristine devices (1.92% versus 2.24%). After an optimum weight percentage of compatibilizers, further enhancement in bottlebrush content in active layers saturated and finally oversaturated the system and, consequently, the cell parameters significantly decreased. Accumulation of bottlebrushes in interfaces and donor/acceptor phases ruined the system function even with large and packed P3HT crystallites and PC71BM clusters. © 2019 Society of Chemical Industry     

The investigation of novel non‐metallocene catalysts with phenoxy‐imine ligands for ethylene (co‐)polymerization

Phthaldialdehyde and phthaldiketone were treated with substituted phenols of 2‐amino‐4‐methylphenol, 2‐amino‐5‐methylphenol and 2‐amino‐4‐t‐butylphenol, respectively, and then treated with transition metal halides of TiCl₄, ZrCl₄ and YCl₃. A series of novel non‐metallocene catalysts (1–12) with phenoxy‐imine ligands was obtained. The structures and properties of the catalysts were characterized by ¹H NMR and elemental analysis. The catalysts (1–12) were used to promote ethylene (co‐)polymerization after activation by methylaluminoxane. The effects of the structures and center atoms (Ti, Zr and Y) of these catalysts, polymerization temperature, Al/M (M = Ti, Zr and Y) molar ratio, concentration of the catalysts and solvents on the polymerization performance were investigated. The results showed that the catalysts were favorable for ethylene homopolymerization and copolymerization of ethylene with 1‐hexene. Catalyst 10 is most favorable for catalyzing ethylene homopolymerization and copolymerization of ethylene with 1‐hexene, with catalytic activity up to 2.93 × 10⁶ gPE (mol Y)^?1 h^?1 for polyethylene (PE) and 2.96 × 10⁶ gPE (mol Y)^?1 h^?1 for copolymerization of ethylene with 1‐hexene under the following conditions: polymerization temperature 50 °C, Al/Y molar ratio 300, concentration of catalyst 1.0 × 10^?4 L^?1 and toluene as solvent. The structures and properties of the polymers obtained were characterized by Fourier transform infrared spectroscopy, ¹³C NMR, wide‐angle X‐ray diffraction, gel permeation chromatography and DSC. The results indicated that the obtained PE catalyzed by 4 had the highest melting point of 134.8 °C and the highest weight‐average molecular weight of 7.48 × 10⁵ g mol^?1. The copolymer catalyzed by 4 had the highest incorporation of 1‐hexene, up to 5.26 mol%, into the copolymer chain. © 2012 Society of Chemical Industry     

Barrier and thermal properties of polyimide derived from a diamine monomer containing a rigid planar moiety

An aromatic polyimide (3,6‐CPI ) was prepared by the polymerization of pyromellitic dianhydride and diamine (3,6‐CDA ) containing a rigid planar carbazole moiety. The synthesized polyimide shows outstanding barrier properties with oxygen permeation rate and water vapor permeation rate low at 7.9 cm³ m^?2 day^?1 and 9.8 g m^?2 day^?1, respectively. Wide angle X‐ray diffraction, positron annihilation lifetime spectroscopy and molecular dynamics simulations reveal that the excellent barrier properties of 3,6‐CPI are mainly due to the crystallinity and low free volume of the polymer, which result from the rigid planar backbone structure and strong interchain hydrogen bonding. In addition, the polyimide exhibits excellent thermal stability and favorable mechanical properties with a 5 wt% weight‐loss temperature of 559 °C in nitrogen, a glass transition temperature (T _g) of 397 °C and a tensile strength of 115.4 MPa . The as‐synthesized polyimide shows potential packaging applications in the field of flexible electronics and displays, flexible and thin film photovoltaics, and light‐emitting diodes. © 2017 Society of Chemical Industry     

Organic/inorganic support for immobilizing (n‐BuCp)2ZrCl2/TiCl3 hybrid catalyst for use in the preparation of polymer blends

Reactor blends of ultrahigh‐molecular‐weight polyethylene (UHMWPE) and low‐molecular‐weight polyethylene (LMWPE) were synthesized by two‐step polymerization using a hybrid catalyst. To prepare the hybrid catalyst, styrene acrylic copolymer (PSA) was first coated onto SiO₂/MgCl₂‐supported TiCl₃; then, (n‐BuCp)₂ZrCl₂ was immobilized onto the exterior PSA. UHMWPE was produced in the first polymerization stage with the presence of 1‐hexene and modified methylaluminoxane (MMAO), and the LMWPE was prepared with the presence of hydrogen and triethylaluminium in the second polymerization stage. The activity of the hybrid catalyst was considerable (6.5 × 10⁶ g PE (mol Zr)^?1 h^?1), and was maintained for longer than 8 h during the two‐step polymerization. The barrier property of PSA to the co‐catalyst was verified using ethylene polymerization experiments. The appearance of a lag phase in the kinetic curve during the first‐stage polymerization implied that the exterior catalyst ((n‐BuCp)₂ZrCl₂) could be activated prior to the interior catalyst (M‐1). Furthermore, the melting temperature, crystallinity, degree of branching, molecular weight and molecular‐weight distribution of polyethylene obtained at various polymerization times showed that the M‐1 catalyst began to be activated by MMAO after 40 min of the reaction. The activation of M‐1 catalyst led to a decrease in the molecular weight of UHMWPE. Finally, the thermal behaviors of polyethylene blends were investigated using differential scanning calorimetry. Copyright © 2011 Society of Chemical Industry     

Kinetics of the anionic ring‐opening polymerization of octamethylcyclotetrasiloxane initiated by potassium isopropoxide

Kinetics of the anionic ring‐opening polymerization of octamethylcyclotetrasiloxane (D₄) in bulk initiated by potassium isopropoxide was studied. Several promoters including N‐methyl‐2‐pyrrolidinone (NMP), N,N‐dimethylformamide (DMF), and diglyme were used. It is indicated that the reactions are first‐order in D₄ during the initial stage of polymerization. The polymerization rate of D₄ is influenced by a number of factors, such as the nature of promoters, the molar ratio of promoter to initiator (C_p/C_i ratio), and the reaction temperatures. With the use of NMP as promoter, the polymerization rate constant at 30°C is 10.482 h^?1 with the C_p/C_i ratio equal to 3.0. As the C_p/C_i ratio increases, the polymerization rate constant increases sharply and the cyclic oligomers content in polymer decreases evidently. The back‐biting reaction that leads to the formation of decamethylcyclopentasiloxane (D₅) occurred in the polymerization of D₄. The rate of the D₅ formation relatively to the rate of D₄ conversion increases with the conversion of D₄. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3510–3516, 2006     

Preparation of high molecular weight poly(vinyl pivalate) with high yield and high molecular weight poly(vinyl alcohol) by emulsion polymerization of vinyl pivalate and saponification

To prepare high molecular weight (HMW) poly(vinyl pivalate) (PVPi) with high yield and high linearity which is a promising precursor for syndiotactic poly (vinyl alcohol) (PVA), vinyl pivalate (VPi) was emulsion polymerized, using 2,2′‐azobis(2‐amidinopropane) dihydrochloride (AAPH) as an initiator and sodium dodecyl sulfate (SDS) as an emulsifier. The effect of the polymerization conditions on the conversion, molecular weight, and degree of branching was investigated. PVA with maximum number‐average degree of polymerization (P_n) of 6200 could be prepared by complete saponification of PVPi, with P_n of 13,300–16,700 obtained at polymerization temperature of 50°C, using SDS and AAPH concentration of 2.0 × 10^?3 mol/L of water and 1.0 × 10^?3 mol/L of water, respectively, and the maximum conversion was about 90%. From the emulsion polymerization of VPi, spherical PVPi with high yield was effectively prepared, which might be useful for the precursor of syndiotactic PVA micro‐ and nano‐spheres with various surface properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 410–414, 2007