丙烯腈水相沉淀聚合研究进展

结合近几年的研究成果,笔者对丙烯腈水相沉淀聚合机理、聚合动力学、动力学数学模型诸方面问题进行了系统的综述,反映了该领域的研究概况和最新研究成果.     

Synthesis,Structure, and Fluxionality of Strained Hypercoordinate Silicon‐Bridged [1]Ferrocenophanes

The first hypercoordinate sila[1]ferrocenophanes [fcSiMe(2‐C₆H₄CH₂NMe₂)] ( 5 a ) and [fcSi(CH₂Cl)(2‐C₆H₄CH₂NMe₂)] ( 5 b ) (fc=(η⁵‐C₅H₄)Fe(η⁵‐C₅H₄)) were synthesized by low‐temperature (?78 °C) reactions of Li[2‐C₆H₄CH₂NMe₂] with the appropriate chlorinated sila[1]ferrocenophanes ([fcSiMeCl] ( 1 a ) and [fcSi(CH₂Cl)Cl] ( 1 d ), respectively). Single‐crystal Xray diffraction studies revealed pseudo‐trigonal bipyramidal structures for both 5 a and 5 b , with one of the shortest reported Si???N distances for an sp³‐hybridized nitrogen atom interacting with a tetraorganosilane detected for 5 a (2.776(2) Å). Elongated Si? C_ipso bonds trans to the donating NMe₂ arms (1.919(2) and 1.909(2) Å for 5 a and 5 b , respectively) were observed relative to both the non‐trans bonds ( 5 a : 1.891(2); 5 b : 1.879(2) Å) and the Si? C_ipso bonds of the non‐hypercoordinate analogues ([fcSiMePh] ( 1 b ): 1.879(4), 1.880(4) Å; [fcSi(CH₂Cl)Ph] ( 1 e ): 1.881(2), 1.884(2)). Solution‐state fluxionality of 5 a and 5 b , suggestive of reversible coordination of the NMe₂ group to silicon, was demonstrated by means of variable‐temperature NMR studies. The ΔG^≠ of the fluxional processes for 5 a and 5 b in CD₂Cl₂ were estimated to be 35.0 and 37.6 kJ mol^?1, respectively (35.8 and 38.3 kJ mol^?1 in [D₈]toluene). The quaternization of 5 a and 5 b by MeOTf, to give [fcSiMe(2‐C₆H₄CH₂NMe₃)][OTf] ( 7 a‐ OTf) and [fcSi(CH₂Cl)(2‐C₆H₄CH₂NMe₃)][OTf] ( 7 b‐ OTf), respectively, supported the reversibility of NMe₂ coordination at the silicon center as the source of fluxionality for 5 a and 5 b . Surprisingly, low room‐temperature stability was detected for 5 b due to its tendency to intramolecularly cyclize and form the spirocyclic [fcSi(cyclo‐CH₂NMe₂CH₂C₆H₄)]Cl ( 9 ‐Cl). This process was observed in both solution and the solid state, and isolation and Xray characterization of 9 ‐Cl was achieved. The model compound, [Fc₂Si(2‐C₆H₄CH₂NMe₂)₂] ( 8 ), synthesized through reaction of [Fc₂SiCl₂] with two equivalents of Li[2‐C₆H₄CH₂NMe₂] at ?78 °C, showed a lack of hypercoordination in both the solid state and in solution (down to ?80 °C). This suggests that either the reduced steric hindrance around Si or the unique electronics of the strained sila[1]ferrocenophanes is necessary for hypercoordination to occur.     

Investigation of the effect of epoxide structure on the initiation efficiency in isobutylene polymerizations initiated by epoxide/TiCl4 systems

The effect of the chemical structure of styrene-based epoxides, namely, styrene epoxide (SE), α-methylstyrene epoxide (MSE), p-methylstyrene epoxide (pM-SE) and α-methyl-p-methylstyrene epoxide (pM-MSE), in conjunction with TiCl₄, on the initiation efficiency (I_eff) in the carbocationic polymerization of isobutylene (IB) was investigated. SE yielded living polymerization, but the initiation efficiency was low when compared to MSE (I_eff=8% and 35%, respectively). pM-SE led to non-living IB polymerization, while pM-MSE revealed linear M_n-conversion plot and narrow MWD with a non-linear first order rate plot. Among the epoxides investigated, MSE was the best initiator to scale up the one-step synthesis of polyisobutylenes (PIBs) carrying one primary hydroxyl head group and one tertiary chloride end group. The hydroxyl functionality of these PIBs determined by ¹H-NMR was F_n=1.09±0.16 from 24 experiments.     

Atom transfer radical polymerization of 1-phenoxycarbonyl ethyl methacrylate monomer

Atom transfer radical polymerization conditions with copper(I) bromide/2,2^′-bipyridine (Cu/2,2^′-bpy) as the catalyst system were employed for the homopolymerization and random copolymerization of 1-phenoxycarbonyl ethyl methacrylate (PCMA) with methyl methacrylate (MMA). Temperature studies indicated that the polymerizations occurred smoothly in bulk at 110 °C. Poly(PCMA)(polydispersity index=1.27) homopolymer was characterized and then used as macroinitiator for increasing its molecular weight. The homopolymerization of PCMA was also carried out under free radical conditions using 2,2^′-azobisisobutyronitrile as an initiator.The monomer and polymers were characterized by FT-IR and ¹H and ¹³C-NMR techniques. The glass transition temperatures, the solubility parameters and average-molecular weights of the polymers were determined. Thermal stabilities of the polymers were given as compared with each other by using TGA curves. Thermal degradation products of poly(PCMA)s obtained by ATRP and free radical polymerization were compared with each other by using ¹H-NMR technique.     

LIGAND EFFECT OF CATALYTIC SYSTEM WCl_6-Et_2Al FOR RING OPENING METATHESIS POLYMERIZATION OF DICYCLOPENTADIENE

INTRODUCTIONInrecentyearsresearchprojectsonROMPofcycloolefinshavebeenattractingattentionofscientistsengagedinthesynthesisanddesignofnewpolyTneric'AprojectsupportedbytheNationalNaturalSCienceFoundationofChina(projectapprovalnumber:29474160).'-Correspondingauthormaterials,amongthemROMPsofnorbornene,norbornenederivativesandDCPDhavefoundgrowingfavourinthechemists,.y.,LI--4].Acrosslinkedpolarer(PDCPD),anewplastic,possessingexcellentmechanicalproperties(highNIS,TSetc)a-ndgoodthermal…     

Synthesis and photopolymerization of monomers bearing isopropenylphenoxy groups

The synthesis of a series of monomers containing isopropenylphenoxy groups was carried out. On irradiation with UV light in the presence of onium salt photoacid generators, these monomers undergo a chain extension reaction consisting of a dimerization followed by a Friedel-Crafts ring closure which results in the formation of polymers with indane groups in the backbone. Aryl imide-containing monomers bearing isopropenylphenoxy groups were also shown to undergo facile photoinduced cationic polymerization. The resulting polymers displayed excellent thermal stability. © 1995 John Wiley & Sons, Inc.     

Influence of camphorsulfonic acid in nitroxide‐mediated styrene miniemulsion polymerization

The rate‐accelerating effects of camphorsulfonic acid (CSA) on nitroxide‐mediated styrene miniemulsion polymerization were studied. Polymerizations were initiated with benzoyl peroxide (BPO) as an initiator and mediated with either 2,2,6,6‐tetramethylpiperidinyloxy (TEMPO) or 4‐hydroxy‐2,2,6,6‐tetramethylpiperidinyloxy (OH‐TEMPO). Although CSA has been used to accelerate the rate in bulk nitroxide‐mediated polymerizations, it has not been well studied in emulsion/miniemulsion. With dispersed systems, the effectiveness of CSA is likely to be affected by partitioning between the aqueous and organic phases. In styrene miniemulsion experiments performed over a range of conditions, the effect of adding CSA varied from negligible to significantly increasing the final conversion and molecular weight, depending on the nitroxide:BPO ratio. At a ratio of nitroxide:BPO = 1.7, the effect of CSA addition is small, whereas the final conversion and molecular weight are dramatically enhanced by CSA addition when the nitroxide:BPO ratio is 3.6. CSA is most effective in enhancing the rate and molecular weight when the initial free‐nitroxide concentration is higher. The magnitude of the rate and molecular weight enhancement was similar for TEMPO and OH‐TEMPO despite their differences in water solubility. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2828–2841, 2002     

Electrical conductance of CHCl3 solutions of polyethylene oxide doped with KCI

CHCl3 solutions containing a few percent polyethylene oxide PEO (M_W = 200 000) or the low-molecular model dioxane are stirred at 50°C during more than 100 h in the presence of small amounts of KCl. The specific conductance, the viscosity and the density of the solutions are measured at 25°C as a function of time. Both PEO and dioxane act as ligands improving the solubility of KCl. The relaxation times are of the order of several hours. After 40 h or more the viscosity of the solutions increases in a spectacular way. However, the most striking observation is that the specific conductance of the polymeric solutions at 25°C is systematically 5% higher than the value measured with the same sample at 45°C, just as for metals. The effect of the dilution of the primary stirred solutions either in the pure solvent or in the initial polymer solution is investigated. These results are discussed in terms of a three-step mechanism in the polymer systems: (1) Loading of the coils to polymeric cations with a full elementary charge, as a consequence of charge transfer interactions of the crown-ether type with numerous K⁺ ions penetrating into the coils; (2) Electron tunnelling conduction of the Hamill—Ceulemans type from one positive coil to the neighbouring one; (3) Alteration of the structure of the coils and of their hydrodynamic radius by the motions of K⁺ in the coils. These ‘brachiation’ motions by a hopping mechanism result from an increased mobility of the complexed K⁺ ions, which is also the origin of the Zundel effect. They do not directly contribute to the conductance but are responsible for the delayed increase of the viscosity.     

水溶性光聚合引发剂研究进展

近几年发展起来的水溶性光聚合引发剂（ＷＳＰ）属自由基引发剂，按结构可分为芳酮类，稠环类烃类，聚硅烷类，酰基膦酸盐等，偶氮类及金属有机配合物类，本文综述了这些光引发剂的结构特性，光化学行为，光引发效率及光反应机理等。     

Vinyl-polymerization of norbornene with novel anilido–imino nickel complexes/methylaluminoxane: Abnormal influence of polymerization temperature on molecular weight of polynorbornenes

Herein reported are investigations of norbornene polymerization by novel anilido–imino nickel complexes [(Ar¹NCHC₆H₄NAr²)NiBr]₂ (Ar¹ = Ar² = 2,6-dimethylphenyl, 1; Ar¹ = 2,6-dimethylphenyl, Ar² = 2,6-diisopropylphenyl, 2; Ar¹ = Ar² = 2,6-diisopropylphenyl, 3; Ar¹ = 2,6-diisopropylphenyl, Ar² = 2,6-dimethylphenyl, 4) activated with methylaluminoxane (MAO). It was found that at polymerization temperatures below 50 °C, the average molecular weights of the obtained polynorbornenes catalyzed by these four catalytic systems increase with raising temperature, displaying bimodal distribution in GPC curves. The abnormal influence of polymerization temperature could be attributed to the existence of two kinds of catalytic species: heterobimetallic species LNi(II)(μ-Me)₂AlMe₂ (I) and monometallic species LNi(II)Me (II) (L = anilido–imino ligand) at lower temperature. The former affords a lower molecular weight polymer and the latter higher molecular weight one. With raising polymerization temperature above 50 °C, the species I disappears and only species II exists in polymerization systems, resulting in a normal relation of molecular weight to polymerization temperature. From a kinetic study of the norbornene polymerization catalyzed by 1/MAO catalyst at 70 °C, the polymerization rate (R_p) can be expressed by the formulation: R_p = k[NBE]^1.93[Ni]^0.88. Moreover, the mechanism of the norbornene polymerization using the anilido–imino nickel complexes activated with MAO is also presented and discussed.