Side‐chain crystallization behavior of graft copolymers consisting of an amorphous main chain and crystalline side chains. II. Poly(n‐hexyl methacrylate)‐graft‐poly(ethylene glycol)

The phase behavior and crystallization of graft copolymers consisting of poly(n‐hexyl methacrylate) (PHMA) as an amorphous main chain and poly(ethylene glycol) (PEG) as crystallizable side chains (HMAx with 15 ≤ x ≤ 73, where x represents the weight percentage of PEG) were investigated. Small‐angle X‐ray scattering profiles measured above the melting temperature of PEG suggested that a microdomain structure with segregated PHMA and PEG domains was formed in HMA40 and HMA46. This phase behavior was qualitatively described by a calculated phase diagram based on the mean‐field theory. Because of the segregation of PEG into microdomains, the crystallization temperature of the PEG side chains in HMAx was higher than that in poly(methyl acrylate)‐graft‐poly(ethylene glycol) having a similar value of x, which was considered to be in a disordered state above the melting temperature. In HMAx with x ≤ 40, PEG crystallization was strongly restricted, probably because the PEG microdomains were isolated in the PHMA matrix. As a result, the growth of PEG spherulite was not observed because the PEG crystallization occurred after vitrification of the PHMA segregated domains. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 129–137, 2007     

Synthesis and characterization of poly(higher‐α‐olefin)s with a nickel(α‐diimine)/methylaluminoxane catalyst system: Effect of chain running on the polymer properties

Homopolymerization of octadecene‐1 at different reaction conditions has been studied. Significant chain running can be seen at higher polymerization temperatures. Interestingly, insertion of octadecene‐1 into a sterically hindered nickel‐cation/carbon (secondary) bond is observed. The microstructure of the polymer was established using NMR spectroscopy. The effects of chain running on polymer melting, crystallization behavior, and dynamic mechanical thermal properties were studied using DSC and DMTA. The extent of chain running (i.e., 2,ω‐, 1,ω‐enchainments) decreases with an increase in the carbon number of α‐olefins. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 191–210, 2007     

Alternating copolyfluorenevinyles with polynuclear aromatic moieties: Synthesis,photophysics, and electroluminescence

Three new copolymers, namely poly(fluorenevinylene‐alt‐naphthalenevinylene) ( N ), poly(fluorenevinylene‐alt‐anthracenevinylene) ( A ) and poly(fluorenevinylene‐alt‐pyrenevinylene) ( P ), were synthesized by Heck coupling of 9,9‐dihexyl‐2, 7‐divinylfluorene with a polynuclear aromatic dibromide. The 9,10‐disubstituted anthracene was obtained exclusively for A while N and P were obtained as a mixture of two isomers with predominant the 1,4‐disubstituted naphthalene and 1,8‐disubstituted pyrene, respectively. The polymers were soluble in common organic solvents and decomposed above 370 °C. Their glass transition temperature increased from 58 to 110 °C by increasing the number of the phenyl rings of the polynuclear aromatic moiety. Rather high‐efficiency blue and blue‐greenish photoluminescence (PL) of these copolymers in solution was largely decreased in their films, indicating the presence of concentration quenching in the solid state. The OLED using these polymers demonstrated green EL in the case of copolymers N and A , and red EL in the P derivative with η_EL = 0.26–0.31%. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4661–4670, 2007     

Synthesis and nuclear magnetic resonance analysis of starch‐g‐poly(1,4‐dioxan‐2‐one) copolymers

A new biodegradable starch graft copolymer, starch‐g‐poly(1,4‐dioxan‐2‐one), was synthesized through the ring‐opening graft polymerization of 1,4‐dioxan‐2‐one onto a starch backbone. The grafting reactions were conducted with various 1,4‐dioxan‐2‐one/starch feed ratios to obtain starch‐g‐poly(1,4‐dioxan‐2‐one) copolymers with various poly(1,4‐dioxan‐2‐one) graft structures. The microstructure of starch‐g‐poly(1,4‐dioxan‐2‐one) was characterized in detail with one‐ and two‐dimensional NMR spectroscopy. The effect of the feed composition on the resulting microstructure of starch‐g‐poly(1,4‐dioxan‐2‐one) was investigated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3417–3422, 2004     

Orientation and relaxation of polymer–clay solutions studied by rheology and small-angle neutron scattering

The influence of shear on viscoelastic solutions of poly(ethylene oxide) (PEO) and clay [montmorillonite, i.e., Cloisite NA+ (CNA)] was investigated with rheology and small-angle neutron scattering (SANS). The steady-state viscosity and SANS were used to measure the shear-induced orientation and relaxation of the polymer and clay platelets. Anisotropic scattering patterns developed at much lower shear rates than in pure clay solutions. The scattering anisotropy saturated at low shear rates, and the CNA clay platelets aligned with the flow, with the surface normal parallel to the gradient direction. The cessation of shear led to partial and slow randomization of the CNA platelets, whereas extremely fast relaxation was observed for laponite (LRD) platelets. These PEO–CNA networklike solutions were compared with previously reported PEO–LRD networks, and the differences and similarities, with respect to the shear orientation, relaxation, and polymer–clay interactions, were examined. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3102–3112, 2004     

Thickness of a silica-tethered poly(ethylene oxide) layer measured by spin labeling

EPR spectroscopy of labeled poly(ethylene oxide) (PEO) grafted on silica has been used to characterize the conformation and local dynamics of the chains. Grafted molecules of MW 2000 with grafting ratios of 0.045, 0.057, 0.126, and 0.42 molecules/nm² were in contact with benzene. The mobility of the label was compared with that observed for solution of PEO from very diluted to highly concentrated and even bulk PEO. Thus, the concentration inside the grafted layer could be evaluated and also the thickness, which evolves rather linearly with the grafting ratio. © 1995 John Wiley & Sons, Inc.     

Influence of humic substances on sorption and methylation processes of inorganic- and organo-tin species

The influence of humic substances on sorption and methylation processes for inorganic- and organotin species is presented. Four sediment samples from different locations of the Rivers Elbe, Mulde and Spittelwasser, Germany, with different organotin and humic contents were selected to extract the humic and fulvic acids. The various fractions—the original sediment, the humic acid, the fulvic acid and the residual sediment—were analysed for their organotin content. The individual buyltin species show quite different distribution patterns. Monobutyltin is found mostly associated with humic acids. Dibutyltin shows a nonunique behaviour. At low total organotin content, dibutyltin is found bonded to humic and fulvic acids, whereas at high organotin content dibutyltin is distributed more with the residual sediment. Most of the tributyltin remains in the sediment unextracted; only small quantities of it are in the fulvic acid fraction. Tetrabutyltin is only in the humic acid fraction when it binds to humic matter; it mostly remains in the sediment. General observations indicate that ionic butyltin species bind to fulvic acids whereas the non-polar tetrabutyltin is not found in the fulvic acid fractions in any of the samples. The appearance of monomethyl- and dimethyl-tin species in the humic and fulvic acid fractions after the alkaline extraction was surprising. There is a correlation between the humic content of the sample and the formation of methyltin species. Evidence is provided by experiments that humic substances act as methylation agents.     

聚丙烯酸接枝聚甲基丙烯酸甲酯共聚物的表面性质及粘度性质的研究

聚丙烯酸接枝聚甲基丙烯酸甲酯共聚物的表面有其特殊性质:水滴在其表面上形成的接触角基本上与其组成无关,而丙烯酸——甲基丙烯酸甲酯无规共聚物的表面接触角却与其组成有密切关系;接枝共聚物在DMF溶液中,其粘度表现出有趣的现象,说明了接枝共聚物在溶液中有微区现象和聚电解质性质     

乳清酸的2.5次微分示波极谱法测定

拟定了乳清酸的2.5次微分示波极谱测定新方法.结果表明在0.8 mol/L HCl介质中,乳清酸产生一灵敏的极谱还原波,峰电位Ep =-0.77 V(vs.SCE);其2.5次微分极谱峰峰电流ep″与乳清酸浓度在4.0×10-8～4.0×10-5 mol/L范围内呈良好线性关系(r=0.999 6,n=9),检测限为1.0×10-8 mol/L;13次平行测量4.0×10-7 mol/L乳清酸的峰电流,所得RSD为1.8%.该方法可直接用于测定牛奶中乳清酸的含量.     

Stereocontrol of diene polymers by topochemical polymerization of substituted benzyl muconates and their crystallization properties

We report the stereocontrol of diene polymers by the topochemical polymerization of alkoxy-substituted benzyl muconates in the solid state. A monomer stacking structure is controlled by the weak intermolecular interactions in the monomer crystals, depending on the structure and position of the alkoxy-substituent. The translational and alternating types of molecular stacking structures in a column provide diisotactic and disyndiotactic polymers, respectively, by the solid-state polymerization under UV and γ-ray irradiation. On the other hand, the meso and racemo structures of the resulting polymers are determined by the molecular symmetry of the used muconate monomers. The various substituted benzyl ester polymers are transformed into the same ethyl ester polymers with the four types of tacticities. The structure and crystallization behavior of the substituted benzyl ester polymers as well as the ethyl ester polymers have been revealed in detail. We clarify the effects of the tacticity on the crystallization property of the stereoregular polymuconates. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4952–4965, 2006