Unexpected end‐groups of poly(acrylic acid) prepared by RAFT polymerization

Low‐molecular‐weight poly(acrylic acid) (PAA) was synthesized by reversible addition fragmentation chain transfer polymerization with a trithiocarbonate as chain‐transfer agent (CTA). With a combination of NMR spectroscopy and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, the PAA end‐groups of the polymer were analyzed before and after neutralization by sodium hydroxide. The polymer prior to neutralization is made up of the expected trithiocarbonate chain‐ends and of the H‐terminated chains issued from a reaction of transfer to solvent. After neutralization, the trithiocarbonates are transformed into thiols, disulfides, thiolactones, and additional H‐terminated chains. By quantifying the different end‐groups, it was possible to demonstrate that fragmentation is the rate limiting step in the transfer reaction. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5439–5462, 2004     

Reversible addition–fragmentation transfer (RAFT) copolymerization of methyl methacrylate and styrene in miniemulsion

In the reversible addition–fragmentation transfer (RAFT) copolymerization of two monomers, even with the simple terminal model, there are two kinds of macroradical and two kinds of polymeric RAFT agent with different R groups. Because the structure of the R group could exert a significant influence on the RAFT process, RAFT copolymerization may behave differently from RAFT homopolymerization. The RAFT copolymerization of methyl methacrylate (MMA) and styrene (St) in miniemulsion was investigated. The performance of the RAFT copolymerization of MMA/St in miniemulsion was found to be dependent on the feed monomer compositions. When St is dominant in the feed monomer composition, RAFT copolymerization is well controlled in the whole range of monomer conversion. However, when MMA is dominant, RAFT copolymerization may be, in some cases, out of control in the late stage of copolymerization, and characterized by a fast increase in the polydispersity index (PDI). The RAFT process was found to have little influence on composition evolution during copolymerization. The synthesis of the well‐defined gradient copolymers and poly[St‐b‐(St‐co‐MMA)] block copolymer by RAFT miniemulsion copolymerization was also demonstrated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6248–6258, 2004     

Influence of Particle Morphology and Flow Conditions on the Dispersion Behavior of Fumed Silica in Silicone Polymers

The dispersion behavior of agglomerates of several grades of fumed silica in poly(dimethyl siloxane) liquids has been studied as a function of particle morphology and applied flow conditions. The effects of primary particle size and aggregate density and structure on cohesivity were probed through tensile and shear strength tests on particle compacts. These cohesivity tests indicated that the shear strength of particle compacts was two orders of magnitude higher than the tensile strength at the same overall packing density. Experiments carried out in both steady and time‐varying simple‐shear flows indicate that dispersion occurs through tensile failure. In the steady‐shear experiments,enhanced dispersion was obtained at higher levels of applied stress and, at comparable levels of applied stress, dispersion was found to proceed faster at higher shear rates. Experiments conducted in time‐varying flows further corroborated the results obtained in tensile cohesivity tests. Experiments in which the mean and maximum stresses in the time‐varying flows were matched to the stresses produced in steady shear flows highlight the influence of flow dynamics on dispersion behavior.     

带有弹性碰撞的离散的凝结方程

带有弹性碰撞的离散的凝结方程是反映粒子增长动力学的数学模型，它刻划了这样一种粒子反应系统；系统中任意两个粒子碰撞后一定的概率或者凝结成为更大的粒子，或者发生弹性碰撞．本文研究了这一系统发生冻肢的可能性，并给出了一个充分条件．     

UV curing of a novel resin derived from poly(ethylene terephthalate)

The synthesis and characterization of photopolymerizable unsaturated polyester resins based on PET waste are described. The resins came from a depolymerization process based on the glycolysis of PET by diethylene glycol (DEG). Different molecular weights of glycolysates were synthesized. Then, the latter was functionalized by a methyl hemiester of maleic acid to obtain unsatured α,ω‐bismaleate PET oligomers. In the presence of an electron donor monomer, such as triethylene glycol divinyl ether, these electron acceptor oligomers were copolymerized by way of charge‐transfer complexes under UV irradiation. The reaction was monitored in situ by real‐time IR spectroscopy to study the kinetics of photopolymerization. This one was studied in relation with the physical and chemical characteristics of oligoesters and the composition of mixtures containing divinyl ethers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1324–1335, 2007     

Elevation of the glass transition temperature in flexible‐chain semicrystalline polymers

In the idealized two‐phase model of a semicrystalline polymer, the amorphous intercrystalline layers are considered to have the same properties as the fully‐amorphous polymer. In reality, these thin intercrystalline layers can be substantially influenced by the presence of the crystals, as individual polymer molecules traverse both crystalline and amorphous phases. In polymers with rigid backbone units, such as poly(etheretherketone), PEEK, previous work has shown this coupling to be particularly severe; the glass transition temperature (T_g) can be elevated by tens of degrees celsius, with the magnitude of the elevation correlating directly with the thinness of the amorphous layer. However, this connection has not been explored for flexible‐chain polymers, such as those formed from vinyl‐type monomers. Here, we examine T_g in both isotactic polystyrene (iPS) and syndiotactic polystyrene (sPS), crystallized under conditions that produce a range of amorphous layer thicknesses. T_g is indeed shown to be elevated relative to fully‐amorphous iPS and sPS, by an amount that correlates with the thinness of the amorphous layer; the magnitude of the effect is severalfold less than that in PEEK, consistent with the minimum lengths of polymer chain required to make a fold in the different cases. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1198–1204, 2007     

GENERALIZED SIMULTANEOUS CHEBYSHEV APPROXIMATION

In this note,we develop,without assuming the Haar condition,a generalized simultaneousChebyshev approximation theory which is similar to the classical Chebyshev theory and con-rains it as a special case.Our results also contain those in[1]and[3]as a special case,and thetwo conjectures proposed by C.B.Dunham in[2]are proved to be true in the case of simulta-neous approximation.     

Fuzzy集的基数

关于Fuzzy集的基数，[1]中曾对有限支集的Fuzzy集以及极苛刻条件下的无限Fuzzy集给出过一种定义。但是，正如本文将要指出的那样，该定义是不合理的。本文将从研究Fuzzy映射入手，给出Fuzzy集基数的一般性定义。基于这一定义，不但得到有关基数的大部分结论，而且有其自身的特殊性。