Controlled structure and density of “living” polystyrene brushes on flat silica surfaces

Thin layers of polystyrene were grown from surface-grafted nitroxide initiators via controlled “living” free radical polymerization. The “reactive” Langmuir-Blodgett deposition method allowed an effective control of the initiator layer density leading to PS brushes with different and high grafting density and stretching. The influence of the grafting density on the layer structure was studied. Comparison with theoretical predictions for monodispersed brushes in bad solvent was discussed. The thickness was found to vary linearly with molecular weight and the density dependence was shown using wetting measurements. Special features of controlled radical nitroxide polymerization from a surface were discussed. A direct comparison of the molecular weight and polydispersity between surface and bulk polymers was made by de-grafting the brushes into a toluene/HF solution. Finally, some evidence of a “surface Fischer” effect was shown from re-initiated layers. Received 20 December 2001     

The transition of spontaneous polymerization of acrylamide to “explosive” regime

Experimental results related to the transition of spontaneous polymerization of acrylamide complexes with metal nitrates to the “explosive” regime at room temperature are presented. It is suggested that the “explosion” has a thermal nature. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 859–861, April, 1997.     

Initiation process of L‐lactide polymerization carried out with zirconium(IV) acetylacetonate

Lactide polymerization using zirconium(IV) acetylacetonate [Zr(acac)₄] as an initiator was investigated. In the reaction between Zr(acac)₄ and the monomer molecule, lactide deprotonation and the release of acetylacetone occurred. The structures of the obtained complexes were analyzed with high‐resolution NMR spectroscopy. A computational method was used to calculate the hypothetical structures. The role of the obtained complexes in the initiation of polymerization and the reaction of chain growth was proposed. The influence of the reaction temperature on the structures of the complexes was investigated. Polylactide chain growth proceeded by an insertion‐coordination mechanism. The polymer chain grew on one ligand, which was formed in advance from a deprotonated lactide. The molecular masses of the obtained polymers were the same as the theoretical masses and were directly proportional to the reaction conversion. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1886–1900, 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 charge distribution on the conformation of neutral polyampholytes

Summary Two polyampholyte copolymers based on sodium-2-acrylamido-2-methylsulfonate (NaAMPS) and methacryloyloxyethyltrimethylammonium chloride (MADQUAT) have been prepared either in homogeneous solution or by an inverse microemulsion polymerization technique. The copolymer microstructure was shown to depend on the method of preparation. The microemulsion polymerization yields copolymers with a monomer sequence distribution not far from random while those obtained by polymerization in solution have a strong tendency to alternation. The aqueous-solution properties of the two samples have been investigated by viscometry. The results show that the charge distribution along the copolymer chain affects considerably its conformation, in good agreement with recent theoretical studies. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994     

NMR Study of the propagation center in the cationic polymerization of N-benzoyl-8-octanelactam. II. Investigation of the propagation center

The nature of the propagation center in the cationic polymerization of N-benzoyl-8-octanelactam initiated by octanoylium hexachlcroantimonate, SbCl₅, and Ph₃CAsF₆ in perdeuterated tetrachloroethane or its mixture with o-dichlorobenzene was studied using ¹H, ¹³C, ¹⁹F, ³¹P, ⁷⁵As, and ¹²¹Sb nuclear magnetic resonance (NMR) of model oligomers and the products of their end-capping with triphenylphosphine. In all cases, the nature of the propagation center has been found to be of an acylium ion pair with an SbCl₆^? or AsF₆^? counterion coordinated with the nearest benzoylamide group and cosolvated by the solvent. © 1994 John Wiley & Sons, Inc.     

CRYSTAL STRUCTURE AND MORPHOLOGY OF NASCENT SAMPLES OF SYMMETRIC AROMATIC POLYESTERS——Ⅱ. POLY(p-PHENYLENE 2,6-NAPHTHALATE)

Confined thin film melt polymerization (CTFMP) of naphthalene chloride/hydroquinone (NCMQ, 1/1, molar)mixtures at polymerization temperatures (T_p) below ca. 300℃ resulted in relatively thick, elongated crystals. Polymerizationof NC/HQ above 300℃ between glass yielded well-formed lamellar crystals ca. 100 A thick. Phase Ⅰ and Ⅱ [001] EDpatterns were obtained for all T_p, the relative amount of phase Ⅰ increasing with T_p. Polymerization of naphthalenedicarboxylic acid/hydroquinione diacetate 1/1 mixtures at high T_p also yielded lamellar crystals that "curled up" off of thesubstrate. When the high temperature CTFMP polymerization was conducted between mica, aggregates of lamellae on-edgedeveloped but epitaxial growth did not occur. Epitaxial growth of lamellae between mica could be obtained, however, byconfined thin film solution polymerization, with both of the latter samples yielding apparently related ED patterns from adifferent unit cell than phase Ⅰ or Ⅱ. Fiber patterns, obtained from sheared samples, indicated considerably greater crystaldisorder than in the nascent crystals. Refinement of the phase Ⅰ unit cell parameters, based on the [001] and [01 1] EDpatterns, with modeling based on Cerius~2, suggests a monoclinic phase Ⅰ unit cell with a = 7.76, b = 5.71, c = 14.99 A, α = γ= 90°, β= 99.7°, ρ = 1.47 g/cm~3, space group P12_1/al.     

Complex polymer architectures through dimethoxymethyl 1,1‐diphenylethylene derivatives

The reactions of polystyryllithium and potassium on dimethoxymethyl 1,1‐diphenylethylene derivatives were studied in different solvents. In a polar medium, A₃ and A₆ star types were formed according to the stoichiometry, whereas in a nonpolar medium, hyperbranched structures were synthesized. Extensions of an already proposed mechanism in polar and nonpolar media were examined. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3329–3335, 2003