Photochemical attachment of polymers on planar surfaces with a covalently anchored monolayer of a novel naphthyl ketone photochemical radical generator

A monolayer of covalently anchored, novel, binaphthyl ketone is used as a surface‐confined photochemical radical generator (PRG) for anchoring a variety of polymers to silicon surfaces. The precursor PRG is synthesized by the application of a facile and novel method for the oxidation of sterically hindered benzylic hydrocarbons to carbonyl compounds. Oxidation was carried out with a stoichiometric amount of potassium peroxydisulfate, in the presence of a catalytic amount of copper sulfate in an acetonitrile/water mixture. The PRG synthesized is characterized by ¹H NMR, UV, and Fourier transform infrared (FTIR). The covalently attached monolayers are characterized by X‐ray photoelectron spectroscopy, ellipsometry, and water contact angle measurements. The method developed is applicable to the preparation of a monolayer of a variety of polymers on a wide range of substrates carrying surface hydroxyl groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5413–5423, 2004     

Tetrafunctional initiators for cationic polymerization of olefins

3,3′,5,5′‐Tetrakis(2‐chloro‐2‐propyl)biphenyl (biphenyl tetracumyl chloride, BPTCC) and 1,3‐bis[3,5‐bis(2‐chloro‐2‐propyl)phenoxy]propane (diphenoxypropane tetracumyl chloride, DPPTCC) were synthesized as initiators for quasiliving cationic polymerization of isobutylene (IB). In the synthesis of BPTCC, tetrafunctionality was achieved via the coupling of dimethyl 5‐bromoisophthalate (DMBI) using nickel dibromide bis(triphenylphosphine) and zinc in the presence of a base; in the synthesis of DPPTCC, two equivalents of dimethyl 5‐hydroxyisophthalate were linked via reaction with 1,3‐dibromopropane in the presence of potassium carbonate. Both initiators were used to initiate the polymerization of IB under quasiliving cationic polymerization conditions. PIB initiated from BPTCC revealed a chain end/molecule value (as determined by ¹H‐NMR) of 3.85, verifying the nearly exclusive production of 4‐arm polyisobutylene (PIB). GPC analysis revealed a narrow peak representing the target four‐arm PIB, with a slight shoulder at high elution volumes (low molecular weights). GPC analysis of the PIB initiated by DPPTCC revealed multimodal distributions, suggesting the formation of two‐, three‐, and four‐arm star polymers during the polymerization. This behavior was attributed to Friedel–Crafts alkylation of the initiator core after the addition of one IB unit, which was activated by the electron‐donating oxytrimethyleneoxy linking moiety. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5942–5953, 2004     

Thermal isomerization of trifluoromethyl trifluorovinyl ether to pentafluoropropionyl fluoride

The thermal rearrangement of trifluoromethyl trifluorovinyl ether (MVE) to pentafluoropropionyl fluoride (PPF) under pressure with and without radical initiators has been studied. The reaction typically gives a mixture of different acyl fluorides. The influence of the reaction parameters (pressure, temperature, concentration, type of initiator and contact time) on the conversion and the selectivity of the process has been carefully examined. In addition, a mechanism which accounts for the formation of all the products has been proposed.     

Chemical Speciation of Amphoteric Ions on Semi‐Dry Scrubber Residue and Bag‐House Ash from MSWI

Two series of size‐fractionated combusted residues, a bag‐house ash and a scrubber residue, from a municipal solid waste incinerator (MSWI) were prepared and extracted by means of sequential chemical extraction (SCE) procedures proposed by Tessier. Concentrations of water‐soluble phase, exchangeable phase, carbonated phase, Fe/Mn oxide phase, organic matter phase, and residual phase bound amphoteric metals (Pb and Zn) were obtained, and have been compared with those of single batch extraction of toxic characteristic leaching procedure (TCLP). In each size fraction of baghouse ash or scrubber residue, lead or zinc shows a common phenomena that the TCLP value is always lower than the content of the water‐soluble fraction. For lead, baghouse ash has a significant size‐dependent distribution on the water‐soluble phase to perform a size‐dependent test of lead in the TCLP test. The zinc TCLP data having less size dependence might be due to that neither the baghouse ash nor the scrubber residue has a size‐dependent distribution on the water‐soluble zinc phase.     

Synthesis of A2B star block copolymers from a heterotrifunctional initiator

We described the obtention of A₂B star block copolymers through the use of a new heterotrifunctional initiator. That way, well‐defined (PCL)₂‐arm‐PtBuMA and (PCL)₂‐arm‐PS star block copolymers have been synthesized from a heterotrifunctional initiator bearing two hydroxyl groups able to initiate ROP of CL (with AlEt₃ or Sn(Oct)₂ as coinitiator) and a bromide function able to initiate ATRP of tBuMA or styrene. Firstly, we have proceeded using a sequential process (two‐steps), leading to an intermediate macroinitiator. Secondly, attempt to polymerize these two monomers in a simultaneous process (one‐step), that is directly from the mixture of monomers, initiator, coinitiators, and solvent, has been realized and has shown that some interferences between the two polymerizations occurred, leading to an inhibition of ATRP when Sn(Oct)₂ was used and an unexpected increase in control when AlEt₃ was used as catalyst for the ROP (obtention of well‐defined (PCL)₂‐arm‐PtBuMA with pdi of 1.18). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1796–1806, 2006     

六甲氧基甲基三聚氰胺-多元醇-丙烯酸酯混杂聚合体系的研究

六甲氧基甲基三聚氰胺 (HMMM) 多元醇 丙烯酸酯 酸催化剂混杂聚合体系在高温下同时进行缩聚和自由基聚合并表现出协同效应 .体系中的活泼亚甲基在HMMM的催化下被空气氧化成过氧化氢物 ;过氧化氢物在酸催化下分解成自由基进而引发自由基聚合反应 .研究结果表明 ,体系中存在固化加速的协同效应 ;同时体系中还存在热互补效应 ,丙烯酸酯的自由基聚合反应放出的热可以传递给缩聚反应 ,满足缩聚反应吸热的要求 .混杂聚合得到的高分子合金膜具有优良的机械性能和耐溶剂性能 ,这是由于在混杂聚合过程中形成了互穿聚合物网络 (IPN)结构 .使用潜酸催化剂作为酸的来源 ,可以提高体系的储存稳定性 ;交联 引发剂的使用可以拓宽它的使用范围 ;对超枝化聚合物在混杂体系中的应用也进行了初步研究     

双官能度自由基引发剂应用研究的进展

双官能度引发剂在自由基聚合中的应用不断受到重视，本文介绍了常用的双官能度引发剂，并综述了其在制备嵌段共聚物及引发乙烯类单体（如苯乙烯、氯乙烯、丙烯酰胺等）聚合的研究进展。     

Synthesis of polystyrene latex with amphoteric surfactant and its characterization

An emulsion polymerization of styrene in the presence of an amphoteric surfactant; N,N-dimethyl-n-laurylbetaine (LNB) was carried out at pH 7.0. The polymerization rate and the concentration of the latex particle were proportional to the LNB concentration of 0.6 power. The latex particle sizes became smaller with increasing concentrations of LNB. The molecular weights of polystyrene latices increased with the concentration of LNB. The zeta-potentials of latex particles were significantly dependent on the pH, and showed the existence of an isoelectric point.     

偏氟乙烯的聚合反应

本文研究了用有机引发剂引发偏氟乙烯的水相聚合,并对制得的聚偏氟乙烯的性质进行了研究。有机引发剂引发聚合的聚偏氟乙烯的热稳定性、强度、结晶度和熔点均比用过硫酸盐引发聚合的聚偏氟乙烯高。     

用多官能团引发剂合成超支化聚苯乙烯及其C60衍生物

通过α-溴丙酰溴与Z5(季戊四醇与2,2-二羟甲基丙酸缩聚的产物)酯化反应制得超支化原子转移自由基聚合(ATRP)引发剂Z5-B(约含19个引发点).在100℃及CuCl/N,N,N,N",N"-五甲基二亚乙基三胺催化下,用Z5-B引发苯乙烯的ATRP聚合(环己酮为溶剂,体积分数为50%),得到超支化的聚苯乙烯,将溴端基叠氮化后与C60反应,获得超支化聚苯乙烯C60衍生物.该超支化C60衍生物可用于光限制材料.