Observation of eliminative cationic polymerization within van der Waals clusters

We report the first observation of eliminative cationic polymerization within van der Waals (vdW) clusters following electron impact ionization at pressures of 10−8 Torr. The elimination reactions of C2H3Cl+ within the clusters terminate after three successive steps, each involving elimination of HCl or Cl. The results provide a mechanism for the early stages of gas phase cationic polymerization of vinyl chloride and demonstrate the feasibility of using vdW clusters as a means of studying gas phase cationic polymerization

Kinetic and Thermodynamic Studies of Carbenium Ion Additions Towards Alkenes

The ionisation (Ar2CHCl + BC13 v=± Ar2CH+BCi;) and dissociation (Ar2CH+BCi; ^=*Ar2CH+ + BCl^) equilibria of diarylmethyl chlorides i n boron trichloride/ dichloromethane solution have been studied by conductimetry, photometry and *H NMR spectroscopy. Small differences i n the UV-vis spectra of diarylcarbenium tetrachloroborates, which have been observed i n solutions of low and high tetrachloroborate concentration, can be attributed to the formation of 1 :1 ion-pairs i n the more concentrated solutions. Low temperature calorimetry was used to determine the heats of addition of diarylcarbenium tetrachloroborates to 2~methyl-1 -pentene (Ar2CH+BCi; + H2C=CRRT ArjCH-CHj-CRR'Cl + BC13), and it is estimated that the standard free enthalpy of t h i s reaction is greater than 0 for systems with pKR+ > -2.6. Kinetic studies have shown that paired and unpaired diarylcarbenium tetrachloroborates exhibit identical reactivity towards alkenes. A rationalisation for the different situation in carbocationic and carbanionic polymerisation i s presented. The rate constants for the initiation of isobutene, styrene and isoprene polymerisation by diarylcarbenium ions have been determined, and it is shown, how propagation rate constants can be estimated from linear free energy relationships

Synthesis of poly(vinyl ether)s with perfluoroalkyl pendant groups

2-Perfluoro(alkyl)ethyl vinyl ethers, F(CF2)nCH2CH2OCHCH2, (n = 6 or 8), were synthesized and polymerized by means of cationic initiators (HI/ZnI2 and CF3SO3H/(CH3)2S). The perfluorohexyl-substituted poly(vinyl ether) is completely amorphous. The polymer with perfluorooctyl segments shows side chain crystallization with a disordering transition. For the corresponding perfluorooctyl monomer a liquid-crystalline phase was observed before melting. Copolymerization experiments of the flurocarbon-segmented monomers with a vinyl ether containing a cyanobiphenyl group in the side chain did not give homogeneous copolymers. This is attributed to the slower rate of polymerization of the fluorinated vinyl ethers as compared with the liquid-crystalline comonomer

Selective Synthesis, Characterization and Kinetics Studies of poly(α-Methyl styrene) induced by Maghnite-Na+ Clay (Algerian MMT)

A new and efficient catalyst of Na-Montmorillonite (Na+-MMT) was employed in this paper for α-methylstyrene (AMS) cationic polymerization. Maghnite clay, obtained from Tlemcen Algeria, was investigated to remove heavy metal ion from wastewater. “Maghnite-Na” is a Montmorillonite sheet silicate clay, exchanged with sodium as an efficient catalyst for cationic polymerization of many vinylic and heterocyclic monomers. The various techniques, including 1H-NMR, 13C-NMR, IR, DSC and Ubbelohde viscometer, were used to elucidate structural characteristics and thermal properties of the resulting polymers. The structure compositions of “MMT”, “H+-MMT” and “Na+-MMT” have been developed. It was found that the cationic polymerization of AMS is initiated by Na+-MMT at 0 °C in bulk and in solution. The influences of reaction temperature, solvent, weight ratio of initiator/monomer and reaction time on the yield of monomer and the molecular weight are investigated. The kinetics indicated that the polymerization rate is first order with respect to the monomer concentration. A possible mechanism of this cationic polymerization is discussed based on the results of the 1H-NMR Spectroscopic analysis of these model reactions. A cationic mechanism for the reaction was proposed. From the mechanism studies, it was showed that monomer was inserted into the growing chains

Thermally induced cationic polymerization of isobutyl vinyl ether in toluene in the presence of solvate ionic liquid

Radical polymerization of isobutyl vinyl ether (IBVE) was attempted with the aid of the interaction between the corresponding propagating radical and lithium cation (Li+). LiN(SO2CF3)2 (LiNTf2) and ester compounds, such as methyl methacrylate (MMA) and vinyl acetate (VAc), were added as a Li+ source and dissolving agent for LiNTf2, respectively. Homopolymers of cationically polymerizable IBVE were obtained despite the presence of radically polymerizable monomers such as MMA and VAc. Contrary to our expectation, the polymerization proceeded via not a radical mechanism but a cationic mechanism. However, this cationic polymerization was found to be unusual. In particular, the polymer yield increased with the polymerization temperature; successful polymerization was observed at 100 °C, whereas no polymerization occurred at lower temperatures such as at 0 °C. The behavior of the present system was therefore defined as “thermally induced cationic polymerization”. The mechanism of thermally induced cationic polymerization is still not clear, but it is assumed that the propagating cation is markedly stabilized through its interaction with the solvate ionic liquid formed between LiNTf2 and the Lewis base

A Novel Nanocomposite with Photo-Polymerization for Wafer Level Application

©2008 IEEE. Personal use of this material is permitted. However, permission to reprint/republish this material for advertising or promotional purposes or for creating new collective works for resale or distribution to servers or lists, or to reuse any copyrighted component of this work in other works must be obtained from the IEEE. This material is presented to ensure timely dissemination of scholarly and technical work. Copyright and all rights therein are retained by authors or by other copyright holders. All persons copying this information are expected to adhere to the terms and constraints invoked by each author's copyright. In most cases, these works may not be reposted without the explicit permission of the copyright holder.A novel nanocomposite photo-curable material which can act both as a photoresist and a stress redistribution layer applied on the wafer level was synthesized and studied. In the experiments, 20-nm silica fillers were modified by a silane coupling agent through a hydrolysis and condensation reaction and then incorporated into the epoxy matrix. A photo-sensitive initiator was added into the formulation which can release cations after ultraviolet exposure and initiate the epoxy crosslinking reaction. The photo-crosslinking reaction of the epoxy made it a negative tone photoresist. The curing reaction of the nanocomposites was monitored by a differential scanning calorimeter with the photo-calorimetric accessory. The thermal mechanical properties of photo-cured nanocomposites thin film were also measured. It was found that the moduli change of the nanocomposites as the filler loading increasing did not follow the Mori–Tanaka model, which indicated that the nanocomposite was not a simple two-phase structure as the composite with micron size filler. The addition of nano-sized silica fillers reduced the thermal expansion and improved the stiffness of the epoxy, with only a minimal effect on the optical transparency of the epoxy, which facilitated the complete photo reaction in the epoxy

Synthesis and Post-Polymerization Modification of Defined Functional Poly(vinyl ether)s

Living cationic polymerization is known for a good control over chain growth yielding polymers with well-defined molar mass distributions and low dispersities. However, the practical challenges involved in the synthesis of poly(vinyl ether)s limited suitable post-polymerization modifications (PPM) via chemoselective click reactions. Herein the successful controlled cationic polymerization of vinyl ethers bearing pendant CC double and C≡C triple bonds using a single-component initiation under ambient conditions is reported. Furthermore, the PPM via thiol-ene/-yne and copper(I)-catalyzed alkyne-azide cycloaddition reaction of the obtained polymers is successfully realized laying the foundation for the synthesis of unprecedented functional poly(vinyl ether)s

Ionic Polymerization in Ionic Liquids

Ionic liquids have emerged as a new class of solvents for ionic polymerization due to their low volatility, chemical stability, high conductivity, wide electrochemical window. The advantages and limitations of application of ionic liquids as solvents for ionic polymerization processes are critically discussed in this chapter. The field of cationic polymerization in ionic liquid has undergone rapid growth in recent years. The most important types of cationic monomers, such as styrene and its derivatives, vinyl ethers and isobutylene have been polymerized in ionic liquids; even undergo living polymerization. Corresponding elementary reactions of cationic polymerization in ionic liquids were proposed. Methyl methacrylate and styrene can undergo anionic polymerization in ionic liquids. However, ionic liquids seem unsuitable solvents for anionic polymerization