Polymerization via zwitterion 25. Alternating copolymerizations of cyclic acyl phosphorite and phosphite with vinyl monomers having an electron withdrawing group

Summary Spontaneous copolymerizations of cyclic acyl phosphonite (SPO) and phosphite (SPI) with an electron-deficient vinyl monomer such as methyl acrylate (MA), methyl vinyl ketone (MVK), and acrolein (AL), gave the corresponding alternating copolymers. These copolymerizations took place without added initiator and proceeded through zwitterion intermediates. Copolymer structures 1a, 1b, 2 and 3 have been established, all of which were derived in a regiospecific manner of ambident anions. The scheme of the copolymerizations is presented.     

Cationic ring-opening polymerization of 2-phenyl-1,3,6,2-trioxaphosphocane

Summary The ring-opening polymerization of 2-phenyl-1,3,-6,2-trioxaphosphocane (4), an eight-membered cyclic phosphonite, has been investigated. Cationic initiators of PhCH₂-Cl and MeOTf gave polymers, whereas anionic and radical initiators did not yield polymer. The structure of polymer was examined by IR, ¹H, ³¹P, and ³¹C NMR spectroscopy of polymers and elemental analysis as well as the alkaline hydrolysis products. The polymer consisted of two different units, i.e., the major part is the normal phosphinate structure 5 and the minor part is the isomerized unit 6 in 7% with PhCH₂Cl initiation and in 34% with MeOTf initiator. The difference in nature of propagating species from these two initiators are discussed in connection with their reactivities.On leave from the Institute of Chemistry, Academia Sinica, Beijing, China     

Cationic ring-opening polymerization of 2-phenyl-1,2-oxaphospholane (deoxophostone)

Summary The ring-opening polymerization of deoxophostone 5, a five-membered cyclic phosphinite, has been studied. Some cationic initiators gave polymer whereas anionic and radical initiators as well as metal chloride (Lewis acid) catalysts did not yield polymer. The polymer consisted of a phosphine oxide repeating unit 6. The polymerization proceeded via the Arbuzov-type reaction. The reduction of polymer 6 with a HSiCl₃/Et₃N system gave polyphosphine 7.     

A novel spin-finishing method for antistatic modification of polyester fiber. Surface reaction onto amine-containing copoly(amide-ethers) blended with polyester fiber

Copoly(amide-ethers) containing two types of tertiary amine units were made as antistatic modifiers for poly(ethylene terephthalate) (PET) fibers. The filaments of the copolymers were melt-spun and reacted with three alkylating agents in order to quaternize the tertiary amine into a sulfo-betaine, a carbobetaine, and an ammonium ion. The apparent electric resistivity of the filaments was greatly reduced by this reaction, being in the range of 10⁶ to 10⁸ Ω/cm. However, because these quaternized copolymers incurred decomposition during blend spinning with PET, a blend PET fiber containing one type of copoly(amide-ether) was melt-spun and subjected to quaternization of the amino groups as well as to surface crosslinking with various alkylating and epoxy agents. The quaternized blend fibers obtained showed improved antistatic properties compared with the original blend fiber. Particularly, the fibers crosslinked with epoxy compounds were found to have the best antistatic properties that had ever been attained with this type of modification. The antistatic properties were retained even after dyeing, because both hydrophilic and ionic groups had been effectively immobilized on the surface. Since this quaternization and crosslinking could be conducted on-line with spinning and drawing within a short reaction time, this modification technique is called “spin-finishing method”, which should be superior to the conventional methods in terms of cost performance and productivity.     

New ring-opening polymerization via a π-allylpalladium complex

Summary A binary system of a palladium complex as catalyst and zinc alkoxide as initiator conducted a novel ring-opening polymerization of cyclic carbonate, i. e., 5,5-dimethyl-4-ethenyl-1,3-dioxan-2-one. The polymerization proceeded along with releasing carbon dioxide to produce the corresponding polyether. The -allylpalladium complex generated from the monomer with the catalyst is the key intermediate for this new polymerization. The propagating end is zinc alkoxide, which nucleophilically attacks the monomer activated as the -allylpalladium complex in the propagation.     

PbTiO3–PbO–SiO2 Glass-Ceramic Thin Film by a Sol–Gel Process

PbTiO₃(PT)-PbO-SiO₂ glass-ceramic thin films were pro-duced by a sol-gel process. The crystallization of PT oc-curred at ∼700°C and was higher than that in PT-PbO-B₂ O₃ sol-gel glass-ceramics. A pinhole-free thin film was obtained by a rapid thermal annealing process when the designed glass-forming phase content in the thin film was >24 vol%. The measured dielectric constants of the films fairly agreed with the predicted values, based on a parallel mixing model. The dielectric constant was 219 and the di-electric loss was 0.04 in the 0.6PT-0.4(PbO-SiO₂) film that was fired at 700°C.     

Effect of Composition and Size of Crystallite on Crystal Phase in Lead Barium Titanate

Lead titanate, barium titanate, and lead barium titanate powders (>99.9% pure), the particle size of which varied from 0.03 to 0.15 μm depending on the calcination temperature and the composition, was prepared from barium lead titanyl oxalate, which was previously prepared by reacting high-purity ammonium titanyl oxalate with barium and lead acetate. The critical crystallite size of BaTiO₃ powder from the cubic to the tetragonal phase is around 1 μm. Pb_0.3Ba_0.7TiO₃ powder with an average size of 0.057 μm showed the tetragonal phase.     

Copolymerization of ethanesultam with 2-methyl-2-oxazoline

Summary This paper describes the so-called No Catalyst Copolymerization between dioxo-1,1-thiazetidine-1,2(Ethanesultam; ESm) and 2-methyl-2-oxazoline. The copolymerization took place without any added initiator to produce copolymers of MeOZO and ESm. The structure of the copolymer was determined by the IR and NMR spectra, elemental analysis, as well as by the result of an alkaline hydrolysis of the copolymer. The reaction scheme of the copolymerization via zwitterion mechanism (Eq 3–5) was proposed.     

A facile antistatic modification of polyester fiber based on ion-exchange reaction of sulfonate-modified polyester and various cationic surfactants

A new technique for imparting antistatic properties to poly(ethylene terephthalate) (PET) fiber has been developed. In this technique, blend polyester fibers containing poly(ethylene terephthalate/5-sulfoisophthalate) (SIP-PET) were prepared by blend spinning and then treated with various cationic surfactants in the process of dyeing. The surfactants could effectively be immobilized on the fiber as the counter cations of the sulfonate groups of the 5-sulfoisophthalate (SIP) units and aid the release of static electrons formed in the fiber. Thus, the half-life time (t_1/2) of leakage of static charge and the surface resistivity (Rs) of the blend PET fibers became much lower after treating. The best result was obtained with a methylated quaternary ammonium salt of a stearylamine-ethylene oxide (EO) adduct or hydrochloride of a laurylamine-EO adduct as the surfactant of which the number of EO units was around ten. Even after five washing cycles the t_1/2 value of the fibers treated with these surfactants was kept lower than 30 s with the Rs value maintained in the order of 10¹³ Ω cm^-2. Therefore, the present technique could be useful for practical production of polyester fibers with “semi-permanent” antistatic properties which can be recovered by re-treatment even if they were lost.