Non-isothermal rheological response in melt spinning and idealized elongational flow

Almost all polymer processing operations involve moving and shaping the polymer as a melt and then cooling it, usually quite rapidly, to a solid state. In order to develop models for such processes we have begun systematic studies in non-isothermal rheology; here we interpret the results in the context of melt spinning. Theoretical predictions of stress vs distance from the spinneret were calculated from generalized (non-isothermal) viscoelastic theory and compared with Dees' melt spinning data on high density polyethylene. Despite certain experimental and theoretical difficulties, the agreement is good. Surprisingly, an additional theoretical curve, based on a simple Trouton viscosity, also gave a reasonable approximation over much of the distance, despite the transient nature of the flow. To understand this phenomenon further, a more tractable theoretical problem was studied in detail; the problem, of constant elongational flow (? = constant) in the presence of a constant rate of temperature change (dT/dt = constant). The results depend on two dimensionless groupings; the first is the usual product of a relaxation time and ?; the second involves the ratio of normalized dT/dt to ?. When the second group is large, a quasi-viscous state exists. The melt spinning data for the HDPE may be near this state.     

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.     

Synthesis of poly(α-thiophenediyl)benzylidene with high molecular weight and its thermal stability

Summary The synthesis of poly(-thiophenediyl)benzylidene (PTB) with high molecular weight is described. Number-average degrees of polymerization reached about 74. The characterizations of the polymer was investigated by ¹H-NMR, ¹³C-NMR, IR, and UV-VIS spectra. The polymer with well-defined structure and high molecular weight was obtained by polymerization at low temperature and in polar solvent. This polymer was thermally stable and a thermal decomposition took place at 391°C under nitrogen and at 370°C under air. The glass transformation temperature was 117°C and this PTB was nonfusible.     

Fabrication of Nonadditive Mica Ceramics by Hot Isostatic Processing

Powder compacts of synthetic mica (fluorphlogopite) encapsulated in a boro–silicate glass tube were isostatically hot–pressed in a Roy–Tuttle–type pressure vessel. Synthetic mica was sintered to a density of 2.60 g/cm³ (91.2% of theoretical density) without additives under 98 MPa of water at 800°C for 45 min.     

Electron-microscopic procedure for acrylic rubber

The electron-microscopic visualization of acrylic rubber dispersed in a heterogeneous structural resin composition consisting of a rubber-modified two-phase plastic comprising essentially a butyl acrylate rubber phase and an acrylonitrile–styrene copolymer phase, respectively, has been accomplished. This procedure consists of the following: The molded resin specimen is treated with hydrazine hydrate solution to produce the acrylic acid hydrazides. Allow the treated specimen to soak in osmium tetroxide solution. The acrylic rubber may be indirectly fixed and stained. Some micrographs of ultrathin sections of two or three resin compositions, cut by an ultramicrotome, are presented.