Reactions of hydroxyl (HO•) and hydroperoxyl (HO) radicals generated chemically and photochemically with poly(ethylene oxide)

Poly(ethylene oxide) (poly(oxy-1,2-ethanediyl) is rapidly oxidized by hydroxyl (HO^?) and hydroperoxyl (HO) radicals generated by photolysis of hydrogen peroxide (H₂O₂) or by the catalytic decomposition of H₂O₂ by metallic silver. This process is accompanied by a chain scission during which the molecular weight decreases and the polydispersity changes. As a result of this process, the crystalline structure of poly(ethylene oxide) disappears, and the polymer becomes completely amorphous. © 1995 John Wiley & Sons, Inc.     

聚氧乙烯／聚酚氧共混体系的结晶行为及相容性研究

对聚氧化乙烯/聚酚氧(PEO/PH)共混体系的研究表明,随共混体系中非晶组份PH含量的增加,Avrami指数n值由2.0～2.3变为1.5～2.0,体系的结晶由盘状生长转化为纤维状生长;成核方式由方式Ⅰ转化为方式Ⅱ.PEO/PH共混体系的平衡熔点随PH含量的增加而降低,相互作用能量密度B=-1.46cal/mol,说明体系是互容的。     

WAXS analysis of structural changes of poly(ethylene terephthalate) fibers induced by supercritical-fluid dyeing

 Supercritical CO₂ fluid, a new environmentally friendly dyeing medium, changes the fiber structure to a certain extent in dependence on the treatment temperature and pressure used. Therefore the changes of crystalline structure in poly(ethylene tereph-thalate) (PET) fibers as brought about under the influence of supercritical CO₂ fluid were investigated. For the data collection of wide-angle X-ray diffraction full patterns a two-circle goniometer, equipped with a position sensitive detector, was used. From the observed two-dimensional fiber diffraction patterns the crystallinities of various treated fibers were evaluated. The equatorial scanning yielded the dimensions of crystallites. To elucidate the fiber-surface morphology changes SEM analyses were performed. The supercritical fluid dyeing of PET fibers with highly developed microfibrillar structure under taut-ends conditions promotes changes which are characterized by an increase in crystallinity and by diminution of the apparent crystallite dimensions. Some changes of surface morphology of dyed fibers were observed as well. Received: 14 May 1997 Accepted: 23 September 1997     

Recovery as a measure of oriented crystalline structure in poly(ether ester)s based on poly(ethylene oxide) and poly(ethylene terephthalate) used as shape memory polymers

Poly(ether ester)s consisting of poly(ethylene oxide) and poly(ethylene terephthalate) segments, EOET copolymers, could be used as shape memory polymers (SMP). Crystalline structural characters of the copolymers during the memory process were investigated by dynamic mechanical analysis, differential scanning calorimeter, wide-angle X-ray diffraction, polarizing microscopy, and recovery measurements. PEO crystals in stretched EOET copolymer preferentially oriented along fiber axis or stretch direction. During stretching, the structure of the copolymer undertake a transformation from spherulite to fiber, resulting in a crystalline morphology similar to shish-kebab, and recovery properties of stretched EOET samples were dependent on as-described crystalline structural characters that can be influenced by draw ratio. Driving forces for contraction come from the oriented chains, and only oriented or extended chains can be contributive to the recovery of deformation; these extended chains involve both crystalline and amorphous segments. The recovery process in shape memory behavior was noticed to be deorientation of oriented chains due to thermodynamic entropy effect, and was divided into three stages. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 101–112, 1999     

ChemInform Abstract: Ring Structure Formation in Transition-Metal Nitrido Chlorides by Donor—Acceptor Formation.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Raman longitudinal acoustic mode studies of poly(ethylene oxide) and α,ω-methoxylated poly(ethylene oxide) fractions during isothermal crystallization from the melt

Raman longitudinal acoustic mode (LAM) spectra have been obtained during isothermal crystallization from the melt at various temperatures of a poly(ethylene oxide) (PEO) fraction of molecular weight about 3000 and an α,ω-methoxylated fraction (MPEO) derived from it. For both fractions, we find that noninteger fold (NIF) chains are formed in the initial stages of crystallization. With time, and more rapidly at higher crystallization temperatures, the NIF chains transform into integer-fold (IF) structures. The final morphologies of the two fractions are similar, consisting of IF mixed-crystal lamellae composed mainly of extended (E) chains with embedded once-folded (F2) chains. This solid-state transformation from the NIF state may proceed through the F2 state. The effect of hydrogen bonds in the case of PEO is not to change the transformation process but to slow it when compared to MPEO. Comparison with small-angle x-ray scattering (SAXS) data indicates that in both cases the NIF chains are tilted to the lamellar surface and that the tilt from perpendicular eventually disappears as IF chains form at the later stages of crystallization. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1117–1126, 1997     

Reversible strain-induced order in the amorphous phase of a low-density ethylene/butene copolymer

This article deals with the characterization of the structural changes induced by uniaxial extension in the amorphous phase of an ethylene/butene copolymer. Volume change measurements indicate a reversible densification relevant to a strain-induced organization in the amorphous phase. The dynamic mechanical behavior shows an improvement of the β relaxation that reveals an important immobilization of the amorphous chains. The vibrational behavior investigated by means of Raman spectroscopy suggests that the strained amorphous chains are structurally analogous to the mesomorphic interfacial component. A discussion is made about the mechanism of the transformation of the amorphous phase into a mesomorphic structure compared to the more common strain-induced crystallization phenomenon. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2151–2159, 1997     

The influence of vacuum-ultraviolet radiation on poly(ethylene terephthalate)

Poly(ethylene terephthalate) was exposed to radiation from different kinds of low-pressure plasmas in an oxygen atmosphere. The lower wavelength limit of the spectrum investigated, λ = 112 nm, is the cut-off of magnesium fluoride used for separating the specimen chamber from the plasma light source. The total surface oxygen concentration, and the formation of hydroxyl, carbonyl, and carboxyl groups were evaluated from XPS measurements in combination with chemical derivatizations, and their dependences on the radiation spectrum and the oxygen pressure in the sample chamber have been investigated. © 1996 John Wiley & Sons, Inc.     

A study of polyethylene-gr-2-tert-butyl amino methacrylate-supported TiCl4 catalyst for ethylene polymerization

The use of a polyethylene-based copolymer with dual functional groups (polyethylene-gr-2-tert-butyl amino ethyl methacrylate) as the support for TiCl₄ catalyst in ethylene polymerization was studied. Different methods for treating the support were examined and treatment with BuMgCl was found to be the most effective. With the BuMgCl-modified support, a 12-run Plackett-Burman design was used to screen 11 factors in catalyst preparation. Statistical analysis of the results from this design identified significant factors with the amount of BuMgCl singled out to be the most important one for the four response variables of interest, Mg loading, Ti loading, catalyst activity per gram catalyst, and catalyst activity per gram Ti. © 1996 John Wiley & Sons, Inc.     

Micelle-like structures of poly(ethylene oxide)-block-poly(2-hydroxyethyl aspartamide)-methotrexate conjugates

The objective of this research was to prepare and characterize a micelle-like structure composed of a diblock copolymer-methotrexate (MTX) conjugate. MTX was attached on poly(ethylene oxide)-block-poly(2-hydroxyethyl aspartamide) (PEO-b-PHAA), obtained by aminolysis of PEO-b-poly(β-benzyl- -aspartate) (PBLA) with ethanolamine. It was hypothesized that after attachment of MTX onto PEO-b-PHAA through an ester bond, the amphiphilic conjugate would self-assemble into a micelle-like structure that would gradually release MTX, owing to unfavorable hydrolysis in a nonpolar core. An active ester of MTX was reacted with PEO-b-PHAA, providing a substitution ratio of 20–45% (molar ratio of drug to aspartamide units). At these levels, PEO-b-PHAA-MTX conjugate may self-assemble in an aqueous medium. Transmission electron microscopy revealed small spherical particles that had a mean diameter of 14 nm. There was no evidence of secondary aggregation. An absence of ¹H-NMR peaks of MTX in D₂O indicated that PEO-b-PHAA-MTX conjugates self-assembled into supramolecular structure where MTX resides in a site with highly restricted mobility, likely a core of a micelle-like structure. Accordingly, the loss of MTX by hydrolysis from PEO-b-PHAA-MTX conjugates was slow at neutral pH, with less than 20% released after 10 days. The stabilization of ester bonds in a nonpolar core of a micelle-like structure is novel in the design of soluble polymer-drug conjugates. PEO-b-PHAA-MTX conjugate micelles may help improve the biodistribution of MTX and help overcome drug resistance.