Polystyrene‐supported polyoxyethylene bound potassium permanganate as a heterogeneous oxidizing agent

Oxidation behavior of a 2 mol % divinylbenzene (DVB)‐crosslinked polystyrene‐supported permanganate function was investigated toward low molecular weight primary and secondary alcohols and aldehydes. The permanganate function was attached to a polystyrene support through cyclic polyoxyethylene (POE) units immobilized on the support. Contrary to the oxidations catalyzed by low molecular weight permanganate reagents, the oxidation of primary alcohol terminated in the aldehyde stage. The secondary alcohols were converted to the respective ketone and aldehyde to acid. The effect of the variable parameters similar to solvent, temperature, and reagent to substrate ratio was followed. Nonpolar cyclohexane was found to be the best solvent for the present study. Also the reactivity increased with increasing temperature. The oxidizing reagent possesses a long shelf life and could be recycled several times without reduction of capacity and mechanical stability. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3708–3717, 2003     

Intramolecular crosslinking of poly(vinyl alcohol)

Poly(vinyl alcohol) is crosslinked in dilute solution (c=0.1 wt%) with glutaraldehyde. The reaction product is characterized by viscometry and gel permeation chromatography (g.p.c.). The intrinsic viscosity decreases with increasing degree of crosslinking and does not depend on temperature. G.p.c. reveals that the reaction product is not homogeneous, but consists of a mixture of particles with different sizes, possibly both intra- and intermolecularly crosslinked molecules. The intramolecularly crosslinked molecules are smaller in size than the initial polymer molecules and their size depends on the degree of crosslinking. They possess a narrow particle size distribution even if the initial polymer sample had a broad molecular weight distribution.     

Preparation of glucose oxidase immobilized in different carriers using radiation polymerization

Glucose oxidase (EC 1.1.3.4) was immobilized on different polymeric materials using different immobilization techniques (entrapping by γ‐irradiation, and covalent binding using epichlorohydrin). Studies were carried out to increase the thermal stability of glucose oxidase (GOD) for different applications. The activity and stability of the resulting biopolymers have been compared with those of free GOD. The effect of different polyvinyl alcohol/polyacrylamide (PVA/PAAm) compositions of the copolymer carrier on the enzymatic activity of the immobilized GOD was studied. The maximum enzymatic activity was obtained with the composition ratio of PVA/PAAm of 60:40. The behaviour of the free and immobilized enzyme was analysed as a function of pH. A broadening in the pH profile (5.5–8) was observed for immobilized preparations. The activity and stability of the resulting biopolymers produced by immobilization of GOD onto different carriers have been compared, in both aqueous and organic media, with those of the free GOD. The enzyme's tolerance toward both heat and organic solvent was enhanced by immobilization onto polymers. The addition of different concentrations of organic solvents (10–50%, v/v) to the enzyme at higher temperature (60 °C) was found to stabilize the enzyme molecule. The strongest stabilizing effect on the enzymatic activity was achieved at a concentration of 10%. Copyright © 2005 Society of Chemical Industry     

Abrasion phenomena in twill tencel fabric

The abrasion characteristics of Tencel fabrics were evaluated by Martindale abrasion and laundering, and the breakdown mechanism of fibers was surveyed by scanning electron microscopy. The fabric was subjected to pad‐dry‐cure treatment with two different types of modified dimethyloldihydroxyethylene urea resins (Reaktant DH and Reaktant FC). Although the degree of dry abrasion varied with different resins, the damage exhibited by individual fibers differed little from untreated to resin‐treated; the major mechanism of abrasion was through friction, and the mechanism of fiber failure was multiple splitting and transverse cracking. In untreated Tencel, the characteristic feature of wet abrasion was massive fibrillation, and in crosslinked fabrics, the wet abrasion mechanism was through fiber slippage and slicing action, although in the Reaktant FC‐treated fabric, the wet abrasion mechanism was more through slicing than through fiber splitting. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1391–1398, 2006     

The radiation crosslinking and scission of ethylene-propylene copolymers studied by solid-state nuclear magnetic resonance

Methyl groups from chain scission and H-crosslinks have been identified by solid-state nuclear magnetic resonance in amorphous ethylene-propylene copolymers containing 23 and 36 mole % propylene after γ-irradiation to 10 MGy at 30°C. G (scission) and G (crosslink) values determined from the n.m.r. spectra and by extraction are in agreement, which suggests that the crosslinks are not clustered. This may differ from the situation in polyethylene where there is a substantial crystalline content. G(S). G(X) and the ratio G(S)/G(X) increase with increasing propylene content of the copolymers.     

Porous elastomeric beads from crosslinked emulsions

The production of porous polymeric particles is attractive for a large number of applications and can be achieved by various techniques. Although numerous production schemes exist for glassy polymers, difficulties arise for soft, rubbery materials that need a chemical crosslinking step, such as elastomers. This is particularly true for poly(dimethylsiloxane) (PDMS), which shows the lowest glass‐transition temperature among the polymers. Recent studies suggest in situ hydrogen bubble formation or vacuum drying of water droplets dispersed in the polymer matrix in order to generate porous PDMS structures. In this work we report early results based on the chemical crosslinking of water in PDMS emulsion droplets in a mechanically stirred thermostated water vessel. This approach is shown to lead to high porosity PDMS beads (ca. 10^?3 m particle diameter) with an open structure whose properties (diameter and porosity) are strongly influenced by the starting composition (solvent, surfactant, and polymer types and ratios), as well as the operating parameters (agitation and temperature). The possible uses of these derived beads are discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 967–971, 2002     

含氟聚酰亚胺的辐射交联及其交联度的XPS表征

含氟聚酰亚胺(FPI)是一种耐高温、耐水解的新型聚酰亚胺。到目前为止,尚未见文献报道它的辐射交联。本文发现它能在高温辐射下交联,交联后的含氟聚酰亚胺的玻璃化转变温度以及高温力学性能有明显提高。本文还首次用XPS方法做了它的交联度表征。用XPS方法求得FPI的凝胶化剂量为50Mrad。     

中原高温高盐油藏疏水缔合聚合物凝胶调剖剂研究

针对中原油田高温(>80℃)、高盐度(>50 g/L)、高硬度(>1 g/L)砂岩油藏,研制了地下成胶的高热稳定性聚合物凝胶调剖剂。所用聚合物为疏水缔合聚合物AP-P4,M=9.0×106,HD=27%,疏水基摩尔分数0.2%;交联剂为可生成酚醛树脂的3种化合物;调剖剂胶液用矿化度160 g/L的马寨油田污水配制;实验温度95℃。根据形成的凝胶黏度(95℃,1.1 s-1)确定交联剂各组分用量为:MZ-YL 0.429%,MZ-BE 0.060%,MZ-XS 0.012%;酸度调整剂用量0.12%;成胶时间10~15小时。2.5、3.0、3.5 g/L AP-P4的凝胶在95℃老化100天后黏度保持在~40 Pa.s及以上。初配制胶液在3000 r/min下剪切15分钟后黏度降低87.5%~89.0%,但成胶后和老化过程中凝胶黏度只比未剪切样降低17.1%~6.6%。3.5 g/L AP-P4的调剖剂对~1μm2的6支储层岩心的堵塞率在88.1%~95.8%范围,平均93.3%,造成的残余阻力系数在15.2~28.6范围,平均19.8,使渗透率级差2.3~8.0的4组双人造岩心的注水流量比发生不同程度的反转。认为该凝胶调剖剂高温下稳定性好的原因,是强化学交联密度低,因而凝胶脱水收缩作用弱。图2表5参5。     

Mechanical properties and antibacterial activity of peroxide‐cured silicone rubber foams

Silicone rubber (SR) foams were prepared by the peroxide curing of a silicone compound with 2,4‐dichlorobenzoyl peroxide (DCBP), di‐t‐butyl peroxide (DTBP), or 2,5‐dimethyl‐2,5‐di(t‐butylperoxy) hexane (DBPH) in the presence of 2,2′‐azobisisobutyronitrile (AIBN) as a blowing agent. The cells were formed in the foam as a result of nitrogen produced by the decomposition of AIBN during the foaming process. The cell size, hardness, and tensile properties of the SR foams were examined as a function of the peroxide concentration. When the peroxide concentration increased, the hardness and tensile strength of the SR foams increased, whereas the cell size and elongation at break decreased. The antibacterial activity of the prepared foams was also evaluated via their effects on Staphylococcus aureus and Escherichia coli. The peroxide‐cured SR foams had antibacterial activity because a toxic residue was generated by the peroxide decomposition. The foam prepared by the AIBN/DCBP system showed more antibacterial activity than the AIBN/DBPH and AIBN/DTBP ones. However, after postcuring at 250°C for 2 h, the antibacterial activity of the SR foams significantly decreased. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008