Physico-chemical aspects of polyethylene processing in an open mixer. Part 26: Formal kinetics of aldehyde and carboxylic acid formation at a constant rate

Formation of carboxylic acids at a constant rate can be easily explained. It seems to result from the formation and decomposition of α,γ-keto-hydroperoxides. Formal kinetics based on formation and decomposition of these structural units is in agreement with the experimental findings. The activation energy deduced from the calculations is negligible, in agreement with the experimental data showing the constant rate to be practically temperature independent. Comparison of the acids with the hydroperoxides and ketones formed initially shows that the rate of oxygen addition to alkyl radicals is significantly smaller than in low molecular mass liquids. The same conclusion is reached on comparing directly the acids formed on decomposition of α,γ-keto-hydroperoxides in polyethylene melt and in hexadecane. The rate of oxygen addition in polyethylene melt is closer to 2 × 10⁵ than to 6 × 10⁵ (s⁻¹) that is valid in hexadecane.It is possible to attribute the relatively small amount of aldehydes that might be formed at a constant rate to different reactions of alkoxy radicals that are not in a cage with other radicals. These alkoxy radicals result from the addition of peroxy radicals to unsaturated bonds. This addition is followed mainly by epoxide formation and simultaneous release of an alkoxy radical.     

Improvement of gas meter performance using polymer materials

The measuring elements of both dry‐ and wet‐type gas meters are composed of a diaphragm and rotary drum. In this article an explanation on the principle of measuring and the structure of the gas meter for each of these two types was discussed. Such applications were made as follows: synthetic rubber was used for the measuring diaphragm, engineering plastic was employed instead of metal for the measuring drum, and poly(butylene terephthalate) (PBT) was used for the casing, respectively. As a result, an improvement in the gas resistance performance and productivity, which led to a lighter weight, more compactness and a lower cost of productions was achieved. Also the influence of the solubility of the measured gas to the plastic on the measured valve was discussed. Copyright © 2003 John Wiley & Sons, Ltd.     

Radiolytic unsaturation decay in polyethylene. Part III—the effect of certain chain transfer agents

Small amounts of certain halogenated compounds are found to have, at most, only a slight enhancing effect on the radiolytic decay rates of added poly-unsaturated compounds in polyethylene, but significantly increase the elastic modulus at 433 K (melt modulus) obtained thereby. Experiments with model chlorine-containing additives suggest that this increase is due to a more random distribution of polymer and monomer mediated crosslinks in the polymer, that it does not result from a significant increase in crosslinking and that it is mediated by chlorine atoms, in a similar manner to radiolytic hydrogen atoms, through facilitation of long range free radical migration. Although low molecular weight chloro-paraffins inhibit radiolytically induced growth of melt modulus in monomer containing polyethylenes, even very small additions of chlorinated polyethylenes, which form a separate phase, increase the melt modulus. This again indicates that the active species is the chlorine radical.     

Permeability of N2, Ar,He, O2, and CO2 through as‐extruded amorphous and biaxially oriented polyester films: Dependence on chain mobility

For as‐extruded amorphous and biaxially orientated polyester films based on poly(ethylene terephthalate), poly(ethylene naphthalate), and copolymers containing poly(ethylene terephthalate) and poly(ethylene naphthalate) moieties, permeability, diffusion, and solubility coefficients are interpreted in terms of chain mobility. The influence of polymer morphology is determined by comparison of the data for as‐extruded amorphous sheets and materials produced with different biaxial draw ratios. The crystallinities of the samples were assessed using differential scanning calorimetry and density measurements. Changes in mobility at a molecular level were investigated using dielectric spectroscopy and dynamic mechanical thermal analysis. The study, in conjunction with our earlier work, leads to the conclusion that the key to understanding differences in gas transport is the difference in local chain motions rather than in free volume. This was illustrated by the permeability results for He, Ar, N₂, and O₂ in the range of polyesters. However, the permeability of CO₂ was found to require alternative explanations because of polymer–penetrant interactions. For biaxially oriented samples, the differences in diffusivity are not only due to differences in local chain motions, but also additional constraints resulting from the increased crystallinity and chain rigidity—which also act to hinder segmental mobility. The effectiveness of the reduction in permeability in the biaxially oriented films is consequently determined by the ability of the polymer chains to effectively align and form crystalline structures. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2916–2929, 2004     

Physico-chemical aspects of polyethylene processing in an open mixer. Part 29: Experimental kinetics and mechanisms of γ-lactone formation

The experimental kinetics for γ-lactone formation shows more complexity than that for acids. Nonetheless, it can be concluded to the existence of a constant rate of formation from the beginning of the experiments with polyethylene melts. There is an additional term contributing to γ-lactone formation in the initial stages that is cubic in processing time. In the advanced stages of processing, in the high temperature range (170-200 °C), the concentration of γ-lactones increases linearly with the processing time.There are many mechanisms susceptible to give γ-lactones on polyethylene melt processing. Some of them are based on decomposition of intermediates formed directly on chain propagation. This is so for the α,γ-keto-hydroperoxides in 4-position to hydroxyl groups. Since decomposition of these intermediates is very fast, the reaction might account for a constant rate of γ-lactone formation from the beginning of polyethylene processing. Decomposition of the α,δ-keto-hydroperoxides formed on intramolecular reactions on chain propagation is not so fast as that of the α,γ-keto-hydroperoxides. Nonetheless, it might account for part of the delayed formation of γ-lactones. The same is valid for the mechanisms based on peroxidation of aldehydes and γ-hydroxy trans-vinylene groups that involve intermediates that are formed on polyethylene peroxidation. They might be important for explaining the cubic term as well as γ-lactone formation in the advanced stages of polyethylene processing.     

Electron beam induced modification of poly(ethylene terephthalate) films

Electron beam processing of poly(ethylene terephthalate) (PET) films is found to promote significant changes in the melting heat, intrinsic viscosity and polymer film-liquid (water, isooctane and toluene) boundary surface tension. These properties are featured with several maximums depending on the absorbed dose and correlating with the modification of PET surface functionality. Studies using adsorption of acid-base indicators and IR-spectroscopy revealed that the increase of PET surface hydrophilicity is determined by the oxidation of methylene and methyne groups. Electron beam treatment of PET films on the surface of N-vinylpyrrolidone aqueous solution provided graft copolymerization with this comonomer at optimum process parameters (energy 700 keV, current 1 mA, absorbed dose 50 kGy).     

Size exclusion chromatographic determination of hydroxypropyl methyl cellulose and polyethylene glycol 400 in an ophthalmic solution

Summary Hydroxypropyl methyl cellulose (HPMC) and polyethylene glycol 400 (PEG 400) content in HypoTears™ Daily Dose ophthalmic solution are determined simultaneously by size exclusion chromatography. The retention times of HPMC and PEG 400 are 10.6 and 15.4 minutes, respectively. The method requires minimal sample pretreatment and is accurate and reproducible. The peak area response from a refractive index detector versus HPMC and PEG 400 concentration is linear over the range of 50–150 % of their label claims of 2.5 mg/mL and 10 mg/mL, respectively. The mean absolute recoveries of HPMC and PEG 400 at their label claim using the described method are 98.9±1.3 % and 100.4±1.2 % (mean±SD, n=12), respectively.     

RPS增容LDPE／PS研究

用ＨＡＡＫＥ、ＤＳＣ、ＩＲ等方法研究了侧基含有过氧键的反聚苯乙烯与ＬＤＰＥ之间的反应，并将其应用到ＬＤＰＥ／ＰＳ共混体系。考察了不同添加方式，交联助剂等对共混物力学性能、流变性能及微观结构的影响。     

Preparation and characterization of poly(amidoamine) dendrimers functionalized with a rhenium carbonyl complex and PEG as new IR probes for carbonyl metallo immunoassay

The first poly(amidoamine) (PAMAM) dendrimers tethered with both (η⁵-cyclopentadienyl) rhenium tricarbonyl (CpRe(CO)₃) units and polyethylene glycol (PEG) chains were prepared and characterized by combining NMR spectroscopy and Fourier-transform IR spectroscopy. Grafting of CpRe(CO)₃ units was achieved by reductive amination of formyl-CpRe(CO)₃ with the peripheral amines of generation 3 and 4 PAMAMs to yield dendrimers labeled with a variable number of CpRe(CO)₃ units, ranging from 8 to 14 for PAMAM-G3 and 17-30 for PAMAM-G4. PEG chains of different lengths were then attached to some of the remaining peripheral amines, and their respective ability to improve the solubility of the metallodendrimers in aqueous buffered media was evaluated. These metallodendrimers represent new infrared probes designed to be coupled to immunological reagents for the amplification of the IR signal in carbonyl metallo immunoassay (CMIA).     

Synthesis of double silylene-bridged binuclear titanium complexes and their use as catalysts for ethylene polymerization

Five new double silylene-bridged binuclear titanium complexes were synthesized by the reaction of RCpTiCl₃ and Li₂[μ,μ-(SiMe₂)₂ (C₅H₃)₂] in toluene. They were all well characterized. These complexes activated with methylaluminoxane (MAO) are highly active catalysts (2.33 × 10⁵ g PE/mol Cat h) for the polymerization of ethylene even at low Al/Ti (Al/Ti = 300). The molecular weight distribution of the polymer indicates broad or bimodal (MWD = 26.76) distribution.