The effect of alcoholic mobile phase modifiers on retention and stereoselectivity on a commercially available cellulose-based HPLC chiral stationary phase: An unexpected reversal in enantiometric elution order

Summary High pressure liquid chromatographic methods for the determination of diphenylmethane-4,4-diisocyanate (MDI) and toluene diisocyanate (TDI) in chemical products are described. The MDI- and TDI monomers were determined as their urea derivative formed by the reaction with 9-(methyl aminomethyl)-anthracene. Using these methods MDI- and TDI monomer concentrations have been determined in 55 chemical products: sealing waxes, insulating- and adhesive foam, hardener, primer, adhesives and surface coatings. The recovery of both MDI and TDI monomers from various types of chemical product was found to be 92–97%, and the relative standard deviations of the methods was <5% for all types of products.     

4,4′-二(硬脂酰胺基)二苯甲烷在乙烯基类单体中的分子组装及其结构形态研究

4,4′-二(硬脂酰胺基)二苯甲烷(BSDM)能在乙烯基类单体中进行聚集、自组装,并可使苯乙烯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸-2-羟基乙酯等凝胶化,形成相应的分子凝胶.凝胶/溶胶相变温度(TGS)与BSDM浓度有关,BSDM质量分数越大,凝胶体系中分子间氢键和π-π键越多,要破坏它们所需要的能量越高,TGS因而也就越高.透射电镜表明,BSDM在各种可聚合溶剂中通过分子间相互作用形成类似纤维状的聚集体结构.BSDM在可聚合溶剂聚合前后的偏光显微照片表明,BSDM在体系中的晶型结构是球晶.     

Sources and Time-Variations of Reactive Hydrocarbon Immissions in the Atmosphere of Different Industrial and Rural Areas

Abstract

The problem of determining the concentration changes of reactive hydrocarbon immissions as a function of time was solved by means of an automatic gas chromatograph which, without enrichment, could record ethylene and acetylene in ppb concentrations. At the same time various other pollutants were covered, so that by a mutual allocation of the individual components it was possible to identify certain emitter groups. The results clearly show that ethylene and acetylene primarily originate from the combustion processes of the automobiles, while the handling and storage of petroleum products and their processing do not exert any influence on the immission of the two components. By way of time series measurements during a summer week in 1976 with very intensive solar radiation it was possible to show indirect secondary photochemical reactions.     

Alternating copolymers of hexafluoroisobutylene with vinyl trifluoroacetate and vinyl pentafluorobenzoate

Copolymerizations of hexafluoroisobutylene (HFIB) with vinyl pentafluorobenzoate (VPFB) and vinyl trifluoroacetate (VTFA) were carried out in bulk using perfluorodibenzoyl peroxide as the radical initiator. The copolymers obtained were characterized by proton and fluorine NMR spectroscopy. The monomer reactivity ratios in the polymerization of HFIB with VPFB were r₁ (HFIB) = 0, r₂ (VPFB) = 0.373, and r₁r₂ = 0. The results indicated that these copolymers have alternating structures. Similarly, the copolymers of HFIB and VTFA also showed alternating structures. The films of HFIB‐co‐VPFB were prepared by casting THF solution of polymers. Films obtained were flexible and transparent. The refractive indices of copolymers were 1.4549, 1.4490, and 1.4438 at 532, 633, and 839 nm, respectively. The average T_gs of HFIB‐co‐VTFA and HFIB‐co‐VPFB were 52 and 71 °C, respectively. From these results, the T_g of the hypothetical HFIB homopolymer is postulated to be in between 70 and 90 °C, which may be useful in the assessment of T_gs of HFIB copolymers with other vinyl monomers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

AGET ATRP of water‐soluble PEGMA: Fast living radical polymerization mediated by iron catalyst

In this work, living radical polymerizations of a water‐soluble monomer poly(ethylene glycol) monomethyl ether methacylate (PEGMA) in bulk with low‐toxic iron catalyst system, including iron chloride hexahydrate and triphenylphosphine, were carried out successfully. Effect of reaction temperature and catalyst concentration on the polymerization of PEGMA was investigated. The polymerization kinetics showed the features of “living”/controlled radical polymerization. For example, M_n,GPC values of the resultant polymers increased linearly with monomer conversion. A faster polymerization of PEGMA could be obtained in the presence of a reducing agent Fe(0) wire or ascorbic acid. In the case of Fe(0) wire as the reducing agent, a monomer conversion of 80% was obtained in 80 min of reaction time at 90 °C, yielding a water‐soluble poly(PEGMA) with M_n = 65,500 g mol^?1 and M_w/M_n = 1.39. The features of “living”/controlled radical polymerization of PEGMA were verified by analysis of chain‐end and chain‐extension experiments. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

RAFT polymerization of alternating styrene‐pentafluorostyrene copolymers

Reversible addition‐fragmentation chain‐transfer (RAFT) polymerization was used to control the alternating copolymerization of styrene and 2,3,4,5,6‐pentaflurostyrene. The RAFT polymerization yields a high degree of control over the molecular weight of the polymers and does not significantly influence the reactivity ratios of the monomers. The controlled free‐radical polymerization could be initiated using AIBN at elevated temperatures or using a redox couple (benzoyl peroxide/N,N‐dimethylaniline) at room temperature, while maintaining control over molecular weight and dispersity. The influence of temperature and solvent on the molecular weight distribution and reactivity ratios were investigated. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1555–1559     

Adaptation of a load-inject valve for a flow injection chemiluminescence system enabling dual-reagent injection enhances understanding of environmental Fenton chemistry

Environmental Fenton chemistry has been poorly constrained within the marine environment at a multi-component level. A simple, unique, reconfiguration of a flow-injection analytical system combined with luminol chemiluminescence allows quasi-simultaneously the measurement, using a single load-inject valve and a single photon multiplier tube, of reduced iron, Fe(II), and hydrogen peroxide. The system enables rapid, every 22 s, measurements with good accuracy at environmentally relevant concentrations, less than 5% relative standard deviations on both a 5 nM Fe(II) standard and a 60 nM hydrogen peroxide standard. Limits of detection were as low as 40 pM Fe(II) and 100 pM hydrogen peroxide. The system showed excellent capability by measuring from within an organic rich seawater the photochemically induced production of Fe(II) and hydrogen peroxide and their subsequent cycling and Fenton like interactions.     

Synthesis and characterization of 9,9‐bis(4‐hydroxyphenyl and 4‐aminophenyl)dibenzofluorenes: Novel fluorene‐based monomers

Two novel 9,9‐difunctionalized fluorene‐type monomers, 9,9‐bis(4‐hydroxyphenyl‐ and 4‐aminophenyl)‐2,3:6,7‐dibenzofluorenes, are synthesized by the reaction of dibenzenzofluorenone with phenol and aniline. These monomers are used for the preparation of polyester and polyimide as the typical polymers to evaluate the property change such as thermal stability caused by the benzene rings fused to the fluorene skeleton with keeping good solubility, in comparison with the polymers derived from simple fluorenone. In fact, these two new polymers have the fairly enhanced thermal stability and refractive index value along with satisfactory solubility in organic solvents, enough to emphasize the fusion effect. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2602–2605     

Chemical modification of poly(lactic acid) and its use as matrix in poly(lactic acid) poly(butylene adipate-co-terephthalate) blends

Poly(lactic acid), PLA, was chemically modified with maleic anhydride (MA) by reactive extrusion. The effect of this modification on molar mass (MM) and acidity was assessed by means of size-exclusion chromatography (SEC) and titration, respectively. PLA MM decreased in the presence of MA solely and of MA and peroxide. Reduction in MM was monitored by the increase in acidity. PLA blends containing poly(butylene adipate-co-terephthalate) (PBAT) were prepared through different mixing protocols, PLA/PBAT, PLA-g-MA/PBAT and PLA/PBAT/MA/peroxide (PLA/PBAT in situ). SEC results and rheological properties revealed reduction in MM and viscosity of the modified blends. PLA/PBAT presented increase in MM and bimodal MM distribution. The calculated interfacial tension was significantly lower for the modified blends, despite the lower average particle area of PLA/PBAT. Surprisingly, the modified blends presented higher yield strength than that predicted by the rule of mixtures, which might indicate interfacial reactions.     

Palladium complexes bearing an N‐heterocyclic carbene–sulfonamide ligand for cooligomerization of ethylene and polar monomers

Herein, we report the synthesis of palladium complexes bearing an N‐heterocyclic carbene (NHC)‐sulfonamide bidentate ligand and their application in ethylene oligomerization and ethylene/polar monomer cooligomerization. These catalysts could smoothly catalyze ethylene oligomerization and ethylene/methyl acrylate cooligomerization albeit the performance was lower compared to that of a NHC–phenoxide catalyst. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 474–477