The effect of carbon black filling and cross-linking in stretched SBR networks: a 2H-NMR study

Summary The line splitting v in ²H-NMR spectra of deuterated benzene in stretched crosslinked SBR depended linearly on the classical stretch term ² – 1/ for samples with and without carbon black filling. The ratio LS = v/(² – 1/) was measured in dependence on the solvent fraction . The extrapolated value L of this ratio at =0 gave a linear dependence on the inverse molecular mass 1/M_c of inter-crosslink chains. This was expected according to a simple model of chain dynamics and offers a further NMR-method for M_c-determination even in filled networks. However, the slope of the L(1/M_c)-line increases with an addition of carbon black which indicates a higher molecular order. Three reasons for this could be discussed. However, one of them is preferable.     

Kinetics of burning-up of carbon in pitch- and coal tar (resin)-impregnated periclase products

Conclusions It was established that the kinetics of the burning-up process of the carbonaceous substance has an exponential nature and in semilogarithmic coordinates, it can be described by a straight line relationship log C=+tan .The intensity of burning-up of the carbonaceous substance increases with increasing test temperature. The rate of burning-up of the carbonaceous substance in the pitch-impregnated specimens is slightly less than that observed in the coal tar (resin)-impregnated specimens.Heat treatment of the impregnated products slows down burning-up of the carbonaceous substance.Translated from Ogneupory, No. 4, pp. 20–22, April, 1987.     

Dose and enantiospecific responses of white pine cone beetles,Conophthorus coniperda,to alpha-Pinene in an eastern white pine seed orchard

The white pine cone beetle, Conophthorus coniperda, exhibited dose and enantiospecific responses to -pinene in stands of mature eastern white pine, Pinus strobus, in a seed orchard near Murphy, North Carolina, USA. (–)--Pinene significantly increased catches of cone beetles to traps baited with (± )-trans-pityol. (+)--Pinene did not increase catches of beetles to pityol-baited traps and interrupted the response of beetles to traps baited with (±)-trans-pityol and (–)--pinene. Maximal attraction of cone beetles to pityol-baited traps was obtained with lures releasing (–)--pinene at a rate of 103 mg/day at 23^°C. Lures releasing (–)--pinene at rates lower or higher than 103 mg/day resulted in reduced catches to traps baited with (±)-trans-pityol. The sex ratio in all catches was heavily male biased. Attraction of the clerid predator, Thanasimus dubius, to traps baited with (±)-trans-pityol increased significantly with the presence of -pinene, irrespective of enantiomeric composition. Maximal attraction of T. dubius to pityol-baited traps occurred with devices releasing (–)--pinene at the highest rate tested, 579 mg/d at 23^°C, a sub optimal rate for cone beetles.     

Occurrence and Correlations of Monoterpene Hydrocarbon Enantiomers in Pinus sylvestris and Picea abies

The relative amounts and enantiomeric compositions of monoterpene hydrocarbons in branch and trunk xylem, in needles, and in resin from apical buds in 18 Pinus sylvestris trees have been determined and compared with the terpene content in branch xylem and needles of Picea abies. Besides the high amount of (+)-3-carene, an excess of (+)--pinene has been found in P. sylvestris, whereas in P. abies (–)--pinene dominates over (+)--pinene. In P. sylvestris, clear positive correlations were found between (+)--pinene and (+)-camphene in the four tissues analyzed. Good positive correlations were also observed between (–)--pinene and (–)-camphene in the two types of xylem, between (+)--pinene and (+)--pinene in the resin, and between tricyclene and (–)-camphene in resin and needles. In P. abies, positive correlations were found between (+)--pinene and (+)-camphene in the branch xylem and between tricyclene and (–)-camphene as well as between (–)--pinene and (–)-camphene in the needles. Complex relationships between (–)--pinene and (–)--pinene were found both in the P. abies and in the P. sylvestris tissues. The importance of the enantiomeric composition of -pinene for the host selection of Ips typographus, Tomicus piniperda, and Hylobius abietis is discussed.     

Preparation and properties of <Emphasis Type="Italic">α</Emphasis>-phenylcinnamylideneacetylated poly(2-hydroxyethyl methacrylate)

A photosensitive polymer, -phenylcinnamylideneacetylated poly(2-hydroxyethyl methacrylate) (poly(HEMA)), was synthesized and characterized. Light irradiation upon the photosensitive poly(HEMA) film induced gel formation via dimerization between the pendent -phenylcinnamylideneacetylates of the polymer. The gel content of the crosslinked polymer increased with increasing irradiation time and reached 60% when irradiated for 30 minutes. Correspondingly, the water content decreased from 27% to 18% with irradiation time increasing from 0 to 30 minutes. The solute permeability of the -phenylcinnamylideneacetylated poly(HEMA) without irradiation is about the same as that of the poly(HEMA) film. The crosslinked -phenylcinnamylideneacetylated poly(HEMA) film prepared by light irradiation had much lower permeability as compared with the non-crosslinked film. More specifically, the photocrosslinked film had the permeability of 5.37 × 10^–7 cm/s, 1.32 × 10^–7 cm/s and 0.53 × 10^–7 cm/s for p-nitrophenol, tryptophan and flurbiprofen, respectively. This photosensitive -phenylcinnamylideneacetylated poly(HEMA) provides a new base material for fabricating poly(HEMA) hydrogel.     

The use of alkali carbonates in carbon concentration cells

The feasibility of using alkali carbonates as electrolytes in carbon concentration cells has been investigated. The following cell was set up: The test electrode (LHS) was a carbon-permeable-iron membrane in contact with a gaseous or liquid metal environment whose carbon activity could be varied. Experiments involving argon and liquid sodium environments at 970 K showed that the potential of the-Fe test electrode was a function of its carbon activity.The potential of the electrode,-Fe, C ¦ CO ₃ ^2– , was also measured as a function of carbonate ion activity and current.It was concluded that the predominant electrode reaction at the iron electrode was reversible and involved carbon and carbonate species or species with which they were in equilibrium.     

Kinetics and Mechanism of Copolymerization of α-terpineol with Methylmethacrylate in Presence of Azobisisobutyronitrile as an Initiator

The radical copolymerization of -terpineol with methyl-methacrylate in xylene at 80±0.1C for 50 minutes in the presence of azobisisobutyronitrile (AIBN) follows ideal kinetics and results in the formation of a functional and random copolymer. The activation energy is 33 KJ/mole. The IR spectrum and NMR spectra of the copolymer(s) shows the bands at 1750 and 3400 cm^–1 for ester group of methylmethacrylate and alcoholic group of -terpineol and peaks at 3 to 4 for methoxy group and at 6.5 to 7.5 due to alcoholic group of methylmethacrylate and -terpineol repectively. The values of reactivity ratios, calculated by Kelen–Tüdos method, are r ₁ (MMA) = 0.18 and r ₂ (-terpineol) = 0.046. The Alfrey-Price; Q–e parameters for -terpineol has been calculated as 0.149 and 2.486. The mechanism of copolymerization has been elucidated and it is concluded that the double bond present in the monocyclic ring of -terpineol is an active site for copolymerization and the alcoholic group of -terpineol remain to give functional copolymer.     

Viscosity properties of concentrated viscoses

Conclusions The physico-chemical properties of viscose containing up to 15% -cellulose by wt. have been investigated.It has been noted that increasing the -content of viscose affects principally the viscosity of solutions, but shows up only a little in the other characteristics of the viscose.At -cellulose contents up to 13.5% by wt. viscoses retain homogeneity and can present immediate interest for technological processing on appropriate selection of such parameters as temperature and NaOH/-cellulose ratio.Translated from Khimicheskie Volokna, No. 5, pp. 45–47, September–October, 1987.     

Mechanisms of Iron Activation on Fe-Containing Zeolites and the Charge of α-Oxygen

According to previous Mössbauer data [1] -sites formation at the activation of Fe-containing zeolites is accompanied by irreversible self-reduction of the iron, proceeding without participation of an external reducing agent. Reduced Fe²⁺ ions are inert to O₂ but are reversibly oxidized to Fe³⁺ by N₂O, generating the -oxygen species, O, which provide selective oxidation of hydrocarbons.In this work, the mechanism of -sites formation was studied via quantitative measurement of the dioxygen amount desorbed into the gas phase at the step of self-reduction. A prominent role of the zeolite matrix chemical composition has been revealed. For example, with zeolites of Al–Si composition (FeZSM-5 and Fe-), heating to 900 °C in a closed vacuum space leads to irreversible evolution of O₂, which is accompanied by the immediate formation of -sites. Similar heating of B–Si and Ti–Si zeolites also leads to dioxygen evolution; however, this evolution is reversible and is not accompanied by formation of -sites. Activation of these zeolites occurs only in the presence of water vapor. Stoichiometric measurements showed that in terms of charge one regular O^2- ion, removed at the activation, is equivalent to two -oxygen atoms. So, -oxygen is identified as an ion-radical species O ^-., whose unique oxidation properties still distinguish it from the generally observed O^-. radicals.The mechanism of -sites formation is proposed, in which the process of strong chemical stabilization of reduced Fe²⁺ atoms in the zeolite structure is a key step, making impossible the reoxidation of the iron with O₂.     

Combustion of the Ti-Zr-N2-H2 composition

Combustion ofTi andZr powders in nitrogen(10–70 atm) with subsequent burn-up of the produced -alloys in hydrogen and alsoTi-Zr powder combustion in anN ₂+H₂ mixture have been studied. The optimal conditions for producing monophase nitrogen-containing alloys and monophase hydronitrides with high hydrogen concentration have been found. The effect of the second metal(Zr) on the combustion regularities, on an increase in the hydrogen solubility in -alloys, and on the thermal stability of the hydronitrides produced has been elucidated. Hydrogen is shown to behave as a homogenizer in combustion of the above compositions.Translated from Fizika Goreniya i Vzryva, Vol. 32, No. 6, pp. 62–67, November–December 1996.     

Calorimetric,X-ray and infra-red investigations on poly(hexamethylene adipamide)

Summary In dependence on crystallization conditions three ranges with different crystal structure and heat of fusion were found by DSC,WAXS,and IR for unoriented PA 6.6 samples of densities between 1.10 and 1.17gcm^–3: Range I:_I triclinic, _c ^I =1.225 gcm^–3,H _M ^I = 235 Jg^–1. Range II:_II triclinic, _c ^II =1.165 gcm^–3, H _M ^II =185 Jg^–1. Range III:Continuous variation from _c ^I ,H _M ^I to _c ^II , H _M ^II . _a=1.095 gcm^–3 is independent of crystallization. conditions. The transition between _I and _II is probably due to changes of the chain conformation.     

Determination of the enantiomeric composition of several insect pheromone alcohols

Details are given for the determination of the enantiomeric composition of several insect pheromone alcohols. The two methods used in the determination were: formation of the derivative with (+)--methoxy--trifluoromethylphenylacetyl chloride and the use of chiral lanthanide shift reagents. The five alcohols studied and their enantiomeric compositions are: sulcatol fromGnathotrichus sulcatus 6535 (+)/(–),trans-verbenol fromDendroctonus frontalis 6040 (+)/(–), 4-methyl-3-heptanol fromScolytus multistriatus 100% (–), seudenol fromDendroctonus pseudotsugae 5050 (+)/(–), and ipsdienol fromIps pini (Idaho) 100% (–). Determinations were done on 50–500 g substrate.     

Some special features in preparing hydrocellulose fibres and yarns from concentrated viscoses

Conclusions The possibility has been demonstrated of preparing hydrocellulose fibres and yarns with good strength and elastic properties from concentrated viscoses at an -cellulose content of 12% with a DP of 250 and an NaOH/-cellulose ratio of 0.68.Translated from Khimicheskie Volokna, No. 2, pp. 25–26, March–April, 1990.     

Alumina production method as a factor in the properties of dense corundum refractories

Conclusions Experimental batches of-alumina containing mineralizing additives were produced at various calcination temperatures in the rotary calcination kilns of the Dneprovsk Aluminum Plant.The problem of producing an actively sintering alumina at a moderate calcination temperature on an industrial scale was resolved by using a mineralizing additive consisting of chlorine- and fluorine-containing compounds in the proportions of 1.0–2.5 and 0.2–0.3 wt. % in terms of Cl^– and F^– on the Al₂O₃.The technology for the manufacture of dense corundum products from-alumina containing the mineralizing mixture has been introduced at the Podolsk Refractories Plant.Translated from Ogneupory, No. 6, pp. 13–20, June, 1978.     

Asymmetric structure analysis of active surface-sites by in situ polarized total-reflection fluorescence EXAFS

An in situ polarization-dependent total reflection fluorescence yield EXAFS system has been developed to analyze the asymmetric structures of catalytically active metal sites on single crystal surfaces. This technique separately reveals the bonding feature parallel and perpendicular to the support surface. The systems of Cu ion on -quartz(0001), Co oxide on -alumina(0001), and Pt₄ on -alumina(0001) were investigated as model surfaces of supported catalytic systems. The location of Cu sites on -quartz(0001), the epitaxial growth mode of Co₃O₄ on -alumina(0001), and the Pt raft structure with metal-support interaction in Pt₄ / -alumina(0001) were observed.     

Highly stereoselective epoxidation of (−)-α-pinene over chiral transition metal (salen) complexes occluded in zeolitic hosts

Various transition metal complexes of seven different salen ligands have been incorporated in specially modified zeolitic host materials. The thus immobilized sterically demanding complexes have been tested in the diastereoselective epoxidation of (–)--pinene in the liquid phase in an autoclave at room temperature and elevated pressure using O₂ as oxidant. In most cases conversions of 100% could be achieved. Best results so far – 100% conversion, 96% epoxide chemoselectivity and 91% diastereomeric excess – have been obtained in the presence of the entrapped [(R,R)-(N,N)-bis(3,5-di-tert-butylsalicylidene)-1,2-diphenylethylenediamino]cobalt(II) = Co(salen-5) complex. Computer simulations were done in order to prove that the reaction can take place inside the pore system, i.e., (–)--pinene is able to diffuse through the microporous entrances of the carrier material.     

Additional male mediterranean fruitfly (Ceratitis capitata wied.) Attractants from Angelica seed oil (Angelica archangelica L.)

Two sesquiterpene hydrocarbons, -copaene and -ylangene, were isolated from bioactive fractions of angelica seed oil and were shown by field bioassays to be attractive to the male Mediterranean fruit fly. Their relative attractiveness, compared with the(+)-and (–)--copaene enantiomers, are: (+)--copaene>angelica -copaene>angelica -ylangene>(–)--copaene. The enantiomer ratios for the two compounds are: -copaene, 61.4% (+), 38.6% (–); -ylangene, 91.9% (+), 8.1% (–).trans--Bergamotene was also isolated from the same fractions, but in sufficient quantity for bioassay [enantiomer ratio: 95.7% (+), 4.3% (–)].     

New main chain nonlinear optical polymers with high glass transition temperatures

Summary Various 4-methoxy-4-carbomethoxy--amino--cyanostilbenes were prepared as mixtures of E and Z isomers, and polymerized via condensation polymerization using dibutyltin diacetate as catalyst. The resulting low molecular weight homopolymers showed higher glass transition temperatures (168–183°C) than previously reported main chain nonlinear optical (NLO) homopolymers. A high molecular weight (M_n30, 200) copolymer possessed an even higher glass transition temperature of 187°C. The hyperpolarizability of the polymers and a model compound were found by EFISH measurements to be in the range of 61 to 79x10^-48 esu.     

Synthesis and thermal analysis of styrene and α-methylstyrene multiblock copolymers

Summary Multiblock copolymers of styrene and -methylstyrene (¯M_n 70.000 g.mole^–1) with various -methylstyrene contents were synthetized by anionic polymerization. The glass transition temperatures (Tg) of these copolymers have been measured by D.T.A. A single Tg was observed over the whole composition range. This Tg obeys the derived GORDON and TAYLOR equation. Moreover these copolymers are heat resistant up to temperatures of at least 280°C.     

Chiral specificity in responses by the bark beetleDendroctonus valens to host kairomones

The attraction of the red turpentine beetle,Dendroctonus valens, to the resin volatiles of its host,Pinus ponderosa, is elicited by three chiral monoterpenes. In field assays response was greatest to (S)-(–)--pinene; 92% (S)-(–)--pinene found inP ponderosa resin was not attractive. However, 75% (R)-(+)--pinene, which occurs inPinus lambertiana, a sympatric host ofD. valens, was attractive. (S)-(–)--Pinene interrupted response to (R)-(+)--pinene. (S)-(+)-3-Carene from both hosts was attractive at the (R)-(+)--pinene level. Three sympatric coniferous nonhosts each have the same attractive monoterpenes but produce less resin. These studies demonstrate the importance of chirality of host compounds in the host finding behavior of this bark beetle.