Rate of radical polymerization of N,N-dimethylaminoethyl methacrylate in cyclohexane

Summary Anions of propene, isobutylene and cycloheptatriene have been prepared using Lochmann's Base. Star polymers in the form of one arm star, two arm star and three arm star polymers of styrene have been synthesized from the allyl anion (2), 2-methylenepropylenyl dianion (4) and the cycloheptatrienyl trianion (6) respectively, with acid end groups by quenching the living polymers with carbon dioxide. The number average molecular weight has been determined by stoichiometry, HPSEC and end group analysis by titration.     

Critical solution point and chain dimension of branched-polystyrene solutions

Summary Critical solution point and chain dimension were measured for branched polystyrene(BPS) in solution as a function of molecular weight(M) and compared with those for linear polystyrene(LPS). The critical concentration _c of BPS was quite different from that of LPS at a fixed M, but the same at a fixed overlap-concentration ^*, i.e., plots of _c vs. ^* fall on a single straight line for both BPS and LPS (gf_c ^*). Reduced critical temperature _c defined by gt_c=(–T_c)/ [T_c: critical temperature, : the -temperature] was related to _c as _{c c} ² for BPS, whereas _{c c} for LPS.     

Microbial susceptibility of condensation products of carboxy-terminated polybutadiene and glycerol

Summary Keeping in view the prospects of biodegradable polymers, a polymer was synthesized by the condensation of carboxy-terminated polybutadiene (CTPB) of M_n-5000 with glycerol and tested for its microbial susceptibility. The results of end group estimations and viscosity measurements indicated a quantitative reaction between the two reactants under experimental conditions. The clear-zone method was employed in this investigation to test biodegradability. Two strains of Serratia and three strains of Staphylococcus did show a clear zone surrounding the colony. However, the microbial growth was found to diminish after 4 or 5 days.Presented at the International Conference on Structure-Property Relations of Rubber held at IIT, Kharagpur (India) Dec. 28–31 (1980)     

Polyisobutylene-containing block polymers by sequential monomer addition

Novel poly(acenaphtylene-b-isobutylene-b-acenaphtylene) (PAc-PIB-PAc) triblock copolymers exhibiting thermoplastic elastomer (TPE) properties have been prepared. The synthesis involved the addition of acenaphtylene (Ac) to living polyisobutylene dications (PIB) obtained by living isobutylene (IB) polymerization induced by the dicumyl methyl ether (DiCumOMe)/TiCl₄ initiating system at-80°C. The triblocks contain very short polyacenaphtylene (PAc) blocks (M_n9,000) and consequently yield very soft, low modulus TPEs. Efforts to develop conditions for the living carbocationic polymerization (LCPzn) of Ac have failed.For Part VIII of this subseries see J. P. Kennedy, S. Midha, B. Keszler: Macromolecules (in press)     

Studies concerning charged nickel hydroxide electrodes IV. Reversible potentials in LiOH,NaOH, RbOH and CsOH

The variation of reversible potential E_r with log a_moh and has been studied for several nickel hydroxide/oxyhydroxide couples in various alkali hydroxides. Both activated and deactivated -phase couples show only a small dependence ofE _r with log_moh (or where known) in LiOH, NaOH, RbOH and CsOH electrolytes. The change in MOH content on oxidation/reduction is found to be about 0.1 mol MOH per two-electron transfer and is the same as found previously in KOH. These results confirm that the bulk oxidized -phase lattice is devoid of alkali cation although a small quantity may be adsorbed by the surface. On the other hand both activated and deactivated /-phase couples show a marked dependence of 0.45 mol MOH per two-electron transfer in LiOH, NaOH and RbOH (at concentrations > 0.5 m), also in good agreement with earlier data for KOH. On the basis of these results a general stoichiometry can be inferred for the -phase, namely M_0.32NiO₂ · 0.7H₂O where M=Li⁺, Na⁺, K⁺ or Rb⁺. Measurements imply that the Cs⁺ ion or the Rb⁺ ion at low concentration (<0.5 m) do not enter the interlayer structure of the -phase. This behaviour is thought to be related to the low Rb-O and Cs-O bond strengths afforded by the -phase structure.     

Biosynthesis and chemical modification of poly(γ-glutamic acid)

Summary The water soluble poly(-glutamic acid) (-PGA) was synthetized by bacteria. A series of new, less water soluble -esters were prepared by repeated esterification.The characterization of the resulted polymers was performed by 200 MHz ¹H and 75.4 MHz ¹³C NMR spectroscopy.     

Note of the estimation of the Θ temperature and Ψ parameter from the critical temperature data

Summary Critical values of the polymer volume fraction _2,c and the interaction parameter _c have been computed for the case that the equation for the chemical potential of solvent contains terms _{c 2} ³ and _{c 2} ⁴ in addition to ₂ ² . For 0 _c 1/3, the limits for infinite chain length are _2,c = 0 and _c = 0.5. Quite different results are obtained for _c > 1/3, _2,c being finite and _c lower than 1/2. Conclusions for the estimation of the temperature and the entropy-of-dilution parameter are discussed.     

Asymmetric polymerization of diphenyl-2-pyridylmethyl methacrylate leading to optically active polymer with high one-handed helicity

Summary Diphenyl-2-pyridylmethyl methacrylate (D2PyMA) was polymerized with organolithium complexes of four novel chiral ligands (1–4) which were prepared from (+)-tartaric acid. The complexes of 3 and 4 gave the optically active poly (D2PyMA) with a highly one-handed helical structure. The fractionation of the polymer afforded the poly (D2PyMA) with almost pure one-handed helicity ([] ₃₆₅ ²⁵ -1400^°) in good yield.These chiral lithium complexes were not effective for the asymmetric polymerization of triphenylmethyl methacrylate.     

Livig carbocationic polymerization

Summary Diblock copolymers of isobytylene (IB) — methyl vinyl ether (MeVE) have been prepared by sequential monomer addition by employing 2-chloro-2, 4, 4-trimethylpentane (TMPCl)/TiCl₄ initiating system in the presence of nBu₄NCl or dimethyl-acetamide (DMA) in CH₂Cl₂/hexanes at –80°C. In line with our earlier observations (1), living carbocationic polymerizations (LCPZn) were obtained in the presence of nBu₄NCl (i.e., the molecular weight of the poly(vinyl methyl ether) segment increased upon TiCl₄ addition), however, extensive chain transfer occurred in the presence of DMA. According to column chromatography analysis, the product prepared in the presence of nBu₄NCl is essentially pure PIB-b-PMeVE diblock (96w%) contaminated with a very small amount (4w%) of PIB. In contrast, the product obtained with DMA contains only 21w% PIB-b-PMeVe together with 72w% PIB and 5w% PMeVe homopolymers. This large difference in blocking efficiencies suggests that the structures of the growing species are different in the presence of the common anion salt,nBu₄NCl, and the electron donor, DMA.For paper LIII in this series see Polym. Bull., vol. 29/1     

Synthesis,characterization and diels-alder extension of cyclopentadiene telechelic polyisobutylene

The use of 1-chlorodicyclopentadiene (DCp-Cl) as a minifer for the polymerization of isobutylene leading to asymmetric telechelic polymers having dicyclopentadienyl head groups and t-chloro tail groups, has been investigated. BCl₃ is ineffective, however, diethylaluminum chloride was found to be a suitable coinitiator for the polymerization. According to kinetic investigations chain transfer to monomer is absent and DCp-Cl is an efficient minifer. Polymer characterization indicated a DCp functionality close to 1.0. The t-chloro functionality was 0.27, probably due to side reactions of the t-chloro group with the strong Lewis acids formed during the polymerization.Part XXXII of the series New Telechelic Polymers and Sequential Copolymers by Polyfunctional Initiator-Transfer Agents (Inifers).The first part of this series was presented at the Kansas City Am. Chem. Soc. Meeting, September 12–17, 1982, Polym. Prepr., 23, 103 (1982) which is considered Part XXXI of the series New Telechelic Polymers and Sequential Copolymers by Polyfunctional Initiator-Transfer Agents (Inifers).     

Ferrocenylenesilylene Polymers as Coatings for Tapered Optical-Fiber Gas Sensors

In this paper we report the use of ferrocenylenesilylene polymers as coatings for tapered optical-fiber sensors. The principle of operation of this device is based upon environmentally induced changes in the refractive index of the polymer layer which change the power transmitted through the tapered fiber. The results for two sensor arrays fabricated using the ferrocenylenesilylene polymer [( ⁵-C₅H₄)Fe( ⁵-C₅H₄)MePhSi] _m and copolymer {[( ⁵-C₅H₄)Fe( ⁵-C₅H₄)SiPhMe] _n [( ⁵-C₅H₄)Fe( ⁵-C₅H₄)Me₂Si] _m are presented. We also show that the sensitivity of this device is a function of the taper beat length.     

Static and dynamic radii of polystyrene in ethylbenzene and tetrahydrofuran

Summary Hydrodynamic radii, R _H ^D and R _H , determined, respectively, from — translational diffusion coefficients and intrinsic viscosities are compared with radii of gyration S_Z for polystyrene of narrow molecular weight distribution in good-solvent systems, ethylbenzene and tetrahydrofuran. The S_Z data indicate THF is of comparable solvating power to ethylbenzene which, in turn, based on literature data is similar to benzene in its affinity for polystyrene. The ratios ₁ = S_z/R _H ^D and ₂=R _H /R _H ^D are much larger for polystyrene in ethylbenzene than in tetrahyaroruran. These results are interpreted to indicate the presence of a large draining effect in the ethylbenzene system.     

Flow-through and flow-by porous electrodes of nickel foam Part III: theoretical electrode potential distribution in the flow-by configuration

This paper deals with the theoretical potential distribution within a flow-by parallelepipedic porous electrode operating in limiting current conditions in a two-compartment electrolytic cell. The model takes into account the influence of the counter-electrode polarization and of the separator ohmic resistance. The results show that the design of the porous electrode requires the knowledge of the solution potential distribution within the whole cell volume.Nomenclature a _c specific surface area per unit volume of electrode - C ₀ entrance concentration (y=0) - C _s exit concentration (y=y ₀) - E electrode potential (= _M – _S ) - E _o equilibrium electrode potential - F Faraday number - i current density - mean mass transfer coefficient - K parameter [a _ea zFi _oa/(_a RT)]^1/2 - L porous electrode thickness - n number of terms in Fourier serials - P specific productivity - Q volumetric flow-rate - mean flow velocity based on empty channel - V constant potential - V _R electrode volume - x thickness variable - X conversion - y length variable - y ₀ porous electrode length - z number of electrons in the electrochemical reaction Greek symbols parameter - parameter - ionic electrolyte conductivity in pores - _S solution potential - _M matrix potential ( _M = constant) - parameter [=n/y ₀ - parameter [=+K] - overpotential Suffices a anodic - c cathodic - eq equilibrium - s separator - S solution     

Water Vapor Sorption on Mesoporous Gamma-Alumina Prepared by the Selective Leaching Method

Water vapor adsorption and desorption properties of mesoporous -alumina prepared by the selective leaching method were investigated. The -alumina was prepared by selective leaching of amorphous silica from calcined kaolinite and mesopores were formed in the inside of the pseudomorph particles of kaolinite. It showed a very narrow unimodal pore size distribution at a radius of 3 nm. The specific surface area and total pore volume measured at –196°C by the BET method using nitrogen gas as adsorbate were around 240 m² g^-1 and 0.7 ml g^-1, respectively. Water vapor sorption isotherm measured at 25°C showed a type IV isotherm and a type H1 hysteresis loop at high partial pressure (P/P₀ region. The steep increase of water adsorption by capillary condensation occurred from around P/P₀=0.8 whereas that of water desorption by evaporation occurred from around P/P₀=0.75. 0These observed P/P₀ values shown were in good agreement with those calculated from the Kelvin equation using the pore radius of 3 nm. The maximum adsorption capacity of water vapor was ca. 600 ml g^-1 at P/P₀ = 0.9 and was larger than that of the commercial -alumina. The statistical thickness of water adsorbed on the surface of the samples calculated from the water adsorption and nitrogen adsorption isotherms of this -alumina was apparently thinner than that of the commercial -alumina and this difference was attributed to the characteristic microtexture of this -alumina. The effects of K₂O and SiO₂ components for the water vapor sorption isotherms of the -alumina were also discussed.     

Cationic bulk polymerization of mesogenic vinyl ethers induced by thermal decomposition of sulfonium salts

Summary Liquid crystalline vinyl ethers have been bulk polymerized cationically in the mesophase using onium salts for thermal initiation. High molecular mass polymers (M_n83 000) with a narrow molecular mass distribution (around 2) were produced at very high temperatures (120°C). Apparently the polymerization system stabilizes the propagating cation and thus reduces chain transfer reactions that are determining the molecular mass. Possible reasons for this stabilization are e.g. influence of the mesophase of the formed polymer, interfacial polymerization, and nucleophilic stabilization by nucleophiles present in the monomer or produced by the initiators.     

Chemistry of Combustion Waves in Substances with a Complicated Structure of Reagent Molecules. 1. Structure of the Front of Rich Isopentane Flame

Results on the structure of the lowtemperature relaxation zone of the front of a laminar Bunsen flame of isoC₅H₁₂ (2methylbutane) under atmospheric pressure are presented. The flame of a premixed mixture isoC₅H₁₂ + O₂ + Ar with a fueltoair equivalence ratio of 1.7 is examined. The mass fluxes, total rates of reactions of matter consumption and expenditure, balance of substances, and profiles of bulk heatrelease rates are calculated on the basis of the experimental concentration and temperature profiles. The results obtained indicate that there is a vast region of lowtemperature conversion of isopentane in the flame front. It is found that only part of the products sampled by the microprobe from different points of the flame front results from transformations in the lowtemperature region, namely, oxygen, isopentane, water, carbon monoxide, propane, methane, and methanol. Ethylene, propylene, hydrogen dioxide, and formaldehyde are present in the lowtemperature zone in insignificant amounts; they are secondary products of conversion of methyl and propyl radicals. It is assumed that the observed feature is a result of the competing interaction of two mechanisms of fuelmixture conversion: selfcatalysis and thermal selfacceleration. Based on the previously suggested mechanism of oxidation pyrolysis by the scheme of intramolecular quadratic destruction, experimentally observed fragmentation of the isopentane molecule is demonstrated. In contrast to npentane, formation of methyl alcohol has been found in isopentane convection products.     

Elucidating the mechanism of carbocationic polymerization of α-methylstyrene

Summary The polymerization of -methylstyrene (MeSt) using the H₂O/SnCl₄ initiating system and ethyl chloride solvent has been investigated over the temperature range from –40° to –122°C in the presence and absence of the proton trap 2,6-di-tert-butylpyridine (DtBP). Arrhenius (In ¯M_n versus 1/T) plots obtained with poly (methylstyrene) (PMeSt) samples prepared in the absence of DtBP reveal the existence of two sharply defined temperature regimes (see Figure 1): at higher temperatures from –40 to –86°C, the slope of the Arrhenius plot yields H_{M n} = –4.90±0.25 kcal/mole whereas at lower temperatures, from –86° to –122°C,H_{M n} = –0.3 kcal/mole. With PMeSt samples prepared in the presence of DtBP the H_{M n} obtained for the higher temperature regime increases to –1.67 ± 0.20 kcal/mole whereas the H_{M n} reflecting the lower temperatures remains the same as that obtained in the absence of DtBP. These observations are readily explained by postulating a change in mechanism at –86°C: Evidently the ¯M_n of PMeSt is determined over the higher temperature regime by chain transfer to monomer which is frozen out at lower temperatures where termination becomes ¯M_n determinant. In the absence of DtBP chain transfer to monomer is operative which leads to the higher Arrhenius slope over the higher temperature regime; however, over the lower temperature regime where chain transfer is absent and termination is ¯M_n controlling, the Arrhenius slope remains unchanged. Evidence obtained from a Mayo plot (negligible intercept in the 1/¯M_n versus 1/[MeSt]_o plot, Figure 2) with samples prepared at –92°C, corroborate this postulate. Molecular weight dispersities (¯M_W/¯M_n) as a function of temperature have been determined in the presence and absence of DtBP (Figure 3). The proton trap affects ¯M_W/¯M_n only over the higher temperature regime which also suggests that chain transfer to monomer is frozen out at –86°C and that the polymerization becomes termination dominated at low temperatures.     

New polyisobutylene based model ionomers

Three-arm star polyisobutylene ionomers (¯M_n=8800) with terminal SO₃ M (M=K or Ca²) groups were synthesized and their mechanical properties investigated. Compression molded films displayed high elongations, i.e., -1000% for Ca² ionomers with lower values for the K counterions. Strain induced crystallinity was observed at higher elongations. Mechanical properties in general compared favorably with conventional covalently linked rubbery networks and were comparable and in some cases superior to EPDM-based ionomers carrying randomly distributed SO₃ M groups.For the first two parts see Proceedings, 28th IUPAC Macromolecular Symposium, Amherst, MA, July 11–16, 1982, p. 905 and 906     

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.     

Phenomenological model of the scale effect of the strength of polymer fibers

A new derivation of the scale effect equation for polymer fibers is proposed. The equation is: AL ^–, where is the average strength of the fiber; L is the length of the fiber; A and are coefficients. The equation was obtained from the general premises of scale effect theory without indication of the concrete form of the probability function F(S).Ukrainian Scientific-Research Institute of Polymer Fibers, Kiev. Translated from Khimicheskie Volokna, No. 4, pp. 34–36, July–August, 1992.