Calculation of Alfrey–Price Q–e Values from 13C-NMR Data

A multiple-correlation analysis program was used to generate equations relating the Alfrey–Price Q and e values of vinyl monomers to the ¹³C-NMR absorption frequencies of the α- and β-carbon atoms of the monomers. Separate equations for the calculation of Q and e values of styrenes, chlorinated olefins, acrylates, methacrylates, vinyl ethers, and esters, nitrogen containing monomers, allyl compounds, and miscellaneous olefins were developed. The correlation coefficients of most of these equations were greater than 0.99 and permit accurate calculation of the Q and e values. The Q and e values so calculated may then be used to obtain estimates of the reactivity ratios in copolymerizations prior to actually performing the experiments. Attempts to develop a single Q value equation and a single e value equation for 63 vinyl monomers of the above classes resulted in relations having correlation coefficients of 0.63 and 0.81, respectively, too low to permit sufficiently accurate calculation of the Q and e values.     

Free radical copolymerization of 1-vinyl naphthalene with styrene,methyl methacrylate,and acrylonitrile

Investigations on free radical copolymerization of 1-vinyl naphthalene (1-VNph, monomerM ₂) with styrene (St), methyl methacrylate (MMA) and acrylonitrile (AN) (monomersm ₁) in bulk at 60°C with AIBN as initiator are presented. Relative reactivity ratios were calculated by the Kelen-Tüdös method yielding:r _st=0.70 ±0.23 andr _1–VNph=2.02 ±0.40 for system St/1-VNph;r _MMA=0.32 ±0.10 andr _1–VNph=0.57 ±0.07 for system MMA/1-VNph andr _AN=0.11 ±0.03 andr _1–VNph=0.45 ±0.09 for system AN/1-VNph.Q, e values for 1-VNph according to Alfrey, Price scheme were calculated toQ _1–VNph=1.02,e ₁–VNph=–0.62.     

Structure and reactivity of peroxide monomers

The reactivity of both the peroxide (2-tert-butylperoxy-2-methyl-5-hexene-3-yne) and hydroperoxide (2-hydroperoxy-2-methyl-5-hexene-3-yne) monomers in the radical copolymerization was compared. Using the Alfrey-Price Q and e scheme, Hammett correlations, and MNDO quantum-chemical model it was shown that both peroxy- and hydroperoxyisopropylic substituents pronounce a similar positive effect of hyperconjugation. Despite that these monomers showed different reactivity due to the ability of the hydroperoxide monomer to form complexes with protonoacceptors. IR spectroscopy was employed for the evaluation of energies of hydrogen bonds and equilibrium constants. © 1996 John Wiley & Sons, Inc.     

Reactivity and Characterization of the Radical Copolymerization of Itaconic Acid with Some Conventional Monomers

Abstract

Radical copolymerizations of itaconic acid (IA) with acrylamide (Am), N-vinyl pyrrolidone (NVP), ethyl methacrylate (EMA), and methyl methacrylate (MMA) were carried out in dioxane in the presence of azobisisobutyronitrile as the initiator at 65°C. The monomer reactivity ratios (r ₁, r ₂), Q, and e for IA with the four monomers were determined. The reactivity ratios show a tendency toward alternation, while the Q and e of IA indicate that it is an electron-accepting monomer. The polymers obtained were characterized by FT-IR, x-ray diffraction, intrinsic viscosity, and thermal stability measurements.     

Synthesis and polymerization of N-[1-(1-substituted-2-oxopropyl)]acrylamides and -methacrylamides. copolymerization of these monomers with styrene and substituent effects

The synthesis and polymerization of N-[1-(1-substituted-2-oxopropyl)]acrylamides and -methacrylamides are described. Seven new monomers were prepared by two kinds of synthetic procedure. The polymerization of these monomers was carried out. Monomer reactivity ratios in the polymerization of these monomers with styrene were determined and the Alfrey-Price Q and e values calculated. The effects of substituents on the reactivities in copolymerization were observed, and an interpretation of the results is given.     

<Emphasis Type="Italic">Ab initio</Emphasis> study of aniline and <Emphasis Type="Italic">n</Emphasis>-propylamine associates with nitrobenzene and <Emphasis Type="Italic">m</Emphasis>-cresol

An ab initio (6-31G**) study of binary associates of aniline and n-propylamine with nitrobenzene and m-cresol has been carried out. The structures corresponding to the total energy minimum of the system have been found for the associates, and their geometrical and energy characteristics have been determined. Basic types of intermolecular interactions have been established, and their effects on the reactivity of the amino group have been investigated.Original Russian Text Copyright © 2004 by I. A. Novakov, V. V. Korolkov, A. I. Pavlyuchko, B. S. Orlinson, and L. A. GribovTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 4, pp. 595–601, July–August, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Chain transfer constants for vinyl monomers polymerized in methyl oleate and methyl stearate

Chain transfer constants were obtained for styrene, methyl methacrylate, methyl acrylate and vinyl acetate, polymerized in methyl oleate and methyl stearate at 60°C. Transfer constants increased in the order: methyl methacrylate < styrene < methyl acrylate ? vinyl acetate in both solvents. Average values of the transfer parameters were: for methyl oleate, Q_tr = 2.04 × 10^?4, e_tr = 1.08; for methyl stearate, Q_tr = 0.373 × 10^?4, e_tr = 1.01. Indication that polar species predominate in the transition state is supported by the observed order of reactivity. The usual rate dependence appeared to be followed by all of the monomers except vinyl acetate, which was retarded, severely in methyl oleate. Transfer in methyl oleate was about 5.8 times greater than that found in methyl stearate for these four monomers. The internal allylic double bond of methyl oleate had about the same reactivity in transfer as had the terminal unsaturation in N-allylstearamide at 90°C. Rough estimates were obtained of the monomer transfer constants for the long side-chain homologs of these four monomers from the respective monomer transfer constants and the experimental transfer constants, corrected for transfer to the labile groups of the solvent. It was concluded that the rate of polymerization would determine in large measure the degree of polymerization for the reactive 18-carbon homologs but that the molecular weight of poly(vinyl stearate) and (oleate) will be regulated primarily by transfer to monomer.     

Molecular orbital study of the Q–e scheme in free radical copolymerization

Molecular orbital calculations were used to study free radical polymerization. Calculations show that the monomer is activated during the reaction and the pi bond becomes a diradical. The radical on the carbon that is about to form the new bond is called the e radical in this article. The other is the Q radical. For different monomers it is shown indirectly that changes in the energies of formation of the Q and e radicals are related to changes in the Q and e terms in the empirical Q–e scheme of Alfrey and Price. The polar effect in the Q–e scheme involves the e-radical, unpaired electron density. Specifically, the Q–e sum (e_x + e_y) is correlated with the e radical spin density. Also the e term is correlated with the electron density on the unsubstituted carbon of the monomer. The relationship of the Q radical to the adjacent substituent is shown by correlating ln Q values with the energy of addition of a hydrogen atom to a monomer. These relationships give theoretical meaning to the Q–e terms and allow calculation of Q and e values from molecular orbital properties for small monomers.     

Pulse radiolysis study of ion-species effects on the solvated electron in alkylammonium ionic liquids

The spectra and kinetic behavior of solvated electrons (e_sol⁻) in alkyl ammonium ionic liquids (ILs), i.e. N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide (DEMMA-TFSI), N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate (DEMMA-BF₄), N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide (TMPA-TFSI), N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide (PP13-TFSI), N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (P13-TFSI), and N-methyl-N-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide (P14-TFSI) were investigated by the pulse radiolysis method. The e_sol⁻ in each of the ammonium ILs has an absorption peak at 1100 nm, with molar absorption coefficients of 1.5–2.3×10⁴ dm³ mol⁻¹ cm⁻¹. The e_sol⁻ decayed by first order with a rate constant of 1.4–6.4×10⁶ s⁻¹. The reaction rate constant of the solvated electron with pyrene (Py) was 1.5–3.5×10⁸ dm³ mol⁻¹ s⁻¹ in the various ILs. These values were about one order of magnitude higher than the diffusion-controlled limits calculated from measured viscosities. The radiolytic yields (G-value) of the e_sol⁻ were 0.8–1.7×10⁻⁷ mol J⁻¹. The formation rate constant of e_sol⁻ in DEMMA-TFSI was 3.9×10¹⁰ s⁻¹. The dry electron (e_dry⁻) in DEMMA-TFSI reacts with Py with a rate constant of 7.9×10¹¹ dm³ mol⁻¹ s⁻¹, three orders of magnitude higher than that of the e_sol⁻ reactions. The G-value of the e_sol⁻ in the picosecond time region is 1.2×10⁻⁷ mol J⁻¹. The capture of e_dry⁻ by scavengers was found to be very fast in ILs.     

Copolymérisations radicalaires sous haute pression. Influence de la pression sur les rapports de réactivité

The pressure effect upon the reactivity of the radicals in copolymerizations can be important. The present work reports the pressure dependence of the reactivity ratios for some radical copolymerizations involving monomers of various polarities and proposes an interpretation concerning their variations with pressure based upon the Q—e scheme (or Alfrey–Price scheme). The direction as well as the magnitude of the pressure effect can thus be predicted.     

N-vinylthiopyrrolidinone

The polymerization reactivity of N-vinylthipyrrolidinone is described. This monomer readily homopolymerizes and forms copolymers with a wide variety of vinyl monomers. Reactivity ratios in the copolymerization of N-vinylthiopyrrolidinone with styrene and methyl methacrylate are reported and the Alfrey-Price Q and e values calculated. These results indicate the high copolymerization reactivity of this monomer in comparison with the oxo-analog, N-vinylpyrrolidinone. Some of the results are in conflict with previously reported data.     

UV-radiation-induced electron emission by hormones. Hypothesis for specific communication mechanisms

The highlights of recently observed electron emission from electronically excited sexual hormones (17β-estradiol, progesterone, testosterone) and the phytohormone genistein in polar media are briefly reviewed. The electron yield, Q(e_aq⁻), dependence from substrate concentration, hormone structure, polarity of solvent, absorbed energy and temperature are discussed. The hormones reactivity with e_aq⁻ and efficiency in electron transfer ensure them the ability to communicate with other biological systems in an organism. A hypothesis is presented for the explanation of the mechanisms of the distinct recognition of signals transmitted by electrons, originating from different types of hormones to receiving centres. Biological consequences of the electron emission in respect to cancer are mentioned.     

Synthesis and polymerization of various vinyl-type monomers containing the pyrrole ring

Vinyl-type monomers containing the pyrrole ring, such as 2-vinylpyrrole (2-VPyrr), N-(pyrrol-2-yl)methylacrylamide (PMA), N-methyl, N-(pyrrol-2-yl)methylacrylamide (MPMA), 2-allylpyrrole (2-AP), β-(pyrrol-1-yl)ethyl vinyl ether (PEVE), 2-diallyl-aminomethylpyrrole (DAMP), and 3-(2-pyrrolylmethyleneimino)propene-1 (PIP) were synthesized by various reactions involving characteristic properties of the pyrrole ring. Radical homopolymerizations and copolymerizations of these monomers were studied. In the homopolymerization of conjugated monomers such as 2-VPyrr and PMA, chain transfer to the pyrrole-containing monomer was remarkable but not degradative. The copolymerization parameters, that is, the values of r₁, r₂, Q₁, and e₁ of 2-VPyrr, were determined to be 0.066, 0.69, 5.53, and ?1.36, respectively in the copolymerization of 2-VPyrr (M₁) with MMA (M₂). The Q and e values of the monomers containing a heteroaromatic ring such as 2-vinylpyrrole, 2-vinylfuran, and 2-vinylthiophene were evaluated by the molecular orbital theory. The e value of PMA was found to be negative (?0.64) in the copolymerization with styrene, although e for acrylamide derivatives is generally positive. This may be explained by the intermolecular hydrogen bonding between the carbonyl group and NH group of PMA. That is, attraction or polarization of π-electrons in the vinyl group of PMA is weakened by such hydrogen bonding. From the results of copolymerization of 2-AP with various comonomers, the comonomers could be classified into three categories: class a monomers, in which both Q and e values are largely positive, can copolymerize with 2-AP; class b monomers, having small e values, homopolymerize and can not copolymerize with 2-AP; class c monomers, in which both Q and e values are small. The Q and e values of the comonomer must be largely positive in order to permit copolymerization with an allyl-type monomer.     

Prediction of the directional effect of pressure on the reactivity ratios in free-radical copolymerizations

The Q–e concept of the Alfrey and Price¹ has been applied successfully to the prediction of the pressure effect on the individual reactivity ratios in free-radical copolymerizations. Although the Q value of a given monomer is generally little affected by an increase in pressure, the e value is pressure dependent. The knowledge of the Q and e values at high pressures permits the prediction of variations in reactivity ratios with pressure. Some important consequences have been drawn from this concept.     

Molecular conformation effects on mesomorphism and twisting ability of chiral cyclohexanones in mesophases

The molecular conformations of 2,6-bis-(4-phenyl)benzylidene-3R-methyl-cyclohexanone and its mono-(4-phenyl)benzylidene methylcyclohexanone isomers were investigated by molecular simulation using the semiempirical AM1 and PM3 methods and by analyzing the experimental spin-spin coupling constants in the PMR spectra. Mesomorphism and the twisting ability of the induced cholesteric mesophases of the title compounds are analyzed using the ratios between conformers with the axial and equatorial methyl groups and other peculiarities of the spatial structure of molecules (differences in anisometricity and in the degree of flattening of the cinnamoyl fragment). The equatorial orientation of the methyl group in the dominant conformations generally favors the formation of mesophases. The twisting ability is higher for chiral compounds with an axial methyl substituent and with the chiral center directly bonded to the enone and arylidene groups.Original Russian Text Copyright © 2004 by L. A. Kutulya, A. I. Krivoshei, N. S. Pivnenko, and N. I. ShkolnikovaTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 419–429, May–June, 2004.     

Analysis and study of novel terpolymers composed of acrylamide, mono-charged and double-charged cationic monomers

The composition of novel terpolymers containing acrylamide (A), acryloyloxyethyltrimethylammonium chloride (Q), and bis-1,3(N,N,N-trimethylammonium)-2-propylmethacrylate dichloride (M) was analyzed combining FTIR and potentiometric titration. Calibration with A–Q and A–M copolymers of known composition was the prerequisite for the quantitative analysis of the terpolymers by FTIR. The analysis revealed deviations from the initial monomer feed composition resulting from different monomer reactivity. The differences became more pronounced when M increased in the feed. This suggests lowest reactivity for M. Lower intrinsic viscosity [η] for higher fraction of M in the feed confirmed the suggestion. The low reactivity results from the electrostatic influence of the two charges of M on the chain propagation, yielding shorter chains for more double-charged M in the monomer feed. For all terpolymers, the counterion activity was lower than theoretically expected and did not correlate with the average charge density. Heterogeneous charge distribution was hypothesized as the reason.     

N‐Vinylpyrrolidone and Ethoxyethyl Methacrylate Copolymer: Synthesis,Characterization and Reactivity Ratios

Free radical copolymerization of N‐vinyl‐2‐pyrrolidone with 2‐ethoxyethyl methacrylates was carried out with 2,2′‐azobisisobutyronotrile as an initiator in 1,4‐dioxane. The resulting copolymer was characterized by FTIR, H¹‐NMR and C¹³‐NMR spectroscopic techniques thermal properties of copolymer were determined by DSC and TGA. The reactivity ratios of the monomers were computed by the Fineman‐Rose (F‐R), Kelen‐Tudos (K‐T) and extended Kelen‐Tudos (EK‐T) method at lower conversion, using the data obtained from both FTIR and elemental analysis studies; the results are in good agreement with each other. The average reactivity ratio, Alfrey‐Price Q and e values were found to be r ₁=0.769, r ₂=0.266 and Q ₁=0.0859, e ₁=0.4508, respectively for NVP/EOEMA copolymer. The distribution of monomer sequence along the copolymer chain was calculated using a statistical method based on obtained reactivity ratio. The number average molecular weight and polydispersity were determined by GPC.     

Copolymerization of novel reactive fluorinated acrylic monomers with styrene: reactivity ratio determination

The radical copolymerization of three polymerizable surfactants with styrene was investigated by NMR spectroscopy to assess their compositions. The reactivity ratios of these monomers were calculated according to the methods of Fineman–Ross and Kelen–Tüdos. Consequently, Q and e values were deduced by the Alfrey and Price method. The results indicated the positive effect of the fluorine chain on the reactivity of monomers bearing a long spacer between the ammonium head and the acrylic function. These monomers exhibit high e values which are in favor of an intramolecular conformation of the surfactant where the ester carbonyl function of the polymerizable group interacts with the onium nitrogen atom via a compact six-sided structure.     

Synthesis and characterization of original functional polymers of tetrafluoroethylene and 4,5,5‐trifluoro‐4‐ene pentyl acetate

The bulk radical copolymerization of tetrafluoroethylene (TFE) with 4,5,5‐trifluoro‐4‐ene pentyl acetate (FAc), initiated by tert‐butyl peroxypivalate to synthesize original, functionalized fluorinated poly(TFE‐co‐FAc), was investigated. FAc monomer was prepared from a five‐step process. The copolymerization was carried out in batch at different initial monomer molar ratios ([TFE]_o/[FAc]_o ranging from 95/5 to 10/90 mol %) and at different initiator concentrations (ranging between 0.075 and 1.100 mol % about the monomers) at 70 °C. All the experiments revealed the production of fluorooligomers as evidenced by an allylic‐transfer reaction from FAc. The microstructure of these copolymers (i.e., the molar percentage of both monomers in the copolymers) was assessed by ¹⁹F NMR spectroscopy. From the kinetics of copolymerization, two key characteristics were determined. First, the reaction order to the initiator (being 1.07) and that of FAc monomer (0.85) showed a heterogeneous character of the copolymerization and monomolecular chain‐transfer reaction to FAc. Second, from the Tidwell and Mortimer method, the reactivity ratios of both comonomers were determined, showing a tendency to alternance in a wide range of initial monomeric ratios (30/70–70/30): r_FAc = 0.20 ± 0.26 and r_TFE = 0.18 ± 0.15. Alfrey and Price's Q and e values of FAc were calculated by Greenley's technique [Q_FAc = 0.098 (from Q_TFE = 0.032) and e_FAc = 1.23 (vs e_TFE = 1.63)], indicating that FAc is a strong electron‐withdrawing monomer as TFE. The normalized monomer‐diad and triad fractions as a function of the polymer composition were obtained from the comonomer sequence‐distribution procedure. The average molecular weights and molecular weight distributions as well as the thermal properties (glass‐transition temperature and decomposition temperature) of the fluorocopolymers were assessed and are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1693–1706, 2004