Kinetics of vinyl chloride and vinyl acetate emulsion polymerization

The kinetics of vinyl chloride and vinyl acetate emulsion polymerization are reexamined. The validity of Ugelstad's model for systems with high desorption rate is confirmed by simulating conversion histories for both systems at different initiator concentrations and particle numbers. On the basis of the model, it is shown that at ordinary initiation rates, termination reactions are unimportant with respect to molecular weight development in both systems, and as a consequence, molecular weight development is independent of number and size distribution of polymer particles and of initiator and emulsifier level. Based on this conclusion, it is shown that in accordance with experimental facts, the molecular weight distribution obtained in vinyl chloride emulsion polymerization is the most probable distribution, and it is concluded that the number of long-chain branch points per repetition unit is less than 2 × 10^?4 at high conversions. In vinyl acetate emulsion polymerization, an almost logarithmic normal distribution is obtained. The distribution is strongly broadened by branching reactions with the number of long-chain branch points increasing rapidly with monomer conversion. The increase of M_n with increasing conversion is due to terminal double-bond polymerization, while the increase in M_w is due mainly to transfer to polymer.     

Photodimers of 9-Haloanthracenes as Initiators in Atom Transfer Radical Polymerization: Effect of the Bridgehead Halogen

Summary Photodimers of 9-chloroanthracene, formed by a [4+4] cycloaddition reaction of 9-chloroanthracene, were used as initiators in the atom transfer radical polymerization of styrene and compared to results previously obtained using photodimers of 9-bromoanthracene as the initiator. Heat-induced cleavage of the photodimer coupled with slow initiation from the bridgehead radical have been used to account for the lack of control in the systems, and thus changing the halogen on the initiating photodimer could support or refute this model. Reactions performed using analogous procedures produced polymers with number average molecular weight (M_n) values significantly higher in the case of 9-chloroanthracene photodimer-initiated systems, with similar polydispersity index (PDI) values observed in trials catalyzed with CuCl or CuBr. Polymer products showed absorbance bands indicative of regenerated anthracene in all cases, consistent with heat-induced cleavage of the photodimer during the course of the polymerization. Kinetic plots demonstrated that the polymerizations initiated with photodimers of 9-chloroanthracene showed maximum M_n values were obtained after approximately 10% monomer conversion, with a decline in M_n as a function of monomer conversion after this point. The data support slower initiation in the case of 9-chloroanthracene photodimers, followed by heat-induced cleavage throughout the polymerization system.     

Preparation of narrowly distributed nanoparticles of poly(n‐butyl methacrylate‐co‐vinyl pyrrolidone) through microemulsion polymerization

Narrowly distributed nanoparticles of poly (n‐butyl methacrylate‐co‐vinyl pyrrolidone) were prepared through microemulsion polymerization with a nonionic surfactant of Tween‐80 as emulsifier (6 wt % of the latex) and n‐butanol as coemulsifier. The polymerizations were initiated with benzoylperoxide (BPO), potassium persulfate (KPS), KPS/ferric sulfate (FeSO₄), and BPO/FeSO₄, respectively, where the initiation in the case of BPO/FeSO₄ took place mainly at the interphase between the oil phase and the reaction media. Namely, this interfacial‐initiated microemulsion polymerization resulted in larger particles with relatively narrower particle size distribution as well as higher limiting monomer conversion but lower polymerization rate compared with the polymerization initiated with KPS/FeSO₄. In this article, the influences of initiation method, monomer ratio, and addition of water‐soluble components on microemulsion polymerization and latex particle size were studied to discuss the mechanism of interfacial‐initiated microemulsion polymerization. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2334–2340, 2004     

Experimental study of the spontaneous thermal homopolymerization of methyl and n‐butyl acrylate

This article presents an experimental study of the spontaneous thermal homopolymerization of methyl acrylate (MA) and n‐butyl acrylate (nBA) in the absence of any known added initiators at 120 and 140°C in a batch reactor. The effects of the solvent type, oxygen level, and reaction temperature on the monomer conversion and polymer average molecular weights were investigated. Three solvents, dimethyl sulfoxide (DMSO; polar, aprotic), cyclohexanone (polar, aprotic), and xylene (nonpolar) were used. The spontaneous thermal polymerization of MA and nBA in DMSO resulted in a lower conversion and higher average molecular weights in comparison to polymerization in cyclohexanone and xylene under the same conditions. The highest final conversion of both monomers was obtained in cyclohexanone. The high polymerization rate in cyclohexanone was most likely due to an additional initiation mechanism where cyclohexanone complexed with the monomer to generate free radicals. Bubbling air through the mixture led to a higher monomer conversion during the early stage of the polymerization and a lower polymer average molecular weight in xylene and cyclohexanone; this indicated the existence of a distinct behavior between the air‐ and nitrogen‐purged systems. Matrix‐assisted laser desorption/ionization time‐of‐flight analysis of the polymer samples taken from nitrogen‐bubbled batches did not reveal fragments from initiating impurities. On the basis of the identified families of peaks, monomer self‐initiation is suggested as the principal mode of initiation in the spontaneous thermal polymerization of MA and nBA at temperatures above 100°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Radiation-induced emulsion polymerization of vinyl acetate and styrene

Studies have been made of the γ-induced emulsion polymerization of styrene and comparisons made with chemically initiated emulsion polymerization. The polymerization proceeded smoothly to high conversions at 0 and 60°C, the reaction showing a high G (monomer) value. Complete conversions were obtained with total doses of less than 0.05 Mrad. In accordance with the behavior expected of systems having a constant rate of initiation, the molecular weight was found to decrease with decreasing temperature. The molecular weight and particle size distributions were narrower than those obtained in chemically initiated emulsion polymerizations at the same temperature. The radiation-induced emulsion polymerization of vinyl acetate proceeded smoothly at temperatures in the range 0–50°C to give polymers of much higher molecular weight than these obtained from chemically initiated polymerizations at the same temperature. Complete conversion was attained after a dose of 0.02 Mrad for latices approaching 50% solids. The elimination of ionic endgroups in the poly(vinyl acetate) radicals tends to drive the polymerization from the aqueous phase, resulting in faster rates and higher molecular weights than are obtained from chemically initiated systems. Rates of polymerization were found to be independent of temperature and the molecular weight of the polymer to be independent of dose rate. Latices of poly(vinyl acetate) of high solids content were evaluated for latex and film properties and found to have improvements over commercially available samples in both areas, especially in clarity of film and scrub resistance. A number of acrylate and maleate esters were copolymerized with vinyl acetate in a radiation-initiated emulsion system. High molecular weight copolymers were produced after low dose.     

Synthesis of syndiotacticity‐rich high molecular weight poly(vinyl alcohol) by suspension polymerization of vinyl pivalate and saponification

Vinyl pivalate (VPi) was suspension‐polymerized to synthesize high molecular weight (HMW) poly(vinyl pivalate) (PVPi) with a high conversion above 95% for a precursor of syndiotacticity‐rich HMW poly(vinyl alcohol) (PVA). Also, the effects of the polymerization conditions on the conversion, molecular weight, and degree of branching (DB) of PVPi and PVA prepared by the saponification of PVPi were investigated. Bulk polymerization was slightly superior to suspension polymerization in increasing the molecular weight of PVA. On the other hand, the latter was absolutely superior to the former in increasing the conversion of the polymer, indicating that the suspension polymerization rate of VPi was faster than that of the bulk one. These effects could be explained by a kinetic order of a 2,2′‐azobis(2,4‐dimethylvaleronitrile) concentration calculated by the initial rate method. Suspension polymerization of VPi at 55°C by controlling various polymerization factors proved to be successful in preparing PVA of HMW [number‐average degree of polymerization (P_n): 8200–10,500], high syndiotactic diad content (58%), and very high yield (ultimate conversion of VPi into PVPi: 94–98%). In the case of the bulk polymerization of VPi at the same conditions, the maximum P_n and conversion of 10,700–11,800 and 32–43% were obtained, respectively. The DB was lower and the P_n was higher with PVA prepared from PVPi polymerized at lower initiator concentrations. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 832–839, 2003     

Liquid–liquid equilibria of ternary mixtures of methanol + MEG + n-C5, ethanol + MEG + n-C5, and n-butanol + MEG + n-C5

New liquid–liquid equilibrium data of ternary systems of mono ethylene glycol + n-pentane + methanol, mono-ethylene glycol (MEG) + n-pentane + ethanol, and mono ethylene glycol + n-pentane + n-butanol from 283.15 to 293 K are presented in this work. Binodal curves were obtained by the cloud point titration method. Tie-line compositions were obtained through density and sound velocity measurements of phases in equilibrium. Results show that the solubility increases with temperature in all systems and decreases as the alcohol chain increases. The relative solubility data indicate that the alcohols are more soluble in MEG than in n-C5. The obtained experimental data were successfully correlated using the CPA and the PC-SAFT equation with appropriate binary interaction parameters.     

Ultrasonically initiated emulsion polymerization of n‐butyl acrylate

Ultrasonically initiated emulsion polymerization of n‐butyl acrylate (BA) without added initiator has been studied. The experimental results show that high conversion of BA can be reached in a short time by employing an ultrasonic irradiation technique with a high purge rate of N₂. The viscosity average molecular weight of poly(n‐butyl acrylate) (PBA) obtained reaches 5.24 × 10⁶ g mol^?1. The ultrasonically initiated emulsion polymerization is dynamic and complicated, with polymerization of monomer and degradation of polymer occurring simultaneously. An increase in ultrasound intensity leads to an increase in polymerization rate in the range of cavitation threshold and cavitation peak values. Lower monomer concentration favours enhancement of the polymerization rate. ¹H NMR, ¹³C NMR and FTIR spectroscopies reveal that there are some branches and slight crosslinking, and also carboxyl groups in PBA. Ultrasonically initiated emulsion polymerization offers a new route for the preparation of nanosized latex particles; the particle size of PBA prepared is around 50–200 nm as measured by transmission electron microscopy. © 2001 Society of Chemical Industry     

Mechanism of the polymerization of n-butyl acrylate initiated by N,N-diethyldithiocarbamate derivatives. Part 2. Investigation of the reaction mechanism

The polymerization of n-butyl acrylate (BuAc) initiated with a model compound (butyl-2-(N,N-diethyldithiocarbamyl)propionate, RTC) has been investigated. The living character of this polymerization has been assessed and compared with those of styrene and methyl methacrylate. The small variation of M_n with yield is explained by the faster propagation than for styrene and methyl methacrylate, which leads to slow initiation and extensive transfer to the initiator. Predominant reversible termination (or deactivation) of the growing chains by the dithiocarbamyl radicals gives, however, polymers of functionality near to unity, which are photoinitiated at the same rate as RTC and reinitiate the polymerization of BuAc with a linear growth of the M_n up to 40% yield. This is better than was obtained with methyl methacrylate. Side reactions also take place leading to a decrease of functionality, to the formation of tetraethylthiuram disulphide and of carbon disulphide. Possible mechanisms are proposed for the secondary reactions. © 1998 SCI.     

Controlled radical polymerization of N‐isopropylacrylamide initiated by photofunctional 2‐(N,N‐diethyldithiocarbamyl)isobutyric acid sodium salt in aqueous medium

Photopolymerizations of N‐isopropylacrylamide (NIPAAm) were carried out in water, initiated by 2‐(N,N‐diethyldithiocarbamyl)isobutyric acid sodium salt (DTCA‐Na) as water‐soluble initiator under UV irradiation. The first‐order time‐conversion plots showed slowly decreasing slopes indicating a slow decrease of the active radical concentration. The number‐average molecular weight (M_n) of the obtained poly(N‐isopropylacrylamide) (PNIPAAm) increased in direct proportion, roughly, to monomer conversion. Until ca. 60% of conversion, the polydispersity was relatively narrow (ca. 1.6). 1‐Vinyl‐2‐pyrrolidone (VP) could also be polymerized in living fashion with such PNIPAAm precursor as a macroinitiator, because PNIPAAm exhibited dithiocarbamate (DC) groups at terminal ends. It was concluded that the polymerization of NIPAAm proceeded via a controlled radical mechanism in the range ～60% of conversion. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3233–3238, 2004     

Part 5. Influence of additives containing heteroatoms on the reactivity of butyl acrylate

The radiation‐induced polymerization of n‐butyl acrylate (nBuA) in the presence of small amounts of organic compounds containing heteroatoms has been investigated to evaluate the tentative explanations proposed to account for the differences in initiation rate observed between tripropyleneglycol diacrylate (TPGDA) and hexanediol diacrylate (HDDA), when subjected to electron‐beam (EB) polymerization. The progress of monomer conversion as a function of increasing dose was monitored by transmission infrared spectroscopy applied to thin films submitted to incremental exposure to EB radiation. Miscible organic additives expected to favour hydrogen abstraction, or free radical generation as a consequence of easy carbon–halogen bond scission, were thus introduced in nBuA at a concentration of 2 wt%. The kinetic changes were examined at low monomer conversion. The presence of di‐n‐butyloxide, diisopropyloxide or diisopropylsulfide was shown not noticeably to affect the conversion–dose dependence for EB‐irradiated nBuA. n‐Butyl chloride or bromide caused a noticeable reduction of nBuA reactivity; this was even greater for the iodide at the same 2 wt% concentration. n‐Butanol (nBuOH) was shown to sensitize nBuA consumption when present at a low concentration (2 wt%), but the enhancement of the polymerization rate was not as high for a larger nBuOH content (10 wt%). These results are discussed in the light of the radical anion mechanism for the radiation‐initiated polymerization of acrylate monomers. The absence of a significant sensitizing effect from additives known to enhance free‐radical formation supports the minor contribution of homolytic bond scission to the initiation mechanism. The observed effects of nBuOH at low concentration, indicate that trace amounts of protonic contaminants can exert a strong influence on the efficiency of initiation by the radical‐anion mechanism. © 2001 Society of Chemical Industry     

Controlled radical polymerization of styrene initiated by diethyldithiocarbamate‐mediated iniferters

We demonstrated that density functional theory calculations provide a prediction of the trends in C‐S bond dissociation energies and atomic spin densities for radicals using two model compounds as diethyldithiocarbamate (DC)‐mediated iniferters. On the basis of this information, we synthesized 2‐(N,N‐diethyldithiocarbamyl)isobutylic acid (DTCA) and (4‐cyano‐4‐diethyldithiocarbamyl)pentanoic acid (CDPA) as DC‐mediated iniferters. Free‐radical polymerizations of styrene (St) were carried out in benzene initiated by DTCA or CDPA under UV irradiation. The first‐order time‐conversion plots showed the straight line for the UV irradiation system initiated by CDPA indicating the first order in monomer. The number‐average molecular weight (M_n) of the polystyrene (PSt) increased in direct proportion to monomer conversion. The molecular weight distribution (M_w/M_n) of the PSt was in the range of 1.3–1.7. It was concluded this polymerization system proceeded with a controlled radical mechanism. However, photopolymerization of styrene initiated by DTCA showed nonliving polymerization consistent with UV initiation. Theoretical predictions supported these experimental results. Methacrylic acid (MA) could also be polymerized in a living fashion with such a PSt precursor as a macroinitiator because PSt exhibited a DC group at its terminal end. This system could be applied to the architecture of block copolymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 413–418, 2005     

Ultrasonically initiated emulsifier-free emulsion copolymerization of n-butyl acrylate and acrylamide. Part I: Polymerization mechanism

The polymerization mechanism of ultrasonically initiated emulsifier-free emulsion copolymerization of n-butyl acrylate (BA) and acrylamide (AM) was investigated. A four-step polymerization mechanism of the ultrasonically initiated emulsifier-free emulsion was put forward based on the monomer conversion and the main reaction locus. Improving the power output would increase the monomer conversion and the rate of polymerization. However, when the reaction temperature was 30 °C and the concentration of Na₂SO₄ was 0.1%, the monomer conversion and the rate of polymerization achieved maximum. The FTIR spectra showed that the sample obtained by this way was the copolymer of BA and AM, but not the blend of poly(butyl acrylate) and polyacrylamide.     

Ultrasonically initiated free radical‐catalyzed emulsion polymerization of methyl methacrylate (i)

The emulsion polymerization of methyl methacrylate initiated by ultrasound has been studied at ambient temperature using sodium lauryl sulfate as the surfactant. The investigation includes the: (1) nature and source of the free radical for the initiation process; (2) effects of different types of cavitation; and (3) dependence of the polymerization rate, polymer particle number generated, and the polymer molecular weight on acoustic intensity, argon gas flow rate, surfactant concentration, and initial monomer concentration. It was found that the polymerization could be initiated by ultrasound in the emulsion systems containing methyl methacrylate, water, and sodium lauryl sulfate at ambient temperature in the absence of a conventional initiator. The source of the free radical for the initiation process was found to come from the degradation of the sodium lauryl sulfate, presumably in the aqueous phase. The weight average molecular weight of the poly(methyl methacrylate) obtained varied from 2,500,000 to 3,500,000 g mol⁻¹, and the conversion for polymerization was up to 70%. Deviations from the Smith–Ewart kinetics were observed. The polymerization rate was found to be proportional to the acoustic intensity to the 0.98 power; to the argon gas flow rate to the 0.086 power; to the surfactant concentration to the 0.08 power, with the 0.035M–0.139M surfactant concentration range; and to the surfactant concentration to the 0.58 power, with the 0.139M–0.243M surfactant concentration range. The polymerization rate was found to increase with increasing initial monomer concentration up to a point where it became independent of initial monomer concentration. The polymer particle number generated per milliliter of water was found to be proportional to the acoustic intensity to the 1.23 power; to the argon gas flow rate to the 0.16 power; to the surfactant concentration to the 0.3 power, with the 0.035M–0.139M surfactant concentration range; and to the surfactant concentration to the 1.87 power, with the 0.139M–0.243M surfactant concentration range. The polymer weight average molecular weight was found to be proportional to the acoustic intensity to the 0.21 power, and to the argon gas flow rate to the 0.02 power. It was found to be inversely proportional to the surfactant concentration to the 0.12 and 0.34 power, with the 0.035M–0.139M and the 0.139M–0.243M surfactant concentration ranges, respectively. The polymer yield and polymerization rate were found to be much larger than those obtained from an ultrasonically initiated bulk polymerization method. The polymerization rates obtained at ambient temperature were found to be similar to or higher than those obtained from the conventional higher temperature thermal emulsion polymerization method. This investigation demonstrated the capability of ultrasound to both initiate and accelerate polymerization in the emulsion system, and to do this at a lower temperature that could offer substantial energy savings. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 797–825, 1999     

Separation of liquid mixtures by using polymer membranes. I. Permeation of binary organic liquid mixtures through polyethylene

The permeation characteristics and the separation behavior of 25 combinations of binary liquid mixtures through low-density polyethylene membrane have been investigated. The organic compounds studied were members of the homologous series of liquid aliphatic hydrocarbons between n-pentane and n-nonane as well as some aromatic and cyclic compounds. A special permeation cell was designed in order to study permeation rates at different temperatures ranging from 25 to 45°C. The rate of permeation increased with temperature, and it was found that the temperature dependence of the permeation rate for both pure compounds and mixtures could be expressed by Arrheniustype relationships. The efficiency of separation, however, decreased with increasing temperature. Activation energies of permeation rànged from 16–22 kcal/mol for pure compounds and binary mixtures of benzene, n-hexane, cyclohexane, and 2–2-dimethylbutane. The effects of chemical nature, molecular size, and molecular shape of the diffusing species on the permeation and separation were studied and qualitative guidelines were suggested. The effect of the composition of the binary mixtures on the permeation rate has been investigated for several systems. Permeation enhancement effects were observed in which the mixtures permeate considerably faster than either of the pure components. Maximum permeation rates occurred at about 50 wt-% mixtures for the systems benzene–n-hexane and benzene–cyclohexane. This phenomenon is explained in terms of a combined internal plasticizing and solubility effect.     

Photo-DSC cure kinetics of vinyl ester resins II: influence of diluent concentration

The photopolymerization kinetics of two commercial vinyl ester resins (VERs) and a model VER photoinitiated by the camphorquinone/amine photoinitiator system were monitored using isothermal DSC. A decrease in styrene concentration in model VERs was found to raise the rate of photopolymerization. In contrast, when the styrene was replaced by a monomethacrylate diluent, the photopolymerization rate passed through a maximum near 70 wt% diluent monomer. This difference in the variation of the rate of polymerization with decreased monomer concentration was attributed to the competition of the effects of the higher reactivity of the methacrylyl radical relative to the styryl radical and the lower termination rate for divinyl-rich systems (both of which tend to raise the maximum polymerization rate) and the effects of the reduction in the initiation efficiency and decrease in k_p due to increased fraction of pendant double bonds (which lower the polymerization rate) when the concentration of diluent monomer was reduced. Subsequent dark polymerization was observed during a temperature ramp and the onset of polymerization was independent of resin composition due to vitrification effects during the isothermal photocuring stage. The kinetics during the dark polymerization stage was discussed in terms of the radical concentration and the propagation rate constant. Increases in the concentration of either diluent monomer raised the extent of isothermal cure during the isothermal polymerization because vitrification was delayed by the lower crosslink density and the plasticizing effect of the diluent. Higher levels of diluent also raised the maximally attainable conversion due to reduced topological restrictions for reaction in networks of lower crosslink density.     

Preparation of high molecular weight poly(vinyl alcohol) with high yield using low‐temperature solution polymerization of vinyl acetate

Vinyl acetate (VAc) was solution‐polymerized in tertiary butyl alcohol (TBA) and in dimethyl sulfoxide (DMSO) having low chain transfer constant at 30, 40, and 50°C, using a low temperature initiator, 2,2′‐azobis(2,4‐dimethylvaleronitrile) (ADMVN). The effects of polymerization temperature and initiator concentration were investigated in terms of polymerization behavior and molecular structures of poly(vinyl acetate) (PVAc) and corresponding poly(vinyl alcohol) (PVA) obtained by saponification with sodium hydroxide. The polymerization rates of VAc in TBA and in DMSO were proportional to the 0.49 and 0.72 powers of ADMVN concentration, respectively. For the same polymerization conditions, TBA was absolutely superior to DMSO in increasing the molecular weight of PVA. In contrast, TBA was inferior to DMSO in causing conversion to polymer, indicating that the initiation rate of VAc in TBA was lower than that in DMSO. These effects could be explained by a kinetic order of ADMVN concentration calculated using initial rate method and by an activation energy difference of polymerization obtained from the Arrhenius plot. Low‐temperature solution polymerization of VAc in TBA or DMSO by adopting ADMVN proved successful in obtaining PVA of high molecular weight (number–average degree of polymerization (P_n): 4100–6100) and of high yield (ultimate conversion of VAc into PVAc: 55–80%) with diminishing heat generated during polymerization. In the case of bulk polymerization of VAc at the same conditions, maximum P_n and conversion of 5200–6200 and 20–30% was obtained, respectively. The P_n and lightness were higher, and the degree of branching was lower with PVA prepared from PVAc polymerized at lower temperatures in TBA. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1003–1012, 2001     

Modelling the Kinetics of Photoinitiated Polymerization of Di(meth)acrylates

The kinetics of photoinitiated polymerization of six analogous di(meth)acrylates and diacrylates was analysed according to the autocatalytic model R_p=kp^m(1-p)ⁿ (where R_p is polymerization rate, p is conversion degree, k is reaction rate constant and m and n are exponents), in order to find the influence of the reaction temperature and atmosphere, as well as monomer structure, on the parameters k, m and n. The best fit between the model prediction and experimental data was for the polymerization of diacrylates in an inert gas atmosphere. The autocatalytic exponent, m, for polymerization in argon of both di-methacrylates and diacrylates was found to be close to unity, whereas the reaction order exponent, n, was twice as high for the former compared with the latter (in the range of c. 3–5 and c. 1·3–2, respectively). An increase in the polymerization temperature caused a drop in both exponents. This drop is much more rapid in the case of the exponent n. Changes in the m and n exponents with temperature, as well as the difference in n exponents for the polymerization of acrylates and methacrylates, may be related to changes and differences in the mobility of reactive species during the reaction. The influence of atmospheric oxygen on the polymerization parameters is manifested by a very high increase in value of the exponent n. In the photochemically initiated process, an increase in the polymerization rate with temperature results mainly from a rapid decrease in the exponent n and, to a much lesser degree, from an increase in the reaction rate constant k. © of SCI.     

A novel direct-contact condensation pattern of vapour bubbles in an immiscible liquid

In addition to the two different condensation patterns revealed respectively in n-pentane (bubble)/glycerol and water (bubble)/silicone oil systems in the authors' previous study (1979), a third pattern has been found in methanol (bubble)/silicone oil system: a condensate appears at the rear part of the bubble surface as several blunt drops, turns into a conical tail through coalescence to each other, and finally drops out from the bubble. The possible mechanism as well as the heat transfer characteristics of the condensation process are discussed.     

Unexpected effect of the monomer concentration on the rate of a radical polymerization

The radical polymerization of vinyl monomers is usually initiated by physical and chemical means. After an increasing polymerization rate, R_p, at low monomer concentrations, some reactive systems show an unexpected minimum for R_p at high enough monomer concentrations. The radical polymerization of methyl methacrylate (MMA) initiated by the redox system D -glucose–ceric ion at varying MMA concentration is discussed. The peculiar behaviour of R_p is explained by the presence of two circumstances: the initiation rate from D -glucose radicals does not depend on MMA concentration when most of the D -glucose radicals formed react by adding to monomer, and the radical chains initiated by D -glucose radicals undergo mutual termination with a portion of the radical chains initiated by monomer radicals. Some information about the nature of the polymer end-groups is reached from the mechanistic approach.