Gamma radiation-initiated polymerization of styrene at high pressure. III. Emulsion polymerization with anionic emulsifiers

Values calculated for the activation volume for chain propagation, ΔV, for the polymerization of styrene in emulsions under a variety of conditions agree closely with that previously obtained in pure styrene (ΔV = ?18.6 cm³ mol^?1). The rate of initiation of emulsion polymerization by radicals produced in the water phase was independent of pressure; therefore ΔV is zero. This differs from initiation in pure styrene which is slightly retarded by pressure (ΔV = 2.0 cm³ mol^?1). The activation energy for the reaction in emulsion, as in pure monomer, decreases slightly with pressure. Chain transfer to monomer occurs to a much greater extent in emulsions than in pure monomer under similar temperature and pressure conditions. Values for the dependence of the polymerization rate on the initiator (i.e., the irradiation dose rate) and emulsifier concentration are consistent with Smith–Ewart, Case II kinetics.     

Gamma radiation-initiated polymerization of styrene at high pressure. IV. Emulsion polymerization with nonionic emulsifier

The effects of pressure, irradiation dose rate, and emulsifier concentration on the rate of polymerization of styrene emulsions stabilized with a nonionic surfactant, Teric GX13, were investigated. Results differed from those previously obtained with anionic surfactants and did not follow Smith–Ewart kinetics. The controlling influence of the surfactant at the particle–water interface on the reaction was demonstrated and results could be interpreted in terms of the Medvedev equation. Using this equation, we determined a value for the activation volume for chain propagation, ΔV, as ?18.7 cm³ mol^?1. This value is the same as that for pure styrene and emulsions that follow Smith–Ewart kinetics.     

Gamma radiation-initiated polymerization of styrene at high pressure. I. Kinetic parameters with intermittent irradiation

By adapting the rotating sector technique to provide an intermittent source of cobalt-60 radiation the activation volumes for all reaction steps of the bulk polymerization of styrene have been shown to be independent of pressure up to 208 MPa. The activation volumes determined for polymerization, initiation, propagation and termination were, respectively, ΔV^≠_pol = ?20.5 ± 0.22, ΔV^≠_i = +2.0 ± 0.18, ΔV^≠_p = ?18.6 ± 0.44, and ΔV^≠_t = +5.8 ± 0.55 cm³ mol^?. The values for the effect of pressure on the degree of polymerization ΔDP and the radical lifetime Δτ were, respectively, ?22.6 ± 0.16 and ?3.9 ± 0.29. The average radical lifetime increased from 4.5 s at atmospheric pressure to 6.3 s at 208 MPa. Because ΔV^≠_t is less than ΔV^≠_t and both are positive, the molecular weight increased with pressure at a faster rate than the polymerization rate. Although fewer radical chains were initiated per second under pressure the macroradical concentration increased with pressure because of the longer average lifetime of the radicals.     

Emulsion polymerization of styrene under high pressure

Summary The emulsion polymerization of styrene was studied at 40 °C over a pressure range of 1 to 1000 bar. By measuring the ratio of the overall reaction rate under high pressure and at atmospheric pressure, the activation volume for the prouagation was obtained as –23.5 cm³/mol which was rather smaller than the literature values. The underestimation by the method of emulsion polymerization would be due to the character of polymerization processes and the emulsion polymerization method is not appropriate to determine the accurate value of the activation volume of propagation reactions.

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Zusammenfassung Es wird die Emulsionspolymerisation von Styrol bei 40 °C über den Druckbereich von 1 bis 1000 bar untersucht. Durch Messung des Verhältnisses der Reaktionsgeschwindigkeit unter hohem Druck und bei Atmosphärendruck wurde das Aktivierungsvolumen für die Ausbreitungsgeschwindigkeit zu –23,5 cm³/mol gefunden, ein Werr, der ziemlich kleiner als die Literaturwerte ist, Die Unterschätzung bei der Methode der Emulsionspolymerisation dürfte dem Charakter des Polymerisationsprozesses zuzuschreiben sein, und die Emulsionspolymerisation ist nicht geeignet, den exakten Wer für das Aktivierungsvolumen zu erhalten.

     

γ-radiation-initiated polymerization of bulk styrene at high pressure

The polymerization of styrene in bulk at pressures up to 273 MPa and temperatures between 3 and 49°C with the use of γ-radiation as the initiator has been studied. The polymerization rate and the molecular weight of the polymer increased with increasing pressure; the molecular weight increased at a slightly faster rate. The difference in the rate is a theoretical expectation which has not previously been observed because chain-transfer reactions obscure the effect in chemically initiated systems. A small but significant retardation of the initiation reaction occurs as the pressure is increased. The results of previous workers are critically reviewed. Chain transfer at 25°C for pressures below 220 MPa is negligible when γ-radiation is the initiator. The activation energy for bulk polymerization decreased with increasing pressure from 28.1 kJ/mole at 0.1013 MPa to 22.3 kJ/mole at 203 MPa. Volumes of activation at 25°C for 0.1013 < p < 273 MPa were calculated to be Initiation, +4.0 < ΔV < +4.4 cm³/mole; polymerization; ?Δ = ?20.9 cm³/mole; degree of polymerization; ΔV = ?25.3 cm³/mole; propagation/termination; ?ΔV = ?22.7 cm³/mole.     

Evolution of the termination rate coefficient in styrene polymerization

Styrene bulk polymerization was conducted at 70 °C with a high initiator concentration, and this ensured that the dominant chain‐stopping mechanism was the combination of free radicals. The evolution of the molecular weight distribution (MWD) of the polymer was measured via the periodic removal of samples during the course of the reaction and their analysis with gel permeation chromatography. The overall termination rate coefficient was independent of the conversion in the dilute regime, as observed from cumulative MWDs. In the middle of the conversion range, the observed trend was compatible with a translational‐diffusion‐controlled mechanism for the termination step. A bimodal distribution of the molecular weights was also found at high conversions and could be explained in terms of an increase in the free‐radical concentration and a very low termination rate coefficient. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 178–187, 2005     

Chain length‐dependent termination in pulsed‐laser polymerization. VIII. The temperature dependence of the rate coefficient of bimolecular termination in the bulk polymerization of styrene

The photosensitized polymerization of styrene in bulk was investigated in the temperature range of 25–70°C with respect to the average rate coefficient of bimolecular chain termination k̄_t, especially its chain length dependence at low conversions, by means of pulsed laser polymerization (PLP). Three methods were applied: two of them were based on equations originally derived for chain length independent termination taking the quantity k_t contained therein as an average k̄_t, while the third one consisted in a nonlinear fit of the experimental chain length distribution (CLD) obtained at very low pulse frequencies (LF‐PLP) to a theoretical equation. The exponent b characterizing the extent of chain length dependence was unanimously found to decrease from about 0.17–0.20 at 25°C to 0.08–0.11 at 70°C, slightly depending on which of the three methods was chosen. This trend toward more “ideal” polymerization kinetics with rise of polymerization temperature is tentatively ascribed to a quite general type of polymer solution behavior that consists in a (slow) approach to a lower critical solution temperature (LCST), which is associated with a decrease of the solvent quality of the monomer toward the polymer, an effect that should be accompanied with a decrease of the parameter b. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 697–705, 2000     

Initiation and termination kinetics in fluid-phase free-radical polymerization up to high pressure

Rate coefficients of peroxyester decomposition in solution of n-heptane have been measured as a function of temperature and pressure. The data is used to determine initiator efficiencies for the ethene high-pressure polymerization. The efficiency strongly depends on the structure of the peroxyester. Free-radical termination rate coefficients of (meth)acrylate systems have been studied up to about 50% monomer conversion. The reaction is controlled by segmental diffusion in the early period and by reaction diffusion at later stages of the polymerization.     

Radiation-induced polymerization of sodium allylsulfonate at high pressure

Irradiation of sodium allylsulfonate in aqueous solution at high pressure (up to 9000 kg/cm²) gave a deliquescent white powder which is insoluble in organic solvent. The product was addition polymer of allylsulfonate from the high-resolution NMR and infrared spectra. The rate of polymerization was proportional to the third and second powers of monomer concentration in the initial and later stages, respectively. From the high dependence of the rate on monomer concentration, the reaction was deduced to proceed in an associated monomer or micelle. The rate of polymerization was increased by addition of sodium chloride. The G value for monomer consumption was about 10⁴ at high pressure, which suggests that the degradative chain transfer is not important in the polymerization. Overall activation volumes were ?7 and ?5 ml/mole in the initial and later stages, respectively.     

Primary radical termination rate constant at high conversion in radical polymerization

A primary radical termination rate constant given by: k_ti = A_1iD_i, where A_1i is a constant and D_i is the diffusion constant of the primary radical, was examined on the basis of the variation of conversion. It was proved that this rate constant is correct at high conversion. A relationship between primary radical termination rate constant and conversion was derived. The effect of variation of conversion on the gel effect is discussed.     

The radiation-induced copolymerization of tetrafluoroethylene and styrene at high pressure

The radiation-induced copolymerization of tetrafluoroethylene (A) and styrene (B) was studied in bulk and in perfluorotoluene at 22°C at autogenous pressure and 260 and 510 MPa. The reactivity ratio for addition to A-ended radicals, r_A, is effectively zero at the two lower pressures and is in the range 0.002–0.008 at 510 MPa. The other reactivity ratio, r_B, is 6 at autogenous pressure and also at 260 and 510 MPa if the A content of the charge is less than 50%. If the A content is greater than 95%, r_B appears to be 100 at pressures of 260 and 510 MPa. The apparent variation in r_B cannot be explained by invoking a penultimate unit effect for B-ended radicals. Polymerization rates scatter somewhat, but all rates are quite small when the A content of the charge is in the range 95–99.8%. Polymers containing as much as 66% A appear to be inherently benzene soluble but frequently contain some gel because of radiation-induced crosslinking after their formation. No very high polymers were formed that contained more than a few percent A, even at high pressure. Features that complicated the study were immiscibility of the liquid monomers, extreme variation of the monomer—copolymer compatibility with charge composition, and freezing of B at high pressure.     

Radiation-induced polymerization of hexafluoropropylene at high temperature and pressure

The radiation-induced polymerization of hexafluoropropylene was studied in the pressure and temperature ranges of 4,500–15,000 atm. and 100–230°C., respectively. Retardation was a serious problem; data thought to apply to the unretarded polymerization are summarized below. At 1,500 rad/hr. the polymerization rate was 15%/hr. at 230°C. and 15,000 atm. The activation enthalpy and volume are 9.5 kcal./mole and ?10 cc./mole, respectively. The rate varies as the square root of the radiation intensity. The largest intrinsic viscosity of the polymer is 2.0 dl./g.; values increase with temperature and pressure. At 130°C. and 10,000 atm. the intrinsic viscosity was the same at two radiation intensities.     

Radiation-induced polymerization of 3,3,4,4,5,5,5-heptafluoropentene-1 at high pressure

A study was made of the radiation-induced polymerization under pressure of 3,3,4,4,5,5,5-heptafluoropentene-1. Polymerization rates increase with pressure (activation volume equals ? 11 cc/mole) and temperature (activation enthalpy equals 6.5 kcal/mole) in liquid phase. At 13800 atm and 25°C, freezing occurs; the polymerization rate in the solid is very small. In liquid phase polymerization can continue for many hours after the irradiation is terminated. An active species is formed by radiation which initiates polymerization in the dark period.     

Syndiospecific polymerization of styrene. II. Monocyclopentadienyltributoxy titanium/methylaluminoxane catalyst

Syndiospecific polymerization of styrene was catalyzed by monocyclopentadienyltributoxy titanium/methylaluminoxane [CpTi (OBu)₃/MAO]. The atactic and syndiotactic polystyrenes were separated by extracting the former with refluxing 2-butanone. The activity and syndiospecificity of the catalyst were affected by changes in catalyst concentration and composition, polymerization temperature, and monomer concentration. Extremely high activity of 5 × 10⁷ g PS (mol Ti mol S h)^?1 with 99% yield of the syndiotactic product were achieved. The concentration of active species, [C^*], has been determined by radiolabeling. The amount of the syndiospecific and nonspecific catalytic species, [C] and [C] respectively, correspond to 79 and 13% of the CpTi(OBu)₃. The rate constants of propagation for C and C at 45°C are 10.8 and 2.0 (M s)^?1, respectively, the corresponding rate constants for chain transfer to MAO are 6.2 × 10^?4 and 4.3 × 10^?4s^?1. There was no deactivation of the catalytic species during a batch polymerization. The rate constant of chain transfer with monomer is 6.7 × 10^?2 (M s)^?1; the spontaneous β-hydride transfer rate constant is 4.7 × 10^?2 s^?1. The polymerization activity and stereospecificity of the catalyst are highest at 45°C, both decreasing with either higher or lower temperature. The stereoregular polymer have broad MW distributions, M?_w/M?_n = 2.8–5.7, and up to three crystalline modifications. The T_m of the s-PS polymerized at 0–90°C decreased from 261.8 to 241°C indicating thermally activated monomer insertion errors. The styrene polymerization behaviors were essentially insensitive to the dielectric constant of the medium.     

Chain transfer reactions in emulsion polymerization of butadiene/styrene

Calculation of regulating index r from M̄_W values determined by experiments is proposed. The calculation is based on the assumption that the M̄_W values only depend on the conversion and the regulating index in emulsion polymerization. On this basis the calculation of regulator concentration in the latex particles was also possible. M̄_W values calculated in this way and experimental M̄_W values show good agreement.     

Mechanism of styrene emulsion polymerization during interval II

A systematic study of the kinetics of styrene emulsion polymerization in the postnucleation stage by the way of seed particle growth of monodisperse latices was undertaken, in which the colloidally important parameters were varied: R_p was independent (within limits) of (a) ionic strength, (b) pH, (c) initiator concentration (potassium persulfate), and (d) surfactant (sodium dodecyl sulfate) concentration; R_pp was independent (within limits) of (a) seed particle number concentration N, (b) oil:water phase ratio, and (c) monomer:polymer ratio; R_p was directly proportional to seed-particle surface area. The viscosity average molecular weight of the polymer formed during interval II, M_v(i–j), was approximately constant and increased linearly with N. Log M_v(i–j) was inversely proportional to reaction temperature; M_v(i–j) was inversely proportional to initiator concentration. The overall activation energy of polymerization E′_p was equal to the activation energy of propagation E_p during interval II. The value of k_p at 60°C was 615 dm³ mol^?1 s^?1. Trace of oxygen seems to affect the average number of radicals per particle ī during interval II polymerization.     

Kinetics of styrene polymerization at ultrahigh conversion

The radical-initiated bulk polymerization of styrene at low conversion can be adequately described by a simple kinetic scheme that involves initiation by the decomposition of a radical initiator, propagation, and termination by combination of polystyryl radicals. An integrated equation can be derived that will describe the relationship between monomer concentration and time. We have investigated the validity of applying equations of this kind in the 98–99.999% conversion range. From our experimental work we conclude that the initial rates at 130°C, when starting the polymerization at that temperature at more than 98% conversion, can be described by an integrated equation over at least two decades of monomer concentration. Deviations from the simple kinetics at ultrahigh conversion were observed after a certain time at 130°C. These are discussed and explained in terms of the kinetic assumptions made and an extended model is suggested to allow for depolymerization reactions that cannot be neglected at ultrahigh conversion.