Abstract: The polymerization of hydrocarbons was investigated by measuring the hydrogen yield during the glow discharge polymerization in a closed system. It was found that the pressure change in the glow discharge polymerization of hydrocarbons was mainly due to the production of hydrogen and to the loss of vapor phase monomer by polymerization. The opening of triple or double bonds and cyclic structures plays an important role in the polymerization of hydrocarbons; however, these are not exclusive mechanisms. The major polymerization mechanism for saturated normal hydrocarbons seems to be by the formation of free radicals due to hydrogen abstraction and the recombination of these primary radicals. The polymerization due to this mechanism also seems to occur concurrently during the polymerization of hydrocarbons with multiple bond and/or cyclic structures. Aromatic hydrocarbons polymerize with very low hydrogen production, indicating that the utilization of an aromatic double bond is the major mechanism of polymerization.

Abstract: A chromatography solid support which is prepared by immersing a microporous inorganic substrate in a radiation-polymerizable monomer and subjecting said monomer to high energy radiation to produce a radiation-induced polymerization of the polymerizable monomer is disclosed.

Abstract: Polymerization rates of N-vinyl pyrrolidone and corresponding activation energies depend on the nature of the polymerization solvent. This is mainly due to the influence of solvent polarity on the propagation reaction. The dependence of the termination rate on the viscosity of the polymerization medium has a relatively minor effect.

Abstract: A process of making a color photographic material comprising a support and a layer comprising gelatin and as a color-coupling agent a water-insoluble homopolymer of a solid water-insoluble ethylenically unsaturated color coupling monomer or a water-insoluble copolymer of said monomer with a water-insoluble ethylenically unsaturated monomer, wherein the color-coupling agent is made by: Polymerizing an emulsion in water of a solution of a solid water-insoluble ethylenically unsaturated color coupling monomer capable of undergoing free radical addition polymerization at a temperature below the melting point of said monomer or a mixture thereof with a water-insoluble ethylenically unsaturated monomer, said solution being in a solvent for said monomer selected from the group consisting of organic solvents substantially inert with respect to said color coupling monomer and the free radical polymerization products thereof, liquid water-insoluble copolymerizable monomers and mixtures of such organic solvents and such liquid copolymerizable monomers.

Abstract: Polymerization of THF in CCl4 solvent was initiated with 1,3-dioxolan-2-ylium eations with AsF6−, PF6−, and SbF6− anions as well as with esters of fluorosulfonic and trifluoromethanesulfonic acids. With these esters polymerization proceeds with a marked acceleration period, due to slow initiation. The corresponding rate constants of initiation and their dependence on the polarity of the THF/CCl4 mixture were determined. The rate constant of propagation on the macroion-pairs (kp±) of the polytetrahydrofurylium cation with AsF6−, PF6−, and SbF6− and CF3SO3−, anions was found to be independent in CCl4 solvent on the anion structure and given by the expression: kp± = 2.93 × 10−2 exp {−4.7 × 103/T} at [THF]0 = 8.0M. This constant depends on the polarity of the polymerization mixture, and at 25°C for the THF-CCl4 system, kp± = 1.78 × 10−2 exp {−4.9/D}; thus, in CCl4 at [THF]0 = 8.0M, and at 25° kp± = 4.0 × 10−21/mole-sec. In the polymerization with derivatives of CF3SO3H (able to form the corresponding macroester) the overall polymerization rate is much lower than that with complex anions because of the reversible conversion of the macroion-pairs into the macroester (internal return). The macroester is much less reactive than the macroionpair (102–103 times) in the monomer addition reaction. At [THF]0 = 8.0M and at 25°C, 96.5% of the growing species exists in the macroester form. Polymerization of THF initiated with derivatives of CF3SO3H is a subject of a strong special salt-effect. At a sufficiently high ratio of [AgSbF6] to [I]0, where the initiator I is C2H5OSO2CF3, the overall polymerization rate is equal to that observed for the polymerization of THF on the macroion-pairs, since the internal return within the triflate ion-pair (the macroester formation) is eliminated and polymerization proceeds on the macroion-pairs with SbF6- anions exclusively.

Abstract: Processes for producing colored toner particles are provided comprising mixing a monomer, a colorant and an initiator to form an oil soluble organic phase; dispersing this oil soluble phase in controlled size between 5 to 20 microns in a water phase, employing a suspending agent, for example polyvinyl alcohol; polymerizing, employing conventional suspension polymerization techniques; introducing a second monomer which is allowed to diffuse into the first polymer and consequently swells the polymer; introducing a water soluble initiator; and heating this reaction mixture to effect a polymerization of the second monomer and form the desired toner.

Abstract: An improved method of removing heat from polymerization reactions of normally gaseous monomers in the gas phase comprising feeding the monomer in liquid form to a polymerization zone, immediately after entering said zone, removing a portion of said gaseous monomer from the polymerization zone, liquefying said portion of monomer by cooling it at the same pressure as that prevailing in the polymerization zone, recycling the liquefied monomer to the polymerization zone together with fresh monomer in liquid form and causing said liquid monomer to change to the gaseous form immediately after entering said zone. The improvement consists in not only condensing the monomer outside the polymerization zone but also storing the same, in keeping the temperature in the polymerization zone constant by regulating the rate at which liquid monomer is fed to the zone, and in keeping the temperature and pressure in the polymerization zone within limits conducive to the gaseous state of the monomer.

Abstract: The solution copolymerization of styrene and methyl methacrylate in acetone, in dimethylformamide and in dioxan has been interpreted on the basis of a proposed model which includes chain end mobility and chemical reactivity. For all systems the derived equation giving the overall rate of copolymerization is in agreement with the experimental data. The effect of the reaction medium on bimolecular termination can be represented by the dependence of the rate-conditioning segmental rearrangement on medium fluidity.There is a marked solvent effect on the propagation rate coefficients. It is more pronounced for styrene than for methyl methacrylate and it shows an opposite trend for the two monomers: compared to the value for bulk polymerization kp for styrene is decreased, whereas kp for methyl methacrylate is increased in solution.

Abstract: Rubber-reinforced thermoplastics are produced commercially by dissolving a rubber in the monomer of a glassy polymer and commencing polymerization with a free-radical initiator. Beyond a few per cent conversion, the incompatibility of the two polymers causes a phase separation, with each phase containing one nearly pure polymer. Subsequent polymerization occurs in each phase. The heterogeneous nature of the reaction can influence both the kinetics of the reaction and the amount of grafting in the product. The fact that only monomer which polymerizes in the rubber phase can possibly graft establishes an upper limit to the amount of grafting and hence influences the mechanical properties of the product. It is shown theoretically how unequal partitioning of monomer and initiator between the phases can influence the extent of grafting, and can also explain the kinetic rate reductions which have been observed in such systems. The distributions of monomer and benzoyl peroxide and azobisisobutyronitrile initiators between the phases have been determined experimentally for a styrene–polystyrene–polybutadiene system. They cannot account for the rate reduction observed in such systems.

Abstract: A process of producing methyl methacrylate polymers is provided wherein the monomer are polymerized by a bulk polymerization procedure at 150° to 180°C with a conversion of 50 to 80% and the volatiles predominantly comprised of the unreacted monomer, separated from the polymer product, are cyclically reused as a part of the monomer feed for polymerization. In such a monomer feed cycle system, oligomers are substantially removed from the volatiles and then the volatiles are blended with a virgin monomer feed for polymerization, the content in the volatiles of impurities having boiling points of lower than 200°C at normal pressure is maintained within the range of 5 to 20% by weight.

Abstract: Organic reinforcing fillers for rubber are prepared by the anionic initiated slurry polymerization of styrene and divinylbenzene in the presence of a block polymer dispersant. The polymerization reaction may be carried out using, as the anionic initiator, an alkali metal-bearing compound capable of initiating polymerization of styrene without imparting to the polymerization product groups reactive with rubber in a rubber cure in which case the polymerization is terminated by reaction of the polymer particles with a terminating agent that provides in the polymer groups reactive with rubber in a normal rubber cure; or the polymerization reaction can be carried out using, as the initiator, an alkali metal-bearing unsaturated polymer that in itself imparts to the polymer groups reactive with rubber in a normal rubber cure. In the latter case, the slurry polymerization may, if desired, be terminated by use of a terminating agent that reacts with and imparts to the polymer additional and different groups tha enhance reactivity of the polymer particles with rubber in a rubber cure operation.

Abstract: The feasibility of potassium permanganate to induce graft polymerization of vinyl monomers onto nylon 6 was investigated. The graft yield is greatly enhanced by increasing the monomer concentration, reaction time, and temperature. The addition of metallic ions as promoters to the grafting medium accelerates the graft polymerization. A mechanism for grafting was proposed. The activation energy of initiation Ei for methyl methacrylate was calculated and found to be 5 kcal/mole. The overall rate of graft polymerization Rp depends on the monomer concentration.

Abstract: Micro-suspension polymerization of vinyl chloride monomers and comonomers with a seed in the form of a previously prepared dispersion of the polymer or copolymer containing all of the organo-soluble initiator required for the polymerization, in which the initiator is activated during the polymerization by the addition of an organo-metallic complex of a water-soluble metal salt reacted with a complexing agent.

Abstract: Polymerization of MMA was carried out in presence of visible light (440 nm), quinoline-bromine charge-transfer complex being used as the photoinitiator. The initiator exponent was observed to be 0.5 up to 0.014 M initiator concentration; when chloroform was used as the solvent, the monomer exponent was found to be unity. The polymerization was inhibited in presence of hydroquinone but little inhibitory effect was observed in the presence of air. An average value of k2p/kt for this photopolymerization system was found to be (1.08 ± 0.22) × 10-2. Kinetic and other evidence indicates that the overall polymerization takes place by a radical mechanism.

Abstract: Or the Disclosure A process for the polymerisation of aromatic vinyl compounds and their copolymerisation with alkyl esters or nitriles of acry-lic and/or methacrylic acid, wherein 1) in a first stage, the monomer or monomers is or are conti-nuously introduced at excess pressure into a first reaction zone and polymerised there to a degree of conversion of 5 -40 % by weight at a temperature of from 80 to 170°C;2) in a second stage, the reaction mixture is conducted at con-stant pressure into a second reaction zone designed for con-ducting highly viscous melts, the mixture flowing through this reaction zone at a rate which is 1.1 to 5 times the in-trinsic rate, and polymerised there to a degree of conversion of 40 to 95% at temperatures of from 120 to 250°C, the ex-cess pressure in the first and second stage being chosen so that the monomer or monomers is or are liquid, and the poly-mer is continuously removed from this zone with release of the pressure; and 3) in a third stage, unreacted monomer is removed by evaporation, the pressure being chosen so that the monomer or monomers is or are evaporated, and the polymer is discharged as a melt.

Abstract: The concentration of water in purified and BaO-dried ..cap alpha..-methylstyrene was found to be 1.1 x 10/sup -4/M. The radiation-induced bulk polymerization of the ..cap alpha..-methylstyrene thus prepared was studied in the temperature range of -20/sup 0/ to 35/sup 0/C. The polymerization rate varied as the 0.55 power of the dose rate. The theoretical molecular weights and molecular weight distribution were calculated from a proposed kinetic scheme and these values were then compared with those found experimentally. The agreement between these two was reasonably close, and therefore it was concluded that, from the molecular weight distribution point of view, the proposed kinetic scheme for the cationic polmerization of ..cap alpha..-methylstyrene is an acceptable one. The rate constant for chain transfer to monomer k/sub f/ changed with temperature and was found to be responsible for the decrease in the molecular weight of the polymer with increase in temperature. k/sub f/ and k/sub p/ at 20/sup 0/C were found to be 0.95 x 10/sup 4/ l./mole-sec and 0.99 x 10/sup 6/ l./mole-sec, respectively.

Abstract: The polymerization of β-propiolactone by aluminum-zinc oxoalkoxides corresponding to the structure has been studied. The overall kinetics of the reaction follow a first current order in monomer and a first order in catalyst. Mechanistic studies also indicate that these initiators operate through selective acyl-oxygen cleavage of the lactone ring with insertion in the aluminum-oxygen bond. Moreover, the polymerization proceeds by a perfectly “living” process.

Abstract: Homopolymers of butadiene having a vinyl content which varies substantially and decreasingly along the longitudinal axis of the macromolecule toward an end thereof are produced by conducting an organolithium-Lewis base catalyzed polymerization at a substantially constantly increasing polymerization temperature throughout the polymerization.

Abstract: A continuous process is described for the manufacture of impact-resistant polyvinyl-aromatic compounds by the bulk polymerization of a vinyl-aromatic monomer in admixture with an elastomeric polymer and in the optional presence of up to 20% by weight of hydrocarbon diluent, calculated on starting vinyl-aromatic monomer. The resulting polyvinyl-aromatic compounds are also described.

Abstract: The effects of temperature, dose rate, and monomer concentration on the heterogeneous polymerization of acrylamide in acetone–water mixtures have been studied. Heterogeneous polymerization takes place in mixtures containing less than 60 vol-% water. The polymerization is steady in acetone and nonsteady in acetone an nonsteady in mixtures containing 10–50 vol-% water. The average rate of polymerization is highest in mixtures with about 20 vol-% water. Polymer molecular weight increases with the increasing water content in range 0–10 vol-% and does not change in the range of 30–70 vol-% water. For the polymerization in acetone and an acetone–water 60/40 mixture the activation energies are 2.3 and −1.8 kcal/mole, the dose rate exponents of rate are 0.78 and 0.52, and the monomer concentration exponents of rate are 0.5 and 1.6, respectively. The polymer molecular weight increases with decreasing dose rate, decreasing temperature, and increasing monomer concentration. These results are discussed in connection with the mechanism of heterogeneous polymerization and the solvent effect.

Abstract: An improved polyvinyl chloride or polyvinyl chloride copolymer containing up to 50 percent of a monomer can be obtained by graft polymerizing in contact with an olefin-acrylic ester copolymer in a process of bulk polymerization comprising single stage or two-stage polymerization wherein high speed agitation is used during the first stage and low speed agitation is used in the second stage. By polymerizing in the presence of an olefin-acrylic ester copolymer, reduced particle size, easy processability, lower melt viscosity and improved impact strength can be obtained in the resin product. Two stage bulk polymerization in contact with small amounts of the olefin-acrylic ester copolymer is effective in providing reduced particle size. Larger amounts of olefin-acrylic ester copolymer can be used in either a two-stage or single stage polymerization process where high impact strength, reduced melt viscosity, improved clarity and easy processability properties are desired in the final product.

Abstract: Novel catalysts and processes are disclosed for producing highly crystalline polypropylene and highly crystalline copolymers of propylene with ethylene or propylene with other alpha-olefins. Such catalysts can reduce the amount of low-molecular-weight and, particularly, amorphous polymers formed without serious effect on the polymerization yield. These novel catalysts and processes involve improving an alkylaluminum compound-titanium chloride catalyst by using in combination small amounts of hydrogen sulfide and a sterically hindered, lower alkyl substituted, cyclic, tertiary amine, a sterically hindered, lower alkyl substituted, cyclic, amine oxide, or a trihydrocarbylphosphite. Such catalyst systems are useful in slurry polymerization, bulk polymerization and techniques in which polymerization is accomplished utilizing monomer substantially in the vapor phase.

Abstract: A non-continuous suspension polymerization process for the production of finely-divided, low molecular weight polymeric particles of an aryl monomer is carried out in a heated aqueous suspension media at a polymerization temperature above the glass transition temperature of the desired polymer. The monomer reactants and the polymerization initiator are substantially simultaneously introduced into the heated suspension media at a slow, substantially continuous rate over a time within the range of from 20 to about 85 percent of the total polymerization reaction time. The suspension media is subjected to high-rate shearing throughout the reaction.

Abstract: Polymers of excellent impact strength, reduced particle size, and enhanced proportions of fines are obtained in the bulk polymerization of a vinyl halide or mixture thereof with comonomer(s) in the presence of high molecular weight polyolefins by removing from the polymerization mass during the thick paste state thereof sufficient vinyl halide to adjust the effective concentration of polyolefin to above about 5.3% based on vinyl halide. The resultant product which contains an enhanced proportion of fines and is devoid of massive agglomerates, requires less mechanical work in comminution or shorter heating in melting in subsequent conventional processing steps.

Abstract: The polymerization of acrylonitrile catalyzed by triethyl phosphite was studied. It was found that the order with respect to the monomer concentration varies from two to three, depending on the polymerization temperature. From the results obtained for the molecular weight of the polymer and the phosphorus content in the polymer, it was thought that the zwitterion formed by the addition of triethyl phosphite to acrylonitrile is responsible for the initiation of polymerization. The following equation was suggested for the rate of the polymerization: