Polymerization in nonuniform latex particles. II. Kinetics of two-phase emulsion polymerization

A new theory, based on the concept of nonuniform distribution of free radicals in polymerizing latex particles, has been developed for the kinetics of two-phase emulsion polymerization reactions. This theory also takes into account the diffusion controlled termination and propagation reactions to describe the gel effect and limiting conversion. The kinetic model permits prediction of the distribution of free radicals in the two polymer phases and rate of polymerization as a function of reaction conditions. Experimental data for polystyrene/polymethyl methacrylate and polymethyl methacrylate/polystyrene (postformed polymer/preformed polymer) in the literature have been used to assess the proposed idea of nonuniform distribution of free radicals in the latex particle.     

Morphology and grafting reactions in core/shell latexes

The particle morphology and percent grafting were investigated as a function of the crosslink density of the seed latex in two systems of core/shell latexes of polybutadiene/polymethyl methacrylate (PB/PMMA) and styrene–butadiene rubber/polymethyl methacrylate (SBR/PMMA) prepared by seeded emulsion polymerization at 50°C. The thin layer chromatography/flame ionization detection (TLC/FID) technique was used to characterize the grafting efficiency of the core/shell latexes. The percent grafting of the shell polymer was found to decrease with increasing the crosslink density of the core material. The particle morphology and precent grafting were also investigated as a function of composition and structure of the core material in four core/shell latex systems: polybutadiene/styrene–acrylonitrile copolymer (PB/SAN), (styrene-butadiene) random copolymer/styrene acrylonitrile copolymer (S:B/SAN), polystyrene : polybutadiene/styrene-acrylonitrile copolymer (PS:PB/SAN) and Kraton/styrene-acrylonitrile copolymer (Kraton/SAN), which were prepared by direct emulsification for the seed followed by emulsion polymerization at 70°C for the shell polymer. Grafting and crosslinking of the core material were found to be competitive reactions depending on the microstructure of the seed latex.     

Grafting onto wool. IV. Interaction of polymer radicals in the viscous media of wool fibers

In order to study the termination reaction of polymer radicals in the viscous media of wool fibers, reduced, methylated, and S-carboxymethylated wool fibers were used for graft copolymerization of methyl methacrylate and styrene. With termination of poly(methyl methacrylate) radicals, two different termination reactions, recombination and disproportionation, were together involved in the grafting systems studied. The occurrences of two termination reactions in the system could be correlated with the mobility of the wool chain controlling the radical end mobility. With decreasing disulfide content in the fibers, disproportionation predominantly takes place among the mobilized chains. At a constant disulfide, the thiol content or the concentration of thiol anions becomes the determining factor for the termination reaction. A possible explanation for these phenomena in terms of the thiol and disulfide interchange reaction is presented. On the grafting of styrene, additional evidence was obtained that prevention and retardation of the interchange reactions followed mechanochemical bond scission of the disulfide and other covalent bonds and produced new free radicals which could initiate chain reactions.     

Radiation-lnduced Graft Polymerization in Emulsion Systems

Abstract

The radiation-induced polymerization of styrene was conducted under emulsion conditions in the presence of polybutadiene latex in an attempt to induce grafting and the results were compared with the corresponding chemically initiated system. The propagation rate constants, kp, for styrene estimated on the assumption of the Smith-Ewart theory and the activation energies derived from the temperature dependence were found to be in good agreement with the values reported in the literature. The grafting efficiency was also measured and the results are discussed in association with the molecular weight of the polystyrene chains on the basis of a simple model. This is presented to explain some aspects of the experimental results and to give clearer ideas of the reactions involved.     

Limiting conversions in two-phase polymer reactions

The concepts of limiting conversion in one-phase polymer reactions have been extended to two-phase reaction systems. The analysis of the two-phase reaction requires the consideration of the glass transition temperature of each phase and the distribution of the reacting monomer between the phases. Predicted limiting conversions are compared with experimental data for simple polystyrene and polystyrene–polybutadiene reactions in latex form. Strong agreement is found for these comparisons.     

Radiation chemistry of polybutadiene and butadiene-styrene block copolymers. II. Kinetics and mechanisms of free-radical decay reactions

The decay of free radicals produced in polybutadiene, polystyrene, and block copolymers of butadiene and styrene by γ irradiation at 77 K has been studied at ?110°C in the case of polybutadiene and at ?95°C for the other samples. The free-radical decay rate is best interpreted in terms of an equation based on a second-order decay mechanism of a fraction of the free radicals decaying in the presence of other nondecaying free radicals. Hydrogen gas accelerates the free-radical decay. Increase of radiation dose increases the fraction of the radicals that decay, while increase of the fraction of styrene segments decreases the decaying fraction. In pure polybutadiene the higher the cis content, the greater fraction of decaying free radicals, but the second-order decay constant is less in the high-cis-content polybutadiene and is also less at the higher dose, probably owing to the hindrance of the radiation-produced crosslinks on the free-radical decay. The decrease of the second-order constant with increase of dose is also true for all the block copolymers studied.     

Free-radical grafting of monomers to polydienes. I. Effect of reaction conditions on grafting of styrene to polybutadiene

The radical-induced grafting of styrene onto polybutadiene (PBD) in benzene solution at 60°C has been studied. Provided the PBD concentration is kept below about 1.0 monomermole/l. the polymerization of styrene shows normal kinetic behavior. The proportion of polystyrene incorporated as graft is independent of the initiator (benzoyl peroxide) concentration but increases as the ratio of PBD to styrene in the reaction medium increases. Azobisisobutyronitrile produces no graft copolymer in this system. It appears that the reaction leading to graft formation is direct attack of initiator radicals on the rubber, probably by a hydrogen-abstraction reaction.     

Fundamental studies of grafting reactions in free radical copolymerization. IV. Grafting of styrene,acrylate, and methacrylate monomers onto vinyl-polybutadiene using benzoyl peroxide and AIBN initiators in solution polymerization.

Vinyl-1,2 polybutadiene (vinyl-PBD) was used as the backbone polymer for the grafting of styrene, methacrylate, and acrylate monomers using both benzoyl peroxide and AIBN initiators. Radical attack on the backbone can occur through the pendant vinyl group or at the tertiary, allylic hydrogen site. Effective graft sites are formed via double bond addition of either primary (initiator) or polymer radicals. The production of tertiary allylic radicals on the backbone chain also occurs and results in moderate to dramatic reaction rate re-tardation in every monomer system. The type of initiator is only important when the polymer radicals are not very reactive, as in the case of styrene, and to a lesser extent for methacrylate monomer. Graft efficiencies are generally higher when using vinyl-PBD than when using cis-PBD. © 1995 John Wiley & Sons, Inc.     

Polymerization in nonuniform latex particles: Distribution of free radicals

Previous kinetic studies in emulsion polymerization have almost always involved an assumption of uniform distribution of free radicals in the latex particle. Such an assumption is not likely to reflect reality in many systems that employ water-soluble initiators because the hydrophilic end-group of the oligomeric free radical will preferentially stay in the surface layer of the particle. This constrained end-group location would result in nonuniform distribution of free radicals in the polymerizing latex particles. A Monte Carlo simulation of the growth of a single polymer chain within the latex particle supports this hypothesis. Such a nonuniform distribution of free radicals in the latex particle is expected to have an influence on reaction kinetics and product properties. The mechanism for transport of free radicals out of polymerizing latex particles is reexamined based on the proposed concept, and a modified expression for the desorption rate constant is presented.     

On the reactivity of cellulose free radicals in graft copolymerization reactions

The formation and behavior of photo-and mechanoinduced free radicals in cellulose were studied by ESR spectroscopy and the capability of these free radicals to initiate graft copolymerization reactions was demonstrated. Although an 11-line ESR signal was detected from cellulose irradiated with ultraviolet (UV) light, a higher-intensity ESR signal with a five-line pattern was detected from a sample mechanically milled at 77 K. The decay of photoinduced free radicals when heated took place monotonously, whereas mechanoradicals exhibited an anomalous behavior with an increased signal intensity at 150 K before decaying at a higher temperature. Mechanoradicals have been found to react more efficiently and rapidly with oxygen and methyl methacrylate (MMA) than photoinduced free radicals. The peroxy mechanoradicals, however, were mobile and decayed more rapidly than the peroxy photoinduced radicals. Simultaneous graft copolymerizations of MMA to cellulose demonstrated that mechano-and photoinduced free radicals are capable of initiating grafting reactions, but a higher degree of grafting efficiency was obtained from cellulose treated mechanically.     

Cationic polymerization of α-methylstyrene from polydienes. I. Synthesis and characterization of poly(butadiene-g-α-methylstyrene) copolymers

The preparation of poly(butadiene-g-α-methylstyrene) copolymers was investigated with three different alkylaluminum coinitiators. The alkylaluminum compounds in conjunction with polybutadiene which contained a low concentration of labile chlorine atoms initiated the polymerization of α-methylstyrene to produce graft copolymers. Trimethylaluminum gave higher grafting efficiencies than diethylaluminum chloride at comparable monomer conversions. Triethylaluminum produced only very low monomer conversions (<5%), even at long reaction times, and for this reason was not studied extensively. The number of grafts per polybutadiene backbone was determined for a number of copolymers and found to increase slightly as the allylic chlorine concentration in the polybutadiene backbone was increased. In all cases, however, only a low percentage of the available labile chlorine sites along the polybutadiene backbone resulted in grafted α-methylstyrene side chains. The addition of small quantities of water to the polymerization solvent greatly enhanced the grafting rate and ultimate monomer conversion during the synthesis of these poly(butadiene-g-α-methylstyrene) copolymers. The mechanistic role of water during these grafting reactions is unknown at the present time.     

Grafting of functional nitroxyl free radicals to polyolefins as a tool to postreactor modification of polyethylene‐based materials with control of macromolecular architecture

Nitroxyl radicals were used as functionalizing agents during the free radical postreactor modification process of polyolefins carried out in the melt. The 4‐hydroxy‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl (HO‐TEMPO) and the 4‐benzoyloxy‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl (BzO‐TEMPO) free radicals were successfully grafted onto a polyethylene‐based material (ethylene‐co‐1‐octene copolymer) by coupling reaction with polymer macroradicals; these last were formed by H‐abstraction through peroxide addition. The macromolecular structure of the functionalized polyolefins was assessed by ¹H‐NMR, FTIR spectroscopy, and SEC measurements which were used to evidence the grafting site, to evaluate the grafting level and to highlight the occurrence of chain extension through crosslinking side reactions. Indeed the use of proper model compounds allowed the preparation of accurate FTIR calibration curves for the quantitative determination of the functionalization degree. Besides the high temperature SEC analysis highlighted that this fast and simple coupling reaction between macroradicals and nitroxyl free radicals grants the grafting of functionalities onto the polyolefin backbone by contemporarily preventing the side reactions liable of the structure and MW modification of the pristine polymer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Effects of copolymer composition on the formation of ionic species,hydrogen evolution,and free-radical reaction in γ-irradiated styrene-butadiene random and block copolymers

Block and random copolymers of butadiene and styrene as well as polybutadiene and polystyrene homopolymers have been investigated with respect to formation of trapped electrons, contribution of ionic species to crosslinking, and hydrogen gas evolution due to γ radiation. The decay kinetics of the disubstituted benzyl radical has also been studied. The yields of electron trapping G(e^?) are measured. The G(e^?) increase linearly with increased polystyrene content in block polymers, while in random copolymer a deviation from a linear relation is observed. The contribution of ionic reactions to crosslinking is about 25–35% of the total crosslinking yield. Hydrogen production in block copolymers is approximately a linear function of the weight-fraction additivity of the yield of hydrogen formation in polystyrene and polybutadiene homopolymers. Energy transfer from butadiene units to styrene units in random copolymers resulted in a deviation from such an additivity relation. The decay of the disubstituted benzyl free radical in block copolymers is a second-order reaction. In random copolymer, the decay is best interpreted in terms of equation based on a second-order decay mechanism of a fraction of the free radicals decaying in the presence of other nondecaying free radicals.     

Studies on Mechanism of Grafting of Polystyrene on Elastomer Backbone

The mechanism of grafting of polystyrene on a polybutadiene (PB) backbone during the preparation of impact-resistant polystyrene was studied by withdrawing samples during propolym-erization from beginning of the reaction to about 25% conversion. Good separation of the “elastomer and graft” fraction of the polymer from the free polystyrene part could be achieved by using 0.24 volume fraction of methanol in (MEK + benzene) + methanol solvent-nonsolvent. IR analysis of the grafted fraction showed that the microstructure of the elastomer remained unaltered. The unsaturation of the samples studied through the bromine number as well as by the perbenzoic acid number was also found to remain unchanged. Formation of free polystyrene started with the onset of polymerization and was faster. During prepolymerization, 80% of styrene converted constantly to form free polystyrene and 20% went into the grafted polymer. The results indicate that grafting is initiated through proton abstraction at the α-carbon of butadiene, most probably by initiator radicals. The grafted polystyrene chains possibly are shorter than free polystyrene chains.     

Free-radical grafting of monomers to polydienes. II. Kinetics and mechanism of styrene grafting to polybutadiene

A kinetic analysis of the grafting reaction has shown that, provided rubber radicals are not involved in termination reactions, the observed normal kinetics of styrene polymerization are to be expected. An expression relating the graft fraction with the rubber and monomer concentrations has been derived and its validity verified from the results reported in Part I. The observation that the molecular weight of the ungrafted PBD falls during the reaction has been explained on a theoretical basis.     

Model simulation studies of complex free radical reactions: The graft copolymerization of styrene and acrylonitrile onto ethylene-propylene-isopropylidendicyclopentadiene terpolymer

A kinetic analysis without steady approximation of the graft copolymerization of styrene-acrylonitrile onto ethylene- propylene-isopropylidendicyclopentadiene terpolymer (EP-IPDCP) is described. Some of the kinetic constants were experimentally determined. The grafting process is interpreted mainly in terms of the attack on EP-IPDCP by benzoyloxy radicals; phenyl radicals play a minor negative role by enhancing the rate of homopolymerization. A major contribution to the grafting yield is made by the propagation steps in graft polymerization and by crossed termination between grafted and ungrafted chains; of minor importance are the cross terminations between ungrafted growing chains and rubber radicals. The ole played by the solvent (benzene) and by saturated and unsaturated units in the EP-IPDCP chains is analyzed. Diffusion effects caused by the poor solvent compatibility of grafted and ungrafted chains were taken into account by allowing the termination and propagation rate constants to change in a controlled way during the reaction. The trapping of EP-IPDCP units caused by the aggregation of polymer particles seems to be indispensable to explain the decreasing trend of the grafting efficiency curve. Other information of interest pertains to the distribution of initiating radicals among the various competing reactions in the process and to the data of concentrations versus reaction time for reactants, products, and free radical intermediates. The results of a sensitivity analysis and the rate constants used in the calculations are given.     

Process parameters and their effect on grafting reactions in core/shell latexes

The grafting of methyl methacrylate (MMA) onto polybutadiene (PB) latexes prepared by seeded emulsion polymerization at 50°C was investigated as a function of: (a) initiator concentration used in the secondary polymerization, (b) monomer-to-polymer ratio, (c) the specific surface area of the seed latex, and (d) the degree of conversion. The thin layer chromatography/flame ionization detection (TLC/FID) technique was used to determine the proportion of graft copolymer in the core/shell latex, It was found that grafting PMMA onto PB depended upon the concentration of initiator, decreasing as the concentration was increased. The amount of grafting increased with increasing specific surface area of the seed latex, while the molecular weight of the acetone-soluble graft copolymer decreased. The amount of graft copolymer was found to decrease concurrently with increasing monomer-to-polymer ratio and degree of conversion. These results suggest a hydrogen abstraction mechanism in the formation of graft PB–PMMA through a chain transfer process.     

Some aspects of graft polymerization of vinyl monomers onto cellulose with the use of tetravalent cerium. V

The presence of occluded air lowers the ceric consumption between the beginning and end of the reaction time, decreases the grafting parameters, and increases the copper number. Grafting reactions carried out in presence of organic solvents show parameters that are lower than those obtained when the reactions are carried out in water. Solvents with high chain-transfer constants cause a marked decrease in the yield relative to the solvents of low chain-transfer constants. Conversion percentages are similarly influenced. However, the donor alcohols enhance polymer formation with the acceptor monomers; this is attributed to the ability of ceric salt solution to oxidize alcohol and hence initiate polymerization reaction. Scavenging of the free radicals by certain alcohols and competition between alcohol and cellulose for the ceric consumption are responsible for the low grafting yields achieved. The order of reactivity of monomers may change when solvents are used; it follows the relative differences in the chaintransfer constant of solvent with the different monomers. Pseudografting and complex formation, when they occur, interfere with the results achieved.     

Radiation-induced grafting polymerization of MMA onto polybutadiene rubber latex

The grafting of methyl methacrylate (MMA) onto polybutadiene rubber latex by the direct radiation method was carried out. The effects of monomer concentration, absorbed dose and dose rate of gamma rays on the grafting yield were investigated. The graft copolymers were characterized by transmission electron microscopy (TEM), FTIR spectroscopy, and differential scanning calorimetry. TEM photographs revealed that the core–shell structures of latex particles are formed at low MMA content, and with the increasing of MMA content, the semi-IPN-like structure with core–shell could be developed due to the high gel fraction of polybutadiene (PBD) seed particles. In addition, infrared analysis confirmed that MMA could be grafted onto PBD molecular chains effectively under appropriate irradiation conditions. The interfacial adhesion between PBD rubber (core) and PMMA (shell) phases could be enhanced with the increase of MMA concentration.     

Kinetics and mechanism of the polymerization of styrene–acrylonitrile in the presence of polybutadiene

The mechanism of free radical grafting of styrene–acrylonitrile with polybutadiene was studied. By assuming a copolymerization mechanism an equation that related the amount of homopolymer formed and its molecular weight to a reactivity ratio and the charged ratio of monomer to polydiene was derived. Polymerizations that contained a variety of ratios of monomer to polybutadiene, two different catalysts, and variable amounts of a mercaptan modifier were studied. The weight fraction of homopolymer and its molecular weight were determined by high-speed GPC. The results were analyzed by the new equation and all showed a constant value of the reactivity ratio, which strongly suggests that the mechanism of the grafting reaction is copolymerization. Evidence that suggests that none of the grafting is a result of a hydrogen abstraction mechanism is also presented.