411
Views
17
CrossRef citations to date
0
Altmetric
Comprehensive Reviews

The Kinetics of Emulsion Polymerization: Some Controversial Aspects

, &
Pages 207-229 | Received 29 Apr 2003, Accepted 08 Dec 2003, Published online: 24 Aug 2007

References

  • Harkins , W. D. 1947 . A general theory of the mechanism of emulsion polymerization . J. Am. Chem. Soc. , 69 : 1428 – 1444 .
  • Smith , W. V. and Ewart , R. H. 1948 . Kinetics of emulsion polymerization . J. Chem. Phys. , 16 ( 6 ) : 592 – 599 .
  • Gardon , J. L. 1968 . Emulsion polymerization. I. Recalculation and extension of the Smith–Ewart theory . J. Polym. Sci. Part A‐1, , 6 : 623 – 641 . [CROSSREF]
  • Backley , D. C. 1975 . Emulsion Polymerization London : Applied Science Publishers LTD .
  • Antonietti , M. and Tauer , K. 2003 . 90 years of polymer latexes and heterophase polimerization: more vital than ever . Makromol. Chem. Phys. , 204 ( 2 ) : 207 – 219 . [CROSSREF]
  • Saldivar , E. , Dafniotis , P. and Ray , W. H. 1998 . Mathematical modeling of emulsion copolymerizations reactors I. Model formulation and application to reactors operating with micellar nucleation . J. Macromol. Sci. Rev. Macromol. Phys. , C38 ( 2 ) : 207 – 325 .
  • Gao , J. and Penlidis , A. 2002 . Mathematical modeling and computer simulator/database for emulsion polymerizations . Prog. Polym. Sci. , 27 : 403 – 535 . [CROSSREF]
  • Lichti , G. , Gilbert , R. G. and Napper , D. H. 1983 . The mechanisms of latex particle formation and growth in the emulsion polymerization of styrene using the surfactant sodium dodecyl sulfate . J. Polym. Sci. Part A: Polym. Chem. , 21 : 269 – 291 .
  • Harkins , W. D. 1945 . A general theory of the reaction of loci in emulsion polymerization . J. Chem. Phys. , 13 : 381
  • Harkins , W. D. 1946 . A general theory of the reaction loci in emulsion polymerization . J. Chem. Phys. , 14 : 47
  • Dunn , A. S. 1997 . “ Harkins, Smith–Ewart and relates theories ” . In Emulsion Polymerization and Emulsion Polymers Edited by: Lovell , P. A. and El‐Asser , M. S. 125 – 163 . Chichester : John Wiley and Sons .
  • Ugelstad , J. , El‐Aasser , M. S. and Vanderhoff , J. W. 1973 . Emulsion polymerization: initiation of polymerization in monomer droplets . J. Polym. Sci. Polym. Lett. Ed. , 11 : 503 – 513 . [CROSSREF]
  • Miller , C. M. , Sudol , E. D. , Silebi , C. A. and El‐Aasser , M. S. 1995 . Miniemulsion polymerization of styrene: evolution of the particle size distribution . J. Polym. Sci. Part A: Polym. Chem. , 33 : 1391 – 1408 .
  • Blythe , P. J. , Morrison , B. R. , Mathauer , K. A. , Sudol , E. D. and El‐Aasser , M. S. 1999 . Enhanced droplet nucleation in styrene miniemulsion polymerization. 1. Effect of polymer type in sodium lauryl sulfate/cetyl alcohol miniemulsions . Macromolecules , 32 : 6944 – 6951 . [CROSSREF]
  • Blythe , P. J. , Klein , A. , Sudol , E. D. and El‐Aasser , M. S. 1999 . Enhanced droplet nucleation in styrene miniemulsion polymerization. 2. Polymerization kinetics of homogenized emulsions containing predissolved polystyrene . Macromolecules , 32 : 6952 – 6957 . [CROSSREF]
  • Sudol , E. D. and El‐Aasser , M. S. 1997 . Emulsion Polymerization and Emulsion Polymers Edited by: Lovell , P. A. and El‐Aasser , M. S. 699 – 722 . London : Wiley .
  • Asua , J. M. 2002 . Miniemulsion polymerization . Prog. Polym. Sci. , 27 : 1283 – 1346 . [CROSSREF] [CSA]
  • Antonietti , M. and Landfester , K. 2002 . Polyreactions in miniemulsions . Prog. Polym. Sci. , 27 : 689 – 757 . [CROSSREF]
  • Odian , G. 1991 . “ Emulsion polymerization ” . In Principles of Polymerization , 3rd Ed. 335 – 353 . New York : Wiley‐Interscience .
  • Hansen , F. K. and Ugelstad , J. 1982 . “ Particle formation mechanism ” . In Emulsion Polymerization Edited by: Piirma , I. 51 – 91 . New York : Academic Press .
  • Priest , W. J. 1952 . Particle growth in the aqueous polymerization of vinyl acetate . J. Phys. Chem. , 56 : 1077 – 1082 .
  • Roe , Ch. P. 1968 . Surface chemistry aspects of emulsion polymerization . Ind. Eng. Chem. , 60 ( 9 ) : 20 – 33 .
  • Fitch , R. M. and Tsai , C. H. 1971 . “ Particle formation in polymer colloids, III: Prediction of the number of particles by a homogeneous nucleation theory ” . In Polymer Colloids Edited by: Fitch , R. M. 73 – 102 . Plenum Press .
  • Hansen , F. K. and Ugelstad , J. 1979 . Particle nucleation in emulsion polymerization. III. Nucleation in systems with anionic emulsifier investigated by seeded and unseeded polymerization . J. Polym. Sci. Part A: Polym. Chem. , 17 : 3047 – 3067 .
  • Hansen , F. K. and Ugelstad , J. 1978 . Particle nucleation in emulsion polymerization. I. A theory for homogeneous nucleation . J. Polym. Sci. Part‐A: Polym. Chem. , 67 : 1953 – 1979 .
  • Goodall , A. R. , Wilkinson , W. C. and Hearn , J. 1977 . Mechanism of emulsion polymerization of styrene in soap‐free systems . J. Polym. Sci. Polym. Chem. Ed. , 15 ( 9 ) : 2193 – 2218 . [CROSSREF]
  • Morrison , B. R. and Gilbert , R. G. 1995 . Conditions for secondary particle formation in emulsion polymerization systems . Makromol. Symp. , 92 : 13 – 30 .
  • Nomura , M. , Harada , M. , Eguchi , W. and Nagata , S. 1976 . Kinetics of the emulsion polymerization of vinyl acetate . ACS Symp. Ser. , 24 : 102 – 121 .
  • Nomura , M. 1982 . “ Desorption and reabsorption of free radicals in emulsion polymerization ” . In Emulsion Polymerization Edited by: Piirma , I. 191 – 219 . New York : Academic Press .
  • Hansen , F. K. and Ugelstad , J. 1979 . The effect of desorption in micellar particle nucleation in emulsion polymerization . Makromol. Chem. , 180 : 2423 – 2434 . [CROSSREF]
  • Nomura , M. , Satpathy , U. S. , Kouno , Y. and Fujita , K. 1988 . Investigation on the locus of particle formation in emulsion polymerization cotaining partially water‐soluble monomers . J. Polym. Sci. Part C: Polym. Lett. , 26 : 385 – 390 .
  • Tauer , K. , Reinisch , G. , Gajewski , H. and Müller , I. 1991 . Modeling of emulsion polymerization of vinyl chloride . J. Macromol. Sci. , 28 : 431 – 460 .
  • Morrison , B. R. , Maxwell , I. A. , Gilbert , R. G. and Napper , D. H. 1992 . Testing nucleation models for emulsion–polymerization systems . Am. Chem. Soc. Symp. Ser. , 492 : 28 – 44 .
  • Morton , M. , Kaizerman , S. and Altier , M. W. 1954 . Swelling of latex particles . J. Colloid Interf. Sci. , 9 : 300 – 312 .
  • Hansen , F. K. 1992 . Is there life beyond micelles. Mechanisms of latex particle nucleation . Am. Chem. Soc. Symp. Ser. , 492 : 12 – 27 .
  • Giannetti , E. 1993 . Nucleation mechanisms and particle size distributions of polymer colloids . AIChE J. , 39 ( 7 ) : 1210 – 1227 . [CROSSREF]
  • Karaman , M. E. , Meagher , L. and Pashley , R. M. 1993 . Surface chemistry of emulsion polymerization . Langmuir , 9 : 1220 – 1127 .
  • Schlueter , H. 1990 . Particle formation and catalyzed agglomeration in emulsion polymerization . Macromolecules , 23 : 1618 – 1625 .
  • Kim , D. R. and Napper , D. H. 1996 . Studies of the validity of the dye leaching method for investigating particle nucleation mechanism in emulsion polymerization . Langmuir , 12 : 3139 – 3142 . [CROSSREF]
  • Varela de la Rosa , L. , Sudol , E. D. , El‐Aasser , M. S. and Klein , A. 1996 . Details of the emulsion polymerization of styrene using a reaction calorimeter . J. Polym. Sci. Part A: Polym. Chem. , 34 : 461 – 473 .
  • Harada , M. , Nomura , M. , Kojima , H. , Eguchi , W. and Nagata , S. 1972 . Rate of emulsion polymerization of styrene . J. Appl. Polym. Sci. , 16 : 811 – 833 . [CROSSREF]
  • Varela de la Rosa , L. , Sudol , E. D. , El‐Aasser , M. S. and Klein , A. 1999 . Emulsion polymerization of styrene using reaction calorimeter. III. Effect of initial monomer/water ratio . J. Polym. Sci. Part A: Polym. Chem. , 37 : 4073 – 4089 . [CROSSREF]
  • Herrera‐Ordóñez , J. and Olayo , R. 2000 . On the kinetics of styrene emulsion polymerization above CMC. I. A mathematical model . J. Polym. Sci. Part A: Polym. Chem. , 38 : 2201 – 2218 .
  • Herrera‐Ordóñez , J. and Olayo , R. 2000 . On the kinetics of styrene emulsion polymerization above CMC. II. Comparison with experimental results . J. Polym. Sci. Part A: Polym. Chem. , 38 : 2219 – 2231 .
  • Coen , E. M. , Gilbert , R. G. , Morrison , B. R. , Leube , H. and Peach , S. 1998 . Modelling particle size distributions and secondary particle formation in emulsion polymerisation . Polymer , 39 ( 26 ) : 7099 – 7112 . [CROSSREF]
  • Gilbert , R. G. 1997 . “ Modelling rates, particle size distribution and molar mass distributions ” . In Emulsion Polymerization and Emulsion Polymers , 1st Ed. Edited by: Lovell , P. A. and El‐Aasser , M. S. 165 – 203 . England : John Wiley and Sons .
  • Peach , S. 1998 . Coagulative nucelation in surfactant‐free emulsion polimerization . Macromolecules , 31 : 3372 – 3373 . [CROSSREF]
  • Tauer , K. 1998 . Comment on the development of particle surface change density during surfactant‐free emulsion polymerization with ionic initiators . Macromolecules , 31 : 9390 – 9391 . [CROSSREF]
  • Gerrens , H. 1959 . Kinetik der emulsionpolymerisation . Fortschr. Hochpolym.‐Forsch. , 1 : 234 – 328 .
  • Robb , I. D. 1969 . Determination of the number of particles/unit volume of latex during the emulsion polymerization of styrene . J. Polym. Sci. Part A: Polym. Chem. , 7 : 417 – 427 . [CROSSREF]
  • Gerrens , H. 1964 . Kintetic der emulsionspolymerisation bei technisch wichtigen monomeren . Dechema Monograph , 49 : 53 – 73 .
  • Min , K. W. and Ray , W. H. 1994 . Tubular reactors for emulsion polymerization: I. Experimental investigation . AIChE J. , 40 ( 1 ) : 73 – 87 . [CROSSREF]
  • Herrera‐Ordoñez , J. and Olayo , R. 2001 . Methyl methacrylate emulsion polymerization a lower monomer concentration: kinetic modeling of nucleation, particle size distribution, and rate of polymerization . J. Polym. Sci. Part A: Polym. Chem. , 39 : 2547 – 2556 . [CROSSREF]
  • Hermes Araujo , P. H. , De la Cal , J. C. , Asua , J. M. and Pinto , J. C. 2001 . Modeling particle size distribution (PSD) in emulsion copolymerization reactions in a continuous loop reactor . Macromol. Theory Simul. , 10 ( 8 ) : 769 – 779 . [CROSSREF]
  • Tank , C. and Antonietti , M. 1996 . Characterization of water‐soluble polymers and aqueous colloids with asymmetrical flow field‐flow fractionation . Macromol. Chem. Phys. , 197 : 2943 – 2959 . [CROSSREF]
  • Jungmann , N. , Schmidt , M. and Maskos , M. 2001 . Characterization of polyorganosiloxane nanoparticles in aqueous dispersion by asymetrical flow field‐flow fractionation . Macromolecules , 34 : 8347 – 8353 . [CROSSREF]
  • Ugelstad , J. , Mork , P. C. and Aasen , J. O. 1967 . Kinetics of emulsion polymerization . J. Polym. Sci. Part: A. , 5 : 2281 – 2288 . [CROSSREF]
  • Ugelstad , J. , Mork , P. C. , Dahl , P. and Rangnes , P. 1969 . A kinetic investigation of the emulsion polymerization of vinyl chloride . J. Polym. Sci. Part: C. , 27 : 49 – 68 .
  • Ugelstad , J. and Hansen , F. K. 1976 . Kinetics and mechanism of emulsion polymerization . Rubber Chem. Technol. , 49 : 536 – 609 .
  • Nomura , M. , Kubo , M. and Fujita , K. 1983 . Kinetics of emulsion copolimerization. III. Prediction of the average number of radicals per particle in an emulsion copolimerization system . J. Appl. Polym. Sci. , 28 : 2767 – 2776 .
  • Gilbert , R. G. 1995 . Emulsion Polymerization Edited by: Ottewill , R. H. and Rowell , R. L. London : Academic Press Inc. .
  • Zaragoza‐Contreras , E. A. , Navarro‐Rodríguez , D. and Maldonado‐Textle , H. 2002 . Evolution of molecular weight and molecular weight distribution in Ab Initio styrene emulsion polymerizations using series of rigid rodlike cationic amphiphiles as surfactants . J. Appl. Polym. Sci. , 84 : 1513 – 1523 . [CROSSREF] [CSA]
  • Bartsch , S. , Kulicke , W. M. , Fresen , I. and Moritz , H. V. 1999 . Seeded emulsion polymerization of styrene: determination of particle sizeby flow field‐flow fractionation coupled with multi‐angle laser light scattering . Acta Polym. , 50 : 373 – 380 . [CROSSREF]
  • Fitch , R. M. , Prenosil , M. B. and Sprick , K. J. 1969 . The mechanism of particle formation in polymer hydrosois. I. Kinetics of aqueous polymerization of methyl methacrylate . J. Polym. Sci. Part C. , 27 : 95 – 118 .
  • Fontenot , K. and Schork , J. F. 1993 . Batch polymerization of methyl methacrylate in mini/macroemulsions . J. Appl. Polym. Sci. , 49 : 633 – 655 . [CROSSREF] [CSA]
  • Santos , A. F. , Lima , E. L. , Pinto , J. C. , Graillat , C. and McKenna , T. 2003 . Online monitoring of the evolution of the number of particles in emulsion polymerization by conductivity measurements. I. Model formulation . J. Appl. Polym. Sci. , 90 : 1213 – 1226 . [CROSSREF] [CSA]
  • Yeliseeva , V. I. 1982 . “ Polimerization in polar monomers ” . In Emulsion Polymerization Edited by: Piirma , I. 247 – 287 . New York : Academic Presss .
  • Penboss , I. A. , Napper , D. H. and Gilbert , R. G. 1983 . Styrene emulsion polymerization . J. Chem. Soc. Faraday Trans. , 79 : 1257 – 1271 .
  • Penboss , I. A. , Gilbert , R. G. and Napper , D. H. 1986 . Entry rate coefficients in emulsion polymerization systems . J. Chem. Soc. Faraday Trans. I , 82 : 2247 – 2268 . [CROSSREF]
  • Feeney , P. J. , Napper , D. H. and Gilbert , R. G. 1987 . Surfactant‐free emulsion polymerizations: prediction of the coagulative nucleation theory . Macromolecules , 20 ( 11 ) : 2922 – 2930 . [CSA]
  • Adams , M. E. , Trau , M. , Gilbert , R. G. , Napper , D. H. and Sangster , D. F. 1988 . The entry of free radicals into polystyrene latex particles . Aust. J. Chem. , 41 : 1799 – 1813 .
  • Gilbert , R. G. and Napper , D. H. 1983 . The direct determination of kinetic parameters in emulsion polymerization systems . J. Macromol. Sci.‐Rev. Macromol. Chem. Phys. , C23 ( 1 ) : 127 – 186 .
  • Marestin , C. , Guyot , A. and Claverie , J. 1998 . Direct measurement of oligomers entry rate onto latex particles in an emulsion polymerization . Macromolecules , 31 : 1686 – 1689 . [CROSSREF]
  • Maeder , S. and Gilbert , R. G. 1998 . Measurement of transfer constant for butyl acrylate free‐radical polymerization . Macromolecules , 31 : 4410 – 4418 . [CROSSREF] [CSA]
  • Colombié , D. , Sudol , E. D. and El‐Aasser , M. S. 2000 . Effect of a mixed anionic‐nonionic system of surfactants on the entry and exit of free radicals into polystyrene particles . Macromolecules , 33 : 4347 – 4353 . [CROSSREF]
  • Asua , J. M. , Adams , M. E. and Sudol , E. D. 1990 . A new approach for the estimation of kinetic parameters in emulsion polymerization systems. I. Homopolimerization under zero‐one conditions . J. Appl. Polym. Sci. , 39 : 1183 – 1213 . [CROSSREF]
  • Maxwell , I. A. , Morrison , B. R. , Napper , D. H. and Gilbert , R. G. 1991 . Entry of free radicals into latex particles in emulsion polymerization . Macromolecules , 24 : 1629 – 1640 .
  • Dong , Y. and Sundberg , D. C. 2002 . Radical entry in emulsion polymerization: estimation of the critical length of entry radicals via a simple lattice model . Macromolecules , 35 ( 21 ) : 8185 – 8190 . [CROSSREF]
  • Berkel , K. Y.V. , Russell , G. and Gilbert , R. G. 2003 . Entry in emulsion polymerization: effects of initiator and particle surface charge . Macromolecules , 36 : 3921 – 3931 . [CROSSREF]
  • Prescott , S. W. , Fellows , C. M. and Gilbert , R. G. 2002 . Maximum achievable particle size in emulsion polymerization: modeling of large particle sizes . Macromol. Theor. Simul. , 11 : 163 – 170 . [CROSSREF]
  • Tauer , K. and Deckwer , R. 1998 . Polymer end groups in persulfate‐initiated styrene emulsion polymerization . Acta Polym. , 49 : 411 – 416 . [CROSSREF]
  • Morbidelli , M. , Storti , G. and Carrra , S. 1983 . Role of micellar equilibria on modelling of batch emulsion polymerization reactors . J. Appl. Polym. Sci. , 28 : 901 – 919 . [CROSSREF]
  • Saldivar , E. , Dafniotis , P. and Ray , H. 1998 . Mathematical modeling of emulsion copolymerization reactors. I. Model formulation and application to reactors operating with micellar nucleation . Macromol. Chem. Phys. , 38 ( 2 ) : 207 – 325 .
  • Liotta , V. , Georgakis , C. , Sudol , E. D. and El‐Aasser , M. S. 1997 . Manipulation of competitive growth for particle size control in emulsion polymerization . Ind. Eng. Chem. Res. , 36 ( 8 ) : 3252 – 3263 . [CROSSREF]
  • Coen , E. M. , Lyons , R. A. and Gilbert , R. G. 1996 . Effects of poly(acrylic acid) electrosteric stabilizer on entry and exit in emulsion polymerization . Macromolecules , 29 : 5128 – 5135 . [CROSSREF]
  • Wang , X. , Sudol , E. D. and El‐Aasser , M. S. 2001 . Mechanism of emulsion polymerization of styrene using a reactive surfactant . J. Polym. Sci. Part A: Polym. Chem. , 39 : 3093 – 3105 . [CROSSREF] [CSA]
  • Leemans , L. , Jérôme , R. and Teyssié , P. 1998 . Diffusive radical entry as rate‐determining step in amphiphilic block polyelectrolyte mediated emulsion polymerization . Macromolecules , 31 : 5565 – 5571 . [CROSSREF] [CSA]
  • Buback , M. , Garcia‐Rubio , L. H. , Gilbert , R. G. , Napper , D. H. , Guillot , J. , Hamielec , A. E. , O'Driscoll , K. F. , Olaj , O. F. , Shen , J. , Solomon , D. , Stickler , M. , Tirrell , M. and Winnik , M. A. 1988 . Consistent values of rate parameters in free radical polymerization systems . J. Polym. Sci. Part C: Polym. Lett. , 26 : 293 – 297 .
  • Buback , M. , Gilbert , R. G. , Russell , G. T. , Hill , D. J. , Moad , G. , O'Driscoll , K. F. , Shen , J. and Winnik , M. A. 1992 . Consistent values of rate parameters in free radical polymerization systems. II. Outstanding dilemmas and recommendations . J. Polym. Sci. Part A: Polym. Chem. , 30 : 851 – 863 . [CROSSREF]
  • Buback , M. , Gilbert , R. G. , Hutchinson , R. A. , Klumperman , B. , Kuchta , F‐D. , Manders , B. G. , O'Driscoll , K. F. , Russell , G. T. and Schweer , J. 1995 . Critically evaluated rate coefficients for free‐radical polymerization, 1 . Macromol. Chem. Phys. , 196 : 3267 – 3280 . [CROSSREF]
  • Buback , M. , Egorov , M. , Gilbert , R. G. , Kaminsky , V. , Olaj , O. F. , Russell , G. T. , Vana , P. and Ziefferer , G. 2002 . Critically evaluated termination rate coefficients for free‐radical polymerization, 1 . Macromol. Chem. Phys. , 203 : 2570 – 2582 . [CROSSREF]
  • Buerman , S. and Buback , M. 2002 . Rate coefficients of free‐ radical polymerization deduced from pulsed laser experiments . Prog. Polym. Sci. , 27 : 191 – 254 . [CROSSREF] [CSA]

Reprints and Corporate Permissions

Please note: Selecting permissions does not provide access to the full text of the article, please see our help page How do I view content?

To request a reprint or corporate permissions for this article, please click on the relevant link below:

Academic Permissions

Please note: Selecting permissions does not provide access to the full text of the article, please see our help page How do I view content?

Obtain permissions instantly via Rightslink by clicking on the button below:

If you are unable to obtain permissions via Rightslink, please complete and submit this Permissions form. For more information, please visit our Permissions help page.