Articles on polymerization, step-growth and chain-growth, are covered and listed in this year’s presentation ROBERT W. LENZ
his review covers material which appeared in print from midT 1968 to mid-1969. in last year’s review, the material is classified according to polymerization reaction mechanisms, with .Is
the two inajor classifications being Step-Growth Polymerization and Chain-Growth Polymerization. This classification attempts to emphasize the major factors controlling the achievement of high molecular weights in a polymerization reaction. As a n oversimplified generalization, it may be said that these factors are principally reaction conversion for a step-growth polymerization and the ratio of propagation rate to either termination or initiation rate for a chain-growth polymerization. hlost, but certainly not all, condensation polymerization reactions are step-growth in character and most, but again not all, addition polymerization reactions are chain-growth in character. This review is based primarily on the journals covered by the bfacromolecular Sections of Chemical Abstracts, and the papers listed in the tables were compiled almost entirely from this source. Where possible, the papers discussed in the body of the review were consulted directly. Step-Growth Polymerizalion
Two assumptions which provide the basis for kinetic treatments of step-growth polymerization reactions were considered in recent articles. In one, the experimental results of Flory and the conclusions reached on the basis of the kinetics of polyesterification reactions of dicarboxylic acids were reviewed, and it was concluded that the third-order kinetics generally applied to this reaction held only over a limited conversion range ( 7 2 A ) . I n a related investigation, the role of protons in catalyzing polyesterification reactions of dicarboxylic acids was confirmed, and previous assumptions on the effect of the first- and second-dissociation constants of the acid on the polyesterification kinetics were considered (7GA). Variations in the bimolecular rate constant with chain length and their effect on the kinetics and molecular weights obtained in step-growth or condensation polymerization reactions were considered in another treatment, and modified equations were derived to take into account a possible linear variation in rate constant with degree of polymerization ( I O A ) . The statistical and kinetic theories of branching and cross-linking in threedimensional polycondensation reactions were reviewed, and a new treatment was developed for calculating sol fractions, molecular weights, and network parameters ( 7 A ) . Several investigations were conducted on the kinetics of polyesterification reactions in general and the preparation of poly(ethylene terephthalate) in particular. For the former, p01.ycondensation reactions of maleic, fumaric, phthalic, succinic, adipic, and sebacic acids with various glycols were studied in the melt without catalyst. The dicarboxylic acid monomers fell into two groups according to the relative and absolute values of the first- and second-dissociation constants; and the reaction order as a measure of the autocatalytic effect differed for these two groups (75A). Several studies on the kinetics of the polycondensation of bis(2-hydroxyethy1)terephthalate revealed the following details about this catalyzed polyesterification reaction : (1) the 54
INDUSTRIAL A N D ENGINEERING CHEMISTRY
Applied PoIymerizatio n Reaction Kinetics
reaction is second order in the region of 3000-30,000 molecular weight but nonlinear at the lower end, apparently because of side reactions ( 4 A ) ; (2) one possible side reaction is the one between a volatile component of the reaction mixture and the catalyst which inactivates the catalyst (73A); ( 3 ) a typical value of the rate constant for the antimony trioxide-catalyzed polyesterification at 275°C was 0.6 l/mol min with an activation energy of 14 kcal/ mol; and (4)in contrast, catalysis with manganese acetate showed an activation energy of approximately 9.7 kcal/mol ( I 7A). Chain-Growth Polymerization
Free-radical polymerization. Considerable attention has been devoted to new initiation systems based on combinations of organic compounds and metal salts or chelates. Kinetic investigations confirm that these initiators are free-radical in mechanism from the one-half order dependence of the initiator concentration in the over-all polymerization rate. In some cases, such as the use of Cu( 11) chelate with methyl methacrylate and an Fe( 11) chelate with both methyl methacrylate and styrene, specific interactions between monomer and initiator were proposed. The phenomenon of selective initiation of free-radical polymerization by certain metal chelates was reviewed by Bamford ( 5 B ) , who has had a n intensive program in this area (ZB, 7GB). Bamford has worked principally with the manganese chelates, but a wide vatiety of other metal ions and ligands has been applied to free-radical initiation including cupric sulfate-hydrazine ( 7ZB) and copper chelates with carbon tetrachloride ( 8 B ) , with ammonium trichloroacetate ( 7 B ) , and with pyridine (707B). In the latter, the mechanism of initiation was proposed to be the transfer of thermally excited electrons in the ligands to the central metal atoms, which in turn reacted with the monomer. Carbon tetrachloride was also combined with reduced nickel as a free-radical initiator (77B),and nickeI and cobalt nitrates in combination with N,N-dimethylaniline N-oxide formed highly active initiators for the polymerization of both styrene and methyl methacrylate (89B). Other combinations used to initiate the polymerjzation of styrene included ceric salts with alcohols or ketones (46B) and silver salts with organic halides ( 4 8 B ) . Vinyl chloride was effectively polymerized with a combination of vanadium and aluminum compounds with ethyl acetate (59B) and acrylonitrile with cyclohexanol-vanadium(V) (87B),both by free-radical mechanisms based upon the one-half order dependence of the rate on the initiator concentration. The anomalous solvent effects of aromatic solvents in freeradical polymerization reactions continues to be of interest ( 5 B ) , particularly for the polymerization of methyl methacrylate in bromobenzene (9B, 76B). Some of the effects reported in this solvent were attributed to changes in the rate constant for termination in one of these studies ( 9 B ) . Particular attention has also been directed recently to the role of solvents as they generate differences in the kinetics of homogeneous and heterogeneous polymerization reactions of both acrylonitrile and vinyl chloride. I n general, these monomers follow the normal rate equations
under homogeneous conditions, but under heterogeneous conditions the rate depends upon the extent of conversion to polymer or, alternatively, upon monomer concentration (79B, 7 70B). The presence of inorganic ions in homogeneous solution polymerization reactions of acrylonitrile generally causes significant increases in the propagation rate constant (50B, 70QB). Another paper in the general area of solvent effects was concerned with polymerization reactions conducted a t high pressures (77B), and on this latter subject, kinetic laws governing high-pressure polymerizations in general were developed (80B). A new sensitive dilatometer was described and its operation demonstrated by determining the rate of emulsion polymerization of methyl methacrylate (27B). A differential scanning calorimeter operated isothermally was also used for rate investigations, in this case for the bulk polymerizations of methyl methacrylate and styrene (36B). In another approach, a number of the important rate parameters were calculated from the time dependencies of polymer yield combined with the number average molecular weight (47B). Rate studies of some unusual systems included the proposed template polymerization of acrylic acid on polyethyleneimine ( 7 B ) , the polymerization rate and grafting efficiency for styrene on cis-1,4-polybutadiene (56B), and the polymerization of an internally activated methacrylate monomer in which the ester substituent forms a r-complex with the double bond of the monomer (67B). Considerable attention has been focused during the past year on kinetic studies of the gel effect. The subject of diffusion control in homogeneous, free-radical polymerization reactions was intensively reviewed by North (70B), and several experimental investigations were devoted to the determination of the effect of viscosity on the propagation and termination reactions. For methyl methacrylate, the kinetic order of the rate of polymerization with respect to monomer concentration was found to increase with increasing viscosity (774B), but there were conflicting reports about the effect of molecular weight on the rate constant for termination (63B, 756’). The role of polymer chain diffusion in the gel effect was considered in several studies (408, 4QB,54B). An equation was derived by probability theory to calculate the moleculnr weight distribution for polymers obtained under conditions oi diffusion-controlled termination (47B). The role of metal ions as inhibitors in free-radica1 polymerization reactions was investigated for Fe(II1) (77B),Cr(V1) (777B), and Ce(1V) (67B). Organic inhibitors were investigated both to evaluate the effectiveness of inhibition itself and to apply this information to the calculation of elementary rate constants for the polymerization reactions. The stable free radical, verdazyl, was evaluated as an inhibitor for the polymerization of several monomers (57B). Quinones were investigated both for their stoichiometric coefficients (Q4B, 775B) and for collecting data on the other component reactions of the polymerization (53B). The kinetic factors involved in popcorn polymerizations were considered in detail in an extensive review of the subject by Breitenbach (75B), and a rate study was carried out on acrylate and methacrylate monomers capable of forming popcorn (Q0B). The role of primary radical termination in the AIBN-initiated polymerization of styrene was evaluated with the conclusion that, in contrast to previous reports, the chain transfer constant of this initiator is substantial (82%). The kinetics of solid-state polymerization, both in the crystalline state and in the glassy state, were treated for both free-radical and ionic mechanisms in a comprehensive review (707B). Kinetic equations and activation energies for free-radical, solid-state polymerization reactions were offered in papers on the radiationinduced polymerization reactions of acrolein (26B) and methacrylic acid (74B). Several papers appeared on the rate of termination in freeradical copolymerization. Included among these were studies on the effect of temperature on cross-termination in the copolymerization of styrene and methyl methacrylate, which indicated that the activation energy for cross-termination was about 2 kcal/mole (7QB),and two papers on the possible role of the penultimate effect in the termination reaction (85B, 86B). The kinetics of the radiation-initiated copolymerization of maleic acid monoesters with styrene were investigated, and the results showed that the activation energy for cross-propagation in this reaction was unusually low, approximately 2.8 kcal/mol (Q7B). The Q-e treatment of copolymerization was modified to take into account the dependence of the rate constant for propagation on resonance and polar factors. From this treatment, abso-
lute rate constants for the reaction of radicals with monomers were calculated (97B). Emulsion Polymerization. The characteristics of the radiationinduced emulsion polymerizations of both styrene and vinyl acetate were studied (Q8B). The molecular weight and particle size distributions were found to be narrower for this type of system than for those obtained in chemically initiated emulsion polymerization reactions at the same temperature. The copolymerization of vinyl acetate with acrylates and maleates by y-initiated emulsion polymerization was also studied. Other papers in the area of emulsion copolymerization were concerned with the characteristics of a semicontinuous system for styrene and methyl acrylate, in which the effect of the feed on the particle size distribution was evaluated (37B),as was the importance of relative particle swelling by the two monomers on the reactivity ratios (30B), and the behavior of three-component monomer systems (23B). A sensitive recording dilatometer was used to follow the buildup and decay of polymerization rates and radical concentrations in a yirradiated system (55B). The apparent half-life of the propagating radicals was found to range from less than 1 min for vinyl acetate to u p to 80 min for styrene. A kinetic investigation of emulsion polymerization of vinyl chloride to high conversions revealed, as expected, that the number of particles was constant between 10 and 90% conversion and independent of the concentration of initiator (708B). However, the order of the reaction with respect to the number of particles increased over this range, and a marked increase in the rate was observed at about 70-80y0 conversion. The effect of pressure on the rate of polymerization was also evaluated in this study. Anionic polymerization. The major event of the year for the literature on anionic polymerization was the publication of a book by Szwarc, “Carbanions, Living Polymers, and Electron Transfer Processes.” Included in this book are thorough coverages of all facets of the kinetics of anionic polymerization of monomers with carbon-carbon double bonds, the application of living polymers to synthetic polymer chemistry, the thermodynamics of propagation in anionic polymerization, a description of important experimental methods used for kinetic studies, the structures and mechanisms of reactions of ion-pairs, the kinetics of electron transfer processes and applications of radical-ions, and a treatment of the kinetics of the anionic polymerization of N carboxy-a-amino acid anhydrides (26C). Considerable attention continues to be devoted to the kinetics of the anionic polymerization of styrene for varying counterions, solvents, and temperatures. The objective of these studies is to understand better the intimate mechanisms of the initiation and propagation steps so that some control can be exercised over the effect of ion-pair structure on rate and stereochemistry of polymerization. I t is known, of course, that the type of solvent is of great
TABLE
I.
STEP-GROWTH POLYMERIZATION
Polymer Type Review Polyesters Polyamides
Polypyrazoles Urea- and melamineformaldehyde Phenol-formaldehyde Phenol-formaldehyde Urea- and melamineformaldehyde
Topic
Ref.
Kinetics of interfacial polycondensation Polycondensation kinetics for phthaloyl chloride with series of nitroalkanediols Kinetic data for poly(amic acid) formation from aliphatic dianhydrides and aromatic diamines Kinetics and mechanism for reaction of bis(P-diketones) with dihydrazides Rate studies on crosslinking of molding compounds Kinetics and mechanism of alkali-catalyzed prepolymer formation Kinetics and mechanism of self-condensation of hydroxymethylphenols Rate and equilibrium constants of methylolation reactions
(3A)
VOL. 6 2
NO.
2
(7A) (QA)
(8A) ( 7 4 )
(5A) (6A) (2A)
FEBRUARY 1970
55
importance to the reactivity of the ion-pair, but recent investigations indicate that there is little solvent effect on the reactivities of free anion end groups, indicating very little solvation of the propagating carbanion itself (22C). The apparent negative activation energy with sodium counterion in this type of reaction and the maxima observed for the
TABLE I I .
FREE-RADICAL POLYMERIZATIONMONOMERS
Monomers Styrene Pentafluorostyrene Methyl methacrylate Methacrylate esters Methacrylate esters Glycol dimethacrylates Allyl methacrylate Vinyl acetate Vinyl chloride
Vinyl chloride Acrylonitrile
Acr ylamide Acrylamide N--t-butylacr ylamide N-vinylphthalimide N-vinylcaprolactam Ethylene Ethylene Ethylene Propylene
Diallylidenepentaerythritol 3,3-Dichloropropane
56
Topic Rate constants for retardation by Fe(I1) ions Rate data on thermal and AlBN Initiation Rate of polymerization initiated by monomeric and polymeric peroxides Kinetics of polymerization using Bz2Oz and AlBN Kinetics for nonquasisteady state polymerization (706B, 7OB) Mathematical analysis and experimental determination of kinetics Rate investigations Rates of bulk and solution polymerizations Energy, volume and entropy of activation for liquid phase, bulk polymerization Rate parameters for polymerization with Et~Al-Bz202 (43B, 44B) Rate expressions for homogeneous polymerization in dimethyl sulfoxide Solvent effects on k, and kt Polymerization rate with KMnOpoxalic acid redox initiator Polymerization kinetics in methanol Rate equation Kinetics for various solvents and initiators ?-Radiation polymerization rates in presence of t-BuOH Calculated rate constants for y-radiation polymerization Rate equation for high pressure polymerization Activation energy, volume and entropy for high pressure polymerization Rate equation and cyclization behavior Rate equations for polymerization at different pressures
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
TABLE I l l .
FREE-RADICAL POLYMERIZATION I N IT IAT1ON
Initiator type
Topzca
Uv photosensitizer
Phenyl phenacyl sulfide and sulfoxide photolysis kinetics with MXLi, AN, S and VAc Sodium benzoyl thiosulfate with MMX and acrylamide Kinetics of photoinitiated polymerization of acrylamide and methacrylamide Ant hraquinonesulfonateITaCl-HClOd with hlMA and methyl acrylate Hot radical reactions from Uv-dissociated initiators Initiation constants with M M A by N h l R impulse method Rate of decomposition with S in aromatic solvents
Uv photosensitizer Uv Co(II1) complex Uv photosensitizer uv '-Dihydroxyperoxides
CY,^
fi-Methoxybenzoyl and p-nitrobenzoyl peroxide Acyl peroxides Acyl peroxides Son-pyridine complex Tetramethyltetrazenebenz yl chloride AIBN Cyclopropane derivatives Thermal Ammonium persulfate-NH*OH
Relation between decomposition rate and radical reactivities Hammett equation for substituent effect on rate of initiation with S Charge-transfer complex for initiation of hIMA in CC14 Rates of polymerization of AN and copolymerization of AN-S Efficiency of radical formation in 02-containing solutions of hZhIA Initiation rates with hIhlA Role of peroxides in thermal polymerization of chloroprene Redox initiator for aqueous polymerization of .AN
a Abbreviations: M h l A , methyl methacrylate ; styrene; AN, acrylonitrile; VAc, vinyl acetate.
S,
rate constant as a function of temperature were both explained on the basis of a two-site mechanism for propagation (ZZC). The two-sites in this case are a slow-reacting contact ion-pair and a reactive solvent-separated ion-pair. Other studies have shown that in dioxane, the solvated ion-pair can exist in at least four different forms, including a monoetherate and a dietherate, and each form has a separate rate constant and activation energy for propagation (2C). Additional studies have been carried out on determining the absolute values of the propagation rate constants for different counterions in tetrahydropyran, in which the maximum rate was shown for the R b cation within the series of alkali metal counterions (5C), and in cyclohexane, in which ion-pair association or aggregate formation was observed for the K cation (ZOC). 'The effects of small amounts of strongly coordinating solvents (50C) and additional amounts of the cations (73C) on the rate of polymerization were considered in other papers. I n the latter investigation, it was observed that the addition of sodium tetraphenylborate had negligible effect on the molecular weight distribution in dimethoxyethane solvent, apparently because the
TABLE IV. FREE-RADICAL POLYMERIZATIONNONHOMOGENEOUS SYSTEMS Emulsion Polymerization Stochastic approach to molecular weight distribution Lowest theoretical limits of k t / k , Equations for determining rate of polymerization and k, Kinetics of particle formation for acrylic monomers Kinetics and mechanism for polymerization of ethylene Kinetics for polymerization of methyl methacrylate using polymeric emulsifiers Kinetics for vinyl acetate using nonionic emulsifiers Rate of radical formation and initiation efficiency for BzzOn-amine systems with styrene Suspension Polymerization Calorimetric method for kinetic study of vinyl acetate polymerization Analog computer study of polymerization rates in vinyl chloride polymerization Equations for heterogeneous bulk and suspension polymerization of vinyl chloride Effect of kinetic parameters in vinyl chloride polymerization on polymer structure and morphology Kinetics of aqueous polymerization of methyl methacrylate and mechanism of particle formations
propagation rate in this solvent is already much faster than the rate of initiation. Finally, the effect of an imposed electric field on the rate of polymerization of styrene in benzene-tetrahydrofuran solvent was examined, and it was observed that while the apparent propagation rate constant increased with increasing field strength, the absolute value of k, was not affected but the increase could be attributed to a change in the equilibrium constant for reversible solvation of the ion-pair end group (8C). Kinetic and molecular weight studies on the polymerization of or-methylstyrene with sodium counterion have led to the conclusion that the polymerization reaction proceeds by a coordination mechanism and four elementary reactions as follows: (1) activation of the ion-pair end group by coordination with the monomer; (2) propagation through the end group so activated; (3) deactivation of the end group but retention of the ion-pair structure; and (4) slower propagation of the deactivated endgroup (18C, 79C). The actual structures of these activated and deactivated end groups were not proposed, but the concept was applied to expIain the overall polymerization kinetics. A more orthodox treatment of the kinetics on the basis of a two-site reaction center was given for the polymerization of this monomer in tetrahydrofuran and dioxane a t different temperatures with different alkali metal counterions (3C). The lithium counterion in this case shows the same type of anomalous behavior as the sodium counterion does for styrene. A similar study was also carried out in tetrahydropyran using a combination of dilatometric and spectrophotometric methods ( 4 C ) . The kinetics and mechanism of the anionic polymerization of isoprene also continue to receive considerable attention. Rate and molecular weight distribution measurements were made for the polymerization of this monomer with various organolithium initiators in heptane and diethyl ether. The calculated molecular weight distribution, based on a six-fold association of polymer end groups, agreed well with the results obtained by column fractionation for the polymerization in heptane (47C). I n contrast, the kinetics of polymerization in diethyl ether indicated
that end-group association was absent in this solvent, but verified that there was no termination or chain transfer under these conditions (48C). I n another study in diethyl ether, however, the rates of initiation and propagation could only be accounted for adequately if association of both the initiator molecules and the end groups was taken into account (23C). Cationic polymerization. The literature of cationic polymerization was particularly blessed during the past year, after a long drought, by a book on synthetic elastomers containing four chapters on cationic polymerization reactions ( 2 5 0 ) , and by a n extensive review article by Plesch (370). Of particular note in the former are chapters by La1 on the kinetics of the cationic polymerization of vinyl ethers, and by Kennedy on the kinetics and mechanism of the low temperature polymerization of isobutene. Included also is a chapter by Uraneck on the kinetics of the freeradical emulsion copolymerization of styrene and butadiene in the preparation of SBR rubber ( 2 5 0 ) . The review article by Plesch covers most of the important kinetic aspects of the carbonium ion polymerization of olefin monomers ( 3 7 0 ) , including discussions of the mechanism of initiation, the nature of the propagating species, and tbe various possible types of chain-breaking reactions. In addition to these more general reviews, an excellent treatment of an important new aspect of cationic polymerization was covered in a review article by Ellinger on the kinetics of charge-transfer polymerization reactions ( 9 D ) . Particular attention was devoted in this review to the kinetics and mechanisms of the cation-radical polymerization reactions of N-vinyl carbazole and related monomers with organic acceptors and of vinyl ethers with iodine. This general subject was also treated in a shorter review ( 1 0 ) . A particularly important paper appeared on cationic polymerization reactions initiated with radiation, devoted particularly to the subject of the cationic polymerization of isobutene under rigorously anhydrous conditions (440). Under these conditions, extremely long kinetic chain lengths and high G( --m) values were obtained, indicating that the propagating species was a free ion. The only termination reaction under these conditions was apparently chain transfer to monomer. The results obtained placed considerable doubt on interpretations in previous studies of radiation-induced polymerization reactions in the presence of solid additives. Propagation rate constants were obtained in another study on the radiation-induced cationic polymerization of gaseous isobutene (360). As with anionic polymerization, the most popular monomer for studying kinetics and mechanisms of cationic polymerization
TABLE V. FREE-RADICAL POLYMERIZATIONSOL I D-STATE POLY M ER I2AT ION
Topic
Ref.
Review
Monomer
Mechanisms of polymerization in the crystalline and glassy states
(707B)
Review
Kinetics and mechanism for vinyl and cyclic monomers, aldehydes, and copolymerization Activation energies and quantum yields for initiation by vacuum ultraviolet rays
(6B)
Acrylonitrile and acetylene Acrylonitrile Vinylene carbonate General
AUTHOR Robert W. Lenz is in the Polymer Science and Engineering Program, Chemical Engineering Department, University of Massachusetts, Amherst, Mass. 07002
(702B)
Polymerization rates as a function of temperature and pressure Kinetic curves and conversion effects on molecular weight and distribution
(93B)
Theoretical treatment of molecular weight distribution from kinetic constants in radiation-induced polymerization
(72~)
VOL. 6 2
NO.
2
(34B)
FEBRUARY 1970
57
reactions was styrene. A careful study of the polymerization of styrene with perchloric acid, reported in two brief communications ( 7 0 , ZQD), should add some light to the heat generated over the mechanism of this cationic polymerization reaction. Rate and molecular weight data indicated that at temperatures below -8O”C, the system had the characteristics of a “living polymer”-
TABLE VI. ANIONIC POLYMERIZATION OF OLEFIN AND CYCLIC MONOMERS Monomer Review
Methyl methacrylate Methacrylate esters
Ethyl Acrylate Acrylonitrile
Nitroethylene 4-Vinylpyridine salts Vinyl silanes Vinyl trimethylsilane 1,2-Dihydronaphthalene Vinyl chloride Caprolactam
Caprolactam Pivalolactone
Alanine NCA Ethylene oxide Propylene sulfide
C yclotetrasiloxanes
58
Tofiic Effect of ion-pair structure and participation on kinetics and mechanism Kinetic curves and equations for polymerization with BuLi in toluene Mechanistic interpretation of kinetic data for formation of isotactic, syndiotactic and block polymers Kinetic constants for polymerization with BuLi in toluene Kinetics of initiation by electrochemically generated radical anions Dose rate dependence in radiation-induced polymerization Kinetics of spontaneous polymerization Kinetics of initiation for polymerization with EtLi Kinetics of polymerization with metallic Li in hydrocarbon solvents Kinetics and molecular weights for polymerization by organolithium initiators Rate studies based upon analysis by gas chromatography Review of kinetics of polymerizations initiated by alkali metals and organometallic compounds Kinetics for initiation by sodium caprolactam Polymerization rate for initiation by triethylamine and a diazonium salt Rate parameters for polymerization with butylamine Polymerization rates for initiation with Na and K alkoxides Dilatometric and conductivity studies of polymerization rates Ultrasonic method for determining kinetics of polymerization
INDUSTRIAL A N D ENGINEERING CHEMISTRY
type of polymerization reaction, but with a reversible termination step ( 7 0 ) . Above -30°C, on the other hand, chain transfer became the dominant termination reaction. I n contrast, initiation with sulfuric acid generated active carbonium ions even at 30°C, and rate constants for propagation and transfer in this system were readily obtained (220,230). Various other papers on this monomer were devoted to the polymerization kinetics for initiation by mercuric nitrate ( 2 6 0 ) ,by a perfluorocarboxylic acid ( 3 5 0 ) , and by electrolytic initiation (80). Continuing investigations on the effect of an electric field on the cationic polymerization of styrene were also reported, with the overall rates of polymerization showing significant changes under the imposition of a field ( 2 0 0 , 270). Two cyclic monomers, trioxane and tetrahydrofuran, received considerable attention in rate investigations for ring-opening, cationic polymerization reactions. Kinetic and thermodynamic investigations of the polymerization of trioxane revealed unusual orders in catalyst and monomer in the rate equation, and showed that both tetraoxane and pentoxane were significant by-products of the polymerization reaction, possibly the result of depolymerization by back-biting reactions ( 3 0 0 ) . This type of ceiling temperature effect for trioxane was also studied in an investigation of variations in rates, yields, and molecular weights with changes in polymerization temperature ( 3 3 0 ) . Additional rate studies on this monomer were concerned with a heterogeneous polymerization reaction ( 3 4 0 ) ,a “crystallization polymerization” reaction of the monomer in concentrated solutions ( 3 2 0 ) ,and a copolymerization of trioxane with styrene (370). Kinetic studies were also carried out on the other major route to the preparation of polyoxymethylene ; namely, the cationic, carbonyl-addition polymerization of formaldehyde, with the primary concern being the effects of chaincapping reagents on the rates of polymerization ( 1 6 0 , 480). Studies on the kinetics o f the polymerization of tetrahydrofuran were concerned with such matters as variations in the concentrations of the propagating species as a function of the nature of the Lewis acid initiator ( 4 7 0 ) , the effect of small amounts of water on the termination reaction and on polymer yield ( 2 8 0 ) , and the polymerization rates and equilibria for initiation with BF3 ( 2 7 0 )and with an Fe(II1)-triphenylphosphite complex ( 4 6 0 ) . Heterogeneous chain-growth polymerization. A number of kinetic studies directed a t ascertaining the nature of the active site in the Ziegler-Natta catalyst were published. ‘The general conclusions of these was that the active site is bimetallic in character. This conclusion was drawn from kinetic investigations of: (1) the polymerization of ethylene with a MeTiCla-TiC13catalyst, in which it was observed that the polymerization rate depended markedly on the MeTiCls concentration but that no polymerization occurred in the presence of this component alone (TOE); (2) the polymerization of ethylene with a n AlEtCla-Ti(II1 and I V ) CIS catalyst, in which it was observed that the rate of polymerization was proportional to concentration of unpaired electrons determined by ESR and concluded that the particle carrying the unpaired electron was probably a complex consisting of Tic13 and dimer aluminum alkyl chloride ( 7 E ) ; (3) the polymerization of ethylene with a soluble Ziegler-h’atta catalyst composed of a cyclopentadienyltitaniuni chloride with a n alkyl aluminum chloride, for which a Ti(1V)-A1 complex with a bridging ethyl group was suggested as the active species ( 7 7 E ) ; and ( 4 ) the polymerization of butene-1 with titanium chloride-aluminum alkyl catalysts, in which it was concluded that the initial complexation of the monomer to the transition metal of the catalyst was the ratecontrolling step, but that the stereospecific catalytic complexes were a t least partially bimetallic (75E). Other rate studies on the polymerization of ethylene with Ziegler-Natta catalyst were concerned with the effect of the AI/Ti ratio on the induction period and rate of polymerization ( 8 E ) ; with rate studies on the polymerization of ethylene with a n Et2A1C1-TiC14 catalyst in the presence of various ethers .to determine the effect of this type of additive on both the polymerization rate and the molecular weight of the polymcr obtained, in which it was concluded that the ether complexes with the catalyst to slow down the rate of chain termination ( 3 E ) ; and finally with a study of the oligomerization of propylene with an i-Bu~AICl-TiClrcatalyst to obtain information on relative rates of chain propagation and chain transfer (78E).
TABLE VII. CATIONIC POLYMERIZATION OF OLEFIN AND CYCLIC MONOMERS
Monomer Indene Vinylcarbazoleoxetane Cyclopentadiene 1,3-Cyclohexadiene 1,3-Cyclooctadiene Epichlorohydrin and glvcidyl nitraG ’ Epichlorohydrin Trimethylethylene oxide Oxetane-epoxide Cyclohexene oxide 3,3-Bis(chloromethy1)oxacyclobutane 1,3-Dioxolane
1,3-Dioxepane N-phenylethyleneimine Hexamethylcyclotrisiloxane Caprolactam Caprolactam
Caprolactam Caprolactam
Topic
Ref.
Reaction order and mechanism for “livingpolymer” system Rate study by N M R
(390)
Kinetics and mechanism of initiation with PhsC’SbClBKinetic observations Kinetic observations Kinetics and mechanism of BF3 polymerization
(430)
TABLE V I I I . HETEROGENEOUS POLY M ER I ZAT ION
(770)
(790) (180) ( 700)
Kinetics and mechanism of BFa-etherate polymerization Rates and activation energies with different initiators Reaction rates of copolymerization Rate of radiation-induced polymerization Reaction orders and activation energy for AlCls polymerization Kinetics and mechanism of polymerization with Et 3 0 +SbCI6 Kinetics and thermodynamics of EtsO+ SbCl6- polymerization Rate and DP studies on “living-polymer” reaction Rate and thermodynamic studies for initiation with Rates of initiation, propagation and termination with carboxylic acids Rate of solid-state polymerization Mechanism of cationic polymerization in the melt Kinetics of melt polymerizations initiated with carboxylic acid hydrazides Kinetics of hydrolytic polymerization initiated with BuNH2-HCl Kinetics of hydrolytic polymerization in 01piperidone
Catalyst EtaAl-Tic13 or EtzAICl-Tic13 ZieglerNatta Et~Al-TiC13 4-R O H EtzAlCICpzTiClz i-AmLivocl3 EtzAlClVClr Anisole i-BusAIC1vc14 $-BugAICIV(Acac)a
Monomer
Kinetic study in toluene
Ethylene
Effect of H P on rate and mol. wt. Rate studies
Propylene Styrene Styrene EthylenePropylene
Ethylene-lbutene Ethylene-lpentene HOFe Propylene oxide [(oc3HB)2
c112 SrC03
To@
Ethylene
Ethylene oxide
Kinetics for soluble catalyst Rates and mechanisms Rate studies Rates and reactivity rdtios Copolymerization kinetics Rate constants and active center populations Same
gations on the polymerization of butadiene with a Zn-Co coupleEt2AICl catalyst revealed that the number of active centers did not depend upon the concentration of RtzAlCl and suggested that the catalyst site was formed by absorption of this component on the solid substrate (23E). Lastly, polymerization rate investigations for this monomer On a n i-Bu3AI-TiIzClz catalyst indicated that this system had a “living-polymer” character, free of both kinetic termination and chain transfer, and that variations in the polymerization rate with time could be explained on the basis of a reversible deactivation and reactivation of the active centers ( 4 E ) . Rate studies combined with ESR investigations of the polymerization of propylene on a supported chromium oxide catalyst indicated that a correlation exists between the signal strength of Cr(V) and the activity of the catalyst, and also between the latter and the proportion of Cr(V1) content (27E). The amount of chromium in these two valence states decreased with increasing chromium content and both were found to be unstable to heat and easily reduced to inactive Cr(II1). Rate and molecular rate studies with this catalyst for the polymerization of ethylene generated rate constants for propagation, spontaneous transfer, and transfer to monomer ( 6 E ) . In another study, the effects of small amounts of CO, 0 2 , COZ,CZHZ,and HZon polymerization rates and molecular weights were determined ( 7 E ) .
REFERENCES Step-Growth Polymerization
As with the polymerization of ethylene and propylene by Ziegler-Natta catalyst, kinetic studies on the polymerization of butadiene also suggest that the active site is a bimetallic structure. I n the catalyst system EtAIClz-CoClz(CsHsN)z rate data indicated that the aluminum component took part in the formatioil of active centers and also accounted for changes ifi molecular weights of the polymeric products (22E). Kinetic studies of a closely related catalyst with the same monomer indicated that in this system two kinds of reactant sites were formed depending upon the presence or absence of small amounts of water. These sites differed both in the stereochemistry and molecular weight of the polymer formed a t each, but two publications on the same subject gave conflicting results (74E, 24E, 25E). Kinetic investi-
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