Terpolymerization of acrylonitrile,styrene, and 2,4,6-tribromophenyl acrylate

Acrylonitrile was terpolymerized with styrene and 2,4,6-tribromophenyl acrylate in aqueous emulsion and dimethylformamide solution. Experimental terpolymerization data agreed well with calculations based on the Alfrey–Goldfinger equation. Triangular coordinate graphs show the feed/terpolymer relationships; the lines of unique and binary azeotropic compositions were identified. No points of true azeotropic composition were found but a “pseudo-azeotropic” region was recognized. The experimental data of the emulsion terpolymerization experiment agreed well with the theoretical curves over a wide range of monomer compositions up to high conversions. Incorporation of 2,4,6-tribromophenyl acrylate in the terpolymer decreased the thermal stability but improved the flame retardancy of the terpolymers.     

Copolymers of Bromine-Containing Monomers. 5. Terpolymerization of Acryionitrile,Styrene, and Pentabromophenyl Acrylate

The terpolymerization of acryionitrile, styrene, and pentabromophenyl acrylate in dimethylformamide solution was investigated. Experimental terpolymerization data agreed well with calculations using the Alfrey-Goldfinger equation. The relationship between monomer feed and terpolymer compositions are presented on triangular coordinate graphs, and the lines of unique and the lines of binary azeotropic composition were identified. No point of true ternary azeotropic composition was found but a “pseudoazeotropic” region was identified. The experimental results of the terpolymerization agreed well with the theoretical curves over a wide range of monomer composition up to high conversions. The influence of pentabromophenyl acrylate units on the thermal and flammability characteristics of the terpolymers are described.     

Terpolymerization of Butadiene,Acrylonitrile, and Methacrylic Acid

Abstract

The terpolymerization of butadiene, acrylonitrile, and methacrylic acid in emulsion, using potassium persulfate as initiator and sodium dioctylsulphosuccinate as emulsifier, was investigated. For the binary system butadiene (M₁) and methacrylic acid (M₂), the following monomer reactivity ratios were determined: r₁₂ = 0.18 ± 0.05 and r₂₁ = 0.52 ± 0.09. When polymerizations were stopped at low conversions they gave terpolymers which show good agreement between experimental and theoretical copolymerization composition data, calculated from the Alfrey-Goldfinger equation. The relationships between monomer feed and terpolymer compositions are presented on triangular coordinate graphs as proposed by Slocombe. By using a computer program, the lines of unique composition and the lines of binary azeotropic composition were established. No point of true azeotropic composition was found, but a “pseudo-azeotropic” region was recognized. The influence of composition on glass transition temperature and thermal characteristics of the terpolymers is described.     

Thermooxidative stabilization of acrylonitrile terpolymers obtained under reversible chain-transfer conditions: Effects of synthesis temperature and initiation method

The terpolymerization of acrylonitrile, methyl acrylate, and itaconic acid mediated by a reversible addition-fragmentation chain transfer agent, dibenzyl trithiocarbonate, and initiated by AIBN at 80°C, potassium persulfate at 45–55°C, and radiolysis at 20°C is studied. In all the cases, polymerization proceeds via the pseudoliving mechanism, which is preserved up to ultimately high monomer conversions (80–90%). According to FTIR ATR and NMR spectroscopy, all the synthesized terpolymers are characterized by close monomer compositions and their degree of branching is too low to be detected spectroscopically. However, the thermal behaviors of terpolymers obtained by polymerizations at various temperatures are different, namely, the lower the temperature of terpolymer synthesis, the slower the thermooxidative stabilization processes occurring in it.     

Terpolymerization of methyl methacrylate, poly(ethylene glycol) methyl ether methacrylate or poly(ethylene glycol) ethyl ether methacrylate with methacrylic acid and sodium styrene sulfonate: determination of the reactivity ratios

Materials bearing ionic monomers were obtained through free radical terpolymerization of methyl methacrylate (MMA), poly(ethylene glycol) methyl ether methacrylate (PMEM) or poly(ethylene glycol) ethyl ether methacrylate (PEEM) with methacrylic acid (MA) and sodium styrene sulfonate (NaSS). The reactions were carried out in dimethyl sulfoxide using azobis(isobutyronitrile) as initiator. The reactivity ratios of the different couple of monomers were calculated according to the general copolymerization equation using the Finnemann-Ross, Kelen-Tüdos and Tidwell-Mortimer methods. The values of the reactivity ratios indicate that the different monomer units can be considered as randomly distributed along the chains for terpolymerizations of MMA, PMEM or PEEM with MA and NaSS. The average composition of the comonomers in the different terpolymers were calculated, showing a good agreement between the experimental and theoretical compositions. The instantaneous compositions are constant until about 70% of conversion. For higher conversions, the insertion of ionic monomers increases or decreases according to the system studied.     

Influence of the third monomer on lauryl methacrylate–methyl methacrylate emulsion terpolymerization

An experimental study shows how the emulsion terpolymerization of lauryl methacrylate (LMA) and methyl methacrylate is influenced by the nature of the third monomer. The third monomer is either glycidyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, or styrene. We report the synthesis of terpolymer particles with an appreciably high content of the very hydrophobic LMA (between 0.2515 and 0.238 molar fraction in the monomer mixture) in 60:40 weight water/ethanol mixture as the continuous phase, poly(vinyl pyrrolidone) as a polymeric steric stabilizer, and potassium peroxodisulfate as the initiator. The emulsion terpolymerization proceeds smoothly without the formation of coagulum and leads to particles with an average diameter clearly below 1 μm. We discuss the overall polymerization behavior regarding conversion–time curves, particle morphology, and glass transition temperature of the terpolymers in dependence of the lyophilicity/lyophobicity of the monomer mixture.     

Terpolymerization of ethyl methacrylate,N‐phenylmaleimide,and itaconic acid

The terpolymerization of ethyl methacrylate (EMA), N‐phenylmaleimide (NPMI), and itaconic acid (IA) was investigated. The terpolymer composition was determined by elemental analysis and ¹H NMR spectroscopy. The reactivity ratios of the three binary systems (EMA/NPMI, EMA/IA, and NPMI/IA) were calculated and used for the calculation of the terpolymer composition with the terminal model equations. A comparison between the experimental and theoretical compositions was made. The rate of the terpolymerization process was measured dilatometrically at two total monomer concentrations; this was done to establish the presence of intermolecular interactions between the investigated monomers. The thermal analysis of the obtained terpolymers was performed by thermogravimetric analysis. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3180–3187, 2003     

Organotin polymers—II.Copolymerization parameters for tributyltin methacrylate with methyl acrylate,ethyl acrylate,butyl acrylate and acrylonitrile

Copolymerizations of tributyltin methacrylate (M₁) with methyl acrylate, ethyl acrylate, n-butyl acrylate and acrylonitrile were carried out in solution at 70° using azobisisobutyronitrile as initiator. Copolymer compositions were determined by tin analysis; monomer reactivity ratios were calculated by Fineman-Ross and Kelen-Tüdös methods. The reactivities of acrylic esters decrease as the alkyl group becomes bulkier. Azeotropic copolymers could be formed from tributyltin methacrylate with butyl acrylate and with acrylonitrile. The structures of M₁ and its azeotropic copolymers have been investigated by infrared spectroscopy.     

Pulsed laser terpolymerization of styrene,methyl methacrylate and methyl acrylate

The propagation rate coefficient of the terpolymerization of styrene, methyl methacrylate and methyl acrylate in bulk was successfully determined at three different monomer compositions. The temperature was varied between 18 and 80°C. The resulting data at 50°C were not in agreement with predictions according to the terminal model with binary reactivity ratios that have been determined by fitting copolymer composition data with the terminal model. This indicates that here also the penultimate unit affects the kinetics.     

High solids content emulsion terpolymerization of vinyl acetate,methyl methacrylate and butyl acrylate. II. Open loop composition control

A method for the calculation of the optimal monomer addition policies for polymer composition control in emulsion terpolymerization is developed. The method is applied to reactors with and without limited heat removal capacity. A mathematical model that incorporates the main features of the vinyl acetate/methyl methacrylate/butyl acrylate high solids content emulsion terpolymerization system allows the calculation of the composition of the initial charge of the reactor and the time-dependent monomer addition rates required. © 1994 John Wiley & Sons, Inc.     

Terpolymerization of sulfur dioxide or maleic anhydride with unsaturated compounds under ultraviolet irradiation

The effect of ultraviolet irradiation on the terpolymerization was investigated. In the terpolymerizations of sulfur dioxide–butene-1–acrylonitrile, sulfur dioxide–butene-1–n-butyl acrylate, and maleic anhydride–allyl chloride–acrylonitrile systems, the composition of the terpolymers prepared under ultraviolet irradiation was different from those prepared in the dark. The unit content of sulfur dioxide and butene-1 or of maleic anhydride and allyl chloride in the terpolymer increased under ultraviolet irradiation. The nature of the growing end under ultraviolet irradiation is supposed to be the same as that of the dark polymerization on the basis of the same solvent effect on the terpolymer composition, the rate of polymerization and the molecular weight of polymer. The experimental results suggest that the complex between sulfur dioxide and butene-1 or maleic anhydride and allyl chloride might be excited by ultraviolet light and the excited complex may participate in the terpolymerization.     

Studies on the nature of multiple glass transitions in low acrylonitrile,butadiene–acrylonitrile rubbers

A study of the occurrence of multiple glass transitions in acrylonitrile–butadiene rubbers (NBR) has been made. Copolymerization theory was used to predict the change in comonomer composition with conversion for comonomer ratios both above and below the calculated azeotropic composition of 64% butadiene/36% acrylonitrile by weight. The results of these calculations suggested that multiple glass transitions, which occur only in NBR of less than 36% acrylonitrile, were due to an incompatibility of copolymer species of divergent comonomer compositions. This was shown by differential thermal analysis to be the case for various experimental polymers of known comonomer composition. A series of NBR's was prepared by incremental addition of acrylonitrile monomer during polymerization, and the resultant glass transition temperatures were evaluated. Results obtained showed that experimental samples which had single glass transitions also had a much narrower spread of comonomer species than the corresponding rubber polymerized with the use of full initial charge of both monomers. The data indicate that NBR's having a single glass transition, regardless of acrylonitrile content, may be prepared by incremental addition of acrylonitrile monomer during polymerization. Existing copolymerization theory appears to be adequate for predicting incremental monomer addition schedules suitable for the polymerization of NBR's having a single glass transition.     

Emulsion co- and terpolymerization of styrene,methyl methacrylate and methyl acrylate. II. Control of emulsion terpolymer microstructure with optimal addition profiles

An optimal addition profile for the preparation of a chemically homogeneous emulsion terpolymer of styrene, methyl methacrylate, and methyl acrylate was determined using a recently developed model for describing composition drift in emulsion co- and terpolymerizations. TRISEPS, described in Part I of this series. The model uses recently published simplified equations to describe monomer partitioning and the terminal model for describing terpolymer composition. The optimal addition rate profile was determined from the calculated optimal addition profile with a purely empirical and iterative method. With gradient polymer elution chromatography (GPEC®) the homogeneity and/or heterogeneity of the terpolymers prepared in the iterative series of experiments could be determined and compared to the heterogeneity of the corresponding batch terpolymer described in Part I. It was shown that a homogeneous terpolymer could be obtained indicating that the simplified equations for monomer partitioning and the terminal model for terpolymer composition describe the system adequately. It was also shown that GPEC® was useful in the determination of the optimal addition rate profile. © 1996 John Wiley & Sons, Inc.     

Studies on the charge-transfer complex and polymerization. Part XIII. Dilution and solvent effects in radical terpolymerization

In the terpolymerization of 2-chloroethyl vinyl ether—maleic anhydride—acrylonitrile and p-dioxene—maleic anhydride—acrylonitrile systems the compositions of the terpolymers obtained from feed of the same mole fraction were found to be changed beyond the limit of error for the given amounts and kinds of solvent. This change was considered to be divided into two parts. The first part, discussed quantitatively, was due to a dilution effect on the equilibrium complex formation between donor and acceptor monomer, and the second, as tentatively proposed, was due to a solvent effect on the reactivity of the complex.     

Quasiliving Carbocationic Polymerization. XVI. Forced Ideal Terpolymerization of Styrene-α-Methylstyrene-lsobutylene

Forced ideal carbocationic terpolymerization of styrene/α-methylstyrene/isobutylene systems has been achieved by continuous addition of mixed monomer feeds to 2-chloro-2,4,4-trimethylpentane/TiCl₄ initiator/coinitiator charges dissolved in n-hexane/methylene chloride solvent mixtures. The compositions of terpolymers were uniform and identical to those of the feeds in the concentration ranges studied. The number-average molecular weights increased monotonously with the amounts of monomers consumed; however, pronounced chain transfer to monomer was evident. The microstructure of the products was investigated ¹³C-NMR spectroscopy. According to dual detector GPC, ¹³C-NMR and DSC data true terpolymers have formed.     

Terpolymerization of maleic anhydride with vinyl monomers

The relative reactivity of vinyl monomers characterized by electron donor and electron acceptor properties in free radical terpolymerization with maleic anhydride has been compared on the basis of product composition analysis. Terpolymers containing ca. 50 mol % of maleic anhydride were obtained in systems containing two electron donor monomers and the relative reactivity of them increases in the following order: 1-hexene < propylene ≈ isobutylene < styrene < isoprene < 1,3-butadiene. In systems consisting of an electron donor monomer and two electron acceptor monomers (i.e., maleic anhydride and an acrylic monomer), the composition of the terpolymers formed depends essentially on the resonance stabilization of the electron donor monomer. With a rise of their resonance stabilization, the content of acrylic monomeric units decreases and the share of alternating sequences of the electron donor and maleic anhydride monomeric units increases. It was found that the relative reactivity of maleic anhydride in all such systems is much greater than that predicted on the basis of reactivity ratios determined in binary systems. The relative reactivity of the studied acrylic monomers decreases in the order: methyl methacrylate > methyl acrylate > acrylonitrile. In the presence of catalytic amounts of ZnCl₂ the content of acrylic monomeric units clearly increases in the products obtained, mainly as a result of homopropagation. The results obtained are discussed in terms of the classical mechanism of propagation and the complex participation model.     

Kinetics of Free Radical Copolymerization. V. Copolymerization of Ethyl Acrylate with Styrene. Composition of Copolymers

The composition of copolymers formed at 50°C in ethyl acrylate/ styrene/azo-bis-isobutyronitrile/benzene systems of different composition was investigated. The experimental composition data (based on the elementary analysis of copolymers) were evaluated by the η-ζ transformation method. Finite monomer conversions were taken into account. The classical composition equation was found to describe the system under investigation. The reactivity ratios are p ₁ = 0.152 ± 0.006; p ₂ = 0.787 ± 0.023. The free radical copolymerization of ethyl acrylate and styrene has been investigated in benzene solution at 50°C. Our results on the initiation kinetics were disclosed in our recent publication [1]. Now we are reporting on our studies concerning the composition of ethyl acrylate/styrene copolymers.     

Complex‐radical terpolymerization of acceptor–donor–acceptor systems: Maleic anhydride (n‐butyl methacrylate)–styrene–acrylonitrile

Some features of radical ternary copolymerization of maleic anhydride (MA)–styrene (St)–acrylonitrile (AN) and n‐butyl methacrylate (BMA)–St–AN acceptor–donor–acceptor monomer systems have been revealed. The terpolymer compositions and kinetics of copolymerizations were studied in the initial and high conversion stages. The considerable divergence in the copolymer compositions was observed when a strong acceptor MA monomer was substituted with BMA having comparatively low acceptor character in the ternary system studied. Obtained results show that terpolymerization proceeded mainly through “complex” mechanism in the state of near binary copolymerization of St…MA (or BMA) and AN…St complexes only in the chosen ratios of complexed monomers. The terpolymers synthesized have high thermal stabilities (295–325 °C), which is explained by possible intermolecular fragmentation of AN‐units through cyclization and crosslinking reactions during thermotreatment in the isothermal heating conditions. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2652–2662, 2000     

Effect of ultraviolet irradiation on terpolymerization of sulfur dioxide with two unsaturated compounds

The terpolymerization of sulfur dioxide, butene-1 and acrylonitrile affords terpolymers containing equimolar amounts of sulfur dioxide and butene-1 with various acrylonitrile contents. Ultraviolet irradiation was found to accelerate the polymerization and decrease the acrylonitrile content in the polymer. This fact is interpreted by a mechanism through a copolymerization of sulfur dioxide–butene-1 complex and acrylonitrile, whereby the polymerizability of sulfur dioxide–butene-1 complexed monomer may be accelerated by ultraviolet light. In fact, a binary system of sulfur dioxide and butene-1 was found to be accelerated by ultraviolet irradiation, and it affords a maximum rate at a 1:1 composition of feed monomer. Ultraviolet light of 250–300 mμ wavelength is effective for the initiation and the propagation. This may be ascribed to the ultraviolet absorption of the sulfur dioxide–butene-1 complex. The temperature coefficient was measured in both dark and ultraviolet irradiation reactions. The ultraviolet irradiation enhances the reactivity of sulfur dioxide–butene-1 complexed monomer at low temperature. In the terpolymerization with sulfur dioxide, isoprene, and butadiene, the ratio of isoprene and butadiene in the terpolymer was not altered by ultraviolet irradiation because both monomers from complexes with sulfur dioxide, perhaps having the same temperature coefficient for the polymerization.     

Controlled copolymerization of acrylonitrile in bulk via the reversible addition-fragmentation chain-transfer mechanism

The pseudoliving radical binary copolymerization of acrylonitrile with methyl acrylate, styrene, n-butyl acrylate, and tert-butyl acrylate in bulk in the presence of the reversible addition-fragmentation chain-transfer agent dibenzyl trithiocarbonate is performed for the first time. The addition of trithiocarbonate makes it possible to prepare a narrowly dispersed visually optically transparent copolymer in a wide range of monomer-feed compositions even at limiting conversions. Conditions for the synthesis of acrylonitrile copolymers with controlled molecular masses and narrow molecular-mass distributions are ascertained. In the above copolymers, the trithiocarbonate group is shown to be located within the chain.