Radical Copolymerization Of Styrene Research Articles

Cationic Graft-Polymerization of 2-Methyl-2-oxazoline on Monodispersed Polymer-Coated Ultrafine Silica Particles

Cationic graft-polymerizations of 2-methyl-2-oxazoline on p-nitrobenzenesulfonate group-introduced silica composite particles, prepared by polymer coating of monodispersed colloidal silica of 470 nm in diameter, were studied. Ring-opening polymerization of the oxazoline was observed to take place on poly(styrene)-coated silica particles, derived from radical copolymerization of styrene, hydroxymethylstyrene and divinylbenzene, but most grafted polymer chains were dragged out for lack of cross-linking in the copolymer layer. The polymerization of the oxazoline on the composite surface, made from poly(maleic anhydride-styrene)-modified silica particles, led to the grafting of oligomer chains of octamer or nanomer, which were terminated by reaction with water molecules inside the particles.

Radical copolymerization behaviors of styrene and coumarin

The radical copolymerizations of styrene (M1) with coumarin (M2) (and 7-acetoxycoumarin) have been first carried out in benzene (and in DMF) at 60° C using AIBN as initiator. The terminal model monomer reactivity ratios (MRR) were determined by Fineman-Ross method, Kelen-Tudos method and nonlinear method. The respective estimated values are r1 = 43.08, r2 = 0.63; r1 = 39.17, r2 = 0.43; and r1 = 49.94, r2 = 1.04 for styrene-coumarin (S-C) system. For styrene-7-acetoxycoumarin (S-AC) system, the values are r1 = 51.44, r2 = 1.24; r1 = 50.56, r2 = 1.20 and r1 = 56.23, r2 = 1.48, respectively. The penultimate model MRRs are determined by Fenn-Barson method and nonlinear method to be r1= 49.18, r1′ = 2.01, r2 = r2′ = 0.43 and r1 = 51.21, r1′ = 0.86, r2= r2′ =0, respectively, for S-C system; r1 = 64.76, r1′= 3.46, r2 = r2′= 1.20 and r1 = 59.90, r1 = 0.57, r2 = r2′ = 0. respectively, for S-AC system. It is found that coumarin is about 1.2 times more reactive toward styrene-terminated radical than 7-acetoxycoumarin for steric reasons. The penultimate model of Fenn-Barson is fairly adequate in describing the copolymerization mechanism of styrene-coumarin system, while the terminal model is more suitable for styrene-7-acetoxycoumarin system.

Synthesis and photolysis of polymers containing crowned acetophenone moieties

Abstract The polymers containing crowned acetophenone moieties were prepared by the radical copolymerization of styrene or methyl acrylate with 4'-acryloylbenzo-15-crown-5 or '4 acryloybenzo-18-crown-6-. Upon irradiation at 313 nm in solution the main-chain scission of the polymers occurred accompanying the photoreduction of the carbonyl group of the crowned acetophenone units. The quantum yields for the main-chain scission and the photoreduction of the carbonyl groups were measured. The main-chain scission of the polymers was slightly enhanced on addition of cations which could be bound to the crown ether moieties. For the photolysis of the polymers in solid film the cross-linking and main-chain scission occurred simultaneously. The quantum yield for the Norrish type I reaction in solid films was 21 times higher than in solution. A mechanism for the photolysis of the polymers was discussed.

Critical Conditions of Microgelation in the Radical Copolymerization of Styrene with p-Divinylbenzene

Critical Conditions of Microgelation in the Radical Copolymerization of Styrene with <I>p</I>-Divinylbenzene

Architectural control of sugar-containing polymers by living polymerization: ring-opening polymerization of 2-oxazolines initiated with carbohydrate derivatives

Living polymerization of 2-oxazolines with bicyclic N-acetyl-D-glucosamines yielded new types of of inter-sugar distance controllable synthetic glycoconjugates. Furthermore, a graft copolymer consisting of a sugar moiety at the end of the side chain, an oligo(2-oxazoline) spacer unit in the side chain and an oligostyrene spacer in the backbone chain was prepared by radical copolymerization of styrene with a monodisperse ω-acryl-type poly(2-oxazoline) macromonomer

Copolymerization of Styrene with Chromium Acrylate Initiated by Styrene-Arsenic Sulfide Complex

Abstract The radical copolymerization of styrene with chromium acrylate in dimethyl formamide at 85±0.1°C was studied in presence of styrene-arsenic sulfide complex. The kinetic expression of styrene-arsenic for the system is Rp×[As2S3 0.5 [Sty]1.0 [Cr-acrylate]1.0, i.e. it follows ideal radical kinetics. The overall activation energy and average value of kp2 /kt are 77.0 kJ mol−1 and 0.45×10−51 mol−l s−1 respectively. The monomer reactivity ratios was determined as follows r1 (sty) = 0.82 and r2 (Cr-acrylate) = .08. The product of reactivity ratios reflect ideal copolymerization and therefore a strong alternating tendency in propagation reaction. The Alfrey-Price Q-e parameters for the metal acrylate was calculated and discussed.

Alternating Copolymerization of Styrene and N-(4-Bromophenyl)Maleimide

Abstract Free radical copolymerization of styrene (St) and N(4-bro-mophenyl)maleimide (4BPMI) in dioxane solution gave an alternating copolymer in all proportions of feed comonomer compositions. The monomer reactivity ratios were found to be r 1, = 0.0218 ± 0.0064 (St) and r 2, = 0.0232 ± 0.0112 (4BPMI), and the activation energy of the copolymerization reaction for the equimolar ratios of comonomer was E a, = 51.1 kJ/mol. The molecular weights of the copolymers obtained are relatively high, the T g's showed similar values (490 K), and the thermal stability is higher than that of polystyrene. The initial rate of copolymerization depends on the total concentration of the comonomers and the maximum occurred at higher 4BPMI mol fractions; however, the overall conversion is highest at equimolar comonomer composition. It has been shown that a charge-transfer complex participates in the process of copolymerization. The initial reaction rate was measured as a function of the monomer molar ratios, and the partici...

Novel Synthesis of a Macromonomer Having Organosilyl and Amino Groups

Abstract Reaction between dimethyldivinylsilane (1) and N,N′-diethyl-N-lithio-ethylenediamine (2a) in the presence of N,N′-diethylethylenediamine (3a) in THF at 20°C gave a monoadduct, 3,3-dimethyl-6-ethyl-3-sila-6,9-diaza-1-undecene (4a). An anionic self-polyaddition reaction of 4a in the presence of lithium diisopropylamide (LDA) proceeded to form oligomers. Each of the oligomers thus obtained was found to carry a polymerizable vinylsilane moiety at the oligomer chain terminal. As a result, a new type of macromonomer having alternating repeating units of ethylenediamine and organosilyl groups was synthesized. Acid-base titration showed the macromonomer to have unique characteristics on protonation of diamine moieties. Anionic polyaddition reactions between 1 and N-lithio-piperazine (2b) in the presence of piperazine (3b) also gave a macromonomer consisting of alternating repeating units of piperazine and organosilyl groups (4b). Radical copolymerizations of styrene with 5b gave comblike graft copolymers.

Synthesis and characterization of amphiphilic and microphase‐separated graft copolymers, 1. Synthesis and bulk characterization of polystyrene‐graft‐ω‐stearyl‐poly(ethylene oxide)

AbstractUsing the rigid and hydrophobic polystyrene (PS) chain as backbone, onto which flexible and hydrophilic stearyl‐poly(ethylene oxide) (SPEO) chains are grafted, a new kind of amphiphilic, microphase‐separated graft copolymer was synthesized using the macromonomer technique. Stearyl‐poly(ethylene oxide) macromonomers with acryloyl end‐group (SPEO‐A) were prepared through an end‐group exchange reaction of α‐stearyl‐ω‐hydroxypoly(ethylene oxide) (SPEO‐OH) and acryloyl chloride in the presence of triethylamine. The radical copolymerization of styrene with SPEO‐A was carried out under various experimental conditions. Following a careful examination of their purity, the structure of the prepared copolymers was characterized by means of IR, 1H NMR and GPC analyses. A new feasible method using first derivative UV spectrometry was developed for quantitative determination of the bulk composition of the graft copolymers. Copolymers with a wide range of bulk composition and satisfactory grafting degree were obtained.

Sequential interpenetrating polymer networks: heterogeneity of the first network and final structure

Various polystyrene/polybutadiene (PS/PB) interpenetrating polymer networks (IPNs) have been prepared by a sequential process. The first-formed network was obtained by radical copolymerization of styrene with divinylbenzene under various experimental conditions. Structural differences were obtained by varying the initial concentration of the solution when forming the network and/or the amount of crosslinker. Liquid PB was crosslinked within the PS network by a hydrosilylation reaction with chloroplatinic acid as catalyst. Transmission electron microscopy has shown that the two-phase morphology of the IPN cannot be attributed to the presence of imperfections in the tridimensional structure but can be related to the apparent swelling degree of the network formed first.

Metal-Ylide Complex-Initiated Radical Copolymerization of Methylmethacrylate and Styrene

Abstract Phenacyl dimethylsulfonium ylide complex of mercuric chloride (PDSY-HgCl2)-initiated radical copolymerization of styrene with methylmethacrylate (MMA) at 85 ± 0.1°C using dioxane as an inert solvent yields random copolymers as evidenced by NMR spectroscopy. The kinetic equation for the present system was Rp α [PDSY-HgCl2]0.5 [Sty]1.0 [MMA]1.0. The values of energy of activation (ΔE) and k2 p/k1 were 48.0 kJ mol−1 and 8.6 × 10−4 L mol−1 s−1, respectively. The mechanism of the reaction has also been proposed for the present system. The properties of copolymer were studied in the form of film. The film was highly absorptive for nitric acid but less absorptive for acetic acid. The film was water impermeable.

Direct polar conjugation in radical copolymerization of styrene with substituted styrenes

The electronic effects of substitutents on the values of monomer reactivity ratios in copolymerization of styrene with substituted styrenes have been isolated. The most important proved to be the direct polar conjugation of the substitutent with the nucleophilic reaction centre. A two-parameter correlation equation has been proposed which describes satisfactorily the experimentally determined reactivity of comonomers. The values of monomer reactivity ratios have been determined for copolymerization of styrene with para and meta-substituted aminostyrenes.

Solvent effect in radical copolymerization of styrene with p‐aminostyrene

Abstractp‐Aminostyrene (1, M1) and styrene (M2) were radically copolymerized at 60°C in various solvents. There is a significant solvent effect on monomer reactivity ratios, especially on r1, suggesting a specific interaction between the solvent and the polymer radical with the p‐aminostyrene moiety at the terminal position. In order to clarify the solvent factor influencing the relative reactivity, the hydrogen‐bond‐accepting basicity of the solvent (β) was determined from enhanced UV shifts for 1 relative to N,N‐dimethyl‐p‐aminostyrene. Regression analysis of r1 with the solvatochromic parameters revealed that β is the major factor responsible for r1‐variations.

Determination of monomer reactivity ratios in radical‐chain copolymerizations at high conversion

Abstract The ratios of the logarithmic concentrations of the two co‐monomers, β, for the radical copolymerizations of styrene with methyl methacrylate, vinyl chloride with vinyl acetate, methyl methacrylate with vinyl acetate, acrylic acid with acrylamide, methacrylic acid with methacrylamide and sodium methacrylate with methacrylamide are found to be independent of the degree of conversion. The monomer reactivivity ratios, r 1 and r2 , for these systems are determined by the relation, The values of r 1 and r2 at zero conversion obtained in this work coincide with the literature values; however, as the degree of conversion increases, significant changes in r 1 and r2 are observed. The onset of deviations of r 1 and r2 from their initial values depends on the pair of monomers being studied. The monomer reactivity ratios of the first two of the discussed systems both show positive deviations, but the latter four systems give one positive deviation and another negative.

Synthesis and characterization of lacquers based on styrene acrylic copolymers for applications in leather industry

Radical copolymerization of styrene with butylacrylate and/or maleic anhydride was carried out at 70°C, using benzoyl peroxide as an initiator in benzene/ethylacetate in order to prepare lacquers for top coats for use in leather industry. Copoly(styrene–butylacrylate) was characterized using IR and 13C-NMR spectroscopy. Thermal properties of the polymers were studied using thermogravimetric analysis and evaluated the integral procedural decomposition temperatures of polymers. The order of reaction and the activation energy for the thermal degradation of polystyrene, poly(ST-co-MAn) and St–BA–MAn terpolymer at different temperatures were calculated. Molecular weights were determined from gel permeation chromatography and viscosity measurements. Physical properties of the films were studied and compared with standard lacquers available for top coats in leather industry.

Copper(II) complexes of “polystyrene-bound DMAP”: Synthesis, structure and catalytic activity in the oxidative coupling of 2,6-dimethylphenol

The oxidative coupling of 2,6-dimethylphenol by Cu(II) complexes of “polystyrene-bound DMAP” was studied. The polymer was prepared by radical copolymerization of styrene and 4-( N-methyl- N- p-vinylbenzylamino)pyridine ( 1). Monomer ( 1) was prepared as described by Tomoi et al. [7]. By purifying the monomer by column chromatography instead of distillation, however, we succeeded in raising its yield by some 20%. Catalytic experiments supported by UV and EPR experiments revealed that in the catalytically active solution an equilibrium exists between dinuclear and mononuclear Cu(II) complexes. The concentration of the catalytically most active, mononuclear species Cu(II)(ligand) 4(OH)Cl increases on enhancing the ligand/Cu ratio and decreases on addition of an excess of copper-coordinating hydroxide ions. From this structural point of view the polymeric catalyst proved to behave just like low molar mass Cu(II)-DMAP complexes, although the mononuclear polymeric catalyst is more stable because of a polydentate effect. From the difference in reaction order in copper for unbound and polystyrene-bound DMAP catalysts, it was concluded that for the reoxidation step dimerization of Cu(I) complexes is needed, whereas mononuclear Cu(II) complexes are the most active species for the oxidation of DMP. The mentioned dimerization is promoted by the polymer chain. The specificity of the polystyrene-bound DMAP catalyst for formation of polyphenyleneoxide exceeds 95%.

Radical copolymerization of styrene with α-methylene-δ-valerolactone: role of depropagation in the mechanism

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTRadical copolymerization of styrene with α-methylene-δ-valerolactone: role of depropagation in the mechanismMitsuru Ueda, Toshiyuki Suzuki, Masami Takahashi, Zao Bang Li, Kiyohito Koyama, and Charles U. PittmanCite this: Macromolecules 1986, 19, 3, 558–565Publication Date (Print):March 1, 1986Publication History Published online1 May 2002Published inissue 1 March 1986https://doi.org/10.1021/ma00157a010RIGHTS & PERMISSIONSArticle Views188Altmetric-Citations15LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (886 KB) Get e-Alerts Get e-Alerts

Copolymerization of styrene with Zn(II), Co(II), Ni(II) and Cu(II) acrylates

AbstractThe radical copolymerization of styrene with Zn(II), Co(II), Ni(II) and Cu(II) acrylates in methanol at 60°C was studied and that of styrene with Cu(II) acrylate also in acetonitrile at 80°C. In a given period of time an increase of conversion was observed with increasing concentration of the first three metal acrylates in mixtures with styrene. With Cu(II) acrylate, however, a decrease of conversion was found. The monomer reactivity ratios were determined as follows: rSt = 1,10, r = 0,90; rSt = 1,74, r = 0,56; rSt = 1,83, r = 0,53; rSt = 5,94, r = 0,12 (in acetonitrile). The products of the reactivity ratios, almost equal to one, reflect an “ideal” copolymerization and therefore a very little alternating tendency in propagation reactions. The Alfrey‐Price Q‐e parameters for the metal acrylates were calculated and discussed.

Solution behavior of ampholytic styrene ionomers

AbstractIn this article are described the solution properties of ampholytic ionomers obtained by the radical copolymerization of styrene with the ion‐pair comonomer 3‐methacrylamidopropyltrimethylammonium, 2‐acrylamido‐2‐methylpropanesulfonate. The solution properties were studied in mixed solvents, with a good solvent for the polystyrene backbone and another for the ionic moieties, and in the individual good solvent of benzyl alcohol. The data obtained strongly support extensive intermolecular ionic interactions in solution.

Kinetic patterns of the synthesis and aspects of the structure of styrene copolymers with divinyl adipate

Radical copolymerization of styrene with divinyl adipate in benzene solution at 348 K initiated by benzoyl peroxide has been studied. A kinetic feature of the system studied is the two-stage character of the process. At the first stage the reaction proceeds with self inhibition leading to “translimitation” of the process on incomplete conversion, the depth of which depends on the composition of the initial monomer blend. At the second stage self-acceleration is observed accompanied by the formation of spatially crosslinked copolymers. The composition and structure of the copolymers obtained for different conversions and initial monomer ratios have been studied. It is shown that at the first stage reactive linear copolymers form with “pendant” double bonds which may be of practical interest in devising polymer-oligomer compositional materials.