Terpolymerization Of Styrene Research Articles

Block Copolymers Featuring Highly Photostable Photoacids Based on Vinylnaphthol: Synthesis and Self-Assembly.

The synthesis of a photoresponsive amphiphilic diblock quarterpolymer containing 5-vinyl-1-naphthol (VN) as a photostable photoacidic comonomer is presented. The preparation is realized via a sequential reversible addition fragmentation chain transfer (RAFT) polymerization starting from a nona(ethylene glycol) methyl ether methacrylate (MEO9 MA/"O") hydrophilic block, which is then used as a macro-RAFT agent in the terpolymerization of styrene (S), 2-vinylpyridine (2VP), and TBS-protected VN (tVN). The terpolymerization proceeds in a controlled fashion and two diblock quarterpolymers, P(Om )-b-P(Sx -co-2VPy -co-VNz ), with varying functional comonomer compositions are prepared. These diblock quarterpolymers form spherical core-corona micelles in aqueous media according to dynamic light scattering (DLS) and cryogenic transmission electron microscopy (cryo-TEM). Upon irradiation, the photoacids within the micellar core experience a drastic increase in acidity causing a proton transfer from the photoacid to neighboring 2VP units. As a result, the hydrophilic/hydrophobic balance of the entire assembly is shifted, and the encapsulated cargo is released.

Stereoselective Copolymerization of Styrene with Terpenes Catalyzed by an Ansa-Lanthanidocene Catalyst: Access to New Syndiotactic Polystyrene-Based Materials

The copolymerization of bio-renewable β-myrcene or β-farnesene with styrene was examined using an ansa-neodymocene catalyst, affording two series of copolymers with high styrene content and unprecedented syndioregularity of the polystyrene sequences. The incorporation of terpene in the copolymers ranged from 5.6 to 30.8 mol % (β-myrcene) and from 2.5 to 9.8 mol % (β-farnesene), respectively. NMR spectroscopy and DSC analyses suggested that the microstructure of the copolymers consists of 1,4- and 3,4-poly(terpene) units randomly distributed along syndiotactic polystyrene chains. The thermal properties of the copolymers are strongly dependent on the terpene content, which is easily controlled by the initial feed. The terpolymerization of styrene with β-myrcene in the presence of ethylene was also examined.

Seeded Semibatch Emulsion Copolymerization of Styrene, Butadiene, and Carboxylic Acids in a Pilot Plant Reactor

The seeded semibatch emulsion terpolymerization of styrene–butadiene–acrylic acid is investigated in a pilot plant scale reactor of 151 L. The effect of the styrene–butadiene ratio (S/BD ratio), amount of tertiary-dodecyl mercaptan as chain transfer agent (CTA), and two temperature profiles on the kinetics of the process (solids content, styrene conversion, particle size, and acid partitioning), by-product formation (4-phenyl cyclohexane, 4-PCH, and 4-vinyl cyclohexane, 4-VCH) and the molar mass distribution of the sol and the fraction of gel are studied.

Synthesis, Kinetics and Mechanism of Terpolymerization of Styrene, Vinyl Acetate with Acrylonitrile Initiated by P-Nitrobenzyl Triphenyl Phosphonium Ylide

Synthesis, Kinetics and Mechanism of Terpolymerization of Styrene, Vinyl Acetate with Acrylonitrile Initiated by P-Nitrobenzyl Triphenyl Phosphonium Ylide

Kinetics and mechanism of triphenylstibonium-ylide-initiated terpolymerization of styrene, methyl acrylate and acrylonitrile

Terpolymerization of styrene, methyl acrylate and acrylonitrile in 1,4-dioxane flushed with nitrogen, initiated by the ylide 1,2,3,4-tetraphenylcyclopentadiene-triphenylstibonium, was carried out for 1 h at 60 ± 0.2°C. The kinetic expression is R p α [I]0.27 [Sty]0.86 [MA]0.91 [AN]0.88. It indicates non-ideal radical kinetics due to primary radical termination, as well as degradative chain-transfer reactions. The overall activation energy, calculated from the slope of the Arrhenius plot, is 47 kJ/mol. The values of reactivity ratios, calculated using the Kelen–Tüdos method, are 0.25 ± 0.05 and 0.22 ± 0.05 for r 1 (Sty) and r 2 (MA + AN) respectively. The NMR spectrum shows a singlet at 7.1δ for the phenyl group in styrene and three distinct peaks at 2.1δ, 2.5δ and (3.4–3.8)δ for the methoxy group in methyl acrylate. The reaction was retarded by hydroquinone, which confirms the radical mode of terpolymerization. The possible mechanism for the synthesis of terpolymer has been elucidated.

A new approach to the joined estimation of the heat generated by a semicontiunuous emulsion polymerization Qr and the overall heat exchange parameter UA

This work is concerned with the coupled estimation of the heat generated by the reaction (Qr) and the overall heat transfer parameter (UA) during the terpolymerization of styrene, butyl acrylate and methyl methacrylate from temperature measurements and the reactor heat balance. By making specific assumptions about the dynamics of the evolution of UA and Q R, we propose a cascade of observers to successively estimate these two parameters without the need for additional measurements of on-line samples. One further aspect of our approach is that only the energy balance around the reactor was employed. It means that the flow rate of the cooling jacket fluid was not required.

Free radical Co‐ and terpolymerization of styrene, hydrogenated cardanyl acrylate, and cardanyl acetate

AbstractHydrogenated cardanyl acrylate (HCA) and cardanyl acetate (CACE) were synthesized from cardanol. The copolymerizations of HCA, CACE, and styrene (S) with methyl ethyl ketone peroxide (MEKP) and cobalt salt as the initiator were studied by FTIR. Based on FTIR results the reactivity ratios of the three copolymerization systems S–HCA, S–CACE, and HCA–CACE were determined by three different methods (Mayo‐Lewis, Fineman‐Ross, and Kelen‐Tüdos). Results obtained from the three methods are in good agreement. Instantaneous compositions and composition shift as a function of conversion is calculated for the S–HCA–CACE system with different feed compositions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1399–1409, 2003

Inhibition of Styrene Thermal Polymerization by Formulations Based on Quinone Dioxime and Sterically Hindered Phenols

A formulation based on quinone dioxime and a mixture of sterically hindered phenols tert-butylpyrocatechol-2,2'-methylenebis(6-tert-butyl-4-methylphenol) (Agidol-2) was suggested for inhibiting terpolymerization of styrene.

N-oxyl mediated free radical donor-acceptor co- and terpolymerization of styrene, cyclic maleimide monomers andn-butyl methacrylate

The N-oxyl mediated donor-acceptor copolymerization of styrene as a donor and the maleimides N-phenylmaleimide (NPI), N-benzylmaleimide (BMI), and N-cyclohexylmaleimide (CMI) as acceptor monomers is studied, using 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) as reversible capping agent and benzoyl peroxide (BPO) as initiator. These copolymerizations are characterized by high polymerization rates and very short induction periods. In bulk, a control of the molecular weights and the polydispersity is only possible for the weakest acceptor CMI. For the stronger acceptors BMI and NPI the polymerizations have to be performed in solution (anisol) to realize a linear increase of the molecular weight with conversion and polydispersities below Mw/Mn 1.55. The polymerization rates (NPI > BMI > CMI), the induction periods (CMI > BMI > NPI) and the total number of polymer chains (NPI > BMI > CMI) of the TEMPO mediated free radical donor-acceptor copolymerizations are a function of the acceptor strength of the maleimide monomers. As the main reason for the observed high reactivity, an “acceptor depending self-initiation”, proceeding via a Diels-Alder reaction mechanism, is discussed. Additionally, the concept of the “acceptor depending self-initiation” is used for the rate of acceleration of S/BuMA copolymerizations leading to poly(S-co-BuMA-co-maleimide) terpolymers with well-controlled molecular weights and narrow molecular weight distributions.

Effect of nonionic emulsifier on the production of multihollow polymer particles by the stepwise acid/alkali method

The effects of nonionic emulsifier on the formation of multihollow structures formed within sub-micron-sized polymer particles by the “acid/alkali method” proposed by the authors were examined. The original acid-swellable particles were produced by seeded emulsion terpolymerization of styrene, butyl acrylate, and dimethylaminoethyl methacrylate. The results indicate that the nonionic emulsifier had a great effect on the formation of multihollow particles.

Study on the Colloidal Stability Mechanisms of Acetal-Functionalized Latexes

In this work the colloid stability mechanisms of polystyrene latexes of acetal functionality are studied. These acetal latexes were prepared by two-step emulsion polymerization. The core was a seed of polystyrene, and the shell was synthesized by terpolymerization of styrene (St), methacrylic acid (MAA), and (methacrylamido)acetaldehyde dimethyl acetal (MAAMA) termonomers. The results were three latexes with different surface characteristics and with charged (carboxyl) and uncharged (acetal) surface groups provided by the MAA and MAAMA monomers, respectively. The anomalous electrokinetic behavior of the acetal latex was a consequence of their electric double layer structure, especially for one of the latexes with a significant highly charged “hairy” surface. The high colloidal stability of the acetal latexes was not explained by the classical Derjaguin−Landau−Verwey−Overbeck theory, and some correction factors, such as the Stern layer thickness (ionic size) and electrosteric stabilization mechanisms, were included in this theory. The last mechanism may be due to the existence of a hairy layer formed during the synthesis method. The stability factor was measured in order to obtain quantitative information about some parameters related to the interfacial properties of the colloidal particles, such as the Hamaker constant and diffuse potential. These parameters and the steric stabilization theory were used to calculate the total interaction energy at several electrolyte concentrations. By using the electrosteric mechanism to explain the stability results, it was possible to find a set of parameters that provide critical coagulation concentration values that were in accordance with the experimental one.

Terpolymerization of Styrene, Norbornene, and Carbon Monoxide with a Palladium Catalyst

In this work, the authors conducted the terpolymerization of carbon monoxide (CO), styrene (St), and norbornene (NBE) with Pd(CH3COO)2 in CH3OH under various molar ratios of norbornene to styrene at 90°C. Infrared spectra, 1H NMR and 13C NMR analyses confirmed that the NBE/St/CO terpolymers contain ketone, styrene unit, and ring structure of norbornene. Physical and thermal properties of the NBE/St/CO terpolyrners were also investigated by a differential scanning calorimeter (DSC), thermogravimetric analysis (TGA), solubility and X-ray diffraction analyses. The results indicated that glass transition temperature (Tg) of the terpolymers increased when norbornene was introduced. Terpolymer increased molar ratio of norbornene to styrene was found to not only be more thermally stable, but also to increase solubility. As the NBE/St molar ratio became larger than 0.375 in terpolymer, the terpolymers were soluble in chloroform, tetrahydrofuran (THF), methylene chloride, ethyl acetate, benzene, dimethylacetamide (DMAC), and pyridine. X-Ray diffraction results indicated that the terpolymer increased molar ratio of NBE/St in the terpolymer decreased the degree of crystallinity and the angle of maximum intensity owing to the bulky norbornene group. Hydrogenation of NBE/St/CO terpolymer with a reducing agent yielded a hydroxyl-containing polymer.

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.

Emulsion co- and terpolymerization of styrene, methyl methacrylate, and methyl acrylate. I. Experimental determination and model prediction of composition drift and microstructure in batch reactions

In Part I of this series the reactivity ratios of the comonomer pair methyl acrylate-methyl methacrylate were determined with low-conversion bulk polymerizations. It was shown that the binary reactivity ratios of the systems styrene-methyl acrylate, styrene-methyl methacrylate, and methyl acrylate-methyl methacrylate describe composition drift in low-coversion bulk terpolymerizations with these monomers reasonably well. A computer model was developed to simulate the composition drift in emulsion co- and terpolymerizations. The composition drift in two batch emulsion copolymerization systems (styrene-methyl acrylate and methyl acrylate-methyl methacrylate) and one emulsion terpolymerization system (styrene-methyl acrylate-methyl methacrylate) was investigated both experimentally and with the model. Experimental results were compared with model calculations. The copolymer chemical composition distributions (CCD) were determined with gradient polymer elution chromatography (GPEC®). This technique was also used for the first time to obtain information about the extent of composition drift in emulsion terpolymerizations. Cumulative terpolymer compositions were determined with 3H-NMR as a function of conversion and with this information the three-dimensional CCD was obtained. The composition drift was analyzed with respect to free radical copolymerization kinetics (reactivity ratios) and monomer partitioning. It was shown that in most emulsion copolymerizations the composition drift is mainly determined by the reactivity of the monomers and to a lesser extent by monomer partitioning, except in systems where there is a large difference in water solubility. The model predictions for cumulative terpolymer composition as a function of conversion and the three-dimensional terpolymer CCD showed excellent agreement with the experiments. The GPEC® elution chromatogram of the terpolymer was found to be in accordance with the predicted CCD and the experimentally determined CCD. © 1996 John Wiley & Sons, Inc.

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

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

Emulsion co‐ and terpolymerization of styrene, methyl methacrylate, and methyl acrylate. I. Experimental determination and model prediction of composition drift and microstructure in batch reactions

Emulsion co‐ and terpolymerization of styrene, methyl methacrylate, and methyl acrylate. I. Experimental determination and model prediction of composition drift and microstructure in batch reactions

Covalent coupling of antibodies to aldehyde groups on polymer carriers

The aim of the present work is to prepare and characterize a functionalized latex with acetal groups on the surface and to obtain the covalent coupling of an a-CRP IgG protein. The acetal latex was synthesized by means of a core-shell emulsion polymerization in a batch reactor. The core was a seed of polystyrene and the shell was obtained by terpolymerization of styrene, methacrylic acid and methacryloylacetaldehyde di(n.methyl)acetal. The latex was characterized by TEM and conductimetric and potentiometric titration, in order to obtain the particle size distribution and the amount of carboxyl and acetal groups on the surface, respectively. Several latex-protein particles with the IgG physically or chemically bound to the surface were obtained by modifying the incubation conditions. In the covalent coupling experiments of the IgG, the protein physically adsorbed was removed by redispersion of the complexes in the presence of a non-ionic surfactant (Tween 20). The latex-protein complexes were characterized from the electrokinetic point of view with the aim to determine the isoelectric point of the complexes and to detect any difference in the electric state of the protein when these molecules are physically or chemically coupled to the surface. The final part of this work was to study the immunoreactivity of several latex-IgG complexes at several experimental conditions. By measuring the change in the turbidity after the addition of CRP antigen into the dispersion, it was possible to compare the immunoreactivity results when the protein is physically or chemically bound to the surface, and to study the effect of the presence of a surfactant in the reaction medium.

Radical copolymerization of an electron‐accepting monomer, methyl cis‐β‐cyanoacrylate, with styrene or acrylonitrile

AbstractThe electron‐accepting property and the radical copolymerizability of methyl cis‐β‐cyanoacrylate (MCA) were studied. The monomer was found to form a contact charge‐transfer complex with styrene (ST) in chloroform at 25°C and behaved as a weak electron acceptor. The copolymerization parameters were determined in dioxane at 50°C for systems involving ST or acrylonitrile (AN) as comonomer. The reactivity ratio of ST or AN was estimated by the Kelen–Tudös method considering both the penultimate unit effect and no homopropagation of MCA. The penultimate effect for the system ST–MCA was large compared with that for the system ST–dimethyl maleate (DMM), indicating that a polar effect is mainly responsible for the penultimate effect. The terpolymerization of ST, MCA, and maleic anhydride (MA) was also studied to compare the reactivity of MCA with that of MA.

Silyl enol ethers as monomer. I. Radical copolymerizability of α‐trimethylsilyloxystyrene

Abstractα‐Trimethylsilyloxystyrene (TMSST), the silyl enol ether of acetophenone, was not homopolymerized either by a radical or a cationic initiator. Radical copolymerization of TMSST with styrene (ST) and acrylonitrile (AN) in bulk and the terpolymerization of TMSST, ST, and maleic anhydride (MA) in dioxane were studied at 60°C and the polymerization parameters of TMSST were estimated. The rate of copolymerization decreased with increased amounts of TMSST for both systems. Monomer reactivity ratios were found as follows: r1 = 1.48 and r2 = 0 for the ST (M1)–TMSST (M2) system and r1 = 0.050 and r2 = 0 for the AN (M1)–TMSST (M2) system. The terpolymerization of ST (M1), TMSST (M2), and MA (M3) gave a terpolymer containing ca. 50 mol % of MA units with a varying ratio of TMSST to ST units and the ratio of rate constants of propagation, k32/k31, was found to be 0.39. Q and e values of TMSST were determined using the values shown above to be 0.88 and −1.13, respectively. Attempted desilylation by an acid catalyst for the copolymer of TMSST with ST afforded polystyrene partially substituted with hydroxyl groups at the α‐position.

Copolymers of Bromine-Containing Monomers. 6. Terpolymerization of Styrene, Acrylonitrile, and 2, 4, 6-Tribromophenyl Methacrylate

Abstract 2,4,6-Tribromophenyl methacrylate was terpolymerized with styrene and acrylonitrile in aqueous emulsion and dimethylformamide solution. Experimental terpolymerization data agreed well with values calculated from the Alfrey-Goldfinger equation. The relationship between monomer feed and terpolymer compositions is presented on a triangular coordinate graph. The lines of unique composition for each monomer and the lines of binary azeotropic composition for monomer pairs were established for both systems. No true azeotropic composition could be determined, but a “pseudo-azeotropic” region was established. The experimental terpolymerization data agreed well with the theoretical values over a wide range of monomer composition up to high conversions. The influence of 2,4,6-tribromophenyl methacrylate on the thermal stability and flammability behavior of the terpolymers is described.