Radical polymerization of methyl methacrylate (MMA) initiated by KHSO5 – BTBAC system - a kinetic study

Kinetics of free radical polymerization of methyl methacrylate using potassium peroxomonosulfate as initiator in the presence of benzyltributylammonium chloride (BTBAC) as phase transfer catalyst was studied. The polymerization reactions were carried out under nitrogen atmosphere and unstirred conditions at a constant temperature of 60°C in ethyl acetate/water bi-phase system. The role of concentrations of monomer, initiator, catalyst, temperature, acid and ionic strength on the rate of polymerization (R_p) was ascertained. The orders with respect to monomer, initiator and phase transfer catalyst were found to be 1.5, 0.5 and 0.5 respectively. The rate of polymerization (R_p) is independent of ionic strength and pH. Based on the kinetic results, a suitable mechanism is proposed.     

Synthesis and polymerisation of maleoyl-L-histidine monomers and addition of histidine to an ethylene-alt-maleic co-polymer

Kinetics of free radical polymerization of methyl methacrylate using potassium peroxomonosulfate as initiator in the presence of benzyltributylammonium chloride (BTBAC) as phase transfer catalyst was studied. The polymerization reactions were carried out under nitrogen atmosphere and unstirred conditions at a constant temperature of 60°C in ethyl acetate/water bi-phase system. The role of concentrations of monomer, initiator, catalyst, temperature, acid and ionic strength on the rate of polymerization (R_p) was ascertained. The orders with respect to monomer, initiator and phase transfer catalyst were found to be 1.5, 0.5 and 0.5 respectively. The rate of polymerization (R_p) is independent of ionic strength and pH. Based on the kinetic results, a suitable mechanism is proposed.     

Polymerization of acrylonitrile using potassium peroxydisulfate as an initiator in the presence of a multisite phase‐transfer catalyst: A kinetic study

In this article, the kinetics and mechanism of the free‐radical polymerization of acrylonitrile (AN) using potassium peroxydisulfate (PDS) as a water‐soluble initiator in the presence of synthesized 1,4‐bis(triethyl methyl ammonium) benzene dichloride (DC‐X) as a phase‐transfer catalyst (PTC) were studied. The polymerization reactions were carried out under inert and unstirred conditions at a constant temperature of 60 ± 1°C in cyclohexane/water biphasic media. The rate of polymerization (R_p) increased with an increase in the concentrations of AN, PTC, and PDS. The order with respect to the monomer, initiator, and PTC was found to be 1.0, 0.5, and 0.5, respectively. R_p was independent of the ionic strength and pH of the medium. However, an increase in the polarity of the solvent slightly increased the R_p value. On the basis of the obtained results, a mechanism is proposed for the polymerization reaction. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Phase‐transfer catalysis: Free‐radical polymerization of acrylonitrile using potassium peroxomonosulphate– tetrabutyl phosphonium chloride catalyst system: A kinetic study

This article presents the systematic study of kinetics and mechanism of phase‐transfer‐catalyzed free‐radical polymerization of acrylonitrile (AN) and water‐soluble initiator potassium peroxomonosulphate (PMS) coupled with tetrabutyl phosphonium chloride (TBPC) in ethyl acetate/water biphase system in the temperature range 45–55°C at fixed pH and ionic strength. The rate of polymerization increases with an increase in concentrations of AN, PMS, and phase transfer catalyst, PTC. It was observed that R_p is proportional to [AN]^1.5, [KHSO5₅⁻]^0.5, and [TBPC]^0.5. A suitable kinetic scheme has been proposed to account for the experimental observations and its significance was discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1564–1571, 2000     

Polymerization of Butyl Acrylate using Potassium Peroxy Disulfate as Initiator in the Presence of Phase Transfer Catalyst—A Kinetic Study

The kinetics and mechanism of free radical polymerization of butyl acrylate (BA), using potassium peroxydisulfate (K₂S₂O₈) as initiator in the presence of propiophenonebenzyldimethylammonium chloride (PPBDMAC) as phase transfer catalyst (PTC) has been studied. The reactions were carried out under inert, unstirred conditions and at a constant temperature of 60°C in cyclohexanone/water biphase media. The dependence of the rate of polymerization (R_p) on various experimental conditions such as different concentrations of monomer, initiator, phase transfer catalyst, varying acid and ionic strength, temperature, and volume fraction of aqueous phase were studied. The order with respect to monomer, initiator, and the phase transfer catalyst were found to be 1.5, 0.5, and 0.5, respectively. The rate of polymerization was independent of acid and ionic strength. Based on the results, a mechanism has been proposed for the polymerization reaction.     

Kinetics of radical polymerization of glycidyl methacrylate initiated by multi‐site phase transfer catalyst–potassium peroxydisulfate in two‐phase system

The kinetics of radical polymerization of glycidyl methacrylate, initiated by the free radicals formed in situ in the multi‐site phase transfer catalyst (PTC), 1,1,2,2‐tetramethyl‐1‐benzyl‐2‐n‐propylethylene‐1,2‐diammonium bromide chloride–potassium peroxydisulfate system was studied in an aqueous–organic two‐phase media at 60°C ± 1°C under inert and unstirred condition. The rate of polymerization (R_p) was determined at various concentrations of the monomer, initiator, catalyst, and volume fraction of aqueous phase. The effect of acid, ionic strength, and water‐immiscible organic solvents on the R_p was examined. The temperature dependence of the rate was studied, and activation parameters were calculated. R_p increased with an increase in the concentrations of monomer, initiator, multi‐site PTC, and increase in the polarity of solvent and temperature. The order with respect to monomer, initiator, and multi‐site PTC was found to be 0.50. A feasible free‐radical mechanism consistent with the experimental data has been proposed, and its significance was discussed. The synthesized polymer was confirmed by Fourier transform infrared spectral analysis. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Aqueous polymerization of methyl methacrylate initiated by ceric ion reducing agent systems in sulfuric acid medium

Polymerization of methyl methacrylate (MMA) was carried out in aqueous sulfuric acid medium at 30°C using ammonium ceric sulfate (ACS)/methyl ethyl ketone (MEK) and ammonium ceric sulfate/acetone as redox initiator systems. A short induction period was observed with both the initiator systems, as well as the attainment of limiting conversion for polymerization reactions. The rate of ceric ion consumption, R_ce, was first order with respect to Ce(IV) concentration in the concentration range (0.5–5.5) × 10⁻³M, and 0.5 order with respect to reducing agent concentration in the concentration ranges (0.0480–0.2967M) and (0.05–0.3912M) for Ce(IV)–MEK and Ce(IV)–acetone initiator systems, respectively. A fall in R_ce was observed at higher reducing agent concentrations. The plots of R_ce versus reducing agent concentrations raised to the half power yielded straight lines passing through the origin, indicating the absence of complex formation between reducing agents and Ce(IV). The addition of sodium sulfate to maintain constant sulfate ion concentration in the reaction medium could bring down the R_ce values in the present reaction systems. The rate of polymerization of MMA, R_p, increased with increase in Ce(IV), reducing agent, and monomer concentrations for the Ce(IV)–MEK initiator. The rate of polymerization of MMA is independent of Ce(IV) concentration and increased with an increase in reducing agent and monomer concentrations for the Ce(IV)–acetone initiator. At higher concentrations of reducing agent (0.4–0.5M), a steep fall in R_p values was observed with both the initiator systems. The orders with respect to Ce(IV), MEK, and MMA using the Ce(IV)–MEK initiator were found to be 0.23, 0.2, and 1.29, respectively. The orders with respect to Ce(IV), acetone, and MMA using the Ce(IV)–acetone initiator were found to be zero, 0.42, and 1.64, respectively. Maintaining constant [SO²⁻₄] in the reaction medium could bring down R_p values for the Ce(IV)–MEK initiator system. On the other hand, a rise in R_p values with an increase in [Na₂SO₄] could be observed when constant [SO²⁻₄] was maintained in the reaction medium for the Ce(IV) on reducing agent, production of radicals, initiation, propagation, and termination of the polymeric radicals by bimolecular interaction is proposed. An oxidative termination of primary radicals by Ce(IV) is also included. © 1996 John Wiley & Sons, Inc.     

Kinetics and mechanism of free radical grafting of methyl acrylate onto sago starch

The graft copolymerization was carried out by methyl acrylate with sago starch in which ceric ammonium nitrate was used as an initiator. It has been found that the rates of graft polymerization and grafting efficiency were dependent upon the concentration of ceric ammonium nitrate (CAN), methyl acrylate (MA), sago starch (AGU, anhydro glucose unit), mineral acid (H₂SO₄), and as well as reaction temperature and period. A rate equation of polymerization was established from the proposed reaction mechanism, and the rate of polymerization (R_p) was the first‐order dependence of the MA monomer concentration and square root of the CAN concentration. A new kinetic model of the grafting reaction has been proposed, and a normal kinetics of methyl acrylate polymerization was observed. An equation of a predicted model relating the graft fraction of poly(methyl acrylate) with the sago starch has been derived, and validity of the predicted model was verified by the experimental results. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 784–791, 2000     

Grafting of acrylonitrile onto styrene-maleic acid copolymer by tetravalent cerium ion

The graft copolymerization of acrylonitrile (AN) onto a styrene-maleic acid copolymer (SY-MAc) with ceric ammonium nitrate (CAN) as a redox initiator in an aqueous medium has been studied. The effects of various reaction parameters, including reaction time and temperature, concentrations of initiator, nitric acid, and monomer, on the grafting yields and the rates of polymerization (R_p), graft copolymerization (R_g), and homopolymerization (R_h) were studied systematically. The results are discussed. The kinetic scheme of free-radical graft copolymerization has been proposed and the equations relating the values of R_p, R_g, and R_h are also suggested. The experimental results are found to be in good agreement with the proposed kinetic scheme. The activation energies of graft copolymerization and total polymerization are calculated. © 1995 John Wiley & Sons, Inc.     

Synthesis and characterization of new soluble multisite phase transfer catalysts and their catalysis in free radical polymerization of methyl methacrylate aided by ultrasound—A kinetic study

Four different soluble phase transfer catalysts (PTCs) containing single, di, tri, and tetra active sites have been prepared and proved by FT-IR, ¹H NMR, ¹³C NMR, mass, elemental analysis, and conductivity measurement. The presence of the number of active sites in each catalyst was also been confirmed by determining their rate of polymerization of methyl methacrylate (MMA) using potassium peroxydisulfate (PDS) as a water soluble initiator in biphase medium. The comparative study reveals that the R_p of MMA determined in the presence of PTC combined with ultrasound has shown twofold enhancement in the activity than PTC alone. The observed order of activity was found to be of single-site < di-site < tri-site < tetra-site. Further, the thorough kinetic study of free radical polymerization of MMA has been investigated using superior tetra site viz., HBTAMPDTC and by varying the experimental parameters such as [MMA], [K₂S₂O₈], [MPTC], and the temperature. Based on the observed kinetic results and activation parameters, a suitable mechanism was proposed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Polymerization of methyl acrylate initiated by V(V)-cyclohexanone redox system in micellar phase

The kinetics of methyl acrylate (MA) polymerization initiated by a V(V)-Cyclohexanone redox system, in the presence of surfactant, over a temperature range of 30–50°C in acidic medium are analyzed. The anionic surfactant (SDS) enhances the rate of polymerization (R_p) as well as the rate of V(V) consumption (−R_v). The cationic surfactant, cetyl trimethylammonium bromide (CTAB), decreases both the rates. The effect of variation of the concentration of surfactant, monomer, substrate, and acid have been examined. A suitable free radical mechanistic scheme has been proposed for the above process. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2081–2088, 1997     

1‐(bromoacetyl)pyrene and its arsonium salt as novel photoinitiators for styrene polymerization

The photopolymerization of styrene (Sty) in DMSO induced by pyrene (Py), 1‐Acetylpyrene (AP), 1‐(Bromoacetyl) pyrene (BP), and 1‐Acetylpyrene triphenyl arsonium bromide (APAS) has been investigated. Under all conditions employed, Py was completely ineffective. Incorporation of a chromophoric (? COCH₃) moiety introduces photoinitiating activity into Py. It was observed that introduction of Br into AP markedly accelerated the rate of UV irradiation‐induced polymerization. BP was further modified to its arsonium salt (APAS). The kinetics and mechanism of polymerization using BP and APAS as initiators have been investigated in detail. The polymerization with BP followed nonideal kinetics (R_p ∝ [BP]^0.8 [Sty]^1.1) with respect to initiator concentration whereas ideal kinetics (R_p ∝ [APAS]^0.48 [Sty]^1.1) was observed when APAS was used as initiator. Degradative transfer is thought to be mainly responsible for this unusual kinetic behavior for BP–Sty system. The kinetic data proved that BP was more effective and faster initiator than APAS. In both the cases, the mechanism of polymerization was free radical as evident by inhibiting the effect of hydroquinone and ESR studies. IR and NMR spectra showed the atactic nature of polystyrene. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1793–1798, 2006     

Free Radical Polymerization of Acrylonitrile Using Potassium Peroxy Disulphate Initiator and a Phase Transfer Catalyst

Free radical polymerization of acrylonitrile with the di-site phase transfer catalyst 1,4-bis(tetramethylhexyl)ethylenediammonium bromide (TMHEDAB) was investigated using the water-soluble initiator PDS (potassium peroxydisulphate) and water-insoluble solvent ethylacetate in an aqueous-organic biphase system at 60±1°C under nitrogen atmosphere at fixed pH and ionic strength. Rp increased with the increase in concentration of the monomer, initiator and catalyst. The order of R_p, with respect to monomer and catalyst concentration was found to be unity and with respect to initiator was found to be 0.5. A suitable mechanism has been proposed and its significance was discussed. The polymers obtained were characterized by spectral studies such as FTIR, ¹H-NMR, XRD, DSC, and TGA.     

Kinetics of graft copolymerization of poly(hexanedioic acid ethylene glycol) and methyl acrylate initiated by potassium diperiodatocuprate(III)

A redox system, potassium diperiodatocuprate(III) [DPC]/poly(hexanedioic acid ethylene glycol) (PEA) system, was employed to initiate graft copolymers of methyl acrylate (MA) and PEA in alkaline medium. The results indicate that the equation of the polymerization rate (R_p) is as follows: R_p = k [MA]^1.62[Cu(III)]^0.69, and that the overall activation energy of graft polymerization is 42.5 kJ/mol. The total conversion at different conditions (concentration of reactants, temperature, concentration of the DPC, and reaction time) was also investigated. The infrared spectra proved that the graft copolymers were synthesized successfully. Some basic properties of the graft copolymer were studied by instrumental analyses, including thermogravimetry and scanning electron microscope. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2376–2381, 2007     

Effect of organized anionic surfactant system on kinetics of polymerization of acrylonitrile initiated by Ce(IV): Citric acid and other organic substrates

The polymerization of acrylonitrile (AN) using the Ce(IV)–citric acid (CA) redox system as an initiator in aqueous nitric acid solution, in the presence of an anionic surfactant, sodium dodecyl sulfate (SDS), has been kinetically studied at a temperature range of 25–45°C. The rate of polymerization (R_p) and disappearance of Ce(IV) (–R_ce) increase with increasing concentration of SDS, above its critical micelle concentration (cmc), when the surfactant molecules are organized. R_p was found to be proportional to [AN]^1.5 and [CA]^0.5. With other organic substrates, R_p follows the increasing order of sorbitol ≥ mannitol > glycerol > CA. But it was found to decrease considerably in the presence of cationic surfactant (CTAB), and nonionic surfactant (Triton-X-100) had no effect on the rate. –R_ce varies linearly with [Ce(IV)] and [CA]. Both R_p and –R_ce increase with increasing temperature. The overall activation energy was found to be 18.31 and 13.72 kcal/mol in the absence and presence of 0.015M SDS, respectively. The chain length of the polyacrylonitrile has also increased with increasing SDS concentration. © 1996 John Wiley & Sons, Inc.     

Radical polymerization of N-[(1-n-butoxycarbonyl)ethyl]maleimide

Poly(N-[(1-n-butoxycarbonyl)ethyl]maleimide) (PBAM) was synthesized by solution polymerization with 2,2′-Azobis(isobutylronitrile) (AIBN) as radical initiator. The resulting polymer(PBAM) was characterized by infrared spectroscopy (IR), themogravimetry (TG), and differential thermal analysis (DTA). The initial decomposition temperature of PBAM is 321.6°C; the glass transition temperature of PBAM was 240.5°C. The effects of solvent, temperature, initiator concentration ([I]), and monomer concentration ([BAM]) on polymerization were also discussed. The overall activation energy (E_a) of homopolymerization was determined (E_a = 93.5 kJ/mol). It was revealed that the rate of polymerization (R_p) can be expressed as R_p ∝ [I]^0.58[BAM]. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 424–427, 2001     

Poly[N-(2-hydroxypropyl)methacrylamide]. IV. Heterogeneous polymerization

Kinetics of radical heterogeneous polymerization of N-(2-hydroxypropyl)methacrylamide was studied in acetone at 55°C. The values of reaction order with respect to the monomer (1.6) and to the initiator (0.5) indicate a bimolecular termination and degradative transfer during the chain growth. The over-all rate constant of polymerization was found to be 5.6.10-4. Addition of a small amount of a solvent (methanol) to the polymerization mixture led to an increased polymerization rate and increased molecular weight of the resulting polymer, but a higher amount of the solvent brought about a decrease of both characteristics. The Occurence of maxima on the dependences of R_p, as well as M?_w on the monomer concentration was interpreted in terms of the classical Bamford and Jenkins theory.     

Preparation of soap‐free cationic emulsion using polymerizable surfactant

A kind of polymerizable surfactant, methacryloyloxyethylhexadecyldimethylammonium bromide (DMHB) was used to synthesis soap‐free cationic emulsion with styrene (St), methyl methacrylate (MMA), and methacryloyloxyethyltrimethylammonium chloride (MATMAC) by emulsion polymerization using 2,2′‐azobis(isobutylamidine hydrochloride) (AIBA) as a cationic initiator. The effects of polymerizable surfactant concentration, initiator concentration, and reaction temperature on the conversion of monomer were investigated. The results indicated that the rate of polymerization could be expressed as R_p = k_p[AIBA]^0.42[DMHB]^0.45 and the apparent activation energy (E_a) was 83.42 kJ/mol. The particle size, ζ potential, and apparent charge density of cationic latices were also measured. The average diameter of copolymer particles decreased with increasing DMHB, MATMAC, and AIBA content; the charge properties of the particles were decided by the DMHB, MATMAC, and AIBA content. The polymerization mechanism is discussed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1111–1116, 2006     

Kinetics of azo‐initiated 1‐vinyl‐2‐pyrrolidone polymerizations at low conversions in aqueous media

The free‐radical polymerization behavior of 1‐vinyl,2‐pyrrolidone (NVP) was studied at low conversions, using capillary dilatometry. The aqueous media were kept at neutral pH and the studies were conducted isothermally, at 40 or 45°C. The azo‐type initiators used were 4,4′‐azobis‐4‐cyanopentanoic acid (ACPA), 2,2′‐azobisisobutyronitrile (AZBN), and 2,2′‐azobis[2‐(2‐imidazolin‐2‐yl)propane dihydrochloride] (ABDH). The monomer concentration and initiator concentration ranges were 1.17–2.34 mol L⁻¹ and 1–8 mmol L⁻¹, respectively. The rates of polymerization (R_p) and orders of reaction with respect to NVP and the initiator were evaluated and the kinetic equations were found to be R_p ∝ [NVP] [ACPA]^1.2; R_p ∝ [NVP] [AZBN]^1.1; and R_p ∝ [NVP]^2.2 [ABDH]^1.1. The polymers obtained were characterized by their viscosity numbers and correlation of the viscosity average molecular weights made with the type and amount of the azo initiator. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 239–246, 2000     

Poly(p-maleimidostyrene) as a macromolecule initiator for polymerization of styrene-type monomers - Synthesis of block copolymers containing poly(p-maleimidostyrene) with highly reactive pendent maleimido groups

4-Substituted styrenes (substituent: methoxy, methyl, acetoxy, maleimido and none), were cationically polymerized with an initiator system involving poly(p-maleimidostyrene)(PMS) as a macroinitiator, having highly reactive pendent maleimide moieties and a α-chlorobenzyl structure at the polymer end. Using PMS/SnCl₄/tetra-n-butylammmonium chloride initiator system, block copolymers of 4-substituted styrenes onto PMS were obtained in CH₂Cl₂ at 0 °C. As for the polymerization of N-(4-vinylphenyl)maleimide and 4-acetoxystyrene, especially, PMS as the macroinitiator was almost completely utilized for initiation reaction and the polymers having PMS-b-poly(4-substituted styrene) platform with very narrow and unimodal molecular weight distribution were formed in contrast with the case of using 4-methoxystyrene and 4-methylstyrene with stronger electron releasing groups, in which the molecular weight distributions of the formed polymeric materials appeared to be bimodal.