Kinetic study of aqueous polymerization of methyl methacrylate initiated by Ce(IV)-maltose redox system

Polymerization of methyl methacrylate initiated by ceric ammonium nitrate-maltose has been investigated in aqueous nitric acid under nitrogen in the temperature range 20.5-35°C. The dependence of the initial rate of polymerization and the initial rate of ceric ion consumption on maltose, Ce(IV), and monomer concentrations has been determined. The reaction orders were found to depend on ceric ion concentration. At a moderately high Ce(IV) concentration (1 × 10^?3mol litre^?1) the orders were 1/2 and 3/2 with respect to maltose and monomer concentration, respectively, and independent of Ce(IV) concentration. But at a low Ce(IV) concentration (4 × 10^?4mol litre^?1) the orders with respect to monomer and Ce(IV) changed to 1 and 1/2, respectively. The effect of temperature was also examined. The average molecular weight, as determined by size-exclusion chromacography, was found to depend on maltose, Ce(IV), and monomer concentrations, as well as on temperature.     

Preparation of multiphase block copolymers by redox polymerization process, 4. Polymerization of methyl methacrylate by the redox system Mn(III)-poly(ethylene glycol) containing azo groups

Redox polymerization of methyl methacrylate using Mn(III) with poly(ethylene glycol) having azo and hydroxy functions was carried out to yield ethylene glycolmethyl methacrylate block copolymers with labile azo linkages in the main chain. These prepolymers were used to initiate free-radical polymerization of styrene through thermal decomposition of the azo groups, resulting in the formation of multiblock copolymers. Successful blocking has been confirmed by fractional precipitation, a strong change in the molecular weight, and spectral measurements.     

Block copolymerization of poly(ethylene glycol) with methyl methacrylate using redox macroinitiators

A series of block copolymers of poly(ethylene glycol) (PEG) with methyl methacrylate (MMA) were prepared using a redox system consisting of ceric ion and PEG of various molecular weights in aqueous medium. The block copolymerization experiments were carried out under such conditions in which there was no homopolymerization of MMA by Ce⁴⁺ alone. The intermediacy of the PEG macroradical in the redox process was substantiated by ESR spectroscopy and a polymerization proceeding through ‘blocking from’ mechanism was postulated. The formation of the block copolymers was confirmed by chemical test and fractional precipitation as well as by FT-IR and FT-NMR (¹H and ¹³C-(¹H)) spectroscopy. The triblock nature of the block copolymers was ascertained through the cleavage of the ether linkage of the PEG segment. Simultaneous TG/DTA studies of the block copolymers revealed multiple stage decomposition patterns and their DSC curves exhibited two glass transition temperatures. GPC investigation of the block copolymers revealed unimodal molecular weight distribution with M_n values showing a smooth increase with ascending molecular weights of PEG. SEM studies indicated a fine dispersion of PEG in the continuous PMMA matrix.     

Graft copolymerization of methyl methacrylate onto biomedical polyvinyl chloride initiated by Ce(IV)–glucose redox system

Graft copolymerization of methyl methacrylate onto PVC was carried out using Ce(IV)–glucose redox system in aqueous sulfuric acid medium under nitrogen atmosphere. To find out the optimum conditions for grafting, effects of concentrations of metal ion, glucose, monomer, and acid on the percentage of grafting was studied. The graft yield was found to be influenced by reaction time, temperature, and amount of PVC. An appreciably high graft yield could be achieved with the present system. On the basis of the results from the present study, a plausible reaction mechanism has been proposed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2105–2111, 2005     

Preparation of multiphase block copolymers by redox polymerization process, 3. Polymerization of methyl methacrylate and acrylamide by the Mn(III)-poly(ethy1ene glycol) redox system

Redox-initiated free-radical polymerization of methyl methacrylate (MMA) and acrylamide (AAm) with poly(ethy1ene glycol) (PEG) using Mn(III) as reduction agent was carried out to yield PMMA-block-PEG-block-PMMA and AAm-block-PEG-block-AAm triblock copolymers. The principal parameters (concentration of the reactants, temperature) affecting the synthesis were examined. Block copolymers were characterized by 'H-NMR and infrared spectroscopy.     

Block copolymerization of poly(diethylene glycol phthalic anhydride) and methyl methacrylate initiated by potassium diperiodatonickelate(IV)

Block copolymers of methyl methacrylate (MMA) and poly(diethylene glycol Phthalic Anhydride) (PPAG) was synthesized using a novel redox system—potassium diperiodatonickelate(IV) [DPN]/PPAG system in an alkaline medium. Block copolymers with high percentage of blocking were obtained, which indicated that DPN/PPAG redox system was an efficient initiator for this blocking. Effects of different factors on the blocking parameters were examined. The overall activation energy of this blocking was calculated to be 55.12 kJ/mol. The structure of the block copolymer was determined by infrared, X‐ray diffraction, and scanning electron microscope (SEM). A mechanism is proposed to explain the generation of radicals and the initiation of block copolymerization. The block copolymer was used as the compatibilizer in blends of PMMA and Nylon6. The SEM photographs show that the block copolymer greatly improved the compatibility of the blend. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1312–1317, 2006     

Graft copolymerization of methyl methacrylate onto jute fiber initiated by cerium(IV)–DMSO redox initiator system

The kinetics of graft copolymerization of methyl methacrylate (MMA) onto chemically modified jute fibers initiated by the Ce(IV)–DMSO redox system was studied in the temperature range of 40–60°C. By studying the effects of the concentration of the monomer, Ce(IV), and DMSO on the rate of grafting, the optimum conditions for grafting were determined. Also, the effect of temperature, time, concentration of the acid, the amount of jute fiber, and some inorganic salts and organic solvents on the rate was investigated. A kinetic scheme was proposed on the basis of the experimental findings. Infrared spectra of chemically modified jute and grafted jute was investigated. More than 120% of grafting could be achieved with the present system. The characterization of MMA-grafted chemically modified jute by TGA and DTA studies was made. The thermal stability of the jute fibers was improved by grafting. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2569–2576, 1998     

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     

Aqueous polymerization of methyl methacrylate initiated by the redox system Ce(IV)—D-glucose. I: General features and kinetics

The polymerization of methyl methacrylate initiated by the ceric ammonium nitrate-D-glucose redox system has been studied in aqueous nitric acid under nitrogen in the temperature range 20-5 to 35°C. The initial rate of polymerization was determined gravimetrically whereas the initial rate of ceric ion disappearance was determined by titration of ceric ion. The relationships between conversion and D-glucose, Ce(IV), and monomer concentrations were determined. The dependence of the rates on D-glucose, Ce(IV), and monomer concentrations was evaluated. The effect of temperature was also examined.     

Aqueous polymerization of methyl methacrylate initiated by the redox system Ce(IV)-D-Glucose. II: Effect of reaction conditions on polymer molecular weight

The dependence of molecular weight of poly(methyl methacrylate) on reaction conditions, as polymerized in aqueous nitric acid with the redox system ceric ammonium nitrate-glucose, has been studied. The average molecular weights and molecular weight distributions were determined by size-exclusion chromatography. The degree of polymerization was found to increase in the course of a run and was also affected by changes of Ce(IV) and glucose concentrations in the range where the rate of polymerization increased, but not where the rate was independent of Ce(IV) concentration and decreased with glucose concentration. The average molecular weights can be controlled by variations in monomer concentration and in temperature. The polymerization rate was found to attain a maximum with nitric acid concentration whereas the rate of ceric ion consumption increased. A fall in the degree of polymerization was observed on increasing the acid concentration. The effect of nitrate ion concentration as well as of that of certain water-miscible solvents on the above-mentioned parameters has also been studied.     

Poly(ethylene glycol)-poly(epsilon-caprolactone) block oligomers as injectable materials

A family of segmented low MW poly(ethylene glycol)-poly(epsilon-caprolactone) (PEG-PCL) oligomers was synthesized by reacting PCL-based macrodiisocyanates and diblocks comprising MPEG and PCL short segments. The oligomers have the following general structure: MPEG350-(CL)_n-HDI-PCL530-HDI-(CL)_n-MPEG350. The composition of the oligomers and their molecular weight was determined by ¹H and ¹³C-NMR, FT-IR and GPC. Depending on the length of the (CL)_n block, soft waxes to hard solids were produced. The isothermal crystallization process was performed at various temperatures and investigated by DSC, FT-IR and WAXS, while the mechanical behavior was determined using a compression test. All the oligomers investigated were able to crystallize at low temperatures (4 and 25 °C), while at body temperature, only oligomers comprising longer (CL)_n blocks (n=5 and above), were able to crystallize.     

Pendant vinyl group reactivity during the free-radical copolymerization of methyl methacrylate and ethylene glycol dimethacrylate

Summary Methyl methacrylate-ethylene glycol dimethacrylate (MMA-EGDM) copolymerization has been investigated in toluene at a monomer concentration of 22 w/v %. The kinetic models developed recently along with the experimental conversion curve and gel point data provided the calculation of the average reactivity of pendant vinyl groups. It was found that the pendant vinyl reactivity for intermolecular links is much less than the monomeric vinyl reactivity and it decreases further as the EGDM concentration increases. At 5–15 mol % EGDM, the average pendant reactivity is 1–2 orders of magnitude lower than the monomeric vinyl reactivity. The reduced pendant reactivity is mainly responsible for the shift of the gel point towards higher conversions.     

Polymerization of methyl methacrylate initiated by the redox system Mn3+/thioglycollic acid

The kinetics of aqueous polymerization of methyl methacrylate initiated by the redox system Mn³⁺–thioglycollic acid was studied in sulfuric acid in the temperature range of 35–50°C, and the rates of polymerization R_p and Mn³⁺ disappearance, etc., were measured. The effect of certain water-miscible organic solvents, neutral electrolytes, and complexing agents on the rates of polymerization has been investigated. A mechanism involving the formation of a complex between Mn³⁺ and thioglycollic acid whose decomposition yields the initiating free radical with the polymerization being terminated by the metal ion has been suggested.     

Radical copolymerization of ethylene glycol bis(methyl fumarate) with N-vinylcarbazole

Summary For the purpose of elucidating copolymerizability of ethylene glycol bis(methyl fumarate), a new multifunctional monomer, its free-radical Copolymerization with N-vinylcarbazole has been studied. The results show that free-radical Copolymerization of ethylene glycol bis(methyl fumarate) with N-vinylcarbazole produces soluble copolymers at low conversions, the compositions of which vary from 1∶1 to increasingly VCZ rich (below 2.0) with an increase in the VCZ content in the monomer feed. It is suggested that 1∶1 alternating Copolymerization proceeds and that cyclo-propagation becomes predominant when the monomer feed composition becomes rich in VCZ. Gelation occurs at relatively high conversions.     

Size distribution of polymers during the photoinitiated free-radical copolymerization of methyl methacrylate and ethylene glycol dimethacrylate

Summary Photoinitiated methyl methacrylate-ethylene glycol dimethacrylate (MMA/EGDM) copolymerization has been investigated in toluene at a monomer concentration of 35 w/v %. Diphenyl-2,4,6-trimethylbenzoylphosphine oxide (DPTPO) was used as a photoinitiator at 0.3 wt% concentration. Monomer conversions and the size distribution of the polymer molecules were measured as a function of the reaction time up to the onset of macrogelation. Compared to the photoinitiators benzoin or benzoin derivatives, gelation process proceeds at much higher rates in the presence of DPTPO. The size distribution curves obtained by size-exclusion chromatography (SEC) change from monomodal to bimodal distributions as the polymerization proceeds. Strongly bimodal SEC curves were obtained in the close vicinity of the gel point. This finding confirms the coagulation type gelation mechanism of compact primary particles. It also indicates that the present gelation theories cannot describe the structure dependent kinetics of free-radical crosslinking copolymerization.     

Mechanochemical copolymerization of methyl methacrylate and styrene initiated by the grinding of quartz

The copolymerization of methyl methacrylate and styrene mechanochemically initiated by the grinding of quartz in the monomer mixture was investigated by using a vibrating ball mill. The effect of the grinding of quartz on the copolymerization was investigated by characterizing both the polymer formed and the ground quartz. The copolymerization proceeds apparently from the quartz grindings and was closely related to the total surface area of the ground quartz. The molecular weight distributions of the copolymers formed were unimodal as found in a homopolymer of only methyl methacrylate. It was clear from the composition analysis of the copolymer that the mechanochemical copolymerization of methyl methacrylate and styrene proceeded with a radical polymerization mechanism because of radicals on the quartz surface produced by the grinding. The monomer reactivity ratios obtained by the Fineman‐Ross method suggested that the copolymers formed were alternating copolymers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2011–2017, 2002; DOI 10.1002/app.10544     

Concentrated emulsion polymerization of methyl methacrylate/butyl acrylate initiated by a redox system

Stable concentrated emulsions of methyl methacrylate/butyl acrylate were prepared with sodium dodecyl sulfate and cetyl alcohol as the compound surfactant and poly(vinyl alcohol) as the major reinforcer of the liquid film. With a redox system based on benzoyl peroxide/N,N′‐dimethyl phenylamine introduced into the concentrated emulsions, polymer particles with different shapes and sizes were obtained by initiation of the polymerization at low temperatures. We investigated the kinetic behaviors of concentrated emulsion polymerization and drew linear regression diagrams of its time–conversion curves in a constant rate phase (conversions ranged from 20 to 70%), and the experimental results show that the variation of the concentrations of the compound surfactant and initiator, the categories of reinforcers of the liquid film, the temperatures, and so on were responsible for the polymerization stability and the polymerization rate. Finally, the kinetics equation and activation energy of the initiator were obtained. The particle size and distribution of particle diameters of latex particles were determined by photon correlation spectroscopy. The determination results reveal that concentrations of the compound surfactant, polymerization temperatures, and so on affected the shape and size of the polymer particles greatly. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1695–1701, 2005     

Graft copolymerization of methyl methacrylate onto jute fibers. Studies on vanadium (V)-cyclohexanol redox system

Graft copolymerization of methyl methacrylate (MMA) onto natural jute (chemically modified) was studied using V⁵⁺ -cyclohexanol redox initiator system. The effects of time, concentration of metal ion (V⁵⁺), monomer (MMA), substrate, amount of jute fibers, temperature, and acid concentration on graft yield have been studied. The effects of some organic solvents and inorganic salts on graft yield have also been studied. A grafting mechanism is proposed and an expression has been derived for the reaction rate. Grafting has improved the thermal stability and the light fastness of jute fibers dyed with basic dyes. IR spectra of the natural jute (chemically modified) and grafted jute have been taken. More than 170% graft yield could be achieved with the present system.     

Graft copolymerization of acrylonitrile onto jute fibers (studies on Ce(IV)-hippuric acid redox system)

Graft copolymerization of acrylonitrile (AN) onto chemically modified bleached jute fibers was studied using Ce(IV)-hippuric acid redox initiator system. The effects of time, temperature, concentration of monomer (AN), metal ion (Ce⁴⁺), hippuric acid, sulfuric acid, and amount of jute fiber on graft yield have been studied. The effects of some organic solvents and inorganic salts on graft yield have also been studied. Infrared spectra of chemically modified bleached jute and grafted jute have been taken and their characteristic bands have been identified. More than 90% graft yield could be achieved with the present system.     

Mechanochemical block copolymerization of poly(vinyl chloride) with methyl methacrylate by ultrasonic irradiation

Summary Mechanical degradation and mechanochemical block copolymerization in systems of poly(vinyl chloride)-methyl methacrylate-solvents have been studied by ultrasonic irradiation at 60°C. The effect of the concentrations of poly(vinyl chloride) on mechanical degradation was investigated. In addition, the effects of poly(vinyl chloride) and methyl methacrylate concentrations on mechanochemical block copolymerization were investigated. The rate equation for mechanochemical block copolymerization has been deduced, and the experimental results were in fairly good agreement with the equation. The changes in the composition of the block copolymer and homopolymers in the reaction products were followed by turbidimetric titration.