Photocatalytic degradation of methyl methacrylate copolymers

The photolytic and photocatalytic degradation of the copolymers poly(methyl methacrylate-co-butyl methacrylate) (MMA-BMA), poly(methyl methacrylate-co-ethyl acrylate) (MMA-EA) and poly(methyl methacrylate-co-methacrylic acid) (MMA-MAA) have been carried out in solution in the presence of solution combustion synthesized TiO₂ (CS TiO₂) and commercial Degussa P-25 TiO₂ (DP 25). The degradation rates of the copolymers were compared with the respective homopolymers. The copolymers and the homopolymers degraded randomly along the chain. The degradation rate was determined using continuous distribution kinetics. For all the polymers, CS TiO₂ exhibited superior photo-activity compared to the uncatalysed and DP 25 systems, owing to its high surface hydroxyl content and high specific surface area. The time evolution of the hydroxyl and hydroperoxide stretching vibration in the Fourier transform-infrared (FT-IR) spectra of the copolymers indicated that the degradation rate follows the order MMA-MAA > MMA-EA > MMA-BMA. The same order is observed for the rate coefficients of photocatalytic degradation. The photodegradation rate coefficients were compared with the activation energy of pyrolytic degradation. In degradation by pyrolysis, it was observed that MMA-BMA was the least stable followed by MMA-EA and MMA-MAA. The observed contrast in the order of thermal stability compared to the photo-stability of these copolymers was attributed to the two different mechanisms governing the scission of the polymer and the evolution of the products.     

Fluorescence of copolymers of 2-naphthyl methacrylate and methyl methacrylate

The fluorescence of a series of copolymers of 2-naphthyl methacrylate (2-NM) and methyl methacrylate (MMA) with various contents of 2-NM (obtained in chloroform, carbon tetrachloride and acetonitrile) was investigated. A linear dependence between the ratio of the excimer to monomer emission intensities (I_D/I_M) and the diad fraction (f_nn) of 2-NM monomer units was established. The relationship between I_D/I_M and f_nn · I_n (I_n = the mean sequence length of 2-NM units) fits a logarithmic curve. The results indicate that the excimer emission is determined mainly by the nearest neighbour naphthalene-containing monomer units in the copolymer chain. The copolymers obtained in acetonitrile have higher values of I_D/I_M than those obtained in chloroform and carbon tetrachloride. This difference is due to the higher content of mm-triads in copolymers from acetonitrile, confirmed by ¹H-NMR analysis of the samples of poly(methyl methacrylate) formed from copolymers of 2-NM and MMA.     

Thermal behaviour of copolymers of methyl methacrylate and 2-ethylhexyl methacrylate

Five copolymer samples containing different mole fractions of methyl methacrylate (MMA) and 2-ethylhexyl methacrylate (EHMA) were prepared by bulk polymerisation at 70°C using 0.2% benzoyl peroxide as an initiator. The copolymer composition was determined by¹H NMR spectroscopy. Molecular weight of copolymers was determined by gel permeation chromatography and viscosity measurements. Thermogravimetric experiments were conducted to evaluate activation energy for the degradation of copolymers. Two to four reaction stages for the weight loss were observed in the copolymers. A decrease in thermal stability was observed by an increase in EHMA content.     

The thermal degradation of polymethacrylamide and copolymers of methacrylamide and methyl methacrylate

Thermal analysis demonstrates that the thermal degradation of polymethacrylamide (PMAM) occurs in two well defined steps. The only volatile products formed in the first step, below 340, are ammonia and water while imide replaces amide absorption in the infra-red spectrum of the residue. Above 340° the major product consists of chain fragments (approximately 50%) in which a high proportion of the amide groups have been converted to cyclic imides. Copolymers with methyl methacrylate (MMA) comprising more than 35% methacrylamide (MAM) also degrade in two similar steps but the overall behaviour becomes progressively more like that of polymethylmethacrylate as the MAM content is decreased below 10%. In the first stage of the reaction in the copolymer, MMA and methanol are important products in addition to ammonia and water. Chain fragments remain the major product in the second stage but a number of minor, but very significant, products are also formed. All these products and the structural features of the chain fragments and residue have been accounted for mechanistically.     

Photothermal degradation of copolymers of methyl methacrylate and n-butyl acrylate

The photothermal degradation of copolymers of methyl methacrylate (MMA) and n-butyl acrylate (n-BuA) covering the whole composition range has been studied at 165°.The gaseous products, which are relatively minor, are hydrogen, carbon monoxide and methane. The liquid products are predominantly MMA, with n-BuA, n-butanol and n-butyraldehyde as minor products. Infra-red spectral changes in the residue were attributed to lactone formation and associated with butanol formation as in the purely thermal reaction The “cold ring” or chain fragment fraction becomes increasingly more abundant as the n-BuA content of the copolymer is increased.All the products and principal features of the reaction are explained in terms of a radical process which is initiated by scission of pendant acrylate units and is propagated by a combination of depropagation and intra- and intermolecular transfer processes, the relative importance of which depends upon copolymer composition. Differences from the thermal reaction and the corresponding reaction in copolymers of methyl methacrylate and methyl acrylate are discussed.     

The thermal degradation of copolymers of methyl methacrylate with methacrylic acid

The degradation has been studied using thermogravimetry and thermal volatilization analysis; product analysis has been carried out by GLC and spectroscopy. The copolymers yield water and methanol below 300°; at higher temperatures, the products also include methyl methacrylate, carbon monoxide, carbon dioxide and methane. Quantitative comparison of the yields of methanol and methyl methacrylate has been made with predicted yields based upon sequence distribution calculations. Methanol is believed to result by two routes (i) intramolecular cyclization of adjacent ester and acid chain units at low temperatures, and (ii) fragmentation of ester units, in competition with depolymerization, at higher temperatures. Methyl methacrylate yields are substantially lower than the MMA content of the copolymer, as a result of these processes; some MMA units also appear in the product fraction volatile at degradation temperatures but not at ambient temperature. The partially-degraded copolymers develop anhydride ring structures in the chain as a result both of dehydration and of methanol production. The mechanisms of the various reactions are discussed.     

Thermal degradation of copolymers of methyl methacrylate and 2,6-dimethoxycarbonyl-1,6-heptadiene

The thermal degradation under vacuum of copolymers of methyl methacrylate and 2,6-dimethoxycarbonyl-1,6-heptadiene of different compositions has been investigated. It has been found that the presence in the polymer chains of small amounts of cyclic structural units from the diene monomer considerably reduces the amount of degradation which occurs in poly(methyl methacrylate) at temperatures lower than 300°C. On the basis of the results of the analysis of the degradation products, a mechanism is suggested which accounts for this effect.     

Conducting graft copolymers of pyrrole and thiophene with random copolymers of methyl methacrylate and 3-methylthienyl methacrylate

Random copolymers of 3-methyl thienylmethacrylate and methyl methacrylate were synthesized via free radical polymerization. Electro-copolymerizations of random copolymers with thiophene and/or pyrrole were carried out in acetonitrile-tetrabutylammonium tetrafluoroborate (TBAFB), water-p-toluene sulfonic acid (PTSA) solvent-electrolyte couples. Oxidative polymerization of thiophene functionalized random copolymer was also achieved by constant current electrolysis and chemical polymerization. The characterizations were done by conductivity measurements, cyclic voltammetry (CV), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermal gravimetry analysis (TGA), scanning electron microscopy (SEM).     

Radiation degradation of methyl α-chloroacrylate–methacrylonitrile copolymers

The radiation degradation behavior of methyl α-chloroacrylate (MCA) and methacrylonitrile (MCN) copolymers has been investigated as part of a program to develop high-sensitivity polymeric resists for integrated circuit manufacture. High-molecular-weight copolymers were prepared by emulsion techniques. Several different copolymer compositions were prepared varying from 19 to 68 mole % MCA. These copolymers were fractionated and then subjected to γ irradiation from a ⁶⁰Co Source. The G_s - G_s, G_s - 4G_s values were determined from M?;F>n_k^?1 and G_u^?1 versus dose plots, and the G_fs and G_s Values were then calculated. Molecular weights of both unirradiated and irradiated polymers were analyzed by membrane osmometry and gel permeation chromatography. All copolymers exhibited higher degradation susceptibilities than that of poly(methyl methacrylate) (PPMA), which has G_x = 1.3. The individual G_x and G_x values of the copolymers were found to fall between those of the two homopolymers, poly(methyl α-chloroacrylate) (G_x = 6.0) and polymethacrylonitrile (G_x ～ 3.1). The dependence of G_x and G_x values on molecular weight was minor. The crosslinking susceptibility of the poly(methyl α-chloroacrylate) (G_x ～ 0.8), was greatly decreased by copolymerization with MCN. Relatively small amounts of MCN caused a large drop in G_x, i.e., G_x ～ 0.15 at 32% MCN and G_x ～ 0.03 at 51% MCN. The observation could be attributed to the decreasing probability that crosslinking sites, in the MCA monomer units on adjacent chains, would lie in close proximity.     

Investigation of the thermal degradation and stability of copolymers of 2-acrylamido-2-methylpropanesulphonic acid and methyl methacrylate

Copolymers of 2-acrylamido-2-methylpropanesulphonic acid (AMPS) and methyl methacrylate (MMA) were prepared. Thermal behaviour was studied by TG and DTG methods. Incorporation of more comonomer units, at various compositions, results in a copolymer more stable than the AMPS homopolymer. Decomposition of the copolymers involves the formation of anhydrides, the majority of which involve six-membered cyclic anhydride rings. Further heating results in the formation of a highly aromatic char at the higher temperatures. The apparent activation energies of decomposition of the homo- and copolymers were established.     

Preparation and degradation of copolymers of methyl methacrylate with alkali metal methacrylates—I. Copolymerization parameters for the systems methyl methacrylate-lithium methacrylate,methyl methacrylate-sodium methacrylate and methyl methacrylate-potassium methacrylate

Copolymerizations of methyl methacrylate with the Li, Na and K salts of methacrylic acid have been studied in methanol solution at 60°. Reactivity ratios have been calculated by the methods due to Mayo and Lewis, Fineman and Ross and Peckham. The rate of copolymerization decreases as the size of the metal cation increases, in contrast to the behaviour in the homopolymerization of the alkali metal methacrylates. The systems have the following reactivity ratios (MMA as monomer-1): Li salt r₁ = 0.59, r₂ = 0.073; Na salt r₁ = 3.97, r₂ = 0·126; K salt r₁ = 5.65, r₂ = 0.143. The MMA-LiMA system shows azeotropic copolymerization for a mole fraction of MMA in the feed equal to 0.7. This system shows a strong tendency towards alternation (r₁r₂ = 0.044). The differences in the reactivity ratios are discussed in relation to steric and electrostatic effects.     

Thermal degradation of bromine-containing polymers. Part 2—Characteristics and products of degradation of copolymers of 2-bromoethyl methacrylate and methyl acrylate

Reactivity ratios for the system 2-bromoethyl methacrylate (M₁)/methyl acrylate (M₂) have been obtained as follows using a nuclear magnetic resonance spectroscopic technique: r₁ = 2·77 ± 0·03, r₂ = 0·19 ± 0·02. The principal characteristics of the thermal degradation of this copolymer system have been established by the application of Thermal Gravimetry, Differential Scanning Calorimetry, Thermal Volatilisation Analysis and Sub-ambient Thermal Volatilisation Analysis, the products being identified principally by infra-red and NMR spectroscopic analysis. A quantitative analysis of the products of degradation is presented.     

The thermal degradation of copolymers of vinyl acetate with methyl methacrylate and other monomers

The thermal degradation of copolymers of vinyl acetate with methyl methacrylate, styrene and ethylene has been investigated using thermal volatilization analysis and thermogravimetry, together with analysis of volatile and involatile degradation products. All three copolymer systems show some of the features characteristic of the homopolymers of the monomers concerned. There is evidence, however, for an intramolecular lactonization process in VA—MMA copolymers, involving reaction of adjacent VA and MMA units with elimination of methyl acetate. This reaction occurs less readily than the analogous process in vinyl chloride—MMA copolymers. Mechanisms of the various degradation reactions are discussed.     

Thermal degradation of copolymers of 36Cl-vinyl chloride and methyl methacrylate

The degradation of copolymers of vinyl ³⁶Cl-chloride and methyl methacrylate has been studied using film samples, slow heating rate and high vacuum conditions. Volatilization has been followed using thermal volatilization analysis and radioactive assay of methyl chloride and hydrogen chloride. By carrying out duplicate experiments with and without an ice trap at ? 100°, it is possible to measure methyl chloride alone and both products, respectively, so that each product can be estimated. Yields have been found to agree well with those predicted from sequence distribution calculations. Some differences in behaviour compared with earlier work using powder samples and nitrogen flow conditions are discussed.     

Thermal degradation of copolymers of 2-hydroxyethyl methacrylate and alkyl methacrylates

Thermal degradation of homopolymers of ethyl methacrylate (I), n-butyl methacrylate (II), 2-hydroxyethyl methacrylate (III), and copolymers of III with I and II were carried out by thermal volatilization analysis (TVA) up to 440°C with subsequent subambient thermal volatilization analysis (SATVA). An on-line mass spectrometry coupled with TVA and SATVA was employed to identify the products of thermal degradations. Isothermal pyrolyses of the polymers were carried out separately at 400°C in vacuum for 30 min and the liquid products of decomposition were collected and analysed by gas chromatography. The relationship between the amounts of I and II obtained from pyrolysis and the amounts of these components actually present in the copolymer samples was determined. Also the amount of III and ethyleneglycol dimethacrylate obtained from pyrolysis increases with the amount of III in the copolymer. The polymers were also characterized by differential thermal analysis.     

Radiation degradation of poly(methyl methacrylate) in the soft x-ray region

The molecular weight distribution change has been measured for the photoresist poly(methyl methacrylate) [PMMA] after in-vacuo exposure to monochromatic soft x-rays from the Canadian Synchrotron Radiation Facility [CSRF]. The experimental changes in the mo-lecular weight distribations derived from gel permeation chromatography [GPC], were compared to a simple Monte Carlo simulation model that assumes random main chain scission. Using this model a scission radiation chemical yield of G(S) = 1.28± 0.10 at room temperature was found to give the best fit at a photon energy of 621 eV. This value is similar to values reported previously in the literature using electron beam and γ-ray sources, but significantly larger than those reported for fast neutrons, α-particles, or energetically charged particles. It was found that in this soft x-ray energy regime, that degradation of PMMA involves primarily a random scission process of the main chain. The results of a least-squares fit of this soft x-ray G(S) data and all available literature values from other radiation sources, to the linear energy transfer [LET] dE/dx are discussed. © 1993 John Wiley & Sons, Inc.     

Thermal degradation of copolymers of methyl methacrylate and methyl acrylate. I. Products and general characteristics of the reaction

The technique of thermal volatilization analysis (TVA), applied to methyl methacrylate–methyl acrylate copolymers having molar composition ratios 112/1, 26/1, 7.7/1, and 2/1, has demonstrated that the stabilization of poly(methyl methacrylate) by copolymerized methyl acrylate is due to inhibition of the depolymerization initiated at terminally unsaturated structures, probably by direct blockage by methyl acrylate units. The molecular weight of the copolymers decreases rapidly during degradation, suggesting that a random scission process is involved. The products of degradation consist of the monomers, carbon dioxide, chain fragments larger than monomer, and a permanent gas fraction which is principally hydrogen. Infrared and ultraviolet spectral measurements suggest that the residual polymer, which is colored, incorporates carbon–carbon unsaturation. The complete absence of methanol among the products is surprising in view of its abundance among the products of degradation of poly(methyl acrylate). These observations have been accounted for qualitatively in terms of acceptable polymer behavior.     

Thermal behaviour of copolymers of methyl methacrylate and iso-octyl/iso-decyl methacrylate

Thermal behaviour of copolymers of methyl methacrylate (MMA) with iso-octyliso-decyl methacrylate was investigated using dynamic thermogravimetry, mass spectroscopy and pyrolysis gas chromatography. The copolymer samples were stable upto 250 °C. Total loss in weight was observed around 400 °C. The degradation in homopolymers as well as copolymers proceeded by predominans loss of monomer.

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Zusammenfassung Mittels dynamischer Thermogravimetrie, Massenspektroskopie und Pyrolysengaschromatographie wurde das thermische Verhalten von Kopolymeren aus Methylmethacrylat (MMA) und Isooktyl/Isodecyl-methacrylat untersucht. Die Kopolymerproben waren bis 250 °C stabil. Ein vollständiger Gewichtsverlust wurde bei 400 °C beobachtet. Der Abbau sowohl der Homopolymere als auch der Kopolymere erfolgt durch eine überwiegende Abgabe von Monomeren.

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, - /- . /- . 250°. 400°. , .

     

Thermal degradation of phenyl methacrylate-methyl methacrylate copolymers

The degradation behaviours of poly(phenyl methacrylate), four phenyl methacrylate-methyl methacrylate copolymers which span the composition range, and poly(methyl methacrylate) have been compared by using thermogravimetry in dynamic nitrogen and thermal volatilisation analysis (TVA) under vacuum, with programmed heating at 10°C/min. Volatile products have been separated by subambient TVA and identified and the cold ring fraction and partially degraded polymer have been examined by ir spectroscopy. Poly(phenyl methacrylate) resembles poly(methyl methacrylate) in degrading completely to monomer. Copolymers of phenyl methacrylate and methyl methacrylate are more stable than the homopolymers. On degradation, the major products are the two monomers. Minor products from all the copolymers include carbon dioxide, dimethylketene, isobutene and formaldehyde. Copolymers with low and moderate phenyl methacrylate contents show the formation of anhydride ring structures in the cold ring fraction and partially degraded copolymer, together with small amounts of methanol in the volatile products. Carbon dioxide is a more significant product at lower phenyl methacrylate contents.The mechanism of degradation is discussed.