Reactive polymers,XXXVIII. Sorption of acid gases on macroporous 2,3-epoxypropyl methacrylate copolymers modified by a reaction with amines

Macroporous copolymers of 2,3-epoxypropyl methacrylate and ethylenedimethacrylate modified by aminolysis yielded sorbents with various contents of amino and hydroxy groups. The dependences of structural characteristics of these sorbents and of the sorption of sulphur dioxide on the content of crosslinking agent and on the cyclohexanol/dodecanol ratio used as the porogenic medium in the preparation of copolymers were investigated. The sorption of sulphur dioxide depends on the geometrical structure of the sorbent, concentration, chemical structure and accessibility of functional groups.     

Synthesis and radical polymerization of p-(2,3-dicyano-2,3-dicarbomethoxycyclopropyl)phenyl acrylate and methacrylate

Summary p-(2,3-Dicyano-2,3-dicarbomethoxycyclopropyl)phenyl acrylate 3a and methacrylate 3b were prepared by the reactions of methyl bromocyanoacetate with methyl acryloyloxybenzylidenecyanoacetate 2a or methyl p-methacryloyloxybenzylidenecyanoacetate 2b, respectively. Monomers 3a and 3b were polymerized with free-radical initiators to obtain polymers with multicyanocyclopropane functionalities in the pendant group. The resulting polymers 4a-b were soluble in acetone and the inherent viscosities were in the range of 0.15–0.25 dL/g. Solution-cast films were brittle, showing T_g values in the range of 120–150°C.     

Thermal decomposition of copolymers of methyl methacrylate and alkyl methacrylates obtained from a CSTR

Thermal decomposition of the copolymers of methyl methacrylate (MMA) with ethyl methacrylate (EMA) or n-butyl methacrylate (BMA) were investigated. The copolymers were obtained in a continuous stirred tank reactor (CSTR) using toluene and benzoyl peroxide, as solvent and initiator, respectively, at 80C. The volume was 1.2 litters and residence time was 3 hours. The thermal decomposition followed the second order kinetics for both MMA/EMA and MMA/BMA copolymers, which were almost in accordance with the order of copolymerization in a CSTR. The activation energies of thermal decomposition were in the ranges of 32-37 kcal/mol and 27-37 kcal/mole for MMA/EMA and MMA/BMA copolymers, respectively and a good additivity rule was observed against each composition for both copolymers. The thermogravimetric trace curve agreed well with the theoretical calculation.     

Functional copolymers of p‐cumyl phenyl methacrylate and glycidyl methacrylate: Synthesis,characterization, and reactivity ratios

Free‐radical polymerization of p‐cumyl phenyl methacrylate (CPMA) was performed in benzene using bezoyl peroxide as an initiator at 80°C. The effect of time on the molecular weight was studied. Functional copolymers of CPMA and glycidyl methacrylate (GMA) with different feed ratios were synthesized by free‐radical polymerization in methyl ethyl ketone at 70°C, and they were characterized by FTIR and ¹H‐NMR spectroscopy. The molecular weights and polydispersity indexes of the polymers and copolymers were determined by gel permeation chromatography. The copolymer composition was determined by ¹H‐NMR. The glass‐transition temperature of the polymer and the copolymers was determined by differential scanning calorimetry. The reactivity ratios of the monomers were determined by the Fineman–Ross and Kelen–Tudos methods. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 336–347, 2005     

Immobilization of enzymes to porous-bead polymers and silica gels activated by graft polymerization of 2,3-epoxypropyl methacrylate

Three types of organic polymers and bead-shape silica gels were activated by graft polymerization of 2,3-epoxypropyl methacrylate; in some cases, epoxide groups on the support surface were modified to NH₂ groups. Eight active matrices so obtained were assessed as supports for immobilized enzymes using peroxidase, glucoamylase and urease. The immobilization yield of protein and specific activities of enzymes were better with supports containing NH₂ groups than with those containing epoxide spacer arms. Maximum enzyme immobilization and storage stabilities were obtained with silica-gel beads activated by graft polymerization of 2,3-epoxypropyl methacrylate. With all eight matrices tested, the immobilized enzymes showed good stability with not less than 82% of the original activity persisting after 28 days. The developed matrices have potential for use in process-scale biotechnological operations.     

Internal structure of porous glass coated with a polymer layer of poly (2,3-epoxypropyl methacrylate)

A change in the internal structure of porous glass due to the formation of a polymer layer of poly(2,3-epoxypropyl methacrylate) by polymerization on its surface was investigated. By using the methods of dynamic desorption of nitrogen and mercury porosimetry, the character of the polymer layer and its effect on the final porosity for various types of the original material were determined.     

Methacrylate-based block ionomers I: Synthesis of block ionomers derived from t-butyl methacrylate and alkyl methacrylates

Diblock and triblock copolymers of t-butyl methacrylate (tBMA) with 2-ethylhexyl methacrylate (EHMA) and n-hexyl methacrylate were prepared via alkyl lithium initiation and sequential addition techniques in THF at ?78°C. The tBMA blocks were quantiatively and selectively hydrolyzed to afford poly(methacrylic acid) (PMAA) blocks which were then neutralized with alkali metal bases to form block ionomers. The unhydrolyzed copolymers had a phase mixed morphology as evidenced by thermal analysis while the hydrolyzed and neutralized polymers were multiphase materials. The carboxylic acid and ioncontaning triblock copolymers formed gels in nonpolar solvents which could be disrupted by the addition of polar additives. Certain carboxylic acid and ioncontaining EHMA/tBMA diblock copolymers also showed this behavior. The triblock ionomers did not show thermoplastic flow prior to degradation, except at the lowest ionic content studied (2%).     

Preparation and characterization of copolymers from methyl methacrylate and cardanyl methacrylate

Copolymers of methyl methacrylate (MMA) and cardanyl methacrylate (CMA) were synthesized, characterized and their physico-mechanical properties were investigated. The benzoyl peroxide-initiated copolymerization was carried out by using different mole fractions of CMA (0.02–0.10) in the initial feed at 80°C. Structural characterization of copolymers was done using FTIR and ¹H NMR spectroscopic techniques. The thermal stability of the copolymers was evaluated using dynamic thermogravimetry. Incorporation of CMA in the MMA backbone leads to an improvement in thermal stability.     

Synthesis of novel functionalized methacrylate copolymers and their copolymerization kinetics,thermal stability,and biocidal properties

In the first step of this study, 2-[(methoxy-1,3-benzothiazole-2-yl)amino]-2-oxoethyl methacrylate (MBAOM) monomer was synthesized and characterized. Then, a series copolymers were obtained by free-radical copolymerization method of MBAOM and glycidyl methacrylate, which is a commercial monomer at 65°C in 1,4-dioxane solvent. Structural characterizations of synthesized monomer and copolymers were carried out using Fourier transform infrared spectrophotometer and nuclear magnetic resonance spectroscopy (¹H and ¹³C-NMR) instruments. The composition of the copolymers was estimated by elemental analysis. The thermal behaviors of all the polymers have been investigated using the differential scanning calorimetry and the thermogravimetric analysis. A kinetic study of the thermal decomposition of copolymers was investigated using thermogravimetric analyzer with non-isothermal methods selected for analyzing solid-state kinetics data. The activation energy (E_a) values were calculated via Kissinger and Ozawa models in a period of α = 0.10–0.80. Photostability of the copolymers was investigated. Also, the biological activity of the copolymers against different bacterial and fungal species has been investigated.     

Synthesis and characterization of oil sorbers based on docosanyl acrylate and methacrylates copolymers

Docosanyl acrylate (DCA) monomer was copolymerized with different monomer feed ratios of cinnamoyloxy ethyl methacrylate (CEMA) or methyl methacrylate (MMA) monomer to produce different compositions for DCA/CEMA or DCA/MMA copolymer with low conversions.¹H NMR spectroscopy was used to confirm the copolymer structure. DCA was crosslinked with different mol % of CEMA or MMA using dibenzoyl peroxide as initiator and various weight percentages of either 1,1,1‐trimethylolpropane triacrylates or 1,1,1‐trimethylolpropane trimethacrylates crosslinkers. The effects of monomer feed composition, crosslinker concentration, and the hydrophobicity of the copolymer units on swelling properties of the crosslinked polymers were studied through the oil absorbency tests. The network parameters, such as polymer solvent interaction (χ), effective crosslink density (υ_e), equilibrium modulus of elasticity (G_T), and average molecular weight between crosslinks (M_c), were determined and correlated with the structure of the synthesized copolymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and properties of semifluorinated block copolymers of 2-(dimethylamino)ethyl methacrylate and fluorooctyl methacrylates

Semifluorinated block copolymers of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(fluorooctyl methacrylates) (PFOMA) were prepared using group transfer polymerisation via sequential monomer addition. Wide ranges of copolymers were obtained with good control over both molecular weight and composition by adjusting the monomers/initiator ratio. The micellar characteristics of the copolymers in water and chloroform were investigated by quasi-elastic light scattering and transmission electron microscopy. The size and morphologies of micelles were greatly influenced by copolymer composition, pH, and temperature. In addition, the solubility of copolymers and the formation of water-in-carbon dioxide (W/C) microemulsions were described in terms of the cloud points. The block copolymers exhibited the excellent ability of stabilizing W/C microemulsions.     

Synthesis,characterization and thermal properties of homo and copolymers of 3,5-dimethoxyphenyl methacrylate with glycidyl methacrylate: Determination of monomer reactivity ratios

The new methacrylic monomer, 3,5-dimethoxyphenyl methacrylate (DMOPM) was synthesized by reacting 3,5-dimethoxyphenol dissolved in ethyl methyl ketone (EMK) with methacryloyl chloride in presence of triethylamine as a catalyst. The homopolymer and copolymers of DMOPM with glycidyl methacrylate (GMA) were synthesized by free radical polymerization in EMK solution at 70 ± 1 °C using benzoyl peroxide as a free radical initiator. The copolymerization behaviour was studied in a wide composition interval with the mole fractions of DMOPM ranging from 0.15 to 0.9 in the feed. The homopolymer and the copolymers were characterized by FT-IR, ¹H NMR and ¹³C NMR spectroscopic techniques. The solubility was tested in various polar and non-polar solvents. The molecular weight and polydispersity indices of the polymers were determined using gel permeation chromatography. The glass transition temperature of the copolymers increases with increase in DMOPM content. The thermogravimetric analysis of the polymers showed that the thermal stability of the copolymer increases with DMOPM content. The copolymer composition was determined using ¹H NMR spectra. The monomer reactivity ratios were determined by the application of conventional linearization methods such as Fineman–Ross (r₁ = 0.520, r₂ = 2.521), Kelen–Tudos (r₁ = 0.629, r₂ = 2.554) and extended Kelen–Tudos methods (r₁ = 0.600, r₂ = 2.502).     

Synthesis and characterization of itaconic anhydride and stearyl methacrylate copolymers

The free-radical copolymerization and the properties of comb-like copolymers derived from renewable resources, itaconic anhydride (ITA) and stearyl methacrylate (SM), are described. The ITA-SM copolymers were nearly random with a slight alternating tendency. The copolymers exhibited a nanophase-separated morphology, with the stearate side-chains forming a bilayer, semi-crystalline structure. The melting point (T_m) of the side-chains and the crystallinity decreased with increasing ITA concentration. The crystalline side-chains suppressed molecular motion of the main chain, so that a glass transition temperature (T_g) was not resolved unless the ITA concentration was sufficiently high so that T_g > T_m. The softening point and modulus of the copolymers increased with the increasing ITA concentration, but the thermal stability decreased.     

Synthesis of ABA triblock copolymers of N-substituted maleimides and methacrylates by group transfer polymerization

Summary ABA type block copolymerization of N-phenylmaleimide (NPM), N-hexyl maleimide (NHM), methyl methacrylate (MMA), and butyl methacrylate (BMA) was investigated by group transfer polymerization (GTP) with [1,5-bis (trimethylsilyloxy)-1,5-dimethoxy-1,4-pentadiene] (1) as difunctional initiator. A novel block copolymers (2) of NPM and MMA (or BMA) could be prepared by sequential addition of NPM to the living PMMA (or PBMA) produced with 1. The reaction did not exhibit the characteristics of living polymerization when NPM was added. The resulting copolymers showed good thermal stability. On the other hand, gelation occurred in GTP of NHM.     

Synthesis of vinyl phenyl acetate and an evaluation of vinyl chloride/vinyl phenyl acetate copolymers

The synthesis of vinyl phenyl acetate, by an ester interchange reaction between phenyl acetic acid and vinyl acetate and utilizing a catalyst, is described. Copolymerization with vinyl chloride, in a suspension system and using a peroxide catalyst, is described on a laboratory and pilot plant scale. Monomer/copolymer compositions, for an initial charge consisting of vinyl chloride/vinyl phenyl acetate (80/20 by weight) are presented over a range of conversions, as an indication of reactivity ratios. Discs, molded from unstabilized copolymers, show very good clarity and color stability, which improve with increased comonomer loading. Some retention of unpolymerized vinyl phenyl acetate monomer occurred, and some increase in softening points resulted following two reprecipitations from acetone into excess methanol. Compound from a 96/4 vinyl chloride/vinyl phenyl acetate copolymer has better color stability than does an equivalent vinyl chloride/vinylidene chloride copolymer compound. The enhanced color and heat stability of the copolymers is attributed to the aromatic character of the comonomer vinyl phenyl acetate.     

Effect of cardinyl acrylate on thermal behavior of methyl methacrylate copolymers

Cardinyl acrylate (CA), prepared by the reaction of acryloyl chloride and cardinol, was copolymerized with methyl methacrylate (MMA) in bulk at 80°C using 2% benzoyl peroxide as an initiator. The copolymer composition was determined by ¹H-NMR spectroscopy. Three copolymer samples containing 0.0048–0.0838 mol fraction of cardinyl acrylate were obtained. A significant improvement in the thermal stability of MMA was observed by incorporating 0.0048–0.0838 mol fraction of CA in the backbone. The activation energy for decomposition in the temperature range 350–480°C for copolymers was higher than PMMA. © 1992 John Wiley & Sons, Inc.     

Synthesis of graft and block copolymers from 2‐dimethylaminoethyl methacrylate and caprolactone

This paper outlines the synthesis of a range of graft and block copolymers containing 2‐dimethylaminoethyl methacrylate and caprolactone sequences by means of two distinct strategies. In the first place, common to both pathways, low‐molar‐mass hydroxyl end‐capped polycaprolactone (PCL‐OH) was prepared by the ring‐opening polymerization of caprolactone in the presence of an aluminium alkoxide Schiff's base (HAPENAlOⁱPr) as initiator followed by hydrolysis of the Al? O bond. For the synthesis of copolymers with a main vinyl carbon–carbon backbone and PCL grafts, PCL‐OH was initially converted into ω‐methacryl‐PCL using methacryloyl chloride. This macromonomer was then copolymerized with 2‐dimethylaminoethyl methacrylate (DMAEMA) by atom transfer radical polymerization (ATRP). For the synthesis of block copolymers, PCL‐OH was first transformed into a bromine end‐capped PCL (PCL‐Br) with 2‐bromoisobutyryl bromide. PCL‐Br was then used as macroinitiator in various concentrations for the ATRP of 2‐dimethylaminoethyl methacrylate, thus leading to PCL and poly(DMAEMA) blocks of varying lengths. The formation of both graft and block copolymers was thoroughly checked using NMR and size exclusion chromatography. Copyright © 2007 Society of Chemical Industry     

Macroporous membranes,IV. Synthesis and properties of poly[(2,3-epoxypropyl methacrylate)-co-(N-vinyl-2-pyrrolidone)-co-(ethylene dimethacrylate)] membranes

Macroporous membranes based on terpolymers of 2,3-epoxypropylmethacrylate, N-vinyl-2-pyrrolidone, and ethylenedimethacrylate were prepared by radical suspension copolymerization and subsequently modified with ammonia. The membranes were characterized by their porosity, specific surface area, pore size, water permeability and mechanical properties. The low content of N-vinyl-2-pyrrolidone improves the mechanical properties of the membranes. The mechanism of formation of the macroporous structure and heterogeneities is discussed.