Methyl methacrylate 4-vinyl pyridine

Fig. 10 Kind of phase portrait describing qualitatively the dynamics of tetrapolymerization of styrene, methyl methacrylate, 4-vinyl pyridine, and methyl acrylate, which is characterized by a set of kinetic parameters (5.23). In the diagram only specific lines (edges and separatrixes) are presented. Visible and invisible lines at a tetrahedron boundary are depicted as solid and dashed lines, respectively, and a line inside a tetrahedron is dotted...

Lithium alkyls initiate polymerization of polar monomers like methyl-methacrylate, vinyl pyridine, acrylo-nitrile, etc. However, these reactions are more complex. The desired addition to the C=C bond is accompanied by other processes, e.g., attack on the -COOEt group with the formation of ketones and lithium methoxide, or in vinyl pyridine polymerization by the metalation of the pyridine moiety. 

It has been shown by Angier and Watson [A8, W2] that if an elastomer is swollen with a vinyl monomer (styrene, chlorostyrene, acrylic acid, methyl acrylate, methacrylic acid, methyl methacrylate, vinyl pyridine, methyl vinyl ketone, etc.), mastication in the absence of oxygen can lead to the formation of block copolymers. This would seem to occur through the mechanism... 

Another kind of anionic initiation is being used by Asahi Chemical Industries Corporation (134) in their patent describing the grafting of methyl methacrylate, acrylamide, acrylic acid, and 2-methyl-5-vinyl-pyridine onto partially cyanoethylated and oximated cotton in presence of TiClg, VO or VC12 as effective agents. 

Dispersancy Solution copolymers are comparatively easy to produce in dispersant form as copolymerization with an appropriate polar monomer is relatively straightforward. If the polar monomer is also a methacrylate, reactivity ratios are essentially the same and no special procedures are required to produce random copolymers. Commercial examples have included dimethyl (or diethyl)aminoethyl methacrylate [11], hydroxyethyl methacrylate [12] and dimethylamino-ethyl methacrylamide [13]. 2-Methyl-5-vinyl pyridine [14] has also been used commercially, reactivity ratios are such that it copolymerizes slightly faster than alkyl methacrylates. Although composition drift is not severe, it should be added in a programmed fashion if a uniform distribution is desired. V-vinyl pyrrolidinone, in contrast, copolymerizes very sluggishly with methacrylates and is best incorporated via a graft reaction [15], sometimes also grafted in combination with V-vinyl imidazole [16]. Since solution chemistry is used to produce dispersant polymethacrylates, like preparation of the base polymer, only relatively simple process modifications are necessary to produce dispersants commercially. 

Other examples of peroxy inisurfs can also be found in Russian scientific papers. As for instance in Ref. [41] Voronov et al. describe a polymeric surfactant with peroxy side chains for application as inisurfs in emulsion polymerization. They obtained the polymeric inisurf (Inisurf 2) by copolymerization of a peroxide containing monomer (dimethyl-vinylethinyl-methyl-tm-butyl-peroxide) with acrylic or methacrylic acid or 2-methyl-5-vinyl pyridine with benzoyl peroxide as initiator in the presence of dodecylmercaptan as chain transfer agent. The resulting copolymers are water soluble at appropriate pH-values, surface active, and exhibit a critical micelle concentratioiL... 

Fibers prepared from straight polyacrylonitrile are difficult to dye. To improve dyeabiUty, manufacturers invariably add to monomer feed minor amounts of one or two comonomers, such as methyl acrylate, methyl methacrylate, vinyl acetate, and 2-vinyl-pyridine. Small amounts of ionic monomers (sodium styrene sulfonate) are often included for better dyeability. ModacryKc fibers are composed of 35-85% acrylonitrile and contain comonomers, such as vinyl chloride, to improve fire retardancy. 

Acrylic fibers are made up of copolymers containing at least 85% acrylonitrile units in combination with one or more comonomers including methyl methacrylate, vinyl acetate, or vinyl pyridine ... 

Peracetic acid, formed in situ from acetic acid and hydrogen peroxide in acid aqueous solution, was found to initiate graft copolymerization of vinyl monomers, e.g. methyl methacrylate and 4-vinyl pyridine, onto wood and cellulosic fibers at a good rate (1-3 h time) at 60°C2. The initiati on reaction is not specific for grafting and considerable amounts of homopolymer is formed. 

Radiation Induced Reactions. Graft polymers have been prepared from poly(vinyl alcohol) by the irradiation of the polymer-monomer system and some other methods. The grafted side chains reported include acrylamide, acrylic acid, acrylonitrile, ethyl acrylate, ethylene, ethyl methacrylate, methyl methacrylate, styrene, vinyl acetate, vinyl chloride, vinyl pyridine and vinyl pyrrolidone (13). Poly(vinyl alcohols) with grafted methyl methacrylate and sometimes methyl acrylate have been studied as membranes for hemodialysis (14). Graft polymers consisting of 50% poly(vinyl alcohol), 25% poly(vinyl acetate) and 25% grafted ethylene oxide units can be used to prepare capsule cases for drugs which do not require any additional plasticizers (15). 

Other monomers have been successfully grafted on polyamide under UV light sources. Hence, organic acids as acrylic (72,73), methacrylic (74), ftimaric (73), itaconic (73), and styrene sulfonic in 25% aqueous solution (73). Methyl acrylate and acrylamide in the presence of photosensitizers (74,75) and acrylonitrile (76) are reported as well. Heterocyclic derivatives as vinyl pyridine and vinyl pyrrolidone under UV light using photosensitizers as benzophenone were grafted on Nylon 66 cloth (77). 

Graft copolymers of polyamides using pre-irradiation gamma-rays techniques have been reported for styrene (130), in solution, in the presence of water (40), in alcohols or acetone solution (131), vinyl acetate (130), methacrylic acid in water (132) or methanol solution (129), methyl (133) and ethyl (130) acrylates, 2-ethylhexyl acrylate (55,134), methyl methacrylate (130), in methanol solution (129), 2-dimethylamino ethyl methacrylate quaternary salts (135), acrylamide in aqueous medium (128,136), acrylonitrile (130,137), and 4-vinyl pyridine in aqueous solution (128). 

The literature reports direct grafting by gamma-rays exposure of Nylon fibers or films to the following monomers carbon monoxide (/65), ethylene (157), propylene (157), acetylene (166), butadiene (157.162,163), styrene (158, 161,163,167,168), vinyl chloride (157,163), vinyl fluoride (169-172), vinyl acetate (161,163,173), vinyl propionate (161), vinyl butyrate (161), vinyl crotonate (161), vinyl 2-ethyl hexanoate (161), acrylic add (173,174), methyl acrylate (162, 163), ethyl acrylate (162,163), allyl acrylate (163), methyl methacrylate (28,161, 163,164), butyl methacrylate (161), acrylamide (158), methylol acrylamide (163), acrylonitrile (157,160-163, 167, 175-179), divinyl sulfone (161), vinyl pyridine (167,173), vinyl pyrrolidone (28) and triallyl cyanurate (158). 

Tt has been observed recently (14, 15) that catalytic concentrations of - sulfur dioxide can easily initiate the polymerization of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and styrene at or near room temperature but fails to initiate polymerization in other monomers such as acrylonitrile, acrylamide, methyl acrylate, ethyl acrylate, vinyl acetate, and vinyl pyridine under similar conditions. However, in the presence of catalytic concentrations of sulfur dioxide and a hydroperoxide, such as tert-butyl hydroperoxide, all the above monomers polymerize readily. The results of further investigations on vinyl polymerization in the presence of low concentrations of sulfur dioxide are reported here. 

Malhotra, B.D., Pethrick, R.A (1985) Positron annihilation in 4-vinyl pyridine methyl methacrylate copolymer . Poly. Comm. 26,14. 

Polystyiene-polybutadiene Polybutadiene-poly(a-methyl styrene) Polybutadiene-poly(vinyl naphthalene) Polystyrene-polybutadlene-polystyrene Polybutadiene-polystyrene-polybutadiene Polystyrene-polyisoprene Pblystyrene-polyisoprene-polystyrene Polyia>prene-poly(vinyl-2-p dine) PofyiK>prene-poly(vinyl-4-pyridine) Polyisoprene-poly(methyl methacrylate) Polystyrene-poly(butadiene or ia>prene)-polystyrene Star polystyrene-polybutadiene with 4 branches Star polybutadiene-polystyrene with n branches Star polystyrene-polybutadiene with n branches Star polystyrene-polyisoprene with n brandies Polystyrene-polyisoprene-poly(vinyl-2-pyridine) Polystyrene-poly vinyl-2-pyridine) Polystyrene-poly(vinyl-4-pyridine) Poly(vinyl-2-pyridine)-poly(vinyl-4-pyridine)... 

The experimental copolymer composition data for styrene(Mi)-fumaroni-trile(M2) give a good fit to Eq. (7.86) with rj = 0.072 and r[ = 1.0 [33], but deviate markedly from the behavior predicted by the st-order Markov model with ri = 0.23. Penultimate effects have been observed in a number of other systems. Among these are the radical copolymerizations of ethyl methacrylate-styrene, methyl methaciylate-4-vinyl pyridine, methyl acrylate-l,3-butadiene, and other monomer pairs. 

Fe(II, III)-protoporphyrin-IX (heme, hemin) (7 a, b) with poly(L-lysine)17-22), poly(L-his-tidine)23, poly(y-benzyl-L-glutamate (with pendant imidazole)19 24, polyethylenimine19,22), poly(4-vinyl-pyridine) (also partly quartemized)19,22,25-3 32, poly(N- or 4(5)-vinylimidazoles) (partly substituted at position 2)19-25-33-37, water soluble imidazole modified polyphophazenes38, macroporous methyl methacrylate, with covalent bound imidazole39,40. ... 

The experimental results that will be examined consist of studies that look at the ability of a random copolymer to improve the properties of mixtures of the two homopolymers relative to the ability of a block copolymer. The three different systems that are examined include copolymers of poly(styrene-co-methyl methacrylate) (S/MMA), poly(styrene-co-2-vinyl pyridine) (S/2VP), and poly(styrene-co-ethylene) (S/E) in mixtures of the two homopolymers. The experiments that have been utilized to examine the ability of the copolymer to strengthen a polymer blend include the examination of the tensile properties of the compatibilized blend and the determination of the interfacial strength between the two homopolymers using asymmetric double cantilever beam (ADCB) experiments. 

AG) due to complex formation were determined. Acrylic acid and acrylamide (AAm] gave the highest value of AG due to complex formation with GA. 4-vinyl pyridine (4-Vp) had intermediate value of AG while, methyl methacrylate (MMA) gave least value of AG due to complex formation with GA. The optimized structure of template-monomer complexes is shown in the Fig. 18.4. 

Polyester fibers are composed of linear chains of polyethylene terephthalate (PET), which produces benzene, benzoic acid, biphenyl, and vinyl terephthalate on pyrolysis. Acrylic fibers comprise chains made up of acrylonitrile units, usually copolymerized with less than 15% by weight of other monomers, e.g., methyl acrylate, methyl methacrylate, or vinylpyrrolidone. Thermolysis results in the formation of acrylonitrile monomer, dimers, and trimers with a small amount of the copolymer or its pyrolysis product. In this case, the acrylic is Orion 28, which contains methyl vinyl pyridine as comonomer. Residual dimethyl formamide solvent from the manufacturing process is also found in the pyrolysis products. Cotton, which is almost pure cellulose, comprises chains of glucose units. The pyrolysis products of cellulose, identified by GC/MS, include carbonyl compounds, acids, methyl esters, furans, pyrans, anhydrosugars, and hydrocarbons. The major pyrolysis products are levoglucosan (1,6-anhydro-B-D-glucopyranose) and substituted furans. 

The acid-base Nafion composite membranes include blends of Nafion with polypyrrole (PPy) [98-104], polybenzimidazole (PBI) [105-107], poly (propyleneoxide) (PPO) [108, 109], polyfurfuryl alcohol (PFA) [110], poly(vinyl alcohol) (PVA) [111-115], sulfonated phenol-formaldehyde (sPF) [116], polyvinylidene fluoride (PVdF) [117-122], poly(p-phenylene vinylene) (PPV) [123], poly(vinyl pyrrolidone) (PVP) [124] polyanifine (PANI) [125-128], polyethylene (PE) [129], poly(ethylene-terephtalate) [130], sulfated p-cyclodextrin (sCD) [131], sulfonated poly(ether ether ketone) (sPEEK) [132-135], sulfonated poly(aryl ether ketone) (sPAEK) [136], poly(arylene ether sulfone) (PAES) [137], poly(vinylimidazole) (PVl) [138], poly(vinyl pyridine) (PVPy) [139], poly (tetrafluoroethylene) (PTFE) [140-142], poly(fluorinated ethylene-propylene) [143], sulfonated polyhedral oligomeric silsesquioxane (sPOSS) [144], poly (3,4-ethylenedioxythiophene) (PEDT) [145, 146], polyrotaxanes (PR) [147], purple membrane [148], sulfonated polystyrene (PSSA) [149, 150], polystyrene-b-poly(ethylene-ran-butylene)-bpolystyrene (SEES) [151], poly(2-acrylamido-2-methyl-l-propanesulphonic acid-co-l,6-hexanediol propoxylate diacrylate-co-ethyl methacrylate) (AMPS) [152], and chitosan [31]. A binary PVA/chitosan [153] and a ternary Nafion composite with PVA, polyimide (PI) and 8-trimethoxy silylpropyl glycerin ether-1,3,6-pyrenetrisulfonic acid (TSPS) has also been reported [154]. 

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