Methyl methacrylate acrylamide, styrene

Hamann et al. (11) have prepared phenylazo-bound silica via four-step reactions from the starting silica (Aerosil 200) and carried out the polymerizations of styrene, methyl methacrylate, acrylamide, acrylonitrile, acrylic acid, and 4-vinylpyri-... 

The ozonization method has been extended to the most varied polymer/monomer systems, such as polybutadiene-03 with acrylamide, methyl methacrylate or styrene, cellulose-03 with styrene or acrylonitrile (127), starch-03 with styrene (126). In this last case the formation of some homopolystyrene as side-product has been mentionned by the authors. The starch-styrene graft copolymers are claimed to be good emulsifiers for water-oil suspensions. 

Copolymers of methyl methacrylate and styrene (and other monomers) are made with acrylamide or methacrylamide and then post-reacted with formaldehyde and alcohols to yield the A-alkoxymethyl derivative of the acrylamide unit ... 

Such materials are used in baking finishes. Assume that a manufacturer wishes to make a polymer based on methyl methacrylate or styrene and about 15 mol% acrylamide. If the following reactivity ratios are correct, is there any advantage in terms of evenly spaced cross-links in using either styrene or methyl methacrylate as the major component ... 

Radical copolymerization of an acryl- or methacryl-type PROZO macromonomer (see Scheme 49) with a vinyl monomer of methyl methacrylate (MMA), styrene (St), or acrylamide (AM) produced graft copolymers (Scheme 24). The surface property of the film from the graft copolymer (R=Me) was made hydrophilic due to the character of PMeOZO chain verified by the contact angle measurement. Such behaviors were also observed in the solution of the graft copolymer of PSt-g-PMeOZO via NMR measurement. 

Fig. 1 Guidelines for the selection of Z-groups and R-groups for the polymerization of methyl methacrylate MMA), styrene (5), methyl acrylate MA), acrylamide AM), acrylonitrile AN) and vinyl acetate (VAc). For Z, addition rate decreases and fragmentation rate increases from to right. For R, fragmentation rates decrease from left to right. Dashed line indicates partial controL Adapted from Moad et al. [9]...

Styrene monomer was also copolymerized with a series of functional monomers by using a single-step dispersion copolymerization procedure carried out in ethanol as the dispersion medium by using azobisizobu-tyronitrile and polyvinylpyrollidone as the initiator and the stabilizer, respectively [84]. The comonomers were methyl methacrylate, hydroxyethyl acrylate, metha-crylic acid, acrylamide, allyltrietoxyl silane, vinyl poly-dimethylsiloxane, vinylsilacrown, and dimethylamino-... 

The compositions of copolymers of styrene, methyl methacrylate, acrylonitrile and acrylamide with diethyl vinyl phosphonate (S-DEVP, MMA-DEVP, AN-DEVP and AM-DEVP), with incorporated FR functionality, were analysed by means of 11 1-NMR in CDC13, DMSO-d6 and D20 [217],... 

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). 

Monomers which can add to their own radicals are capable of copolymerizing with SO2 to give products of variable composition. These include styrene and ring-substituted styrenes (but not a-methylstyrene), vinyl acetate, vinyl bromide, vinyl chloride, and vinyl floride, acrylamide (but not N-substituted acrylamides) and allyl esters. Methyl methacrylate, acrylic acid, acrylates, and acrylonitrile do not copolymerize and in fact can be homopolymer-ized in SO2 as solvent. Dienes such as butadiene and 2-chloro-butadiene do copolymerize, and we will be concerned with the latter cortpound in this discussion. 

Figure 3. Copolymerization of glucosyloxyethyl methacrylate (GEMA) with other vinyl monomers. (Q) with acrylamide (AAm), (0) with styrene (St), ( ) with acrylonitrile (AN), and ( ) with methyl methacrylate (MMA).

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). 

Guzman (53) investigated the ceric ion initiated grafting of acrylonitrile, acrylamide, methyl methacrylate, styrene, vinyl acetate, methacrylate, acrylic anhydride, and isoprene to cellulose. Intense grafting was obtained with acrylonitrile, acrylamide, methacrylate and acrylic anhydride. 

Photolysis of this polymer gives radicals on which side chains can be formed, giving graft polymerization 122, 123, 153). Similarly the polymerization of styrene (152) or vinyl acetate (157) in the presence of bromotrichloromethane gives telomers carrying terminal bromine atoms and trichloromethyl groups. By ultraviolet irradiation (3500 A) in the presence of methyl methacrylate the carbon-bromine links are broken and block copolymers are formed. The telomerization of acrylonitrile and acrylic acid with bromoform is based on the same technique the end groups of both polyacrylonitrile and polyacrylic acid were photolyzed in the presence of acrylamide and afforded polyacrylamide blocks linked to polyacrylonitrile or polyacrylic acid blocks (164, 165). 

Functionalized alkenes are used for the cooligomerization. Phenyl-1,4,8-decatriene (104) is obtained by the Ni-catalysed 1 2 addition of styrene and butadiene [42a], Pd catalyst affords the 1 1 adduct [43], Co or Fe catalyst gives the 1 1 adducts 105 and 106 of methyl acrylate and butadiene [44,42a], The 1 1 adducts 107 and 108 are obtained by the Ru-catalyzed coupling of butadiene and acrylamide [45]. Reaction of methyl methacrylate affords the 1 2 adduct 109 with Ni—PhjP catalyst at 0°C, whereas the oligomer 110 is obtained at higher temperature [46],... 

Banks, M., Ebdon, J. R., and Johnson, M., The flame-retardant effect of diethylvinyl phosphonate in copolymers with styrene, methyl methacrylate, acrylonitrile and acrylamide, Polymer, 1994, 35, 3470-3473. 

Dainton and coworkers (11) investigated the polymerization of various monomers with solutions of potassium in dimethoxyethane. Acrylonitrile gave low irreproducible yields of polymer, whereas methyl methacrylate and acrylamide gave no polymer. Styrene polymerized in a reproducible manner to give "living polystyrene. Their data support an ion-radical mechanism with a slow dimerization of the radicals. A 100% yield of polymer was obtained in < 3 seconds, but the optimum molecular weight was not obtained for > 8—9 seconds. 

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. 

The polymerization process of two monomers with different polarities in similar ratios is a difficult task due to the solubility problems. Using the miniemulsion process, it was possible to start from very different spatial monomer distributions, resulting in very different amphiphilic copolymers in dispersion [88]. The monomer, which is insoluble in the continuous phase, is miniemulsified in order to form stable and small droplets with a low amount of surfactant. The monomer with the opposite hydrophilicity dissolves in the continuous phase (and not in the droplets). As examples, the formation of acryl-amide/methyl methacrylate (AAm/MMA) and acrylamide/styrene (AAm/Sty) copolymers was chosen using the miniemulsion process. In all cases the synthe-... 

More or less similar behavior has been observed (8) in the blends of the copolymer or the terpolymer with the following bis-A polycarbonate, polyvinyl chloride, poly (ethyl methacrylate), and a terpolymer made from methyl methacrylate, N,N -dimethyl acrylamide, and N-phenyl-maleimide. Because of this unique miscibility characteristic of the a-methyl styrene interpolymers, an attempt was made at compati-bilizing polyarylethers with the interpolymers by attaching pendant chemical groups known to exist in systems with which the interpolymers are miscible. 

Acrylamide, 2-methyl-5-vinylpyridine and /V-vinylpyrrolidone can be polymerized under similar conditions, and also after decomposition of a monomer-peroxide complex. On the other hand, styrene, methyl methacrylate, isoprene, methyl acrylate, vinyl acetate and ascorbic acid do not polymerize under these conditions. Complex formation between persulphate and these monomer donors is more favourable energetically [165]. The complex is more stable, it is not decomposed into initiating radicals and polymerization does not occur. 

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