Vinyl copolymers with methyl methacrylate

Block copolymers of vinyl acetate with methyl methacrylate, acryflc acid, acrylonitrile, and vinyl pyrrohdinone have been prepared by copolymeriza tion in viscous conditions, with solvents that are poor solvents for the vinyl acetate macroradical (123). Similarly, the copolymeriza tion of vinyl acetate with methyl methacrylate is enhanced by the solvents acetonitrile and acetone and is decreased by propanol (124). Copolymers of vinyl acetate containing cycHc functional groups in the polymer chain have been prepared by copolymeriza tion of vinyl acetate with A/,A/-diaIlylcyanamide and W,W-diaIl5lamine (125,126). 

The series of copolymers of 1-vinyl naphthalene with methyl methacrylate used in a recent study is shown in Table 3 ete the fonctions are the mole fraction of naphthalene chromophores in the copolymer, fn the fraction of linkages between naphthalene species in the polymer chain, f n, and the mean sequence length of aromatic species, 1 . Fluorescence decays in the monomer and excimer emission... 

The MA-VA copolymers of maleic anhydride (MA) with vinyl acetate (VA), (Chitanu et al., 2006) and MA-MMA copolymers with methyl methacrylate (MMA), (Chitanu et aL, 2007) are synthesized by free radical polymerization, purified by extraction and washed with diethyl ether. The composition is estimated by conductometric titration with aqueous O.IN NaOH in 1 1 acetone-water mixture and the molecular weight (Mw) by viscosimetric measurements in acetone at 30 °C. 

It is interesting that cationic initiators can be used to produce copolymers between vinyl ether and acrylate monomers. For example, the polymerization of n-butyl vinyl ether with methyl methacrylate gives an alternating copolymer when carried out in toluene at 0°C using butyl chlorotriethyldialuminum [153,154]. Copolymers produced by cationic... 

While most copolymers of vinyl acetate are random copolymers, alternating copolymers are formed when the reactivity ratios for the two monomers are suitable. This occurs spontaneously when vinyl acetate is polymerized with electron-poor monomers such as maleic anhydride [273]. Alternatively, it has been reported that acrylonitrile which has been precomplexed with zinc chloride gives alternating polymers with vinyl acetate [274]. Block polymers of vinyl acetate with methyl methacrylate, acrylonitrile, acrylic acid, and n-vinyl pyrrolidone have been prepared by the strategy of preparing poly(vinyl acetate) macroradicals in poor solvents in which the macroradicals are occluded. Addition of a second monomer swells the polymer coils, and polymerization continues with the addition of the new monomer [275]. 

O.JVI. Scott Sons. The O.M. Scott Sons Co. (Scotts) has developed a series of coated products which utilize copolymer blends of vinyHdene chloride copolymerized with methyl methacrylates, acrylonitriles, methyl acrylates, and/or vinyHdene—vinyl chloride monomers. 

When the polymer was prepared by the suspension polymerization technique, the product was crosslinked beads of unusually uniform size (see Fig. 16 for SEM picture of the beads) with hydrophobic surface characteristics. This shows that cardanyl acrylate/methacry-late can be used as comonomers-cum-cross-linking agents in vinyl polymerizations. This further gives rise to more opportunities to prepare polymer supports for synthesis particularly for experiments in solid-state peptide synthesis. Polymer supports based on activated acrylates have recently been reported to be useful in supported organic reactions, metal ion separation, etc. [198,199]. Copolymers are expected to give better performance and, hence, coplymers of CA and CM A with methyl methacrylate (MMA), styrene (St), and acrylonitrile (AN) were prepared and characterized [196,197]. 

Polyvinyl alcohol is a main ingredient in latex paints, hairsprays, shampoos, and glues. It forms polymers and copolymers with other monomers, such as vinyl acetate and methyl methacrylate... 

II. B polyethylene glycol, ethylene oxide, polystyrene, diisocyanates (urethanes), polyvinylchloride, chloroprene, THF, diglycolide, dilac-tide, <5-valerolactone, substituted e-caprolactones, 4-vinyl anisole, styrene, methyl methacrylate, and vinyl acetate. In addition to these species, many copolymers have been prepared from oligomers of PCL. In particular, a variety of polyester-urethanes have been synthesized from hydroxy-terminated PCL, some of which have achieved commercial status (9). Graft copolymers with acrylic acid, acrylonitrile, and styrene have been prepared using PCL as the backbone polymer (60). 

Bauer et al. describe the use of a noncontact probe coupled by fiber optics to an FT-Raman system to measure the percentage of dry extractibles and styrene monomer in a styrene/butadiene latex emulsion polymerization reaction using PLS models [201]. Elizalde et al. have examined the use of Raman spectroscopy to monitor the emulsion polymerization of n-butyl acrylate with methyl methacrylate under starved, or low monomer [202], and with high soUds-content [203] conditions. In both cases, models could be built to predict multiple properties, including solids content, residual monomer, and cumulative copolymer composition. Another study compared reaction calorimetry and Raman spectroscopy for monitoring n-butyl acrylate/methyl methacrylate and for vinyl acetate/butyl acrylate, under conditions of normal and instantaneous conversion [204], Both techniques performed well for normal conversion conditions and for overall conversion estimate, but Raman spectroscopy was better at estimating free monomer concentration and instantaneous conversion rate. However, the authors also point out that in certain situations, alternative techniques such as calorimetry can be cheaper, faster, and often easier to maintain accurate models for than Raman spectroscopy, hi a subsequent article, Elizalde et al. found that updating calibration models after... 

Terpolymers made from two different olefins and CO are known. They were first described in Brubaker s initial patent and involved the free radical initiated terpolymerization of CO and C2H with another olefin such as propylene, isobutylene, butadiene, vinyl acetate, diethyl maleate or tetrafluoroethylene More recently, in another patent, Hammer has described the free radical initiated terpolymerization of CO and C2H with vinyl esters, vinyl ethers or methyl methacrylate 26Reaction temperatures of 180-200 °C and a combined pressure of 186 MPa were employed. Typically a CO QH4 olefin molar ratio of 10 65 25 was observed in the terpolymers. In other patents, Hammer 27,28) has described the formation of copolymers with pendant epoxy groups by the free radical initiated polymerization of CO, QH4, vinyl acetate and glycidyl methacrylate. Reaction conditions similar to those stated above were employed, and a typical CO C2H vinyl acetate glycidyl methacrylate molar ratio of 10 65 20 5 was observed in the product polymer. 

The polymerization of vinyl monomers in the presence of natural rubber, which is also an unsaturated polymer, has been examined initially by Le Bras and Compagnon (67, 740, 141). Jacobson (118) described graft copolymers of rubber latex with methyl methacrylate, styrene, acrylonitrile, etc. 

ABA copolymers poly(methyl methacrylate)-polyisoprene-poly(methyl methacrylate) having polyisoprene with a high vinyl content as central block have been synthetized by Cole et al. 2I°. Dynamic mechanical properties of films of these ABA copolymers have been studied as a function of the copolymer composition, the temperature and the nature of the solvent (carbon tetrachloride, toluene, ethyl acetate, methylethyl ketone, dioxane) used for film preparation210. ... 

None of the factors that affect particle morphology operate alone. In particular, the mode of monomer addition is an interacting factor. This is illustrated by procedures used to produce core-and-shcll polymers for use in architectural paints [26]. Polymers used for this purpose are primarily copolymers of butyl acrylate with either vinyl acetate or methyl methacrylate. The goal here was to make particles with conventional film-forming polymer shells and cores comprised of less expensive monomers than were used in the shells. In practice, this could mean poly(vinyl acetate) cores inside vinyl acetate/butyl acrylate shells or the same or poly(methyl... 

Studies of hydrolytic stability were performed with LS containing benzotriazole moieties. It was reported [293] that copolymers prepared from various vinyl or isopropenyl derivatives of 2- 2-hydroxyphenyl)-2if-benzotriazole were hydrolytically stable. However, acryloyloxy and methacryloyloxy groups linked directly to the 2-hydroxyphenyl ring of the benzotriazole moiety were suspected of lower hydrolytic stability. Therefore, systems having the benzotriazole moiety coimected with the main chain via an aliphatic spacer were prepared, e.g. copolymers of 2-[2-hydroxy-4-(2-hydroxy-3-methacryloyloxy)propoxy]-2H-benzotriazole with methyl methacrylate [293]. 

The permeation, selectivity, and flux variation with methanol concentration has been explained using the solubiUty parameter approach Copolymers of acrylonitrile with methyl methacrylate and vinyl acetate showed good selectivity and moderate flux Membrane (I) gave high selectivity and acceptable flux... 

Problem 32.8 Graft copolymers can be made by each of the following processes. Show the chemistry most likely involved, and the structure of the product, (a) Polybutadiene is treated with styrene in the presence of a free-radical initiator, (b) Poly-(vinyl chloride) is treated with methyl methacrylate in the presence of benzoyl peroxide, (C,H5C00)2. 

In 1991, the production of methyl methacrylate was 1.84 million tons per year [41]. The United States, Western Europe, and Japan produced 0.66, 0.54, and 0.46 million tons per year, respectively [42], The cost for methyl methacrylate in 1991 was 0.62/lb [43]. Most acrylics start with methyl methacrylate monomer (MMA). Methyl methacrylate is used in the production of poly(methyl methacrylate) and in copolymers to improve the impact resistance of other vinyl polymers [44], Poly(methyl methacrylate) is a colorless transparent plastic with a higher softening point, better impact strength, and better weatherability than polystyrene [45]. 

---