Maleic anhydride copolymers with methyl methacrylate

If the polymer is not compatible with the impact modifier, a compatibiliser (see earlier in this chapter) may be needed. The choice will depend on both the main constituents. Maleated ethylene-octene and maleated SEBS are often used, since they also contribute to the impact modifying action. When polyamide-6 is mixed with ABS, the compatibiliser can be styrene-maleic anhydride copolymer, poly(methyl methacrylate co-maleic anhydride) or poly(methyl methacrylate co-glycidyl methacrylate). 

Macroradicals obtained by the copolymerization of equimolar quantities of styrene and maleic anhydride in benzene or in cumene were also used as initiators to produce block copolymers with methyl methacrylate, ethyl methacrylate, and methyl acrylate. The yields of these block copolymers were less than those obtained with styrene, but as much as 38% of methyl methacrylate present in the benzene solution added to the macroradical to produce a block copolymer. The amount of ethyl methacrylate and methyl acrylate that was abstracted from the solution to form block copolymers was 35 and 20%. 

The rate of polymerization of polar monomers, for example, maleic anhydride, acrylonitrile, or methyl methacrylate, can be enhanced by coraplexing them with a metal halide (zinc or vanadium chloride) or an organoaluminum halide (ethyl aluminum sesqui-chloride). These complexed monomers participate in a one-electron transfer reaction with either an uncomplexed monomer or another electron-donor monomer, for example, olefin, diene, or styrene, and thus form alternating copolymers (11) with free-radical initiators. An alternating styrene/acrylonitrile copolymer (12) has been prepared by free-radical initiation of equimolar mixtures of the monomers in the presence of nitrile-coraplexing agents such as aluminum alkyls. 

Copolymers maleic anhydride copolymer with ethylene or vinyl methyl ether, acrylic acid copolymers, and methacrylic acid copolymers (Eudragit)... 

Maleic copolymers having variable hydrophobicity (maleic anhydride copolymers with a hydrophilic comonomer - vinyl acetate and a hydrophobic comonomer - methyl methacrylate), are obtained in anhydrous form by "Petru Poni" Institute of Macromolecular... 

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. 

PolyCACN) has a rigid chain structure yet can form excimers with alternate units along the chain (8), or by stacking in a helical conformation. Excimer formation has been reported for alternate copolymers of ACN with styrene (9) and for ACN with maleic anhydride CIO). The situation is different for 2-vinylnaphthalene since alternating copolymers of 2VN with methyl methacrylate or methacrylic acid did not form excimers, yet random copolymers of the same systems showed excimer fluorescence Cll). Only random copolymers of ACN were prepared in this work. 

Block copolymers in good yield were obtained when the styrene-maleic anhydride macroradicals were heated with methyl methacrylate in benzene at 50°C. (see Figure 2). Unlike what happened when... 

Figure 4. Chromatograms of pyrolyzates from copolymers of methyl methacrylate (MMA) with equimolar concentration of maleic anhydride (MA) [A] and with fourfold molar excess of MA [B]...

Glycidyl methacrylate has also been grafted to polyethylene and to poly(ethylene-co-propylene) using peroxides in extruders.87 The reactive group need not be pendant. It can be part of a copolymer. Ethylene-methyl acrylate copolymers and styrene-maleic anhydride copolymers have been reacted with ammonia and with amines in extruders.88... 

Styrene-maleic anhydride copolymer (SMA) and terpolymers with methyl methacrylate (SMA-MMA) and acrylonitrile (SMA-AN)... 

Methyl methacrylate-maleic anhydride copolymer matrices with different percentages of surface anhydride functional groups were prepared by solution copolymerisation. Acriflavine was bound on the matrix surfaces by chemical bonding in organic medium. The amount of acriflavine bound to the matrix was spectroscopically characterised, and the in-vitro release rate of acriflavine in weakly basic medium was established along with the determination of its antimicrobial activity. 9 refs. 

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]. 

The copolymers obtained by radical copolymerization of maleic anhydride (MA) with acrylic or vinyl comonomers, and the maleic add copolymers, generally obtained by the hydrolysis of the maleic anhydride copolymers (Figure 10.1), can be called maleic copolymers. They were intensively studied from a theoretical perspective, but also for their applications [1-3]. Copolymers ofMA with electron-donating comonomers, such as styrene, vinyl acetate, N-vinyl pyrrolidone, and methyl vinyl ether, have an alternant structure [ 1 ], but when MA is copolymerized with electron-acceptor comonomers like methyl methacrylate, acrylonitrile, statistic copolymers are obtained [1,2]. MA units from the copolymers are very reactive active agents with amine or hydroxyl groups... 

Side-chain polymers are usually prepared in the form of copolymers with NLO-active moieties attached on the backbone via flexible spacers such as methylene units. Examples are copolymers of methyl methacrylate and chromophore-substituted methacrylate monomers [53,61-63], poly(styrene-fy -acrylic acid ester) [54], and alternating styrene-maleic-anhydride copolymer [64], and there are many others. 

A special case of asymmetric enantiomer-differentiating polymerization is the isoselective copolymerization of optically active 3-methyl-1-pentene with racemic 3,7-dimethyl-1-octene by TiCl4 and diisobutylzinc [Ciardelli et al., 1969]. The copolymer is optically active with respect to both comonomer units as the incorporated optically active 3-methyl-l-pentene directs the preferential entry of only one enantiomer of the racemic monomer. The directing effect of a chiral center in one monomer unit on the second monomer, referred to as asymmetric induction, is also observed in radical and ionic copolymerizations. The radical copolymerization of optically active a-methylbenzyl methacrylate with maleic anhydride yields a copolymer that is optically active even after hydrolytic cleavage of the optically active a-methylbenzyl group from the polymer [Kurokawa and Minoura, 1979]. Similar results were obtained in the copolymerizations of mono- and di-/-menthyl fumarate and (—)-3-(P-styryloxy)menthane with styrene [Kurokawa et al., 1982],... 

An appropriate formalism for Mark-Houwink-Sakurada (M-H-S) equations for copolymers and higher multispecies polymers has been developed, with specific equations for copolymers and terpolymers created by addition across single double bonds in the respective monomers. These relate intrinsic viscosity to both polymer MW and composition. Experimentally determined intrinsic viscosities were obtained for poly(styrene-acrylonitrile) in three solvents, DMF, THF, and MEK, and for poly(styrene-maleic anhydride-methyl methacrylate) in MEK as a function of MW and composition, where SEC/LALLS was used for MW characterization. Results demonstrate both the validity of the generalized equations for these systems and the limitations of the specific (numerical) expressions in particular solvents. 

In this paper a generalized approach is presented to the derivation of H-H-S equations for multispecies polymers created by addition polymerization across single double bonds in the monomers. The special cases of copolymers and terpolymers are derived. This development is combined with experimental results to evaluate the numerical parameters in the equations for poly(styrene-acrylonitrile ) (SAN) in three separate solvents and for poly(styrene-maleic anhydride-methyl methacrylate) (S/HA/MM) in a single solvent. The three solvents in the case of SAN are dimethyl formamide (DMF), tetrahydrofuran (THF), and methyl ethyl ketone (MEK) and the solvent for S/HA/HH is HER. 

In fact, the copolymers of methacrylic acid with maleic anhydride (14) and the copolymers of vinyl alcohol with maleic anhydride (127) obtained respectively from optically active (l-methyl-benzyl)-methacrylate or (l-methyl-benzyl)-vinyl-ether and maleic anhydride, were optically active, but their rotatory power was rather small. 

Comparable results were observed for the copolymerization of maleic anhydride and methyl methacrylate (8 = 10.8 for copolymer), methyl acrylate (8 = 10.7 for copolymer), and butyl methacrylate (8 = 10.7 for copolymer). However, the copolymers of maleic anhydride and stearyl methacrylate (8 = 10.3) and maleic anhydride and isobutyl methacrylate (8 = 10.4) have lower solubility parameter values, and hence, a slow homogeneous copolymerization was observed when these monomers were copolymerized with maleic anhydride in benzene. 

The formation of block copolymers from styrene-maleic anhydride and acrylic monomers was also indicated by pyrolytic gas chromatography and infrared spectroscopy. A comparison of the pyrograms of the block copolymers in Figure 7 shows peaks comparable with those obtained when mixtures of the acrylate polymers and poly(styrene-co-maleic anhydride) were pyrolyzed. A characteristic infrared spectrum was observed for the product obtained when macroradicals were added to a solution of methyl methacrylate in benzene. The characteristic bands for methyl methacrylate (MM) are noted on this spectogram in Figure 8. 

In addition, borane-containing POs can be prepared by copolymerization of olefin with borane monomers or by hydroboration of polyolefins including unsaturated groups, such as olefin-divinylbenzene copolymer and olefin-diene copolymers. Many kinds of graft copolymers, such as poly-elhylene-gra/f-poly( vinyl alcohol), PE-g-PMMA, polypropylcnc-gra/f-poly-(maleicanhydride-co-styrene), polypropylene-gra/f-poly(methacrylic acid), polypropylene-gra/f-poly(vinyl alcohol), polypropylene-gra/f-polycaprolac-tone (PP-g-PCL), polypropylcnc-gra/f-poly(methyl methacrylate) (PP-g-PMMA), poly( ethylene-co-propylene)-gra/f-poly(methyl methacrylate) (EPR-g-PMMA), and poly(ethylene-co-propylene)-gra/f-poly(maleic anhydride-costyrene), have been synthesized by such a method resulting in controllable composition and molecular microstructures [63-66]. 

Examples of acid modified polyolefins are the copolymers of ethylene with acrylic acid or methacrylic acid. Variations include the partially neutralised acid copolymers with metal ions (ionomers) or terpolymers of ethylene, an acid and an acrylate such as methyl acrylate or isobutyl acrylate. Acid-containing extrudable adhesives are widely used to bond to aluminium foil. Examples of anhydride-modified polyolefins include terpolymers of ethylene, maleic anhydride and acrylates such as ethyl acrylate or butyl acrylate and the anhydride-grafted polyolefins. Some typical applications and stmctures of a variety of multilayer materials with extruded polymer tie-layer adhesives, as described in Du-Pont trade literature, are detailed in Table 16.2. 

The electron richness of vinylferrocene as a monomer has been demonstrated in its copolymerization with maleic anhydride, in which 1 1 copolymers were obtained over a wide range of feed ratios and ri r2 = 0.003 [13]. Subsequent copolymerization of vinylferrocene with classic organic monomers, such as styrene [13], Ai-vinyl-2-pyrrolidone [15], methyl methacrylate [13] and acrylonitrile [13] were carried out and the Alfrey-Price Q and e parameters [16] determined. The value of e is a semiempirical measure of the electron richness of the vinyl group. The best value of e for vinylferrocene is about —2.1, which, when compared with the e values of maleic anhydride (-H 2.25), p-nitrostyrene (-1-0.39), styrene (—0.80), p-Ai,Ai -dimethyl-aminostyrene ( — 1.37) and l,T-dianisylethylene ( — 1.96), again emphasizes the electron rich nature of the vinyl group in vinylferrocene. 

TWO organometallic polymers previously developed, tributyl-tin methaczylate/methyl methacrylate copolymer (TBTM/MeM) and the tributyltin ester of methyl vinyl ether/maleic anhydride (TBT-MVEt-MAn), were selected for use as wood impregnants. Full Cell and Enpty Cell Methods were used to treat wood with TBTCVMeM in "Rule 66" mineral spirits and in combination with P13 creosote. Although the polymers seem to be miscible with the creosote, this combination results in only surface penetration of wood when... 

The rates of radical-monomer reactions are also dependent on considerations of steric effects. It is observed that most common 1,1-disubstituted monomers — for example, isobutylene, methyl methacrylate and methacrylo-nitrile—react quite readily in both homo- and copolymerizations. On the other hand, 1,2-disubstituted vinyl monomers exhibit a reluctance to ho-mopolymerize, but they do, however, add quite readily to monosubstituted, and perhaps 1,1-disubstituted monomers. A well-known example is styrene (Ml) and maleic anhydride (M2), which copolymerize with r — 0.01 and T2 = 0 at 60°C, forming a 50/50 alternating copolymer over a wide range of monomer feed compositions. This behavior seems to be a consequence of steric hindrance. Calculation of A i2 values for the reactions of various chloroethylenes with radicals of monosubstituted monomers such as styrene, acrylonitrile, and vinyl acetate shows that the effect of a second substituent on monomer reactivity is approximately additive when both substituents are in the 1- or cr-position, but a second substituent when in the 2- or /3-position of the monomer results in a decrease in reactivity due to steric hindrance between it and the polymer radical to which it is adding. 

Consider the copolymerization of 1,3-butadiene with the following monomers n-butyl vinyl ether, methyl methacrylate, methyl acrylate, styrene, vinyl acetate, acrylonitrile, maleic anhydride. If the copolymerizations were carried out using cationic initiation, what would be expected qualitatively for the copolymer compositions List the copolymers in order of their increasing butadiene content. Would copolymers be formed from each of the comonomer pairs Explain what would be observed if one used anionic initiation ... 

Since the Arimoto/Haven report of vinylferrocene polymerization was not detailed, this monomer was made and both its homopolymerization and its copolymerization were studied with a variety of organic comonomers such as styrene, methylacrylate, maleic anhydride, acrylonitrile, methyl methacrylate, N-vinylpyrolidone, vinyl acetate, and so on.31-38 The polymers were as well characterized as possible, and copolymer compositions were obtained versus feed mole ratios. 

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