Maleic anhydride copolymerization

Figure 3. GPC molecular weight data for poly-(styrene-co-maleic anhydride) copolymerized in acetone...

Figure 5. Molecular weight data for poly(styrene - co -maleic anhydride) copolymerized in benzene. Gel permeation chromatographic data obtained from THF solution containing hydroquinone...

XS = sulfonation, M = methylolation, MO = miscellaneous oxidation, G = grafting, P = phenolation, CM = carboxymethylation, MAC = maleic anhydride copolymerization, MCR = miscellaneous carboxyla-tion reactions, E = epichlorohydrin (also in conjunction with pheno-lated lignin), A = alkoxylation (i.e., ethylene, propylene, and butylene oxides), M+EP = modification with compounds containing unsaturated end groups ( divalent hydrocarbons ) followed by epoxidation with peroxide, MA = methacrylic acid. 

Maleic anhydride copolymerization with cis, trans, trans-, and trans, trans, trans-cyclododtcairiene have also been explored.Copolymerization in dioxane, with AIBN, gave white powders showing softening points >300°C. The copolymer was soluble in polar solvents and exhibited an NMR spectrum supportive of structure 44. 

Maleic anhydride-donor complexomers, neutral monomer copolymerization, 412-418 Maleic anhydride copolymerization with acetylene monomers, 334, 660 with acrolein, 286 with acrylamides, 285, 382, 660 with acrylates and methacrylates, 279-285, 291, 382, 383, 416... 

Maleic anhydride is used in a multitude of appHcations in which a vinyl copolymer is produced by the copolymerization of maleic anhydride with other molecules having a vinyl functionaHty. Typical copolymers and their end uses are Hsted in Table 11. 

Vinyl resins ie, copolymers of vinyl chloride and vinyl acetate which contain hydroxyl groups from the partial hydrolysis of vinyl acetate and/or carboxyl groups, eg, from copolymerized maleic anhydride, may be formulated with alkyd resins to improve their appHcation properties and adhesion. The blends are primarily used in making marine top-coat paints. 

Styrene Copolymers. Acrylonitrile, butadiene, a-methylstyrene, acryUc acid, and maleic anhydride have been copolymerized with styrene to yield commercially significant copolymers. Acrylonitrile copolymer with styrene (SAN), the largest-volume styrenic copolymer, is used in appHcations requiring increased strength and chemical resistance over PS. Most of these polymers have been prepared at the cross-over or azeotropic composition, which is ca 24 wt % acrylonitrile (see Acrylonithile polya rs Copolyp rs). 

Styrene readily copolymerizes with many other monomers spontaneously. The styrene double bond is electronegative on account of the donating effect of the phenyl ring. Monomers that have electron-withdrawiag substituents, eg, acrylonitrile and maleic anhydride, tend to copolymerize most readily with styrene because their electropositive double bonds are attached to the electronegative styrene double bond. Spontaneous copolymerization experiments of many different monomer pair combiaations iadicate that the mechanism of initiation changes with the relative electronegativity difference between the monomer pairs (185). 

VEs can also copolymerize by free-radical initiation with a variety of comonomers. According to the and rvalues of 0.023 and —1.77 (isobutyl vinyl ether), VEs are expected to form ideal copolymers with monomers of similar and e values or alternating copolymers with monomers such as maleic anhydride (MAN) that have high values of opposite sign (Q = 0.23 e = 2.25). 

A variety of trichloroethylene copolymers have been reported, none with apparent commercial significance. The alternating copolymer with vinyl acetate has been patented as an adhesive (11) and as a flame retardant (12,13). Copolymerization with 1,3-butadiene and its homologues has been reported (14—16). Other comonomers include acrylonitrile (17), isobutyl vinyl ether (18), maleic anhydride (19), and styrene (20). 

Vinyls. Vinyl resins are thermoplastic polymers made principally from vinyl chloride other monomers such as vinyl acetate or maleic anhydride are copolymerized to add solubUity, adhesion, or other desirable properties (see Maleic anhydride, maleic acid, and fumaric acid). Because of the high, from 4,000 to 35,000, molecular weights large proportions of strong solvents are needed to achieve appHcation viscosities. Whereas vinyls are one of the finest high performance systems for steel, many vinyl coatings do not conform to VOC requirements (see Vinyl polymers). 

The refined grade s fastest growing use is as a commercial extraction solvent and reaction medium. Other uses are as a solvent for radical-free copolymerization of maleic anhydride and an alkyl vinyl ether, and as a solvent for the polymerization of butadiene and isoprene usiag lithium alkyls as catalyst. Other laboratory appHcations include use as a solvent for Grignard reagents, and also for phase-transfer catalysts. 

Poly(MA-CDA) was synthesized by a free radical copolymerization of maleic anhydride and 7,12-diox-aspiro-[5,6]-dodec-9-ene, followed by hydrolysis in... 

Copolymerization of Furan and Homologues with Maleic Anhydride... 

In this section wc consider systems where the radical formed by propagation can eyclizc to yield a new propagating radical. Certain 1,4-dicncs undergo cyclocopolymerization with suitable olefins. For example, divinyl ether and MAH are proposed to undergo alternating copolymerization as illustrated in Scheme 4.19.167 These cyclo-copolymerizations can he quantitative only for the case of a strictly alternating copolymer. This can be achieved with certain electron donor-electron acceptor pairs, for example divinyl ether-maleic anhydride. 

Common chemistries include tannins and lignins but also more modem polyacrylates and derivatives, which often act as carriers for specific functional groups and provide novel chemistry molecules. The polyacrylates may also be copolymerized, perhaps with maleates [maleic anhydride, cis-butenedioic anhydride (OCOCHrCHCO) is the usual starting point material], styrene (vinylbenzene, phenylethylene,... 

The largest single use of maleic anhydride is in the preparation of unsaturated polyester resins. It is first esterihed with a polyalcohol (two or more hydroxyls) and then the double bond is copolymerized (crosslinked) with a vinyl monomer such as styrene to form a rigid structure. Such resins are usually reinforced with hberglass (FRP). Maleic anhydride is also used to make oil additives and agricultural chemicals. 

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