Maleic vinyl monomer copolymers

Radical copolymerization is used in the manufacturing of random copolymers of acrylamide with vinyl monomers. Anionic copolymers are obtained by copolymerization of acrylamide with acrylic, methacrylic, maleic, fu-maric, styrenesulfonic, 2-acrylamide-2-methylpro-panesulfonic acids and its salts, etc., as well as by hydrolysis and sulfomethylation of polyacrylamide Cationic copolymers are obtained by copolymerization of acrylamide with jV-dialkylaminoalkyl acrylates and methacrylates, l,2-dimethyl-5-vinylpyridinum sulfate, etc. or by postreactions of polyacrylamide (the Mannich reaction and Hofmann degradation). Nonionic copolymers are obtained by copolymerization of acrylamide with acrylates, methacrylates, styrene derivatives, acrylonitrile, etc. Copolymerization methods are the same as the polymerization of acrylamide. 

Hydroxyl containing polymers may be cross-linked with diisocyanates. Fordyce and Ferry cross-linked styrene-maleic anhydride copolymers through the action of glycols. The copolymerization of divinyl with vinyl monomers may be looked upon as a method of cross-linking chain polymers. The cross-linkages are introduced simultaneously with the growth of the linear polymer chains, rather than afterwards, but this difference is secondary. 

The double bond of maleic anhydride may undergo free radical polymerization with the proper initiator. Polymers of maleic anhydride (or copolymers made with another monomer) are commercially available (Polysciences). They consist of a linear hydrocarbon backbone (formed from the polymerization of the vinyl groups) with cyclic anhydrides repeating along the chain. Such polymers are highly reactive toward amine-containing molecules. 

The high electron richness of vinylferrocene as a monomer is illustrated in its copolymerization with maleic anhydride, where 1 1 alternation copolymers are formed over a wide range of monomer feed ratios and ri -2 = 0.003. Subsequently, a large number of detailed copolymerization studies have been undertaken using metal-containing vinyl monomers. 

The stabilizer, gelled in the presence of ferric ions, is aptly selected from a hydro-lyzate of a copolymer of a vinyl monomer and an unsatd acid anhydride, or a water-sol acrylic polymer. Thus a preblend of AN 130, aq HNO3(60%) 60, NaNOg 10, MeOCH CH2-maleic anhydride copolymer hydrolyzate 6, and Fe2(S04)3 1 part was maintained at 43° and mixed with. a blend of paraffin 8, sorbitan monopa Imitate 5, and mineral oil. 1 part, maintained at 32° During mixing, sufficient air was introduced to yield a compri having a d of 0.75 at 43°]... 

Chirality induction can be achieved in homo- and copolymerization of vinyl monomers based on chiral monomer structure [1,3,8,9]. The first example of this type of polymerization was the copolymerization of (S)-a-methylbenzyl methacrylate with maleic anhydride the polymerization product showed [a]D +23° after removal of the chiral side group [73]. For another example, the copolymerization of an optically active styrene derivative (39) with N-phenylmaleimide (17, R = -Ph) followed by removal of the optically active side group and deboronation gave an optically active N-phenylmaleimide-styrene copolymer [74]. 

Multicomponent Systems from Copolymers of Maleic Anhydride and Vinyl Monomers... 

The latter technique is more rapid than the former (27, 31). In 1930 Wagner-Jauregg showed that alternating copolymers are obtained when maleic anhydride is copolymerized with vinyl monomers (34). This is true for copolymerization in good solvents, but when the molar ratio of styrene to maleic anhydride is greater than 1, styrene may add to the alternating copolymer in poor solvents to produce block copolymers. 

Compound 35 contains a thermolabile C-C bond which, on thermally induced fragmentation, yields a high proportion of macroradicals. The PDMS diradical also acts as a counter radical and can undergo chain extension at both ends in the presence of vinylic monomers (acrylonitrile, maleic anhydride, diethylfumarate) or styrenic monomers, leading to diblock copolymers in 95% yield according to the following scheme [211, 212] ... 

Some typical values of reactivity ratios for monomers that will copolymerize via a free-radical route are shown in Table 1.15 (Tirrell, 1989, Allcock and Lampe, 1981). These have been selected in order to span the range of values shown in the preceding tables. It may be noted that the copolymerization of vinyl monomers with maleic anhydride will invariably lead to alternating copolymers since rj 2 0. The mechanism of alternating... 

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. 

T t has previously been shown that the rate of the free-radical-initiated copolymerization of maleic anhydride and vinyl monomers is faster in poor solvents than in good solvents, and that the copolymerization rates in these poor solvents decrease as the difference in the solubility parameter values between that of the copolymer and the solvent increases (6, 10). Other investigators have suggested that this free-radical initiation involves hydrogen abstraction, and that the free-radical precursor increases the yield of the alternating copolymer regardless of the monomer charge (3). 

To prepare the copolymers, enough solvent was added to 0.5 gram of equimolar quantities of maleic anhydride and vinyl monomer and 0.0125 gram azobisisobutyronitrile to make a total volume of 5 ml. The copolymerizations were conducted in sealed glass containers in the absence of oxygen. The precipitate was removed from heterogeneous systems, washed well with fresh solvent after filtration, and dried under a vacuum at 0°C. 

Nyloprint, of BASF is a solid type of photosensitizer compound coated plate, around 1967. The solid photopolymerizing material is a combination of an alcohol-soluble polyamide (such as a polyamide copolymer of hexamethylene diammonium adipate and e-caprolactam), a vinyl monomer (such as bis-acrylamide, hexamethylene bis-acrylamide, triethylene glycol diacrylate, etc.), a photo-initiator such as benzoin methyl ether, and an inhibitor (such as hydroquinone) and maleic anhydride to function as a... 

Block (or graft) copolymers have been obtained by the addition of styrene and N,N-dimethylformamide (DMF) to acrylonitrile macroradicals, and add by the addition of methyl methacrylate or styrene to vinyl chloride macroradicalsBlock copolymers have also been produced by the addition of various vinyl monomers to styrene-maleic anhydride macroradicals (122) ... 

Industrial suspension polymerizations of vinyl chloride are often carried out in large batch reactors or stirred jacketed autoclaves. Continuous reactors, however, have been introduced in several manufacturing facilities [315]. Typical recipes call for 100 parts of vinyl chloride for 180 parts of water, a suspending agent, like maleic acid-vinyl acetate copolymer, a chain transferring agent, and a monomer soluble initiator. The reaction may be carried out at 100 Ib/in. pressure and 50°C for approximately 15 h. As the monomer is consumed the pressure drops. The reaction is stopped at an... 

Both polymers were formed from their vinyl monomers. Pendant benzoin groups can be introduced into the polymers by other techniques. One can start, for instance, with a copolymer of styrene and maleic anhydride and form ester groups ... 

As an introduction, our previous studies on the conformations of maleic acid copolymers with aromatic vinyl monomers are summarized. To characterize the compact form and the pH-indueed conformational transition of the maleic acid copolymer with styrene in aqueous NaCl, 400 MHg H-NMR spectra were measured. The spectral form depended on the molecular conformation. Because each of proton resonance peaks could not be separated, the spin-lattice relaxation time T was estimated by using the inversion recovery technique (tf-t-tf/2). The T s for both side chain and backbone protons reflected the transition, and the protons were considered to be in a more restricted motional state in the compact form than in the coil form. Also, from temperature dependence of each Tj, motion of the copolymer in the coil form was described in terms of the local segmental jump (D) combined with the isotropic rotational motion (O), when a ratio between both the correlation times tq and Tq was about 0.07. For the compact form, the ratio was found to be about 10. By referring to theoretical diagram of Tj vs. tq for the methylene protons on the backbone, value of Tn for the compact form was compared with that for the coil form at 35 C. 

On the other hand, copolymers of maleic acid with various vinyl monomers had been investigated in studying the influence of local charge density on polyelectrolyte properties, and some alternating copolymers of maleic acid with n-alkyl vinyl ethers were found to undergo the conformational transitions from the compact form to the extended coil upon ionization of primary carboxyl groups in maleic acid. " The hydrophobic interaction seems to be responsible for stabilization of the compact form. Viscometric, potentiometric and calorimetric measurements have been used to study the transition mechanisms. 

The tendency for alternation of monomers in a styrene-maleic anhydride and styrene-acrylonitrile copolymers at moderate temperatures has been attributed to the formation of a charge transfer complex (CTC) between a donor (D) and an acceptor (A). This CTC is readily detectable by UV or nmR spectroscopy. More important, the equilibrium constant decreases as the temperature is increased and this effect can be followed by instrumental analysis. Thus it is possible to extrapolate to a higher temperature at which the CTC does not exist (16). Thus, by proper temperature control, it is possible to produce SMA alternating copolymers, block copolymers of vinyl monomers with both alternating and random SMA (17) and completely random copolymers of SMA (18). Half esters of SMA have been used as viscosity control agents in petroleum crudes (19). 

Whereas homopolymerizations of maleic or fumaric add derivatives have not yet found technical interest, copolymers derived from MAH and various vinyl monomers are commercialized by several chemical companies. Such commerdal copolymers may be based on styrene (Scriptset or SMA), ethene (EMA, Malethamer, VINAC), isobutene (ISOBAM), butadiene (Maldene), vinyl alkyl ethers (Gantrez AN or Viscofres), and vinyl acetate (Lyfron, Benex, Amoco DriUing Aid 420,421, or Baroid X tend). 

Activity of A,A-diallyl-A -acetylhydrazine in reactions of radical homo- and copolymerization has been studied. It was determined, that A,A-diallyl-A -acetylhydrazine does not homopolymerize aceording to fi"ee-radical mechanism, but copolymerize with N-vinylpyrrolidone, acrylamide, methaerylic and maleic acids resulting in formation of water-soluble copolymers with a random distribution of the comonomer units in a maeromoleeule. A,A-diallyl-A -acetylhydrazine is less active if compared with vinyl monomers. A,A-diallyl-A -acetylhydrazine exhibits high activity at copolymerization with sulphur dioxide. The reaction results in alternating of copolymers of equimolar eomposition irrespeetive of reaetion conditions. NMR and electron spectroscopy data proved A,A-diallyl-A -aeetylhydrazine to copolymerize (both double bonds are involved) with formation of pyrrolidine struetures. Cyclolinear copolymers obtained are soluble owing to intramoleeular eyelization of N,N-diallyl-A -acetylhydrazine when formation of the polymer ehain and to the absenee of intermolecular crosslinks. Kinetic regularities of the proeess, stmeture and some properties of copolymers have been studied. 

Being virtually inert at homopolymerization, DAAH appeared to copolymerize with vinyl monomers at the presence of radical initiators. The results of investigation on DAAH copolymerization with acrylic and maleic acids, N-vinylpyrrolidone and acrylamide, resulting in obtaining of water-soluble polymers, have been given in present paper. Copolymerization reactions proceed both in bulk and in solution with formation of copolymers, characterized by a random distribution of the comonomer units in a macromolecule (Table 1). DAAH is less active if compared with vinyl monomers (VM) - copolymers are enriched by VM units at all ratios of the monomers in the initial mixture. In particular, DAAH content in copolymers at initial equimolar monomer ratio is 15-20 mol % (Table 1). When conducting reaction at 80-90°C and initiator concentration 2.5-3.0 mas.% at equimolar monomer ratio the reaction rate of investigated systems is 2.7-4.1% per hour. The increase of DAAH fraction in the initial mixture allows to increase its content in the copolymer, but at the same time reaction rate decreases. 

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