Vinyl acetate comonomer with acrylonitrile

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). 

Graft copolymerization of acrylonitrile with various vinyl comonomers such as methyl acrylate, ethyl acrylate, vinyl acetate, and styrene onto cellulose derivatives using ceric ion was studied [24]. The results showed that... 

Copolymers of acrylonitrile and methyl methacrylate (115) and terpolymers of acrylonitrile, styrene, and methyl methacrylate (116,117) are used as barrier polymers. Acrylonitrile copolymers and multipolymers containing butyl acrylate (118—121), ethyl acrylate (122), 2-etliylliexyl acrylate (118,121,123,124), liydroxyethyl acrylate (120), vinyl acetate (119,125), vinyl ethers (125,126), and vinylidene chloride (121,122,127—129) are also used in barrier films, laminates, and coatings. Environmentally degradable polymers useful in packaging are prepared from polymerization of acrylonitrile with styrene and methyl vinyl ketone (130). Table 5 gives the structures, formulas, and CAS Registry Numbers for several comonomers of acrylonitrile. 

Acrylics. Acrylics are produced by the polymerization of acrylonitrile. They have a chemical structure essentially comprising the repeating unit, [ —CH2—CH(CN)—]n, with up to 15 percent of the polymer comprising one or two other monomeric units. As comonomers, vinyl acetate and an acrylate or methacrylate ester is used to vary the properties of the polymer for both ease of processing into a fiber and for improved fiber properties [8]. 

We have studied excited states in polyacenaphthylene (PACN) and in random copolymers of acenaphthylene with the following comonomers 2-vinylnaphthalene (2VN), acrylonitrile (AN), methacrylonitrile (MAN) and N-vinylcarbazole (VCz) (5.6). Also ACN was copolymerized with vinyl acetate, and the acetate groups were removed by hydrolysis. 

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. 

FIGURE 12.4 Illustration of drift in copol rmer composition with conversion in a batch reactor for two commercially important comonomer pairs. VA content in copolymer increases sharply with conversion in acrylonitrile-vinyl acetate copol merization (i i/iJ2 = 4.05/0.061) and content of MA in copolymer changes very little with conversion in acrylonitrile-methyl acrylate copolymerization (i i/i 2=l 02/0.70). 

In any case, the free or incorporated benzoquinone free radicals do not induce any further polymerization benzoquinone is an inhibitor for this polymerization. Quinones with very high oxidation potentials, as, for example, 2,5,7,10-tetrachlorodiphenoquinone, are, however, comonomers. They are built into the chain their free radicals induce the polymerization. But this quinone does not polymerize with either acrylonitrile or with vinyl acetate, so a simple copolymerization is not involved in this case. 

The polymerization proceeds spontaneously at room temperature or elevated temperatures. The proposed matrix of the comonomer complexes is described in Reference 96. Examples of alternating acrylonitrile copolymerizations involve vinyl cyclohexanes with AlEC2H5tCl2 (97), vinyl acetate with ZnCl2 (98) or Ziegler-Natta catalyst (99), and styrene. 

Fig. 3. Monomer-copolymer composition in the copolymeri zation of vinyl fluoride at 30°C with 02/B(i-C4H9)3 = 0.5 initiator (based on total monomer charged) and ethyl acetate as solvent. Comonomers vinyl chloride (VCl), acrylonitrile (AN), vinyl acetate (VA), chlorotri-fluoroethylene, ethylene, tetrafluoroethylene, cis-l-hydropentafluoropropene (C3F5H), hex-afluoropropene (CsFe), hexafluorocyclobutene (c-C4Fe), and vinylidene fluoride (VF2). From Ref. 86.

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... 

Jenner and Kellou recently studied the pressure effect on azeotropy in free-radical terpolymerization of MA with acrylonitrile, dielthyl fumarate, methyl acrylate, methyl methacrylate, methyl vinyl ketone, vinylidene chloride, norbornene, a-methylstyrene, indene, and vinyl acetate, with styrene as the second comonomer common in all cases. It was found that ternary azeotropes were only possible for those systems where the first comonomers had positive e values, i.e., diethyl fumarate, acrylonitrile, methyl acrylate, methyl methacrylate, methyl vinyl ketone, and vinylidene chloride. Surprisingly, the coordinates of the ternary azeotropes were very little affected by variations of the pressure from 1-3,000 bars. Since reactivity ratios in multi-component polymerizations are sensitive to pressure, causing terpolymer composition to also be pressure dependent, a shift of the ternary azeotropic point would be expected. Why this occurs awaits further clarification. 

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