Methyl acrylate copolymerization

Scheme 2 Proposed mechanism for ethylene/methyl acrylate copolymerization...

Scheme 10 Activity reduction in ethylene-methyl acrylate copolymerizations due to the formation of stable chelate 1.30...

MOLECULAR DYNAMICS IN THE STUDIES OF THE ETHYLENE - METHYL ACRYLATE COPOLYMERIZATION... 

Figure 4-22. Mechanism of ethylene-methyl acrylate copolymerization monomer insertion...

Michalak A, Ziegler T, DFT Studies on the Copolymerization of a-Olefins with Polar Monomers Ethylene-Methyl Acrylate Copolymerization Catalyzed by a Pd-based Diimine Catalyst, J Am Chem Soc, 123, 12266-12278 (2001)... 

Scheme 13. Illustrative Products in Methyl Acrylate Copolymerization with a-Methylstyrene ...

The results of the static and dynamic DPT calculations for the methyl acrylate copolymerization suggest that there are two factors inhibiting the polar co-polymerization in the Ni-catalyst case (1) the initial 0-complex formation (2) a difficult chelate opening prior to insertion of the next monomer. Both of those factors may be overcome by the use of the complexes with reduced oxophihcity of the metal on the catalyst. 

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). 

Park MJ, Rhee HK. Control of copolymer properties in a semibatch methyl methacrylate/methyl acrylate copolymerization reactor by using a learning-based nonlinear model predictive controller, hid Eng Chem Res 2004 43 2736-2746. 

Copolymerization can be carried out with styrene, acetonitrile, vinyl chloride, methyl acrylate, vinylpyridines, 2-vinylfurans, and so forth. The addition of 2-substituted thiazoles to different dienes or mixtures of dienes with other vinyl compounds often increases the rate of polymeriza tion and improves the tensile strength and the rate of cure of the final polymers. This allows vulcanization at lower temperature, or with reduced amounts of accelerators and vulcanizing agents. 

AH-acryHc (100%) latex emulsions are commonly recognized as the most durable paints for exterior use. Exterior grades are usuaHy copolymers of methyl methacrylate with butyl acrylate or 2-ethyIhexyl acrylate (see Acrylic ester polymers). Interior grades are based on methyl methacrylate copolymerized with butyl acrylate or ethyl acrylate. AcryHc latex emulsions are not commonly used in interior flat paints because these paints typicaHy do not require the kind of performance characteristics that acryHcs offer. However, for interior semigloss or gloss paints, aH-acryHc polymers and acryHc copolymers are used almost exclusively due to their exceUent gloss potential, adhesion characteristics, as weU as block and print resistance. 

Fig. 2. Relationship between relative rate and monomer composition in the copolymerization of DAP with vinyl monomers A, styrene or methyl methacrylate B, methyl acrylate or acrylonitrile C, vinyl chloride D, vinyl acetate, and E, ethylene (41).

Vinyhdene chloride copolymerizes randomly with methyl acrylate and nearly so with other acrylates. Very severe composition drift occurs, however, in copolymerizations with vinyl chloride or methacrylates. Several methods have been developed to produce homogeneous copolymers regardless of the reactivity ratio (43). These methods are appHcable mainly to emulsion and suspension processes where adequate stirring can be maintained. Copolymerization rates of VDC with small amounts of a second monomer are normally lower than its rate of homopolymerization. The kinetics of the copolymerization of VDC and VC have been studied (45—48). 

Studies of the copolymerization of VDC with methyl acrylate (MA) over a composition range of 0—16 wt % showed that near the intermediate composition (8 wt %), the polymerization rates nearly followed normal solution polymerization kinetics (49). However, at the two extremes (0 and 16 wt % MA), copolymerization showed significant auto acceleration. The observations are important because they show the significant complexities in these copolymerizations. The auto acceleration for the homopolymerization, ie, 0 wt % MA, is probably the result of a surface polymerization phenomenon. On the other hand, the auto acceleration for the 16 wt % MA copolymerization could be the result of Trommsdorff and Norrish-Smith effects. 

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. 

Polymer Composition. Ethylene—acrylic elastomer terpolymers ate manufactured by the addition copolymerization of ethylene [74-85-1] and methyl acrylate [96-33-3] in the presence of a small amount of an alkenoic acid to provide sites for cross-linking with diamines (4). 

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... 

The diimine palladium compounds are less active than their nickel analogs, producing highly branched (e.g., 100 branches per 1,000 carbons) PE. However, they may be used for the copolymerization of Q-olefins with polar co-monomers such as methyl acrylate.318,319 Cationic derivatives, such as (121), have been reported to initiate the living polymerization of ethylene at 5°C and 100-400 psi.320 The catalyst is long-lived under these conditions and monodisperse PE (Mw/Mn= 1.05-1.08) may be prepared with a linear increase in Mn vs. time. 

IR absorption spectra were superimposable onto those of the physical mixtures of the respective homopolymers. The molar ratio of the poly(MMA) and polyethylene blocks, however, decreased as the Mn of the prepolymer increased, especially when it exceeded ca. 12 000 at which polyethylene began precipitating as fine colorless particles. It is noteworthy that smooth block copolymerization of ethyl acrylate or methyl acrylate to the growing polyethylene chain (Mn = 6 600-24 800) can be realized by the sequential addition of the two monomers. 

The Lewis acidity and reactivity of these alkyl aluminum cocatalysts and activators with Lewis basic polar monomers such as acrylates make them impractical components in the copolymerization of ethylene with acrylates. To address this shortcoming, Brookhart et al. developed well-defined cationic species such as that shown in Fig. 2, in which the counterion (not illustrated) was the now-ubiquitous fluorinated arylborate family [34] such as tetrakis(pentaflurophenyl)borate. At very low methyl acrylate levels the nickel catalysts gave linear copolymers but with near-zero levels of acrylate incorporation. 

In order to incorporate polar-functionalized olefins, the catalyst system must exhibit tolerance to the functionality as described above. Therefore, polar monomer incorporation by the Ni(II) catalysts is generally not observed. Traces of methyl acrylate can be incorporated by the Ni(II) catalyst only under low loadings of that monomer [85], Acrylamide has been incorporated after prior treatment with tri-isobutylaluminum to block the amide donor sites, although polymerization activities are still relatively low [86], A similar protection of Lewis-basic functionalities by the coactivator has been cited to explain the copolymerization of certain monomers by early transition metal systems as well [40],... 

The cationic Pd(II) catalysts exhibit effective copolymerizations of ethylene and other a-olefins with polar-functionalized comonomers, with the majority of insertions occurring at the ends of branches. Among the best tolerated monomers are those bearing fluorine or oxygen-containing functionalities, such as esters, ketones, and ethers. The copolymerization of ethylene and acrylates, attractive because the monomers are inexpensive and the copolymers exhibit unique physical properties, has been well-studied mechanistically [27,69], Examples of copolymerizations of ethylene and a-olefins with methyl acrylate are shown in Table 4. In general, the amount of comonomer incorporation varies linearly with its reaction concentration and... 

Table 4 Copolymerizations of ethylene and a-olefins with methyl acrylate (MA) by Pd(II) a-diimine catalysts3...

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