Ethylene methyl acrylate system

The ethylene methyl acrylate system is amenable to low-temperature NMR mechanistic studies with all of the critical intermediates visible spectroscopically." " Acrylate insertion occurs predominantly in a 2,1-fashion, yielding a strained four-membered chelate ring in which the carbonyl oxygen atom is coordinated to the palladium atom. This insertion is followed by a series of /3-hydride eliminations and readditions expanding the ring stepwise to the six-membered chelate complex this is the catalyst resting state shown in Scheme 6. 

Ethylene Methyl Acrylate System. EMA, new encapsulant adhesive, Hluride deveTopf Preliminary work showed excellent adhesion of EMA to glass when the glass is primed with A11861-1. Long-term soaking in cold water reduced the adhesion. Additional work and samples are needed. 

Heteroatom functionalized terpene resins are also utilized in hot melt adhesive and ink appHcations. Diels-Alder reaction of terpenic dienes or trienes with acrylates, methacrylates, or other a, P-unsaturated esters of polyhydric alcohols has been shown to yield resins with superior pressure sensitive adhesive properties relative to petroleum and unmodified polyterpene resins (107). Limonene—phenol resins, produced by the BF etherate-catalyzed condensation of 1.4—2.0 moles of limonene with 1.0 mole of phenol have been shown to impart improved tack, elongation, and tensile strength to ethylene—vinyl acetate and ethylene—methyl acrylate-based hot melt adhesive systems (108). Terpene polyol ethers have been shown to be particularly effective tackifiers in pressure sensitive adhesive appHcations (109). 

The oxygen scavenging polymer system consists of an oxidizable resin, ethylene methyl acrylate cyclohexene methyl acrylate (EMCM) and a masterbatch containing a photoinitiator and a cobalt... 

In all cases, an ELSD was the only possible detection system because of the solvent gradient. Pasch et al. [112] reported the separation of EVA and ethylene-methyl acrylate (EMA), and also combined the solvent gradient separation with collection of germanium disks for FTIR measurement. 

Radiation Induced Reactions. Graft polymers have been prepared from poly(vinyl alcohol) by the irradiation of the polymer-monomer system and some other methods. The grafted side chains reported include acrylamide, acrylic acid, acrylonitrile, ethyl acrylate, ethylene, ethyl methacrylate, methyl methacrylate, styrene, vinyl acetate, vinyl chloride, vinyl pyridine and vinyl pyrrolidone (13). Poly(vinyl alcohols) with grafted methyl methacrylate and sometimes methyl acrylate have been studied as membranes for hemodialysis (14). Graft polymers consisting of 50% poly(vinyl alcohol), 25% poly(vinyl acetate) and 25% grafted ethylene oxide units can be used to prepare capsule cases for drugs which do not require any additional plasticizers (15). 

Another immobilized system was recently reported by Wei and Liu [64] using amphiphilic coblock polymers consistent of ethylene glycol and methyl acrylate monomers that had been functionalized with imidazole groups. In combination with oxone (KHS05) as the oxidant in an ethyl acetate/water mixture, this system yields the 1,2-diol product in 62% yield, which is probably formed by ring opening of the epoxide by the acidic oxone. 

Methyl cyclobutane carboxylate decomposes cleanly and unimolecularly to ethylene and methyl acrylate in the gas phase between 653 and 693 °K in static systems. The reaction can be well represented, both qualitatively and quantitatively by the biradical mechanism, viz. 

Figure 3.36 The effect of ethanol and acetone cosolvents on the cloud point pressure of the poly(ethylene-co-methyl acrylate) (90mol% ethylene and 10 mol% methyl acrylate)-propane system. The copolymer concentration is fixed at 5 wt% and the weight-average molecular weight of the copolymer is 34,000 with a molecular weight polydispersity of 2.0. This copolymer is —15% crystalline. (Hasch et al., 1993.)...

Figure 5.10 Comparison of calculated (lines) and experimental cloud point data (symbols) of the poly(ethylene-co-methyl acrylate) (69 mol%/ 31 mol%)-acetone-propane system (Hasch et al., 1993). The polymer concentration is fixed at 5wt%. The calculations are performed with the Sanchez-Lacombe EOS with kij and 17,y set equal to zero for the EMAt9/3i-acetone pair, kij = 0.030 and rj/y = 0.000 for the propane-acetone pair, and kij = 0.023 and 77,/ = -0.002 for the EMA soi-propane pair. The weight average and number average molecular weights of EMA69/31 are 58,900 and 31,000, respectively.

McHugh and coworkers describe the fractionation of various poly(ethylene-co-methyl acrylate) copolymers using supercritical propane, propylene, 1-butene, and chlorodifluoromethane (Meilchen, Hasch, and McHugh, 1991 Pratt, Lee, and McHugh, 1993). The objective of their work was to extend the work of Krukonis and coworkers (Scholsky et al., 1987 Watkins and Krukonis, 1991) who demonstrated the ability of fractionating by chemical composition of the polymer as well as molecular weight. This concept is also described with other polymer-SCF solvent systems in the next few sections of this chapter. 

Meilchen, M. A., 64, 69, 81, 87, 126, 196, 205, 206, 359, 360 Melhem, G. A., 104 Melting point, 21, 46 Merrill, R. C, 77 Methane, 20, 22, 115 Methane-carbon dioxide system, 48 Methane-ethane, 114 Methane-ethane-octane system, 115-117 Methane-hydrocarbon system, 37 Methane-methanol system, 183, 188 Methane-octane system, 114, 116 Methanol, 102,109, 110 Methanol-methane system, 184 Methyl acrylate, 81, 214, 215, 322 Methyl ethyl ketone (MEK)-water-ethylene system, 76... 

Most addition polymers are formed from polymerizations exhibiting chain-growth kinetics. Such processes include the typical polymerizations of the vast majority of vinyl monomers such as ethylene, styrene, vinyl chloride, propylene, methyl acrylate, and vinyl acetate. Furthermore, most condensation polymers are formed from systems exhibiting stepwise kinetics. Industrially, such systems include those used for the formation. pa of polyesters and polyamides. Thus, a large overlap exists between the terms... 

Figure 17 presents the energy profiles for the methyl acrylate insertion into the Pd-alkyl and Ni-alkyl bond in the generic diimine systems [31,32]. The results clearly indicate that it is not the insertion barrier which makes the Ni-system inactive in polar copolymerization. The acrylate insertion barrier is substantially lower for the Ni-catalyst then for the Pd-complex. This, in fact, should not be surprising, as the ethylene insertion barriers are also lower for the Ni-system. 

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