Olefinic copolymers Ethylene-methyl acrylate

ATBN - amine terminated nitrile rubber X - Flory Huggins interaction parameter CPE - carboxylated polyethylene d - width at half height of the copolymer profile given by Kuhn statistical segment length DMAE - dimethyl amino ethanol r - interfacial tension reduction d - particle size reduction DSC - differential scanning calorimetry EMA - ethylene methyl acrylate copolymer ENR - epoxidized natural rubber EOR - ethylene olefin rubber EPDM - ethylene propylene diene monomer EPM - ethylene propylene monomer rubber EPR - ethylene propylene rubber EPR-g-SA - succinic anhydride grafted ethylene propylene rubber... 

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... 

However, a method to improve the flow properties of such fuel oils of animal or vegetable origin, has been developed (26). This consists in adding a EVA copolymer or a comb polymer based on methyl acrylate and a-olefins. In addition, terpolymers of ethylene, vinyl acetate and isobutylene have been found to be useful as cold flow improvers (29). 

In later communications (27, 28) Hirooka reported that in addition to acrylonitrile, other conjugated monomers such as methyl acrylate and methyl methacrylate formed active complexes with organoaluminum halides, and the latter yielded high molecular weight 1 1 alternating copolymers with styrene and ethylene. However, an unconjugated monomer such as vinyl acetate failed to copolymerize with olefins by this technique. 

Phase behavior studies with poly(ethylene-co-methyl acrylate), poly (ethylene-co-butyl acrylate), poly(ethylene-co-acrylic add), and poly(ethylene-co-methacrylic acid) were performed in the normal alkanes, their olefinic analogs, dimethyl ether, chlorodifluoromethane, and carbon dioxide up to 250 °C and 2,700 bar. The backbone architecture of the copolymers as well as the solvent quality greatly influences the solution behavior in supercritical fluids. The effect of cosolvent was also studied using dimethyl ether and ethanol as cosolvent in butane at varying concentrations of cosolvent, exhibiting that the cosolvent effect diminishes with increasing cosolvent concentrations. 

Smooth, but one-way, mechanistic crossover from olefin polymerization to group-transfer polymerization is possible with lanthanocene catalysts, since insertion of an acrylate into the propagating metal alkyl to form an enolate is energetically favorable. Block copolymers of ethylene with MMA, methyl acrylate, ethyl acrylate, or lactones have been prepared by sequential monomer addition to lanthanide catalysts and exhibit superior dyeing capabilities. However, the reverse order of monomer addition, i.e., (meth)acrylate followed by ethylene, does not give diblocks since the conversion of an enolate (or alkox-ide) to an alkyl is not favored. Therefore, although... 

LDPE Copolymers. A variety of comonomers can be added to the polymerization of ethylene to make copolymers. The free-radical polymerization mechanism of LDPE production allows for the copolymerization of polar comonomers. At this time, the incorporation of polar comonomers is unique to LDPE. The transition metals used to catalyze HDPE and LLDPE production are generally poisoned by polar comonomers and therefore, only copolymers containing alpha-olefins like 1-butene, 1-hexene, and 1-octene can be made. Because the polar copolymers can be made only by the LDPE process, they command a premium in the market. The most common comonomers (and their corresponding copol5uners) are vinyl acetate (EVA), methyl acrylate (EMA), ethyl acrylate (EEA), and acrylic acid... 

For example, this method was carried out for various copolymers, namely styrene-methyl methacrylate copolymer [65-67], epoxide resins [68], styrene-acrylic acid copolymer [69], styrene-2-methoxyethyl methacrylate copolymer [70, 71], ethylene-ot-olefin copolymer [72], partially modified dextran-ethyl carbonate copolymer [73], vinyl chloride-vinyl acetate copolymer [43], styrene-acrylonitrile copolymer [74], and styrene-butadiene copolymer [75]. 

I. Organic carbochain polymers and copolymers of poly-4-methylpentene-l [4] PMMA or methyl methacrylate (MMA) copolymers with other alkyl-(meth)acrylates (AMA) [1-3, 5] poly(vinyl acetate) vinyl acetate copolymer with ethylene [4, 6-8] polymers of chlorine-containing olefins [9]. 

There has been a slight increase in activity in this area compared with that in the previous two year period. For the polymeric esters of acrylic, methacrylic acids, and related polymers the simplest reaction, apart from thermal depolymerization, is hydrolysis, and one or two papers on this subject have appeared. One of these concerns a comparison of the kinetics of hydrolysis of a number of methacrylate esters and a further two deal with the formation of copolymers containing carboxylic acid functions. Methyl trifluoroacrylate forms alternating copolymers with cE-olefins (ethylene, propylene, isobutylene) and these are readily hydrolysed in boiling aqueous methanolic sodium hydroxide to yield hydrophilic fluoropolymers. Hydrolysis is reported to be nearly quantitative with no chain scission. An alternating copolymer is also formed by radical polymerization of maleic anhydride with A-vinyl succinimide. On hydrolysis this copolymer is... 

There is a large amount of literature and many patents in this area, as well as many good reviews and books [8,9,10,11,12,13,14,15,16,17,18,19]. The recent review by Coates [10] describing stereoselective polymerization overlaps considerably with this chapter, and is recommended for consultation. In this chapter, metallocene-catalyzed olefin polymerization is discussed, focusing on the synthesis of stereoregulated polymers. The aim of this review is not to be a complete survey the outline and some recent topics in polymerization of propylene, higher a-olefins, styrene, acrylate esters such as methyl methacrylate (MMA), 1,3-butadienes, and cycloolefins will be described. Polyethylene is one of the most important commercially manufactured polymers. The homopolymer, as well as the copolymer with ethylene and other olefins, is an important subject in the polyolefin industry. However, it will be only briefly mentioned because the stereochemistry is less involved. 

---