Methyl acrylate polymerization

Breitenbach and Frank (5) showed that with styrene-divinylbenz-ene, no further additives (such as peroxides) are necessary for popcorn polymer formation. Breitenbach and Fally (6) found, in methyl acrylate polymerization, the possibility of crosslinking in the polymerization of a monovinyl compound. Miller and coworkers (7) developed the kinetics of the process Pravednikow and Medvedev (8) studied the chain scission, and assumed radical formation by that process as an important step. 

Exploration of the template controlled free-radical oligomerization of other activated olefins began with standard monomers utilized in bulk polymer synthesis and the template 63. Vinyl acetate and acrylonitrile led only to uncontrolled polymerization, while vinylene carbonate did not react under the standard experimental conditions. More exotic monomers, such as vinyl trifluoroacetate and rert-butyl acrylate, were also unsuccessful. Only methyl acrylate polymerization was arrested by template 64 to provide the macrocyclized product 96 in modest yield as a mixture of five diastereomers (Scheme 8-25). Subsequent studies with the more effective thiophenyl-bearing template 63 at lower temperatures improved this yield to 35%. The diastereomer distribution was reminiscent of the methyl methacrylate-derived product, although no stereochemical assignments were made in this case either. 

Methyl acrylate polymer Synonyms Methyl acrylate, polymerized Polymerized methyl acrylate Empirical C4H6O2... 

Methyl acrylate, polymerized. See Methyl acrylate polymer... 

Waveguides consist of a thin layer of a high-refractive index material surrounded by/embedded in a low-refractive material. One way of making these layers uses of photolocking of a second component in a polymeric layer, followed by removal of this component from the unexposed area In this way, fiber optic sheet systems have been made as well as beam splitters, couplers, etc. In a typical example (Fig. 13) a dilute solution of polycarbonate, methyl acrylate and a photoinitiator in a solvent is spin-coated on a substrate, pattemwise exposed such that the methyl acrylate polymerizes in the exposed area and finally evaporation of unreacted monomer from the unexposed areas. 

CuPFg, complexed with two molecules of pyridine, is an efficient system for ATRP of styrene and methyl acrylate [8]. Notably, ligand exchange occurring with mixed systems such as CuBr/R-Q was not observed due to the noncoordinating nature of CuPF. For styrene polymerization employing phenylethylchloride as the alkyl halide, better control of the molecular weight and linear kinetic behavior was observed. The rates of polymerization were enhanced in methyl acrylate polymerization. 

Detailed kinetic studies and kinetic simulations for the formation and decay of complexes that can only occur by radical interchange were analyzed to give a radical exchange constant (k f) for the vinyl acetate and methyl acrylate polymerizations in the presence of (TMP)Co-P. The rate constants deduced for radical exchange (kex(333 K) = 0.5-1.0 x 10 s ) (P + (TMP)Co-Pn Pm-Co(TMP) + Pn )... 

CHjlCH COOH. Colourless liquid having an odour resembling that of ethanoic acid m.p. 13 C, b.p. I4I°C. Prepared by oxidizing propenal with moist AgO or treating -hy-droxypropionitrile with sulphuric acid. Slowly converted to a resin at ordinary temperatures. Important glass-like resins are now manufactured from methyl acrylate, see acrylic resins. Propenoic acid itself can also be polymerized to important polymers - see acrylic acid polymers. 

Poly (methyl Acrylate). The monomer used for preparing poly(methyl acrylate) is produced by the oxidation of propylene. The resin is made by free-radical polymerization initiated by peroxide or azo catalysts and has the following formula ... 

Poly(acrylic acid) and Poly(methacrylic acid). Poly(acryHc acid) (8) (PAA) may be prepared by polymerization of the monomer with conventional free-radical initiators using the monomer either undiluted (36) (with cross-linker for superadsorber appHcations) or in aqueous solution. Photochemical polymerization (sensitized by benzoin) of methyl acrylate in ethanol solution at —78° C provides a syndiotactic form (37) that can be hydrolyzed to syndiotactic PAA. From academic studies, alkaline hydrolysis of the methyl ester requires a lower time than acid hydrolysis of the polymeric ester, and can lead to oxidative degradation of the polymer (38). Po1y(meth acrylic acid) (PMAA) (9) is prepared only by the direct polymerization of the acid monomer it is not readily obtained by the hydrolysis of methyl methacrylate. 

The relatively low flash points of some acrylates create a fire hazard. Also, the ease of polymerization must be home in mind in ah. operations. The lower and upper explosive limits for methyl acrylate are 2.8 and 25 vol %, respectively. Corresponding limits for ethyl acrylate are 1.8 vol % and saturation, respectively. All possible sources of ignition of monomers must be eliininated. 

Historically, the development of the acrylates proceeded slowly they first received serious attention from Otto Rohm. AcryUc acid (propenoic acid) was first prepared by the air oxidation of acrolein in 1843 (1,2). Methyl and ethyl acrylate were prepared in 1873, but were not observed to polymerize at that time (3). In 1880 poly(methyl acrylate) was reported by G. W. A. Kahlbaum, who noted that on dry distillation up to 320°C the polymer did not depolymerize (4). Rohm observed the remarkable properties of acryUc polymers while preparing for his doctoral dissertation in 1901 however, a quarter of a century elapsed before he was able to translate his observations into commercial reaUty. He obtained a U.S. patent on the sulfur vulcanization of acrylates in 1912 (5). Based on the continuing work in Rohm s laboratory, the first limited production of acrylates began in 1927 by the Rohm and Haas Company in Darmstadt, Germany (6). Use of this class of compounds has grown from that time to a total U.S. consumption in 1989 of approximately 400,000 metric tons. Total worldwide consumption is probably twice that. 

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. 

An example of this improvement in toughness can be demonstrated by the addition of Vamac B-124, an ethylene/methyl acrylate copolymer from DuPont, to ethyl cyanoacrylate [24-26]. Three model instant adhesive formulations, a control without any polymeric additive (A), a formulation with poly(methyl methacrylate) (PMMA) (B), and a formulation with Vamac B-124 (C), are shown in Table 4. The formulation with PMMA, a thermoplastic which is added to modify viscosity, was included to determine if the addition of any polymer, not only rubbers, could improve the toughness properties of an alkyl cyanoacrylate instant adhesive. To demonstrate an improvement in toughness, the three formulations were tested for impact strength, 180° peel strength, and lapshear adhesive strength on steel specimens, before and after thermal exposure at 121°C. 

A substantial number of photo-induced charge transfer polymerizations have been known to proceed through N-vinylcarbazole (VCZ) as an electron-donor monomer, but much less attention was paid to the polymerization of acrylic monomer as an electron receptor in the presence of amine as donor. The photo-induced charge-transfer polymerization of electron-attracting monomers, such as methyl acrylate(MA) and acrylonitrile (AN), have been recently studied [4]. In this paper, some results of our research on the reaction mechanism of vinyl polymerization with amine in redox and photo-induced charge transfer initiation systems are reviewed. 

Methyl Acrylate CH2=CHCOOCH3 Non-inhibitors such as Biphenyl, Bibenzyl, Tri-phenyl, etc Methyl Acrylate Vap plus air > Ambient > 120 Inhibitor—H ydro quino ne or Methyl Ether of Hydro-quinone 10-20ppm. Store Store below 10° no inert atmosphere. No sparks 18.58-18.8 463 Self polymerizing above ambient press temp accelerates polymerization... 

Other commercially relevant monomers have also been modeled in this study, including acrylates, styrene, and vinyl chloride.55 Symmetrical a,dienes substituted with the appropriate pendant functional group are polymerized via ADMET and utilized to model ethylene-styrene, ethylene-vinyl chloride, and ethylene-methyl acrylate copolymers. Since these models have perfect microstructure repeat units, they are a useful tool to study the effects of the functionality on the physical properties of these industrially important materials. The polymers produced have molecular weights in the range of 20,000-60,000, well within the range necessary to possess similar properties to commercial high-molecular-weight material. 

In addition, Bamford, Jenkins and coworkers (19) previously reported on the behavior of occluded radicals in the heterogeneous polymerizations of acrylonitrile, methyl acrylate, methyl methacrylate and vinylidene chloride. From their electron spin resonance studies, they concluded that the degree of occlusion was ... 

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