Acrylate, n-butyl

In 1975 Wacker-Chemie introduced silicones under the name of m-polymers. These are also room temperature curing liquid polymers which give rubbery materials on cross-linking and are available both as one- and two-component systems. Their particular feature is that they contain dispersions of copolymers such as those of styrene and n-butyl acrylate in the shape of rods or rice grains in the fluid silicone polymer. A small amount of the organic copolymer is also grafted onto the silicone backbone. 

The micellar effect on the endo/exo diastereoselectivity of the reaction has also been investigated. The endo/exo ratio of the reaction of cyclopentadiene with methyl acrylate is affected little (compared to water) by the use of SDS and CTAB [73b], while a large enhancement was observed in SDS solution when n-butyl acrylate was the dienophile used [74]. The ratio of endo/exo products in the reaction of 1 with 113c is not affected by CTAB, SDS and C12E7 [72a]. 

A recent report [90] investigated the Diels-Alder reaction of cyclopentadiene with various acrylates in SC-CO2 catalyzed by Sc(OTf)j. The results relative to n-butyl acrylate, in SC-CO2 and in conventional solvents, are reported in Scheme 6.34. The catalyzed reaction carried out under supercritical conditions went to completion within 15 h at 50 °C, whereas the uncatalyzed reaction proceeded only to 10 % after 24 h. An increase of endo/exo diastereoselectivity was also observed. 

Since this pioneering work a number of IPNs have been prepared. Poly(styrene) has been used as the second network polymer in conjunction with several other polymers, including poly(ethyl acrylate), poly(n-butyl acrylate), styrene-butadiene, and castor oil. Polyurethanes have been used to form IPNs with poly(methyl methacrylate), other acrylic polymers, and with epoxy resins. 

To assess the utility of this resin, we chose to employ it in the evaluation of the heterogeneity of a commercial polymer-entrapped Pd(OAc)2 precatalyst, Pd-EnCat, also sold by Reaxa. This precatalyst was designed with the goal of providing a heterogeneous catalyst that would allow simple removal of palladium from reactions (24-26). PVPy and QTU were first used as poisons in the Heck reaction of iodobenzene and n-butyl acrylate in DMF using PdfC as the palladium... 

The greatest use of latex paints for indoor applications is based upon vinyl acetate, which constitutes 85% of the total polymer usage, the remainder being acrylates (e.g., n-butyl acrylate). For outdoors or bathroom usage, acrylates are the major components. For various applications, e.g., wood paints, styrene copolymerised with acrylates are used. Flowever, yellowing of the styrene units occurs. 

ARGET ATRP has been successfully applied for polymerization of methyl methacrylate, ft-butyl acrylate and styrene in the presence of Sn(EH)2 (10 mol% vs. alkyl halide initiator or 0.07 mol% vs. monomer) [164,165]. For all monomers, polymerizations were well controlled using between 10 and 50 ppm of copper complexes with highly active TPMA and Me6TREN ligands. ARGET ATRP has also been utilized in the synthesis of block copolymers (poly(n-butyl acrylate)— -polystyrene and polystyrene-Z -poly(n-butyl acrylate) [164,165] and grafting... 

Living radical polymerizations have received considerable attention because they provide a convenient alternative for synthesizing block copolymers, polymers of narrow polydispersity and complex polymer structures (1-5). Because of their ability to initiate living free radical polymerizations, iniferters have been examined extensively after Otsu et al. (6) introduced them in 1982. In particular, dithiocarbamate derivatives have been studied more closely by several researchers. Lambrinos et al (7) have examined the molecular weight evolution during the polymerization of n-butyl acrylate using p-x ylylene bis(A,A-diethyl... 

Figure 2.3 Relationship between polydispersity of the resulting random copolymers and mole percent of styrene in the feed mixture for the copolymerization of (i) styrene and n-butyl acrylate (Ob and (ii) styrene and methyl methacrylate ( ) mediated by 14...

Although the above demonstrated that product control could be achieved in scC02, the difference in selectivity was relatively small. However, later work using a Lewis acid catalyst, scandium triflate, on the Diels-Alder reaction of n-butyl acrylate and cyclopentadiene (Scheme 7.7) showed that the endo exo ratio was again found to rise to a maximum and then decrease again as the pressure, and hence density, was increased (Figure 7.3) [19]. 

Figure 7.3 Density dependent enhancement of the endo.exo ratio for the Sc(OTf)3 catalysed reaction between n-butyl acrylate and cyclopentadiene in scCCF. Reproduced by permission of the Royal Society of Chemistry...

The two examples of adsorbed side chain substituted macromolecules, i.e., the poly(n-butyl acrylate) brush and the tris(p-undecyloxybenzyloxo) benzoate jacketed polystyrene, demonstrate two rather complementary aspects of the interaction of such molecules with a planar surface. In the first case the two-dimension to three-dimension transition results in a cooperative collapse of an extended coil conformation to a globule. The second case shows a rather high degree ordering with a distinct orientation of the backbone in the substrate plane. Combination of both effects and partial desorption can lead to a repta-tion-hke directed motion as depicted schematically in Fig. 36. 

Bauer et al. describe the use of a noncontact probe coupled by fiber optics to an FT-Raman system to measure the percentage of dry extractibles and styrene monomer in a styrene/butadiene latex emulsion polymerization reaction using PLS models [201]. Elizalde et al. have examined the use of Raman spectroscopy to monitor the emulsion polymerization of n-butyl acrylate with methyl methacrylate under starved, or low monomer [202], and with high soUds-content [203] conditions. In both cases, models could be built to predict multiple properties, including solids content, residual monomer, and cumulative copolymer composition. Another study compared reaction calorimetry and Raman spectroscopy for monitoring n-butyl acrylate/methyl methacrylate and for vinyl acetate/butyl acrylate, under conditions of normal and instantaneous conversion [204], Both techniques performed well for normal conversion conditions and for overall conversion estimate, but Raman spectroscopy was better at estimating free monomer concentration and instantaneous conversion rate. However, the authors also point out that in certain situations, alternative techniques such as calorimetry can be cheaper, faster, and often easier to maintain accurate models for than Raman spectroscopy, hi a subsequent article, Elizalde et al. found that updating calibration models after... 

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