Poly alkyl acrylates

Copolymerization of macromonomers formed by backbiting and fragmentation is a second mechanism for long chain branch formation during acrylate polymerization (Section 4.4.3.3). The extents of long and short chain branching in acrylate polymers in emulsion polymerization as a function of conditions have been quantified.20  

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Unlike most crystalline polymers, PVDF exhibits thermodynamic compatibiUty with other polymers (133). Blends of PVDF and poly(methyl methacrylate) (PMMA) are compatible over a wide range of blend composition (134,135). SoHd-state nmr studies showed that isotactic PMMA is more miscible with PVDF than atactic and syndiotactic PMMA (136). MiscibiUty of PVDF and poly(alkyl acrylates) depends on a specific interaction between PVDF and oxygen within the acrylate and the effect of this interaction is diminished as the hydrocarbon content of the ester is increased (137). Strong dipolar interactions are important to achieve miscibility with poly(vinyhdene fluoride) (138). PVDF blends are the object of many papers and patents specific blends of PVDF and acryflc copolymers have seen large commercial use. 

Fig. 1. T vs 8 for poly(alkyl acrylates). = number of C atoms in alkyl side chain. To convert MPa to (cal/cm ), divide by 2.05.

If q = 1, r and p = 0 and X = oxygen, the family of alkoxyalkyl acrylates is obtained. The improvement of the solubiUty parameter for this family compared to poly( -alkyl acrylates) is shown in Figure 2. 

Morimoto, K. and Suzuki, S., "Ultraviolet Irradiation of Poly(alkyl Acrylates) and Poly(alkyl Methacrylates)", J. Appl. Polym. Sci., 1972, 16, 2947-2961. 

Poly(methyl methacrylate) Poly(alkyl acrylates) Triblock, branched... 

Yamauchi K, Lizotte JR, Long TE. Thermoreversible poly(alkyl acrylates) consisting of self-complementary multiple hydrogen bonding. Macromolecules 2003 36 1083-1088. 

Ionizing radiation on poly(alkyl acrylates) results in cross-linking efficiencies, which are sensitive to the structure of the alkyl ester group."... 

In the first stage, the elastomeric component, typically a poly-(alkyl acrylate) rubber, is produced. This reaction can be carried out either in a water-based emulsion or in a solution polymerization process. 

From its architecture, ASA is closely related to ABS however, instead of polybutadiene rubber particles grafted with poly(styrene-acrylonitrile) (PSAN), poly(alkyl acrylate)-based graft rubber particles are used as the impact modifier (Figure 16.1). 

Generally, the poly(alkyl acrylate) core is slightly crosslinked to exhibit the needed elastomeric properties. Grafted chains, tethered to the acrylate rubber surface, serve as chemically bonded compatibilizers between the rubber particles and the PSAN matrix (Figure 16.2). 

Chlorinated, sulfonated, chlorosulfonated or epoxidized polymers, homopolymers and copolymers of functionalized monomers, e.g. poly(methacryl aldehyde), poly(2,3-epoxypropyl acrylate), poly(4-vinylphenol), poly(propylene-co-10-unde-cene-l-ol), poly(butadiene-co-methacryl aldehyde), poly(butadiene-co-acrylic acid), poly(ethylene-co-alkyl acrylate), poly(alkyl acrylate-co-2,3-epoxypropyl acrylate), poly(alkyl acrylate-co-maleic anhydride), poly(styrene-co-4-vinylbenzyl chloride)... 

Poly(Alkyl Acrylate)s and Poly(Alkyl Methacrylate)s. . . . 161... 

The effect of the length and structure of side groups on the conformation of polymer molecules and the equilibrium rigidity of the main chain has been studied systematically for homologous series of poly(alkyl acrylate)s... 

The theoretical dependence described by Eq. (77) is comi red with experimental data obtained for poly(alkyl methacrylate)s and poly(alkyl acrylate)s (Figs. 52 and 53). 

One difficulty associated with polymer-based gene therapy is that delivery efficiency is generally low, due to redirection of the polymer complexes to and enzymatic hydrolysis of the DNA in the lysosome, rather than release of DNA from the endosome (see Figure 2). A strategy to circumvent this is to include polymers that disrupt the endosomal membrane. This is achieved if they are active i.e. protonated) at pH 6.5 or below, but inactive (deprotonated) at pH 7.4, since the endosomal pH is around one unit lower than the cytoplasm. Hoffman, Tirrell and co-workers have developed synthetic polymers such as poly(alkyl acrylic acid)s and poly(acrylate-co-acrylic acid)s that show en-... 

In PMMA and similar systems such as poly(alkyl acrylates) with long side chains the quasi-continuous barrierless character of the motion of the main... 

In ASA terpolymer acrylic acid brings more flexibility and the material has very good mechanical properties and weather resistance. For these reasons ASA is extensively used in automotive industry and in the fabrication of various appliances. Even more frequently than acrylic acid itself, various acrylates are used in copolymers. Among these can be mentioned the copolymers of acrylic acid esters with methacrylic acid esters such as poly(methyl methacrylate-co-methyl acrylate), poly(methyl methacrylate-co-ethyl acrylate), poly(methyl methacrylate-co-butyl acrylate), poly(ethyl methacrylate-co-ethyl acrylate), poly(acrylonitrile-co-methyl acrylate), poly(alkyl acrylate-co-methyl methacrylates), and poly(alkyl acrylate-co-hydroxyethyl methacrylates) where alkyl can be methyl, ethyl, butyl, etc. Some literature information regarding thermal decomposition of copolymers including acrylic acid and acrylic acid esters is given in Table 6.7.8 [6],... 

McHugh M A, Rindfleisch F, Kuntz PT, Schmaltz C, Buback M. Cosolvent effect of alkyl acrylates on the phase behavior of poly(alkyl acrylates)-supercritical CO2 mixtures. Pol5mier 1998 39 6049-6052. 

Poly(alkyl acrylates) form soft segments. As acrylate polymerization terminates by combination, multiblock copolymers are formed if styrene is the second monomer. These block copolymers show two glass transition temperatures ( 30°C. and 90°C.). Phase separation occurs with domain structures depending on the stjnrene/methyl acrylate ratio (18). 

Lora, M., Rindfleisch, R, and McHugh, M.A., Influence of the alkyl tail on the solubility of poly(alkyl acrylates) in ethylene and COj at high pressures experiments and modeling, J. Appl. Polym. ScL, 73, 1979-1991, 1999. 

Oxidation of waste plastics, such as polyethylene, polypropylene, polystyrene, poly (alkyl acrylates), and nylon 6,6, with NO/O2 for 16 h at 170°C, led to mixtures of carboxylic acids, for which uses would have to be developed if this method was applied to large volumes of waste plastics.180 Hydrogenation of polyethylene at 150C>C for 10 h over a sil-ica/alumina-supported zirconium hydride catalysts gave a 100% conversion to saturated oligomers.181 Polypropylene gave a 40% conversion to lower alkanes at 190°C for 15 h. It is not clear what use these materials would have, other than serving as a feedstock for a petroleum refinery. 

The halogen end group can be transformed into other functionalities by means of standard organic procedures, such as a nucleophilic displacement reaction. Different authors have investigated this process of the nucleophilic displacement reactions with model compounds, to confirm the feasibility and selectivity. Compounds such as 1-phenylethyl halide, methyl 2-bromopropionate, and ethyl 2-bromoisobutane mimic the end groups of PSs, poly(alkyl acrylates), and poly(alkyl methacrylates), respectively. Different compounds have been tested, such as sodium azide, n-butylamine, and n-butylphosphine. 

For example, poly(alkyl acrylates) with bromine end groups were reacted with allyl tri-n-butyltin and Cu(0) in benzene. After 3h, complete radical addition reaction was obtained, ll NMR confirmed the presence of the allyl function. 

Similar reaction conditions were used with allyl alchohol [131,133,136, 137], and the addition of allyl alcohol to the poly(alkyl acrylate) chain is shown in Scheme 20 [137]. 

A one-pot synthesis of telechelic and semitelechelic poly(alkyl acrylates) with unsaturated end groups has been developed by Bielawski et al. [1]. ATRP of methyl acrylate or -BA was initiated with either ethyl cy-bromomethyl-acrylate or methyl dichloro acetate, as a monofunctional or a difunctional initiator, respectively, and was mediated with various Cu-amine complexes. Addition of excess ethyl 2-bromomethylacrylate was found to immediately quench the polymerization, but also to insert 2-carbethoxyallyl moieties at the ends of the polymer chains (Scheme 24). Thus, the synthesis of telechelic poly(alkyl acrylates) with unsaturated end groups has been accomplished, with very good functionality (f 2) (Scheme 24). 

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