Polymers, methacrylates hydroxyl functionalized

In the preparation of monohydroxypolymethyl methacrylate described in Fig. 2,2-mercaptoethanol provides the terminal hydroxyl group. Azobisisobutyronitrile (AIBN) derived initiator fragments make polymer without hydroxyl functionality, but this apparently does not interfere with the development of a high level of physical properties in the completed ABA block polymer. 

Polymers. The molecular weights of polymers used in high energy electron radiation-curable coating systems are ca 1,000—25,000 and the polymers usually contain acryUc, methacrylic, or fumaric vinyl unsaturation along or attached to the polymer backbone (4,48). Aromatic or aUphatic diisocyanates react with glycols or alcohol-terrninated polyether or polyester to form either isocyanate or hydroxyl functional polyurethane intermediates. The isocyanate functional polyurethane intermediates react with hydroxyl functional polyurethane and with acryUc or methacrylic acids to form reactive p olyurethanes. 

Another approach is to use an initiator for ATRP that produces a polymer with a functional group capable of initiating a non-ATRP polymerization. ATRP polymerization of methyl methacrylate with 2,2,2-tribromoethanol produces an HO-terminated poly(methyl methacrylate). The hydroxyl group acts as an initiator in the presence of triethyl aluminum for the ring-opening polymerization of caprolactone. 

Graft copolymers were prepared by both classical strategies, that is, from enzymatically obtained macromonomers by subsequent chemical polymerization and by enzymatic grafting from hydroxyl functional polymers. Kalra et al. studied the synthesis of PPDL graft copolymers from macromonomers, which were obtained by the enzymatic ROP of pentadecalactone (PDL) from hydroxyethyl methacrylate (HEMA) and polyethylene glycol) methacrylate (PEGMA) [40]. Subsequently graft copolymers were obtained by free radical polymerization of the macromonomers. A similar approach was published by Srivastava for the HEMA-initiated enzymatic ROP of CL and subsequent free radical polymerization [41]. 

Poly(2-alkyl oxazoline)s having methacrylate or acrylate end groups were prepared by two methods [182]. a) Living polyoxazoline chains, prepared using methyl p-toluene sulphonate as initiator, were end-capped by reaction with metal salts or tetraalkylammonium salts of acrylic or methacrylic acid or a trialky-lammonium salt or trimethylsilyl ester of methacrylic acid (functional termination). b) The living polymers were terminated with water in the presence of Na2C03 to provide hydroxyl-terminated chains. Subsequent acylation with acry-loyl or methacryloyl chloride in the presence of triethylamine led to the formation of the macromonomers. The procedures are outlined in the following Scheme 51. 

Among three common classes of monomers including (meth)acrylates, styrenics and acrylamides, (meth)acrylates were the most widely used because various functional polymers with hydroxyl, carboxyl, amino and other groups can be facilely obtained from the corresponding functional (meth)acrylate monomers, except the commonly used monomers of methyl methacrylate (MMA) and u-butyl methacrylate ( -BMA). 

The exo-olefin is a precursor to a variety of chain-end-functionalized polymers via postpolymerization reaaions as shown in Scheme 37. Hydroxy-functionalized PIB has been utilized as a precursor for the preparation of RAFT macromo-lecular CTAs and carboxylic acid end-fimctionalized polymers. Telechelic PIB diols have been prepared using p-dicumyl chloride/BCU initiator system followed by dehydro-chlorination, hydroboration, and alkaline peroxide oxidation. Aldehyde end-fiinctionalized PIBs have been used to prepare carboxyl- and hydroxyl-terminated poly-mers. Carboxylic acid-functionalized PIBs have also been prepared from the oxidation of the methyl ketone-functionalized PIBs." The hydroxyl-functionalized PIBs have also been used to prepare methacrylate macromonomers by their reaction with methacryloyl chloride in the presence of triethylamine. The homopolymerization and copolymerization of these maaomonomers with methyl methacrylate were also reported. Cyanoacrylate-funaionalized PIBs prepared via the hydroxyl-functionalized PIB were also reported by Kennedy et al. ... 

A wide variety of other specialty monomers are also used to provide specialized performance properties for coating applications. For example, amine functional monomers can be used to improve adhesion to aged alkyd substrates. Specialized monomers can also be used to improve exterior durability, for example VEOVA (vinyl ester of vesatic acid) monomers can improve the hydrolysis resistance of vinyl acetate polymers, and n-butyl methacrylate can be used to enhance the durabiHty of BA-MMA acrylics. Polymer hydrophobicity can be fine tuned by varying the levels of hydrophobic and hydrophilic monomers in the composition and styrene or ethyl hexyl acrylate are used to increase film hydrophobicity and reduce water permeability in BA-MMA systems. Specialty monomers are also used to provide specific chemical functionality to polymer compositions. For example, hydroxyethyl methacrylate can be used to provide hydroxyl functionality to acrylic resins, allowing these polymers to be used in cross-linkable thermoset coatings which cure via melamine chemistry. While specialty monomers are used at relatively low levels in polymer compositions, they frequently provide the performance features needed for the successful application of emulsion polymers in many coating areas. 

Due to the fact that the primary structure of the Ultrahydrogel packing is a hydroxylated methacrylate, the interaction of many polar polymers with the packing is minimized easily. The presence of small amounts of anionic functions on the surface of the polymer usually requires the addition of salt to the mobile phase. A common mobile phase for many applications is 0.1 M NaN03. Detailed eluent selection guidelines are given in Table 11.6. 

SW series and Alltech Macrosphere series), hydroxylated methacrylate (e.g., TosoHaas TSK PW series. Waters Ultrahydrostyragel, Shodex OHPak), functionalized styrene/DVB (Polymer Laboratories PL aquagel-OH), poly(vinyl alcohol) (Shodex OHPak), and others. 

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