Meth acrylates

Polylacrylic Acid) and Poly(methacrylic Acid). Glacial acrylic acid and glacial meth-acrylic acid can be polymerized to produce water-soluble polymers having the following structures ... 

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. 

Of the commercially available EB-curable adhesives [9-12], the resins fall within one of two categories based on their curing mechanisms. The majority of EB-curable resins are based on (meth)acrylate-functionalized oligomers involving a free-radical curing mechanism. The second category is the epoxy resins that cure by a cationic mechanism. 

Methacrylates and acrylates are readily synthesized from low-cost commercially available resins and (meth)acrylate intermediates or (meth)acrylic acid [19]. A wide range of structural backbones are available, including epoxies, urethanes. 

Polyacrylates are an industrially important class of polymers. The name polyacrylate is variously used to refer to polymers of acrylate esters [e.g., poly(methyl methacrylate)] as well as polymers of acrylic acids [e.g., poly(meth-acrylic acid)]. Because the former is organic soluble while the latter is not, chromatographic analysis of these two requires quite different conditions. This chapter discusses both types of polymers, separating their consideration when necessary. We will refer to both types of polymers as polyacrylates, letting the context indicate whether we are referring to an ester or to an acid polymer. 

Table 7.4 Rate Constants (298 K) for Addition of Substituted Propyl Radicals to (Meth)acrylate Esters (Scheme 7.4)35...

Radical induced grafting may be carried out in solution, in the melt phase,292 29 or as a solid state process.296 This section will focus on melt phase grafting to polyolefin substrates but many of the considerations are generic. The direct grafting of monomers onto polymers, in particular polyolefins, in the melt phase by reactive extrusion has been widely studied. Most recently, the subject has been reviewed by Moad1 9 and by Russell.292 More details on reactive extrusion as a technique can be found in volumes edited by Xanthos," A1 Malaika and Baker et a 21 7 The process most often involves combining a frcc-radical initiator (most commonly a peroxide) and a monomer or macromonomer with the polyolefin as they are conveyed through the extruder. Monomers commonly used in this context include MAII (Section 7.6.4.1), maleimidc derivatives and malcate esters (Section 7.6.4.2), (meth)acrylic acid and (meth)acrylate esters (Section 7.6.43), S, AMS and derivatives (Section 7.6.4.4), vinylsilancs (Section 7.6.4.5) and vinyl oxazolines (Section 7.6.4.6). 

Various (meth)acrylic monomers have been successfully grafted onto polyolefins. Most studies deal with functional monomers. Grafting yields obtained with PP are usually low (<20%) and are dependent on the particular monomer. Liu et al.jM carried out a comparative study on the grafting of various functional methacrylates onto PP. The experiments were performed in a batch mixer at 180 °C with 7 wt% monomer and 0.05 wt% 22 as an initiator. Grafting levels (wt%) obtained under these conditions were as follows HPMA (I), TBAEMA (1), GMA (0.8), IIEMA (0.4), DMAEMA (0.3), 32 (0.2). Grafting yields to PE appear generally higher. 

A1 Malaika et a/.35" 754 have reported on the grafting of antioxidant moieties onto PP as mono- (e.g. 33) or bis-(meth)acrylic derivatives (34). Moderate grafting yields (10—40%) and some homopolymerization was observed in the case of the monoacrylate. However, with the bis-acrylate (34) close to 100% grafting yield was reported. 

Polymerization, including radical polymerization, in supercritical C02 has been reviewed.1 6 137 It should be noted supercritical C()2 while a good solvent for many monomers is a very poor solvent for polymers such as the (meth)acrylates and S. As a consequence, with the exception of certain fluoropolymers and polymerizations taken to very low conversion, most polymerizations in supercritical CCb are of necessity precipitation, dispersion or emulsion polymerizations. 

Nickel complexes (156-159) used as ATRP catalysts for polymerization of (meth)acrylates are shown in Table 9.8. 

Early reports focused on the dithiobenzoale RAFT agents (Z=Ph e.g. 171-180, Table 9.10).3S2 410 Cumyl dithiobenzoate (175) shows utility with S and (meth)acrylic monomers.38 However, retardation is an issue with the acrylates... 

Aqueous, removable, pressure-sensitive adhesive compositions, useful for high-performance applications, comprise a mixture of a copolymer of alkyl (meth)acrylate and N-substituted (poly)amide of (meth)acrylic acid and a copolymer of alkyl (meth)acrylate and ethylenically unsaturated carboxylic acid, where at least one of the copolymers is an emulsion copolymer. Polyoxyalkyl-enes and phosphate esters may be used as surfactants [234]. 

Manufacture of highly water-absorbent polymers with uniform particle size and good flowability can be carried out by reverse phase suspension polymerization of (meth)acrylic acid monomers in a hydrocarbon solvent containing crosslinker and radical initiator. Phosphoric acid monoester or diester of alka-nole or ethoxylated alkanole is used as surfactant. A polymer with water-absorbent capacity of 78 g/g polymer can be obtained [240]. 

Mori H, Muller A (2003) Hyperbranched (Meth)acrylates in Solution, in the Melt, and Grafted From Surfaces. 228 1-37 Mrksich M, see Houseman BT (2002) 218 1-44... 

Hyperbtanched (Meth)acrylates in Solution, Melt,and Grafted From Surfaces 3... 

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