2-Hydroxyethyl methacrylate copolymerization with

Copolymerization of di- and trimethacrylates with functionalized monomers, like glycidyl methacrylate, leads to low-viscosity oligomers capable of nonradical cross-linking. This process promises substantial value for industrial applications. Star polymers useful in coatings were prepared by copolymerizing methacrylate macromonomers with diacrylates.519 For instance, a star polymer was synthesized by copolymerization of a 2-ethylhexyl methacrylate/isobutyl methacrylate/hydroxyethyl methacrylate macromonomer with butanediol diacrylate. 

Styrene monomer was also copolymerized with a series of functional monomers by using a single-step dispersion copolymerization procedure carried out in ethanol as the dispersion medium by using azobisizobu-tyronitrile and polyvinylpyrollidone as the initiator and the stabilizer, respectively [84]. The comonomers were methyl methacrylate, hydroxyethyl acrylate, metha-crylic acid, acrylamide, allyltrietoxyl silane, vinyl poly-dimethylsiloxane, vinylsilacrown, and dimethylamino-... 

The effect of hydrophobicity of the polymer on the permeability of poly(2-hydroxyethyl methacrylate (HEMA)-co-methacrylic acid (MAAc) hydrogels was studied [12], The hydrophobicity was controlled by copolymerization with butyl methacrylate (BMA). The dependence of permeability on pH increased as the hydrophobicity increased even though the rate of diffusion decreased. Cross-link density of the hydrogel also contributed to pH-dependent permeability. 

For example, a proline-based chiral ligand was attached to a vinyl-substituted monomer (Fig. 42.15) by reacting vinylbenzoyl chloride with the amine functionality of the ligand [106]. As mentioned previously, the apolar Merrifield resin as a support is not swollen in polar solvents. Hence, in order to match the polarity of the resin with that of the typically used substrates in enantioselective hydrogenation, the functionalized monomer was copolymerized with polar units of methacrylic acid 2-hydroxyethyl ester. 

The chain transfer reaction played an important role, particularly because of abstraction of the active hydrogen at a-carbon from the allyl group. Moreover, unreacted double bonds were present in the copolymer obtained. The influence of chain transfer reaction could be diminished by applying multimonomers which do not contain allyl groups. This was shown in the example of copolymerization of multimethacrylate prepared by esterification of poly(2-hydroxyethyl methacrylate) with methacryloyl chloride. Copolymerization of the multimethacrylate with vinyl monomers such as styrene or acrylonitrile can be represented by the reaction ... 

Monomers like iron (III) methacrylate [CH2=C(CH3)-COO] 3Fe and tributyltin methacrylate have been synthesized [3]. They undergo free radical polymeriz-ation/copolymerization with other acrylates such as cyclohexyl, 2-ethoxyethyl, 2-hydroxyethyl and 2-hydroxypropyl. Synthesis of a metailo-macrocyclic acrylic monomer is illustrated by the reaction between a metallophthalocyanine tetracarbonyl chloride (1) and 2-hydroxyethyl methacrylate (2-HEMA) [4]... 

Polyesters synthesized from terephthaloyl chloride and isohexides were prepared, and characterized by differential scanning calorimetry, n.m.r. spectroscopy, and viscosity measurement.25,128 Another polyester, prepared by copolymerization of (2-hydroxyethyl)methacrylate with isoman-nide dimethacrylate (172), forms a hydrogel when allowed to swell in isotonic sodium chloride solution. This gel has useful properties for manufacturing contact-lens material.265... 

Fig. 6.29. Electrochromatographic performance of monoliths prepared by copolymerization of ethylene dimethacrylate and chiral monomer 25 with glycidyl methacrylate (a) and 2-hydroxyethyl methacrylate (b) as comonomers. (Reprinted with permission from [60]. Copyright 2000 American Chemical Society). Conditions capillary column 335 mm (250 mm active length) x 0.1 mm i.d., pore size 993 nm (a) and 1163 nm (b), analyte DNB-(R,S)-leucine, mobile phase 400 mM acetic acid and 4 mM triethylamine in acetonitrile-methanol (80 20, v/v), 25 kV, temperature 30°C.

Peters et al. reported on rod-CEC on a chiral monolith [50] which was prepared by copolymerization of the chiral monomer 2-hydroxyethyl methacrylate (A -L-valine-3,5-dimethylanilide) carbamate with ethylene dimethylacrylate, 2-acrylamido-2-methyl-l-propanesulfonic acid and butyl or glycidyl methacrylate in the presence of a porogenic solvent. The electrochromatographic enantiomer separation of 7V-(3,5-dinitrobenzoyl)leucine diallylamide was feasible at 25 kV the inlet and outlet buffer vials were both pressurized. 

Monoliths (2-hydroxyethyl methacrylate carbamate copolymerized with four different chiral selectors)... 

The anionic polymerization of masked disilenes proceeds via living anions, and therefore block copolymerization with a conventional vinyl monomer is possible. Recently, interesting hydrophobic block copolymer of PMHS with poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(methacrylic acid) (PMMA) have been prepared (Scheme 11). These polymers can be self-assembled and are transformed into polysilane micelles, shell cross-linked micelles (SCM), and nanometer-sized hollow particles. ... 

Davis, T.P. Huglin, M.B. Studies on copolymeric hydrogels of V-vinyl-2-pyrrolidone with 2-hydroxyethyl methacrylate. Macromolecules 1989, 22, 2824-2829. 

Branched polymers can also be obtained by copolymerization of MMA with dimethacrylates based upon the condensation product of hexamethylenedi-isocyanate with two hydroxyethyl methacrylates.335... 

Branched acrylic polymers based upon the copolymerization of acrylates and related monomers with methacrylate macromonomers are particularly useful in waterborne coatings. A macromonomer based upon isobutyl methacrylate, 2-ethylhexyl methacrylate, and 2-hydroxyethyl methacrylate was copolymerized with butyl acrylate, 2-hydroxyethyl acrylate, meth-acrylic acid, methyl methacrylate, and styrene.518 After neutralization with dimethylethanolamine or inorganic bases, the polymer could be cross-linked with melamine resin on a metal surface. These systems may be used for either pigmented layers or clear coats. 

Dispersancy Solution copolymers are comparatively easy to produce in dispersant form as copolymerization with an appropriate polar monomer is relatively straightforward. If the polar monomer is also a methacrylate, reactivity ratios are essentially the same and no special procedures are required to produce random copolymers. Commercial examples have included dimethyl (or diethyl)aminoethyl methacrylate [11], hydroxyethyl methacrylate [12] and dimethylamino-ethyl methacrylamide [13]. 2-Methyl-5-vinyl pyridine [14] has also been used commercially, reactivity ratios are such that it copolymerizes slightly faster than alkyl methacrylates. Although composition drift is not severe, it should be added in a programmed fashion if a uniform distribution is desired. V-vinyl pyrrolidinone, in contrast, copolymerizes very sluggishly with methacrylates and is best incorporated via a graft reaction [15], sometimes also grafted in combination with V-vinyl imidazole [16]. Since solution chemistry is used to produce dispersant polymethacrylates, like preparation of the base polymer, only relatively simple process modifications are necessary to produce dispersants commercially. 

In recent years, there have been significant developments in the field of living carbocationic polymerization (LCCP) of vinyl monomers, such as isobutylene (IB), styrene and its derivatives, and vinyl ethers, leading to a wide variety of functional polymers (for recent reviews see Refs. 1-4). Due to the attractive properties of polyisobutylene (PIB) available only by carbocationic polymerization, coupling this hydrophobic, thermally, oxidatively, and hydrolytically stable polymer with a low Tg to a variety of other chain segments is expected to result in new useful products. For instance, methacrylate-telechelic PIB (MA-PIB-MA) obtained by LCCP and subsequent chain end derivatization has been successfully used to synthesize novel amphiphilic networks by radical copolymerization of MA-PIB-MA with a variety of monomers, such as N,N-dimethylacrylamide and 2-trimethylsilyloxyethyl methacrylate, a protected 2-hydroxyethyl methacrylate... 

Mention may also be made here of the 2-hydroxyethyl ester of methacrylic acid, which is the monomer used for soft contact lenses. Copolymerization with ethylene glycol dimethacrylate produces a hydrophilic network polymer (a hydrogel). Hydrogel polymers are brittle and glassy when dry but become soft and plastic on swelling in water. 

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