Methacrylate derivatives

Kammerer ei aL1(n m have conducted extensive studies on the template polymerization of acrylate or methacrylate derivatives of polyphenolic oligomers 22 with X n < 5 (Scheme 8.14). Under conditions of low "monomer" and high initiator concentration they found that X n for the daughter polymer was the same as X n for the parent. The possibility of using such templates to control microstructure was considered but not reported. 

Another way for covalent immobilisation is to synthesise indicator chemistry with polymerizable entities such as methacrylate groups (Figure 4). These groups can then be copolymerized with monomers such as hydrophobic methyl methacrylate or hydrophilic acryl amide to give sensor copolymers. In order to obtain self-plasticized materials, methacrylate monomers with long alkyl chains (hexyl or dodecyl methacrylate) can be used. Thus, sensor copolymers are obtained which have a Tg below room temperature. Similarly, ionophores and ionic additives (quaternary ammonium ions and borates) can be derivatised to give methacrylate derivatives. 

Other efforts based on the macromonomer approach to homopolymers having dendritic side chains, include the work of Draheim and Ritter on acrylate and methacrylate derived structures having dendritic chiral side chains based on L-aspartic esters [17a], and of Xi and coworkers with poly(methacrylate) structures containing very small benzyl ether dendritic side-chains [17b]. Unfortunately, both of these approaches met with limited success due to a significant drop in degree of polymerization (DP) when the size of the dendron used as pendant group in the macromonomers increased from G-l to G-2. 

Braun et al. [258] used a combination of tert-butyllithium (t-BuLi) and tetramefhy-lethylenediamine to create initiator sites at the surface of carbon black for the LASIP of styrene. Schomaker et al. [259] first immobilized a methyl methacrylate derivative on colloidal silica and after activation by a Grignard reagent polymerized MMA. 

Some of the most important critical points in RAFT polymerizations are the relative concentrations of the free radical initiator, the CTA, and the monomer, since these will establish the delicate balance between the dormant and active species. Acrylate and methacrylate derivatives can be successfully polymerized using 2-cyano-2-butyl dithio benzoate (CBDB) as a CTA. However, the amount of free radical initiator (a, a-azobisisobutyronitrile (AIBN) is used in general) compared to CTA determines the rate of control over the polymerization. Therefore, eight different acrylates or methacrylates were polymerized with different ratios of CTA to AIBN [54]. The structures of the monomers and the design of the experiment are shown in Fig. 6. 

Exciton coupling is also observed in methacrylate derivatives of allylic alcohols151 and in a benzoate derivative of a homoallylic alcohol152. For benzoates of propargylic alcohols of S configuration 11 in which the O-Bz bond is assumed anti to the C-R1 bond, a Dc Voe calculation predicts a positive benzoate Cotton effect, in accordance with experimental153. 

Silsesquioxane epoxide derivatives, (I), were prepared by Inagaki et al. (1) and used as pressure-sensitive polyether adhesives. Silsesquioxane methacrylate derivatives, (II), prepared by Morimoto et al. (2) were also used as pressure-sensitive adhesives. 

Lewandowski et aL (2) prepared containing polymers of carbosilane and methacrylate derivatives, (II), which were effective in dental compositions and had a Watts shrinkage of less than 2%. Crosslinkable carbosilane methacrylate monomers, (HI), effective in dental compositions were also prepared by Lewandowski et al. (3) in an earlier investigation that had a Watts shrinkage of less than 2%. Carbosilane derivatives effective in dental compositions were prepared by Bissinger et aL (4) and are described. 

From Table 19 it appears that the differences between the optical activity of the model compounds and of the polymers are more marked in the case of the methacrylic derivatives than in the case of not substituted acrylic derivatives. 

Triazolines with an electron-withdrawing substituent in the 5-position are rare they are obtained as secondary products in the nonregioselective addition of azides to methacrylic derivatives (Scheme 75). Their thermolysis is similar to that of the 4-isomers a mixture of aziridine and enamine is formed.67... 

In order to investigate the effect of the ring substitution on preferential adsorption of water in poly(phenyl methacrylate) derivatives, it has been studied the preferential adsorption behavior of poly(2,4 - dimethylphenyl methacrylate) (2,4 - DMP), poly(2,5 - dimethylphenyl methacrylate) (2,5 - DMP) and poly(3,5 -dimethylphenyl methacrylate) (3,5 - DMP) in THF/water mixtures [109],... 

Analogous poly(itaconate)s polymers like poly(ditetrahydrofurfuryl methacrylate) have been also studied because there are at least two advantages in using ita-conate acid based polymers over methacrylate acid derivatives itaconic acid can be obtained through fermentation from renewable, non petrochemical sources and the toxicity of its derivatives is lower than for methacrylate derivatives [64,140],... 

The maleic Surfmers were tested in core-shell emulsion polymerization of styrene/butyl acrylate in comparison with a standard nonreactive surfactant (nonyl phenol reacted with 30 mol of EO - NP30). While the methacrylic-derived Surfmer was completely incorporated during the polymerization (although about one-third of it was buried inside the particles) the NP30, the maleic Surfmer and the allylic and vinyl Surfmers were not incorporated and could be extracted with acetone (for the last two probably because of the formation of acetone-extractable oligomers due to a chain transfer behavior) [31]. 

A new family of perfluoroacrylate and methacrylate based positive and negative tone photoresist compositions activated at 193 run has been prepared by free radical homo-or co-polymerization of acrylate or methacrylate derivatives. Polymeric agents prepared in this manner had Mn s between 5,000 and 50,000 daltons and were readily soluble in organic solvents. 

Asymmetric Polymerization. Polymerization of methacrylate derived from (1) affords optically active polymer of helical conformation of single screw sense. ... 

Mosbach et al. also attempted to use metal-coordination interaction to prepare polymeric adsorbents for selective recognition of proteins [27]. Using the monomer (3), they polymerised the protein-monomer complex on methacrylate-derived silica particles in the presence of ribonuclease A as the template protein. After removing the template, the imprinted functionalised silica particles were used as packing... 

Another procedure that has been followed is synthesizing a monomer with the active substance, and then polymerizing this new molecule. Chloramphenicol has thus been attached to a methacrylic derivative by an acetal function, and then copolymerized with 2-hydroxy ethyl-methacrylate (148). The copolymer can then, in addition, be dispersed into a biocompatiblenondegradable polymer such as Eudragit, playingthe role of a polymer matrix (149). 

Table 3. NMR1H spectral characteristics of methacrylate derivatives...

Exploration of the template controlled free-radical oligomerization of other activated olefins began with standard monomers utilized in bulk polymer synthesis and the template 63. Vinyl acetate and acrylonitrile led only to uncontrolled polymerization, while vinylene carbonate did not react under the standard experimental conditions. More exotic monomers, such as vinyl trifluoroacetate and rert-butyl acrylate, were also unsuccessful. Only methyl acrylate polymerization was arrested by template 64 to provide the macrocyclized product 96 in modest yield as a mixture of five diastereomers (Scheme 8-25). Subsequent studies with the more effective thiophenyl-bearing template 63 at lower temperatures improved this yield to 35%. The diastereomer distribution was reminiscent of the methyl methacrylate-derived product, although no stereochemical assignments were made in this case either. 

Fig.(9) The transformation of the Wieland-Miescher ketone (1) to the conjugated diene (93) is described. It was converted to the diketone (95) whicch proved a potencial intermediate for the epoxy dilactone (98). The cleavage of the lactone ring of (98) yielded alcohol which was converted a-methylene-Y-butyrolactone (101) by a series of organic reactions. The opening of the epoxide ring of (101) gave the product (102) whose methacrylate derivative on deformylaton provided eriolanin (104).

Functionalised Antimicrobial Polymers Based on Poly(hydroxystyrene-co-methyl methacrylate) Derivatives... 

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