Methacryloyl residue

Polymer formation from monomeric butadiene lipid vesicles is demonstrated by the decrease of the monomer absorption at 260 nm as well as by GPC of the residue of a freeze dried polymer vesicle dispersion. The latter method was also used for proving the formation of polymeric vesicles from the methacryloyl lipids. 

The step 4 product (2.9 mmol) and triethylamine (3.5 mmol) was dissolved in 30 ml of CH2C12 and then cooled to 0°C and treated with methacryloyl chloride (3.5 mmol). The mixture stirred at ambient temperature overnight and was then washed with water and dried using MgSC>4. The residue was purified by column chromatography on silica gel using hexane/ethyl acetate, 98/2, respectively, and 2.01 g product isolated as a bright yellow solid, mp = 213-215°C. 

In this process, epoxidation of the double bonds was followed by reduction to obtain the tert-alcohol which was esterified with methacryloyl chloride in the subsequent step. While epoxidation was found to be close to quantitative based on double bond content, reduction was incomplete and the residual epoxy functional PIB (24-47%) had to be separated by column chromatography before esterification. It should be noted that this macromonomer was a tert-ester which might be quite unstable in acidic conditions, and is also more hindered than the... 

A 200 ml reaction flask charged with 9-fluorenol (11 mmol), 180 ml of benzene, and triethylamine (13.75 mmol) was cooled to 6°C and then treated with the slow addition of methacryloyl chloride (13.75 mmol). Thereafter the mixture was stirred at ambient temperature for 24 hours. The solution was washed with water and saturated NaHCOs, and the organic layer was isolated, dried with MgS04, and concentrated. The residue... 

Under ice cooling a reactor was charged with the entire Step 1 product, triethylamine (70 g), and CH2CI2 (400 g) and then treated with methacryloyl chloride (55 g) and stirred 12 hours at ambient temperature. The reaction was quenched by adding water followed by a conventional aqueous workup. The mixture was concentrated, and the residue was washed with hexane and dried 86 g of product were isolated. 

The hydroxy oxaspiro intermediate 7 (3.28 g, 20 mmol) was combined with triethylamine (2.23 g, 22 mmol) in 30 mL of toluene. The solution was cooled to 5 C under argon and freshly distilled methacryloyl chloride (2.09 g, 20 mmol) diluted with 7 mL of toluene was added dropwise. The mixture was stirred at room temperature for 18 h and then filtered to remove the amine hydrochloride precipitate. The majority of the solvent was removed under reduced pressure and the residue was eluted through a small silica gel pad with hexane-ethyl acetate (1 1). Evaporation of the solvent under reduced pressure provided the SOCM monomer 3 as a pale yellow liquid in 93% yield. 

Also, when copolymers of polystyrene and 4-(methacryloyl-amino)azobenzene containing 2.2-6.5% of the latter are irradiated in a cyclohexane soluticMi with 15 flashes of 347 nm of Ught. The polymeric chains contract [221], This occurs at a high rate per second as a consequence of isomerization. At a later stage, several hundred seconds after the flash, there is evidence of polymer aggregation and precipitation [221], In addition, when azobenzene residues are introduced into the main chain of poly(dimethylsiloxane), reversible solution viscosity changes can be obtained by irradiation with ultraviolet light [221],... 

Liska reported preparation of water-soluble photoinitiators that contain carbohydrate residues as well as copolymerizable derivatives of the carbohydrate residues. These materials consist of alkylphenones, benzophenones and thioxanthones. To these compounds were attached carbohydrates like glucose, cellobiose, and 1-amino-1-deoxy-D-glucitol. In addition selected initiators were reacted with methacryloyl chloride to form polymerizable photoinitiators. The glucose modified photoinitiators were claimed to yield the best results with respect to compatibility with resins, reactivity and gel content. ... 

A/-Methacryloyl-D,L-phenylalanine Methyl Ester. The enantiodiscrim-inating influence of cyclodextrin in the free-radical polymerization of the racemic monomer iV-methacryloyl-D,L-phenylalanine methyl ester (2e) (41) was investigated for the first time. 2e was synthesized in 99% yield by the reaction of phenylalanine methyl ester hydrochlorides with methacryloyl chloride in the presence of triethylamine. The racemic monomer was subsequently added to an aqueous solution of RAMEB yielding a clear colorless solution of complexed monomer. Homopolymerizations were carried out in the presence of redox initiator at various temperatures. It was showed that the L-enantiomer is enriched in the residual monomer mixture. This observation confirms that complexed D-enantiomer polymerizes faster than the complexed L-enantiomer. No polymerization of 2e was observed without cyclodextrin under the same conditions. 

The photoreactive nanomatrix structure was formed by graft copolymerization of the inclusion complex of NDMA with p-CD onto deproteinized natural rubber. The content, conversion and residual methacryloyl group of NDMA for the graft copolymerization were 1.81%, 58.5% and 45.3%, respectively, at NDMA feed of 150 g/kg rubber and initiator concentration of 0.033 mol/kg rubber. The TEM observation of the resulting graft copolymer showed that natural rubber particles of about 1.0 pm in diameter were dispersed in a poly(NDMA) matrix of 10 nm in thickness. 

Both TEA (1.44 g, 14.3 mmol) and methacryloyl chloride (0.97 g, 10.7 mmol) were sequentially added at 0 °C to a solution of rhodamine B alcohol (19) (5.93 g, 9.80 mmol) in DCM (100 mL),. After 1 h, the temperature was raised to ambient temperature and the mixture stirred for a further 12 h. The volatiles were then removed under reduced pressure and the residue purified by a preeluted flash chromatography (Si02) using methaiiol/triethylamine (95/5), to give rhodamine B methacrylate monomer as purple glassy solid in 72% yield. 

---