Methacryloyl chloride

Following is an ester type macroazoinimer [51] starting from the poly(ethylene glycol), 4,4 -azobiscy-ano pentanoyl chloride, and methacryloyl chloride. 

Hazer [20,25] reported on the reaction of a po]y(eth-ylene g]ycol)-based azoester with methacryloyl chloride in the presence of (CH3CH2)3N. In this reaction double bonds were attached to the chain ends of the poly(ester) thus obtaining a macroinimer. Being used for the thermal polymerization of styrene, the material formed an insoluble gel [20]. Probably, both the C=C double bonds and the azo bonds reacted in the course of the thermal treatment. The macroninimer in a later work [25] was used for thermally polymerizing poly(butadiene) thus leading to poly(ethylene glycol-/ -butadiene) block copolymers. 

Poly (ethylene oxide) macromonomers72 761 are made in a similar way, as the alkoxide end group is reactive enough towards benzylic halides. With methacryloyl chloride, side reactions are involved. It is better to first protonate the PEO, and then to have it react with methacryloyl chloride in the presence of some triethyl amine. One can also react co-hydroxy polyethylene oxide) with methacryloyl imidazole, or with methacrylic acid in the presence of dicyclohexyl carbodiimide (DCCf)77). 

A methacrylate function has been introduced using the reaction of T8[OSi Me2H]8 with allyl alcohol and then methacryloyl chloride. Preliminary studies on polymerization under UV irradiation of the reaction product showed the formation of nanocomposites (Table 19, entries 5 and 7). The bromo-terminated compound formed by the reaction of T8[0SiMe2(CH2)30H]8 with 2-bromo-... 

Materials. Tetrahydrofuran (THF) was freshly distilled from sodium, and triethylamine from P2O5. Methacryloyl chloride (Aldrich Chemical Co.) and NJV-dimethylacrylamide (DMAAm), (Aldrich Chemical Co.) were distilled under reduced pressure prior to use. 2,2 -Azobisisobutyronitrile (AIBN) (Eastman Kodak) and theophylline (Mp 275 °C) (Aldrich Chemical Co.) were recrystallized from methanol and water, respectively. Hexanes, /i-heptane, and ethanol were used as received. 

Synthesis of PIB prepolymers. fm-Chlorine-telechelic PIB (Mn=4,000 MVf/Mn 1.09) (7), and an allyl-telechelic PIB (Mn=9,500 Mw/Mn 1.14) (7,8) were prepared by living carbocationic polymerizations. The tert-chlorine ended PIB was quantitatively dehydrochlorinated (9) to -C(CH3)=CH2 terminated polymer. Both olefin-telechelic PIBs were then hydroborated and oxidized (10) to prepare the primary hydroxyl termini. The hydroxyl-telechelic polymers were esterified with methacryloyl chloride to methacrylate-telechelic PIBs, MA-PIB-MA (11). 

In the condensation of methacrylic acid and N-dansylethylenediamine to give the corresponding methacrylamide in 19% yield (part of the monomer polymerized during the purification process), the methacryloylimidazole prepared from the acid with CDI proved to be more efficient than methacryloyl chloride [36]... 

Hexafluoro-2-hydroxy-2-(4-fluorophenyl)propane (HFAF) was obtained from Central Glass Co., Japan, and was distilled under argon prior to use. Ethyl bromoacetate, methyl acrylate, acryloyl chloride, and methacryloyl chloride were obtained from Aldrich and were used as received. Hydroxyethyl methacrylate and hydroxypropyl methacrylate, also from Aldrich, were purified as described in the literature.6... 

Hexafluoro-2-(4-fluorophenyl)-2-propyl acrylate (la) and hexafluoro-2-(4-fluorophenyl)-2-propyl methacrylate (lb)7 were prepared by gradually adding a solution of 0.06 mol of acryloyl or methacryloyl chloride, respectively, in 20 ml of tetrahydrofuran (THF), to a cooled solution of 0.04 mol of HFAF in 50 ml of THF containing 0.06 mol oftriethylamine. The mixture was stirred for 10-12 h at room temperature it then was poured into 200ml of water, and the new product was extracted with diethyl ether. After the diethyl ether was evaporated, the crude product was purified by column chromatography using a mixture of hexane and dichloromethane (1 1 by volume) as the elution solvent. Distillation afforded la, b.p. 72-74°C/10"3 mm Hg, and lb, b.p. 48-52oC/103 mm Hg. 

The preparation of fluorinated alcohols was carried out in multistep routes according to the reported procedures.1012 The synthesis of acrylic and methacrylic esters as shown in Table 11.1 was carried out in a fluorocarbon solvent such as Freon 113 by the reaction of the respective fluorinated alcohol with acryloyl chloride or methacryloyl chloride and an amine acid acceptor such as triethyla-mine with examples shown in Scheme 1. Other attempts to esterify the fluoroalcohols directly with acrylic acid or acrylic anhydride were not successful.11 Product purification by distillation was not feasible because of the temperature required, but purification by percolation of fluorocarbon solutions through neutral alumina resulted in products of good purity identified by TLC, FTIR, and H-, 13C-, and 19F- FTNMRs. 

Methacrylonitrile process, 16 256—257 Methacryloyl chloride, in polyhydric alcohol formation, 2 46 Methacycline, 24 592 Methallyl chloride, production from butylenes, 4 427... 

COPOLYMERIZATION WITH PARTICIPATION OF MULTIMONOMERS Synthesis of various multimonomers and their copolymerization with styrene, acrylonitrile or acrylic acid was described in a set of papers. Most of the early work on the copolymerization of multimonomers with vinyl monomers employed p-cresyl formaldehyde resins, esterified by methacryloyl chloride or acryloyl chloride, as one of the comonomers, and a simple vinyl monomer such as styrene or acrylonitrile as the other monomer. 

Another type of multimonomer was prepared from poly(methacryloyl chloride) and allilamine, and was used in order to examine copolymerization process with sty-rene. ° The copolymerization was carried out in dioxane with AIBN as initiator. The basic reaction leads to the product with ladder-type blocks of allylmethacrylamide units, and blocks consist of styrene units ... 

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 ... 

The living anionic ends can be functionalized by adding such agents as ethylene oxide, carbon dioxide, and methacryloyl chloride [33]. The resulting new polymer is capable of being copolymerized with additional monomers. This process can lead to the formation of various graft copolymers [29-32]. 

Butyl isopropenyl ketone was prepared by the reaction of methacryloyl chloride with BuLi in ether at -78°C. The crude product was purified by the fractional distillation under reduced nitrogen pressure. Bp 56.5°C(14mmHg). ]., 4363. Anal. Found ... 

The intermediate was esterified with methacryloyl chloride then copolymerized with methyl methacrylate followed by a retro Diels -Adler in situ to generate a pendant maleimide where the nucleophilic dye became covalently bonded to the reaction product. 

A solution of the step 2 product (18 mmol) dissolved 30 ml of CH2C12 was treated with 3 ml triethylamine and methacryloyl chloride (18 mmol) at ambient temperature and then stirred overnight. The mixture was then diluted with 200 ml CH2C12, washed twice with 50 ml water, and 50 ml brine, and then dried over Na2S04, concentrated, and 4.57 g of product isolated as a white solid. The material was used without further purification. 

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. 

A reaction vessel containing the step 2 product (0.23 mol) and triethylamine (0.64 mol) dissolved in 500 ml CH2CI2 was treated with the dropwise addition of methacryloyl chloride (0.58 mol) at 0-5°C. The mixture was stirred for 3 hours and then quenched by adding 100 ml of water. The organic phase was extracted with... 

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