Methacrylyl chloride

Some interesting resins have been obtained from the dianhydrides through their acrylic or methacrylic esters. Thus, 2,5-dimethacrylyl-l,4 3,6-dianhydro-mannitol (XIX) was formed by treating dianhydro-mannitol with methacrylyl chloride in the presence of sodium hydroxide. The product, a crystalline compound, polymerized extremely rapidly to a colorless, transparent, infusible resin. The corresponding sorbitol derivative, however, was an oil which polymerized to a softer resin. On the other hand, 2,5-diacrylyl-l,4 3,6-dianhydro-sorbitol (XX) was a crystalline compound, which polymerized to a hard, infusible, glass-like resin. 

Similarly by reacting cellulose with methacrylyl chloride, cellulose methacrylate has been obtained, to which vinyl monomers have been grafted, e.g. methyl methacrylate (35). 

The introduction of vinyl functionality by acrylation has been reported by Naveau (43), Methacrylyl chloride and methacrylic anhydride were used to introduce 10 to 20% methacrylate groups into lignin (Figure 9). Acrylated... 

Figure 9. Reaction of lignin with methacrylyl chloride and methacrylic anhydride [adapted from ( 5)].

The acrylate- and methacrylate-derivatized r 5-(benzene)tricarbonylchromium monomers 20 65,66,68,72 21,69>72 and 2273 (Scheme 1.2) were synthesized from benzyl alcohol or 2-phenylethanol when reacted with Cr(CO)6. The alcohols were esterified with either acrylyl or methacrylyl chloride in ether/pyridine and purified by multiple recrystallizations from CS2. Homopolymerizations proceeded in classic fashion with no special electronic effects from the rr-complexed Cr(CO)3 moiety.65,73 Acrylate 20 was copolymerized with styrene and methyl methacrylate and the reactivity ratios were obtained.65 Acrylate 21 and methacrylate, 22, copolymerized readily with styrene, methyl acrylate, acrylonitrile, and 2-phenylethyl acrylate to give bimodal molecular-weight distributions using AIBN initiation.69 Copolymerization of 20 with ferrocenylmethyl acrylate, 2, generates copolymers with varying mole ratios of two transition metals, Cr and Fe (see structure 34).65... 

Kydonieus and Sandler [10] reported that mercaptans, especially fluorinated mercaptans, can react with acrylyl chloride or methacrylyl chloride in the presence of ferric chloride catalyst using a methylene chloride solution to yield... 

Figure 7.19 illustrates a typical procedure for the synthesis of a methacrylate LCP. The monomer can be prepared, as shown, by esterification of methacrylyl chloride. Polymerizations are usually initiated via thermal homolysis of azobisisobutyronitrile (AIBN) in a solvent such as toluene, chlorobenzene or tetrahydrofuran. After termination, the polymer is isolated using several reprecipitations from a non-solvent such as methanol. Techniques such as gel-permeation chromatography, high-performance liquid chromatography or thin-layer chromatography should be used... 

Unsaturated Acids. The formation of olefinic acid azides by the sodium azide procedure appears to be limited only by the availability of the acid chloride. Examples of a,/3-olefinic acid azides prepared by this method are crotonyl, cinnamoyl, and methacrylyl azides. The hydrazide route to the azide is sometimes complicated by ride reactions. The esters of oleic acid and elaidic acid give the respective hydra-zides in good yield under the usual conditions, but severe treatment causes reduction of the unsaturated hydrazides to stearoyl hydrazide. ... 

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