Allyl methacrylate

Mention may also be made here of a number of polyfunctional compounds such as allyl methacrylate and glycol dimethacrylates which have been used to produce a cross-linked sheet of enhanced heat resistance compared with conventional poly(methyl methacrylate). Some manufacturers supply the sheet in an incompletely cross-linked state which allows a limited amount of forming after which the sheet may be further heated to complete the cure. 

Figure 3.4 Relative reactivity of indicated site towards /-butoxy radicals for allyl methacrylate (99) and allyl acrylate (100)...

The results of this work are not limited to just S-b-MM and S-b-tBM, but may be extended to include styrene derivatives such as p-methylstyrene and p-t-butylstyrene 1). In addition to t-butyl methacrylate, other alkyl esters capable of stabilizing a carbonium ion, such as benzyl methacrylate and allyl methacrylate, should exhibit similar reactivity toward acidic hydrolysis and TMSI. In contrasting the hydrolysis of tBM blocks with TsOH and their reaction with TMSI, it should be noted that the hydrolysis is reportedly catalytic in nature (7-10), whereas the reaction with TMSI is stoichimetric. Therefore the latter approach may allow one to more easily "dial in" a desired level of methacrylic acid or metal methacrylate. 

Previous work on allyl methacrylate homopolymers and statistical copolymers clearly showed that the allyl group is a very effective cross-linking function when exposed to x-rays (2) ... 

Allylic intermediate, 27 185-187 ii-Allylic nickel intermediates, 33 15-18, 22 Allylic oxidation, see Oxidation, allylic Allylic species, 30 21 formation, isomerization, 30 18-19 free allyl radicals, 30 149 a-hydrogen abstraction, 30 147 Allyl methacrylate oxidation, 41 305 Allyls... 

Uses Ingredient in textile softeners and water repellent epoxy resins including allyl methacrylate, diallyl phthalates, and triallyl cyanurate. 

Saillenfait AM, Bonnet P, Gallissot F, et ah Developmental toxicities of methacrylic acid, ethyl methacrylate, w-butyl methacrylate, and allyl methacrylate in rats following inhalation exposure. Toxicol Sci 50(1) 136-145, 1999... 

Group transfer polymerization allows the synthesis of block copolymers of different methacrylate or acrylate monomers, such as methyl methacrylate and allyl methacrylate [Hertler, 1996 Webster and Sogah, 1989]. The synthesis of mixed methacrylate-acrylate block copolymers requires that the less reactive monomer (methacrylate) be polymerized first. The silyl dialkylketene acetal propagating center from methacrylate polymerization is more reactive for initiation of acrylate polymerization than the silyl monoalkylketene acetal propagating center from acrylate polymerization is for initiation of methacrylate polymerization. Bifunctional initiators such as l,4-bis(methoxytri methyl si loxymethylene)cyclohexane (XXXIII) are useful for synthesizing ABA block copolymers where the middle block is methacrylate [Steinbrecht and Bandermann, 1989 Yu et al., 1988]. 

The third case is the copolymerization of a monomer A with the diene BC where groups A and B have equal reactivity, but group C has a much lower reactivity. An example of such a case would be methyl methacrylate-allyl methacrylate, where A and B are the two methacrylate groups and C is the allyl group. If r is the reactivity ratio between the C and B groups, then the following hold for the radicals derived from the A and B groups ... 

The tendency toward cyclization decreases considerably (lower kjkp value) for unsym-metric 1,6-dienes, such as allyl methacrylate, where the two double bonds have significantly different reactivities. The polymer contains linear repeat units, rings, and pendant double bonds in relative amounts determined by kc/kp. The pendant double bonds eventually react to yield a crosslinked structure. Reactants with more than two double bonds per molecule,... 

In a reaction vessel equipped with mechanic propeller stirrer, argon inlet, and reflux condenser an emulsion is prepared of distilled water (300 g), methyl methacrylate (MMA 9.5 g),allyl methacrylate (ALMA 0.5 g) and sodium dodecyl sulfate (5D5 ... 

Methacrylic acid Acrylic acid Di-isobutylene Acrylonitrile Allyl acrylate Allyl methacrylate n-Butyi acrylate n-Butyl methacrylate isobutyl methacrylate 2-Chloroethyl methacrylate -Ethoxyethyl methacrylate Ethyl acrylate 2-Ethylhexyl acrylate Ethyl methacrylate Lauryl methacrylate Nonyl methacrylate N-Vinyl pyrrolidone Octyl acrylate 2-Vinyl pyridine... 

Acrylonitrile Allyl acrylate Allyl methacrylate n-Butyl acrylate n-Butyl methacrylate Isobutyl methacrylate Divinyl benzene 2-Choroethyl methacrylate Ethyl acrylate /i-Ethoxyethyl methacrylate 2-Ethylhexyl methacrylate Ethyl methacrylate Methyl methacrylate Methylisopropenylketone Methyl vinyl ketone N-Vinyl pyrrolidone Styrene Vinylpyridine Acrylonitrile Allyl acrylate Allyl methacrylate... 

A round-bottom flask consisting of a mixture of 1,4-bis-dimethylsilylbenzene (25.7 mmol), allyl methacrylate (51.4 mmol), 20 ml of toluene, and two drops of platinum divinyltetramethyldisiloxane complex dissolved in xylene were stirred at ambient temperature for 17 hours. The mixture was then loaded onto a silica gel column and eluted with a mixture of ethyl acetate/hexane, 20,80, respectively, and then concentrated and 7.8 g product isolated as a colorless oil having a viscosity of 136 cP. 

A 300-ml flask containing dimethylacetamide (100.00 g) was heated to 80°C and then treated with the dropwise addition of allyl methacrylate (13.00 g), the step 1 product (7.00 g), and 2,2 -azobisisobutyronitrile (0.40 g) dissolved in dimethylacetamide (80.00 g) over 2 hours. One hour after dropwise addition was completed the mixture was treated with additional 2,2 -azobisisobutyronitrile (0.20 g) and then heated for 5 hours. The reaction solution was then precipitated into 1 liter of water, washed with water, dried, and the product isolated as a yellowish white polymer in 95% yield. 

Allyl methacrylate and allyl acrylate are difunctional monomers, triallyl phosphate is a trifunctional monomer, and polyethylene glycol dimethacrylate is a polyfunctional monomer. All these lead to cross-linked graft copolymers. 

In contrast, allyl methacrylate is produced by the esterification of methacrylic acid and allyl alcohol (13), or by the transesterification of allyl alcohol with an ester of methacrylic acid, preferably with methyl methacrylate. The latter reaction is catalyzed with zirconium acetylacetonate (14). The esterification reactions are shown in Figure... 

Figure 12.2 Synthesis of Allyl acrylate and Allyl methacrylate...

Another straightforward method to reduce the gloss consists in admixing a dull graft copolymer as dulling agent (33). Such copolymers may be prepared from n-butyl acrylate, allyl methacrylate, and hydroxypropyl methacrylate. Likewise, hydroxypropyl methacrylate may be substituted by maleic anhydride. The polymerization is started by 2,2 -azobi sisobu ty roni trile and peroxides. 

K. Tamura and S. Suzuki, Method for producing (meth)allyl (methacrylate, JP Patent 2 005 314 248, assigned to Mitsubishi Rayon Co. and Osaka Organic Chem. Ind., November 10, 2005. 

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