ABSTRACT:An investigation of effects of alkylaluminum chlorides on the cyclopolymerization was extended to 2-(o-allylphenoxy)ethyl, 4-(o-allylphenoxy)butyl, 6-(o-allylphenoxy)hexyl, and 10-(o-allylphenoxy)decyl methacrylates (2-AOEM, 4-AOBM, 6-AOHM, and 10-AODM) which are capable of forming 11-, 13-, 15-, and 19-membered rings, respectively. The addition of alkylaluminum chlorides to these monomers was effective for increasing the extent of cyclization. The effect of alkylaluminum chlorides was remarkable in formation of the 11-membered ring, but was suddenly less for lower membered rings. Considerable along with previous results, the present data provide insight into the difference in the reactivities between the acrylates and the methacrylates. Although the cyclopolymerization tendency was larger for the former than for the latter, the relation of log (kPikJ against ring size gave straight lines having about the same slope in the ring-size range from 8 to 15 for both monomer series. Therefore, there is not substantial difference in a mechanism of the cyclopolymerization between the acrylates and the methacrylates.KEY WORDS Cyclopolymerization I Alkylaluminum Chlorides I 2-(oAllylphenoxy)ethyl Methacrylate I Nonconjugated Diene I Methacrylates I Acrylates I Radical Polymerization I Large-Size Ring I Cyclization I acrylate (10-AODA) 3 of 19-membered rings. In a previous paper 1 the authors reported that the cyclopolymerization tendency of o-allylphenyl acrylate (AP A) containing electro-positive and electro-negative double bonds greatly increased by alkylaluminum chlorides. Highly cyclized polymers were obtained not only from APA in the formation of 8-membered rings, but also from 2-(o-allylphenoxy)ethyl and 4-(o-allylphenoxy)butyl acrylate (2-AOEA and 4-AOBA) 2 in the formation of 11-and 13-membered rings, respectively. The alkylaluminum chlorides function as a complexing agent between the electron-donor and the electronacceptor groups in the molecule; the ability of complex formation decreased with increasing ring size to be formed. These agents caused a moderate increase in the cyclopolymerization tendency of 6-(o-allylphenoxy)hexyl acrylate (6-AOHA) 3 capable of forming 15-membered rings, but had little effect on the polymerization of 10-(o-allylphenoxy)decyl Otsu et a/. 4 showed that Lewis acids, such as SnC1 4 and have a marked effect on the cyclopropagation in the polymerizations of allyl acrylate and methacrylate.The addition of alkylaluminum chlorides to oallylphenyl methacrylate (APM) produced effects different from that of AP A. 5 The oligomers were preferentially obtained above the Al/M molar ratio of 1.0 in the presence of A1Et 2 Cl. Such an oligomerization was observed on the reaction of methyl methacrylate with A!Et2 Cl as well, and trimers composed of the bridged bicyclic lactone were isolated. 6 • 7 This paper reports the effect of alkylaluminum chlorides upon the methacrylates, namely, 2-(oallylphenoxy)ethyl, 4-(o-allylphenoxy)butyl, 6-(oallylphenoxy)hexyl, and 10-(o-allylphenoxy)decyl methac...
ABSTRACT:The addition of alkylaluminum chlorides to o-allylphenyl methacrylate (APM) has been reported to produce effects different from that of o-allylphenyl acrylate (APA). For the cyclopolymerization of APM in the presence of A!Et 2 CI, a rapid polymerization was induced. The extent of cyclization, however, was extremely small as compared with that of APA. Moreover, it was characteristic of APM that the oligomers were preferentially produced above the AIIM molar ratio of 1.0. In the presence of A!EtCI2 , the rate of polymerization was smaller than that in the case of AIEt2CI, but the extent of cyclization was far larger and increased to 92% at a AIIM molar ratio of 1.25. The value of kPI k" the ratio of rate constants for linear propagation and cyclization, for APM capable of forming eight -membered rings, was comparable to those values of the analogous acrylic monomers capable of forming eleven-and thirteen-membered rings. There were indications that the effects of alkylaluminum chlorides on the cyclopolymerization should be smaller for the methacrylic monomers than for the acrylic monomers.
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