Novel Synthesis of Self-Sensitized Photosensitive Polymers by Addition Reaction of Pendant Epoxide Groups in the Polymer with Some Cinnamic Esters

Soluble Polymer-Supported Catalysts Containing Pendant Quaternary Onium Salt Residues for Regioselective Addition Reaction of Epoxy Compound with Active Ester

“…The above results suggest that the catalytic activity of the soluble polymer-supported quaternary onium salts was significantly affected by the lipophilic interaction between the pendant onium salt residue in the polymer and the reactants and that catalyst 14 containing pendant benzyltributylphosphonium chloride residue was relatively more lipophilic than catalysts 16 and 17 containing pendant benzyltriethylphosphonium or benzyltripropylphosphonium chloride residues. On the other hand, increasing the alkyl chain length on the quaternary onium salts increased the lipophilicity of the catalyst; however, the introduction of relatively more bulky residues such as benzyltrihexylphosphonium or benzyltrioctylphosphonium chloride in catalysts 18 and 19 might have caused an increase in steric hindrance and decrease in catalytic activity.…”

“…Correlation between the observed pseudo-first-order rate constants and the carbon numbers of the trialkyl groups on the pendant benzyltrialkylphosphonium salt is shown in Figure 6, where the reaction was accomplished with 1 mol % of soluble polymer-supported catalysts containing about 9 mol % of pendant onium salts in DMF at 90 °C. Interestingly, catalyst 14 showed the highest activity, and the activity of catalysts 16,17,18, and 19 was depressed with either a decrease or an increase of the carbon number of the trialkyl groups on the phosphonium salts. The observed firstorder rate constants (&i) and the yields of main product PPA and hydrolysis byproduct PPP for the reaction for 5 h are given in Table 4.…”

Aryl (meth)acrylates and polymers based on them

“…These monomers are light-sensitive and belong to the group of self-sensitised ones. 131 Poly(4-cinnamoylphenyl methacrylate) obtained in the presence of benzoyl peroxide as an initiator with a degree of conversion of 78% is insoluble in common organic solvents. 132 In contrast to MMA, radical telomerisation of aryl (meth)acrylates with the use of bromotrichloromethane as the telogen is not accompanied by the formation of lactones; 133 however, the distribution with regard to the degree of polymerisation and tacticity are analogous.…”

Synthesis and characterization of fluorine‐containing polyesters by the polyaddition of bis(epoxide)s with active diesters

“…These reactions could also be applied to the synthesis and chemical modification of a polymer, that is, a polymer with pendant oxirane groups was modified with active esters with quaternary onium salts as catalysts to give the corresponding polymers in satisfactory yields. [17][18][19] We also reported the chemical modification of the polymers having active ester groups in the side chain with oxiranes. 20,21 Furthermore, the polyaddition of bis(epoxide)s with active diesters 22 and diacyl chlorides 23 proceeded satisfactory to produce the corresponding polyesters with pendant phenoxymethyl groups and chloromethyl groups, respectively.…”

“…These reactions could also be applied to the synthesis and chemical modification of a polymer, that is, a polymer with pendant oxirane groups was modified with active esters with quaternary onium salts as catalysts to give the corresponding polymers in satisfactory yields 17–19. We also reported the chemical modification of the polymers having active ester groups in the side chain with oxiranes 20, 21.…”