The invention relates to a process for the synthesis of a thermally-sensitive polymeric structure used as temperature sensor. According to the invention, the process consists in the radical copolymerization of N,N-dimethylacrylamide and 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane in the presence of benzoyl peroxide as initiator, in dimethyl acrylamide as reaction medium, for a theoretical content of solid substance of maximum 40%, in dynamic regime, while magnetically stirring at 240 rpm, at a temperature of 75°C, for 8...12 h, followed at the end by the purification of the polymeric structure by lyophilization.
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