Dual curable vitrimers

A process for synthesizing an ester and acrylate moieties-containing benzoxazine monomer of formula (I), comprising:

• a) reacting a phenolic carboxylic acid of formula (II), comprising at least one R* group on the phenolic ring:
• wherein
• Rac has the definition of Ra and w=1, 2 or 3;
• with a hydroxyl moiety bearing compound of formula (III)
• wherein R has the definition of R″ and n has the same definition than above, at a temperature of from 25° C. to 200° C., during 1 h-72 h, in the presence of a catalyst of Bronsted acid type and under inert atmospheric conditions, resulting in a phenol terminated oligomer or molecule (compound (IV),
• b) reacting the compound (IV) with a mixture of:
• an amino-alcohol of formula (V):
• an aldehyde compound selected from formaldehyde and paraformaldehyde of formula
• where m is an integer of from 8 to 100,
• a primary amine of formula (VI),
• at a temperature of from 50° C. to 200° C., during 1 h-12 h, under inert atmospheric conditions, providing a compound of formula (VII), and
• c) reacting the compound (VII) with a compound bearing acrylate or methacrylate groups, said compound being at least one defined by compounds (VIII)—(XII), (meth)acrylic acid chloride of formula (VIII)
• in polar solvents, at temperatures from −5° C. to 25° C.;
• or
• methyl(meth)acrylate of formula (IX)
• in the presence of a catalyst and a polymerization inhibitor;
• or
• (meth)acrylic acid of formula (X)
• in the presence of a catalyst and an azodicarboxylate in a solvent at temperatures from −10° C. to reflux;
• or
• an excess of (meth)acrylic acid of formula (X) in the presence of a catalyst;
• or
• (meth)acrylic acid anhydride of formula (XI) or asymmetric anhydride of formula (XII)
• in the presence of a catalyst;
• wherein
• R″″ is H or CH3.
• R′″″ is CH3 or C2H5;
• at temperatures of from −10° C.-50° C., during 12 h-48 h, for obtaining the ester and acrylate moieties-containing benzoxazine monomer of formula (I), x, y, z, in formula (I), represent the proportion between benzoxazine groups when prepared from an aminoalcohol and the other amine(s) and methacrylate groups, the latter obtained after step c),
• x
• =
• n
• aminoalcohol
• n
• functional
• ⁢
• groups
• total
• y
• =
• n
• acrylate
• n
• functional
• ⁢
• groups
• z
• =
• n
• amines
• n
• functional
• ⁢
• groups
• wherein
• n
• functional
• ⁢
• groups
• total
• =
• n
• aminoalcohol
• +
• n
• amines
• +
• n
• acrylate
• ,
• and
• ⁢
• n
• aminoalcohol
• being the number of aminoalcohol, namines represent the number of amines (exception the number of aminoalcohol), nacrylate corresponds to the number of acrylate/methacrylate groups, and
• n
• funtional
• ⁢
• groups
• total
• is the total number of functional groups bore by the benzoxazine rings,
• with the proviso that when at least one R* of the phenolic acid derivative is in ortho position with regard to —OH group, then R* is H.
• wherein the respective stoichiometry of starting reactants on step a), phenolic carboxylic acid:hydroxyl moiety bearing compound is n eq.:1.0 eq, resulting in an 1.0 eq. of the phenol terminated oligomer or molecule (compound (IV)), and
• wherein the temperature range of step b) is of from 70° C. to 150° and step b) is performed from 1 h to 8 h.