Methods of making stable and thermally polymerizable vinyl, amino or oligomeric phenoxy benzocyclobutene monomers with improved curing kinetics
View Patent ↗The present invention provides methods of making low energy polymerizable monomers and resins for use in making dielectric materials. The methods comprise deprotecting or deacylating an organic alkali cleavable protecting group containing addition polymerizable, amine containing aromatic monomer or oligoaromatic phenol resin containing an organic alkali cleavable protecting group, such as a C 2 to C 9 alkanoyl group, preferably, an acyl group, by hydrolyzing to remove the protecting group in organic alkali in a polar solvent containing an excess of alkali C 1 to C 7 alkoxide and form a hydroxyl functional monomer or resin, followed by; reacting via nucleophilic substitution the resulting hydroxyl functional monomer or resin with an alpha-halide (α-halide) or strong acid conjugate leaving group containing arylcyclobutene compound in a polar solvent, to yield a product an arylcyclobutene-containing addition polymerizable or amine containing aromatic monomer or oligoaromatic phenol resin having an ether linkage from the cyclobutene ring to an aromatic group of the addition polymerizable aromatic monomer, aromatic amine or oligoaromatic phenol.
1. A method of making a monomer comprises:
deprotecting or deacylating an organic alkali cleavable protecting group containing aromatic monomer selected from the group consisting of an addition polymerizable group containing aromatic monomer, an amine containing aromatic monomer, and an oligoaromatic phenol compound containing a phenolic hydroxyl by hydrolyzing it to remove the protecting group in organic alkali in a polar solvent containing an excess of alkali C 1 to C 7 alkoxide to form an hydroxyl functional addition polymerizable aromatic monomer, hydroxyl functional aromatic amine functional group containing monomer or hydroxyl functional oligoaromatic compound, followed by;
reacting via nucleophilic substitution the resulting hydroxyl functional addition polymerizable aromatic monomer, aromatic amine functional group containing aromatic monomer or oligoaromatic compound with an alpha-halide (α-halide) or strong acid conjugate leaving group containing arylcyclobutene compound in a polar solvent, to yield an arylcyclobutene-containing addition polymerizable aromatic monomer, aromatic amine containing monomer or oligoaromatic phenol resin having an ether linkage from the cyclobutene ring to an aromatic group of the addition polymerizable aromatic monomer aromatic amine or oligoaromatic phenol.
2. The method as claimed in claim 1 , wherein the organic alkali cleavable protecting group in the organic alkali cleavable protecting group containing addition polymerizable aromatic monomer, amine functional group containing aromatic monomer or oligoaromatic phenol compound containing a phenolic hydroxyl is chosen from a C 2 to C 9 alkanoyl group or an alkyl carbonate group.
3. The method as claimed in claim 2 , wherein, the addition polymerizable aromatic monomer, amine containing aromatic monomer or oligoaromatic phenol compound containing an organic alkali cleavable protecting group is acetoxystyrene.
4. The method as claimed in claim 1 , wherein in the hydrolyzing, the organic alkali is a C 1 to C 4 alkoxide.
5. The method as claimed in claim 1 , wherein the alpha-halide (α-halide) or strong acid conjugate leaving group containing arylcyclobutene compound has a bromide on the cyclobutene ring.
6. The method as claimed in claim 1 , wherein the reacting via nucleophilic substitution comprises heating the hydroxyl functional addition polymerizable aromatic monomer, hydroxyl functional aromatic amine functional group containing monomer or hydroxyl functional oligaromatic phenol compound with the alpha-halide (α-halide) or strong acid conjugate leaving group containing arylcyclobutene compound in the organic alkali in the polar solvent at a temperature of from 55 to 80° C.
7. The method as claimed in claim 6 , wherein the reacting takes place in the presence of a free radical inhibitor.
8. The method as claimed in claim 1 , wherein the hydroxyl functional addition polymerizable aromatic monomer, hydroxyl functional aromatic amine functional group containing monomer or hydroxyl functional oligoaromatic phenol compound formed by deprotecting or deacylating is selected from the group consisting of a vinylphenol; an allyl phenol; an alkynyl phenol; a vinyl oligophenol; a vinyl naphthol; a vinylphenol having multiple vinyl groups; a vinylphenol having multiple vinyl groups and multiple aromatic rings; an allyloligophenol having from 2 to 10 aromatic rings or phenolic rings; an alkynyl oligophenol having from 2 to 10 aromatic rings or phenolic rings; an aminophenol; an amino oligophenol; and an oligoaromatic phenol containing the hydroxyl functional group and a phenolic hydroxyl.
9. The method as claimed in claim 1 , wherein when the hydroxyl functional addition polymerizable aromatic monomer, hydroxyl functional aromatic amine or hydroxyl functional oligoaromatic phenol formed by deprotecting or deacylating comprises a vinyl oligophenol having from 2 to 10 aromatic rings or phenolic rings, an aminophenol, an amino oligophenol or any oligoaromatic phenol, it is substantially free of aldehydes.
10. The method as claimed in claim 1 , further comprising:
purifying the arylcyclobutene-containing addition polymerizable aromatic monomer, aromatic amine functional group containing monomer or oligoaromatic phenol having an ether linkage from the cyclobutene ring to an aromatic group of the addition polymerizable aromatic monomer, aromatic amine functional group containing monomer or oligoaromatic phenol.