Amine-functional monomers and methods of making same

A difunctional addition-polymerizable monomer composition comprising an amine-derivatized alpha-methyl styrene (ADAMS) monomer according to structure (V) and/or an aminated conjugated aliphatic methylated polyene (ACAMP) monomer according to structure (VI):

• wherein:
• k is an integer from 1 to 3;
• R1 and R2 are each independently a hydrocarbyl group or a hydrocarbonaceous group having 1 to 4 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof,
• in structure (V), each R is independently hydrogen, a phenyl ring co-attached at two neighboring ring carbon positions with the phenyl ring shown so as to form a naphthalene assembly, a phenyl group attached at a single carbon of the phenyl ring shown, a C1-C4 hydrocarbyl group, or a C1-C6 hydrocarbyl group containing 1 to 4 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, and
• in structure (VI), R3 and R4 are each independently hydrogen, a methyl group, or an alkenyl group having structure (IV)
• attached via the asterisk, but specifically which do not collectively achieve aromaticity in combination with the other alkenes in structure (VI), and with the proviso that R3 and R4 are not both alkenyl groups having structure (IV) and are not both methyl groups.

A method of making an addition-polymerizable monomer composition comprising the steps of:

• providing reactants comprising a source of formaldehyde, a source of a secondary amine, and a polymerizable reactant comprising one or more of alpha-methylstyrene, alpha-methyl-para-methylstyrene, alpha-methyl-ortho-methylstyrene, alpha-methyl-para-ethylstyrene, alpha-methyl-ortho-ethylstyrene, alpha-methyl-para-propylstyrene, alpha-methyl-ortho-propylstyrene, alpha-methyl-para-butylstyrene, alpha-methyl-ortho-butylstyrene, alpha-methyl-para-methoxystyrene, alpha-methyl-ortho-methoxystyrene, alpha-methyl-para-ethoxystyrene, alpha-methyl-ortho-ethoxystyrene, isopropenylnaphthalene, diisopropenylbenzene, diisopropenylnaphthalene, isoprene, 2,3-dimethylbuta-1,3-diene, 2-methylhexa-1,3,5-triene, 2,5-dimethylhexa-1,3,5-triene, 2-methyl-3-methylenepenta-1,4-diene, and 2,4-dimethyl-3-methylenepenta-1,4-diene;
• providing an acidic reaction medium sufficient to provide, in the presence of the reactants, a pH from 0.8 to 4.8;
• reacting the reactants in the acidic reaction medium for a sufficient reaction time and at a sufficient reaction temperature to thereby yield an amine-derivatized alpha-methyl styrene (ADAMS) monomer according to structure (I) and/or an aminated conjugated aliphatic methylated polyene (ACAMP) monomer according to structure (II):
• wherein:
• k is an integer from 1 to 3;
• R1 and R2 are each independently a hydrocarbyl group or a hydrocarbonaceous group having 1 to 4 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, or wherein R1 and R2 are connected to form a moiety containing at least one 5- to 12-membered ring, from 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof;
• in structure (I), R is hydrogen, a phenyl ring co-attached at two neighboring ring carbon positions with the phenyl ring shown so as to form a naphthalene assembly, a phenyl group attached at a single carbon of the phenyl ring shown, a C1-C4 hydrocarbyl group, a C1-C6 hydrocarbyl group containing 1 to 4 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, or a second amino-functional group having structure (III)
• attached via the asterisk, with R′1 and R′2 being independently the same or different as R1 and R2 but defined identically;
• and
• in structure (II), R3 and R4 are each independently hydrogen, a methyl group, a second amino-functional group having structure (III) attached via the asterisk, with R′1 and R′2 being independently the same or different as R1 and R2 but defined identically, or an alkenyl group having structure (IV)
• attached via the asterisk, but specifically which do not collectively achieve aromaticity in combination with the other alkenes in structure (II), and with the proviso that R3 and R4 are not both alkenyl groups having structure (IV) and are not both methyl groups.

A method of making an addition-polymerizable monomer composition comprising the steps of:

• providing reactants comprising a source of formaldehyde, a source of a primary amine, and a polymerizable reactant comprising one or more of alpha-methylstyrene, alpha-methyl-para-methylstyrene, alpha-methyl-ortho-methylstyrene, alpha-methyl-para-ethylstyrene, alpha-methyl-ortho-ethylstyrene, alpha-methyl-para-propylstyrene, alpha-methyl-ortho-propylstyrene, alpha-methyl-para-butylstyrene, alpha-methyl-ortho-butylstyrene, alpha-methyl-para-methoxystyrene, alpha-methyl-ortho-methoxystyrene, alpha-methyl-para-ethoxystyrene, alpha-methyl-ortho-ethoxystyrene, isopropenylnaphthalene, isoprene, 2-methylhexa-1,3,5-triene, and 2-methyl-3-methylenepenta-1,4-diene;
• providing an acidic reaction medium sufficient to provide, in the presence of the reactants, a pH from 0.8 to 4.8;
• reacting the reactants in the acidic reaction medium for a sufficient reaction time and at a sufficient reaction temperature to thereby yield the amine-derivatized alpha-methyl styrene (ADAMS) monomer according to structure (V) and/or an aminated conjugated aliphatic methylated polyene (ACAMP) monomer according to structure (VI):
• wherein:
• k is an integer from 1 to 3;
• R1 and R2 are each independently a hydrocarbyl group or a hydrocarbonaceous group having 1 to 4 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, in structure (V), each R is independently hydrogen, a phenyl ring co-attached at two neighboring ring carbon positions with the phenyl ring shown so as to form a naphthalene assembly, a phenyl group attached at a single carbon of the phenyl ring shown, a C1-C4 hydrocarbyl group, or a C1-C6 hydrocarbyl group containing 1 to 4 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, and
• in structure (VI), R3 and R4 are each independently hydrogen, a methyl group, or an alkenyl group having structure (IV)
• attached via the asterisk, but specifically which do not collectively achieve aromaticity in combination with the other alkenes in structure (VI), and with the proviso that R3 and R4 are not both alkenyl groups having structure (IV) and are not both methyl groups.

A method of making an addition-polymerizable monomer composition comprising the steps of:

• providing reactants comprising a secondary amine, a source of methyltriphenylphosphonium halide, and a ketone reactant comprising a C1-C3 alkyl optionally substituted phenyl or naphthalenyl ketone, a C1-C3 alkyl olefinic mono- or di-unsaturated ketone, a phenylene- or naphthalene-bis(C1-C3 alkan-1-one), 1,1-ethylenebis(k-alkanone), 1,2-ethylenebis(k-alkanone), and/or bis(C1-C3 alkyl)diketone, wherein the ketone reactant includes a terminal alkyl carbon bearing a suitable leaving group or wherein the ketone reactant does not include a terminal alkyl carbon bearing a suitable leaving group and a source of formaldehyde is added to the reaction;
• first reacting the secondary amine with the ketone reactant to form an aminated ketone condensation intermediate;
• then reacting the aminated ketone condensation intermediate with the source of methyltriphenylphosphonium halide under strong basic (Wittig reaction) conditions to thereby yield the amine-derivatized alpha-methyl styrene (ADAMS) monomer according to structure (I) and/or an aminated conjugated aliphatic methylated polyene (ACAMP) monomer according to structure (II):
• wherein:
• k is an integer from 1 to 3;
• R1 and R2 are each independently a hydrocarbyl group or a hydrocarbonaceous group having 1 to 4 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, or wherein R1 and R2 are connected to form a moiety containing at least one 5- to 12-membered ring, from 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof;
• in structure (I), R is hydrogen, a phenyl ring co-attached at two neighboring ring carbon positions with the phenyl ring shown so as to form a naphthalene assembly, a phenyl group attached at a single carbon of the phenyl ring shown, a C1-C4 hydrocarbyl group, a C1-C6 hydrocarbyl group containing 1 to 4 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, or a second amino-functional group having structure (III)
• attached via the asterisk, with R′1 and R′2 being independently the same or different as R1 and R2 but defined identically;
• and
• in structure (II), R3 and R4 are each independently hydrogen, a methyl group, a second amino-functional group having structure (III) attached via the asterisk, with R′1 and R′2 being independently the same or different as R1 and R2 but defined identically, or an alkenyl group having structure (IV)
• attached via the asterisk, but specifically which do not collectively achieve aromaticity in combination with the other alkenes in structure (II), and with the proviso that R3 and R4 are not both alkenyl groups having structure (IV) and are not both methyl groups;
• and
• optionally removing condensation byproduct from the first reacting step and/or triphenylphosphine oxide byproduct from the second reacting step.