Method for preparing glycidyloxystyrene monomers and polymers thereof
AssigneeE. I. Du Pont de Nemours and Company
InventorsKEITH KUNITSKY, Mukesh C. Shah, Steven W. Shuey, Mark E. Wagman
Life of this patent
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Abstract
It was found that glycidyloxystyrenes, including glycidyloxystyrene and substituted glycidyloxystyrene, can be synthesized from hydroxycinnamic acid or substituted hydroxycinnamic acids in a one-pot, two-step process. The substrate can be thermally decarboxylated and then without purification, reacted in the presence of a halomethyl-oxirane and a base. The resulting product can be polymerized or coppolymerized to a fully substituted product.
Claims21
A method for the synthesis of a glycidyloxystyrene monomer or a substituted glycidyloxystyrene monomer comprising the steps of:
- a) providing a phenolic substrate having the general structure:
- wherein R1, R2, R3, R4, and R5 are H, OH, OCH3, OR8, or linear or branched alkyl, aryl, halo, or cyano;
- R6 and R7 are H, halo, or cyano;
- R8 is linear or branched alkyl or aryl;
- provided that at least one of R1, R3, or R5 is OH;
- b) providing a reaction mixture comprising:
- i) a non-amine basic catalyst;
- and
- ii) at least one aprotic, polar solvent;
- and
- c) contacting the phenolic substrate of (a) with the reaction mixture of (b) at a temperature of at least about 100° C. for a time sufficient for the decarboxylation of the phenolic substrate to a decarboxylated product;
- d) contacting the decarboxylated product of (c) with a halomethyl-oxirane and a basic catalyst at a temperature between about 20° C. and about 120° C. for a time sufficient for glycidyloxystyrene monomer or substituted glycidyloxystyrene monomer synthesis;
- and
- e) optionally recovering the glycidyloxystyrene monomer or substituted glycidyloxystyrene monomer.
A method for the synthesis of homopolymers and copolymers of glycidyloxystyrene monomer or substituted glycidyloxystyrene monomer comprising:
- a) providing a phenolic substrate having the general structure:
- wherein R1, R2, R3, R4, and R5 are H, OH, OCH3, OR8, or linear or branched alkyl, aryl, halo, or cyano;
- R6 and R7 are H, halo, or cyano;
- R8 is linear or branched alkyl or aryl;
- provided that at least one of R1, R3, or R5 is OH;
- b) providing a first reaction mixture comprising:
- i) a non-amine basic catalyst;
- and
- ii) at least one aprotic, polar solvent;
- c) contacting the phenolic substrate of (a) with the reaction mixture of (b) at a temperature of at least about 100° C. for a time sufficient for the decarboxylation of the phenolic substrate to a decarboxylated product;
- d) contacting the decarboxylated product of (c) with a halomethyl-oxirane and a basic catalyst at a temperature between about 20° C. and about 120° C. for a time sufficient for glycidyloxystyrene monomer or substituted glycidyloxystyrene monomer synthesis;
- e) optionally recovering the glycidyloxystyrene monomer or substituted glycidyloxystyrene monomer;
- and
- f) reacting the glycidyloxystyrene monomer or substituted glycidyloxystyrene monomer, with a second reaction mixture comprising:
- 1) optionally at least one co-monomer;
- and
- 2) a polymerization initiator;
- at a temperature and time sufficient to produce a glycidyloxystyrene homopolymer or copolymer, or substituted glycidyloxystyrene homopolymer or copolymer.
A composition comprising a glycidyloxystyrene homopolymer or copolymer, or substituted glycidyloxystyrene homopolymer or copolymer prepared by a method comprising:
- a) providing a phenolic substrate having the general structure:
- wherein R1, R2, R3, R4, and R5 are H, OH, OCH3, OR8, or linear or branched alkyl, aryl, halo, or cyano;
- R6 and R7 are H, halo, or cyano;
- R8 is linear or branched alkyl or aryl;
- provided that at least one of R1, R3, or R5 is OH;
- b) providing a reaction mixture comprising:
- i) a non-amine basic catalyst;
- and
- ii) at least one aprotic, polar solvent;
- c) contacting the phenolic substrate of (a) with the reaction mixture of (b) at a temperature of at least about 100° C. for a time sufficient for the decarboxylation of the phenolic substrate to a decarboxylated product;
- d) contacting the decarboxylated product of (c) with a halomethyl-oxirane and a basic catalyst at a temperature between about 20° C. and about 120° C. for a time sufficient for glycidyloxystyrene monomer or substituted glycidyloxystyrene monomer synthesis;
- and
- e) optionally recovering the glycidyloxystyrene monomer or substituted glycidyloxystyrene monomer.
- f) reacting the glycidyloxystyrene monomer or substituted glycidyloxystyrene monomer, with optionally at least one co-monomer, with a polymerization initiator at a temperature and time sufficient to produce a glycidyloxystyrene homopolymer or copolymer, or substituted glycidyloxystyrene homopolymer or copolymer.
A composition of claim 25 wherein the comonomer of (f) is hydroxystyrene or styrene.
Dependencies are inferred from the claim text.