Compositions of oxygenated amines and quinone methides as antifoulants for vinylic monomers
Described are compositions and methods for inhibiting polymerization of a monomer (e.g., styrene) composition a quinone methide polymerization retarder and an oxygen-containing amine compound that is a tertiary amine or hydroxylamine. In a mixture, the oxygen-containing amine compound improves the efficacy of the quinone methide polymerization retarder and provides greater antipolymerant activity. In turn, the mixture reduces or prevents apparatus fouling and improves the purity of monomer streams.
1. A composition for inhibiting monomer polymerization comprising:
a quinone methide; and
an oxygen-containing amine compound of Formula I:
where R 1 , R 2 and R 3 are independently selected from a) a carbon- and oxygen-containing group having 1-18 carbon atoms and that includes i) an ether group, ii) an ester group, or iii) wherein a) is of Formula IIa: —CH 2 —(R 9 )(OH), wherein R 9 is a 6-17 carbon group comprising an aryl or alkylaryl group, and the hydroxyl group is bonded to any carbon in R 9 , b) a carbon-containing group having 1-18 carbon atoms, and c) OH, with the proviso that at least one of R 1 , R 2 , and R 3 is a).
2. The composition of claim 1 wherein the carbon- and oxygen-containing group having 1-18 carbon atoms includes i) an ether group, or iii) an ester group.
3. The composition of claim 1 , wherein the carbon- and oxygen-containing group having 1-18 carbon atoms includes i) an ether group and ii) a hydroxyl group.
4. The composition of claim 1 wherein two of R 1 , R 2 and R 3 are a).
5. The composition of claim 1 wherein all of R 1 , R 2 , and R 3 are a).
6. The composition of claim 1 wherein R 1 and R 2 are a), and R 3 is c).
7. The composition of claim 1 where:
in a), the carbon- and oxygen-containing group has 2-12 carbon atoms, in b) the carbon-containing group has 2-12 carbon atoms, or both a) and b).
8. The composition of claim 1 wherein the compound of Formula I has a total number of carbon atoms in the compound is in the range of 2-54.
9. The composition of claim 1 , wherein any one or more of R 1 , R 2 and R 3 is of Formula IIa.
10. The composition of claim 1 , where one or more of R 1 , R 2 and R 3 includes a first hydrocarbon portion and a second hydrocarbon portion separated by and bonded to an oxygen atom (ether group), and one or more hydroxyl groups bonded to a carbon atom in the first hydrocarbon portion, the second hydrocarbon portion, or both first and second hydrocarbon portions.
11. The composition of claim 10 , wherein one or more of R 1 , R 2 and R 3 is of sub Formula IIIa: —CH 2 CH(OH)—CH 2 —OR 10 wherein R 10 is a aryl, alkyl, alkylaryl or arylalky group of 1-18 carbons.
12. The composition of claim 11 wherein the oxygen-containing amine compound is:
tris-(3-butoxy-3-hydroxypropyl)amine (TriBHPA)
or
bis-(3-butoxy-2-hydroxypropyl)hydroxylamine (BBHPHA).
13. The composition of claim 1 , wherein one or more of R 1 , R 2 and R 3 is of sub Formula IVa: —R 7 (CO(O))R 8 wherein R 7 is a (divalent) linear, branched, or cyclic alkylene group of 1-10 carbons, and R 8 is a linear, branched or cyclic alkyl or aryl group of 1-8 carbons.
14. The composition of claim 13 wherein the oxygen-containing amine compound is:
tris-(2-hydroxypropyl)hydroxylamine triacetate (TriACTIPA).
15. The composition of claim 1 wherein the oxygen-containing amine compound has a boiling point of greater than 150° C.
16. The composition of claim 1 wherein the quinone methide is of Formula VI:
wherein R 1 and R 2 are independently selected from C4-C18 alkyl, C5-C12 cycloalkyl, phenyl, and C7-C15 cycloalkyl, wherein R 3 and R 4 are independently selected from —H, C1-C18 alkyl, phenyl, substituted phenyl, C5-C12 cycloalkyl, —CN, —COOH, —C≡CR 5 , —C≡CR 5 , —COOR 5 , —COR 5 , —OCOR 5 , —CONR 5 , wherein R 5 is selected from H, C1-C18 alkyl, C5-C12 cycloalkyl, phenyl, and C7-C15 cycloalkyl, and substituted phenyl.
17. The composition of claim 1 wherein quinone methide is present in a molar amount in the range of 5 to 20 times greater than the oxygen-containing amine compound.
18. The composition of claim 1 wherein
the quinone methide is in an amount in the range of 5 to 70% (wt); the oxygen-containing amine compound is in an amount in the range of 0.5 to 10% (wt); and the composition further comprises an organic solvent in an amount in the range of 15 to 50% (wt).
19. A method for inhibiting the polymerization of monomers in a monomer-containing composition, the method comprising either:
(a) adding the composition of claim 1 to a second composition comprising polymerizable monomer or capable of forming a polymerizable monomer, wherein the first composition inhibits the polymerization of the polymerizable monomer; or
(b) adding the quinone methide and the oxygen-containing amine compound of Formula I of claim 1 separately to a composition comprising polymerizable monomer or capable of forming a polymerizable monomer,
which inhibits the polymerization of the polymerizable monomer.
20. The method of claim 19 wherein the polymerizable monomer is selected from the group consisting of acrylic acid, acrylonitrile, alkylated styrene, butadiene, chloroprene, divinylbenzene, ethyl acrylate, ethyl methacrylate, isoprene, methacrylic acid, methyl methacrylate, methyl acrylate, α-methylstyrene, methacrylonitrile, styrene, styrene sulfonic acid, vinyltoluene, and vinylpyridine.
21. The method of claim 19 wherein after addition of the first composition, the second composition is subject to a distillation step and oxygen-containing amine compound has a boiling point that is greater than the polymerizable monomer, or a boiling point that is at least 25° C. greater than the polymerizable monomer.
22. The composition of claim 1 wherein the oxygen-containing amine compound is:
tris-(1-hydroxy-1-phenylethyl)hydroxylamine (TriHPhEHA) or
bis-(1-hydroxy-1-phenylethyl)hydroxylamine (BHPhEHA).