Quinone methide and ammonium salt antipolymerant composition and method

Patent metadata

Field	Value
Publication number	US-11396629-B2
Application number	US-202017067164-A
Country	US
Kind code	B2
Filing date	Oct 9, 2020
Priority date	Oct 11, 2019
Publication date	Jul 26, 2022
Grant date	Jul 26, 2022

Abstract

Described are compositions and methods for inhibiting polymerization of a monomer (e.g., styrene) composition a quinone methide polymerization retarder and an ammonium salt. In a mixture, the ammonium salt 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.

First claim

What is claimed is:

1. A composition comprising:
a quinone methide and an ammonium salt, wherein (A) the ammonium salt is present in a molar amount that is less than a molar amount of the quinone methide, (B) the ammonium salt comprises a protonated cation, or both (A) and (B), and wherein the ammonium salt improves an ability of the composition to inhibit polymerization of a polymerizable monomer by more than 1.2-fold as compared to a composition containing the quinone methide but without the ammonium salt under the same conditions.

2. The composition of claim 1 wherein the quinone methide is of Formula I:

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═CHR 5 ,
—C≡CR 5 , —COOR 5 , —COR 5 , —OCOR 5 , —CONHR 5 , wherein R 5 is selected from H, C1-C18 alkyl, C5-C12 cycloalkyl, phenyl, and C7-C15 cycloalkyl, and substituted phenyl.

3. The composition of claim 2 wherein the quinone methide is 2,6-di-tert-butyl-4-benzylidene-cyclohexa-2,5-dienone.

4. The composition of claim 1 wherein the ammonium salt comprises:
(i) a cation of Formula III:

where R 1 , R 2 , R 3 , and R 4 are independently selected from (a) —H, (b) a carbon-containing group, (c) an oxygen-containing group, and (d) an oxygen- and carbon-containing group; or
(ii) a cation of Formula IV:

where R 5 is a monovalent or multivalent carbon-containing group, y is an integer in the range of 1-4, and R 6 , R 7 , and R 8 are independently selected from (a)-(d).

5. The composition of claim 4 where in the cation of Formula III: at least three of R 1 , R 2 , R 3 , and R 4 are any one or a combination of (b)-(d), or in the cation of Formula IV at least two of R 6 , R 7 , and R 8 are any one or a combination of (b)-(d).

6. The composition of claim 4 wherein (b) the carbon-containing group consists of carbon, oxygen, and hydrogen, (c) the oxygen-containing group consists of oxygen and hydrogen, (d) the oxygen- and carbon-containing group consists of carbon, oxygen, and hydrogen, or more than one of (b)-(d).

7. The composition of claim 1 wherein the cation of the ammonium salt has (a) a total amount of carbon atoms in the range of 0-18, 1-12, or 2-10; (b) a total amount of oxygen atoms in the range of 0-6, 1-4, or 1-3; (c) a total amount of hydrogen atoms in the range of 4-40, 6-30, or 8-24; or any combination of (a)-(c).

8. The composition of claim 4 wherein the carbon-containing group is selected from C1-C18 alkyl, aryl, alkyl aryl, and aryl alkyl.

9. The composition of claim 4 wherein the carbon-containing group is
(b1) a linear or branched C1-C12 alkyl group, or is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl;
(b2) a C1-C12 cycloalkyl group, or is selected from the group consisting of cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl,
(b3) a C1-C14 aryl group, or is selected from the group consisting of phenyl, ethylphenyl, tolyl, naphthyl, and anthracyl; or
(b4) a linear or branched C1-C12 alkylene group, or is selected from the group consisting of allyl and isobutenyl.

10. The composition of claim 4 wherein the oxygen- and carbon-containing group is of Formula VIII:

where R 15 , R 16 , R 17 , R 18 , and R 19 are independently selected from H, C 1 -C 18 alkyl, aryl, alkyl aryl, aryl alkyl, and —OR 20 , wherein R 20 is selected from H, C 1 -C 18 alkyl, aryl, alkyl aryl, aryl alkyl, or R 16 and R 17 are divalent hydrocarbon-containing groups bonded to one another to form a cyclic alkyl or aryl group, and wherein y is an integer in the range of 1-3, wherein Formula VIII includes at least one —OR 20 group.

11. The composition of claim 4 wherein the oxygen- and carbon-containing group is a linear or branched C1-C18 hydroxyalkyl group, or is selected from the group consisting of hydroxymethyl, 1- or 2-hydroxyethyl, 1-, 2-, or 3-hydroxypropyl, 2-hydroxyisopropyl, 1-, 2-, 3-, or 4-hydroxybutyl, and 1-, 2-, or 3-hydroxyisobutyl.

12. The composition of claim 4 wherein the oxygen- and carbon-containing group is selected from the group consisting of 2-benzoxazolyl, adipyl, glutaryl, succinyl, malonyl, acetyl, acrylyl, methacrylyl, caproyl, benzoyl, phthaloyl, terephthaloyl, carbethoxy, carbonyl, and formyl.

13. The composition of claim 4 wherein (c1) the oxygen-containing group is hydroxyl, (a1) one of R 1 , R 2 , R 3 , and R 4 is —H or one of R 6 , R 7 , and R 8 is —H, or both (c1) and (a1).

14. The composition of claim 4 wherein the ammonium salt comprises a cation of the Formula VI:

15. The composition of claim 1 wherein the ammonium salt comprises an anion comprising a carboxylate group, a sulfonate group, a phosphonate group, a nitrate group, or a combination thereof.

16. The composition of claim 15 , wherein the anion has (a) an amount of carbon atoms in the range of 2-18, 3-12, or 4-10, (b) an amount of oxygen atoms in the range of 2-4, or both (a) and (b).

17. The composition of claim 16 , wherein the anion is selected from the group consisting of
acetate (ethanoate);
propionate (propanoate);
butyrate (butanoate), isobutyrate (2-methylpropanoate);
valerate (pentanoate), isovalerate (3-methylbutanoate), 2-methylbutanoate, pivalate (2,2-dimethylpropanoate);
caproate (hexanoate), 2-methylvalerate, 3-methylvalerate, 4-methylvalerate, 2,2-2,2-dimethylbutanoate, 2-ethylbutanoate;
heptanoate (enanthoate), 2-methylcaproate, 3-methylcaproate, 4-methylcaproate, 5-methylcaproate, 2,2-dimethylvalerate, 2-ethylvalerate;
caprylate (octanoate), 2-methylheptanoate, 3-methylheptanoate, 4-methyl heptanoate, 5-methylheptanoate, 6-methylheptanoate, 2,2-dimethylcaproate, 2-ethylcaproate (2-ethylhexanoate), and 2-propylvalerate.

18. The composition of claim 1 wherein the quinone methide is present in a molar amount greater than the ammonium salt.

19. The composition of claim 1 wherein the ammonium salt is in the form of an ionic liquid at room temperature (25° C.).

20. The composition of claim 1 wherein the molar amount of the quinone methide is greater than 1.5-times, greater than 2.5-times, or greater than 5-times the molar amount of the ammonium salt in the composition.

21. The composition of claim 1 having no or less than 50 ppm of a nitroxyl group containing antipolymerant.

22. A composition formed by adding the composition of claim 1 to a hydrocarbon-containing composition comprising a polymerizable monomer, the hydrocarbon-containing composition optionally being a petroleum product.

23. A composition comprising:
a quinone methide and an ammonium salt,
wherein the ammonium salt comprises a cation of Formula VI:

Assignees

• Ecolab Usa Inc

Inventors

• Masere Jonathan

Classifications

• C07C7/20 Primary

  Use of additives, e.g. for stabilisation · CPC title

• C09K15/18

  containing an amine or imine moiety · CPC title

• C08F2/40

  using retarding agents · CPC title

• C07B63/04

  Use of additives {(anti-oxidant compositions or compositions inhibiting chemical change in general C09K15/00)} · CPC title

• C07C211/06

  containing only n- or iso-propyl groups · CPC title