Abating unwanted emulsion polymerization during extractive distillation of conjugated diene monomers
Inhibitor compositions for abating undesirable emulsion polymerization during processing of hydrocarbon stream laden with reactive vinylic monomers are provided. The polymerization inhibitor compositions include at least a first inhibitor compound having a stable nitroxide radical and a second inhibitor including phenylenediamine. Methods of inhibiting the polymerization of monomers using the compositions of the disclosure are also provided. The methods of inhibiting polymerization of monomers include a step of adding a composition of the disclosure to a process stream. The process stream includes an ethylenically unsaturated monomer that is suspended in the bulk-phase and highly polar solvents as distractive distillation solvents.
1. A method of inhibiting monomer polymerization, comprising:
adding a composition to a process stream comprising an ethylenic unsaturated monomer in an extractive distillation process,
wherein the composition comprises a first inhibitor compound comprising a stable nitroxide radical; and a second inhibitor compound comprising a phenylenediamine,
wherein the process stream further comprises micelles, at least one polar extractive distillation solvent, and at least one non-polar extractive distillation solvent, in which the ethylenic unsaturated monomer is present, and wherein the at least one polar extractive distillation solvent and the at least one non-polar extractive distillation solvent are immiscible with each other.
2. The method of claim 1 , wherein the first inhibitor compound is of formula (I):
wherein R 1 is C 1 -C 22 alkyl or aryl, wherein the alkyl and aryl are optionally substituted with one or more C 1 -C 22 alkyl or aryl.
3. The method of claim 1 , wherein the first inhibitor is selected from the group consisting of: 1-oxyl-2,2,6,6-tetramethylpiperin-4-ol; 4-methoxy-2,2,6,6-tetramethylpiperidin-1-oxy; 4-ethoxy-2,2,6,6-tetramethylpiperidin-1-oxy; 4-propoxy-2,2,6,6-tetramethylpiperidin-1-oxy; 4-butoxy-2,2,6,6-tetramethylpiperidin-1-oxy; 4-pentoxy-2,2,6,6-tetramethylpiperidin-1-oxy; 4-hexyloxy-2,2,6,6-tetramethylpiperidin-1-oxy; 4-heptyloxy-2,2,6,6-tetramethylpiperidin-1-oxy; 4-octyloxy-2,2,6,6-tetramethylpiperidin-1-oxy; 4-nonyloxy-2,2,6,6-tetramethylpiperidin-1-oxy; 4-decyloxy-2,2,6,6-tetramethylpiperidin-1-oxy; 4-undecyloxy-2,2,6,6-tetramethylpiperidin-1-oxy; 4-dodecyloxy-2,2,6,6-tetramethylpiperidin-1-oxy; 4-tridecyloxy-2,2,6,6-tetramethylpiperidin-1-oxy; 4-tetradecyloxy-2,2,6,6-tetramethylpiperidin-1-oxy; 4-pentadecyloxy-2,2,6,6-tetramethylpiperidin-1-oxy; 4-hexadecyloxy-2,2,6,6-tetramethylpiperidin-1-oxy; 4-heptadecyloxy-2,2,6,6-tetramethylpiperidin-1-oxy; 4-octadecyloxy-2,2,6,6-tetramethylpiperidin-1-oxy; 4-nodecyloxy-2,2,6,6-tetramethylpiperidin-1-oxy; 4-decyloxy-2,2,6,6-tetramethylpiperidin-1-oxy; 4-icosyloxy-2,2,6,6-tetramethylpiperidin-1-oxy; 4-henicosyloxy-2,2,6,6-tetramethylpiperidin-1-oxy; 4-docosyloxy-2,2,6,6-tetramethylpiperidin-1-oxy; 4-(phenoxy) 2,2,6,6-tetramethylpiperidin-1-oxy; 4-(benzyloxy)-2,2,6,6-tetramethylpiperidin-1-oxy; 2,2,6,6-tetramethyl-4-(naphthalen-2-yloxy) piperidin-1-oxy; and any combination thereof.
4. The method of claim 1 , wherein the first inhibitor is a compound of formula III:
wherein R 3 is −O· or −OH; and R 4 is C 1 -C 22 alkyl or aryl, wherein the alkyl and aryl are optionally substituted with one or more C 1 -C 22 alkyl or aryl.
5. The method of claim 1 , wherein the first inhibitor is selected from the group consisting of: 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl acetate; 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl propanoate; 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl butyrate; 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl pentanoate; 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl hexanoate; 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl heptanoate; 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl octanoate; 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl nonanoate; 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl decanoate; 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl undecanoate; 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl dodecanoate; 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl 2-ethylhexanoate; 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl stearate; 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl benzoate; 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl palmitoate; 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl behenoate; 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl 4-tert-butylbenzoate; and any combination thereof.
6. The method of claim 1 , wherein the second inhibitor compound is a phenylenediamine of formula (IV) or formula (V):
wherein X 1 and X 2 are independently C 1 -C 22 alkyl, or aryl, wherein the alkyl and aryl are optionally substituted with one or more C 1 -C 22 alkyl or aryl.
7. The method of claim 1 , wherein the second inhibitor is selected from the group consisting of: 1,2-phenylenediamine, 1,4-phenylenediamine, N,N′-di-methyl-p-phenylenediamine, N,N′-di-sec-butyl-1,4-phenylenediamine, N,N′-di-1,4-dimethylpentyl-1,4-phenylenediamine, N, N′-di-acetyl-1,4-phenylenediamine, N-tert-butyl-N′-phenyl-1,4-phenylenediamine, N,N′-di-phenyl-1,4-phenylenediamine, and any combination thereof.
8. The method of claim 1 , wherein the first inhibitor compound is present in the composition at a concentration of about 0.01% by weight to about 80% by weight and/or wherein the second inhibitor compound is present in the composition at a concentration of about 0.01% by weight to about 50% by weight.
9. The method of claim 1 , wherein a mole ratio of the first inhibitor compound to the second inhibitor compound is about 100:1 to about 1:100.
10. The method of claim 1 , wherein the ethylenic unsaturated monomer partitions into one of the at least one non-polar extractive distillation solvent to a greater extent compared to the at least one polar extractive distillation solvent.
11. The method of claim 10 , wherein the first inhibitor or the second inhibitor partition into the at least one non-polar extractive distillation solvent to a greater extent compared to the at least one polar extractive distillation solvent.
12. The method of claim 1 , wherein the at least one non-polar extractive distillation solvent is selected from the group consisting of furfural, vinyl acetate, acrylonitrile, 1 , 3 -butadiene, styrene, isoprene, cyclopentadiene, dicyclopentadiene, acrylic acid, methacrylic acid, tetrahydrofuran, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, benzene, toluene, ethyl benzene, ethyltoluene, dichloromethane, tetrachloromethane, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, dicyclopentane, cyclopentadiene, dicyclopentadiene, ethyl acetate, ethyl propionate, ethyl butanoate, ethyl pentanoate, ethyl hexanoate, ethyl heptanoate, ethyl nonanoate, ethyl decanoate, ethyl undecanoate, ethyl dodecanoate, ethyl tridecanoate, ethyl tertradecanoate, ethyl pentadecanoate, ethyl hexadecanoate, ethyl octadecenoate, ethyl behenate, methyl acetate, methyl propionate, methyl butanoate, methyl pentanoate, methyl hexanoate, methyl heptanoate, methyl nonanoate, methyl decanoate, methyl undecanoate, methyl dodecanoate, methyl tridecanoate, methyl tetradecanoate, methyl pentadecanoate, methyl hexadecanoate, methyl octadecenoate, methyl behenate, propyl acetate, propyl propionate, propyl butanoate, propyl pentanoate, propyl hexanoate, propyl heptanoate, propyl nonanoate, propyl decanoate, propyl undecanoate, propyl dodecanoate, propyl tridecanoate, propyl tertradecanoate, propyl pentadecanoate, propyl hexadecanoate, propyl octadecenoate, propyl behenate, butyl acetate, butyl propionate, butyl butanoate, butyl pentanoate, butyl hexanoate, butyl heptanoate, butyl nonanoate, butyl decanoate, butyl undecanoate, butyl dodecanoate, butyl tridecanoate, butyl tertradecanoate, butyl pentadecanoate, butyl hexadecanoate, butyl octadecenoate, butyl behenate, hexyl acetate, hexyl propionate, hexyl butanoate, hexyl pentanoate, hexyl hexanoate, hexyl heptanoate, hexyl nonanoate, hexyl decanoate, hexyl undecanoate, hexyl dodecanoate, hexyl tridecanoate, hexyl tertradecanoate, hexyl pentadecanoate, hexyl hexadecanoate, hexyl octadecenoate, hexyl behenate, octyl acetate, octyl propionate, octyl butanoate, octyl pentanoate, octyl hexanoate, octyl heptanoate, octyl nonanoate, octyl decanoate, octyl undecanoate, octyl dodecanoate, octyl tridecanoate, octyl tertradecanoate, octyl pentadecanoate, octyl hexadecanoate, octyl octadecenoate, octyl behenate, and any combination thereof.
13. The method of claim 1 , wherein the at least one polar extractive distillation solvent is selected from N,N-dimethyl formamide, furfural, N-methyl pyrrolidone, acetonitrile, water, and combinations thereof.
14. The method of claim 1 , wherein the composition is added to the process stream such that a concentration of the first inhibitor compound is about 0.1 ppm to about 10,000 ppm and/or wherein the composition is added to the process stream such that a concentration of the second inhibitor compound is about 0.1 ppm to about 10,000 ppm.
15. The method of claim 1 , wherein the ethylenic unsaturated monomer is selected from the group consisting of vinyl acetate, acrylonitrile, an acrylate, a methacrylate, 1,3-butadiene, styrene, isoprene, cyclopentadiene, dicyclopentadiene, acrylic acid, methacrylic acid, and any combination thereof.
16. A method of inhibiting polymerization of a monomer, comprising:
adding a composition to a process stream comprising the monomer in an extractive distillation process,
wherein the composition comprises 4-acetoxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 2,2,6,6-tetramethylpiperidine-1,4-diol, a hydroxylamine of 4-acetoxy-2,2,6,6-tetramethylpiperidin-1-oxyl, a phenylenediamine, and dimethylformamide.
17. The method of claim 16 , wherein the composition further comprises an organic solvent.
18. The method of claim 16 , wherein the process stream further comprises an ethylenic unsaturated monomer selected from the group consisting of vinyl acetate, acrylonitrile, an acrylate, a methacrylate, 1,3-butadiene, styrene, isoprene, cyclopentadiene, dicyclopentadiene, acrylic acid, methacrylic acid and any combination thereof.