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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/42—Separation; Purification; Stabilisation; Use of additives
  • C07C51/50—Use of additives, e.g. for stabilisation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/58—Preparation of carboxylic acid halides
  • C07C51/64—Separation; Purification; Stabilisation; Use of additives
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/002—Scale prevention in a polymerisation reactor or its auxiliary parts
  • C08F2/005—Scale prevention in a polymerisation reactor or its auxiliary parts by addition of a scale inhibitor to the polymerisation medium
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C11/00—Aliphatic unsaturated hydrocarbons
  • C07C11/12—Alkadienes
  • C07C11/16—Alkadienes with four carbon atoms
  • C07C11/167—1, 3-Butadiene
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C11/00—Aliphatic unsaturated hydrocarbons
  • C07C11/12—Alkadienes
  • C07C11/173—Alkadienes with five carbon atoms
  • C07C11/18—Isoprene
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
  • C07C15/40—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals
  • C07C15/42—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic
  • C07C15/44—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic the hydrocarbon substituent containing a carbon-to-carbon double bond
  • C07C15/46—Styrene; Ring-alkylated styrenes
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C253/00—Preparation of carboxylic acid nitriles
  • C07C253/32—Separation; Purification; Stabilisation; Use of additives
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C255/00—Carboxylic acid nitriles
  • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
  • C07C255/06—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton
  • C07C255/07—Mononitriles
  • C07C255/08—Acrylonitrile; Methacrylonitrile
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
  • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
  • C07C57/03—Monocarboxylic acids
  • C07C57/04—Acrylic acid; Methacrylic acid
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/48—Separation; Purification; Stabilisation; Use of additives
  • C07C67/62—Use of additives, e.g. for stabilisation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
  • C07C69/12—Acetic acid esters
  • C07C69/14—Acetic acid esters of monohydroxylic compounds
  • C07C69/145—Acetic acid esters of monohydroxylic compounds of unsaturated alcohols
  • C07C69/15—Vinyl acetate
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
  • C07C69/54—Acrylic acid esters; Methacrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C7/00—Purification; Separation; Use of additives
  • C07C7/20—Use of additives, e.g. for stabilisation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
  • C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
  • C07D211/94—Oxygen atom, e.g. piperidine N-oxide
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
  • C07D295/24—Oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
  • C08F18/02—Esters of monocarboxylic acids
  • C08F18/04—Vinyl esters
  • C08F18/08—Vinyl acetate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2438/00—Living radical polymerisation
  • C08F2438/02—Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]

Definitions

• the present disclosure generally relates to compositions that include a blend of polymerization inhibitors and methods of using the same. More particularly, the present disclosure relates to compositions that include at least one compound having a stable nitroxide radical and at least one compound having a hydroxylamine, useful for inhibiting polymerization of ethylenic unsaturated monomers. The present disclosure further relates to methods of preparing compounds having a stable nitroxide radical, as well as methods of preparing compounds having a hydroxylamine.
• the manufacture of ethylenically unsaturated monomers typically comprises three stages: reaction, recovery, and purification. Distillation operations at elevated temperatures are often involved in the recovery and the purification stages.
• Ethylenically unsaturated monomers such as vinyl acetate, acrylate, and methacrylate monomers, can be present in processing streams or in refined products made by various chemical industrial processes.
• these monomer types may undesirably polymerize through radical polymerization especially at elevated temperature and when polymerization initiators are present.
• solid deposits of polymer can form on the surface of the process equipment during industrial manufacture, processing, handling, or storage. The resulting polymers can be problematic and lead to equipment "fouling" and product contamination.
• the premature polymerization of these monomers is generally controlled by dosing polymerization inhibitors capable of reducing the premature polymerization of the monomers.
• Conventional polymerization inhibitors include stable free radicals that can effectively scavenge carbon-centered radicals.
• Conventional polymerization inhibitors such as 4- hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl (HTEMPO) and 4-oxo-2, 2,6,6- tetramethylpiperidin-1-oxyl (OTEMPO), generally degrade and lose their efficacy as polymerization inhibitors under acidic environments.
• HTEMPO 4- hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl
• OFTEMPO 4-oxo-2, 2,6,6- tetramethylpiperidin-1-oxyl
• compositions for inhibiting the polymerization of monomers include a first inhibitor compound having a stable nitroxide radical and a second inhibitor compound having a hydroxylamine.
• the compositions are useful for inhibiting the polymerization of ethylenically unsaturated monomers including vinyl acetate, acrylonitrile, acrylates, methacrylates, 1 ,3-butadiene, styrene, isoprene, (meth)acrylic acid, and combinations thereof.
• compositions of the disclosure demonstrate synergy with respect to their ability to inhibit polymerization of a monomer.
• the compositions of the disclosure demonstrate greater polymerization inhibition than the individual components present within the composition, controlling for the dosage of the active components.
• compositions of the disclosure are active even under acidic conditions, unlike conventional polymerization inhibitors known in the art.
• the compositions of the disclosure also include one or more acids.
• Methods of inhibiting the polymerization of a monomer are also disclosed herein.
• the methods of inhibiting the polymerization of a monomer include the step of adding a composition of the disclosure to the monomer. Addition of the polymerization inhibitor composition of the disclosure to the monomer inhibits polymerization of the monomer.
• Processes for preparing the polymerization inhibitors and compositions of the disclosure are also disclosed herein.
• the processes for preparing a polymerization inhibitor include the step of treating a compound of formula (Illa) with a compound of formula (II lb) within a solution to afford the polymerization inhibitor compound.
• FIG. 1 shows gelation test results of acrylic acid treated with Formulation 2 or Formulation 4 at a dosage of 3.2 ppm to 3.3 ppm. The results are compared to gelation test results of acrylic acid treated with 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl (HTEMPO) or 4-oxo-2,2,6,6-tetramethylpiperidin-1-oxyl (OTEMPO).
• HTEMPO 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl
• OFTEMPO 4-oxo-2,2,6,6-tetramethylpiperidin-1-oxyl
• FIG. 2 shows gelation test results of vinyl acetate in the presence of acetic acid treated with Formulation 1 or Formulation 4 at a dosage of about 50 ppm. The results are compared to gelation test results of acrylic acid treated with HTEMPO or OTEMPO.
• the present disclosure relates to compositions that include a blend of polymerization inhibitors and methods of using the same to inhibit the polymerization of ethylenic unsaturated monomers.
• Polymerization inhibitor compositions of the present disclosure include at least one compound having a stable nitroxide radical and at least one compound having a hydroxylamine.
• the polymerization inhibitor compositions can be blends of multiple components, including components in addition to the aforementioned compounds having a stable nitroxide radical and a hydroxylamine.
• the present disclosure further relates to methods of preparing compounds having a stable nitroxide radical, as well as methods of preparing compounds having a hydroxylamine.
• Any of the presently disclosed polymerization inhibitor compositions are effective in scavenging free radicals that would otherwise cause the initiation and propagation of a polymerization reaction involving ethylenic unsaturated monomers.
• Polymerization inhibitors and polymerization retarders can be considered generally as "antipolymerants" which are compounds that can inhibit or reduce the formation of polymers from one or more radically polymerizable compounds.
• fouling refers to the formation of polymers, prepolymers, oligomer and/or other materials, which would become insoluble in and/or precipitate from a stream and deposit on equipment underthe conditions of operation of the equipment.
• the inhibitor, retarder, and amine stabilizer components and compositions of the disclosure can be referred to as “antifouling” as they inhibit or reduce such formation.
• compositions for inhibiting monomer polymerization where the compositions include a first inhibitor compound having a stable nitroxide radical and a second inhibitor compound having a hydroxylamine.
• the compositions are for inhibiting monomer polymerization, where the monomer is an ethylenic unsaturated monomer.
• the compositions of the disclosure are useful for inhibiting polymerization of ethylenic unsaturated monomers including, but not limited to, vinyl acetate, acrylonitrile, acrylates, methacrylates, 1 ,3- butadiene, styrene, isoprene, (meth)acrylic acid, and combinations thereof.
• the first inhibitor compound having a stable nitroxide radical is a compound of formula (I): where Ri is selected from H, C1-C22 alkyl, C1-C22 alkenyl, C1-C22 alkynyl, C1-C22 cycloalkyl, aryl,
• -C1-C22 alkylene aryl -C(O)(Ci-C 2 2 alkyl), -C(O)(Ci-C 22 alkenyl), -C(O)(Ci-C 22 alkynyl), -C(O)(Ci-C 22 cycloalkyl), -C(O)(aryl), and -C(O)(Ci-C 22 alkylene aryl), where the cycloalkyl and aryl are optionally substituted with one or more Ci-C 22 alkyl, Ci-C 22 alkenyl, Ci-C 22 alkynyl, or aryl.
• R1 is selected from -C(O)(Ci-C 22 alkyl), -C(O)(Ci-C 22 alkenyl), -C(O)(Ci-C 22 alkynyl), -C(O)(Ci-C 22 cycloalkyl), -C(O)(aryl), and -C(O)(Ci-C 22 alkylene aryl), wherein the cycloalkyl and aryl are optionally substituted with one or more Ci-C 22 alkyl, Ci-C 22 alkenyl, Ci-C 22 alkynyl, and aryl.
• R1 is H. In some embodiments, R1 is Ci-C 22 alkyl. In some embodiments, R1 is Ci-C 22 alkenyl. In some embodiments, R1 is Ci-C 22 alkynyl. In some embodiments, R1 is Ci-C 22 cycloalkyl, where the cycloalkyl is optionally substituted with one or more Ci-C 22 alkyl, Ci-C 22 alkenyl, Ci-C 22 alkynyl, or aryl. In some embodiments, R1 is aryl, where the aryl is optionally substituted with one or more Ci-C 22 alkyl, Ci-C 22 alkenyl, Ci-C 22 alkynyl, or aryl.
• R1 is -Ci-C 22 alkylene aryl, where the aryl is optionally substituted with one or more Ci-C 22 alkyl, Ci-C 22 alkenyl, Ci-C 22 alkynyl, or aryl.
• Ri is -C(O)(Ci-C 2 2 alkyl). In some embodiments, Ri is -C(O)(Ci-Ci 2 alkyl). In some embodiments, Ri is -C(O)(Ci-C e alkyl). In some embodiments, Ri is -C(O)(methyl). In some embodiments, Ri is
• Ri is -C(O)(ethyl). In some embodiments, Ri is -C(O)(propyl). In some embodiments, Ri is -C(O)(butyl). In some embodiments, Ri is -C(O)(Ci-C22 alkenyl). In some embodiments, Ri is
• Ri is -C(O)(Ci-C22 cycloalkyl), where the cycloalkyl is optionally substituted with one or more C1-C22 alkyl, Ci-C 22 alkenyl, Ci-C 22 alkynyl, or aryl. In some embodiments, Ri is -C(O)(aryl), where the aryl is optionally substituted with one or more
• Ci-C 22 alkyl C1-C22 alkenyl, Ci-C 22 alkynyl, or aryl.
• Ri is -C(O)(Ci-C 22 alkylene aryl), where the aryl is optionally substituted with one or more C1-C22 alkyl, Ci-C 22 alkenyl, Ci-C 22 alkynyl, or aryl.
• the second inhibitor compound having a hydroxylamine is a compound of formula (II): where R 2 is selected from H, C1-C22 alkyl, C1-C22 alkenyl, C1-C22 alkynyl, C1-C22 cycloalkyl, aryl,
• -C1-C22 alkylene aryl -C(O)(Ci-C 2 2 alkyl), -C(O)(Ci-C 2 2 alkenyl), -C(O)(Ci-C 2 2 alkynyl), -C(O)(Ci-C 22 cycloalkyl), -C(O)(aryl), and -C(O)(Ci-C 2 2 alkylene aryl), wherein the cycloalkyl and aryl are optionally substituted with one or more C1-C22 alkyl, C1-C22 alkenyl, C1-C22 alkynyl, or aryl.
• R 2 is -C(O)(Ci-C 22 alkyl), -C(O)(Ci-C 22 alkenyl), -C(O)(Ci-C 22 alkynyl), -C(O)(Ci-C 22 cycloalkyl), -C(O)(aryl), and -C(O)(Ci-C 22 alkylene aryl), where the cycloalkyl and aryl are optionally substituted with one or more Ci-C 22 alkyl, Ci-C 22 alkenyl, Ci-C 22 alkynyl, or aryl.
• R 2 is H. In some embodiments, R 2 is Ci-C 22 alkyl. In some embodiments, R 2 is Ci-C 22 alkenyl. In some embodiments, R 2 is Ci-C 22 alkynyl. In some embodiments, R 2 is Ci-C 22 cycloalkyl, where the cycloalkyl is optionally substituted with one or more Ci-C 22 alkyl, Ci-C 22 alkenyl, Ci-C 22 alkynyl, or aryl. In some embodiments, R 2 is aryl, where the aryl is optionally substituted with one or more Ci-C 22 alkyl, Ci-C 22 alkenyl, Ci-C 22 alkynyl, or aryl.
• R 2 is -Ci-C 22 alkylene aryl, where the aryl is optionally substituted with one or more C1-C22 alkyl, C1-C22 alkenyl, C1-C22 alkynyl, or aryl.
• R 2 is -C(O)(Ci-C 2 2 alkyl).
• R 2 is -C(O)(Ci-Ci 2 alkyl).
• R 2 is -C(O)(Ci-C 6 alkyl).
• R 2 is -
• R2 is -C(O)(ethyl). In some embodiments, R2 is -
• R2 is -C(O)(butyl). In some embodiments, R2 is -
• R2 is -C(O)(Ci-C 22 alkenyl).
• R2 is -C(O)(Ci-C22 alkynyl).
• R2 is -C(O)(Ci-C22 cycloalkyl), where the cycloalkyl is optionally substituted with one or more C1-C22 alkyl, C1-C22 alkenyl, C1-C22 alkynyl, or aryl.
• R 2 is -C(O)(aryl), where the aryl is optionally substituted with one or more C1-C22 alkyl, C1-C22 alkenyl, C1-C22 alkynyl, or aryl.
• R 2 is -C(O)(Ci-C 2 2 alkylene aryl), where the aryl is optionally substituted with one or more C1-C22 alkyl, C1-C22 alkenyl, C1-C22 alkynyl, or aryl.
• compositions of the disclosure include first and second inhibitor compounds of formula (I) and (II), respectively, where R1 and R 2 are the same.
• the compositions of the disclosure include first and second inhibitor compounds of formula (I) and (II), respectively, where R1 and R 2 are each, independently, -C(O)(Ci-C 22 alkyl).
• the compositions of the disclosure include first and second inhibitor compounds of formula (I) and (II), respectively, where R1 and R 2 are different.
• the first inhibitor compound having a stable nitroxide radical is a compound selected from the group consisting of:
• the first inhibitor compound having a stable nitroxide radical is a compound selected from: In some embodiments, the first inhibitor compound having a stable nitroxide radical is:
• the first inhibitor compound having a stable nitroxide radical is:
• the first inhibitor compound having a stable nitroxide radical is:
• the first inhibitor compound having a stable nitroxide radical is:
• the second inhibitor compound having a hydroxylamine is selected from the group consisting of: In some embodiments, the second inhibitor compound having a hydroxylamine is:
• the second inhibitor compound having a hydroxylamine is:
• the second inhibitor compound having a hydroxylamine is:
• the second inhibitor compound having a hydroxylamine is:
• the presently disclosed second inhibitor compound having a hydroxylamine has benefits over the corresponding nitroxide, such as the capability to provide additional polymerization inhibition, as will be more fully explained below.
• a general synthetic route to produce a hydroxylamine of a nitroxide is to reduce its corresponding nitroxide with a reducing reagent as follows:
• a hydroxylamine of a nitroxide has the potential to provide additional polymerization inhibition as compared to the corresponding nitroxide when carbon-centered and oxygen-centered radical initiators are present. This is explained as follows:
• the hydroxylamine of a nitroxide is an excellent hydrogen donor due to its weak NO-H bond in the compound, and thus it is an efficient antioxidant.
• the hydroxylamine of a nitroxide easily reacts with oxygen-centered radicals, such as peroxide radicals, while it's converted to its corresponding nitroxide.
• Nitroxides are generally known as the most effective inhibitors because of their superior inhibiting capabilities through scavenging carbon-centered free radicals at a nearly diffusion controlled rate. This rate is several orders of magnitude faster than phenolic compounds. However, their kinetic superiority is not always advantageous. For instance, it may lose its superiority when oxygencentered radicals are present as the predominant free radicals.
• nitroxide inhibitor dosages are often required for a given inhibition efficacy, thereby making their use economically unattractive or even infeasible.
• each hydroxylamine of a nitroxide is equivalent to one hydrogen donor plus one nitroxide antipolymerant when oxygen-centered radicals and carbon-centered radicals are both present, which is an attractive incentive offered by the hydroxylamines of nitroxides. That is, one hydroxylamine of a nitroxide is able to eliminate one oxygen-centered radical and one carbon-centered radical whereas a nitroxide is only capable to eliminate a carbon-centered radical.
• the composition unexpectedly demonstrates synergy, where the combination of the first and second inhibitor compounds produces a greater degree of polymerization inhibition than would be expected for the combination. This unexpected synergy is demonstrated in the Examples presented herein, as well as in FIGS. 1 and 2.
• the first inhibitor compound having a stable nitroxide radical is present in the composition at a concentration of about 0.01% by weight to about 80% by weight. In some embodiments, the first inhibitor compound having a stable nitroxide radical is present in the composition at a concentration of about 0.01% by weight to about 70% by weight. In some embodiments, the first inhibitor compound having a stable nitroxide radical is present in the composition at a concentration of about 0.01% by weight to about 60% by weight. In some embodiments, the first inhibitor compound having a stable nitroxide radical is present in the composition at a concentration of about 0.01% by weight to about 50% by weight.
• the first inhibitor compound having a stable nitroxide radical is present in the composition at a concentration of about 0.01% by weight to about 40% by weight. In some embodiments, the first inhibitor compound having a stable nitroxide radical is present in the composition at a concentration of about 0.01% by weight to about 30% by weight. In some embodiments, the first inhibitor compound having a stable nitroxide radical is present in the composition at a concentration of about 0.01% by weight to about 20% by weight. In some embodiments, the first inhibitor compound having a stable nitroxide radical is present in the composition at a concentration of about 0.01% by weight to about 10% by weight.
• the first inhibitor compound having a stable nitroxide radical is present in the composition at a concentration of about 0.01% by weight, about 0.1% by weight, about 1% by weight, about 5% by weight, about 10% by weight, about 15% by weight, about 20% by weight, about 25% by weight, about 30% by weight, about 35% by weight, about 40% by weight, about 45% by weight, about 50% by weight, about 55% by weight, about 60% by weight, about 65% by weight, about 70% by weight, about 75% by weight, or about 80% by weight.
• the second inhibitor compound having a hydroxylamine is present in the composition at a concentration of about 0.01% by weight to about 50% by weight. In some embodiments, the second inhibitor compound having a hydroxylamine is present in the composition at a concentration of about 0.01% by weight to about 40% by weight. In some embodiments, the second inhibitor compound having a hydroxylamine is present in the composition at a concentration of about 0.01% by weight to about 30% by weight. In some embodiments, the second inhibitor compound having a hydroxylamine is present in the composition at a concentration of about 0.01% by weight to about 20% by weight.
• the second inhibitor compound having a hydroxylamine is present in the composition at a concentration of about 0.01% by weight to about 10% by weight.
• the second inhibitor compound having a hydroxylamine is present in the composition at a concentration of about 0.01 % by weight, about 0.1% by weight, about 1% by weight, about 5% by weight, about 10% by weight, about 15% by weight, about 20% by weight, about 25% by weight, about 30% by weight, about 35% by weight, about 40% by weight, about 45% by weight, or about 50% by weight.
• a mole ratio of the first inhibitor compound having a stable nitroxide radical to the second inhibitor compound having a hydroxylamine is about 100:1 to about 1 :100. In some embodiments, a mole ratio of the first inhibitor compound having a stable nitroxide radical to the second inhibitor compound having a hydroxylamine is about 90:1 to about 1 :90. In some embodiments, a mole ratio of the first inhibitor compound having a stable nitroxide radical to the second inhibitor compound having a hydroxylamine is about 80:1 to about 1 :80.
• a mole ratio of the first inhibitor compound having a stable nitroxide radical to the second inhibitor compound having a hydroxylamine is about 70:1 to about 1 :70. In some embodiments, a mole ratio of the first inhibitor compound having a stable nitroxide radical to the second inhibitor compound having a hydroxylamine is about 60:1 to about 1 :60. In some embodiments, a mole ratio of the first inhibitor compound having a stable nitroxide radical to the second inhibitor compound having a hydroxylamine is about 50:1 to about 1 :50. In some embodiments, a mole ratio of the first inhibitor compound having a stable nitroxide radical to the second inhibitor compound having a hydroxylamine is about 40:1 to about 1 :40.
• a mole ratio of the first inhibitor compound having a stable nitroxide radical to the second inhibitor compound having a hydroxylamine is about 30:1 to about 1 :30. In some embodiments, a mole ratio of the first inhibitor compound having a stable nitroxide radical to the second inhibitor compound having a hydroxylamine is about 20:1 to about 1 :20. In some embodiments, a mole ratio of the first inhibitor compound having a stable nitroxide radical to the second inhibitor compound having a hydroxylamine is about 10:1 to about 1 :10. In some embodiments, a mole ratio of the first inhibitor compound having a stable nitroxide radical to the second inhibitor compound having a hydroxylamine is about 1 :1.
• the composition also includes one or more additional compounds selected from the group consisting of 2,2,6, 6-tetramethylpiperidin-1-oxyl; 2, 2,6,6- tetramethylpiperidin-1-ol; 4-hydroxyl-2,2,6,6-tetramethylpiperidin-1-oxyl; 4- hydroxy-2, 2,6,6- tetramethylpiperidin-1-ol; 4-oxo-2,2,6,6-tetramethylpiperidin-1-oxyl; 4-oxo-2, 2,6,6- tetramethylpiperidin-1-ol; 4-acetoxy-2,2,6,6- tetramethylpiperidin-1-oxyl; 4-acetoxy-2, 2,6,6- tetramethylpiperidin-1 -ol; 4-propionoxy-2,2,6,6- tetramethylpiperidin-1-oxyl; 4-propionoxy- 2,2,6,6-tetramethylpiperidin-1-ol; and bis((2,2,6,6-tetramethylpiperidin)
• the composition also includes 2,2,6,6-tetramethylpiperidin-1-oxyl. In some embodiments, the composition also includes 2,2,6,6-tetramethylpiperidin-1-ol. In some embodiments, the composition also includes 4-hydroxyl-2, 2, 6, 6-tetramethylpiperidin-1-oxyl. In some embodiments, the composition also includes 4-hydroxy-2,2,6,6-tetramethylpiperidin-1- ol. In some embodiments, the composition also includes 4-oxo-2,2,6,6-tetramethylpiperidin-1- oxyl. In some embodiments, the composition also includes 4-oxo-2,2,6,6-tetramethylpiperidin- 1-ol.
• the composition also includes 4-acetoxy-2, 2,6,6- tetramethylpiperidin-1-oxyl. In some embodiments, the composition also includes 4-acetoxy- 2,2,6,6-tetramethylpiperidin-1-ol. In some embodiments, the composition also includes 4- propionoxy-2,2,6,6- tetramethylpiperidin-1-oxyl. In some embodiments, the composition also includes 4-propionoxy-2,2,6,6-tetramethylpiperidin-1-ol. In some embodiments, the composition also includes bis((2,2,6,6-tetramethylpiperidin-1-oxyl)-4-yl) oxalate.
• the composition may optionally also include one or more organic solvents.
• organic solvents are selected from vinyl acetate, dimethyl phthalate, dimethylformamide, toluene, xylene, highly aromatic naphtha, acetonitrile, ethyl acetate, acetone, dichloromethane, tetrahydrofuran, hexanes, dimethyl sulfoxide, N-methyl-2- pyrrolidone, and combinations thereof.
• the composition also includes vinyl acetate.
• the composition also includes dimethyl phthalate.
• the composition also includes dimethylformamide. In certain embodiments, the composition also includes toluene. In certain embodiments, the composition also includes xylene. In certain embodiments, the composition also includes highly aromatic naphtha. In certain embodiments, the composition also includes acetonitrile.
• the composition also includes one or more ethylenic unsaturated monomers.
• the one or more ethylenic unsaturated monomers are selected from vinyl acetate, acrylonitrile, acrylates, methacrylates, 1 ,3-butadiene, styrene, isoprene, (meth)acrylic acid, and combinations thereof.
• the composition also includes vinyl acetate.
• the composition also includes acrylonitrile.
• the composition also includes acrylates.
• the composition also includes methacrylates. In certain embodiments, the composition also includes 1 ,3-butadiene. In certain embodiments, the composition also includes styrene. In certain embodiments, the composition also includes isoprene. In certain embodiments, the composition also includes (meth)acrylic acid.
• compositions of the disclosure are stable and remain useful polymerization inhibitors even under acidic conditions.
• the compositions of the disclosure are useful for inhibiting the premature polymerization of monomers during manufacturing process, particularly those that are performed under acidic conditions.
• the compositions of the disclosure are useful for preventing polymerization of acrylates, which may include, but are not limited to, acrylonitrile, acrylic acid, methyl methacrylic acid and its esters, and vinyl acetate.
• the compositions of the disclosure are generally stable under acidic conditions, a significant improvement over conventional polymerization inhibitors known in the art.
• the composition also includes one or more acids.
• the composition also includes one or more acids selected from the group consisting of mineral acids and carboxylic acids.
• Mineral acids include, but are not limited to, hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, perchloric acid, and the like.
• Carboxylic acids include, but are not limited to, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, ethanic acid, caprylic acid, undecylic acid, lauric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and the like.
• the compositions of the disclosure also include hydrochloric acid.
• the compositions of the disclosure also include nitric acid.
• the compositions of the disclosure also include phosphoric acid.
• the compositions of the disclosure also include sulfuric acid.
• compositions of the disclosure also include acetic acid. In some embodiments, the compositions of the disclosure also include propionic acid. In some embodiments, the compositions of the disclosure also include butyric acid. In some embodiments, the compositions of the disclosure also include valeric acid.
• the composition also includes acetaldehyde.
• compositions of the disclosure have balanced partition coefficients between polar organic phases and polar phases.
• the compositions of the disclosure are also useful in butadiene extraction processes.
• the present disclosure also relates to methods of inhibiting polymerization of monomers that include adding a composition of the disclosure to the monomer.
• a composition of the disclosure to the monomer.
• an effective amount of the composition of the disclosure is added to the monomer, where an effective amount is any amount sufficient to inhibit the polymerization of the monomer.
• the monomer is an ethylenic unsaturated monomer.
• the monomer is an ethylenic unsaturated monomer selected from vinyl acetate, acrylonitrile, acrylates, methacrylates, 1 ,3-butadiene, styrene, isoprene, (meth)acrylic acid, and combinations thereof are disclosed.
• the methods disclosed herein are useful in inhibiting the polymerization of vinyl acetate.
• the methods disclosed herein are useful in inhibiting the polymerization of acrylonitrile.
• the methods disclosed herein are useful in inhibiting the polymerization of acrylates.
• the methods disclosed herein are useful in inhibiting the polymerization of methacrylates. In some aspects, the methods disclosed herein are useful in inhibiting the polymerization of 1 ,3- butadiene. In some aspects, the methods disclosed herein are useful in inhibiting the polymerization of styrene. In some aspects, the methods disclosed herein are useful in inhibiting the polymerization of isoprene. In some aspects, the methods disclosed herein are useful in inhibiting the polymerization of (meth)acrylic acid.
• the composition of the disclosure can be added manually or automatically to the fluid.
• the composition can also be added continuously and/or intermittently. Automatic addition may be accomplished through the use of chemical injection pumps.
• the chemical injection pumps may be programmed to add particular amounts of the polymerization inhibitor composition, or any components thereof, at certain time intervals to the fluid.
• the chemical injection pumps can be manually controlled to add particular amounts of the polymerization inhibitor composition, or any components thereof, to the fluid. Addition of the presently disclosed polymerization inhibitor compositions to the monomer will thereby inhibit polymerization of the monomer.
• the monomer is provided as a neat liquid. In other aspects, the monomer is provided within a solution, hereafter referred to as “the monomer solution”.
• the monomer solution also includes one or more additional components selected from an acid, an organic solvent, water, and combinations thereof.
• the monomer solution includes one or more organic solvents selected from vinyl acetate, dimethyl phthalate, dimethylformamide, toluene, xylene, highly aromatic naphtha, acetonitrile, ethyl acetate, acetone, dichloromethane, tetrahydrofuran, hexanes, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and combinations thereof.
• the monomer solution includes one or more acids selected from hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, perchloric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, ethanic acid, caprylic acid, undecylic acid, lauric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, and suberic acid.
• the monomer solution includes water.
• the monomer solution has a pH value of about 1 to about 7. In some aspects, the monomer solution has a pH value of about 1 to about 6. In some aspects, the monomer solution has a pH value of about 2 to about 6. In some aspects, the monomer solution has a pH value of about 3 to about 6. In some aspects, the monomer solution has a pH value of about 4 to about 6. In some aspects, the monomer solution has a pH value of about 5 to about 6. [0052] In some aspects, the composition is added to the monomer such that a concentration of the first inhibitor compound is about 0.1 ppm to about 10,000 ppm.
• the composition is added to the monomer such that a concentration of the first inhibitor compound is about 0.1 ppm to about 5,000 ppm. In some aspects, the composition is added to the monomer such that a concentration of the first inhibitor compound is about 0.1 ppm to about 1 ,000 ppm. In some aspects, the composition is added to the monomer such that a concentration of the first inhibitor compound is about 0.1 ppm to about 500 ppm.
• the composition is added to the monomer such that a concentration of the second inhibitor compound is about 0.1 ppm to about 10,000 ppm. In some aspects, the composition is added to the monomer such that a concentration of the second inhibitor compound is about 0.1 ppm to about 5,000 ppm. In some aspects, the composition is added to the monomer such that a concentration of the second inhibitor compound is about 0.1 ppm to about 1 ,000 ppm. In some aspects, the composition is added to the monomer such that a concentration of the second inhibitor compound is about 0.1 ppm to about 500 ppm.
• the methods of the disclosure are useful for inhibiting the premature polymerization of monomers during manufacturing process, particularly those that are performed under acidic conditions.
• the methods of the disclosure are useful for preventing polymerization of acrylates, which may include, but are not limited to, acrylonitrile, acrylic acid, methyl methacrylic acid and its esters, and vinyl acetate.
• the methods of the disclosure are also useful for preventing the premature polymerization of styrene during manufacturing and purification processes.
• the methods of the disclosure are also useful in butadiene extraction processes. This utility stems from the balanced partition coefficients between polar organic phases and organic phases.
• the present disclosure also relates to processes for preparing a compound of formula (III): wherein:
• R 3 is — O* or -OH; and R 4 is C1-C22 alkyl, C1-C22 alkenyl, C1-C22 alkynyl, C1-C22 cycloalkyl, aryl, and C1-C22 alkylene aryl, wherein the cycloalkyl and aryl are optionally substituted with one or more Ci- 022 alkyl, C1-C22 alkenyl, C1-C22 alkynyl, or aryl.
• the process for preparing a compound of formula (III) includes treating a compound of formula (Illa): with a compound of (111 b) : wherein R 5 is C1-C22 alkyl or C1-C22 alkenyl, within a solution, to afford the compound of formula (III).
• R3 is -O «.
• R3 is -OH.
• R 4 is C1-C22 alkyl. In some aspects, R 4 is C1-C12 alkyl. In some aspects, R 4 is C1-C6 alkyl. In some aspects, R 4 is ethyl. In some aspects, R 4 is methyl. [0061] In one aspect, R3 is -O « and R 4 is methyl. In another aspect, R3 is -O « and R 4 is ethyl. In another aspect, R3 is -OH and R 4 is methyl. In another aspect, R3 is -OH and R 4 is ethyl.
• R 5 is C1-C22 alkyl. In some aspects, R 5 is C1-C12 alkyl. In some aspects, R 5 is Ci-C 6 alkyl.
• R 5 is C1-C22 alkenyl. In some aspects, R 5 is C1-C12 alkenyl. In some aspects, R 5 is Ci-C 6 alkenyl. In some aspects, R 5 is C 2 alkenyl.
• the process for preparing a compound of formula (III) includes treating a compound of formula (Illa): with a compound of (I I Ic): within a solution, to afford the compound of formula (III).
• the compound of formula (Illa) is treated with the compound of formula (111 b) in the presence of a catalyst and heat.
• the compound of formula (Illa) is treated with the compound of formula (lllc) in the presence of a catalyst and heat.
• the catalyst is an amine-containing compound.
• the catalyst is 4-dimethylaminopyridine, also known as DMAP.
• the solution of the compound of formula (Illa) and (lllb), or (lllc), is heated to a temperature of about 50 °C to about 100 °C. In some aspects, the solution is heated to a temperature of about 50 °C to about 85 °C.
• the process for preparing a compound of formula (III) also includes purging the solution with a stream of nitrogen.
• the step of purging the solution with a stream of nitrogen is performed concurrently with the step of treating a compound of formula (Illa) with a compound of formula (lllb) to afford the compound of formula (III).
• the step of purging the solution with a stream of nitrogen is performed concurrently with the step of treating a compound of formula (Illa) with a compound of formula (lllc) to afford the compound of formula (III).
• the step of purging the solution with a stream of nitrogen is performed after the step of treating a compound of formula (Illa) with a compound of formula (lllb) to afford the compound of formula (III). In some aspects, the step of purging the solution with a stream of nitrogen is performed after the step of treating a compound of formula (Illa) with a compound of formula (lllc) to afford the compound of formula (III).
• the step of purging the solution with a stream of nitrogen may be useful in removing certain reaction byproducts that pushes the reaction equilibrium towards formation of the compound of formula (III).
• a composition of the disclosure hereafter referred to as Formulation 1 , was prepared using the following procedure.
• a reaction vessel was charged with 206 g 4-hydroxy-2,2,6,6-tetramethylpiperidin- 1-oxyl (HTEMPO) and 290 g vinyl acetate. The resulting solution was subsequently agitated until all of the HTEMPO dissolved, and the resulting mixture was heated to 65 °C. This was followed by the addition of 1.5 g 4-dimethylaminopyridine (DMAP). The reaction temperature was maintained at 65 °C and the mixture was stirred for 30 minutes. The reaction temperature was subsequently increased to 75 °C and the solution was stirred for an additional 30 minutes. 2.4 g of DMAP were then added slowly to the reaction mixture, which was then stirred for an additional 1 hour, maintaining the reaction temperature at 75 °C.
• HTEMPO 4-hydroxy-2,2,6,6-tetramethylpiperidin- 1-oxyl
• DMAP 4-dimethylaminopyridine
• the reaction mixture was then heated to a temperature between 80 °C and 85 °C and stirred for an additional 2 hours.
• the reaction mixture was then adjusted to a temperature of 75 °C and purged with a stream of nitrogen for 150 minutes.
• the reaction mixture was then cooled to room temperature and an additional 762 g of vinyl acetate was added.
• the final product solution was transferred into a storage container.
• a composition of the disclosure hereafter referred to as Formulation 2, was prepared using the following procedure.
• a reaction vessel was charged with 206 g HTEMPO, 114 g vinyl acetate, 6.18 g DMAP, and 50 g dimethyl phthalate. The resultant solution was heated to 65 °C and agitated until all of the HTEMPO was dissolved. The reaction mixture was then agitated for 30 minutes at a temperature of 50 °C. The reaction mixture was then heated to 83 °C and stirred for 1 hour. Subsequently, the reaction mixture was maintained at a temperature of 75 °C and purged with a stream of nitrogen for 150 minutes. The reaction mixture was then cooled to room temperature and 635 g dimethyl phthalate were added. The final product solution was transferred into a storage container. [0072] The final product of Formulation 2 is a solution having the following components:
• a composition of the disclosure hereafter referred to as Formulation 3, was prepared using the following procedure.
• a reaction vessel was charged with 206 g HTEMPO, 114 g vinyl acetate, 6.18 g DMAP, 50 g DMF.
• the resultant solution was heated to 65 °C to dissolve HTEMPO after which the reaction temperature was kept at 50 °C for 30 minutes.
• the temperature was increased to 83 °C as the reaction solution was kept stirring for 60 minutes.
• the resultant solution was heated to 65 °C and agitated until all of the HTEMPO was dissolved.
• the reaction mixture was then agitated for 30 minutes at a temperature of 50 °C.
• the reaction mixture was then heated to 83 °C and stirred for 1 hour.
• reaction mixture was maintained at a temperature of 75 °C and purged with a stream of nitrogen for 150 minutes to remove the acetaldehyde byproduct.
• the reaction mixture was then cooled to room temperature and 635 g dimethylformamide were added.
• the final product solution was transferred into a storage container.
• a composition of the disclosure hereafter referred to as Formulation 4, was prepared using the following procedure.
• a reaction vessel was charged with 206 g HTEMPO, 132 g vinyl propionate, 6.18 g DMAP, and 50 g dimethyl phthalate.
• the resultant solution was heated to 65 °C and agitated until all of the HTEMPO was dissolved.
• the reaction mixture was then agitated for 30 minutes at a temperature of 50 °C.
• the reaction mixture was then heated to 83 °C and stirred for 1 hour. Subsequently, the reaction mixture was maintained at a temperature of 75 °C and purged with a stream of nitrogen for 150 minutes to remove the reaction byproduct.
• the reaction mixture was then cooled to room temperature and 635 g dimethyl phthalate were added.
• the final product solution was transferred into a storage container.
• compositions of the disclosure to inhibit the polymerization of acrylic acid was assessed via the following protocol.
• Formulation 2 and Formulation 4 show an unexpectedly higher antipolymerant activity than 4-acetoxy-2,2,6,6-tetramethylpiperidin-1-oxyl (4-Acetoxy TEMPO), 4-acetoxy- 2,2,6,6-tetramethylpiperidin-1-ol (4-acetoxy TEMPOH), 4-propionoxy-2, 2,6,6- tetramethylpiperidin-1-oxyl (4-proprionate TEMPO), 4-propionoxy-2, 2,6,6- tetramethylpiperidin-1-ol (4-propionate TEMPOH), 4-hydroxy-2,2,6,6-tetramethylpiperidin-1- oxyl (HTEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-ol (HTEMPOH), and 4-oxo-2, 2,6,6- tetramethylpiperidin-1-oxyl (OTEMPO), alone.
• 4-acetoxy-2,2,6,6-tetramethylpiperidin-1-oxyl (4-Acetoxy TEMPO
• Formulations 2 and 4 demonstrate synergy, in that the combination of the polymerization inhibitor having a stable nitroxide radical with a polymerization inhibitor having a hydroxylamine produced greater polymerization inhibition than either component alone, controlling for the total dosage of the active component.
• compositions of the disclosure to inhibit the polymerization of vinyl acetate in the presence of acetic acid was assessed via the following protocol.
• Formulation 2 and Formulation 4 show an unexpectedly higher antipolymerant activity than 4-acetoxy-2,2,6,6-tetramethylpiperidin-1-oxyl (4-Acetoxy TEMPO), 4-acetoxy- 2,2,6,6-tetramethylpiperidin-1-ol (4-acetoxy TEMPOH), 4-propionoxy-2, 2,6,6- tetramethylpiperidin-1-oxyl (4-proprionate TEMPO), 4-propionoxy-2, 2,6,6- tetramethylpiperidin-1-ol (4-propionate TEMPOH), 4-hydroxy-2,2,6,6-tetramethylpiperidin-1- oxyl (HTEMPO), and 4-oxo-2,2,6,6-tetramethylpiperidin-1-oxyl (OTEMPO), alone.
• 4-acetoxy-2,2,6,6-tetramethylpiperidin-1-oxyl (4-Acetoxy TEMPO
• 4-acetoxy- 2,2,6,6-tetramethylpiperidin-1-ol (4-ace
• Formulations 1 and 4 demonstrate synergy, in that the combination of the polymerization inhibitor having a stable nitroxide radical with a polymerization inhibitor having a hydroxylamine produced greater polymerization inhibition than either component alone, controlling for the total dosage of the active component.
• composition disclosed herein may comprise, consist of, or consist essentially of any element, component and/or ingredient disclosed herein or any combination of two or more of the elements, components or ingredients disclosed herein.
• Any method disclosed herein may comprise, consist of, or consist essentially of any method step disclosed herein or any combination of two or more of the method steps disclosed herein.
• the term "about” refers to the cited value being within the errors arising from the standard deviation found in their respective testing measurements, and if those errors cannot be determined, then “about” may refer to, for example, within 5% of the cited value.

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