阅读说明：本技术 氨基醌抗聚合剂及其使用方法 (Amino quinone anti-polymerization agents and methods of use thereof ) 是由 J·玛萨拉 于 2019-09-24 设计创作，主要内容包括：本发明描述了用于使用胺化醌抗聚合剂(例如具有一个或多个仲胺或叔胺基团的胺化苯醌或胺化萘醌抗聚合剂)抑制单体(例如,苯乙烯)组合物聚合的方法和组合物。所述胺化醌抗聚合剂可以与含很少或不含硝酰基基团的抗聚剂一起使用,但仍在含单体组合物中提供优异的抗聚合活性。(Methods and compositions for inhibiting polymerization of a monomer (e.g., styrene) composition using an aminated quinone anti-polymerization agent, such as an aminated benzoquinone or aminated naphthoquinone anti-polymerization agent having one or more secondary or tertiary amine groups, are described. The aminated quinone anti-polymerization agent can be used with anti-polymerization agents containing little or no nitroxyl groups, but still provide excellent anti-polymerization activity in monomer-containing compositions.)

1. A method for inhibiting polymerization of a monomer in a monomer-containing composition, the method comprising:

adding to a composition comprising a polymerizable monomer or capable of forming a polymerizable monomer an aminated quinone anti-polymerization agent, said anti-polymerization agent being a compound of formula I or II:

wherein, -R¹、–R²、–R³and-R⁴At least one of which is-NR⁵R⁶Wherein R is⁵And R⁶Selected from the group consisting of: hydrogen, alkyl, aryl, alkylaryl and arylalkyl groups of 1 to 24 carbon atoms, with the proviso that R is⁵And R⁶Neither is hydrogen, and-R¹、–R²、–R³and-R⁴Is not-NR⁵R⁶Is selected from the group consisting of: hydrogen, alkyl, aryl, alkylaryl and arylalkyl, alkoxy, SO₂Ar、COOH、SO₃H、COOR⁹、NHCOR⁹、OCOR⁹Wherein R is⁹Selected from alkyl, aryl, alkylaryl and arylalkyl, or-R¹、–R²、–R³and-R⁴Is not-NR⁵R⁶Any two adjacent groups of (a) form one or more ring structures, and

wherein the composition is free of nitroxyl group-containing anti-polymerization agent or has less than 50ppm of nitroxyl group-containing anti-polymerization agent.

2. The method of claim 1, wherein-R¹、–R²、–R³or-R⁴One of them is-NR⁵R⁶、R⁵Is H, and R⁶Selected from the group consisting of: alkyl, aryl, alkylaryl and arylalkyl groups of 1 to 24 carbon atoms, and-R¹、–R²、–R³or-R⁴Is not-NR⁵R⁶Is selected from the group consisting of: hydrogenAnd C1-C6 alkyl.

3. The method of claim 2, wherein-R¹、–R²、–R³or-R⁴Is not-NR⁵R⁶And three of (a) are hydrogen.

4. The method of any one of claims 1 to 3, wherein R⁶Selected from the group consisting of: alkyl, aryl, alkylaryl and arylalkyl groups of 2 to 22 carbon atoms or 3 to 20 carbon atoms.

5. The method of claim 1, wherein the compound of formula II is selected from the group consisting of: (a) 2-methylamino-1, 4-benzoquinone, 2-ethylamino-1, 4-benzoquinone, 2-propylamino-1, 4-benzoquinone, 2-butylamine-1, 4-benzoquinone, 2-pentylamine-1, 4-benzoquinone, 2-hexylamine-1, 4-benzoquinone, 2-anilino-1, 4-benzoquinone, 2-heptylamine-1, 4-benzoquinone, 2-octylamine-1, 4-benzoquinone, 2-nonylamine-1, 4-benzoquinone, 2-decylamine-1, 4-benzoquinone, 2-undecylamino-1, 4-benzoquinone, 2-dodecyl-1, 4-benzoquinone, 2-tridecyl-1, 4-benzoquinone, 2-tetradecyl-1, 4-benzoquinone, 2-pentadecylamino-1, 4-benzoquinone, 2-hexadecylamino-1, 4-benzoquinone, 2-heptadecylamino-1, 4-benzoquinone, 2-octadecylamino-1, 4-benzoquinone, 2-oleylamino-1, 4-benzoquinone, 2-nonadecylamino-1, 4-benzoquinone, 2-eicosylamino-1, 4-benzoquinone, 2-heneicosylamino-1, 4-benzoquinone and 2-docosylamino-1, 4-benzoquinone, and partially unsaturated alkyl derivatives thereof, or (b) 2-anilino- (5-methyl) -1, 4-benzoquinone, 2-anilino- (5-methyl) -1, 4-benzoquinone, 2-anilino- (5-ethyl) -1, 4-benzoquinone, 2-anilino- (5-propyl) -1, 4-benzoquinone, 2-anilino- (5-butyl) -1, 4-benzoquinone and 2-anilino- (5-phenyl) -1, 4-benzoquinone.

6. The method of claim 1, wherein-R of formula I or II¹、-R²、-R³and-R⁴Any two adjacent groups of (a) form an aryl ring structure and provide an aminated quinone anti-polymerization agent according to formula III or IV:

wherein, -R⁷and/or-R⁸One or both of which are-NR⁵R⁶Wherein R is⁵And R⁶Selected from the group consisting of: hydrogen, alkyl, aryl, alkylaryl and arylalkyl groups of 1 to 24 carbon atoms, with the proviso that R is⁵And R⁶Both are not hydrogen, and R¹、R²、R³Or R⁴Any one or more of which are selected from the group consisting of: hydrogen, alkyl, aryl, alkylaryl and arylalkyl, alkoxy, SO₂Ar、COOH、SO₃H、COOR⁹、NHCOR⁹、OCOR⁹Wherein R is⁹Selected from alkyl, aryl, alkylaryl and arylalkyl, or R¹、R²、R³Or R⁴Two adjacent groups in (a) form one or more ring structures.

7. The method of claim 6, wherein R⁷is-NR⁵R⁶And R is⁶Selected from the group consisting of: alkyl, aryl, alkylaryl and arylalkyl groups of 1 to 24 carbon atoms, and R⁸Is H, and R¹、R²、R³And R⁴Selected from the group consisting of: hydrogen, alkyl, aryl, alkylaryl and arylalkyl groups.

8. The method of claim 6 or 7, wherein R¹、R²、R³And R⁴One, two, three or all of which are hydrogen.

9. The method of any one of claims 6 to 8, wherein R⁶Selected from the group consisting of: alkyl of 2 to 22 carbon atoms or 3 to 20 carbon atoms,Aryl, alkylaryl and arylalkyl groups.

10. The method of claim 6, wherein the compound of formula III is selected from the group consisting of: (a) 2-methylamino-1, 4-naphthoquinone, 2-ethylamino-1, 4-naphthoquinone, 2-propylamino-1, 4-naphthoquinone, 2-butylamine-1, 4-naphthoquinone, 2-pentylamine-1, 4-naphthoquinone, 2-hexylamine-1, 4-naphthoquinone, 2-anilino-1, 4-naphthoquinone (2-aniline-1, 4-naphthoquinone), 2-heptylamine-1, 4-naphthoquinone, 2-octylamine-1, 4-naphthoquinone, 2-nonylamine-1, 4-naphthoquinone, 2-decylamine-1, 4-naphthoquinone, 2-undecylamino-1, 4-naphthoquinone, 2-dodecyl-1, 4-naphthoquinone, 2-tridecyl-1, 4-naphthoquinone, 2-tetradecyl-1, 4-naphthoquinone, 2-pentadecylamino-1, 4-naphthoquinone, 2-hexadecylamino-1, 4-naphthoquinone, 2-heptadecylamino-1, 4-naphthoquinone, 2-octadecylamino-1, 4-naphthoquinone, 2-oleylamino-1, 4-naphthoquinone, 2-nonadecylamino-1, 4-naphthoquinone, 2-eicosylamino-1, 4-naphthoquinone, 2-heneicosylamino-1, 4-naphthoquinone, and 2-docosylamino-1, 4-naphthoquinone, and partially unsaturated alkyl derivatives thereof, and (b) 2-anilino-1, 4-naphthoquinone.

11. The method of any of the preceding claims, wherein the aminated quinone anti-polymerization agent is present in the composition in an amount ranging from 10 to 50000 ppm.

12. The method of claim 11 wherein said aminated quinone anti-polymerization agent is present in said composition in an amount ranging from 50 to 5000 ppm.

13. The method of claim 12 wherein said aminated quinone anti-polymerization agent is present in said composition in an amount ranging from 100 to 300 ppm.

14. The method of any preceding claim, wherein the polymerizable monomer comprises a vinyl group or an ethylenically unsaturated group.

15. The method of claim 14, wherein the polymerizable monomer is selected from the group consisting of: acrylic acid, acrylonitrile, alkylated styrenes, butadiene, chloroprene, divinylbenzene, ethyl acrylate, ethyl methacrylate, isoprene, methacrylic acid, methyl methacrylate, methyl acrylate, alpha-methylstyrene, methacrylonitrile, styrene, styrenesulfonic acid, vinyltoluene, vinylpyridine, divinylbenzene and primary olefins, for example ethylene, acetylene, methylacetylene, vinylacetylene, propylene, butylene, butyne, butadiene, and unsaturated cyclic aliphatic compounds, for example cyclopentadiene, dicyclopentadiene and indene.

16. The method of any one of claims 1 to 13, wherein the composition comprises styrene or ethylbenzene.

17. The method of any one of the preceding claims, wherein the composition comprises one or more non-polymerizable hydrocarbons.

18. The method of any one of the preceding claims, which is performed during purification or treatment of one or more components of the composition.

19. The method of any of the preceding claims, wherein the composition is free of nitroxyl group-containing anti-polymerization agent or has less than 5ppm nitroxyl group-containing anti-polymerization agent.

20. The method of claim 19, wherein the composition is free of nitroxyl group-containing anti-polymerization agent or has less than 0.5ppm nitroxyl group-containing anti-polymerization agent.

21. The method of any one of the preceding claims, wherein the inhibitor is a nitroxide-containing compound selected from the group consisting of: 2,2,6, 6-tetramethylpiperidinyl-1-oxy (TEMPO), 4-hydroxy-2, 2,6, 6-tetramethylpiperidinyl-1-oxy (HTMPO), 4-oxo-2, 2,6, 6-tetramethylpiperidinyl-1-oxy (otecpo), or a combination thereof.

22. The method of any preceding claim, wherein the aminated quinone anti-polymerization agent inhibits polymerization of monomers by more than 50% compared to a composition having non-aminated quinones under the same conditions.

23. The method of claim 22, wherein the aminated quinone anti-polymerization agent inhibits polymerization of monomers by more than 90% compared to a composition having non-aminated quinones under the same conditions.

24. An aminated quinone anti-polymerization agent containing composition comprising or to which one or more polymerizable monomers, or one or more compounds capable of forming polymerizable monomers, can be added, wherein said composition comprises an aminated quinone anti-polymerization agent of formula I, II, III or IV, with the proviso that said anti-polymerization agent is not 4-anilino-1, 2-naphthoquinone.

Technical Field

The present invention relates to compositions of aminated quinone anti-polymerizer compounds and uses for preventing premature polymerization of monomers.

Background

High temperature processing of hydrocarbon streams laden with ethylenically unsaturated monomers (e.g., styrene, isoprene, butadiene) can be very challenging. In various chemical industrial processes, the use of high temperatures to purify the monomer can lead to unwanted and problematic polymers. These vinyl monomers undesirably polymerize by free radical polymerization, especially at elevated temperatures. Similarly, the transport and storage of hydrocarbon streams containing vinyl species can result in premature polymerization unless an anti-polymerization agent is added to the stream. The polymer thus formed precipitates out of solution, fouling the process equipment. Removal of the dirt is necessary. Equipment for physically removing or cleaning the scale is often expensive. These unwanted polymerization reactions also result in loss of production efficiency and consumption of valuable products. In compositions with vinylaromatic monomers, undesirable polymerization reactions are particularly problematic.

To prevent unwanted polymerization, free radical polymerization anti-polymerization agents are typically added to the process stream or stored composition. However, these compounds are often consumed very rapidly. For example, in the event of an emergency situation arising from a mechanical or handling problem and no more inhibitor can be added, the previously added inhibitor will be quickly consumed. Subsequently, unwanted polymerization reactions will then occur rapidly.

Examples of polymerization inhibitors known in the art include dialkylhydroxylamines, such as hydroxypropyl hydroxylamine (HPHA), and stabilized nitroxide radicals. Other inhibitors include N, N ' -dialkylphenylenediamines, N ' -diarylphenylenediamines, and N-aryl-N ' -alkylphenylenediamines. Quinone diimide compounds are also another class of inhibitors. However, compounds containing nitroxide radicals are capable of releasing NO_XMaking their use undesirable in some situations.

Other types of anti-polymerization agents, commonly referred to as "retarders," slow the rate of polymerization. However, they are generally not as effective as polymerization inhibitors, in particular stable nitric oxide radicals. However, the consumption rate of the polymerization retarders is generally less than that of the polymerization inhibitors, and therefore they tend to be more useful in the case of emergency shutdown.

First, a retarder, such as sulfur and Dinitrophenol (DNP) compounds represented by 2, 6-dinitrophenol, 2, 4-dinitrocresol, and 2-sec-butyl-4, 6-Dinitrophenol (DNBP), is used. However, DNP and sulfur retarders release NO_XAnd SO_XEmissions, making their use problematic. Furthermore, DNP-based retarders are highly toxic and thus the safety of personnel handling DNP-based anti-polymerization agents is a major concern.

One class of compounds intended for use as safe alternatives to DNP retarders is based on quinone methide chemistry. Under static conditions, the quinone methide slows the rate of polymer formation without the need for frequent re-feeding into the process stream. However, some quinone methide compounds do not exhibit good stability. Examples of quinone methide compounds are found in U.S. Pat. Nos. 4,003,800, 5,583,247, and 7,045,647. The production of styrene typically involves the use of inhibitors (e.g., nitrogen oxide-containing inhibitors such as TEMPO) and retarders (e.g., quinone methide). Although it is desirable to eliminate nitrogen oxide-containing inhibitors in various styrene production scenarios, it has been found that the use of retarders alone does not provide sufficient polymerization inhibition, making it difficult to eliminate or minimize the use of inhibitors.

Technical challenges remain in the art related to efficacy and stability and safety issues of compounds used to inhibit or slow down polymerization reactions. Despite concerns about toxicity, DNP-based anti-polymerization agents remain the most effective retarders. For safety reasons, there is a need for an anti-polymerization agent that is at least as effective as the DNP-type retarder, but is non-toxic.

Disclosure of Invention

The present disclosure relates to compositions and methods that include or utilize aminated quinone anti-polymerization agents to inhibit polymerization of ethylenically unsaturated monomers (e.g., styrene and butadiene) in a variety of processes and situations (e.g., purification, fractionation, separation, compression, transportation, and storage of various monomer-containing compositions). Advantageously, the aminated quinone anti-polymerization agent can be used with no or only little nitroxyl-based anti-polymerization agent, but still have excellent ability to inhibit polymerization of monomers in solution.

The use of the aminated quinone anti-polymerization agent composition of the present invention mitigates fouling of handling, transportation and storage equipment while avoiding the disadvantages of using nitroxyl-based anti-polymerization agents. Furthermore, polymer contamination of the purified monomer product can be greatly reduced and maintenance costs of the equipment can be minimized.

In an embodiment, the present disclosure provides a method for inhibiting polymerization of a monomer in a monomer-containing composition or a composition capable of forming a monomer. The method comprises the following steps: a step of adding an aminated quinone anti-polymerization agent to a composition comprising a polymerizable monomer or capable of forming a polymerizable monomer, the anti-polymerization agent being a compound of formula I or II:

wherein, -R¹、–R²、–R³and-R⁴At least one of which is-NR⁵R⁶Wherein R is⁵And R⁶Selected from the group consisting of: hydrogen, alkyl, aryl, alkylaryl and arylalkyl groups of 1 to 24 carbon atoms, with the proviso that R is⁵And R⁶Neither is hydrogen, and-R¹、–R²、–R³and-R⁴Is not-NR⁵R⁶Is selected from the group consisting of: hydrogen, alkyl, aryl, alkylaryl and arylalkyl, alkoxy, SO₂Ar、COOH、SO₃H、COOR⁹、NHCOR⁹、OCOR⁹Wherein R is⁹Selected from alkyl, aryl, and mixtures thereof,Alkylaryl and arylalkyl radicals, or-R¹、–R²、–R³and-R⁴Is not-NR⁵R⁶Any two adjacent groups of (a) form one or more ring structures. In this method, the aminated quinone of formula I or formula II is added without or with minimal nitroxyl containing anti-polymerization agent (less than 50% wt) or is added to a composition comprising polymerizable monomers, or capable of forming polymerizable monomers, which composition has no or very little nitroxyl containing anti-polymerization agent (less than 50 ppm).

In an embodiment, the formula I or II-R¹、–R²、–R³and-R⁴Any two adjacent groups of (a) form an aryl ring structure and provide an aminated quinone anti-polymerization agent according to formula III or IV:

wherein, -R⁷and/or-R⁸One or both of which are-NR⁵R⁶Wherein R is⁵And R⁶Selected from the group consisting of: hydrogen, alkyl, aryl, alkylaryl and arylalkyl groups of 1 to 24 carbon atoms, with the proviso that R is⁵And R⁶Both are not hydrogen, and R¹、R²、R³Or R⁴Any one or more of which are selected from the group consisting of: hydrogen, alkyl, aryl, alkylaryl and arylalkyl, alkoxy, SO₂Ar、COOH、SO₃H、COOR⁹、NHCOR⁹、OCOR⁹Wherein R is⁹Selected from alkyl, aryl, alkylaryl and arylalkyl, or R¹、R²、R³Or R⁴Two adjacent groups in (a) form one or more ring structures. In this method, the aminated quinone of formula III or IV is added with no or minimal nitroxyl containing anti-polymerization agent as described herein.

In embodiments, the aminated quinone anti-polymerization agent can be provided in the composition for addition to a monomer-containing composition or a composition capable of forming a monomer. For example, the composition can include a solvent and a solid component consisting essentially of the aminated quinone anti-polymerization agent of formula I, II, III or IV. Alternatively, the composition may include a solvent and an aminated quinone anti-polymerization agent of formula I, II, III or IV, provided that the composition includes little or no nitroxyl containing anti-polymerization agent.

In an embodiment, the present invention also provides an aminated quinone anti-polymerization agent containing composition comprising or to which one or more polymerizable monomers, or one or more compounds capable of forming a polymerizable monomer, can be added, wherein the composition comprises an aminated quinone anti-polymerization agent of formula I, II, III or IV, with the proviso that the anti-polymerization agent is not 4-aniline-1, 2-naphthoquinone.

Drawings

FIG. 1 is a graph of the amount of polystyrene polymer formed from a styrene monomer solution in the presence of various aminated quinone anti-polymerization agents of the present disclosure (sBANQ, OANQ, and ANQ) and comparative anti-polymerization agents (QMPh and HTEMPO).

Detailed Description

Although the present disclosure provides reference to preferred embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention. Reference to various embodiments does not limit the scope of the claims attached hereto. Furthermore, any embodiments set forth in this specification are not intended to be limiting and merely set forth some of the many possible implementations for the appended claims.

Additional advantages and novel features of the invention will be set forth in part in the description which follows and in part will become apparent to those skilled in the art upon examination of the following or may be learned by practice of the invention through routine experimentation.

The present disclosure provides methods and compositions comprising aminated quinone anti-polymerization agents to prevent undesired polymer formation. Aminated quinone anti-polymerizer compounds provide excellent anti-polymerization activity similar to many nitroxyl-containing anti-polymerizers, and thusIt is not necessary to add the nitroxyl containing anti-polymerization agent at the same time in order to treat the monomer stream. This, in turn, allows greater flexibility in inhibiting polymerization of the monomer composition, such as when nitroxyl-containing anti-polymerization agents are not recommended. The compositions and methods of the present disclosure are also advantageous in that they can avoid NO that would otherwise result from the use of nitroxyl-containing anti-polymerization agents_XAnd is non-toxic.

The composition comprising the aminated quinone anti-polymerization agent and any one or more optional components can be in a desired form, for example, in liquid form, in dry form, or as a suspension or dispersion. The aminated quinone anti-polymerization agent can be in a desired physical state in the composition, for example, in solution, partially dissolved, suspended or in a dry mixture. Also, the aminated quinone anti-polymerization agent can be in the desired form in the composition, for example optionally in particulate form. If the aminated quinone anti-polymerization agent is in the form of particles, the particles can optionally be described in terms of particle size (e.g., particles in a range of particle sizes) and/or shape. The form of the composition and the state of one or more of the components therein may be selected by selecting the aminated quinone anti-polymerization agent, with knowledge of its physical properties.

The form of the composition and the state of one or more of the components therein may also be affected by the inclusion of one or more optional components (e.g., solvents or solvent mixtures) or other excipient compounds (e.g., surfactants, dispersants, etc.). The form of the composition and the state of the components therein may also be affected by temperature, and the properties of the composition may optionally be described at a particular temperature (e.g., at a storage temperature such as 5 ℃ or less, at room temperature (25 ℃), or at a temperature for monomer synthesis and/or processing (e.g., about 100 ℃ or more, about 150 ℃, about 175 ℃, etc.).

As noted above, the aminated quinone anti-polymerization agent composition can include other components such as solvents, surfactants, dispersants, and the like. Optional components, if present in the composition, can be described with respect to the weight of the aminated quinone anti-polymerization agent. The optional components may be present in an amount greater than, about equal to, or less than the aminated quinone anti-polymerization agent.

As used herein, the term "optional" or "optionally" means that the subsequently described object (e.g., compound) or event (e.g., process step) or environment may, but need not, occur, and that the description includes instances where the object, event or environment occurs and instances where it does not.

The compositions of the present disclosure can include those enumerated compounds, and optionally can include other components of the composition, but in very small amounts (e.g., described in terms of a composition that "consists essentially of" the enumerated components). For example, such compositions may include one or more other components, but at a level of no greater than about 1% (wt), greater than about 0.5% (wt), greater than about 0.1% (wt), or greater than about 0.01% (wt) of the total composition. The composition consisting essentially of the solid component that is the aminated quinone anti-polymerization agent (e.g., dissolved in a solvent) can optionally include one or more other (e.g., solid) components, but in an amount less than about 1% (wt) of the total weight of the composition. In a composition "consisting of" the components, there are no other measurable amounts of the components other than the components. In some embodiments, the nitroxyl-containing anti-polymerization agent can optionally be present in the total composition in an amount of less than 1% (wt), less than 0.5% (wt), less than 0.1% (wt), or less than 0.01% (wt), and more preferably, no detectable level of nitroxyl-containing anti-polymerization agent is present in the composition.

"anti-polymerization agent" broadly refers to "polymerization inhibitors" and "polymerization retarders," which are compounds that generally inhibit or reduce the formation of polymers from one or more free-radically polymerizable compounds.

In the presence of polymerizable monomers, "polymerization inhibitors", e.g., nitroxyl containing compounds such as HTEMPO, inhibit the formation of polymers from these monomers for an induction time. After the induction time has elapsed, the formation of the polymer occurs at substantially the same rate as in the absence of the polymerization inhibitor.

A "polymerization retarder," can include an aminated quinone compound disclosed herein that does not exhibit an induction time, but rather reduces the rate of polymer formation upon addition to the polymerizable monomer composition relative to the rate of polymer formation in the absence of the polymerization retarder.

In contrast to polymerization inhibitors, polymerization retarders are generally rapidly consumed. Polymerization retarders, while slowing the rate of polymerization, are not as effective as polymerization inhibitors. However, the polymerization retarder is generally not consumed as fast as the polymerization inhibitor.

As used herein, the terms "substantially" and "consisting essentially of" that modify, e.g., the type or amount of an ingredient in a composition, a property, an amount, a method, a location, a value, or a range in describing an embodiment of the present disclosure, mean that the change in the overall composition, property, amount, method, location, value, or range thereof is not affected in a manner that would negate the effect of the intended composition, property, amount, method, location, value, or range. Examples of desired properties include, by way of non-limiting example only, dispersibility, stability, rate, solubility, and the like; the desired values include the weight of the added components, the concentration of the added components, and the like. Effects on modified methods include those caused by variations in the type or amount of materials used in the process, variations in machine settings, effects of environmental conditions on the process, etc. (wherein the manner or degree of effect does not negate one or more of the desired properties or results), and similar approximation considerations. Where modified by the term "substantially" or "consisting essentially of, the appended claims include equivalents to these types and amounts of material.

As used herein, the term "about" used in describing modifications such as amounts, concentrations, volumes, process temperatures, process times, yields, flow rates, pressures, and the like of ingredients in compositions, and ranges thereof, employed in embodiments of the present disclosure, refers to procedures that may be performed, for example, by typical measurement and handling procedures used to prepare compounds, compositions, concentrates, or use formulations; through inadvertent errors in these procedures; variations in numerical quantities occur through differences in the manufacture, source, or purity of the starting materials or ingredients used to carry out the process, and similar close considerations. The term "about" also encompasses amounts that differ from a particular starting concentration or mixture due to aging of the formulation, as well as amounts that differ from a particular starting concentration or mixture due to mixing or processing the formulation. Where modified by the term "about," the claims appended hereto include equivalents to these amounts. Further, when "about" is employed to describe any range of values, e.g., "about 1 to 5," the list means "1 to 5" and "about 1 to about 5" and "about 1 to 5," unless the context clearly limits.

The compositions and methods of the present disclosure include or use an anti-polymerization agent having aminated quinone chemistry. In an embodiment, the aminated quinone anti-polymerization agent comprises a partially unsaturated 6-carbon ring structure having at least two, preferably two carbonyl groups (-R-C (O) -R-), and at least one, preferably one, secondary or tertiary amine group (see, e.g., NR described herein)⁵R⁶)。

In some embodiments, the aminated quinone anti-polymerization agent is a compound of formula I or II:

wherein, -R¹、–R²、–R³and-R⁴At least one of which is-NR⁵R⁶Wherein R is⁵And R⁶Selected from the group consisting of: hydrogen, alkyl, aryl, alkylaryl and arylalkyl groups of 1 to 24 carbon atoms, with the proviso that R is⁵And R⁶Neither is hydrogen, and-R¹、–R²、–R³and-R⁴Is not-NR⁵R⁶Is selected from the group consisting of: hydrogen, alkyl, aryl, alkylaryl and arylalkyl, alkoxy, SO₂Ar、COOH、SO₃H、COOR⁹、NHCOR⁹、OCOR⁹Wherein R is⁹Selected from alkyl, aryl, alkylaryl and arylalkyl, or-R¹、–R²、–R³and-R⁴Is not-NR⁵R⁶Any two adjacent groups of (a) form one or more ring structures.

If R is⁵And R⁶One or both of which are one or more alkyl groups, then the alkyl groups may be unsaturated, partially saturated, or fully saturated. Fully saturated alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, oleyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl and tetracosyl. Exemplary partially saturated alkyl groups include those based on the saturated alkyl groups described herein. The partially saturated group may have one unsaturated group (e.g., a monounsaturated alkyl group), such as oleyl or palmitoyl, or more than one unsaturated group (polyunsaturated groups, e.g., diunsaturated groups, triunsaturated groups, etc.), such as linoleyl, and arachidonyl. In a preferred embodiment, R⁵Is a partially saturated or fully saturated alkyl group, e.g. as described herein, and R⁶Is hydrogen.

Reflecting the location of the carbonyl and amine groups on the ring, exemplary aminated quinone anti-polymerization agents can have the following general chemical properties: 2-amino, 1, 4-benzoquinone, 2, 3-diamino, 1, 4-benzoquinone, 3, 5-diamino, 1, 4-benzoquinone, 3-amino, 1, 2-benzoquinone, 4-amino, 1, 2-benzoquinone, 3, 4-diamino, 1, 2-benzoquinone, 4, 5-diamino, 1, 2-benzoquinone, 3, 6-diamino, 1, 2-benzoquinone, 4, 6-diamino, 1, 2-benzoquinone. The one or more amino groups may be according to the sub-formula-NR as described herein⁵R⁶Any one or more amino groups of (a).

In some embodiments, referring to formulas I and II, R¹、R²、R³Or R⁴One of them is-NR⁵R⁶，R⁵Is H, and R⁶Is selected from alkyl and aryl radicals of 1 to 24 carbon atomsAlkyl aryl and arylalkyl. Preferably, R⁶Selected from the group consisting of alkyl, aryl, alkylaryl and arylalkyl groups of from 2 to 22 carbon atoms, more preferably from 3 to 20 carbon atoms. R¹、R²、R³And R⁴Is not-NR⁵R⁶Is preferably selected from the group consisting of hydrogen, alkyl, aryl, alkylaryl and arylalkyl, from the group consisting of hydrogen and C1-C6 alkyl, from the group consisting of hydrogen and C1-C3 alkyl, preferably R¹、R²、R³And R⁴Is not-NR⁵R⁶Is hydrogen.

Exemplary compounds include 2-alkylamino-1, 4-benzoquinones or 2-arylamino-1, 4-benzoquinones, for example 2-methylamino-1, 4-benzoquinone, 2-ethylamino-1, 4-benzoquinone, 2-propylamino-1, 4-benzoquinone, 2-butylamine-1, 4-benzoquinone, 2-pentylamino-1, 4-benzoquinone, 2-hexylamino-1, 4-benzoquinone, 2-anilino-1, 4-benzoquinone, 2-heptylamine-1, 4-benzoquinone, 2-octylamino-1, 4-benzoquinone, 2-nonylamino-1, 4-benzoquinone, 2-decylamine-1, 4-benzoquinone, benzoquinone, 2-undecylamino-1, 4-benzoquinone, 2-dodecyl-1, 4-benzoquinone, 2-tridecyl-1, 4-benzoquinone, 2-tetradecyl-1, 4-benzoquinone, 2-pentadecylamino-1, 4-benzoquinone, 2-hexadecylamino-1, 4-benzoquinone, 2-heptadecylamino-1, 4-benzoquinone, 2-octadecylamino-1, 4-benzoquinone, 2-oleylamino-1, 4-benzoquinone, 2-nonadecylamino-1, 4-benzoquinone, 2-eicosylamino-1, 4-benzoquinone, 2-heneicosylamino-1, 4-benzoquinone and 2-docosylamino-1, 4-benzoquinone, and partially unsaturated (e.g., mono-or polyunsaturated) alkyl derivatives thereof.

Further exemplary compounds include 2-alkylamino- (3,5 and/or 6-alkyl) -1, 4-benzoquinones or 2-arylamino- (3,5 and/or 6-alkyl) -1, 4-benzoquinones, for example 2-methylamino- (3,5 and/or 6-methyl) -1, 4-benzoquinone, 2-ethylamino- (3,5 and/or 6-methyl) -1, 4-benzoquinone, 2-propylamino- (3,5 and/or 6-methyl) -1, 4-benzoquinone, 2-butylamino- (3,5 and/or 6-methyl) -1, 4-benzoquinone, 2-pentylamino- (3,5 and/or 6-methyl) -1, 4-benzoquinone, 2-hexylamino- (3,5 and/or 6-methyl) -1, 4-benzoquinone and 2-anilino- (3,5 and/or 6-methyl) -1, 4-benzoquinone.

Exemplary compounds include 4-alkylamino-1, 2-benzoquinones and 4-arylamino-1, 2-benzoquinones, for example 4-methylamino-1, 2-benzoquinone, 4-ethylamino-1, 2-benzoquinone, 4-propylamino-1, 2-benzoquinone, 4-butylamine-1, 2-benzoquinone, 4-pentylamine-1, 2-benzoquinone, 4-hexylamine-1, 2-benzoquinone, 4-phenylamino-1, 2-benzoquinone, 4-heptylamine-1, 2-benzoquinone, 4-octylamine-1, 2-benzoquinone, 4-nonylamine-1, 2-benzoquinone, 4-decylamine-1, 2-benzoquinone, 4-undecylamino-1, 2-benzoquinone, 4-dodecylamino-1, 2-benzoquinone, 4-tridecylamino-1, 2-benzoquinone, 4-tetradecylamino-1, 2-benzoquinone, 4-pentadecylamino-1, 2-benzoquinone, 4-hexadecylamino-1, 2-benzoquinone, 4-heptadecylamino-1, 2-benzoquinone, 4-octadecylamino-1, 2-benzoquinone, 4-oleylamino-1, 2-benzoquinone, 4-octadecylamino-1, 2-benzoquinone, 4-eicosylamino-1, 2-benzoquinone, 4-eicosenylamino-1, 2-benzoquinone and 4-docosylamino-1, 2-benzoquinone, and partially unsaturated alkyl (e.g., mono-or polyunsaturated) derivatives thereof.

Further exemplary compounds include 4-alkylamino- (3,5 and/or 6-alkyl) -1, 2-benzoquinones and 4-arylamino- (3,5 and/or 6-alkyl) -1, 2-benzoquinones, for example 4-methylamino- (3,5 and/or 6-methyl) -1, 2-benzoquinone, 4-ethylamino- (3,5 and/or 6-methyl) -1, 2-benzoquinone, 4-propylamino- (3,5 and/or 6-methyl) -1, 2-benzoquinone, 4-butylamino- (3,5 and/or 6-methyl) -1, 2-benzoquinone, 4-pentylamino- (3,5 and/or 6-methyl) -1, 2-benzoquinone, 4-hexylamino- (3,5 and/or 6-methyl) -1, 2-benzoquinone and 4-anilino- (3,5 and/or 6-methyl) -1, 2-benzoquinone.

In some embodiments, referring to formulas I and II, R¹、R²、R³And R⁴Two of which are-NR⁵R⁶，R⁵Is H, and R⁶Selected from the group consisting of alkyl, aryl, alkylaryl and arylalkyl groups of 1 to 24 carbon atoms. Preferably, R⁶Selected from the group consisting of alkyl, aryl, alkylaryl and arylalkyl groups of from 2 to 22 carbon atoms, more preferably from 3 to 20 carbon atoms. R¹、R²、R³And R⁴Is not-NR⁵R⁶Are preferably selected from the group consisting of hydrogen, alkyl, aryl, alkylaryl and arylalkyl, selected fromSelected from the group consisting of hydrogen and C1-C6 alkyl, preferably R is hydrogen and C1-C3 alkyl¹、R²、R³And R⁴Is not-NR⁵R⁶One or both of (a) and (b) are hydrogen.

Exemplary compounds include 2, 5-dialkylamino-1, 4-benzoquinones (e.g., 2, 5-bis (dialkylamino) -1, 4-benzoquinone), 2, 3-dialkylamino-1, 4-benzoquinone, 3, 5-dialkylamino-1, 4-benzoquinone, 2-alkylamino-5-arylamino-1, 4-benzoquinone, 2-alkylamino-3-arylamino-1, 4-benzoquinone, and 3-alkylamino-5-arylamino-1, 4-benzoquinones, such as 2, 5-bis (dimethylamino) -1, 4-benzoquinone, 2, 5-bis (diethylamino) -1, 4-benzoquinone, 2, 5-bis (dipropylamino) -1, 4-benzoquinone, 2, 5-bis (dibutylamino) -1, 4-benzoquinone, 2, 5-bis (dipentylamino) -1, 4-benzoquinone, 2, 5-bis (dihexylamino) -1, 4-benzoquinone, 2, 5-bis (diphenylamino) -1, 4-benzoquinone, 2, 3-dimethylamino-1, 4-benzoquinone, 2-methylamino-3-ethylamino-1, 4-benzoquinone, 2-methylamino-3-hexylamino-1, 4-benzoquinone and 2-methylamino-3-anilino-1, 4-benzoquinone.

In an embodiment, in formula I or II, -R¹、–R²、–R³and-R⁴Any two adjacent groups form one or more ring structures and provide an aminated quinone anti-polymerization agent according to formula III or IV:

wherein, -R⁷and/or-R⁸One or both of which are-NR⁵R⁶. in-NR⁵R⁶In, R⁵And R⁶Selected from the group consisting of hydrogen of 1 to 24 carbon atoms, alkyl, aryl, alkylaryl and arylalkyl groups, with the proviso that R is⁵And R⁶Is not hydrogen. Furthermore, R¹、R²、R³Or R⁴Is selected from the group consisting of: hydrogen, alkyl, aryl, alkylaryl and arylalkyl, alkoxy, SO₂Ar、COOH、SO₃H、COOR⁹、NHCOR⁹、OCOR⁹Which isIn R⁹Selected from the group consisting of alkyl, aryl, alkylaryl, and arylalkyl. Or, R¹、R²、R³Or R⁴Two adjacent groups (i.e. R) in (B)¹And R²；R²And R³(ii) a Or R³And R⁴) One or more ring structures are formed. In this method, the aminated quinone of formula III or IV is added without or with minimal nitroxyl containing anti-polymerization agent, as described herein.

Exemplary aminated naphthoquinone anti-polymerization agents can have the following general chemical properties: 2-amino, 1, 4-naphthoquinone, 2, 3-diamino, 1, 4-naphthoquinone, 2-amino, 1, 3-naphthoquinone, 4-amino, 1, 3-naphthoquinone, 2, 4-diamino, 1, 3-naphthoquinone, 3-amino, 1, 2-naphthoquinone, 4-amino, 1, 2-naphthoquinone and 3, 4-diamino, 1, 3-naphthoquinone.

The amino group of formula III or IV may be according to the sub-formula-NR as described herein⁵R⁶Any amino group of (a). As described herein, if R⁵And R⁶One or both of which are one or more alkyl groups, then the alkyl groups may be unsaturated, partially saturated, or fully saturated. In a preferred embodiment, R⁵Is a partially saturated or fully saturated alkyl group, e.g. as described herein, and R⁶Is hydrogen.

In some embodiments of formula III or IV, R⁷Or R⁸is-NR⁵R⁶And R is⁶Selected from the group consisting of alkyl, aryl, alkylaryl and arylalkyl groups of 1 to 24 carbon atoms, and R⁴Is H. Preferably, R⁶Selected from the group consisting of alkyl, aryl, alkylaryl and arylalkyl groups of from 2 to 22 carbon atoms, more preferably from 3 to 20 carbon atoms. Preferably, R¹、R²、R³And R⁴Selected from the group consisting of: hydrogen, alkyl, aryl, alkylaryl and arylalkyl groups, and more preferably hydrogen, C1-6 alkyl or C1-3 alkyl.

Exemplary compounds of formulas III and IV include 2-alkylamino-1, 4-naphthoquinones and 2-arylamino-1, 4-naphthoquinones, such as 2-methylamino-1, 4-naphthoquinone, 2-ethylamino-1, 4-naphthoquinone, 2-propylamino-1, 4-naphthoquinone, 2-butylamine-1, 4-naphthoquinone, 2-pentylamine-1, 4-naphthoquinone, 2-hexylamine-1, 4-naphthoquinone, 2-anilino-1, 4-naphthoquinone (2-anilino-1, 4-naphthoquinone), 2-heptylamino-1, 4-naphthoquinone, 2-octylamine-1, 4-naphthoquinone, 2-nonylamino-1, 4-naphthoquinone, 2-decylamino-1, 4-naphthoquinone, 2-undecylamino-1, 4-naphthoquinone, 2-dodecylamino-1, 4-naphthoquinone, 2-tridecylamino-1, 4-naphthoquinone, 2-tetradecylamino-1, 4-naphthoquinone, 2-pentadecylamino-1, 4-naphthoquinone, 2-hexadecylamino-1, 4-naphthoquinone, 2-heptadecylamino-1, 4-naphthoquinone, 2-octadecylamino-1, 4-naphthoquinone, 2-oleylamino-1, 4-naphthoquinone, 2-octadecylamino-1, 4-naphthoquinone, 2-eicosylamino-1, 4-naphthoquinone, 2-eicosylamino-1, 4-naphthoquinone and 2-docosylamino-1, 4-naphthoquinone and their partially unsaturated alkyl (e.g. mono-or polyunsaturated) derivatives.

Other exemplary compounds include 2-alkylamino-1, 3-naphthoquinones or 2-arylamino-1, 3-naphthoquinones, such as 2-methylamino-1, 3-naphthoquinone, 2-ethylamino-1, 3-naphthoquinone, 2-propylamino-1, 3-naphthoquinone, 2-butylamine-1, 3-naphthoquinone, 2-pentylamine-1, 3-naphthoquinone, 2-hexylamine-1, 3-naphthoquinone, and 2-anilino-1, 3-naphthoquinone (2-anilino-1, 3-naphthoquinone).

Further exemplary compounds include 2-alkylamino- (5,6,7 and/or 8-alkyl) -1, 4-naphthoquinone and 2-arylamino- (5,6,7 and/or 8-alkyl) -1, 4-naphthoquinone, for example 2-methylamino- (5,6,7 and/or 8-methyl) -1, 4-naphthoquinone, 2-ethylamino- (5,6,7 and/or 8-methyl) -1, 4-naphthoquinone, 2-propylamino- (5,6,7 and/or 8-methyl) -1, 4-naphthoquinone, 2-butylamino- (5,6,7 and/or 8-methyl) -1, 4-naphthoquinone, 2-pentylamino- (5,6,7 and/or 8-methyl) -1, 4-naphthoquinone, 2-hexanamido- (5,6,7 and/or 8-methyl) -1, 4-naphthoquinone and 2-anilino- (5,6,7 and/or 8-methyl) -1, 4-benzoquinone.

Further exemplary compounds include 2-alkylamino- (5,6,7 and/or 8-alkyl) -1, 3-naphthoquinone and 2-arylamino- (5,6,7 and/or 8-alkyl) -1, 3-naphthoquinone, for example 2-methylamino- (5,6,7 and/or 8-methyl) -1, 3-naphthoquinone, 2-ethylamino- (5,6,7 and/or 8-methyl) -1, 3-naphthoquinone, 2-propylamino- (5,6,7 and/or 8-methyl) -1, 3-naphthoquinone, 2-butylamino- (5,6,7 and/or 8-methyl) -1, 3-naphthoquinone, 2-pentylamino- (5,6,7 and/or 8-methyl) -1, 3-naphthoquinone, 2-hexanamido- (5,6,7 and/or 8-methyl) -1, 3-naphthoquinone and 2-anilino- (5,6,7 and/or 8-methyl) -1, 3-benzoquinone.

In some embodiments, the present disclosure provides an aminated quinone anti-polymerization agent containing composition comprising or to which one or more polymerizable monomers, or one or more compounds capable of forming a polymerizable monomer, can be added, wherein the composition comprises an aminated quinone anti-polymerization agent of formula I, II, III, or IV, with the proviso that the anti-polymerization agent is not 4-anilino-1, 2-naphthoquinone.

The aminated quinone compound can be prepared by any one or more of the methods known in the art. For example, U.S. Pat. No. 3,114,755 discloses the synthesis of monosubstituted aminonaphthoquinones by reacting 1, 4-benzoquinone or 1, 4-naphthoquinone with a soluble complex of a copper salt and a primary amine, such as 2-methylamino-1, 4-naphthoquinone, 2-ethylamino-1, 4-naphthoquinone, 2-n-propylamino-1, 4-naphthoquinone, 2-isopropylamino-1, 4-naphthoquinone, 2-n-butylamino-1, 4-naphthoquinone, 2-sec-butylamino-1, 4-naphthoquinone, 2-allylamino-1, 4-naphthoquinone, 2, 5-bis (ethylamino) 1, 4-benzoquinone, 2, 5-bis (sec-butylamino) -1, 4-benzoquinone. U.S. Pat. No. 3,379,739 teaches the production of 2, 5-diarylamino-1, 4-benzoquinone compounds. The Synthesis of 2, 5-diamino-1, 4-benzoquinone is described in the article published by Mereyala et al (Synthesis (No.2), 0187-. The synthesis of aminated benzoquinones and aminated naphthoquinones is described in MacGregor et al (European Journal of Medicinal Chemistry85,191-206, 2014).

The amount of aminated quinone anti-polymerization agent and any other (optional) components in the composition can be described in various ways, such as by the weight percentage (% wt.) or molar amount of aminated quinone anti-polymerization agent in the composition. When other components are used with the aminated quinone anti-polymerization agent, such compounds can also be described in terms of weight ratios in the composition or relative amounts with respect to each other.

As described herein, the aminated benzoquinone of any of formulas I, II, III or IV can be used with no or minimal nitroxyl containing anti-polymerization agent. If included, the nitroxyl-containing anti-polymerization agent can be present in very small amounts, for example in a composition comprising the polymerizable monomer, where the nitroxyl-containing anti-polymerization agent is not present at all or is present in very small amounts (less than 50 ppm).

For example, in a composition comprising a polymerizable monomer and an aminated quinone anti-polymerization agent, the nitroxyl-containing anti-polymerization agent can optionally be present in an amount of less than 50ppm, less than 25ppm, less than 10ppm, less than 5ppm, less than 2.5ppm, less than 2ppm, less than 1.5ppm, less than 1ppm, less than 0.75ppm, or less than 0.5 ppm.

Nitroxyl containing compounds trap propagating monomer radicals in thermally unstable species and inhibit polymerization. Nitroxyl/nitroso oxide groups, which may also be referred to as amine-N-oxide groups, are functional groups that include NO bonds and pendant groups attached to nitrogen. Nitric oxide (nitroxyl) radicals are oxygen-centered radicals, the free electrons being delocalized over the NO bond. The nitric oxide containing polymerization inhibitor may comprise an NO resonance structure that contributes to the formation of nitric oxide radical stability.

Exemplary nitroxyl/nitroxide containing compounds that are excluded from, or used in limited amounts in, the compositions of the present disclosure include, but are not limited to: 2,2,6, 6-tetramethylpiperidyl-1-oxyl (TEMPO), 4-hydroxy-2, 2,6, 6-tetramethylpiperidyl-1-oxyl (HTMPO), 4-oxo-2, 2,6, 6-tetramethylpiperidyl-1-oxyl (OTEMPO), di-tert-butylnitrooxyl, 1-oxo-2, 2,6, 6-tetramethyl-4-n-propoxypiperidine, 1-oxo-2, 2,6, 6-tetramethyl-4-n-butoxypiperidine, 1-oxo-2, 2,6, 6-tetramethyl-4-tert-butoxypiperidine, 1-oxo-2, 2,6, 6-tetramethyl-4-sec-butoxypiperidine, and, 1-oxo-2, 2,6, 6-tetramethyl-4- (2-methoxyethoxy) piperidine, 1-oxo-2, 2,6, 6-tetramethyl-4- (2-methoxyethoxyacetoxy) piperidine, 1-oxo-2, 2,6, 6-tetramethylpiperidin-4-yl stearate, 1-oxo-2, 2,6, 6-tetramethylpiperidin-4-yl acetate, 1-oxo-2, 2,6, 6-tetramethylpiperidin-4-yl butyrate, 1-oxo-2, 2,6, 2-ethylhexanoic acid-tetramethylpiperidin-4-yl ester, octanoic acid 1-oxo-2, 2,6, 6-tetramethylpiperidin-4-yloctanoate, 1-oxo-2, 2,6, 6-tetramethylpiperidin-4-yllaurate, 1-oxo-2, 2,6, 6-tetramethylpiperidin-4-ylbenzoate, 1-oxo-2, 2,6, 6-tetramethylpiperidin-4-yl-4-tert-butylbenzoate, 1-oxo-2, 2,6, 6-tetramethyl-4-allyloxy-piperidine, 1-oxo-2, 2,6, 6-tetramethyl-4-acetylaminopiperidine, 1-oxo-2, 2,6, 6-tetramethyl-4- (N-butylcarboxamido) piperidine, n- (1-oxo-2, 2,6, 6-tetramethylpiperidin-4-yl) -caprolactam, N- (1-oxo-2, 2,6, 6-tetramethylpiperidin-4-yl) -dodecylsuccinimide, 1-oxo-2, 2,6, 6-tetramethyl-4- (2, 3-dihydroxypropoxy) piperidine, 1-oxo-2, 2,6, 6-tetramethyl-4- (2-hydroxy-4-oxalyl-pentoxy) piperidine and mixtures thereof. See, for example, U.S. patent No. 9,266,797. Any of these compounds may be present in the polymerized monomer composition in very low amounts (less than 50ppm, 25ppm, 10ppm, etc., as described herein) or may be excluded from the composition altogether.

Other exemplary nitroxyl/nitroxide containing compounds include two or three nitroxyl groups. Such compounds may be di-or tri-compounds. Typical bis-nitroxide and tris-nitroxide polymerization inhibitor compounds include bis (1-oxy-2, 2,6, 6-tetramethylpiperidin-4-yl) succinate, bis (1-oxy-2, 2,6, 6-tetramethylpiperidin-4-yl) adipate, bis (1-oxy-2, 2,6, 6-tetramethylpiperidin-4-yl) sebacate, n-butyl bis (1-oxy-2, 2,6, 6-tetramethylpiperidin-4-yl) malonate, bis (1-oxy-2, 2,6, 6-tetramethylpiperidin-4-yl) ester, phthalic acid, bis (1-oxy-2, 2,6, 6-tetramethylpiperidin-4-yl) isophthalate, bis (1-oxy-2, 2,6, 6-tetramethylpiperidin-4-yl) terephthalate, bis (1-oxy-2, 2,6, 6-tetramethylpiperidin-4-yl) hexahydroterephthalic acid, N '-bis (1-oxy-2, 2,6, 6-tetramethylpiperidin-4-yl) adipamide, 2,4, 6-tris- [ N-butyl-N- (1-oxy-2, 266-tetramethylpiperidin-4-yl) ] -s-triazine, 2,4, 6-tris- [ N- (1-oxy-2, 2,6, 6-tetramethylpiperidin-4-yl) ] -s-triazine, bis (1-oxy-2, 2,6, 6-tetramethylpiperidin-4-yl) hexahydroterephthalic acid, N' -bis (1-oxy-2, 2,6, 6-tetramethylpiperidin-4-yl) adipamide, 4,4' -ethylenebis (1-oxy-2, 2,6, 6-tetramethylpiperazine-3-one) and mixtures thereof. See, for example, U.S. patent No. 9,266,797. Any of these compounds may be present in the polymerized monomer composition in very low amounts (less than 50ppm, 25ppm, 10ppm, etc., as described herein) or may be excluded from the composition altogether.

The aminated quinone anti-polymerization agent can be present in the composition with a solvent or a combination of solvents. The solvent or combination of solvents can be selected such that the one or more aminated quinone anti-polymerization agents are soluble in the solvent or combination of solvents. Miscible solvents may be chosen if the aminated quinone anti-polymerization agent is a liquid at ambient conditions.

Useful solvents include any solvent in which the aminated quinone anti-polymerization agent is soluble or can be stably suspended. In some embodiments, the solvent or solvent combination may be selected from water-soluble or water-miscible solvents, such as ethylene glycol-based solvents and hydrophobic or hydrocarbon solvents, such as aromatic solvents, paraffinic solvents, or mixtures of both.

Exemplary glycol solvents include, but are not limited to, C₁-C₈Glycols such as ethylene glycol, propylene glycol, diethylene glycol, and triethylene glycol, ethers of such glycols such as diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, liquid polyethylene glycols, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and low molecular weight polypropylene glycols and the like, and combinations thereof. Commercial solvents such as butyl carbitol and butyl cellosolvet, which contain predominantly butyl carbitol, which consists predominantly of ethylene glycol monobutyl ether, available from DOW, may be used.

Other exemplary hydrophobic or hydrocarbon solvents include heavy aromatic naphtha, toluene, ethylbenzene, the isomeric hexanes, benzene, xylenes such as o-, p-or m-xylene, and mixtures of two or more thereof.

In some embodiments, the solvent is selected from the group consisting of ethylene glycol and aromatic naphtha and combinations thereof.

The amount of aminated quinone anti-polymerization agent (with one or more optional components) in the solvent or solvent combination can be described in one or more ways, such as by the percentage (wt) composition of solids in the components, or by the molar amount of solid components in the composition.

For example, the starting composition of the aminated quinone anti-polymerization agent can be dissolved in the solvent to a concentration of about at least about 0.00001% (wt), at least about 5% (wt), for example, from about 0.00001% (wt) to about 50% (wt).

An amount of the feedstock composition comprising the aminated quinone anti-polymerization agent can be added to the monomer-containing composition or the composition capable of forming monomers to provide the anti-polymerization agent at a concentration effective to inhibit polymerization of the monomers.

Polymerizable monomers inhibited from polymerization by the aminated quinone can include vinyl or ethylenically unsaturated groups. For example, the components of the aminated quinone anti-polymerization agent and any optional components can be added to a composition comprising one or more of the following polymerizable monomers: acrolein, acrylic acid, acrylonitrile, alkylated styrenes, butadiene, chloroprene, divinylbenzene, ethyl acrylate, ethyl methacrylate, isoprene, methacrylic acid, methyl methacrylate, methyl acrylate, alpha-methylstyrene, methacrylonitrile, styrene sulfonic acid, vinyl acetate, vinyl toluene, and vinyl pyridine.

The polymerizable monomer may be present in a crude mixture of compounds, a semi-purified mixture of compounds, or a fully purified mixture of compounds. For example, the aminated quinone anti-polymerization agent can be added to a process stream that includes a polymerizable monomer and one or more other components different from the polymerizable monomer. In the method, the aminated quinone anti-polymerization agent can be added before, during, or after (or a combination thereof) the treatment step such as distillation, wherein the compounds in the composition are separated from each other. The aminated quinone anti-polymerization agent can inhibit polymerization of the monomers at any one or more stages of the processing system, thereby reducing or preventing equipment fouling.

Alternatively, the aminated quinone anti-polymerizer can be added to a process stream that includes a compound capable of forming a polymerizable monomer (e.g., a monomer precursor), such as ethylbenzene (a precursor to styrene). For example, in embodiments, the composition may comprise a compound capable of forming a polymerizable monomer as an unwanted byproduct. In this case, the presence of the aminated quinone anti-polymerization agent, if indeed formed as a by-product, can inhibit polymerization of the monomer, and thus can reduce or prevent equipment fouling.

In practice, the aminated quinone anti-polymerization agent is introduced into the monomer-containing composition or the composition containing the compound capable of forming a polymerizable monomer at a desired concentration effective to inhibit polymerization of the monomer. The aminated quinone anti-polymerization agent can be added to a composition comprising one or more polymerizable monomers, or one or more compounds capable of forming a polymerizable monomer. The monomers and/or monomer-forming compounds can be present in the composition in any concentration, for example, in a very small amount (ppm) or an amount wherein the monomers and/or monomer-forming compounds are present in the composition in a substantial amount (e.g., 50% (wt) or greater). Exemplary ranges are from any of about 5ppm, about 20ppm, about 50ppm, or about 100ppm (0.1%) to about 10% (wt), about 25% (wt), about 50% (wt), or about 75% (wt). In some modes of practice, the polymerizable monomer concentration used is from about 50ppm to about 200 ppm.

The amount of aminated quinone anti-polymerization agent in the composition comprising monomers and/or monomer-forming compounds can be selected based on: monomer/compound type, amount of monomer/compound in the composition, type of component having the monomer/compound, any processing, handling, or storage conditions of the composition, and the presence of any one or more optional compounds that are different from the aminated quinone anti-polymerization agent and added to the composition. The aminated quinone anti-polymerization agent can be added to the composition in an amount to provide the desired level of polymerization inhibition.

In embodiments, the aminated quinone anti-polymerization agent can be used in an amount of at least about 0.10ppm, such as in the range of about 0.10ppm to about 50,000ppm, in the range of about 0.10ppm to about 25,000ppm, about 0.10ppm to about 10,000ppm, about 25ppm to about 5,000ppm, about 25ppm to about 2,500ppm, about 50ppm to about 1,000ppm, about 75 to about 500ppm, about 100 to 300ppm, about 125 to about 275ppm, or about 150 to about 250 ppm.

In some modes of practice, the aminated quinone anti-polymerization agent is used before or after the polymerizable monomer-containing composition is treated with a polymerization inhibitor other than an aminated quinone, such as a nitroxide-containing polymerization inhibitor (e.g., HTEMPO, etc.). In some implementations, the aminated quinone anti-polymerization agent is added to the polymerizable monomer composition after the composition is treated with the nitrogen oxide-containing polymerization inhibitor, and the inhibitor has been at least substantially consumed, or at least lost most of its inhibitor activity. For example, a nitroxide group-containing polymerization inhibitor can be added to the monomer-containing composition at a first point in time, and the composition can then be monitored to determine any increase in polymer formation and/or the presence of the inhibitor, and if there is an increase in polymer formation or decrease in the inhibitor, an aminated quinone anti-polymerization agent can be added at a second point in time to maintain inhibition of polymerization.

In other implementations, the aminated quinone anti-polymerization agent can be added to the monomer-containing composition at a first point in time, and then one or more additional compounds for inhibiting polymerization, other than the aminated quinone, can be added to the composition at room temperature at one or more later points in time (e.g., second, third, etc.).

The aminated quinone anti-polymerization agent can be added to the polymerizable monomer composition in any one or more of a variety of ways, such as by adding the anti-polymerization agent in the following manner: single dose addition, continuous addition, semi-continuous addition, intermittent addition, or any combination of these methods. In a continuous addition, the aminated quinone anti-polymerization agent can be added at a constant or variable rate. The manner of addition of the aminated quinone anti-polymerization agent can be selected based on the polymerizable monomer-containing composition and how it is stored, processed, or otherwise. For example, in a process stream involving the movement and separation of polymerizable monomers or compounds that can form polymerizable monomers from other components, such as distillation apparatus, the aminated quinone anti-polymerization agent can be added in a continuous or semi-continuous manner to account for the continued introduction of new monomers or monomer precursors.

The term "fouling" refers to the formation of polymers, prepolymers, oligomers, and/or other materials that are insoluble in and/or precipitate from the stream and deposit on equipment under the conditions at which the equipment is operated. Further, the aminated quinone anti-polymerization agent may also be referred to as an "anti-fouling agent" because it prevents or reduces this formation.

Alternatively, the ability of the compositions of the present disclosure to inhibit polymerization can be described relative to compositions that do not include the aminated quinone anti-polymerization agent or that include the comparative compound. The effect of aminated quinone anti-polymerization agents can be understood by measuring the formation of polymer (e.g., polystyrene) over time in a monomeric (e.g., styrene) composition in the presence of the following composition: the composition includes an aminated quinone anti-polymerization agent as compared to a composition that does not include an aminated quinone polymerization agent or a composition that uses an anti-polymerization agent having a different chemical nature than the present disclosure.

For example, the composition of the present invention with an aminated quinone anti-polymerization agent can inhibit polymerization of monomers by more than 50%, more than 60%, more than 70%, more than 80%, more than 85%, more than 90%, more than 92.5%, more than 95%, or more than 97% compared to a composition with a non-aminated quinone (e.g., dibutyl 1, 4-phthalate) under the same conditions.

The aminated quinone anti-polymerizer can be used in conjunction with a composition containing polymerizable monomers and "process equipment" (e.g., reactors, reactor beds, piping, valves, distillation columns, trays, condensers, heat exchangers, compressors, fans, impellers, pumps, recyclers, intercoolers, sensors, etc.) associated with the process and that may foul by the polymerization of the monomers. The term also includes a collection of these components, where one of the components is part of a "system".

In a preferred method of use, the composition of the present invention having an aminated quinone anti-polymerization agent and a solvent (e.g., a glycol) is used with a process involving a distillation column for separating and purifying a vinyl monomer, such as styrene. For example, ethylbenzene may be subjected to a catalytic dehydrogenation reaction in a process known in the art, resulting in the formation of styrene. The reaction product comprising styrene also comprises other compounds, such as aromatics (e.g., toluene and benzene), unreacted ethylbenzene, and other materials (e.g., polymers). This mixture of compounds is usually fractionated using one or more distillation columns. Typically, heat is used to help separate the components in the distillation column. After distillation, the fractionated components can be separated into a pure product stream of higher purity. Optionally, the aminated quinone anti-polymerization agent is used with one or more auxiliary components, such as stabilizers, e.g., Butylated Hydroxytoluene (BHT) and Tertiary Butyl Catechol (TBC). In exemplary practice, these components are used in a distillation column that is used to separate and purify the vinyl monomer.

The composition containing the aminated quinone anti-polymerization agent can be introduced into the stream from the reaction bed to the distillation column or can be added directly to the distillation column. The composition may be added prior to heating the monomer composition or while heating the monomer composition in a distillation column. In embodiments, the boiling point of the aminated quinone anti-polymerization compound is higher than the boiling point of the desired compound or distillate (e.g., monomer such as styrene) subjected to the distillation column, and during distillation, the desired compound is separated from the aminated quinone anti-polymer compound due to temperature differences. In embodiments, the boiling point difference between the compound of interest and the aminated quinone anti-polymerization agent can be about 10 ℃ or greater, about 15 ℃ or greater, about 20 ℃ or greater, about 25 ℃ or greater, about 30 ℃ or greater, about 35 ℃ or greater, about 40 ℃ or greater, about 45 ℃ or greater, or about 50 ℃ or greater.

Alternatively, or in addition to the addition of the aminated quinone anti-polymerization agent during distillation, the composition may alternatively or further be added to a distillation effluent stream, such as a purified styrene stream. Alternatively, another anti-polymerization agent may be added to the distillation effluent stream prior to or along with the amination of the quinone anti-polymerization agent.

The aminated quinone anti-polymerization agent, optionally in combination with one or more other components, can be used with any "hydrocarbon process stream" that can include unsaturated monomers to stabilize the stream during transport and storage. In certain modes of practice, the aminated quinone anti-polymerization agent may be used in conjunction with "petroleum products," which refers to any hydrocarbon product obtained from a subterranean reservoir, any product derived from a subterranean reservoir, or any mixture thereof. The polymerizable monomer is present in the petroleum product or may be chemically derived from the petroleum product. Non-limiting examples of petroleum products include, but are not limited to, crude oil, distilled crude oil, crude oil fractions, heavy oil or bitumen, hydrogenated oil, refined oil, byproducts of petroleum product processing (such as pyrolysis, hydrotreating, or phase separation), or mixtures of two or more of these. The liquid petroleum product is a petroleum product that is substantially liquid at 20 ℃.

The aminated quinone anti-polymerization agent can be added to or can be present in a "petroleum process stream," which refers to any petroleum product placed within a petroleum process facility and in fluid contact with the interior surface thereof.

The petroleum process stream may include, or be capable of forming as a byproduct, one or more polymerizable monomers. The process stream may be substantially static, e.g., placed in a settler (separator) or storage vessel for a selected contact time, e.g., up to two years of petroleum production. The process stream may be substantially dynamic, such as a liquid petroleum product disposed within a pipe during transport of the product from a first location to a second location. In some embodiments, the process stream includes one or more other components associated with petroleum processing; these components are not particularly limited.

As used herein, the terms "petroleum processing equipment," "petroleum processing plant," and similar terms mean a manufactured article having an interior surface comprising a metal, wherein one or more petroleum products are contacted with a metal fluid at any temperature for any period of time as further determined from the context. Petroleum processing facilities include items for removing petroleum products from a subterranean reservoir, for transporting one or more petroleum products from a first location to a second location, or for separating, refining, treating, separating, distilling, reacting, metering, heating, cooling, or containing one or more petroleum products.

In embodiments, the treated petroleum product and treated petroleum process stream are pyrolytically stable at a temperature of about 20 ℃ to 400 ℃, e.g., about 100 ℃ to 400 ℃, or about 100 ℃ to 350 ℃, or about 100 ℃ to 300 ℃, or about 100 ℃ to 250 ℃, or about 100 ℃ to 200 ℃, or about 100 ℃ to 150 ℃.

In embodiments, the composition comprising the aminated quinone anti-polymerization agent can be introduced into a composition having polymerizable monomers, such as a liquid petroleum process stream, in a batch, continuous, or semi-continuous manner. In some embodiments, the aminated quinone anti-polymerization agent (and any other optional components) is introduced manually; and in other embodiments, its introduction is automatic. In embodiments, the amount of aminated quinone anti-polymerization agent introduced in a selected time unit varies with the variable composition of the associated process stream. Such dose variability can be done manually: passing periodic tests of the internal surfaces of the process equipment and then adjusting the amount of the composition up or down based on the results of the tests; or by automatically monitoring one or more conditions within the petroleum processing facility and signaling a need to apply more composition to the process stream.

In some embodiments, the aminated quinone anti-polymerization agent is added to a petroleum product that is a crude oil, a reduced crude oil, a heavy oil, a bitumen, a coker charge, a hydrotreater feed, a hydrotreater effluent, a flashed crude oil, a light cycle oil, or a diesel or naphtha refinery stream. In an embodiment, the anti-polymerization agent is added to a petroleum processing facility, which is typically associated with the collection, processing, transportation, or storage of one or more of crude oil, distilled crude oil, crude oil fractions, heavy oil, bitumen, coker charge, flashed crude oil, light cycle oil, or diesel or naphtha refinery streams, and with the infrastructure used to fluidly connect the items of the processing facility together to facilitate the processing of the process streams disposed therein.

The equipment comprising the polymerizable monomer-containing composition treated with the aminated quinone anti-polymerization agent, as well as any other optional ingredients, can reduce or eliminate fouling of the interior surfaces of the equipment. In embodiments, fouling is measured as the relative increase in solids retention in a treated composition compared to the solids retention in an untreated composition over the same period of time. In an embodiment, fouling is measured by the relative reduction in precipitate weight or volume resulting from a selected contact time of a treated process stream in an associated process equipment item relative to the same time of the process equipment and the corresponding untreated process stream. In other words, the reduction in fouling is a relative reduction in the measured weight or volume of solids deposited or precipitated from process equipment in contact with the treated process stream over a selected period of time as compared to the weight or volume of solids deposited or precipitated from the untreated process stream over the same period of time.

The aminated quinone anti-polymerization agent can also inhibit undesirable polymerization and fouling of process equipment during primary fractionation, light ends, non-aromatic halovinyl fractionation and stabilization, process gas compression, dilution steam systems, caustic towers, quench water separators (pyrolysis gasoline), butadiene extraction, propane dehydrogenation, diesel and gasoline fuel stabilization, olefin metathesis, styrene purification, hydroxyl hydrocarbon purification, stabilization of vinyl monomers, or delay polymerization of resins and compositions containing ethylenically unsaturated materials during transportation and storage.

The aminated quinone anti-polymerization agent can be added at any given point and at one or more locations in the process. For example, the anti-polymerizer composition may be added in an interstage cooler or compressor or directly upstream of an intercooler or compressor. The aminated quinone anti-polymerization agent can be added to the process equipment continuously or intermittently as needed to prevent or reduce fouling.

The aminated quinone anti-polymerization agent can be introduced into the desired system by any suitable method. For example, it may be added as a pure solution or as a dilute solution. In some embodiments, the composition comprising the aminated quinone anti-polymerization agent can be applied in the form of a solution, emulsion, or dispersion that is sprayed, dropped, poured, or injected into the desired opening in the system or process equipment or process condensate. In some embodiments, wash oil or conditioner water may be added to the composition.

Upon introduction of the composition into the process equipment, it was observed that the treated process equipment deposited less on the equipment than process equipment without the addition of the composition. Reduction or prevention of fouling may be assessed by any known method or test. In some embodiments, fouling may be reduced or prevented by measuring the time required for the samples with and without the antifoulant composition to gel.

Example 1: synthesis of aminonaphthoquinones

According to European JournalThe method described in detail in of Medicinal chemistry85,191-206(2014) synthesizes a prototype of the aminonaphthoquinone structure, 2-anilino-1, 4-naphthoquinone. In a 1L three-necked apparatus with a condenser and a dropping funnel, 24.0g (147.2mmol) of 1, 4-naphthoquinone and a magnetic follower were charged. A large amount of methanol was added and then the contents were vigorously stirred into a slurry. 13.5mL (147.2mmol) of aniline diluted with methanol was added to the dropping funnel, from which the solution was added dropwise to the flask. After completion of the reaction, the solvent was removed in vacuo. The purity of the target compound was confirmed using gas chromatography. Using H-NMR and¹³the structure of 2-anilino-1, 4-naphthoquinone was confirmed by analysis by C-NMR.

EXAMPLE 2 Synthesis of 2-Sec-butylaminonaphthoquinone

The procedure of example 1 was used to synthesize, isolate and analyze other aminated naphthoquinones for prototype testing.

Example 3.2 Synthesis of oleylnaphthonaphthonaphthoquinones

2-oleylnaphthonaphthoquinone was synthesized, recovered and characterized using the method in example 1.

Example 4: performance of 2-aniline-1, 4-naphthoquinone in styrene

A solution of 300g of styrene containing 200ppm of 2-anilino-1, 4-naphthoquinone was prepared. The 4-tert-butylcatechol (TBC) stabilizer in commercial styrene was removed just prior to treatment of the composition. The stabilizer was removed using an alumina column. For polymerization, twenty-four Ace Glass #15 threaded pressure pipes equipped with PTFE nuts and fluoroelastomer (FETFE) O-rings were used as polymerization reactors. To each tube was added 10mL of the reaction solution. Each tube was immediately sealed and the solution was maintained under a nitrogen headspace by purging dissolved oxygen in each solution in the tube by bubbling nitrogen for 2 minutes. The tube was loaded into a heating block preheated to 120 ℃. At regular intervals, four tubes were removed from the block and the polymerization was quenched by cooling in an ice bath. The cooled polymer solution was immediately diluted with toluene. Proprietary methods are also used to measure polymer content.

Example 5: performance of 2-sec-butylaminonaphthoquinone in styrene

The performance of 2-sec-butylaminonaphthoquinone was determined using the method in example 3.

Example 6: properties of 2-oleylaminonaphthoquinone in styrene

The performance of 2-oleylaminonaphthoquinone as an anti-polymerization agent was tested using the method in example 3.

Example 7: HTEMPO in styrene

Similarly, HTEMPO was dissolved in de-inhibited styrene to give 200ppm in 300g of solution. Using the procedure in example 2, the anti-polymer agent activity of HTEMPO was determined.

Example 4: 7-Phenylquinone methyl methane in styrene (7-PhQM)

For another comparison purpose, a solution of 200ppm of 7-PhQM in 300g of inhibitor-free styrene was prepared and then tested for polymerization resistance according to the method of example 1.

Example 6: untreated styrene

Immediately after removal of TBC from styrene, a 10mL aliquot of the styrene was charged into each of the above pressure tubes. After removing dissolved oxygen from the solution, polymerization and polymer analysis were performed according to the method of example 1.

Table 1: at 200ppm, the performance of the anti-polymerizer in styrene.

2-sec-butylaminonaphthoquinone:

OANQ: 2-oleylaminonaphthoquinone:

ANQ: 2-anilino naphthoquinones