WO2002033026A1

WO2002033026A1 - Blends of quinone alkide and nitroxyl compounds as polymerization inhibitors

Info

Publication number: WO2002033026A1
Application number: PCT/US2001/030954
Authority: WO
Inventors: Brigitte Benage
Original assignee: Uniroyal Chemical Company, Inc.
Priority date: 2000-10-16
Filing date: 2001-10-02
Publication date: 2002-04-25
Also published as: US7045647B2; KR100812038B1; US20060155140A1; US7473795B2; US20040010159A1; JP2004513985A; MXPA03003405A; KR20030051716A; JP4248875B2; EP1332196A1; CA2422655A1

Abstract

Disclosed herein is a method for inhibiting the premature polymerization of ethylenically unsaturated monomers comprising adding to said monomers an effective amount of: A) at least one nitroxyl compound, and B) at least one quinone alkide compound having an electron-withdrawing group at the 7-position. Additionally, a composition is disclosed that comprises: A) at least one nitroxyl compound, and B) at least one quinone alkide compound having an electron-withdrawing group at the 7-position.

Description

BLENDS OF QUINONE ALKIDE AND NITROXYL COMPOUNDS AS POLYMERIZATION INHIBITORS

I claim the benefit under Title 35, United States Code, § 120 to U.S. Provisional Application Number 60/240,085, filed October 16, 2000, entitled

BLENDS OF QUINONE ALKIDE AND NITROXYL COMPOUNDS AS POLYMERIZATION INHIBITORS.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention is directed to the use of a combination of at least one quinone alkide and at least one nitroxyl compound to inhibit the polymerization of ethylenically unsaturated monomers.

2. Description of Related Art Many ethylenically unsaturated monomers undesirably polymerize at various stages of their manufacture, processing, handling, storage, and use. A particularly troublesome problem is equipment fouling caused by polymerization in the purification stages of the production processes of such monomers. Polymerization, such as thermal polymerization, during their purification results in the loss of the monomer and a loss in production efficiency owing to the deposition of polymer in or on the equipment being

used in the purification, the deposits of which must be removed from time to time. Additionally, the formation of soluble polymer leads to loss of monomer, i.e., a lower

yield, and an increase in the viscosity of any tars that may be produced. The processing of the tars then requires higher temperature and work (energy cost) to remove residual

monomer.

A wide variety of compounds has been proposed and used for inhibiting uncontrolled and undesired polymerization of ethylenically unsaturated monomers. In particular, there is a need for an inhibitor that not only provides highly effective

inhibition of polymerization during normal operation of a continuous manufacturing or purification process, but also provides satisfactory protection in the event of a loss of continuous inhibitor feed. While many inhibitors are known to provide sufficient protection in one of these scenarios, these inhibitors have not been fully satisfactory under both normal and upset operating conditions. Accordingly, there has been a substantial need in the art for improved compositions for inhibiting the polymerization of such monomers during their production and the distillation process for purifying or separating them from impurities, as well as during transport and storage.

Quinone methides and nitroxyl compounds are known polymerization inhibitors. Quinone methides act mainly as retarders, giving a significant amount of polymer during normal inhibition usage, but providing protection in the event of a plant upset during monomer purification by slowing the rate of polymer formation under static conditions. Because of the poor normal inhibition performance, quinone methides must be used in fairly high dosages, making them not very economical to use.

U.S. Patent Nos. 4,003,800 and 4,040,91 1 disclose the use of quinone alkides in a styrene purification process.

The following patents, assigned to Ciba-Geigy Corporation or Ciba Specialty

Chemicals Corporation, relate to quinone methides and uses thereof.

U.S. Patent Nos. 5,583,247; 5,670,692; and 5,750,765 disclose the protection of ethylenically unsaturated monomers from premature polymerization during manufacture and storage by the incorporation therein of an effective stabilizing amount of a quinone methide compound having an electron withdrawing substituent at the 7-methylene group.

U.S. Patent No. 5,616,774 discloses the protection of ethylenically unsaturated

monomers from premature polymerization during manufacture and storage by the

incorporation therein of an effective stabilizing amount of a 7-aryl quinone methide

. ? - compound wherein the 7-aryl substituent is 2-, 3- or 4-pyridyl, 2- or 3-thienyl, 2- or 3- pyrryl, 2- or 3-fiιryl, aryl of 6 to 10 carbon atoms, or said aryl substituted by one to three alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms, alkylthio of 1 to 8 carbon atoms, alkylamino of 1 to 8 carbon atoms, dialkylamino of 2 to 8 carbon atoms, alkoxycarbonyl of 2 to 8 carbon atoms, hydroxy, nitro, amino, cyano, carboxy, aminocarbonyl, chloro, or mixtures of said substituents. The combination of these quinone methides with at least one stable nitroxyl compound is also disclosed.

U.S. Patent No. 5,912, 106 discloses a method of improving the quality and resolution of photoimages by incorporating into the photocurable resin composition to be used a selected amount of a polymerization inhibitor so that photopolymerization of the photocurable resin is inhibited in those areas not directly impinged by light. Inhibitors that can be used are selected from the group consisting of N-oxyl or nitroxide compounds, quinone methides, nitroso compounds, phenothiazine and selected phenols.

Hindered nitroxyl compounds are known to be very active inhibitors of free radical polymerizations of unsaturated monomers such as styrene, acrylic acid, methacrylic acid, and the like.

U.S. Patent Number 3, 163,677 discloses N,N,O-trisubstituted hydroxylamines

and N,N-disubstituted nitroxides of the formulae:

wherein R,, R₂, and R₃ are each an alkyl radical having 1 to 15 carbon atoms. (As used herein, the designation N-O* denotes a stable free radical wherein the asterisk is an

unpaired electron.) The N,N,0-trisubstituted hydroxylamines can be used to make the N,N-disubstituted nitroxides, which are stable free radicals and are said to be useful as polymerization inhibitors.

U.S. Patent Number 3,334, 103 discloses that nitroxides can be prepared from the corresponding heterocyclic amine wherein the nitrogen atom of the nitroxide group is attached to other than a tertiary carbon of an aliphatic group (i.e., the nitrogen atom forms a part of a heterocyclic nucleus). These nitroxides are said to have useful properties similar to those described for the ,N-disubstituted nitroxides of U.S. Patent Number 3, 163,677.

U.S. Patent Number 3,372,182 discloses that a great variety of N,N- disubstituted, stable, free radical nitroxides not otherwise readily available can be prepared by a simple and convenient process that comprises pyrolyzing in an inert reaction medium virtually any hydroxylamine that is susceptible to cleavage of the O-C bond, e.g., tri-t-butylhydroxylamine.

U.S. Patent Number 3,422, 144 discloses stable, free radical nitroxides of the formula:

O* I c

I

R

wherein R is selected from the group consisting of tertiary alkyl, aryl, alkaryl, haloaryl, carboxyaryl, alkoxyaryl, alkylthioaryl, pyridyl, and dialkylaminoaryl, and R' is tertiary

alkyl. These nitroxides are said to be useful as traps for reactive free radicals both in the counting of free radicals and for inhibiting oxidation and free radical polymerization.

U.S. Patent Number 3,494,930 discloses free radicals of the nitroxide type for use as initiators of free radical reactions, collectors of free radicals, polymerization

inhibitors or antioxidants. They are constituted by nitrogenous bicyclic compounds in which one of the bridges comprises solely the nitroxide radical group and, in particular, by aza-9-bicyclo (3,3, 1) nonanone-3-oxyl-9, and by aza-9-bicyclo (3,3, 1) nonane oxyl-9.

U.S. Patent Number 3,873,564 discloses compounds and a method for assaying enzymes by adding to a medium containing an enzyme a stable free radical compound having a stable free radical functionality which, when subjected to an enzyme-catalyzed reaction, changes the environment of the free radical functionality. By following the change in the electron spin resonance spectrum as affected by the change in environment, the type of enzyme and the activity of the enzyme can be determined. The compounds found useful are normally stable nitroxide radicals with an enzyme labile functionality. Other compounds include two cyclic nitroxide containing rings joined by a chain having an enzyme labile functionality.

U.S. Patent Number 3,966,71 1 teaches that 2,2,7,7-tetraalkyl- and 2,7- dispiroalkylene-5-oxo- l ,4-diazacycloheptanes substituted in the 4-position by mono- or tetravalent radicals are powerful light-stabilizers for organic polymers. They are said to possess higher compatibility than their 4-unsubstituted homologues, from which they can be synthesized by reactions known for N-alkylation. Preferred substituents in the 4-

position are alkyl, alkylene, alkenyl, aralkyl, and esteralkyl groups, The 1-nitroxyls derived from the imidazolidines by oxidation with hydrogen peroxide or percarboxylic

acids are also said to be good light stabilizers. U.S. Patent Number 4, 182,658 discloses a method for preventing the polymerization of a readily polymerizable vinyl aromatic compound during distillation at elevated temperatures within a distillation apparatus that is subject to an emergency condition, such as a power outage. This method comprises force-feeding a

supplemental polymerization inhibitor having a high solubility in the vinyl aromatic

compound and a long duration of efficiency into each of the distillation vessels of a conventional distillation apparatus in an amount sufficient to prevent polymerization therein,

U.S. Patent Number 4,665, 185 discloses a process for the efficient preparation of nitroxyls of sterically hindered amines by the oxidation of the amine using a hydroperoxide in the presence of a small amount of a metal ion catalyst, at moderate temperature for a short period of time, to give the nitroxyl in high yield and purity.

U.S. Patent Number 4,774,374 discloses a vinyl aromatic composition stabilized against polymerization comprising (a) a vinyl aromatic compound and (b) an effective amount of a stabilizer system in which the active ingredient consists essentially of an oxygenated species formed by the reaction of oxygen and an N-aryl-N'-alkyl-p- phenylenediamine. Also disclosed is a process for inhibiting the polymerization of vinyl aromatic compounds employing such an oxygenated species,

U.S. Patent Number 5,254,760 teaches that the polymerization of a vinyl aromatic compound, such as styrene, is very effectively inhibited during distillation or purification by the presence of at least one stable nitroxyl compound together with at least one aromatic nitro compound,

U.S. Patent Numbers 5,545,782 and 5,545,786 disclose that nitroxyl inhibitors in

combination with some oxygen reduce the premature polymerization of vinyl aromatic

monomers during the manufacturing processes for such monomers. Even small quantities of air used in combination with the nitroxyl inhibitors are said to result in vastly prolonged inhibition times for the monomers.

U.S. Patent Number 5,71 1,767 discloses that the use of nitroxide compounds alone or in combination with aromatic amines, such as substituted phenylenediamines, or

phenolic antioxidants provides an effective way to prevent oxidative degradation and

gum formation in gasolines U.S. Patent Number 5,907,071 discloses that the polymerization of vinyl

aromatic monomers such as styrene is inhibited by the addition of a composition of a stable hindered nitroxyl radical and an oxime compound.

U.S. Patent Number 5,910,232 teaches that inhibition performance in styrene

processing is improved through the addition of a stable nitroxide free radical compound to the styrene feed and to the reflux of at least one column. A non-toxic retarder, such as phenylenediamine, may also optionally be added to the styrene feed and to the reflux. European Patent Application 0 178 168 A2 discloses a method for inhibiting the polymerization of an θ.,β-ethylenically unsaturated monocarboxylic acid during its recovery by distillation by using a nitroxide free radical.

European Patent Application 0 765 856 Al discloses a stabilized acrylic acid composition in which the polymerization of the acrylic acid is inhibited during the

distillation process for purifying or separating the acrylic acid as well as during transport and storage. The compositions comprise three components: (a) acrylic acid, (b) a stable nitroxyl radical, and (c) a dihetero-substituted benzene compound having at least one transferable hydrogen (e.g., a quinone derivative such as the monomethyl ether of

hydroquinone (MEHQ)). During the distillation process, transport, and storage, components (b) and (c) are present in a polymerization-inhibiting amount. During the

distillation process, oxygen (d) is preferably added with components (b) and (c), WO 97/46504 concerns substance mixtures containing: (A) monomers containing vinyl groups; and (B) an active amount of a mixture which inhibits premature polymerization of the monomers containing vinyl groups during their purification or distillation and contains: (i) between 0.05 and 4.5 wt %, relative to the total mixture (B),

of at least one N-oxyl compound of a secondary amine which has no hydrogen atom at the α-C atoms; and (ii) between 99.95 and 95.5 wt % relative to the total mixture (B), of at least one nitro compound. The publication also discloses a process for inhibiting the premature polymerization of monomers, and the use of mixture (B) for inhibiting the premature polymerizatin of monomers, WO 98/14416 discloses that the polymerization of vinyl aromatic monomers such as styrene is inhibited by the addition of a composition of a stable hindered nitroxyl

radical and an oxime compound.

WO 98/25872 concerns substance mixtures containing: (A) compounds containing vinyl groups; (B) an active amount of a mixture which inhibits premature polymerization of the compounds containing vinyl groups and contains: (i) at least one N-oxyl compound of a secondary amine which does not carry any hydrogen atoms on the α-carbon atoms; and (ii) at least one iron compound; (C) optionally nitro compounds; and (D) optionally co-stabilizers. The publication also discloses a process for inhibiting the premature polymerization of compounds (A) containing vinyl groups, and the use of (B) optionally mixed with nitro compounds (C) and/or co-stabilizers (D) for inhibiting the premature polymerization of radically polymerizable compounds and

stabilizing organic materials against the harmful effect of radicals.

WO 99/20584 (U.S. Patent No, 5,955,643) discloses that polymerization can be

inhibited during the anaerobic production of styrene through the addition of a combination of a stable nitroxide free radical compound and a non-toxic phenylenediamine compound. U.K. Patent Number 1 , 127, 127 discloses that acrylic acid can be stabilized against polymerization by the addition thereto of a nitroxide having the essential skeletal structure:

o* γi ' ?3

R-, - C c- 2 I

wherein R,, R₂, R₃, and R₄ are alkyl groups and no hydrogen is bound to the remaining valencies on the carbon atoms bound to the nitrogen. The two remaining valencies that are not satisfied by R, to R₄ or nitrogen can also form part of a ring (e.g., 2,2,6,6

tetramethyl-4-hydroxy-piperidine-l -oxyl).

CS-260755 B l is directed to the preparation of 4-substituted-2, 2,6,6- tetramethylpiperidine nitroxyls as olefin stabilizers.

SU-334845 A l is directed to the inhibition of the radical polymerization of oligoester acrylates using iminoxyl radical inhibitors of a given formula. SU-478838 is directed to the inhibition of the radical polymerization of oligoester acrylates and the prevention of oligomeric peroxides using a binary polymerization inhibitor comprising quinone.

FR 2,761,060 relates to the prevention of premature polymerization of styrene during its production by dehydrogenation of ethylbenzene by injecting into the process

effluent a radical inhibitor based on an oxyl-tetramethylpiperidine derivative.

The disclosures of the foregoing are incorporated herein by reference in their entirety. SUMMARY OF THE INVENTION

As mentioned above, (a) nitroxyl compounds and (b) quinone methides are each known to be inhibitors or retarders of free radical polymerizations of unsaturated monomers. The present invention is directed to the discovery that the combination of at

least one nitroxyl compound with at least one quinone alkide, preferably a quinone methide, having an electron withdrawing group at the 7-position provides better performance than either component alone, as indicated by both the low polymer numbers at steady state and the slow rate of polymerization after shutoff of feed in a steady state dynamic testing system. More particularly, the present invention is directed to a method for inhibiting the premature polymerization of ethylenically unsaturated monomers comprising adding to said monomers an effective amount of:

A) at least one nitroxyl compound, and

B) at least one quinone alkide compound having an electron withdrawing group at the 7-position.

In another aspect, the present invention is directed to a composition comprising:

A) at least one nitroxyl compound, and

B) at least one quinone alkide compound having an electron-withdrawing group at the 7-position,

DESCRIPTION OF THE PREFERRED EMBODIMENTS

If a relatively small amount of a quinone alkide substituted with an electron withdrawing group at the 7-position (relative to the quantity necessary for its use alone) is added to a small amount of a nitroxyl compound (relative to the quantity necessary for

its use alone), polymerization inhibition under normal usage conditions can be obtained

that is equivalent to the use of the nitroxyl compound alone (indicated by wt % polymer at steady state in a reboiler test) and provides excellent protection in the event of a plant

upset (indicated by slow polymer increase over time). This very effective inhibitor

mixture is used at very reasonable dosages, providing an economically viable

combination with enhanced performance characteristics.

The nitroxyl compounds that can be employed in combination with the quinone

alkides in the practice of the present invention are preferably of the structure:

γl γ2

^Rl - ? — ? ^{" R}4 R₂ I R₃ o*

wherein R_[ and ₄ are independently selected from the group consisting of hydrogen,

alkyl, and heteroatom-substituted alkyl and R₂ and R₃ are (1) independently selected

from the group consisting of alkyl and heteroatom-substituted alkyl, or (2) taken

together, form a ring structure with the nitrogen; and X, and X₂ (1) are independently

selected from the group consisting of halogen, phosphorus (in any of it oxidation states),

cyano, COOR₇, -S-COR₇, -OCOR₇, -S-R₇ (wherein R₇ is alkyl or aryl), amido, carbonyl,

alkenyl, or alkyl of 1 to 15 carbon atoms, or (2) taken together, form a ring structure

with the nitrogen.

Tn a particularly preferred embodiment, the nitroxyl compound has the structural

formula:

wherein R, and R₄ are independently selected from the group consisting of hydrogen, alkyl, and heteroatom-substituted alkyl and R₂ and R₃ are independently selected from the group consisting of alkyl and heteroatom-substituted alkyl, and the

portion represents the atoms necessary to form a five-, six-, or seven-membered

heterocyclic ring,

Accordingly, one of the several classes of cyclic nitroxides that can be employed in the practice of the present invention can be represented by the following structural formula:

wherein Z_1; Z₂, and Z₃ are independently selected from the group consisting of oxygen, sulfur, secondary amines, tertiary amines, phosphorus of various oxidation states, and

substituted or unsubstituted carbon atoms, such as CH₂, >CHCH₃, >C=O, >C(CH₃)₂, >CHBr, >CHC1, >CHI, >CHF, >CHOH, >CHCN, >C(OH)CN, >CHCOOH, >CHCOOCH₃, >CHCOOC₂H₅, >C(OH)COOC₂H₅, >C(OH)COOCH₃, >C(OH)CHOHC₂H₅, >CNR₅R_6, >CCONR₅R₆, >CH=NOH, >C= H-C₆H₅, >CF₂, >CC1₂, >CBr₂, >CI₂, >CPR,₃R,₄R₁₅, and the like, where R₅ and R₆ are independently selected from the group consisting of hydrogen, alkyl, aryl, and acyl and R_I R₁₄ and R₁₅ are independently selected from the group consisting of unshared electrons, alkyl, aryl, =O,

OR₁₆, and NR₁₇R_1!(, where R,₆, R₁₇ and R₁₈ are independently selected from the group

consisting of hydrogen, alkyl, and aryl. Where R₅ and/or R₀ are alkyl, it is preferred that they be a lower alkyl (i.e., one having one to four carbon atoms, e.g., methyl, ethyl, propyl, butyl, and isomers thereof^

Where R₅ and/or R₆ are aryl, it is preferred that they be aryl of from 6 to 10 carbon atoms, e.g., phenyl or naphthyl, which, in addition, may be substituted with noninterfering substituents, e.g., lower alkyl groups, halogens, and the like.

Where R₅ and/or R-^ are acyl, it is preferred that they be acyl of the structure

where R₁₉ is alkyl, aryl, OR₂₀, or NR₂₀R_2I and where R₂₀ and R₂₁ are alkyl, aryl, or

where R₂₂ is alkyl or aryl. Where R₁₉, R₂₀, R₂₁, or R₂₂ are alkyl, they are preferably alkyl of from 1 to 15 carbon atoms, more preferably lower alkyl of from one to four carbon atoms, as described above, Where R₁₉, R₂₀, R₂₁, or R₂₂ are aryl, they are preferably aryl of from 6 to 10 carbon atoms, as described above.

Another of the several classes of cyclic nitroxides that can be employed in the practice of the present invention can be represented by the following structural formula:

- u wherein Z, and Z₂, which may be the same or different, are nitrogen or substituted or unsubstituted carbon atoms, such as =C(H)-, =C(CH₃)-, =C(COOH)-, =C(COOCH₃)-,

=C(COOC₂H₅)- =C(OH)-, =C(CN)-, -C(NR₅R₆)- =C(CONR₅R₆>, and the like, and where Z₃, R₅, and R₆ are as described above.

The cyclic nitroxides employed in the practice of the present invention can also be derived from five-membered rings. These compounds are of the structure:

wherein Z₂ and Z₃, which may be the same or different, are sulfur, oxygen, secondary amines, tertiary amines, phosphorus of various oxidation states, or substituted or unsubstituted carbon atoms, such as >CH₂, >CHCH₃, >C=O, >C(CH₃)₂, >CHBr, >CHC1, >CHI, >CHF, >CHOH, >CHCN, >C(OH)CN, >CHCOOH, >CHCOOCH₃, >CHCOOC₂H₅, >C(OH)COOC₂H₅, >C(OH)COOCH₃, >C(OH)CHOHC₂H₅, >CNR₅R_6> >CCONR₅R₆, >CH=NOH, >C=CH-C₆H₅, CF₂, CC1₂, CBr₂, CI₂, >CPR₁₃R,₄R₁₅, and the like, wherein the several R groups are as described above.

The cyclic nitroxides employed in the practice of the present invention can also

have the structure;

wherein Z and Z₅, which can be the same or dilTerent, can be nitrogen or a substituted

or unsubstituted carbon atom, such as =C(H)-, =C(CH _)., =C(COOH)-, =C(COOCH₃)- =C(COOC₂H₅)- =C(OH)-, -C(CN)-, =C(NR₅R_ή)-_, =C(CONR₅R_f , and the like, where R₅ and R₆ are as described above.

Another class of cyclic nitroxides that can be employed in the practice of the present invention is of the structure:

wherein Z₂ and Z₃, which may be the same or different, are sulfur, oxygen, secondary amines, tertiary amines, or substituted or unsubstituted carbon atoms, such as >CH₂, >CHCH₃, >C=O, >C(CH₃)₂, >CHBr, >CHC1, >CHI, >CHF, >CHOH, >CHCN, >C(OH)CN, >CHCOOH, >CHCOOCH₃, >CHCOOC₂H₅, >C(OH)COOC₂H₅, >C(OH)COOCH₃, >C(OH)CHOHC₂H₅, >CNR₅R₆ >CCONR₅R₆, >CH=NOH, >C=CH- C₆H₅, CF₂, CC1₂, CBr₂, CI₂, and the like, where R₅ and R₆ are as described above, Further, two or more nitroxyl groups can be present in the same molecule, for example, by being linked through one or more of the Z-type moieties by a linking group E, as disclosed in U.S. Patent Number 5J54J60, which is incorporated herein by

reference.

As stated above, R, and R₄ are independently selected from the group consisting of hydrogen, alkyl, and heteroatom-substituted alkyl and R₂ and R₃ are independently selected from the group consisting of alkyl and heteroatom-substituted alkyl. The alkyl

(or heteroatom-substituted alkyl) groups R, through R can be the same or different and preferably contain 1 to 15 carbon atoms, e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl,

heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and the

like, and isomers thereof, e,g., t-butyl, 2-ethylhexyl, and the like. It is more preferred that R, through R₄ be independently selected lower alkyl (or heteroatom-substituted lower alkyl) of one to four carbon atoms (e.g., methyl, ethyl, propyl, butyl, and isomers thereof). Where heteroatom substituents are present, they can, for example, include halogen, oxygen, sulfur, nitrogen, and the like. It is most preferred that all of R, through R₄ be methyl.

Examples of suitable nitroxide free radical compounds that can be used in combination with the quinone alkide inhibitor in the practice of the present invention, include, but are not limited to:

2,2,6,6-tetramethyl-piperidinyloxy; 4-amino-2,2,6,6-tetramethyl-piperidinyloxy;

4-hydroxy-2J,6,6-tetramethyl-piperidinyloxy;

4-oxo-2J,6,6-tetramethyl-piperidinyloxy;

4-dimethylamino-2J,6,6-tetramethyl-piperidinyloxy;

4-ethanoyloxy-2,2,6,6-tetramethyl-piperidinyloxy; 2,2,5,5-tetramethylpyrrolidinyloxy;

3-amino-2J,5,5-tetramethylpyrrolidinyloxy;

2J,4,4-tetramethyl-l-oxa-3-azacyclopentyl-3-oxy;

2J,4,4-tetramethyl- l-oxa-3-pyrrolinyl-l-oxy-3-carboxylic acid;

2,2,3,3,5,5,6,6-octamethyl- l,4-diazacyclohexyl- l,4-dioxy;

4-bromo-2,2,6,6-tetramethyl-piperidinyloxy;

4-chloro-2J,6,6-tetramethyl-piperidinyloxy;

4-iodo-2J,6,6-tetramethyl-piperidinyloxy;

4-fluoro~2,2,6,6-tetramethyl-piperidinyloxy;

4-cyano-2J,6,6-tetramethyl-piperidinyloxy;

4-carboxy-2J,6,6-tetramethyl-piperi(linyloxy; -carbomethoxy-2J,6,6-tetramethyl-piperidinyloxy; -carbethoxy-2J,6,6-tetramethyl-piperidinyloxy;

-cyano-4-hydroxy-2J,6,6-tetramethyl-piperidinyloxy; -methyl-2J,6,6-tetramethyl-piperidinyloxy; -carbethoxy-4-hydroxy-2J,6,6-tetramethyl-piperidinyloxy; -hydroxy-4-(l-hydroxypropyl)-2J,6,6-tetramethyl-piperidinyloxy; -methyl-2,2,6,6-tetramethyl- l ,2,5,6-tetrahydropyridine -1-oxyl; -carboxy-2J,6,6-tetramethyl-l ,2,5,6-tetrahydropyridine -1-oxyl; -carbomethoxy-2J,6,6-tetramethyl- 1 ,2,5,6-tetrahydropyridine - 1 -oxyl; -carbethoxy-2J,6,6-tetramethyl- 1 ,2,5,6-tetrahydropyridine - 1 -oxyl; -amino-2J, 6, 6-tetramethyl-l ,2,5,6-tetrahydropyridine - 1-oxyl; -amido-2J,6,6-tetramethyl- 1 ,2,5,6-tetrahydropyridine - 1 -oxyl; ,4-diketo-2J,5,5-tetramethylpyrroIidinyloxy; -keto-4-oximino-2J,5,5-tetramethylpyrrolidinyloxy; -keto-4-benzylidine-2J,5,5-tetramethylpyrrolidinyloxy;

-keto-4,4-dibromo-2J,5,5-tetramethylpyrrolidinyloxy; ,2JJ,5,5-hexamethylpyrrolidinyloxy;

-carboximido-2J,5,5-tetramethylpyrrolidinyloxy; -oximino-2J,5,5-tetramethylpyrrolidinyloxy; -hydroxy-2J,5,5-tetramethylpyrrolidinyloxy; -cyano-3-hydroxy-2J,5,5-tetramethylpyrrolidinyloxy; -carbomethoxy-3-hydroxy-2J,5,5-tetramethylpyrrolidinyloxy; -carbethoxy-3-hydroxy-2J,5,5-tetramethylpyrrolidinyloxy;

,2,5,5-tetramethyl-3-carboxamido-2,5-dihydropyrrole- 1 -oxyl;

,2,5,5-tetramethyl-3-amino-2,5-dihydiOpyrrole- 1 -oxyl; 2J,5,5-tetramethyl-3-carbethoxy-2,5-dihydropyrrole- 1-oxyl;

2J,5,5-tetramethyl-3-cyano-2,5-dihydropyrrole- 1 -oxyl; bis(l-oxyl-2J,6,6-tetramethylpiperidin-4-yl)succinate; bis(l-oxyl-2J,6,6-tetramethylpiperidin-4-yl)adipate; bis(l-oxyl-2J,6,6-tetramethylpiperidin-4-yl)sebacate; bis(l -oxyl-2J,6,6-tetramethylpiperidin-4-yl)n-butylmalonate;

bis( 1 -oxyl-2J,6,6-tetramethylpiperidin-4-yl)phthalate; bis( 1 -oxyl-2J,6,6-tetramethylpiperidin-4-yl)isophthalate; bis(l-oxyl-2J,6,6-tetramethylpiperidϊn-4-yl)terephthalate; bis(l-oxyl-2J,6,6-tetramethylpiperidin-4-yl)hexahydroterephthalate;

N,N'-bis(l-oxyl-2J,6,6~tetramethylpiperidin-4-yl)adipamide;

N-(l -oxyl-2J,6,6-tetramethylpiperidin-4-yl)-caprolactam;

N-(l-oxyl-2J,6,6-tetramethylpiperidin-4-yl)-dodecylsuGcinimide;

2,4,6-tris-[N-butyl-N-(l -oxyl-2J,6,6-tetramethylpiperidin-4-yl)]-s-triazine;

4,4'-ethylenebis(l-oxyl-2J,6,6-tetramethylpiperazin-3-one); and the like,

It is preferred that one member of the combination employed in the practice of

the present invention be 4-amino-2J,6,6-tetramethyl-piperidinyloxy (4-amino-TEMPO),

4-oxo-2J,6, 6-tetramethylpiperidinyloxy (4-oxo-TEMPO), 4-hydroxy-2J,6,6-

tetramethylpiperidinyloxy (4-hydroxy-TEMPO), or 2,2,6,6-tetramethyl-piperidinyloxy (TEMPO).

Blends of two or more of the foregoing, e.g., 4-amino-TEMPO and 4-oxo- TEMPO, can also be employed.

.8 - Such stable nitroxide free radical compounds can be prepared by known methods. (See, for example, U.S. Patent Numbers 3, 163,677; 3,334, 103; 3,372, 182; 3,422, 144; 3,494,930; 3,502,692; 3,873,564; 3,966,71 1 ; and 4,665, 185; which are incorporated herein by reference.) They are suitable for use over a wide range of temperatures, but distillation temperatures employed with the ethylenically unsaturated monomers that are stabilized by the process of the present invention typically range from about 60°C to about 180°C, preferably from about 70°C to about 165°C, and, more preferably, from about 80°C to about 150°C. Such distillations are generally performed at an absolute pressure in the range of about 10 to about 1 ,200 mm of Hg.

Quinone alkide compounds that are useful in the practice of the present invention include those disclosed in, for example, U.S. Patent No. 5,583,247. More specifically, it is preferred that the quinone alkide be a compound of formula

wherein:

R₃₁ and R₃₂ are independently alkyl of 4 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms or phenylalkyl of 7 to 15 carbon atoms, and

R₃₃ is -CN, -COOH, -COOR₃ , -COR₃₅, -OCOR_3G, -CONR₃₇R₃₈ or -PO(OR₃₉)₂ where R₃ is alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl or

benzyl,

R₃₅ is alkyl of 1 to 18 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted

by 1 or 2 alkyl of 1 to 4 carbon atoms or by hydrυxyl, R₃₆ is alkyl of 1 to 18 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by 1 or 2 alkyl of 1 to 4 carbon atoms or by hydroxyl,

R₃₇ and R₃₈ are independently hydrogen, alkyl of 1 to 18 carbon atoms or said alkyl substituted by alkylamino of 1 to 4 carbon atoms, by dialkylamino of 2 to 8 carbon

atoms or by hydroxyl; benzyl, aryl of 6 to 10 carbon atoms or said aryl substituted by alkyl of 1 to 4 carbon atoms, by alkylamino of 1 to 4 carbon atoms, by dialkylamino of 2 to 8 carbon atoms, by phenylamino or by hydroxyl, or

-NR₃₇R₃₈ is morpholino, piperidino or pyrrolidino,

R₃₉ is hydrogen or alkyl of 1 to 18 carbon atoms, and

R₄₀ is hydrogen, alkyl, aryl, hydroxyl, alkoxy, -CN, -COOH, -COOR₃₄, -COR₃₅,

-OCOR₃₆, -CONR₃₇R₃₈ or -PO(OR₃₉)₂.

Preferably, R₃, and R₃₂ are tert-butyl, tert-amyl, tert-octyl, cyclohexyl, α- methylbenzyl or α,oi-dimethylbenzyl.

Most preferably, R₃₁ and R₃₂ are tert-butyl, tert-amyl or tert-octyl, Preferably, R₃₃ is -CN, -COOH, -COOR₃₄, -COR₃₅, -OCOR₃₆, -CONR₃₇R₃₈ or

-PO(OR₃₉)₂ wherein:

R₃₄ is alkyl of 1 to 8 carbon atoms,

R₃₅ is methyl or phenyl,

R₃₆ is alkyl of 1 to 18 carbon atoms or phenyl, R₃₇ and R₃₈ are independently hydrogen or alkyl of 1 to 18 carbon atoms, or

-NR₃₇R_3S is morpholino or piperidino, and

R₃₉ is alkyl of 1 to 4 carbon atoms.

Most preferably, R₃₃ is -CN, -COOH, -COOR₃₄, -COR₃₅, -OCOR_3β,

-CONR₃₇R_3!! or -PO(OR₃₉)₂ wherein:

R₃₄ is alkyl of 1 to 4 carbon atoms, R₃₅ is methyl or phenyl,

R₃₇ and R₃₈ are independently hydrogen or alkyl of 1 to 4 carbon atoms, or

-NR₃₇R ₈ is morpholino, and

R₃₉ is alkyl of 1 to 4 carbon atoms, Preferably, the quinone alkides of the present invention are selected from the group consisting of:

(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)acetonitrile,

(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)acetic acid,

(3,5-di-tert-amyl-4-oxocyclohexa-2,5-dienylidene)acetic acid, methyl (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)acetate, ethyl (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)acetate, n-butyl (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)acetate,

2,6-di-tert-butyl-4-(2-oxopropylidene)-cyclohexa-2,5-dienone, diethyl (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)methanephosphonate, (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)methyl acetate,

(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)methyl pivalate,

(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)methyl benzoate, and

N,N-diethyl-2-(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)acetamide.

The quinone alkides of the present invention can, if desired, be combined with a 7-aryl quinone alkide, such as those described in U.S. Patent No, 5,616,774, Preferably, such 7-aryl quinone alkides can be those of the formula:

wherein

E, and E₂ are independently alkyl of 4 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms or phenylalkyl of 7 to 15 carbon atoms, and

E₃ is 2-, 3- or 4-pyridyl, 2- 3-thienyl, 2- 3-pyrryl, 2- 3-furyl, aryl of 6 to 10 carbon atoms, or said aryl substituted by one to three alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms, alkylthio of 1 to 8 carbon atoms, alkylamino of 1 to 8 carbon atoms, dialkylamino of 2 to 8 carbon atoms, alkoxycarbonyl of 2 to 8 carbon atoms, hydroxy, nitro, amino, cyano, carboxy, aminocarbonyl, chloro or mixtures of said substituents.

Preferably such compounds are selected from the group consisting of: 2,6-di-tert-butyl-4-benzylidene-cyclohexa-2,5-dienone, 2,6-di-tert-butyl-4-(4-nitrobenzylidene)-cyclohexa-2,5-dienone, 2,6-di-tert-butyl-4-(3-nitrobenzylidene)-cyclohexa-2,5-dienone, 2,6-di-tert-butyl-4-(4-cyanobenzylidene)-cyclohexa-2,5-dienone, 2,6-di-tert-butyl-4-(4-dimethylaminobenzylidene)-cyclohexa-2,5-dienone, 2,6-di-tert-amyl-4-benzylidene-cyclohexa-2,5-dienone, 2,6-di-tert-butyl-4-(4-methoxybenzylidene)-cycIohexa-2,5-dienone, and

2,6-di-tert-butyl-4-(3,5-di-tert-butyl-4-hydroxybenzylidene)-cyclohexa-2,5- dienone.

9? The effective amount of the combination of (i) nitroxyl compound and (ii) quinone alkide compound is typically about 1 to 2,000 ppm, based on the weight of the ethylenically unsaturated monomer, although amounts outside this range may be appropriate depending upon the conditions of use. The amount of the combination of nitroxyl compound and quinone alkide is preferably about 5 to about 1 ,000 ppm, based on the weight of the ethylenically unsaturated monomer,

The preferred amounts of components (i) and (ii) are 1 to 99 percent by weight of component (i) and, correspondingly, 99 to 1 percent by weight of component (ii); more preferably, 20 to 80 percent by weight of component (i) and, correspondingly, 80 to 20 percent by weight of component (ii); and most preferably, 20-50 percent by weight of component (i) and 50-80 percent by weight of component (ii).

The inhibitor combination of the present invention is suitable for use over a wide range of temperatures, but distillation temperatures employed with the ethylenically unsaturated monomers that are stabilized by the process of the present invention typically range from about 60° C to about 180° C, preferably from about 70° C to about

165° C, and, more preferably, from about 80° C to about 150° C, Such distillations are generally performed at an absolute pressure in the range of about 10 to about 1,200 mm ofHg.

The ethylenically unsaturated monomer, the premature polymerization of which is an object of the present invention, can be any such monomer for which unintended polymerization during its manufacture, storage, and/or distribution is a problem, Among those monomers that will benefit from the practice of the present invention are: styrene, oc-methylstyrene, styrene sulfonic acid, vinyltoluene, divinylbenzenes, polyvinylbenzenes, alkylated styrene, 2-vinylpyridine, acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, acrylic acid, methacrylic acid, butadiene, chloroprene, isoprene, and the like.

The ethylenically unsaturated monomers will not necessarily be stabilized indefinitely by the presence of the inhibitor blend, especially when the monomers are heated as in distillation, but they can be considered to be stabilized as long as there is a measurable increase in the time for which they can be heated before the onset of polymerization in a static system and/or the amount of polymer made at constant temperature remains constant over time in a dynamic system.

Those skilled in the art will understand that, if desired, additional free radical scavengers can be included in the stabilized compositions. For example, air or O₂, as disclosed in U.S. Patent Numbers 5,545,782 and 5,545,786, can be added, as can the aromatic nitro compounds disclosed in U.S. Patent Number 5,254,760, the dihetero- substituted benzene compounds having at least one transferable hydrogen, e.g., a quinone derivative such as the mono-methyl-ether of hydroquinone disclosed in European Patent Application 0 765 856 Al, and other inhibitors, e.g., phenolics and certain inorganic salts, well-known to those skilled in the art,

The polymerization inhibitor composition can be introduced into the monomer to be protected by any conventional method. It can be added as a concentrated solution in suitable solvents just upstream from the point of desired application by any suitable means, For example, the individual inhibiting components can be injected separately or in combination to the monomer feed tank prior to injection into a distillation train. The individual inhibiting components can also be injected separately into the distillation train along with the incoming feed or through separate entry points, provided there is an efficient distribution of the inhibitors. Since the inhibitors are gradually depleted during the distillation operation, it is generally advantageous to maintain the appropriate amount of the inhibitor mixture in the distillation apparatus by adding inhibitors during the course of the distillation process, Adding inhibitors can be done either on a generally continuous basis or intermittently, in order to maintain the concentration of inhibitor mixture above the minimum required level. The advantages and the important features of the present invention will be more apparent from the following examples. EXAMPLES Procedure for Dynamic Reboiler Test with Feed Shut-Off Preparation of Feed Solution.

T-Butylcatechol (TBC) is removed from commercially available styrene by distillation under vacuum. Removal of TBC is verified by caustic titration. The desired amount of inhibitor(s) is added to this TBC-free styrene either directly or by first making a concentrated solution of the inhibitor in TBC-free styrene followed by further dilution with TBC-free styrene. Procedure for Reboiler Test. A quantity of the Feed Solution containing inhibitor (blend) at the desired charge

(stated as a wt/wt total inhibitor to styrene) is added to a round-bottom flask (the "Pot") and heated to the desired temperature (usually 1 16° C) and brought to reflux by adjusting the pressure/vacuum. Once the Pot contents are at temperature, a continuous stream of fresh Feed Solution is begun at a rate that will add the volume of the initial Pot solution to the Pot over a period of time called the residence time (typically one hour).

At the same time that the fresh Feed Solution flow is begun, the Bottoms Stream flow is also begun. The Bottoms Stream is solution in the Pot that is removed at the same rate as the fresh Feed Solution is added. The equal flows of Feed and Bottoms streams cause the quantity in the Pot to remain constant over the time of the experiment while allowing continuous replenishment of inhibitor. This procedure simulates the way inhibitors are used in a distillation train of a plant producing vinyl monomers. The experiment continues with flow in and out of the Pot for a specified period of time, typically seven hours. Samples are collected hourly from the Bottoms Stream, These samples are analyzed for polymer content via the methanol turbidity method. The amount of polymer in the samples is an indication of effectiveness of the inhibitor being tested. The lower the amount of polymer in the hourly samples, the more effective the inhibiting system should be during normal operation of a continuous manufacturing or purification process. Procedure for Feed Shut-Off.

At the end of the Reboiler Test Run (typically seven hours), a sample is collected from the Bottoms Stream. This sample corresponds to Feed Shut-Off Time = 0 minutes. The flows of fresh Feed Solution and Bottoms Stream are stopped. The vacuum and temperature are monitored and adjusted to maintain boiling at the desired temperature of the experiment, Samples are periodically removed from the Pot (typically every five minutes). These samples are analyzed for polymer content via the methanol turbidity method. A longer period of time before initiation of significant polymer formation is an indication of a more effective inhibiting system in the event of a loss of feed in the plant. Additionally, the lower the polymer number at a specific length of time after feed shut-off, the more effective the inhibitor system at providing protection for that length of time,

The results in Table 1 show that the performance of the combination of nitroxyl with quinone alkide is improved compared to either component alone in both steady state and feed shut-off tests. Thus, this blend should provide improved performance under both normal and upset operating conditions in a plant.

QM acid is 3,5-di-t-butyl-4-oxo-cyclohexa-2,5-dienylidene acetic acid, the structure of which is

QM ester is ethyl 3,5-di-tert-butyl-4-oxo-cyclohexa-2,5-dienylidene acetate,

In view of the many changes and modifications that can be made without departing from principles underlying the invention, reference should be made to the appended claims for an understanding of the scope of the protection to be afforded the invention.

Claims

What is claimed is"

1 , A method for inhibiting the premature polymerization of ethylenically unsaturated monomers comprising adding to said monomers an effective amount of: A) at least one nitroxyl compound, and B) at least one quinone alkide compound having an electron withdrawing group at the 7-position.

2. The method of claim 1 wherein the nitroxyl compound is of the structure:

γl _T2

^■ c . . C - R

I

R , R -,

wherein R, and R₄ are independently selected from the group consisting of hydrogen, alkyl, and heteroatom-substituted alkyl and R₂ and R₃ are (1) independently selected from the group consisting of alkyl and heteroatom-substituted alkyl, or (2) taken together, form a ring structure with the nitrogen; and X, and X₂ (1) are independently selected from the group consisting of halogen, phosphorus (in any of it oxidation states), cyano, COOR₇, -S-COR₇₎ -OCOR₇, -S-R₇ (wherein R₇ is alkyl or aryl), amido, carbonyl, alkenyl, or alkyl of 1 to 15 carbon atoms, or (2) taken together, form a ring structure with the nitrogen.

3. The method of claim 2 wherein the nitroxyl compound has the structural formula:

wherein R, and R₄ are independently selected from the group consisting of hydrogen, alkyl, and heteroatom-substituted alkyl and R, and R₃ are independently selected from the group consisting of alkyl and heteroatom-substituted alkyl, and the

portion represents the atoms necessary to form a five-, six-, or seven-membered heterocyclic ring.

4. The method of claim 1 wherein the nitroxyl compound is selected from the group consisting of: 2,2,6,6-tetramethyl-piperidinyloxy; 4~amino-2J,6,6-tetramethyl-piperidinyloxy; 4-hydroxy-2J, 6, 6-tetramethyl-piperidinyloxy; 4-oxo-2,2, 6, 6-tetramethyl-piperidinyloxy; 4-dimethylamino-2J,6,6-tetramethyl-piperidinyloxy; 4-ethanoyloxy-2,2, 6, 6-tetramethyl-piperidinyloxy; 2,2,5,5-tetramethylpyrrolidinyloxy; 3-amino-2J,5,5-tetramethylpyrrolidinyloxy; 2,2,4, 4-tetramethyl- 1 -oxa-3-azacyclopentyl-3-oxy; 2,2,4,4-tetramethyl- l -oxa-3-pyrrolinyl- l-oxy-3-carboxylic acid; 2,2,3,3,5,5,6,6-octamethyl- 1 ,4-diazacyclohexyl- 1 ,4-dioxy; 4-bromo-2,2, 6, 6-tetramethyl-piperidinyloxy; 4-chloro-2J, 6, 6-tetramethyl-piperidinyloxy; 4-iodo-2J, 6, 6-tetramethyl-piperidinyloxy; 4-fluoro-2J, 6, 6-tetramethyl-piperidinyloxy; 4-cyano-2J,6,6-tetramethyl-piperidinyloxy; 4-carboxy-2J, 6, 6-tetramethyl-piperidinyloxy; 4-carbomethoxy-2J, 6, 6-tetramethyl-piperidinyloxy; 4-carbethoxy-2,2, 6, 6-tetramethyl-piperidinyloxy; 4-cyano-4-hydroxy-2J, 6, 6-tetramethyl-piperidinyloxy; 4-methyl-2J, 6, 6-tetramethyl-piperidinyloxy; 4-carbethoxy-4-hydroxy-2J, 6, 6-tetramethyl-piperidinyloxy; 4-hydroxy-4-( 1 -hydroxypropyl)-2,2, 6, 6-tetramethyl-piperidinyloxy; 4-methyl-2J,6,6-tetramethyl- l ,2,5,6-tetrahydropyridine - 1-oxyl; 4-carboxy-2J,6,6-tetramethyl- l ,2,5,6-tetrahydropyridine -1-oxyl; 4-carbomethoxy-2J,6,6-tetramethyl-l ,2,5,6-tetrahydropyridine -1-oxyl; 4-carbethoxy-2,2,6,6-tetramethyl- 1 ,2,5,6-tetrahydropyridine - 1 -oxyl; 4-amino-2,2,6,6-tetramethyl-l ,2,5,6-tetrahydropyridine - 1-oxyl; 4-amido-2J,6,6-tetramethyl- 1 ,2,5,6-tetrahydropyridine - 1 -oxyl; 3,4-diketo-2J,5,5-tetramethylpyrrolidinyloxy; 3-keto-4-oximino-2J,5,5-tetramethylpyrrolidinyloxy; 3-keto-4-benzylidine-2J,5,5-tetramethylpyrrolidinyloxy; 3-keto-4,4-dibromo-2J,5,5-tetramethylpyrrolidinyloxy; 2,2,3,3, 5, 5-hexamethylpyrrolidinyloxy; 3-carboximido-2J,5,5-tetramethylpyrrolidinyloxy; 3-oximino-2J,5,5-tetramethylpyrrolidinyloxy; 3-hydroxy-2J,5,5-tetramethylpyrrolidinyloxy; 3-cyano-3-hydroxy-2J,5,5-tetramethylpyrrolidinyloxy; 3-carbomethoxy-3-hydroxy-2J,5,5-tetramethylpyrrolidinyloxy; 3-carbethoxy-3-hydroxy-2J,5,5-tetramethylpyrrolidinyloxy; 2J,5,5-tetramethyl-3-carboxamido-2,5-dihydropyrrole- 1 -oxyl; 2J,5,5-tetramethyl-3-amino-2,5-dihydropyrrole- 1 -oxyl; 2J,5,5-tetramethyl-3-carbethoxy-2,5-dihydropyrrole- 1-oxyl; 2,2, 5, 5-tetramethyl-3-cyano-2,

5-dihydropyrrole- 1-oxyl; bis( 1 -oxyl-2J,6,6-tetraιnethylpiperidin-4-yl)succinate; bis(l -oxyl-2J,6,6-tetramethylpiperidin-4-yl)adipate; bis(l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)sebacate; bis( 1 -oxyI-2J,6,6-tetramethylpiperidin-4-yl)n-butylmalonate; bis( l-oxyl-2J,6,6-tetramethylpiperidin-4-yl)phthalate; bis( 1 -oxyl-2J,6,6-tetramethylpiperidin-4-yl)isophthalate; bis( 1 -oxyl-2J,6,6-tetramethylpiperidin-4-yl)terephthalate; bis(l -oxyl-2J,6,6-tetramethylpiperidin-4-yl)hexahydroterephthalate; N,N'-bis(l-oxyl-2J,6,6-tetramethylpiperidin-4-yl)adipamide; N-(l -oxyl-2J,6,6-tetramethylpiperidin-4-yl)-caprolactam; N-(l -oxyl-2J,6,6-tetramethylpiperidin-4-yl)-dodecylsuccinimide; 2,4,6-tris-[N-butyl-N-( l -oxyl-2J,6,6-tetramethylpiperidin-4-yl)]-s-triazine; and 4,4'-ethylenebis(l -oxyl-2,2,6,6-tetramethylpiperazin-3-one).

The method of claim 1 wherein the quinone alkide is a compound of the formula

wherein:

R₃₃ is -CN, -COOH, -COOR₃₄, -COR₃₅, -OCOR_3β, -CONR₃₇R₃₈ or -PO(OR₃₉)₂ where

R₃₄ is alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl or benzyl,

R₃₅ is alkyl of 1 to 18 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by 1 or 2 alkyl of 1 to 4 carbon atoms or by hydroxyl,

R₃₆ is alkyl of 1 to 18 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by 1 or 2 alkyl of 1 to 4 carbon atoms or by hydroxyl, R₃₇ and R₃₈ are independently hydrogen, alkyl of 1 to 18 carbon atoms or said alkyl substituted by alkylamino of 1 to 4 carbon atoms, by dialkylamino of 2 to 8 carbon atoms or by hydroxyl; benzyl, aryl of 6 to 10 carbon atoms or said aryl substituted by alkyl of 1 to 4 carbon atoms, by alkylamino of 1 to 4 carbon atoms, by dialkylamino of 2 to 8 carbon atoms, by phenylamino or by hydroxyl, or -NR₃₇R₃₈ is morpholino, piperidino or pyrrolidino, R₃₉ is hydrogen or alkyl of 1 to 18 carbon atoms, and R₄₀ is hydrogen, alkyl, aryl, hydroxyl, alkoxy, -CN, -COOH, -COOR₃₄, -COR₃₅, -OCOR₃₆, -CONR₃₇R₃₈ or -PO(OR₃₉)₂.

6. The method of claim 5 wherein the quinone alkide is selected from the group consisting of: (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)acetonitrile, (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)acetic acid, (3,5-di-tert-amyl-4-oxocyclohexa-2,5-dienylidene)acetic acid, methyl (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)acetate, ethyl (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)acetate, n-butyl (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)acetate, 2,6-di-tert-butyl-4-(2-oxopropylidene)-cyclohexa-2,5-dienone, diethyl (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)methanephosphonate, (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)methyl acetate, (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)methyl pivalate, (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)methyl benzoate, and N,N-diethyl-2-(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)acetamide.

7 A method for inhibiting the premature polymerization of ethylenically unsaturated monomers comprising adding to said monomers an effective amount of A) at least one nitroxyl compound of the structure

ϊⁱ

C - R ,

R₂ I O *

wherein R, and R₄ are independently selected from the group consisting of hydrogen, alkyl, and heteroatom-substituted alkyl and R₂ and R₃ are (1) independently selected from the group consisting of alkyl and heteroatom-substituted alkyl, or (2) taken together, form a nng structure with the nitrogen, and X, and X₂ (1) are independently selected from the group consisting of halogen, phosphorus (in any of it oxidation states), cyano, COOR₇, -S-COR₇, -OCOR₇, -S-R₇ (wheiein R₇ is alkyl or aryl), amido, carbonyl, alkenyl, or alkyl of 1 to 15 carbon atoms, or (2) taken together, form a ring structure with the nitrogen, and

B) at least one quinone alkide compound of the formula

wherein

R₃₁ and R₃₂ are independently alkyl of 4 to 18 caibon atoms, cycloalkyl of 5 to 12 carbon atoms oi phenylalkyl of 7 to 15 carbon atoms, and

R₃₃ is -CN, -COOH, -COOR,₄ -COR₃₅, -OCOR_v>, -CONR₃₇R₃₈ or -PO(OR₃₉)₂ where

R₃₄ is alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl or benzyl, R₃₅ is alkyl of 1 to 1 8 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by 1 or 2 alkyl of 1 to 4 cai bon atoms or by hydi oxyl, R₃₆ is alkyl of 1 to 18 carbon atoms aryl of 6 to 10 caibon atoms or said aryl substituted by 1 or 2 alkyl of 1 to 4 carbon atoms or by hydroxyl, R₃₇ and R₃₈ are independently hydrogen, alkyl of 1 to 18 carbon atoms or said alkyl substituted by alkylamino of 1 to 4 carbon atoms, by dialkylamino of 2 to 8 carbon atoms or by hydroxyl, benzyl, aryl of 6 to 10 carbon atoms or said aryl substituted by alkyl of 1 to 4 carbon atoms, by alkylamino of 1 to 4 carbon atoms, by dialkylamino of 2 to 8 carbon atoms, by phenylamino or by hydroxyl, or -NR₃₇R₃₈ is morpholino, piperidino or pyrrolidmo, R₃₉ is hydrogen or alkyl of 1 to 18 carbon atoms, and R₄₀ is hydrogen, alkyl, aryl, hydroxyl, alkoxy, -CN, -COOH, -COOR₃₄, -COR₃₅, -OCOR₃₆, -CONR„R₃₈ or -PO(OR,₉),

8 The method of claim 1 cai πed out in the presence of oxygen

9 The method of claim 7 carried out in the presence of oxygen

10 A composition comprising A) at least one nitroxyl compound, and B) at least one quinone alkide compound having an electron-withdrawing group at the 7-posιtιon

1 1 The composition of claim 10 wherein the nitroxyl compound is of the structure

]4 - wherein R, and R₄ are independently selected fiom the group consisting of hydrogen, alkyl, and heteroatom-substituted alkyl and R, and R₃ are ( 1) independently selected from the group consisting of alkyl and heteroatom-substituted alkyl, or (2) taken together, form a ring structure with the nitrogen; and X, and X₂ (1) are independently selected from the group consisting of halogen, phosphorus (in any of it oxidation states), cyano, COOR₇, -S-COR₇, -OCOR₇, -S-R₇ (wherein R₇ is alkyl or aryl), amido, carbonyl, alkenyl, or alkyl of 1 to 15 carbon atoms, or (2) taken together, form a ring structure with the nitrogen,

12 The composition of claim 1 1 wherein the nitioxyl compound has the structural formula.

wherein K and R₄ are independently selected from the group consisting of hydrogen, alkyl, and heteroatom-substituted alkyl and R₂ and R are independently selected from the group consisting of alkyl and heteroatom-substituted alkyl, and the

13. The composition of claim 10 wherein the nitroxyl compound is selected from the group consisting of 2,2,6,6-tetramethyl-piperidinyloxy; 4-amino-2J, 6, 6-tetramethyl-piperidinyloxy, 4-hydroxy-2J,6,6-tetramethyl-piρeιidinyloxy; 4-oxo-2J,6,6-tetramethyl-pipeι idinyloxy, -dimethylamino-2J, 6, 6-tetramethyl-piperidinyloxy; -ethanoyloxy-2J, 6, 6-tetramethyl-piperidinyloxy; ,2,5,5-tetramethylpyrrolidinyloxy; -amino-2J,5,5-tetramethylpyrrolidinyloxy; ,2,4,4-tetramethyl- l-oxa-3-azacyclopentyl-3-oxy; ,2,4,4-tetramethyl- l-oxa-3-pyrrolinyl-l -oxy-3-carboxylic acid; ,2,3,3, 5,5, 6,6-octamethyl-l,4-diazacyclohexyl- l ,4-dioxy; -bromo-2,2, 6, 6-tetramethyl-piperidinyloxy; -chloro-2,2, 6, 6-tetramethyl-piperidinyloxy; -iodo-2J,6,6-tetramethyl-piperidinyloxy; -fluoro-2J, 6, 6-tetramethyl-piperidinyloxy; -cyano-2,2,6,6-tetramethyl-piperidinyloxy; -carboxy-2J, 6, 6-tetramethyl-piperidinyloxy; -carbomethoxy-2J, 6, 6-tetramethyl-piperidinyloxy; -carbethoxy-2J, 6, 6-tetramethyl-piperidinyloxy; -cyano-4-hydroxy-2J,6,6-tetramethyl-piperidinyloxy; -methyl-2,2, 6, 6-tetramethyl-piperidinyloxy; -carbethoxy-4-hydroxy-2J, 6, 6-tetramethyl-piperidinyloxy; -hydroxy-4-(l-hydroxypropyl)-2,2, 6, 6-tetramethyl-piperidinyloxy; -methyl-2,2,6,6-tetramethyl- 1 ,2,5,6-tetrahydropyridine - 1 -oxyl; -carboxy-2,2,6,6-tetramethyl- 1 ,2,5,6-tetrahydropyridine - 1 -oxyl; -carbomethoxy-2J,6,6-tetramethyl- 1 ,2,5,6-tetrahydropyridine - 1 -oxyl; -carbethoxy-2J,6,6-tetramethyl- l ,2,5,6-tetrahydropyridine - 1-oxyl; -amino-2J,6,6-tetramethyl-l ,2,5,6-tetrahydropyridine - 1-oxyl; -amido-2J,6,6-tetramethyl- l ,2,5,6-tetrahydropyridine - 1 -oxyl; ,4-diketo-2J,5,5-tetramethylpyrrolidinyloxy; -keto-4-oximino-2J,5,5-tetramethylpyrrolidinyloxy; -keto-4-benzylidine-2J,5,5-tetramethylpyrrolidinyloxy; -keto-4,4-dibromo-2J,5,5-tetramethylpyriOlidinyloxy; 2,2,3,3,5,5-hexamethylpyrrolidinyloxy; 3-carboximido-2J,5,5-tetramethylpyrrolidinyloxy; 3-oximino-2J,5,5-tetramethylpyrrolidinyloxy; 3-hydroxy-2,2,5,5-tetramethylpyrrolidinyloxy; 3-cyano-3-hydroxy-2J,5,5-tetramethylpyrroiidinyloxy; 3-carbomethoxy-3-hydroxy-2J,5,5-tetramethylpyrrolidinyloxy; 3-carbethoxy-3-hydroxy-2J,5,5-tetramethylpyrrolidinyloxy; 2J,5,5-tetramethyl-3-carboxamido-2,5-dihydropyrrole- 1 -oxyl; 2J,5,5-tetramethyl-3-amino-2,5-dihydropyrrole- 1 -oxyl; 2J,5,5-tetramethyl-3-carbethoxy-2,5-dihydropyrrole- 1 -oxyl; 2,2,5, 5-tetramethyl-3-cyano-2,5-dihydropyrrole- 1 -oxyl; bis(l-oxyl-2J,6,6-tetramethylpiperidin-4-yl)succinate; bis(l-oxyl-2J,6,6-tetramethylpiperidin-4-yl)adipate; bis(l-oxyl-2J,6,6-tetramethylpiperidin-4-yl)sebacate; bis(l -oxyl-2J,6,6-tetramethylpiperidin-4-yl)n-butylmalonate; bis(l-oxyl-2J,6,6-tetramethylpiperidin-4-yl)phthalate; bis(l-oxyl-2J,6,6-tetramethylpiperidin-4-yl)isophthalate; bis(l-oxyl-2J,6,6-tetramethylpiperidin-4-yl)terephthalate; bis(l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)hexahydroterephthalate; N,N'-bis(l -oxyI-2,2,6,6-tetramethylpiperidin-4-yl)adipamide; N-(l-oxyl-2J,6,6-tetramethylpiperidin-4-yl)-caprolactam; N-(l-oxyl-2J,6,6-tetramethylpiperidin-4-yl)-dodeGylsuccinimide; 2,4,6-tris-[N-butyl-N-(l -oxyl-2J,6,6-tetramethylpiperidin-4-yl)]-s-triazine; and 4,4'-ethylenebis( l -oxyl-2,2,6,6-tetramethylpiperazin-3-one),

14, The composition of claim 10 wherein the quinone alkide is a compound of the formula

wherein:

R₃₃ is -CN, -COOH, -COOR₃₄, -COR₃₅, -OCOR₃₆, -CONR₃₇R₃₈ or -PO(OR₃₉)₂ where

R₃ is alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl or benzyl,

R₃₆ is alkyl of 1 to 18 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by 1 or 2 alkyl of 1 to 4 carbon atoms or by hydroxyl,

R₃₇ and R₃₈ are independently hydrogen, alkyl of 1 to 18 carbon atoms or said alkyl substituted by alkylamino of 1 to 4 carbon atoms, by dialkylamino of 2 to 8 carbon atoms or by hydroxyl; benzyl, aryl of 6 to 10 carbon atoms or said aryl substituted by alkyl of 1 to 4 carbon atoms, by alkylamino of 1 to 4 carbon atoms, by dialkylamino of 2 to 8 carbon atoms, by phenylamino or by hydroxyl, or

-NR₃₇R₃₈ is morpholino, piperidino or pyrrolidino,

R₃₉ is hydrogen or alkyl of 1 to 18 carbon atoms, and

R ₀ is hydrogen, alkyl, aryl, hydroxyl, alkoxy, -CN, -COOH, -COOR ₄, -COR₃₅,

-OCOR₃₅, -CONR₃₇R₃₈ or -PO(OR₃₉)₂.

- 31

15. The composition of claim 14 wherein the quinone alkide is selected from the group consisting of: (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)acetonitrile, (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)acetic acid, (3,5-di-tert-amyl-4-oxocyclohexa-2,5-dienylidene)acetic acid, methyl (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)acetate, ethyl (3,5-di-tert-butyl-4-oxocycIohexa-2,5-dienylidene)acetate, n-butyl (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)acetate, 2_J6-di-tert-butyl-4-(2-oxopropylidene)-cyclohexa-2,5-dienone, diethyl (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)methanephosphonate, (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)methyl acetate, (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)methyl pivalate, (3,5-di-tert-butyl-4-oxocyGlohexa-2,5-dienylidene)methyl benzoate, and N,N-diethyl-2-(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)acetamide.

16. A composition for inhibiting the premature polymerization of ethylenically unsaturated monomers wherein said composition comprises: A) at least one nitroxyl compound of the structure:

ϊⁱ

, C - R , ^R ₂ I ^R3 o*

wherein R, and R are independently selected from the group consisting of hydrogen, alkyl, and heteroatom-substituted alkyl and R₂ and R₃ are (1) independently selected from the group consisting of alkyl and heteroatom-substituted alkyl, or (2) taken together, form a ring structure with the nitrogen; and X, and X₂ ( 1) are independently selected from the group consisting of halogen, phosphorus (in any of it oxidation states), cyano, COOR₇, -S-COR₇, -OCOR₇, -S-R₇ (wherein R₇ is alkyl or aryl), amido, carbonyl, alkenyl, or alkyl of 1 to 15 carbon atoms, or (2) taken together, form a ring structure with the nitrogen, and

B) at least one quinone alkide compound of the formula

wherein:

R₃₁ and R₃₂ are independently alky! of 4 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms or phenylalkyl of 7 to 15 carbon atoms, and

R₃₇ and R₃₈ are independently hydrogen, alkyl of 1 to 18 carbon atoms or said alkyl substituted by alkylamino of 1 to 4 carbon atoms, by dialkylamino of 2 to 8 carbon atoms or by hydroxyl; benzyl, aryl of 6 to 10 carbon atoms or said aryl substituted by alkyl of 1 to 4 carbon atoms, by alkylamino of 1 to 4 carbon atoms, by dialkylamino of 2 to 8 carbon atoms, by phenylamino or by hydroxyl, or -NR₃₇R₃₈ is morpholino, piperidino or pyrrolidino, R₃₉ is hydrogen or alkyl of 1 to 18 carbon atoms, and R₄₀ is hydrogen, alkyl, aryl, hydroxyl, alkoxy, -CN, -COOH, -COOR₃₄, -COR₃₅, -OCOR₃₆, -CONR₃₇R₃₈ or -PO(OR₃₉)₂,