# US 2014/0194559 A1 · Novel Inhibitor Compositions and Methods of Use > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2014/0194559 A1 - Document ID: US20140194559A1 - Status: Published application - Kind: A1 - Application number: 14/239,333 - Filed: 2012-08-20 - Published: 2014-07-10 - Earliest claimed: 2011-08-19 - Assignees: Nufarm UK Limited - Inventors: Peter Price; Guillaume Duchamp; Angela Jane Glossop; Andrew Nigel Fawbert; Stephanie Mary Dwyer - Web page: https://patentgrep.com/patent/US20140194559A1 ## CPC - C07C 51/50: Use of additives, e.g. for stabilisation - C07C 7/20: Use of additives, e.g. for stabilisation - C08F 2/40: using retarding agents - C08F 12/08: Styrene - C08F 20/04: Acids, Metal salts or ammonium salts thereof - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## Abstract The invention concerns a formulation and method which allow for the efficient delivery of antipolymerants of low solubility into processes for the production of ethylenically unsaturated monomers, and associated process streams, and which avoid the potential health and safety problems and economic disadvantages which are associated with the methods of the prior art and facilitate the safe and efficient production of these monomers. Specifically, the invention provides an antipolymerant composition for the prevention of unwanted polymerisation reactions during the production and processing of ethylenically unsaturated compounds, the composition comprising a concentrated liquid formulation, wherein said concentrated liquid formulation is a suspension concentrate which comprises: (a) at least one compound selected from the group comprising phenols, quinones, thiazines, hydroxylamines and aromatic amines; (b) at least one dispersing agent; and (c) at least one polar or non-polar liquid carrier. Optionally the composition additionally comprises at least one stable free radical compound, typically a nitroxyl compound, and/or at least one thickening agent and/or at least one preservative agent. ## Claims ### Claim at position 1 1-37. (canceled) ### Claim 38 An antipolymerant composition for the prevention of unwanted polymerisation reactions during the production and processing of ethylenically unsaturated compounds, said composition comprising a concentrated liquid formulation, wherein said concentrated liquid formulation is a suspension concentrate which comprises: (a) at least one compound selected from the group comprising phenols, quinones, thiazines, hydroxylamines and aromatic amines; (b) at least one dispersing agent; and (c) at least one polar or non-polar liquid carrier. ### Claim 39 (depends on 38) A composition as claimed in claim 38 wherein said phenol compounds are hydroquinone compounds of the general formula (i-a): wherein: R1 to R4 are each independently selected from the group consisting of H, C1, C2, C3, C4, C5, C6, C7 or C8 straight or branched chain saturated or unsaturated hydrocarbons and optionally substituted phenyl and benzyl, wherein said hydroquinones are optionally selected from 2,5-di-alkyl substituted hydroquinones, optionally 2,5-di-tert-butylhydroquinone. ### Claim 40 (depends on 38) A composition as claimed in claim 38 wherein said quinones are of the general formula (i-b): wherein: R1 to R4 are each independently selected from the group consisting of H, C1, C2, C3, C4, C5, C6, C7 or C8 straight or branched chain saturated or unsaturated hydrocarbons and optionally substituted phenyl and benzyl, wherein said quinones are optionally selected from 2,5-di-alkyl substituted quinones, optionally 2,5-di-tert-butyl-p-benzoquinone. ### Claim 41 (depends on 38) A composition as claimed in claim 38 wherein said hydroxylamines are selected from the group of compounds (ii): wherein: R5 to R6 are each independently selected from the group consisting of C1, C2, C3, C4, C5, C6, C7 or C8 straight or branched chain saturated or unsaturated hydrocarbons or hydroxyhydrocarbons and C5, C6 or C7 saturated or unsaturated hydrocarbon rings which may optionally be substituted rings, and arylakyls which may optionally be substituted on the aryl moiety, and wherein the alkyl moiety comprises C1, C2, C3 or C4 straight or branched chain hydrocarbons, and wherein the aryl moiety comprises one or more rings which are optionally substituted and, in the case of more than one ring, these may include fused rings, wherein said hydroxylamines are optionally selected from aliphatic hydroxylamines and aromatic hydroxylamines, optionally bis(hydroxypropyl) hydroxylamine or N,N-dibenzyl hydroxylamine. ### Claim 42 (depends on 38) A composition as claimed in claim 38 which additionally comprises at least one thickening agent, wherein said thickening agents are optionally selected from xanthan gum and guar gum. ### Claim 43 (depends on 38) A composition as claimed in claim 38 wherein said composition additionally comprises at least one preservative agent, wherein said preservative agents are optionally selected from 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 1,2-benzisophiazolin-3-one, 2,2′-methylenebis(5-chlorophenol), 2-bromo-2-nitropropane-1,3-diol and 1,2-octandiol. ### Claim 44 (depends on 38) A composition as claimed in claim 38 which additionally comprises at least one stable free radical compound. ### Claim 45 (depends on 44) A composition as claimed in claim 44 wherein said at least one free radical compound comprises at least one nitroxyl compound of formula (iii): wherein: R10 to R15 are each independently selected from the group consisting of C1, C2, C3, C4, C5, C6, C7 or C8 straight or branched chain saturated or unsaturated hydrocarbons and C5, C6 or C7 saturated or unsaturated hydrocarbon rings, and R10 plus R11 may together form a saturated or unsaturated ring optionally containing a further hetero atom, wherein the ring is optionally further substituted with one or more branched or straight chain alkyl or alkenyl groups or one or more moieties selected from hydroxyl, oxyl, amino and alkoxyl, and wherein two or more such nitroxyl containing rings may be joined by any linking groups. ### Claim 46 (depends on 45) A composition as claimed in claim 45 wherein said linking groups include C1 to C18 alkylene, C4 to C18 alkenylene, xylylene, a divalent acyl radical of an aliphatic, araliphatic or aromatic dicarboxylic acid or of a dicarbamic acid or of a phosphorous-containing acid or of a sulphur containing acid or a bivalent silyl radical or a sulphone, a sulphide or a nitrogen containing group or a bisether. ### Claim 47 (depends on 46) A composition as claimed in claim 46 wherein said linking groups are selected from an acyl radical of an aliphatic C2 to C36 dicarboxylic acid, or of a C8 to C14 cycloaliphatic acid or of a C8 to C14 aromatic dicarboxylic acid or of a C8 to C14 aromatic dicarbamic acid. ### Claim 48 (depends on 45) A composition as claimed in claim 45 wherein said nitroxyl compound is selected from 2,2,6,6-tetramethyl piperidine-1-oxyl compounds (TEMPOs). ### Claim 49 (depends on 45) A composition as claimed in claim 45 wherein said nitroxyl compound is selected from 4-hydroxy-2,2,6,6-tetramethylpiperidin-N-oxyl and 4-oxo-2,2,6,6-tetramethylpiperidin-N-oxyl. ### Claim 50 (depends on 38) A composition as claimed in claim 38 wherein said dispersing agents are selected from at least one ionic or non-ionic surfactant, and optionally selected from polyacrylate esters and polyarylphenylether salts. ### Claim 51 (depends on 38) A composition as claimed in claim 38 wherein said carrier liquids are selected from polar and non-polar liquids, and optionally selected from water, alcohols, glycols, ketones, aldehydes, aromatic hydrocarbons and alkanes. ### Claim 52 (depends on 38) A composition as claimed in claim 38 wherein the weight content of component (a) is in the range of from 30:70 to 70:30 relative to the remaining components in the composition. ### Claim 53 (depends on 38) A composition as claimed in claim 38 wherein the particle sizes are less than 10 microns. ### Claim 54 (depends on 38) A process stream comprising an antipolymerant composition as claimed in claim 38 in combination with at least one ethylenically unsaturated compound. ### Claim 55 (depends on 54) A process stream as claimed in claim 54 wherein said at least one ethylenically unsaturated compound comprises a vinyl aromatic monomer or other ethylenically unsaturated monomer, wherein said vinyl aromatic monomer is optionally styrene or divinyl benzene and said ethylenically unsaturated monomer is optionally selected from acrylonitrile, (meth)acrylic acid and esters thereof, butadiene and isoprene. ### Claim 56 (depends on 54) A process stream as claimed in claim 54 wherein the weight ratio of antipolymerant composition to ethylenically unsaturated compound is in the range of from 1:200 to 1:40000. ### Claim 57 (depends on 38) A method for the prevention of unwanted polymerisation reactions during the production and processing of ethylenically unsaturated compounds, said method comprising treating a composition comprising at least one ethylenically unsaturated compound with a composition as claimed in claim 38 wherein, optionally, at least one antipolymerant is prepared as a suspension concentrate and said suspension concentrate is injected into a process stream.