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WO2010094982A1 - Composition pour réguler la polymérisation - Google Patents

Composition pour réguler la polymérisation Download PDF

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Publication number
WO2010094982A1
WO2010094982A1 PCT/GB2010/050310 GB2010050310W WO2010094982A1 WO 2010094982 A1 WO2010094982 A1 WO 2010094982A1 GB 2010050310 W GB2010050310 W GB 2010050310W WO 2010094982 A1 WO2010094982 A1 WO 2010094982A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
vinyl aromatic
compound
saturated
aromatic monomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/GB2010/050310
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English (en)
Inventor
Colin Richard Loyns
Andrew Nigel Fawbert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nufarm UK Ltd
Original Assignee
Nufarm UK Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nufarm UK Ltd filed Critical Nufarm UK Ltd
Publication of WO2010094982A1 publication Critical patent/WO2010094982A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/20—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/06—Hydrocarbons
    • C08F12/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C08K5/08—Quinones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/50—Phosphorus bound to carbon only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only

Definitions

  • This invention relates to the production and processing of vinyl aromatic monomers. More particularly, it provides a composition which is useful for the prevention of unwanted polymerisation reactions during the production and processing of said monomers.
  • DD-A-234020 teaches the use of compositions containing phenols
  • US-A-4654451 discloses nitrosophenolic compounds
  • phenylenediamine compounds are disclosed in US-A-4774374
  • US-A-4252615 and US-A-4086147 are both concerned with the use of nitrophenols
  • SU-A- 819078 and EP-A-550754 describe the use of quinone methides for this purpose
  • nitroxyl compounds are the focus of JP-A-01 165534, GB-A-1 127127 and CS-B-260755.
  • the desired characteristics for a composition for use in controlling the amount of polymerisation which occurs during the production and processing of vinyl aromatic monomers include a low potential for harm to humans as well as a high efficacy of control of the amount of polymerisation under the process conditions.
  • the conditions which prevail during the industrial processing of vinyl aromatic monomers can involve the use of elevated temperatures, for example up to about 14O 0 C, for extended periods, e.g. two hours or more, and with zero or very low oxygen levels.
  • non-standard operating conditions of temperature, dwell time and oxygen content can occur from time to time, thereby resulting in greater than normal reliance on the polymerisation control composition.
  • the non-standard conditions can, for example, involve an interruption in the flow of the polymerisation control composition into the vinyl aromatic monomer process stream, which may be necessary because a distillation column needs to be run under total reflux for a specified time.
  • it is a requirement of the polymerisation control composition that its efficacy should not be quickly exhausted, but that it should continue to give control over the whole duration of the period of the non-standard operating conditions.
  • Such long-lasting compositions are normally referred to as retarders, whereas compositions which control polymerisation but do not have such longevity of efficacy are commonly referred to as inhibitors.
  • nitroxyl compounds such as A- amino-2,2,6,6-tetramethyl piperidine-N-oxyl (amino tempo) and 4-hydroxy-2,2,6,6-tetramethyl piperidine-N-oxyl (hydroxy tempo) are known to be very effective components of compositions for controlling the amount of unwanted polymerisation of vinyl aromatic monomers at low and intermediate temperatures (e.g. up to about 10O 0 C), their efficacy decreases with increasing temperature, such that above about 12O 0 C they cease to control the amount of polymerisation and merely modify the characteristics of the polymer which is formed. Furthermore, it is found that these nitroxyl compounds are inhibitors rather than retarders. Therefore, nitroxyl compounds do not have the persisting action required for controlling the amount of polymerisation in the event of, for example, a period of total reflux operation.
  • nitrophenols such as 2,4-dinitro-ortho-cresol (DNOC), 2,6-dinitro-para- cresol (DNPC), 2,4-dinitro-phenol (DNP) or 2,4-dinitro-ortho-sec-butyl-phenol (DNBP or
  • Dinoseb are known to be effective components of polymerisation retarder compositions for controlling the polymerisation of vinyl aromatic monomers under the above mentioned conditions. These nitrophenols are particularly effective as retarders, and so they are the most frequently used class of material in commercial use for controlling the amount of thermal polymerisation of vinyl aromatic monomers in processing plants. However, these nitrophenols are toxic materials with potential to cause harm to humans and to the environment. Similarly, the nitrosophenolic compounds, such as paranitrosophenol, are found to be effective products in this context, but such aromatic nitroso compounds are solid products which are difficult to handle; in addition, the toxicity properties of these compounds are such that they have potential to cause harm to humans.
  • compositions of the prior art there exists a need for new, effective and non-toxic polymerisation retarder compositions for controlling the amount of unwanted polymerisation of vinyl aromatic monomers during their production and processing which specifically do not contain materials which are toxic to humans.
  • the present invention seeks to provide compositions which offer significant improvement over these prior art compositions in terms of efficacy in use, long lasting activity, and low toxicity.
  • compositions which possess all the desirable attributes for the control of the amount of unwanted polymerisation of a vinyl aromatic monomer, whilst not displaying the disadvantageous features of the compositions of the prior art.
  • the compositions of the present invention possess low potential for harm to humans with a high efficacy of control of the amount of polymerisation under the process conditions of the vinyl aromatic monomer, and long-lasting retarder type activity.
  • a retarder composition for the prevention of unwanted polymerisation reactions during the production and processing of vinyl aromatic monomers said composition comprising:
  • R 1 to R 4 are each independently selected from the group comprising H, C 1 , C 2 , C 3 , C 4 , C 5 , C 6 , C 7 or C 8 straight or branched chain saturated or unsaturated hydrocarbons or either or both of (R 1 and R 2 ) and (R 3 and R 4 ) comprise a saturated or unsaturated hydrocarbon ring and at least one and not more than three of R 1 to R 4 are hydrogen, and R 5 to R 7 are each independently selected from the group comprising Ci, C 2 , C 3 , C 4 , C 5 ,
  • composition may also comprise:
  • R 10 to R 15 are each independently selected from the group comprising C 1 , C 2 , C 3 , C 4 , C 5 , C 6 , C 7 or C 8 straight or branched chain saturated or unsaturated hydrocarbons and C 5 , C 6 or C 7 saturated or unsaturated hydrocarbon rings and R 10 plus R 11 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 e.g.
  • the preferred weight ratio of component (a) (comprising a compound of structure (i)) to component (b) (comprising a compound of structure (N)) is in the range of from 9:1 to 1 :9.
  • compositions may also contain one or more formulation adjuvants selected from the known classes of solvents, solubilising agents, liquid carrying agents, emulsifiers and dispersants.
  • the present invention also envisages a vinyl aromatic monomer process stream which comprises a retarder composition as hereinbefore disclosed in combination with at least one vinyl aromatic monomer.
  • a retarder composition as hereinbefore disclosed in combination with at least one vinyl aromatic monomer.
  • the weight ratio of retarder composition comprising components (a), (b) and optionally (c)) to vinyl aromatic monomer is in the range from 1 :200 to 1 :100000.
  • a method for the prevention of unwanted polymerisation reactions during the production and processing of vinyl aromatic monomers comprising treating a composition comprising at least one vinyl aromatic monomer with a composition according to the first aspect of the invention.
  • the process streams consist essentially of vinyl aromatic monomers and are substantially free from polymerisable unsaturated polymers.
  • compositions of the present invention contain at least one quinone compound and at least one phosphorus-containing antioxidant compound and optionally at least one stable free radical compound and one or more formulation adjuvants for the purpose of enabling a stable mixture thereof.
  • the invention also envisages vinyl aromatic monomer process streams which additionally comprise at least one vinyl aromatic monomer.
  • the quinone compounds which are useful in the compositions and method of the present invention are in the group of quinones of the general formula (i) wherein R 1 to R 4 are each independently selected from the group comprising H, Ci, C 2 , C 3 , C 4 , C 5 , C 6 , C 7 or C 8 straight or branched chain saturated or unsaturated hydrocarbons or either or both of (R 1 plus R 2 ) and (R 3 plus R 4 ) may comprise a saturated or unsaturated hydrocarbon ring optionally further substituted with branched or straight chain alkyl or alkenyl groups.
  • R 1 to R 4 are each independently selected from the group comprising H, Ci, C 2 , C 3 , C 4 , C 5 , C 6 , C 7 or C 8 straight or branched chain saturated or unsaturated hydrocarbons or either or both of (R 1 plus R 2 ) and (R 3 plus R 4 ) may comprise a saturated or unsaturated hydrocarbon ring optionally further substituted with branched or straight
  • the compounds of use in the composition and method of the invention are not limited to single ring compound benzoquinones, but additionally include naphthoquinones, anthraquinones, and the like, which are optionally substituted with branched or straight chain alkyl or alkenyl groups, as previously discussed.
  • Preferred quinones of use in respect of the present invention are alkyl substituted benzoquinones, preferably 2,5-dialkyl benzoquinones, such as 2,5-dimethyl benzoquinone and 2,5-di-te/t-butyl benzoquinone.
  • the phosphorus-containing antioxidants used in the compositions and method of the present invention are antioxidants of the structure (ii) comprising organic compounds of trivalent phosphorous including, but not limited to, phosphites and phosphines, wherein R 5 to R 7 are each independently selected from the group comprising C 1 , C 2 , C 3 , C 4 , C 5 , C 6 , C 7 or C 8 straight or branched chain saturated or unsaturated hydrocarbons and C 5 , C 6 or C 7 saturated or unsaturated hydrocarbon rings.
  • the preferred trivalent phosphorous compounds are phosphites or phosphines containing aromatic or alkylated aromatic groups including, by way of example, triphenyl phosphite.
  • compositions of the present invention may also optionally contain one or more nitroxyl compounds of formula (v), wherein R 10 to Ri 5 are each independently selected from the group comprising C 1 , C 2 , C 3 , C 4 , C 5 , C 6 , C 7 or C 8 straight or branched chain saturated or unsaturated hydrocarbons and C 5 , C 6 or C 7 saturated or unsaturated hydrocarbon rings, and Ri 0 plus Rn 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 e.g.
  • Preferred nitroxyl compounds are 4-hydroxy-2, 2,6,6- tetramethylpiperidin-N-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidin-N-oxyl and 4-butoxy-2, 2,6,6- tetramethylpiperidin-N-oxyl
  • compositions of the present invention also optionally contain one or more formulation adjuvants, said adjuvants being selected from the known classes of solvents, solubilising agents, liquid carrying agents, emulsifiers and dispersants.
  • Typical solvents or cosolvents or liquid carrying agents include aromatics, for example ethyl benzene, and vinyl aromatics, for example styrene monomer, and nonaromatics, for example glycol ethers exemplified by the alkyl ethers of diethylene glycol.
  • the compositions of the present invention find application in the prevention of unwanted polymerisation reactions during the production and processing of vinyl aromatic monomers, and are added to vinyl aromatic monomer process stream.
  • Typical vinyl aromatic monomers which are present in such process streams include, for example, styrene monomer or divinyl benzene.
  • the method of the present invention may be carried out by any of the standard techniques known in the art, for example by injecting into a vinyl aromatic monomer process stream one or more quinones as hereinbefore defined and one or more phosphorus-containing antioxidants as hereinbefore defined, either separately or together, e.g. by premixing the quinone and the phosphorus-containing, with or without the addition of one or more adjuvants for the purpose of enabling a stable mixture thereof, for example one or more carrier solvents and/or cosolvents as hereinbefore defined.
  • either or both of the quinone and the phosphorus-containing antioxidant may be in the form of a liquid formulation in one or more solvents or carrier liquids as hereinbefore defined.
  • the injection location can be any of those known to those skilled in the art, for example, injection may take place into the crude monomer feed entering the distillation section or the materials may be injected directly into one, any or all of the distillation columns.
  • Controls 1 and 2 are Dinoseb, which is the product of the prior art most commonly employed in commercial production of vinyl aromatic monomers.
  • DMBQ is a quinone representing quinones of the prior art.
  • TPPT triphenyl phosphite
  • TPPN triphenyl phosphine
  • DNBP dinoseb
  • the vinyl aromatic monomer composition containing a polymerisation retarder and/or a phosphorus-containing antioxidant was fed at a constant rate into a stirred vessel fitted with an outlet so that, by adjusting the feed rate, a dwell time of two hours in the vessel was achieved.
  • the contents of the vessel were maintained under reduced pressure, so that a steady reflux occurred at the test temperature. Samples were taken at intervals of time and tested for polymer content in order to assess the effectiveness of control of the amount of polymerisation.
  • compositions of the present invention are better than that of Dinoseb, the material most commonly used in the vinyl aromatic monomer processing industry, with notably less polymer being produced in the given time.
  • This superior activity of the compositions of the present invention is a surprising and unexpected improvement over the preexisting state of the art.
  • the compositions of the present invention are demonstrated to have the desired efficacy for controlling the amount of polymerisation which occurs when producing or processing vinyl aromatic monomers.
  • compositions of the present invention do not contain substances which are toxic to humans and, consequently, they are of considerable benefit when compared to the formulations of the prior art , typically containing dinitrophenols such as Dinoseb which, as previously noted, is the material most commonly used in the vinyl aromatic monomer processing industry.
  • Dinoseb dinitrophenols
  • Table 3 A comparison of the properties of the substances of the current invention with those of the prior art material Dinoseb is provided in Table 3.
  • compositions of the present invention pose much less hazard to humans than does Dinoseb.
  • the need to control the exposure of plant operators can be greatly reduced by using compositions of the present invention instead of Dinoseb during production and processing operations using vinyl aromatic monomers. Therefore, the compositions of the present invention provide both a more effective and a safer means of controlling unwanted polymerisation of vinyl aromatic monomers when compared to the compositions of the prior art.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne une composition retardatrice permettant de prévenir des réactions de polymérisation indésirables pendant la production et le traitement de monomères vinyliques aromatiques. Ladite composition comprend : (a) au moins un composé quinone et (b) au moins un composé antioxydant contenant du phosphore. La composition comprend éventuellement au moins un composé nitroxyle stable à radicaux libres et un ou plusieurs adjuvants de formulation. L'invention concerne également un flux de processus de monomères vinyliques aromatiques qui comprend la composition retardatrice combinée à au moins un monomère vinylique aromatique, et un procédé permettant de prévenir des réactions de polymérisation indésirables pendant la production et le traitement de monomères vinyliques aromatiques, ledit procédé consistant à : traiter une composition comprenant au moins un monomère vinylique aromatique combiné à la composition retardatrice de l'invention.
PCT/GB2010/050310 2009-02-23 2010-02-23 Composition pour réguler la polymérisation Ceased WO2010094982A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0903005A GB0903005D0 (en) 2009-02-23 2009-02-23 Composition for controlling polymerisation
GB0903005.7 2009-02-23

Publications (1)

Publication Number Publication Date
WO2010094982A1 true WO2010094982A1 (fr) 2010-08-26

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018156914A1 (fr) * 2017-02-27 2018-08-30 Ecolab USA, Inc. Formulation anti-encrassement pour compresseurs
US12098070B2 (en) 2019-04-02 2024-09-24 Ecolab Usa Inc. Pure chlorine dioxide generation system with reduced acid usage
US12304980B2 (en) 2022-04-01 2025-05-20 Ecolab Usa Inc. Antifoulant compositions for vapor-space applications
US12344581B2 (en) 2022-04-01 2025-07-01 Ecolab Usa Inc. Antifoulant compositions for high-severity processing of vinylic monomer streams
US12428360B2 (en) 2022-04-01 2025-09-30 Ecolab Usa Inc. Abating unwanted emulsion polymerization during extractive distillation of conjugated diene monomers

Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1127127A (en) 1966-04-26 1968-09-11 Bp Chem Int Ltd Stabilization of acrylic acid
US4086147A (en) 1976-12-10 1978-04-25 Cosden Technology, Inc. Polymerization inhibitor for vinyl aromatic compounds
US4252615A (en) 1978-07-18 1981-02-24 Cosden Technology, Inc. Polymerization inhibitor for vinyl aromatic compounds
SU819078A1 (ru) 1978-07-07 1981-04-07 Ордена Трудового Красного Знамениинститут Органической И Физической Химииим. A.E.Арбузова Казанского Филиалаан Cccp Способ ингибировани термополимеризацииСТиРОлА
DD234020A1 (de) 1985-01-18 1986-03-19 Buna Chem Werke Veb Verfahren zur stabilisierung polymerisationsfaehiger monomermischungen
US4654451A (en) 1985-12-27 1987-03-31 Atlantic Richfield Company Inhibiting polymerization of vinyl aromatic monomers
EP0240297A1 (fr) 1986-04-01 1987-10-07 Betz Europe, Inc. Procédé pour inhiber la polymérisation de composés vinylaromatiques
US4774374A (en) 1987-06-12 1988-09-27 Uniroyal Chemical Company, Inc. Stabilized vinyl aromatic composition
JPS63235390A (ja) 1987-03-25 1988-09-30 Nippon Steel Chem Co Ltd ビニル化合物の重合防止剤
CS260755B1 (sk) 1985-06-26 1989-01-12 Milan Karvas Sposob přípravy 4-substituovaných-2,2,e,6-tetrainetylpiperidín-N-oxylov
JPH01165534A (ja) 1987-12-22 1989-06-29 Mitsubishi Petrochem Co Ltd スチレン類の重合防止剤
US4929778A (en) 1989-06-05 1990-05-29 Betz Laboratories, Inc. Methods and compositions for inhibiting styrene polymerization
JPH0585964A (ja) 1991-09-20 1993-04-06 Inukai Sangyo Kk スチレン樹脂よりスチレンモノマーを得る方法
EP0550754A1 (fr) 1991-07-24 1993-07-14 Nizhnekamskoe Proizvodstvennoe Obiedenenie " Nizhnekamskneftekhim" Agent inhibiteur de polymerisation pour composes a teneur en vinyle
US5254760A (en) 1992-07-29 1993-10-19 Ciba-Geigy Corporation Inhibiting polymerization of vinyl aromatic monomers
WO1996041783A1 (fr) 1995-06-12 1996-12-27 Betzdearborn Inc. Traitements destines a empecher la polymerisation de monomere aromatique vinylique
WO2000036052A1 (fr) * 1998-12-17 2000-06-22 Nalco/Exxon Energy Chemicals, L.P. Utilisation de melanges cynergiques contenant des stabiliseurs nitroxides pour inhiber la polymerisation de monomeres aromatiques vinyliques
US20020037958A1 (en) 1999-12-02 2002-03-28 Brigitte Benage Inhibition of polymerization of unsaturated monomers
US20040019247A1 (en) * 1999-02-26 2004-01-29 Basf Aktiengesellschaft Continuous recovery of styrene from a styrene-containing mixture
US20040147650A1 (en) * 2003-01-24 2004-07-29 General Electric Company Process for stabilization of polymer compositions
CN1962582A (zh) 2005-11-11 2007-05-16 中国石油化工股份有限公司 用于抗苯乙烯聚合的方法

Patent Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1127127A (en) 1966-04-26 1968-09-11 Bp Chem Int Ltd Stabilization of acrylic acid
US4086147A (en) 1976-12-10 1978-04-25 Cosden Technology, Inc. Polymerization inhibitor for vinyl aromatic compounds
SU819078A1 (ru) 1978-07-07 1981-04-07 Ордена Трудового Красного Знамениинститут Органической И Физической Химииим. A.E.Арбузова Казанского Филиалаан Cccp Способ ингибировани термополимеризацииСТиРОлА
US4252615A (en) 1978-07-18 1981-02-24 Cosden Technology, Inc. Polymerization inhibitor for vinyl aromatic compounds
DD234020A1 (de) 1985-01-18 1986-03-19 Buna Chem Werke Veb Verfahren zur stabilisierung polymerisationsfaehiger monomermischungen
CS260755B1 (sk) 1985-06-26 1989-01-12 Milan Karvas Sposob přípravy 4-substituovaných-2,2,e,6-tetrainetylpiperidín-N-oxylov
US4654451A (en) 1985-12-27 1987-03-31 Atlantic Richfield Company Inhibiting polymerization of vinyl aromatic monomers
EP0240297A1 (fr) 1986-04-01 1987-10-07 Betz Europe, Inc. Procédé pour inhiber la polymérisation de composés vinylaromatiques
JPS63235390A (ja) 1987-03-25 1988-09-30 Nippon Steel Chem Co Ltd ビニル化合物の重合防止剤
US4774374A (en) 1987-06-12 1988-09-27 Uniroyal Chemical Company, Inc. Stabilized vinyl aromatic composition
JPH01165534A (ja) 1987-12-22 1989-06-29 Mitsubishi Petrochem Co Ltd スチレン類の重合防止剤
US4929778A (en) 1989-06-05 1990-05-29 Betz Laboratories, Inc. Methods and compositions for inhibiting styrene polymerization
EP0550754A1 (fr) 1991-07-24 1993-07-14 Nizhnekamskoe Proizvodstvennoe Obiedenenie " Nizhnekamskneftekhim" Agent inhibiteur de polymerisation pour composes a teneur en vinyle
JPH0585964A (ja) 1991-09-20 1993-04-06 Inukai Sangyo Kk スチレン樹脂よりスチレンモノマーを得る方法
US5254760A (en) 1992-07-29 1993-10-19 Ciba-Geigy Corporation Inhibiting polymerization of vinyl aromatic monomers
WO1996041783A1 (fr) 1995-06-12 1996-12-27 Betzdearborn Inc. Traitements destines a empecher la polymerisation de monomere aromatique vinylique
WO2000036052A1 (fr) * 1998-12-17 2000-06-22 Nalco/Exxon Energy Chemicals, L.P. Utilisation de melanges cynergiques contenant des stabiliseurs nitroxides pour inhiber la polymerisation de monomeres aromatiques vinyliques
US20040019247A1 (en) * 1999-02-26 2004-01-29 Basf Aktiengesellschaft Continuous recovery of styrene from a styrene-containing mixture
US20020037958A1 (en) 1999-12-02 2002-03-28 Brigitte Benage Inhibition of polymerization of unsaturated monomers
US20040147650A1 (en) * 2003-01-24 2004-07-29 General Electric Company Process for stabilization of polymer compositions
CN1962582A (zh) 2005-11-11 2007-05-16 中国石油化工股份有限公司 用于抗苯乙烯聚合的方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018156914A1 (fr) * 2017-02-27 2018-08-30 Ecolab USA, Inc. Formulation anti-encrassement pour compresseurs
US10745345B2 (en) 2017-02-27 2020-08-18 Ecolab Usa Inc. Anti-foulant formulation for compressors
US11186540B2 (en) 2017-02-27 2021-11-30 Ecolab Usa Inc. Anti-foulant formulation for compressors
US12098070B2 (en) 2019-04-02 2024-09-24 Ecolab Usa Inc. Pure chlorine dioxide generation system with reduced acid usage
US12304980B2 (en) 2022-04-01 2025-05-20 Ecolab Usa Inc. Antifoulant compositions for vapor-space applications
US12344581B2 (en) 2022-04-01 2025-07-01 Ecolab Usa Inc. Antifoulant compositions for high-severity processing of vinylic monomer streams
US12428360B2 (en) 2022-04-01 2025-09-30 Ecolab Usa Inc. Abating unwanted emulsion polymerization during extractive distillation of conjugated diene monomers

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