WO2000027780A1 - Methods and compositions for inhibiting polymerization of ethylenically unsaturated hydrocarbons - Google Patents
Methods and compositions for inhibiting polymerization of ethylenically unsaturated hydrocarbons Download PDFInfo
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- WO2000027780A1 WO2000027780A1 PCT/US1999/023996 US9923996W WO0027780A1 WO 2000027780 A1 WO2000027780 A1 WO 2000027780A1 US 9923996 W US9923996 W US 9923996W WO 0027780 A1 WO0027780 A1 WO 0027780A1
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- WIPO (PCT)
- Prior art keywords
- compound
- aminophenol
- phenylenediamine
- composition
- hydroxylamine
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- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/16—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen
- C09K15/18—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen containing an amine or imine moiety
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S585/00—Chemistry of hydrocarbon compounds
- Y10S585/949—Miscellaneous considerations
- Y10S585/95—Prevention or removal of corrosion or solid deposits
Definitions
- the present invention provides for methods and compositions for inhibiting the polymerization of ethylenically unsaturated hydrocarbons, such as oleflns and diolefms.
- ethylenically unsaturated monomers include a variety of purification processes such as distillation to remove impurities. Purification operations are often carried out at elevated temperatures and this can increase the rate of undesired polymerization. Polymerization, such as thermal polymerization, during the monomer purification process, results not only in loss of desired monomer end-product, but also in production efficiency caused by polymer formation and agglomeration on process equipment. In heat requiring operations, such agglomeration adversely affects heat transfer efficiency.
- the monomers are stabilized with the addition of substances which will act as inhibitors or retarders of polymerization.
- ethylenically unsaturated monomers such as the diolefms butadiene and isoprene will polymerize when left in storage tanks and during transportation at temperatures as low as room temperature. This polymerization is initiated by reaction of the diolefin monomer with oxygen present in the monomer containing system. This reaction will form peroxides and free radical species which will perpetuate the reaction with the diolefin monomer.
- U.S. Pat. No. 5,510,547 teaches that a combination of a phenylenediamine compound and a hydroxylamine compound is effective as inhibiting the polymerization of vinyl aromatic monomers during processing conditions.
- U.S. Pat. No. 4,720,566 teaches that a combination of a hydroxylamine and a phenylenediamine compound is effective at inhibiting the polymerization of acrylonitrile during its production.
- the present invention provides for methods and compositions for inhibiting the polymerization of ethylenically unsaturated hydrocarbons comprising adding an effective inhibiting amount of a composition comprising an aminophenol compound and at least one of a phenylenediamine compound and a hydroxylamine compound "(Aminophenol compositions").
- the ethylenically unsaturated monomers are characterized as polymerizable ethylenically unsaturated hydrocarbons and include olefins and diolefms.
- the olefms contain about 2 to about 20 carbon atoms, preferably 2 to 8 carbon atoms and the diolefms are conjugated and contain about 2 to about 20 carbon atoms with 4 to 6 carbon atoms preferred.
- these compounds include ethylene dichloride, ethylene glycol, aromatics from ethylene plants and pyrolysis gasoline.
- the aminophenol compound generally have the formula:
- amino group can be ortho, meta or para to the hydroxyl group.
- o-aminophenol is preferred.
- the phenylenediamine compounds useful in the present invention generally have the formula:
- hydroxylamine compounds useful in the present invention generally have the formula:
- R 5 and R 6 are the same or different and are hydrogen, alkyl, aryl, alkaryl, aralkyl or hydroxyalkyl groups and have about three to about twenty carbon atoms.
- the preferred hydroxylamine compounds are selected from the group consisting of
- N,N'-diethylhydroxylamine DEHA
- HPHA bis-N, N'-(hydroxypropyl-hydroxylamine)
- the aminophenol compositions of the present invention are effective at inhibiting the polymerization of ethylenically unsaturated monomers during both storage and processing conditions.
- Storage conditions also include transportation of the monomers. These conditions will usually have oxygen present and can be at elevated temperatures of up to 100°C.
- the processing conditions are usually distillation and purification processes and are run at elevated temperatures of 95°C and 125°C where oxygen can be present or absent.
- the term "effective amount for the purpose” is that amount of aminophenol compositions necessary to inhibit polymerization of the ethylenically unsaturated monomers. This amount will vary according to the conditions under which the monomers are subjected during the storage and/or handling thereof. During processing, for example, high temperatures and higher monomers contamination will require larger amounts of the aminophenol compositions.
- the total amount of the aminophenol compositions added to the ethylenically unsaturated monomer will range from about 1 part to about 10,000 parts per million parts of monomer. More preferably, the aminophenol compositions are added at a range of about 1 part to about 100 parts per million parts monomer.
- Table A The weight ratios of aminophenol compound to the other compounds present in the aminophenol compositions is presented in Table A below.
- the aminophenol compositions of the present invention may be added to the ethylenically unsaturated hydrocarbon as either a dispersion or as a solution using a suitable liquid carrier or solvent. Any solvent that is compatible with the individual ingredients and with the monomer may be employed.
- the aminophenol compositions may be added to the ethylenically unsaturated hydrocarbon vinyl aromatic by any conventional method, either as individual components or as a combination of components. It is preferred that the ingredients be added to the monomer as a single treatment.
- PDA II 2 45 o-AP/DEHA (l :l) 2 21 o-AP/PDA I (l :l) 2 34 o-AP/PDA II (l:l) 2 35 o- AP/DEHA/PD A I ( 1 : 1 : 1 ) 2 11
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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)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Methods and compositions for inhibiting the polymerization of ethylenically unsaturated hydrocarbons are disclosed. Combinations of aminophenol compound and either of phenylenediamine or hydroxylamine compounds are effective at inhibiting this polymerization under both processing and storage conditions.
Description
METHODS AND COMPOSITIONS FOR INHIBITING POLYMERIZATION OF ETHYLENICALLY UNSATURATED HYDROCARBONS
FIELD OF THE INVENTION The present invention provides for methods and compositions for inhibiting the polymerization of ethylenically unsaturated hydrocarbons, such as oleflns and diolefms.
BACKGROUND OF THE INVENTION Common industrial methods for producing ethylenically unsaturated monomers include a variety of purification processes such as distillation to remove impurities. Purification operations are often carried out at elevated temperatures and this can increase the rate of undesired polymerization. Polymerization, such as thermal polymerization, during the monomer purification process, results not only in loss of desired monomer end-product, but also in production efficiency caused by polymer formation and agglomeration on process equipment. In heat requiring operations, such agglomeration adversely affects heat transfer efficiency.
Typically the monomers are stabilized with the addition of substances which will act as inhibitors or retarders of polymerization.
Certain ethylenically unsaturated monomers such as the diolefms butadiene and isoprene will polymerize when left in storage tanks and during transportation at temperatures as low as room temperature. This polymerization is initiated by reaction of the diolefin monomer with oxygen present in the monomer containing system. This reaction will form peroxides and free radical species which will perpetuate the reaction with the diolefin monomer.
Various approaches have been attempted with regard to this problem of polymerization. U.S. Pat. No. 3,148,225 teaches that N,N-dialkylhydroxylamines will inhibit the polymerization of popcorn polymer formation in olefm monomer recovery systems. In comparative studies, p-aminophenol was less effective than the hydroxylamines at inhibiting popcorn polymer formation. U.S. Pat. No. 3,342,723 tests p- and o-aminophenols for inhibiting fouling of hydrocarbon liquids. These compounds proved effective at inhibiting the formation and adhesion of coke-like deposits during refinery operations, o-phenylenediamine was also demonstrated to be effective in the oil refining apparatus.
U.S. Pat. No. 5,510,547 teaches that a combination of a phenylenediamine compound and a hydroxylamine compound is effective as inhibiting the polymerization of vinyl aromatic
monomers during processing conditions. U.S. Pat. No. 4,720,566 teaches that a combination of a hydroxylamine and a phenylenediamine compound is effective at inhibiting the polymerization of acrylonitrile during its production.
DETAILED DESCRIPTION OF THE INVENTION The present invention provides for methods and compositions for inhibiting the polymerization of ethylenically unsaturated hydrocarbons comprising adding an effective inhibiting amount of a composition comprising an aminophenol compound and at least one of a phenylenediamine compound and a hydroxylamine compound "(Aminophenol compositions"). The ethylenically unsaturated monomers are characterized as polymerizable ethylenically unsaturated hydrocarbons and include olefins and diolefms. The olefms contain about 2 to about 20 carbon atoms, preferably 2 to 8 carbon atoms and the diolefms are conjugated and contain about 2 to about 20 carbon atoms with 4 to 6 carbon atoms preferred. Examples of these compounds include ethylene dichloride, ethylene glycol, aromatics from ethylene plants and pyrolysis gasoline.
The aminophenol compound generally have the formula:
where the amino group can be ortho, meta or para to the hydroxyl group. Preferably, the o-aminophenol is preferred.
The phenylenediamine compounds useful in the present invention generally have the formula:
The hydroxylamine compounds useful in the present invention generally have the formula:
wherein R5 and R6 are the same or different and are hydrogen, alkyl, aryl, alkaryl, aralkyl or hydroxyalkyl groups and have about three to about twenty carbon atoms. The preferred hydroxylamine compounds are selected from the group consisting of
N,N'-diethylhydroxylamine (DEHA) and bis-N, N'-(hydroxypropyl-hydroxylamine) (HPHA). The aminophenol compositions of the present invention are effective at inhibiting the polymerization of ethylenically unsaturated monomers during both storage and processing conditions. Storage conditions also include transportation of the monomers. These conditions will usually have oxygen present and can be at elevated temperatures of up to 100°C. The processing conditions are usually distillation and purification processes and are run at elevated temperatures of 95°C and 125°C where oxygen can be present or absent.
For purposes of the present invention, the term "effective amount for the purpose" is that amount of aminophenol compositions necessary to inhibit polymerization of the ethylenically unsaturated monomers. This amount will vary according to the conditions under which the monomers are subjected during the storage and/or handling thereof. During processing, for example, high temperatures and higher monomers contamination will require larger amounts of the aminophenol compositions.
Preferably, the total amount of the aminophenol compositions added to the ethylenically unsaturated monomer will range from about 1 part to about 10,000 parts per million parts of monomer. More preferably, the aminophenol compositions are added at a range of about 1 part to about 100 parts per million parts monomer. The weight ratios of aminophenol compound to the other compounds present in the aminophenol compositions is presented in Table A below.
TABLE A
Aminophenol Compound Phenylenediamine Compound 1 :9 to 9: 1 Hydroxylamine Compound 1 :9 to 9:1
Accordingly, it is possible to produce a more effective vinyl aromatic monomer polymerization inhibition treatment than is obtainable by the use of one ingredient alone when measured at comparable treatment levels. This enhanced activity will allow for the concentration of each of these ingredients to be lowered and the total quantity of polymerization inhibitor particularly at higher processing temperatures may be reduced.
The aminophenol compositions of the present invention may be added to the ethylenically unsaturated hydrocarbon as either a dispersion or as a solution using a suitable liquid carrier or solvent. Any solvent that is compatible with the individual ingredients and with the monomer may be employed.
The aminophenol compositions may be added to the ethylenically unsaturated hydrocarbon vinyl aromatic by any conventional method, either as individual components or as a combination of components. It is preferred that the ingredients be added to the monomer as a single treatment. This invention will now be further described with reference to a number of specific examples which are to be regarded solely as illustrative and not as restricting the scope of the invention.
EXAMPLES 20% uninhibited isoprene in heptane was placed in a pressure vessel. This mixture was then purged once with nitrogen before placing it under 100 psi nitrogen. The pressure vessel was then placed in a 100°C water bath for 4 hours allowing polymerization of the diolefin.
The mixture was then allowed to cool at room temperature. The sample was evaporated and the remaining gums/polymer weight was obtained.
The chemicals employed in the testing are summarized in Table B.
TABLE B o-AP ortho-aminophenol
DEHA N, N'-diethylhydroxylamine
PDA I N, N'-bis-di-sec-butyl-p-phenylenediamine
PDA II N-phenyl-N'-( 1 ,4-dimethylpentyl)-p-phenylenediamine
The results of this testing for a combination of aminophenol compound and phenylenediamine are presented in Table I.
TABLE I
Heat Induced Gum Test
Treatment Total (μ Moles) Gums fme/lOO mn o-AP 1.1 52
DEHA 1J 50
PDA I 1.1 6 o-AP/DEHA (l :l) 1J 16 o-AP/PDA I (l:l) 1J 0.4
These results demonstrate that the combination of an aminophenol compound and either a hydroxylamine compound or a phenylenediamine compound was more effective than the particular individual component.
The concentration of the individual components was lowered by half, but the ratio between two component treatments was kept equimolar in the next study. These results are presented in Table II.
TABLE II
Treatment Total (μ Moles) Gums Cm--/100 mn o-AP 0.55 59
DEHA 0.55 102
PDA I 0.55 32 o-AP/DEHA (l :l) 0.55 54 o-AP/PDA I O J) 0.55 16
These results also demonstrate that the combination of an aminophenol compound with either a hydroxylamine compound or a phenylenediamine compound is more effective at inhibiting polymerization than the individual components.
Additional studies were performed using the same components, but with a constant final dosage. These results are presented in Table III.
TABLE III
Heat Induced Gum Test
Treatment Total (ppn Gums (mg/lOO mD o-AP 2 46
DEHA 2 55
PDA I 2 64
PDA II 2 45 o-AP/DEHA (l :l) 2 21 o-AP/PDA I (l :l) 2 34 o-AP/PDA II (l:l) 2 35 o- AP/DEHA/PD A I ( 1 : 1 : 1 ) 2 11
These test results not only demonstrate the enhanced activity occasioned by use of the combination of aminophenol compound with either a phenylenediamine or a hydroxylamine compound, but also the excellent results occasioned by use of all three compounds together.
Further testing was performed with DEHA and o-AP at a constant dosage of 1 ppm. These results are presented in Table IV.
TABLE IV
Heat Induced Gum Test o-AP(%) DEHA (%) Gums Cms/I 00 ml)
100 0 51
75 25 45
67 33 46
50 50 31
33 67 38
25 75 47
0 100 81
These results demonstrate the synergy between o-AP and DEHA at inhibiting ethylenically unsaturated hydrocarbon polymerization.
While this invention has been described with respect to particular embodiments thereof, it is apparent that numerous other forms and modifications of this invention will be obvious to those skilled in the art. The appended claims and this invention generally should be construed to cover all such obvious forms and modifications which are within the true spirit and scope of the present invention.
Claims
1. A method for inhibiting the polymerization of ethylenically unsaturated hydrocarbons comprising adding to said hydrocarbons an effective inhibiting amount of a composition comprising an aminophenol compound and at least one of a phenylenediamine compound and a hydroxylamine compound.
2. The method as claimed in claim 1 wherein said aminophenol compound is selected from the group consisting of para-aminophenol, meta-aminophenol and ortho-aminophenol.
3. The method as claimed in claim 1 wherein said phenylenediamine compound has the formula:
wherein R,, R2, R3 and R4 are the same or different and are hydrogen, alkyl, aryl, alkaryl, andaralkyl having about 1 to about 20 carbon atoms.
4. The method as claimed in claim 1 wherein said hydroxylamine compound has the formula:
wherein R5 and R6 are the same or different and are hydrogen, alkyl, aryl, alkaryl, aralkyl or hydroxyalkyl groups and have about three to about twenty carbon atoms.
5. The method as claimed in claim 2 wherein said aminophenol compound is ortho-aminophenol.
6. The method as claimed in claim 3 wherein said phenylenediamine compound is selected from the group consisting of N, N'-bis-di-sec-butyl-p-phenylenediamine and N-phenyl-N'-( 1 ,4-dimethylρentyl)-p-phenylenediamine.
7. The method as claimed in claim 4 wherein said hydroxylamine compound is selected from the group consisting of N, N'-diethylhydroxylamine and bis-N, N'-(hydroxypropyl-hydroxylamine).
8. The method as claimed in claim 1 wherein said ethylenically unsaturated hydrocarbons are undergoing processing.
9. The method as claimed in claim 1 wherein said ethylenically unsaturated hydrocarbons are in storage conditions.
10. The method as claimed in claim 1 wherein said processing conditions are at temperatures of about 95°C to about 125°C.
11. The method as claimed in claim 1 wherein said ethylenically unsaturated hydrocarbons are selected from the group consisting of olefins and diolefms.
12. The method as claimed in claim 11 wherein said olefins and said diolefms contain about 2 to about 20 carbons.
13. The method as claimed in claim 1 wherein said composition is added to said hydrocarbon in an amount ranging from about 1 to about 10,000 parts per million parts of said hydrocarbon.
14. A composition comprising an aminophenol compound and at least one of a phenylenediamine compound and a hydroxylamine compound.
15. The composition as claimed in claim 14 wherein said aminophenol compound is selected from the group consisting of para- aminophenol, meta- aminophenol and ortho-aminophenol.
16. The composition as claimed in claim 14 wherein said phenylenediamine compound has the formula:
wherein R,, R2, R3 and R4 are the same or different and are hydrogen, alkyl, aryl, alkaryl, and aralkyl having about 1 to about 20 carbon atoms.
17. The composition as claimed in claim 14 wherein said hydroxylamine compound has the formula:
Rc
N-OH
Rβ
wherein R5 and R6 are the same or different and are hydrogen, alkyl, aryl, alkaryl, aralkyl or hydroxyalkyl groups and have about three to about twenty carbon atoms.
18. The composition as claimed in claim 15 wherein said aminophenol compound is ortho-aminophenol.
19. The composition as claimed in claim 16 wherein said phenylenediamine compound is selected from the group consisting of N,N'-bis-di-sec-butyl-p-phenylenediamine and N-phenyl-N'-(l ,4-dimethylpentyl)-p-phenylenediamine.
20. The composition as claimed in claim 17 wherein said hydroxylamine compound is selected from the group consisting of N, N'-diethylhydroxylamine and bis-N,
N'-(hydroxypropyl-hydroxylamine).
21. The composition as claimed in claim 14 further comprising either a phenylenediamine compound and a hydroxylamine compound.
22. The composition as claimed in claim 14 further comprising an ethylenically unsaturated hydrocarbon.
23. The composition as claimed in claim 14 wherein the weight ratio of aminophenol compound to either of said phenylene-diamine compound and hydroxylamine compound ranges from about 1 :9 to about 9:1.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU13143/00A AU1314300A (en) | 1998-11-05 | 1999-11-03 | Methods and compositions for inhibiting polymerization of ethylenically unsaturated hydrocarbons |
| EP99956553A EP1127040B1 (en) | 1998-11-05 | 1999-11-03 | Methods and compositions for inhibiting polymerization of ethylenically unsaturated hydrocarbons |
| DE69905273T DE69905273T2 (en) | 1998-11-05 | 1999-11-03 | METHOD AND COMPOSITION FOR INHIBITING THE POLYMERIZATION OF ETHYLENICALLY UNSATURATED HYDROCARBONS |
| BRPI9915031-0A BR9915031B1 (en) | 1998-11-05 | 1999-11-03 | processes and compositions for the polymerization inhibition of ethylenically unsaturated hydrocarbons. |
| JP2000580962A JP4499921B2 (en) | 1998-11-05 | 1999-11-03 | Methods and compositions for inhibiting polymerization of ethylenically unsaturated hydrocarbons |
| CA002347885A CA2347885C (en) | 1998-11-05 | 1999-11-03 | Methods and compositions for inhibiting polymerization of ethylenically unsaturated hydrocarbons |
| AT99956553T ATE232191T1 (en) | 1998-11-05 | 1999-11-03 | METHOD AND COMPOSITION FOR INHIBITING THE POLYMERIZATION OF ETHYLENEICALLY UNSATURATED HYDROCARBONS |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/186,832 US6200461B1 (en) | 1998-11-05 | 1998-11-05 | Method for inhibiting polymerization of ethylenically unsaturated hydrocarbons |
| US09/186,832 | 1998-11-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2000027780A1 true WO2000027780A1 (en) | 2000-05-18 |
Family
ID=22686436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1999/023996 Ceased WO2000027780A1 (en) | 1998-11-05 | 1999-11-03 | Methods and compositions for inhibiting polymerization of ethylenically unsaturated hydrocarbons |
Country Status (12)
| Country | Link |
|---|---|
| US (2) | US6200461B1 (en) |
| EP (1) | EP1127040B1 (en) |
| JP (1) | JP4499921B2 (en) |
| KR (1) | KR100638292B1 (en) |
| CN (1) | CN1211326C (en) |
| AT (1) | ATE232191T1 (en) |
| AU (1) | AU1314300A (en) |
| BR (1) | BR9915031B1 (en) |
| CA (1) | CA2347885C (en) |
| DE (1) | DE69905273T2 (en) |
| ID (1) | ID29195A (en) |
| WO (1) | WO2000027780A1 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU5817099A (en) * | 1998-09-09 | 2000-03-27 | Baker Hughes Incorporated | Vinyl monomer polymerization inhibition using hindered hydroxylamines |
| US6262323B1 (en) * | 1999-12-14 | 2001-07-17 | Baker Hughes Incorporated | Polymerization inhibition of isoprene |
| US6376728B1 (en) * | 2000-06-20 | 2002-04-23 | Hercules Incorporated | Method, composition and mixture for inhibiting monomer polymerization |
| US6579442B2 (en) | 2001-05-22 | 2003-06-17 | Ge Betz, Inc. | Methods and compositions for inhibiting polymerization of vinyl monomers |
| US6639026B2 (en) * | 2001-05-22 | 2003-10-28 | Ge Betz, Inc. | Methods and compositions for inhibiting polymerization of vinyl monomers |
| US20040211702A1 (en) * | 2003-04-24 | 2004-10-28 | General Electric Company | Water-soluble phenylenediamine compositions and methods for stabilizing ethylenically unsaturated compounds and monomers |
| US20060069219A1 (en) * | 2004-09-28 | 2006-03-30 | Vilan Kosover | Sulfonated phenols with nitrophenols as polymerization inhibitors |
| CN102101814B (en) * | 2009-12-16 | 2013-04-24 | 中国石油天然气股份有限公司 | A polymerization inhibitor for inhibiting the polymerization of C5 fractions from petroleum cracking |
| JP2011256142A (en) * | 2010-06-10 | 2011-12-22 | Seiko Kagaku Kk | Polymerization inhibitor and method for preventing polymerization |
| CN102464555B (en) * | 2010-11-04 | 2013-12-04 | 中国石油天然气股份有限公司 | A polymerization inhibitor used in thermal dimerization of C5 fractions from petroleum cracking |
| JP6043937B2 (en) * | 2012-08-16 | 2016-12-14 | 株式会社片山化学工業研究所 | Composition for inhibiting polymerization of vinyl aromatic monomer |
| IN2013MU01165A (en) * | 2013-03-26 | 2015-04-24 | Dorf Ketal Chemicals India Private Ltd | |
| US20170158621A1 (en) * | 2015-12-04 | 2017-06-08 | Baker Hughes Incorporated | Substituted phenol derivatives for mitigating fouling |
| CN105754749B (en) * | 2016-03-28 | 2018-03-23 | 天津市瑞德赛恩新材料开发有限公司 | A kind of caustic wash tower on-line cleaning medicament and its preparation, application method |
| WO2020223224A1 (en) * | 2019-04-29 | 2020-11-05 | Ecolab Usa Inc. | Oxygenated aminophenol compounds and methods for preventing monomer polymerization |
| JP2022533004A (en) | 2019-04-29 | 2022-07-21 | エコラボ ユーエスエー インコーポレイティド | Use as an oxygenated aromatic amine and antioxidant |
| TWI880966B (en) * | 2019-10-11 | 2025-04-21 | 美商藝康美國公司 | Quinone methide and ammonium salt antipolymerant composition and method |
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| US2415009A (en) * | 1941-10-25 | 1947-01-28 | Shell Dev | Butadiene stabilization |
| GB1295794A (en) * | 1970-03-20 | 1972-11-08 | ||
| US5426257A (en) * | 1994-06-30 | 1995-06-20 | Betz Laboratories, Inc. | Compositions and methods for inhibiting vinyl aromatic monomer polymerization |
| US5446220A (en) * | 1994-08-24 | 1995-08-29 | Betz Laboratories, Inc. | Methods for inhibiting vinyl aromatic monomer polymerization |
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| US2399340A (en) * | 1942-07-16 | 1946-04-30 | United Gas Improvement Co | Distillation of aromatic olefins |
| US2510847A (en) * | 1946-03-21 | 1950-06-06 | Standard Oil Dev Co | Distillation of polymerizable diolefins |
| JPS493966B1 (en) * | 1968-09-27 | 1974-01-29 | ||
| US3654129A (en) * | 1970-04-20 | 1972-04-04 | Universal Oil Prod Co | Hydrorefining of coke-forming hydrocarbon distillates |
| US4439278A (en) * | 1982-06-21 | 1984-03-27 | Eastman Kodak Company | Process inhibitor for readily polymerizable ethylenically unsaturated aromatic compounds |
| JPH0753688B2 (en) * | 1987-10-12 | 1995-06-07 | 三井東圧化学株式会社 | Method for purifying methacrylic acid |
| US4775458A (en) * | 1986-12-18 | 1988-10-04 | Betz Laboratories, Inc. | Multifunctional antifoulant compositions and methods of use thereof |
| US4927519A (en) * | 1988-04-04 | 1990-05-22 | Betz Laboratories, Inc. | Method for controlling fouling deposit formation in a liquid hydrocarbonaceous medium using multifunctional antifoulant compositions |
| US4929778A (en) * | 1989-06-05 | 1990-05-29 | Betz Laboratories, Inc. | Methods and compositions for inhibiting styrene polymerization |
| US5128022A (en) * | 1991-01-18 | 1992-07-07 | Betz Laboratories, Inc. | Antioxidant compositions and methods using p-phenylenediamine compounds and organic acid compounds |
| US5221498A (en) * | 1991-07-22 | 1993-06-22 | Betz Laboratories, Inc. | Methods and compositions for inhibitoring polymerization of vinyl monomers |
| US5173213A (en) * | 1991-11-08 | 1992-12-22 | Baker Hughes Incorporated | Corrosion and anti-foulant composition and method of use |
| US5282957A (en) * | 1992-08-19 | 1994-02-01 | Betz Laboratories, Inc. | Methods for inhibiting polymerization of hydrocarbons utilizing a hydroxyalkylhydroxylamine |
| US5714055A (en) * | 1996-08-12 | 1998-02-03 | Nalco/Exxon Energy Chemicals, L.P. | Caustic tower trap for acetaldehyde |
-
1998
- 1998-11-05 US US09/186,832 patent/US6200461B1/en not_active Expired - Lifetime
-
1999
- 1999-11-03 KR KR1020017005624A patent/KR100638292B1/en not_active Expired - Lifetime
- 1999-11-03 BR BRPI9915031-0A patent/BR9915031B1/en not_active IP Right Cessation
- 1999-11-03 CN CNB998126330A patent/CN1211326C/en not_active Expired - Lifetime
- 1999-11-03 JP JP2000580962A patent/JP4499921B2/en not_active Expired - Lifetime
- 1999-11-03 ID IDW00200101204A patent/ID29195A/en unknown
- 1999-11-03 EP EP99956553A patent/EP1127040B1/en not_active Expired - Lifetime
- 1999-11-03 DE DE69905273T patent/DE69905273T2/en not_active Expired - Lifetime
- 1999-11-03 WO PCT/US1999/023996 patent/WO2000027780A1/en not_active Ceased
- 1999-11-03 AU AU13143/00A patent/AU1314300A/en not_active Abandoned
- 1999-11-03 CA CA002347885A patent/CA2347885C/en not_active Expired - Lifetime
- 1999-11-03 AT AT99956553T patent/ATE232191T1/en not_active IP Right Cessation
-
2001
- 2001-01-24 US US09/767,692 patent/US20010009968A1/en not_active Abandoned
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2415009A (en) * | 1941-10-25 | 1947-01-28 | Shell Dev | Butadiene stabilization |
| GB1295794A (en) * | 1970-03-20 | 1972-11-08 | ||
| US5426257A (en) * | 1994-06-30 | 1995-06-20 | Betz Laboratories, Inc. | Compositions and methods for inhibiting vinyl aromatic monomer polymerization |
| US5446220A (en) * | 1994-08-24 | 1995-08-29 | Betz Laboratories, Inc. | Methods for inhibiting vinyl aromatic monomer polymerization |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9915031A (en) | 2001-07-17 |
| EP1127040A1 (en) | 2001-08-29 |
| JP4499921B2 (en) | 2010-07-14 |
| ID29195A (en) | 2001-08-09 |
| CA2347885C (en) | 2007-06-26 |
| CA2347885A1 (en) | 2000-05-18 |
| DE69905273D1 (en) | 2003-03-13 |
| CN1324338A (en) | 2001-11-28 |
| BR9915031B1 (en) | 2011-07-26 |
| AU1314300A (en) | 2000-05-29 |
| KR20010082287A (en) | 2001-08-29 |
| ATE232191T1 (en) | 2003-02-15 |
| EP1127040B1 (en) | 2003-02-05 |
| US6200461B1 (en) | 2001-03-13 |
| DE69905273T2 (en) | 2003-08-28 |
| CN1211326C (en) | 2005-07-20 |
| KR100638292B1 (en) | 2006-10-26 |
| JP2002529432A (en) | 2002-09-10 |
| US20010009968A1 (en) | 2001-07-26 |
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