EP1324969A1 - Procede de stabilisation de monomeres acryliques - Google Patents
Procede de stabilisation de monomeres acryliquesInfo
- Publication number
- EP1324969A1 EP1324969A1 EP01972199A EP01972199A EP1324969A1 EP 1324969 A1 EP1324969 A1 EP 1324969A1 EP 01972199 A EP01972199 A EP 01972199A EP 01972199 A EP01972199 A EP 01972199A EP 1324969 A1 EP1324969 A1 EP 1324969A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ppm
- dtpa
- acid
- liquid phase
- acrylic monomers
- 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.)
- Withdrawn
Links
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000000178 monomer Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000003019 stabilising effect Effects 0.000 title abstract 2
- 239000003381 stabilizer Substances 0.000 claims abstract description 31
- 239000003352 sequestering agent Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 238000004821 distillation Methods 0.000 claims abstract description 18
- 239000007791 liquid phase Substances 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 18
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 13
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 10
- 229950000688 phenothiazine Drugs 0.000 claims description 10
- 230000000087 stabilizing effect Effects 0.000 claims description 10
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 9
- IXPUJMULXNNEHS-UHFFFAOYSA-L copper;n,n-dibutylcarbamodithioate Chemical compound [Cu+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC IXPUJMULXNNEHS-UHFFFAOYSA-L 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 229960004337 hydroquinone Drugs 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical class C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- -1 transition metal salts Chemical class 0.000 claims description 5
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 4
- 229960003505 mequinol Drugs 0.000 claims description 4
- 229960003330 pentetic acid Drugs 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 150000004897 thiazines Chemical class 0.000 claims description 4
- FCKYPQBAHLOOJQ-UWVGGRQHSA-N 2-[[(1s,2s)-2-[bis(carboxymethyl)amino]cyclohexyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)[C@H]1CCCC[C@@H]1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UWVGGRQHSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 3
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 3
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 claims 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims 1
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 238000000746 purification Methods 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- 238000009434 installation Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- KKZZSTCINUMTGD-UHFFFAOYSA-N 1,2,2,3-tetramethylpiperidin-4-ol Chemical compound CC1C(O)CCN(C)C1(C)C KKZZSTCINUMTGD-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001944 continuous distillation Methods 0.000 description 1
- OBBCYCYCTJQCCK-UHFFFAOYSA-L copper;n,n-diethylcarbamodithioate Chemical compound [Cu+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S OBBCYCYCTJQCCK-UHFFFAOYSA-L 0.000 description 1
- ZOUQIAGHKFLHIA-UHFFFAOYSA-L copper;n,n-dimethylcarbamodithioate Chemical compound [Cu+2].CN(C)C([S-])=S.CN(C)C([S-])=S ZOUQIAGHKFLHIA-UHFFFAOYSA-L 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B63/00—Purification; Separation; Stabilisation; Use of additives
- C07B63/04—Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/50—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
Definitions
- the present invention relates to a process for stabilizing acrylic monomers, in particular acrylic acid, by stabilizers containing a metal sequestering agent.
- phenolic derivatives such as hydroquinone or thiazine derivatives such as phenothiazine are known.
- patent JP 05320205 describes the use of a nitroxide derivative with a metal sequestering agent having a stability constant greater than 10 for Fe complexes under acidic conditions to improve the stability of (meth) acrylic monomers.
- patent JP 05295011 describes the use of one or more phenothiazine compounds (PTZ), aromatic or phenolic amines with a sequestering agent having a stability constant greater than 10 for Fe complexes under acidic conditions.
- PTZ phenothiazine compounds
- aromatic or phenolic amines with a sequestering agent having a stability constant greater than 10 for Fe complexes under acidic conditions.
- EP 048 51 69 discloses polymerization inhibitors comprising one or more stabilizers as well as oxygen.
- these known stabilizations do not completely prevent the formation of polymers during the stages of purification of the acrylic monomers.
- the problem that the invention proposes to solve is therefore to provide a method for stabilizing acrylic monomers having improved stabilizing efficiencies and at the same time making it possible to reduce the corrosion caused by acrylic monomers.
- the object of the invention is therefore to propose a process for stabilizing acrylic monomers, in particular in a distillation column.
- the method for stabilizing acrylic monomers in a distillation column according to the invention comprises the steps of adding at least one stabilizer of acrylic monomers in a total concentration in the liquid phase of between 1 ppm and 5000 ppm, from 1 injection of oxygen into the distillation column with an O 2 / organic vapor molar ratio of between 0.01% and 1%, and the addition of a metal sequestrant at a concentration in the liquid phase of between 0 , 1 ppm and 1000 ppm.
- the stabilizer is chosen from phenolic and thiazine derivatives, transition metal salts and nitroxide derivatives.
- the stabilizer is advantageously chosen from hydroquinone, hydroquinone methyl ether, phenothiazine, methylene blue, copper dibutyldithiocarbamate, manganese acetate, 2,2,6,6 tetramethyl-4-acetoxy- piperidine-oxyl, 2,2,6,6-tetramethyl-4-hydroxypiperidine-oxyl, 2,2,6,6-tetramethyl-4-methoxypiperidine-oxyl and mixtures thereof.
- the concentration of the stabilizer in the liquid phase is preferably between 5 ppm and 3000 ppm, preferably between 10 and 1000 ppm.
- the molar ratio between the oxygen injected and the organic vapor is preferably between 0.05% and 0.5%, preferably between 0.1 and 0.25%.
- the metal sequestering agent is advantageously chosen from tetraethylenediaminetetraacetic acid (EDTA), trans-1,2-cyclohexane diamine-tetraacetic acid (CYDTA), diethylenetraiminepentaacetic acid (DTP A), pentasodium salt diethylenetriamine-pentaacetic acid (Na 5 DTPA) as well as their mixtures.
- EDTA tetraethylenediaminetetraacetic acid
- CYDTA trans-1,2-cyclohexane diamine-tetraacetic acid
- DTP A diethylenetraiminepentaacetic acid
- Na 5 DTPA pentasodium salt diethylenetriamine-pentaacetic acid
- the metal sequestrant is present in the liquid phase preferably in a concentration of between 0.5 ppm and 500 ppm, in particular between 5 ppm and 100 ppm.
- the acrylic monomer is chosen from acrylic acid, methacrylic acid, acrylates, methacrylates, acrylonitrile or their mixtures.
- at least two stabilizers are used.
- the following mixtures are particularly preferred: PTZ / HQ / Na 5 DTPA, CB / HA / Na 5 DTPA, CB / PTZ / HQ / Na 5 DTPA, CB / PTZ / HQ / Na 5 DTP A and 4 -OH-TEMPO / EMHQ / Na 5 DTPA.
- metals facilitate redox reactions. Such an effect is for example known for lowering the temperature for generating free radicals in the persulfate / metabisulfite system by adding iron sulfate.
- the problems mentioned are solved according to the invention by adding a stabilizer and a metal sequestrant, and by injecting oxygen into the distillation column.
- the method according to the present invention makes it possible to substantially improve the operating time of a column for distilling a flow based on acrylic monomers and to significantly reduce the corrosion of the industrial tool made of stainless steel.
- acrylic monomers is meant in the present description acrylic acid, methacrylic acid, acrylates, methacrylates as well as acrylonitrile and their mixtures.
- phenolic derivatives such as, for example, hydroquinone, p-methoxyphenol, cresol, phenol, l ' hydroquinone methyl ether, and 2,5-butyl 1 hydroxytoluene.
- Thiazine derivatives such as for example phenothiazine or methylene blue and substituted paraphenylenediamines can also be used.
- transition metal salts such as, for example, copper dimethyl dithiocarbamate, copper diethyldithiocarbamate, copper dibutyldithiocarbamate or the corresponding manganese salts, as well as manganese acetate, are suitable.
- nitroxide derivatives such as for example 2,2,6,6 tetramethyl-4-acetoxy-piperidine-oxyl, 2,2,6,6-tetraméfhyl-4-hydroxypi réelledine -oxyl or 2,2,6,6-tetramethyl-4-methoxypiperidine-oxyl.
- the concentration of stabilizers in the liquid phase is between 1 ppm and 5000 ppm.
- the concentration is between 5, ppm and 3000 ppm, particularly preferred being a concentration between 10 and 1000 ppm.
- the method according to the invention also provides for the injection of oxygen into the distillation column.
- Oxygen improves the effectiveness of stabilizers. It also turns out that it makes it possible to stabilize the gas phase.
- the molar ratio between the oxygen injected into the distillation column and the organic vapor condensed at the head of the column is between 0.01% and 1%. Preferably, the molar ratio is between 0.1% and 0.8%, a ratio between 0.1 and 0.5% being particularly preferred.
- Organic vapor is formed in processes for the purification of substantially the acrylic monomer. Thus, the molar ratio is calculated relative to the vapor pressure of the acrylic monomer under the given temperature and pressure conditions.
- the process according to the invention is also carried out in the presence of a metal sequestering agent.
- a metal sequestering agent can be used for example: tetraethylenediaminetetraacetic acid (EDTA), trans-1, 2-cyclohexane diaminetetraacetic acid (CYDTA) and diethylenetraiminepentaacetic acid (DTP A) and pentasodium salt of l diethylene triaminepentaacetic acid (Na 5 DTPA), Na 5 DTPA being preferred.
- the metal sequestrant is present in the liquid phase in a concentration of between 0.1 ppm and 1000 ppm.
- the sequestering concentration is between 0.5 ppm and 500 ppm, a concentration between 5 ppm and 100 ppm being particularly preferred.
- the simultaneous presence of a stabilizer and a sequestering agent gives rise to a synergistic effect which is manifested by a stabilization efficiency greater than the sum of the effects attributable to the individual components.
- the process according to the present invention is particularly useful on distillation of streams rich in acrylic acid, but it can also be applied with other acrylic monomers.
- the assembly consists of a distillation column equipped with a multikit packing in stainless steel 316, a thermosyphon boiler, surmounted by a swan neck.
- the organic vapors are condensed using a conventional refrigerant. Part of the condensed liquid is recycled to the top of the column after addition of liquid phase stabilizers.
- the distillation is carried out under reduced pressure of approximately 200 mm Hg with a temperature of 105 ° C in the boiler. The distillation is carried out for 6 hours, then the multi-kit filling is dried and weighed.
- the stabilizing efficiency of the mixture studied is evaluated by comparing the mass of polymer formed in the lining. For the tests carried out with 4-OH TEMPO, the duration of the tests was fixed at 3 hours.
- the flux used for all the tests presented consists of crude acrylic acid at 94%. This flow continuously feeds the distillation column with a flow rate of 500 g / h. 445 g / h of distillate and 75 g / h at the bottom are drawn off at the head of the column. The flow rate of organic vapor in the column is 850 g / h. A reflux of 425 g / h is ensured.
- the stabilizers used in the examples are abbreviated as follows: phenothiazine (PTZ), hydroquinone (HQ), copper dibutyldithiocarbamate (CB), 4-hydroxy tetramethyl piperidine N-oxyl (4-OH TEMPO), and hydroquinone methyl ether (EMHQ).
- PTZ phenothiazine
- HQ hydroquinone
- CB copper dibutyldithiocarbamate
- EMHQ 4-hydroxy tetramethyl piperidine N-oxyl
- EMHQ hydroquinone methyl ether
- the stabilizers are combined with one another in the proportions indicated in Table 1 below.
- Oxygen is injected into the distillation column.
- the metal sequestrant is the pentasodium salt of diethylenetriaminepenta-acetic acid (Na 5 DTP A).
- a double jacket heated glass reactor is filled with stabilized acrylic acid and kept at 120 ° C for 72 hours.
- the acrylic acid is fed continuously with a flow rate of 120 ml / h which ensures an average residence time of the acrylic acid in the reactor of 5 hours.
- This same reactor contains elements made of 316L stainless steel, either in the form of 4 rectangular plates of approximately 40 cm 2 , or in the form of 2 spirals of approximately 800 cm 2 .
- the elements have been passivated beforehand. For this, the elements are first degreased with acetone, then oxidized with a fluoro-nitric mixture at 60 ° C for 20 min.
- Bubbling of a nitrogen stream containing 900 molar ppm of oxygen is also ensured in the reactor.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0012422 | 2000-09-29 | ||
| FR0012422A FR2814741B1 (fr) | 2000-09-29 | 2000-09-29 | Procede de stabilisation de monomeres acryliques |
| PCT/FR2001/002965 WO2002026685A1 (fr) | 2000-09-29 | 2001-09-25 | Procede de stabilisation de monomeres acryliques |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1324969A1 true EP1324969A1 (fr) | 2003-07-09 |
Family
ID=8854820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP01972199A Withdrawn EP1324969A1 (fr) | 2000-09-29 | 2001-09-25 | Procede de stabilisation de monomeres acryliques |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20040011638A1 (https=) |
| EP (1) | EP1324969A1 (https=) |
| JP (1) | JP2004513089A (https=) |
| KR (1) | KR100806558B1 (https=) |
| CN (1) | CN1250509C (https=) |
| AU (1) | AU2001291986A1 (https=) |
| FR (1) | FR2814741B1 (https=) |
| WO (1) | WO2002026685A1 (https=) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10339633A1 (de) * | 2002-10-17 | 2004-04-29 | Basf Ag | Verfahren zur Herstellung von (Meth)acrylsäure und (Meth)acrylsäureestern |
| JP2005343845A (ja) * | 2004-06-04 | 2005-12-15 | Hakuto Co Ltd | アクリロニトリルの重合抑制剤および重合抑制方法 |
| JP4959158B2 (ja) * | 2005-08-05 | 2012-06-20 | 旭化成ケミカルズ株式会社 | アクリロニトリルの分離回収方法 |
| EP2135656A1 (en) * | 2008-05-30 | 2009-12-23 | Rohm and Haas Company | Method for production of purified (Meth)acrylic acid |
| DE102012223695A1 (de) * | 2012-12-19 | 2014-06-26 | Basf Se | Verfahren zur Stabilisierung von polymerisationsfähigen Verbindungen |
| EP3426287A4 (en) | 2016-03-09 | 2020-03-11 | Los Angeles Biomedical Research Institute at Harbor-UCLA Medical Center | Methods and kits for use in preventing and treating vulvovaginal candidiasis |
| CN111051488B (zh) * | 2017-08-31 | 2021-11-26 | 富士胶片株式会社 | 药液的纯化方法及药液 |
| JP7159453B2 (ja) | 2018-08-24 | 2022-10-24 | ビーエル テクノロジーズ、インコーポレイテッド | 重合を阻害するための相乗的組み合わせ |
| US20250263387A1 (en) | 2022-03-25 | 2025-08-21 | Mitsubishi Gas Chemical Company, Inc. | Method for purifying (meth)acrylic acid monomer and/or (meth)acrylic acid ester monomer |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1601979A (en) * | 1978-01-06 | 1981-11-04 | Rohm & Haas | Polymerization inhibition |
| US4929660A (en) * | 1986-03-14 | 1990-05-29 | The Kendall Company | Acrylic adhesive compositions having improved stability |
| JP2758780B2 (ja) * | 1992-04-15 | 1998-05-28 | 株式会社クラレ | （メタ）アクリル酸の重合防止方法 |
| JP3197947B2 (ja) * | 1992-05-21 | 2001-08-13 | 株式会社クラレ | （メタ）アクリル酸の重合防止法 |
| TW294658B (https=) * | 1994-06-02 | 1997-01-01 | Nippon Catalytic Chem Ind | |
| FR2750696B1 (fr) * | 1996-07-08 | 1998-10-30 | Atochem Elf Sa | Solutions aqueuses stabilisees de sels d'ammoniums quaternaires insatures |
| DE19920796A1 (de) * | 1999-05-06 | 2000-11-09 | Roehm Gmbh | Verfahren zur Herstellung von Isobornylmethacrylat |
| FR2801306B1 (fr) * | 1999-11-24 | 2001-12-28 | Atofina | Procede de purification des monomeres (meth) acryliques par distillation |
-
2000
- 2000-09-29 FR FR0012422A patent/FR2814741B1/fr not_active Expired - Fee Related
-
2001
- 2001-09-25 KR KR1020037004262A patent/KR100806558B1/ko not_active Expired - Fee Related
- 2001-09-25 CN CNB018166059A patent/CN1250509C/zh not_active Expired - Fee Related
- 2001-09-25 EP EP01972199A patent/EP1324969A1/fr not_active Withdrawn
- 2001-09-25 AU AU2001291986A patent/AU2001291986A1/en not_active Abandoned
- 2001-09-25 US US10/381,795 patent/US20040011638A1/en not_active Abandoned
- 2001-09-25 JP JP2002531072A patent/JP2004513089A/ja not_active Withdrawn
- 2001-09-25 WO PCT/FR2001/002965 patent/WO2002026685A1/fr not_active Ceased
Non-Patent Citations (1)
| Title |
|---|
| See references of WO0226685A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2814741B1 (fr) | 2004-02-27 |
| KR100806558B1 (ko) | 2008-02-27 |
| JP2004513089A (ja) | 2004-04-30 |
| CN1531521A (zh) | 2004-09-22 |
| AU2001291986A1 (en) | 2002-04-08 |
| WO2002026685A1 (fr) | 2002-04-04 |
| KR20030081308A (ko) | 2003-10-17 |
| US20040011638A1 (en) | 2004-01-22 |
| FR2814741A1 (fr) | 2002-04-05 |
| CN1250509C (zh) | 2006-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2164912C (fr) | Procede de recuperation des produits nobles legers contenus dans les residus de distillation des procedes de fabrication de l'acide acrylique et de ses esters | |
| EP1324969A1 (fr) | Procede de stabilisation de monomeres acryliques | |
| US5932735A (en) | Derivatives of 1-oxyl-4-hydroxy-2,2,6,6-tetramethylpiperidine as polymerization inhibitors for (meth)acrylate monomers | |
| CN1051986C (zh) | 一种在蒸馏过程中抑制乙烯基化合物聚合的方法 | |
| WO2005019160A1 (fr) | Procede de fabrication et de separation de composes dinitriles | |
| EP3551603A1 (fr) | Procede pour eviter le depot de polymeres dans un procede de purification d'acide (meth)acrylique | |
| FR3064630B1 (fr) | Procede de purification d'acide (meth)acrylique incluant une colonne de distillation a paroi separatrice | |
| EP3914581B1 (fr) | Procede de purification d'esters (meth)acryliques a l'aide d'une colonne a partition | |
| EP0946486B1 (fr) | Purification de l'acide acrylique obtenu par oxydation catalytique du propylene | |
| EP1232138B1 (fr) | Procede de purification des monomeres (meth) acryliques par distillation | |
| CN1277798C (zh) | (甲基)丙烯酸的制备方法 | |
| FR2854891A1 (fr) | Procede de preparation de dinitriles | |
| WO2019020889A1 (fr) | Procede de purification d'esters (meth)acryliques | |
| EP1095006B1 (en) | Derivatives of 1-oxyl-4-hydroxy-2,2,6,6-tetramethylpiperidine as polymerization inhibitors for (meth) acrylate monomers | |
| JP4575383B2 (ja) | アクリル酸含有液体の精留分離法 | |
| EP1802564A1 (fr) | Utilisation d'esters phosphoriques comme agents anti-depots lors de la synthese, la purification ou la regeneration de monomeres (meth ) acryliques . | |
| CA2476357C (en) | Nitrosophenols and c-nitrosoanilines as polymerization inhibitors | |
| WO2020201661A1 (fr) | Production d'acide acrylique de grade polymere | |
| CA2337321C (fr) | Procede de distillation d'ammoniac | |
| US7977503B2 (en) | Polymerization inhibition method | |
| JP3885486B2 (ja) | ビニル単量体用重合防止剤組成物及び高純度（メタ）アクリル酸の製造方法 | |
| EP1288185A2 (fr) | Stabilisation de l'acroleine | |
| JP3312638B2 (ja) | （メタ）アクリル酸の重合防止剤組成物および該組成物を用いた（メタ）アクリル酸の重合防止方法 | |
| FR2696171A1 (fr) | Procédé de préparation du divinylbenzène. | |
| BE558027A (https=) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 20030429 |
|
| AK | Designated contracting states |
Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
| AX | Request for extension of the european patent |
Extension state: AL LT LV MK RO SI |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: ARKEMA |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: ARKEMA FRANCE |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: ARKEMA FRANCE |
|
| 17Q | First examination report despatched |
Effective date: 20071213 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
| 18D | Application deemed to be withdrawn |
Effective date: 20090313 |