EP1608621A1 - Procede pour preparer de la pyridine 2,6-divinyle et de la pyridine 2-methyl-6-vinyle a partir de la 2,6-lutidine au moyen de zeolites modifiees - Google Patents
Procede pour preparer de la pyridine 2,6-divinyle et de la pyridine 2-methyl-6-vinyle a partir de la 2,6-lutidine au moyen de zeolites modifieesInfo
- Publication number
- EP1608621A1 EP1608621A1 EP03717530A EP03717530A EP1608621A1 EP 1608621 A1 EP1608621 A1 EP 1608621A1 EP 03717530 A EP03717530 A EP 03717530A EP 03717530 A EP03717530 A EP 03717530A EP 1608621 A1 EP1608621 A1 EP 1608621A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lutidine
- catalyst
- zsm
- formaldehyde
- modified
- 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- Withdrawn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
Definitions
- the present invention relates to a process for the preparation of 2,6- divinylpyridine and 2-methyl-6-vinylpyridine over modified zeolite catalysts.
- it relates to the method for the synthesis of 2,6-divinylpyridine and 2- methyl-6-vinylpyridine from 2,6-lutidine and formaldehyde in vapour phase in an eco- friendly method with high yield and selectivity.
- This invention provides a non- corrosive, eco-friendly process, where the catalyst can be reused for many times.
- 2,6- Divinylpyridine is useful starting material in polymer industry. BACKGROUND OF THE INVENTION
- 2,6-Divinylpyridine is used in the preparation of an aminated ion-exchange resins containing divinyl substituted heterocyclic co-monomers as cross-linkers.
- 2,6- Divinylpyridine (2,6-DVP) and 2-methyl-6-vinylpyridine (2M6VP) were synthesized by condensation of 2,6-lutidine and formaldehyde using potassium salts as catalysts. This method involves homogeneous conditions alongwith the high temperature and pressure [E.G. Martin, US 2,824,844 (1958); Chem. Abstract.52 (1958) 9482i; J. Michalski, K. Studniarski, Roczniki Chem. 29 (1955) 1141; Chem. Abstract. 51 (1957) 10530c and Chem. Abstract 62 (1965) 1627c].
- 2,6-DVP and 2M6VP were also prepared by oxidative dehydrogenation of dialkyl heteroaromatics over V 2 O 5 /MgO and MoO 3 /MgO catalysts in the presence of O 2 [I.P. Belomestnykh, N.N. Rozhdestvenskaya, G.V. Isagulyants, Khim. Geterotsikl. Soedian. 6 (1994) 802; Chem. Abstract. 122 (1995) 31287r.].
- the main object of the invention is to provide a process for the synthesis of 2,6-divinylpyridine and 2-methyl-6-vinylpyridine over modified zeolites in a heterogeneous eco-friendly method.
- Another object of the invention is to provide a process for the preparation of
- the present invention relates to develop a process for the preparation of 2,6- divinylpyridine and 2-methyl-6-vinylpyridine from 2,6-lutidine and formaldehyde in vapour phase over zeolite/ molecular sieve catalysts.
- the catalyst comprises of particularly ZSM-5 (pentasil family) with sodium, potassium, rubidium, cesium, magnesium, calcium, strontium and/or barium, etc cation or their species.
- the present invention provides a process for the simultaneous production of 2,6-divinylpyridine and 2-methyl-6-vinylpyridine comprising reacting 2,6-lutidine with formaldehyde in a catalytic zone containing a modified zeolite catalyst, the temperature of the catalytic zone being in the range of 200 to 450°C, the reaction being carried out at a weight hourly space velocity in the range of 0.25 to 1.0 h "1 , the molar ratio of 2,6-lutidine to formaldehyde being 1 :1 to 1:4.
- the modified zeolite catalyst comprises a modified ZSM-5 pentasil type zeolite catalyst, preferably modified by an alkali or alkaline earth metal ion selected from the group consisting of Li + , Na + , K + , Rb + , Cs + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ .
- the modified ZSM-5 catalyst is a two cation modified ZSM-5, such as Cs-K-ZSM-5.
- the weight percent of the alkali or alkaline earth metal ion in ZSM-5 is in the range of 1 wt % to 4 wt %.
- the ZSM-5 catalyst is modified by potassium ion, the potassium ion source being selected from the group consisting of KO'Bu, KOH, KF, KNO 3 , K 3 PO 4 and KOAc, to improve the yield and selectivity of 2,6-divinylpyridine.
- the modified zeolite is 3 wt% KZSM-
- the temperature of the catalytic zone is
- Another embodiment of the present invention provides a process for the preparation of 2,6-divinylpyridine and 2M6VP form 2,6-lutidine and formaldehyde in the presence of catalyst which comprises ZSM-5 containing one or two elements(s) from alkali and/ or alkaline earth metal ions like Na + , K + , Rb + , Cs + , Mg 2+ , Ca + , Sr 2+ , Ba etc which can be reused for several times.
- catalyst comprises ZSM-5 containing one or two elements(s) from alkali and/ or alkaline earth metal ions like Na + , K + , Rb + , Cs + , Mg 2+ , Ca + , Sr 2+ , Ba etc which can be reused for several times.
- the modified HZSM-5 catalyst was used in the development of the process. Each zeolite was pelleted without binder, crashed and sized 18-30 mesh before the impregnation.
- the ZSM-5 catalyst was modified by using required amount of alkali or alkaline earth cation nitrate by an impregnation method.
- the required amount of precursor was taken in the form of nitrate or other soluble salts in 30 ml of distilled water.
- 4.0 g of the meshed catalyst was added to it and kept for soaking for 12 h. Then it was dried at 110°C over night and calcined at 420°C for 4 h before using for the reaction.
- KO l Bu modified ZSM-5 (30) catalyst In a typical procedure for the synthesis of KO l Bu modified ZSM-5 (30) catalyst is as follows; 7 g of HZSM-5 (30) was taken in 250 ml two-necked round bottom flask. Prior to modification the catalyst was predried in oven at 100°C for 1 h followed by flushing with nitrogen gas to remove water content present in the channels of the catalyst. In another round bottom flask required amount of KO l Bu was dissolved in dry DMSO solvent. This solution was added to HZSM-5 (30) catalyst and kept stirring for 24 h in presence of nitrogen atmosphere. After 24 h stirring the resultant mixture was filtered, dried at 120°C overnight and calcined at 400°C for 4 h.
- the reactions were carried out in a fixed bed, continuous, down-flow pyrex reactor with internal diameter of 20 mm at atmospheric pressure. All the catalysts were activated by calcination in a flow of air at 420°C for 4 h and brought to the reaction temperature in situ. A mixture of 2,6-lutidine and formaldehyde 37%wt/v was fed from a syringe pump at a rate of 2 ml. h "1 . The effluents from the reactor were cooled and periodically collected with an ice trap. The samples were analyzed by gas chromatography (SCHIMADZU-14B) fixed with an OV-17 (2 mm x 1/8" OD) on chromosorb W-HP column and flame ionization detector.
- SCHIMADZU-14B gas chromatography
- the carrier gas was N 2 (100 kPa) and the column temperature programme was 90°C (5 min), 2°C. min "1 , 120°C (10 min), 180°C (injector) and 250°C (detector). Products were confirmed by GC-Ms and NMR techniques. 2,6-DVP and 2M6VP are formed as major products during side-chain alkylation of 2,6-lutidine and formaldehyde with all the catalysts studied here. Other products include 2-methyl-6- ethylpyridine and isomerized product 2,5-divinylpyridine.
- Example 3 Modified ZSM-5 was used in the following reaction for the preparation of 2,6- divinylpyridine and 2-methyl-6-vinyl ⁇ yridine.
- the reaction of 2,6-lutidine and formaldehyde was carried out over K-ZSM-5 (30, 3 wt% K) in the reaction temperature range of 250 to 400°C.
- the catalyst was 4 g with 18-30 mesh size and feed rate 2 ml.h "1 .
- the molar ratio of 2,6-lutidine: formaldehyde was 1:4.
- EXAMPLE 11 EXAMPLE 11:
- the molar ratio of 2,6-lutidine: formaldehyde was varied in the range of 1:1 to 1:5.
- the catalyst was 4 g with 18-30 mesh size and feed rate 2 ml.h "1 .
- EXAMPLE 12 The reaction of 2,6-lutidine and formaldehyde was carried out over K-ZSM-5
- the calcination or activation temperature of the ZSM-5 catalyst was also varied in the temperature range of 420°C to 700°C.
- the reaction of 2,6-lutidine and formaldehyde was carried out over KZSM-5 (30, 3wt%).
- the catalyst was 4 g with 18-30 mesh size and feed rate 2 ml.h "1 .
- EXAMPLE 14 EXAMPLE 14:
- the weight percent potassium impregnated in the HZSM-5 catalyst was also varied from 1 wt% to 4 wt%.
- the reaction of 2,6-lutidine and formaldehyde was carried out over K-ZSM-5 (30) at 300°C and 0.5 h "1 W.H.S.V.
- the molar ratio of 2,6- lutidine: formaldehyde was 1:4.
- the weight of the catalyst was 4 g with 18-30 mesh size and feed rate 2 ml.h "1 .
- the potassium precursor in the process of impregnation was also varied.
- the reaction of 2,6-lutidine and formaldehyde was carried out at 300°C and 0.5 h "1 W.H.S.V.
- the molar ratio of 2,6-lutidine: formaldehyde was 1:4.
- the weight of the catalyst was 4 g with 18-30 mesh size and feed rate 2 ml.h "1 .
- the molar ratio of 2,6- lutidine to formaldehyde was 1:4.
- the following precursors were studied, KNO 3 , KF, KOAc, K 3 PO 4 and KOH.
- the conversion of 2,6-lutidine was varied from 51% to 80% with 36 to 56 % of selectivity for 2,6-
Landscapes
- Catalysts (AREA)
- Pyridine Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
L'invention concerne un procédé pour préparer de la pyridine 2,6-divinyle et de la pyridine 2-méthyl-6-vinyle par catalyseurs modifiés à base de zéolite. Elle concerne en particulier un procédé pour faire la synthèse de la pyridine 2,6-divinyle et de la pyridine 2-méthyl-6-vinyle à partir de la 2,6-lutidine et du formaldéhyde en phase vapeur, ce procédé étant respectueux de l'environnement et présentant un haut rendement et une grande sélectivité. La procédé de l'invention est non-corrosif et respectueux de l'environnement, le catalyseur pouvant être réutilisé plusieurs fois. La pyridine 2,6-divinyle sert de matière première dans l'industrie des polymères.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/IN2003/000111 WO2004087664A1 (fr) | 2003-03-25 | 2003-03-31 | Procede pour preparer de la pyridine 2,6-divinyle et de la pyridine 2-methyl-6-vinyle a partir de la 2,6-lutidine au moyen de zeolites modifiees |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1608621A1 true EP1608621A1 (fr) | 2005-12-28 |
Family
ID=34385759
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03717530A Withdrawn EP1608621A1 (fr) | 2003-03-31 | 2003-03-31 | Procede pour preparer de la pyridine 2,6-divinyle et de la pyridine 2-methyl-6-vinyle a partir de la 2,6-lutidine au moyen de zeolites modifiees |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1608621A1 (fr) |
JP (1) | JP4430549B2 (fr) |
AU (1) | AU2003222442A1 (fr) |
-
2003
- 2003-03-31 JP JP2004570080A patent/JP4430549B2/ja not_active Expired - Fee Related
- 2003-03-31 AU AU2003222442A patent/AU2003222442A1/en not_active Abandoned
- 2003-03-31 EP EP03717530A patent/EP1608621A1/fr not_active Withdrawn
Non-Patent Citations (1)
Title |
---|
See references of WO2004087664A1 * |
Also Published As
Publication number | Publication date |
---|---|
AU2003222442A1 (en) | 2004-10-25 |
JP2006522009A (ja) | 2006-09-28 |
JP4430549B2 (ja) | 2010-03-10 |
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