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 modifiees

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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Withdrawn
Application number
EP03717530A
Other languages
German (de)
English (en)
Inventor
Shivanand Janardan Kulkarni
Madhavi Gangapuram
Vijaya Raghavan Kondapuram
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.)
Council of Scientific and Industrial Research CSIR
Original Assignee
Council of Scientific and Industrial Research CSIR
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 Council of Scientific and Industrial Research CSIR filed Critical Council of Scientific and Industrial Research CSIR
Priority claimed from PCT/IN2003/000111 external-priority patent/WO2004087664A1/fr
Publication of EP1608621A1 publication Critical patent/EP1608621A1/fr
Withdrawn legal-status Critical Current

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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.
EP03717530A 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 Withdrawn EP1608621A1 (fr)

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

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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)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
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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