WO2000056688A2 - Production of butane 1-3 diol, propane 1-3 diol and other diols and polyols - Google Patents

Production of butane 1-3 diol, propane 1-3 diol and other diols and polyols Download PDF

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Publication number
WO2000056688A2
WO2000056688A2 PCT/IN2000/000024 IN0000024W WO0056688A2 WO 2000056688 A2 WO2000056688 A2 WO 2000056688A2 IN 0000024 W IN0000024 W IN 0000024W WO 0056688 A2 WO0056688 A2 WO 0056688A2
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WO
WIPO (PCT)
Prior art keywords
polyols
diol
catalyst
manufacture
formaldehyde
Prior art date
Application number
PCT/IN2000/000024
Other languages
English (en)
French (fr)
Other versions
WO2000056688A3 (en
Inventor
Vinod Chintamani Malshe
Manish Vijay Kumar Mandlecha
Original Assignee
Vinod Chintamani Malshe
Manish Vijay Kumar Mandlecha
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 Vinod Chintamani Malshe, Manish Vijay Kumar Mandlecha filed Critical Vinod Chintamani Malshe
Priority to AU54247/00A priority Critical patent/AU5424700A/en
Publication of WO2000056688A2 publication Critical patent/WO2000056688A2/en
Publication of WO2000056688A3 publication Critical patent/WO2000056688A3/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the diols are important raw materials for production of polymers. Their utility is constantly increasing due to the wide variety of structural variation.
  • the new applications of polymers in the field of surface coating require special raw materials in different areas of application.
  • the UV curable coatings and coil coatings require a high degree of flexibilization to accomplish certain properties in the final finish. This is accomplished by using highly branched diols which prevent crystallization of polymeric molecules and provide it clarity, low temperature flexibility and toughness. These properties are achieved by using butane 1-3 diol, propane 1-3 diol, hexane 2,5 diol, cyclohexane ⁇ methanol and others.
  • Propane 1-3 diol has been classically prepared by reduction of ethyl glymoore with lithium aluminum hydride. (Walborsky, Colombini. J. Org. Chem. 27, 2387, 1962). This route has remained a laboratory curiosity. Commercial interest in this monomer started only after it was realized that the its polyester with terephthalic acid is a better fibre forming polymer compared to ethylene glycol polyester (PET). Recently Shell Chemicals announced a 75,000 TPY plat to manufacture propane diol required to manufacture PTT (Poly trimethylene terephthalate)(European Chemical News, 13-26 Dec 1999). The primary uses of PTT are envisaged in carpets and Textiles. It is also expected to replace a part of Nylon and PET in films and engineering applications. Presently four commercial routes have been reported for the manufacture of propane 1-3 diol (PDO). These are
  • Boenigk et al (Applied Microbiology Biotechnology, 1993, 38(4)453-7) have reported the conversion of glycerol at a rate of 3.7 g/l-hr in a two stage fermentation process. A 62.2% molar yield is reported with a 1.38g/l-h productivity.
  • Major c t-ficulties with fermentation processes (which require large reactors for commercial production) are the low concentration of the substrate and high cost of recovery from dilute solutions.
  • butane 1-3 diol starts from acetaldehyde condensation to acetaldol. This is, then isolated and hydrogenated to produce butane 1-3 diol.
  • the acetaldol is associated with acetaldehyde. In the process of hydrogenation this acetaldehyde is also required to be hydrogenated to ethyl alcohol. This represents a waste of efforts.
  • alcohol is de hydrogenated to a acetaldehyde and can be recycled to the process. But the energy consumed in each cycle adds to the cost.
  • propane 1-3 diol acrolein is first hydrated and then catalytically hydrogenated to produce propane 1-3 diol. The cost of starting raw materials in this case is high.
  • the main object of present invention therefore relates to a process for the production of diols from aldol condensation products with aluminum iso propoxide and a secondary alcohol, such as isopropanol.
  • the conventional techniques of aldol condensation require aqueous alkaline catalysts which cause considerable polymerization of the aldol.
  • the neutralization of the alkali causes dehydration leading to formation of tarry products.
  • the yield of typical aldol condensation products is less than 60-70 % with attendant problems of disposal of by products.
  • the reactions are applicable to aldehydes and ketones to produce diols , triols and polyols. This process has several advantages over the conventional processes.
  • propane 1-3 diol In the case of propane 1-3 diol the starting materials are acetaldehyde and formaldehyde. The molar ratio of acetaldehyde and formaldehyde is maintained slightly below 1 : 1. In this way the reaction can be stopped at slightly deficient conversion of acetaldehyde. This prevents formation of by-products. The excess acetaldehyde is removed by distillation and the hydroxy propenal is reduced with the system described above. Thus propane 1-3 diol can be made from elementary raw materials. In the case there is slight excess of formaldehyde over acetaldehyde, the additional product formed is trimethylol methane, a very useful triol which can substitute ' glycerol in several application with superior properties.
  • reaction is carried out with three moles of formaldehyde with acetaldehyde, it produces pentaerythritol without the byproduct sodium formate produced in the conventional process of manufacture of pentaerythritol, which causes serious problems of separation due to identical water solubility.
  • butane 1-3 diol the starting materials are acetone and formaldehyde.
  • the 2-Keto Butanol so produced is reduced with isopropanol which in turn produces acetone and butane 1-3 diol.
  • the acetone recovered from the process is recycled. This effectively means that butane 1-3 diol is produced from isopropanol and formaldehyde.
  • the repeated hydrogenation , de hydrogenation and recycle of ethyl alcohol is completely avoided.
  • isopropanol is used as a solvent which also is a reactant.
  • the starting raw material could simply be industrial MIBK which is produced by aldol condensation of acetone.
  • the by-product acetone could then be recycled to the plant as starting raw material.
  • the product was distilled under vacuum to yield 0.45 gram mole butane 1-3 diol or 90% based on formaldehyde.
  • the residue consisted of a triol formed by multiple addition of formaldehyde on acetone. The acetone so formed is recycled to the next batch as a solution in isopropanol.
  • Example 4 in all the above examples a catalyst prepared from one mole of aluminum Iso propoxide and one mole of trifluoro acetic acid was used to improve the conversion and the yield of the finished products. In addition, this catalyst also helped to reduce the reaction time from several hours to a few minutes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/IN2000/000024 1999-03-22 2000-03-21 Production of butane 1-3 diol, propane 1-3 diol and other diols and polyols WO2000056688A2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU54247/00A AU5424700A (en) 1999-03-22 2000-03-21 Production of butane 1-3 diol, propane 1-3 diol and other diols and polyols

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN205BO1999 IN192074B (en]) 1999-03-22 1999-03-22
IN205/BOM/99 1999-03-22

Publications (2)

Publication Number Publication Date
WO2000056688A2 true WO2000056688A2 (en) 2000-09-28
WO2000056688A3 WO2000056688A3 (en) 2001-03-29

Family

ID=11078479

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IN2000/000024 WO2000056688A2 (en) 1999-03-22 2000-03-21 Production of butane 1-3 diol, propane 1-3 diol and other diols and polyols

Country Status (3)

Country Link
AU (1) AU5424700A (en])
IN (1) IN192074B (en])
WO (1) WO2000056688A2 (en])

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2653096C2 (de) * 1976-11-23 1985-04-11 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von 2,2-disubstituierten Propan-1,3-diolen

Also Published As

Publication number Publication date
AU5424700A (en) 2000-10-09
IN192074B (en]) 2004-02-14
WO2000056688A3 (en) 2001-03-29

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