Title:
PRODUCTION OF BUTANE 1-3 DIOL, PROPANE 1-3 DIOL AND OTHER DIOLS AND POLYOLS
Document Type and Number:
WIPO Patent Application WO/2000/056688
Kind Code:
A2
Abstract:
Diols are important raw materials for the polymer industry. These are conventionally prepared by the aldol condensation and hydrogenation of the resultant keto alcohols or aldehydes using a catalyst and hydrogen gas. The catalytic processes have their own operational problems such as risk of fire, high operating pressure, deactivation of catalyst, recovery of the catalyst, etc. Propane 1-3 diol has recently acquired importance for fibre forming polymer (PTT) which is superior to Poly ethylene terephthalate (PET) in several of its properties and is projected as a polymer of the future. The commercial routes to produce propane 1-3 diol are from fermentation of glucose and sacharides or by hydration of acrolein followed by hydrogenation. In the present invention, a new route to synthesize diols has been reported which starts with the aldol formation of aldehydes or ketons followed by MPV reduction. The process has the advantage of operating at very mild conditions and freedom from complication of catalytic processes.
Inventors:
MALSHE VINOD CHINTAMANI (IN)
MANDLECHA MANISH VIJAY KUMAR (IN)
MANDLECHA MANISH VIJAY KUMAR (IN)
Application Number:
PCT/IN2000/000024
Publication Date:
September 28, 2000
Filing Date:
March 21, 2000
Export Citation:
Assignee:
MALSHE VINOD CHINTAMANI (IN)
MANDLECHA MANISH VIJAY KUMAR (IN)
MANDLECHA MANISH VIJAY KUMAR (IN)
International Classes:
C07C29/14; (IPC1-7): C07C29/16; C07C31/20; C07C35/08
Foreign References:
| US4181810A | 1980-01-01 |
Other References:
A.T. NIELSEN, ET AL.: "A 13C and 1H n.m.r. study of formaldehyde reactions with acetaldehyde and acrolein. Synthesis of 2-(hydroxymethyl)-1,3-propanediol" POLISH JOURNAL OF CHEMISTRY, vol. 55, no. 6, 1981, pages 1393-1403, XP000971563 Polish Chemical Society, Warsaw, PL
R. HELG, ET AL.: "Der Einfluss der Substituenten auf die Cyclisation der Terpene" HELVETICA CHIMICA ACTA, vol. 39, no. 5, 1 August 1956 (1956-08-01), pages 1269-1290, XP002155676 Verlag Helvetica Chimica Acta, Basel, CH ISSN: 0018-019X
J. MARCH: "Advanced Organic Chemistry, 4th Edition, pages 910-918" 1993 , JOHN WILEY & SONS , NEW YORK, US XP002155677 page 913
R. HELG, ET AL.: "Der Einfluss der Substituenten auf die Cyclisation der Terpene" HELVETICA CHIMICA ACTA, vol. 39, no. 5, 1 August 1956 (1956-08-01), pages 1269-1290, XP002155676 Verlag Helvetica Chimica Acta, Basel, CH ISSN: 0018-019X
J. MARCH: "Advanced Organic Chemistry, 4th Edition, pages 910-918" 1993 , JOHN WILEY & SONS , NEW YORK, US XP002155677 page 913
Attorney, Agent or Firm:
Malshe, Vinod Chintamani (Matunga Mumbai 9, Matunga Mumbai 9, IN)
Malshe, Vinod Chintamani (Matunga Mumbai 9, Matunga Mumbai 9, IN)
Malshe, Vinod Chintamani (Matunga Mumbai 9, Matunga Mumbai 9, IN)
Download PDF:
Claims:
Claims:
| 1. | (1) A simple process to manufacture diols and polyols from elementary raw materials and mild conditions. We have developed a new process to prepare the aldol condensation products, which essentially has following steps. |
| 2. | Dissolution of aldehyde or ketone in dry isopropanol. |
| 3. | Cooling the mixture to 1015 °C. |
| 4. | Dissolution of paraformaldehyde in isopropanol. |
| 5. | Drying the solution of step 3 with the help of desiccants. |
| 6. | Mixing the two solutions prepared in step 2 and step 4 in specified molar ratio of aldehyde and formaldehyde 6 Addition of a dry hydroxide form of strong base anion exchanger as a catalyst and holding it till the two aldehydes fully react to form the methylol group 7. Separation of the ion exchange resin by filtration 8. Addition of aluminum isopropoxide catalyst to cause reduction of the carbonyl group to alcool. (If the'starting compound was an aldehyde it results in the formation of a primary diol. If the starting compound in step 1 is a ketone, the final product is a secondary alcool). |
| 7. | 9 Distillation of the product acetone to completely shift the equilibrium to alcohol formation. |
| 8. | 10 Neutralization of the isopropoxide with water to deactivate the reaction. |
| 9. | 11 Recovery of the diol by distillation and purification by fractionation (2) A process for manufacture of Polyols as described in Example1 where highpressure hydrogenation is not required. (3) A process for manufacture of Polyols as described in Example12 where a catalyst prepared from nonnoble metals can be used without hydrogen or carbon monoxide, a poisonous gas. (4) A process for manufacture polyols as described in Example13 using a modified aluminum isopropoxide catalyst which reduces the reaction time from several hours to a few minutes. (5) A process for manufacture polyols as described in Example1to 4 where by modifying the mole ratio of aldehyde and formaldehyde, or ketone and formaldehyde, it is possible to produce diols triols, polyols all without hydrogenation. (6) A process for manufacture polyols as described in Example1to 5 where the conventional process for the production of penta erythritol produces by product sodium formate which poses considerable difficulty in separation due to similar water solubility. In addition, sodium formate does not have high commercial value and is an undesirable by product. By using our process, it is possible to manufacture penta erythritol of nitration grade with high monomer content without formation of sodium formate. (7) A process for manufacture polyols as described in Example1 to 6 where a process is equally applicable to trimethylol propane, and neopentyl glycol which are made from butyraldehyde and isobutyraldehyde by condensation with formaldehyde. In addition, there is a potential to develop totally new products from aldehydes, ketones and formaldehyde for example from cyclohexanon or propanoldehyde and formaldehyde. The examples described above are to illustrate the invention and in no way limit the scope of the invention. The procedures described above are general and applicable to different varieties of Aldehydes, and ketones to produce diols triols and polyols. |
Description:
INTERNATIONALSEARCHREPORTInter nal Application No Inter nal Application No PCT/IN00/00024 C.(Continuation)DOCUMENTSCONSIDEREDTOBERELEVANT Category° Citation ot documenl,withindication,whereappropriate,oftherelevantpassag
esRelevanttoclaimNo AR.HELG,ETAL.:"DerEinflussder1 SubstituentenaufdieCyclisationder Terpene" HELVETICACHIMICAACTA, vol.39,no.5, 1August1956(1956-08-01),pages 1269-1290,XP002155676 VerlagHelveticaChimicaActa,Basel,CH ISSN:0018-019X page1279,lastparagraph-page1280, paragraph1 AJ.MARCH:"AdvancedOrganicChemistry,1 4thEdition,pages910-918" 1993,JOHNWILEY&SONS,NEWYORK,US XP002155677 page913 1 INTERNATIONALSEARCHREPORTInter, nal Application No . ormation on patent family members PCT/IN00/00024 PatentdocumentPublication Patent family Publication citedinsearchreportdate member(s)date US4181810A01-01-1980DE 2653096 A 24-05-1978 BE 861077 A 23-05-1978 FR 2371407 A 16-06-1978 GB 1566048 A 30-04-1980 IT 1091791 B 06-07-1985 JP 1359632 C 30-01-1987 JP 53065808 A 12-06-1978 JP 61026767 B 21-06-1986 NL 7712799 A 25-05-1978