SK612008A3 - Process for the preparation of hydroxypivalic acid - Google Patents
Process for the preparation of hydroxypivalic acid Download PDFInfo
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- SK612008A3 SK612008A3 SK61-2008A SK612008A SK612008A3 SK 612008 A3 SK612008 A3 SK 612008A3 SK 612008 A SK612008 A SK 612008A SK 612008 A3 SK612008 A3 SK 612008A3
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- Prior art keywords
- oxidation
- hydroxypivalic acid
- preparation
- hydrogen peroxide
- iba
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- RDFQSFOGKVZWKF-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)C(O)=O RDFQSFOGKVZWKF-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- JJMOMMLADQPZNY-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanal Chemical compound OCC(C)(C)C=O JJMOMMLADQPZNY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims abstract description 4
- VUZNLSBZRVZGIK-UHFFFAOYSA-N 2,2,6,6-Tetramethyl-1-piperidinol Chemical class CC1(C)CCCC(C)(C)N1O VUZNLSBZRVZGIK-UHFFFAOYSA-N 0.000 claims 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 abstract description 7
- HHWBUNWYLYZWPX-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)C(O)=O.OCC(C)(C)C(O)=O HHWBUNWYLYZWPX-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 45
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JWUXJYZVKZKLTJ-UHFFFAOYSA-N Triacetonamine Chemical compound CC1(C)CC(=O)CC(C)(C)N1 JWUXJYZVKZKLTJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- OGUZVTSKLWNOJO-UHFFFAOYSA-N butyl acetate;cyclohexane Chemical compound C1CCCCC1.CCCCOC(C)=O OGUZVTSKLWNOJO-UHFFFAOYSA-N 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- -1 2,2,6,6-tetramethyl-4-hydroxy piperidinoxy Chemical group 0.000 description 1
- VDVUCLWJZJHFAV-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1 VDVUCLWJZJHFAV-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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- Hydrogenated Pyridines (AREA)
Abstract
Description
Oblasť technikyTechnical field
Vynález sa týka spôsobu prípravy kyseliny hydroxypivalovej (3-hydroxy-2,2-dimetylpropionovej kyseliny) oxidáciou hydroxypivalaldehydu s peroxidom vodíka.The invention relates to a process for the preparation of hydroxypivalic acid (3-hydroxy-2,2-dimethylpropionic acid) by oxidation of hydroxypivalaldehyde with hydrogen peroxide.
Doterajší stav technikyBACKGROUND OF THE INVENTION
Podľa najstarších údajov sa kyselina hydroxypivalová pripravovala oxidáciou neopentylglykolu s manganistanom draselným (Wessely: Monatshefte 22, 66) alebo Cannizzarovou reakciou z hydroxypivalaldehydu pomocou roztoku hydroxidu draselného (Wessely: Monatshefte 21, 222). Nevýhodou oboch spôsobov bol nízky výťažok, a preto boli priemyselne neatraktívne.According to the earliest data, hydroxypivalic acid was prepared by oxidation of neopentyl glycol with potassium permanganate (Wessely: Monatshefte 22, 66) or Cannizzar reaction from hydroxypivalaldehyde using potassium hydroxide solution (Wessely: Monatshefte 21, 222). The disadvantage of both methods was the low yield and therefore they were industrially unattractive.
Známa je tiež oxidácia neopentylglykolu so vzduchom alebo s kyslíkom na Pd/C alebo Pt/C katalyzátore [US 3 799 977; JP 53/77 010 (1978)]. V patente US 3 799 977 chýbajú údaje o výťažkoch. Firma Mitsui Toatsu Chemicals (JP 53/077 010) pripravuje kyselinu hydroxypivalovú z neopentylglykolu v neutrálnom, resp. slabo alkalickom roztoku kyslíkom za prítomnosti Pd-katalyzátora. Pd je nanesené na aktívnom uhlí alebo alumine o koncentrácii 0,5 až 10 % hmotn. a oxidácia sa uskutočňuje pri teplote do 150 °C a tlaku do 1,0 MPa.It is also known to oxidize neopentyl glycol with air or oxygen on a Pd / C or Pt / C catalyst [US 3,799,977; JP 53/77 010 (1978)]. U.S. Pat. No. 3,799,977 lacks data on yields. Mitsui Toatsu Chemicals (JP 53/077 010) prepares hydroxypivalic acid from neopentyl glycol in neutral and resp. a weakly alkaline solution with oxygen in the presence of a Pd catalyst. Pd is deposited on activated carbon or alumina at a concentration of 0.5 to 10% by weight. and the oxidation is carried out at a temperature of up to 150 ° C and a pressure of up to 1.0 MPa.
Oxidácia hydroxypivalaldehydu peroxidom vodíka bola prvý raz popísaná v Monatshefte fur Chemie, 95 (1964), 410 a prepracovaná varianta v patente JP 43/24 888 (1968). Nevýhodou postupov je príprava znečistenej kyseliny hydroxypivalovej a nízky výťažok čistej kyseliny (65 až 68 %).The oxidation of hydroxypivalaldehyde with hydrogen peroxide was first described in Monatsheft fur Chemie, 95 (1964), 410 and a revised variant in JP 43/24 888 (1968). The disadvantages of the processes are the preparation of impure hydroxypivalic acid and low yield of pure acid (65-68%).
Podľa novších informácií (patenty firmy Bayer AG DE 19 632 922 a DE 19 632 924) sa kyselina hydroxypivalová vyrába oxidáciu hydroxypivalaldehydu s peroxidom vodíka pri teplote 60 až 80 °C. Koncentrácia peroxidu vodíka v reakčnom roztoku sa udržuje jeho dávkovaním do koncentrácie 4 % hmota., pokiaľ koncentrácia peroxidu vodíka neklesne pod 1 % hmota. Pritom, zatiaľ čo po aldolizácii sa dosahuje výťažok hydroxypivalaldehydu 89,5 %, po oxidácii aldehydu sa dosahuje výťažok kyseliny hydroxypivalovej 74 %. Izoláciou po oddestilovaní vody za pomoci zmesi n-butylacetát-cyklohexán sa kryštalizáciou získa kyselina hydroxypivalová vo výťažku 49,5 % na nasadený izobutyraldehyd (DE 19 632 924).According to more recent information (patents of Bayer AG DE 19 632 922 and DE 19 632 924), hydroxypivalic acid is produced by oxidizing hydroxypivalaldehyde with hydrogen peroxide at a temperature of 60 to 80 ° C. The concentration of hydrogen peroxide in the reaction solution is maintained by dosing it to a concentration of 4% by weight until the concentration of hydrogen peroxide falls below 1% by weight. While the yield of hydroxypivalaldehyde is 89.5% after aldolization, the yield of hydroxypivalic acid is 74% after oxidation of the aldehyde. Isolation after distilling off the water with n-butyl acetate-cyclohexane gave crystalline hydroxypivalic acid in 49.5% yield on the isobutyraldehyde used (DE 19 632 924).
Podstata vynálezu .SUMMARY OF THE INVENTION.
Podstatou tohto vynálezu je spôsob prípravy kyseliny hydroxypivalovej oxidáciou hydroxypivalaldehydu peroxidom vodíka, pri ktorom sa oxidácia uskutočňuje za prítomnosti katalytického množstva oxylov 2,2,6,6-tetrametylpiperidínu alebo jeho v polohe 4 substituovaných derivátov alebo ich prekurzorov.The present invention provides a process for the preparation of hydroxypivalic acid by oxidation of hydroxypivalaldehyde with hydrogen peroxide, wherein the oxidation is carried out in the presence of a catalytic amount of 2,2,6,6-tetramethylpiperidine or its 4-substituted derivatives or precursors thereof.
Uvedené látky sa používajú v katalytickom množstve, pričom ich prítomnosť počas oxidácie podstatne zvyšuje množstvo izolovanej hydroxypivalovej kyseliny. Oxidácia sa môže robiť aj so surovinami, z ktorých sa in situ môžu oxyly pripraviť a to 2,2,6,6tetrametylpiperidínu, 2,2,6,6-tetrametyl-4-hydroxy-, resp. 2,2,6,6-tetrametyl-4-oxo-piperidínu.Said substances are used in catalytic amounts, the presence of which during the oxidation substantially increases the amount of hydroxypivalic acid isolated. Oxidation can also be carried out with the raw materials from which in situ oxyly can be prepared, namely, 2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-hydroxy-, respectively. 2,2,6,6-tetramethyl-4-oxo-piperidine.
Celý postup podľa vynálezu je zrejmý z uvedených príkladov.The entire process of the invention is evident from the examples given.
Príklady uskutočnenia vynálezuDETAILED DESCRIPTION OF THE INVENTION
Príklad 1 - porovnávacíExample 1 - Comparative
Kondenzácia 25 % formaldehydu (Fd) s 99,5 % izobutyraldehydom (IBA) sa uskutočnila v 1,0 1 banke, opatrenej spätným chladičom, miešadlom, teplomerom a dávkovacím lievikom, pri mólovom pomere 1,17 mólu Fd na 1 mól IBA s použitím trietylamínu (TEA) v množstve 0,05 mólu/1 mól IBA ako katalyzátora pri teplote 55 °C, udržiavanej vodným kúpeľom.Condensation of 25% formaldehyde (Fd) with 99.5% isobutyraldehyde (IBA) was carried out in a 1.0 L flask equipped with a reflux condenser, stirrer, thermometer and dosing funnel, at a molar ratio of 1.17 mole Fd per mole of IBA using triethylamine (TEA) in an amount of 0.05 mole / 1 mole of IBA catalyst at 55 ° C maintained by a water bath.
Po 3 h reakcie pri teplote 55 °C sa zmes ohriala na teplotu 85 °C 1 h a následne sa zmes ochladila na teplotu 70 °C. Do zmesi sa pri tejto teplote počas 2 h nadávkoval peroxid vodíka (H2O2) o koncentrácii 50 %, pri použití 0,74 móla peroxidu na 1 mól izobutyraldehydu.After reaction at 55 ° C for 3 h, the mixture was heated to 85 ° C for 1 h and then cooled to 70 ° C. 50% hydrogen peroxide (H2O2) was metered into the mixture at this temperature over 2 h using 0.74 mol of peroxide per mole of isobutyraldehyde.
V reakčnom roztoku sa na plynovom chromatografe stanovil obsah hydroxypivalovej kyseliny (HPA), pričom sa dosiahol výťažok kyseliny 54,5 %, počítané na nadávkovaný izobutyraldehyd. Z uvedeného roztoku po oddestilovaní vody pri 106 °C a následne na vákuovej rotačnej odparke pri teplote kúpeľa 80 °C a tlaku 13 až 1,3 kPa sa po ochladení roztoku v zmesi n-butylacetát-cyklohexán získal produkt o čistote 97,1 % s výťažkom 53 %, počítané na hydroxypivalovú kyselinu prítomnú v roztoku. Celkový výťažok na IBA bol 33,7 %, t.j. 0,55 kg HPA na 1,0 kg nadávkovaného izobutyraldehydu.In the reaction solution, the hydroxypivalic acid (HPA) content was determined on a gas chromatograph to obtain an acid yield of 54.5% calculated on the isobutyraldehyde to be metered. From this solution, after distilling off the water at 106 ° C and then using a vacuum rotary evaporator at a bath temperature of 80 ° C and a pressure of 13 to 1.3 kPa, a product of 97.1% purity was obtained after cooling the solution in n-butyl acetate-cyclohexane. yield 53% calculated on hydroxypivalic acid present in the solution. The overall yield on IBA was 33.7%, i. 0.55 kg HPA per 1.0 kg dosed isobutyraldehyde.
Príklad 2Example 2
Aldolizácia formaldehydu s izobutyraldehydom sa zopakovala za rovnakých podmienok (zariadenie aj postup) ako je uvedené v príklade 1.The aldolization of formaldehyde with isobutyraldehyde was repeated under the same conditions (apparatus and procedure) as in Example 1.
Oxidácia aldolizačnej zmesi sa robila navyše s prídavkom 3,6 milimólu oxylu 2,2,6,6-tetrametylpiperidínu na 1 mól izobutyraldehydu za rovnakých podmienok, ako je uvedené v príklade 1. Podobne sa spracovala reakčná zmes, pričom sa získalo 0,87 kg HPA o koncentrácii 98 % na 1 kg nadávkovaného IBA. Uvedeným postupom sa dosiahlo zvýšenie výťažku o 58,2 % v porovnám s príkladom 1.The oxidation of the aldolization mixture was additionally carried out with the addition of 3.6 millimoles of 2,2,6,6-tetramethylpiperidine oxy to 1 mole of isobutyraldehyde under the same conditions as in Example 1. Similarly, the reaction mixture was treated to yield 0.87 kg HPA at a concentration of 98% per kg of dosed IBA. This procedure resulted in an increase in yield of 58.2% compared to Example 1.
Príklad 3Example 3
V zariadení podľa príkladu 1, ale s použitím rovnakého molámeho množstva trimetylamínu v prepočte na izobutyraldehyd, sa uskutočnila kondenzácia formaldehydu s izobutyraldehydom za ináč nezmenených reakčných podmienok.In the apparatus of Example 1, but using the same molar amount of trimethylamine calculated as isobutyraldehyde, the condensation of formaldehyde with isobutyraldehyde was performed under otherwise unchanged reaction conditions.
Následne sa oxidácia s peroxidom vodíka za prítomnosti 7,2 milimólu/1 mól IBA 2,2,6,6tetrametyl-4-oxo-piperidínoxylu robila za rovnakých technologických podmienok, podobne ako izolácia produktu.Subsequently, oxidation with hydrogen peroxide in the presence of 7.2 millimoles / 1 mole of IBA 2,2,6,6-tetramethyl-4-oxo-piperidinoxy was performed under the same process conditions, similar to the isolation of the product.
Uvedeným postupom sa získalo v prepočte 0,65 kg HPA na 1,0 kg nadávkovaného IBA o čistote 99,0 %.This procedure yields 0.65 kg of HPA per 1.0 kg of 99.0% pure IBA being metered.
Príklad 4Example 4
Kondenzácia sa uskutočnila v zariadení podľa príkladu 1, ale s použitím dimetyletanolamínu v rovnakom molámom množstve na izobutyraldehyd, za nezmenených reakčných podmienok.Condensation was carried out in the apparatus of Example 1 but using dimethylethanolamine in equal molar amount to isobutyraldehyde, under unchanged reaction conditions.
Oxidácia s peroxidom vodíka sa robila s predsadeným 2,2,6,6-tetrametyl-4-hydroxy piperidínoxylom v množstve 1,8 milimólu na 1 mól IBA, za podmienok ako v príklade 1. Rovnako sa robilo aj spracovanie reakčného roztoku.The oxidation with hydrogen peroxide was carried out with a precursor 2,2,6,6-tetramethyl-4-hydroxy piperidinoxy in an amount of 1.8 millimoles per 1 mole of IBA, under the conditions of Example 1. The reaction solution was worked up as well.
Za uvedených podmienok sa získalo 0,68 kg HPA na 1 kg IBA o čistote 99,5 % stanovené titračne.Under these conditions, 0.68 kg HPA was obtained per kg IBA with a purity of 99.5% determined by titration.
Príklad 5Example 5
V zariadení podľa príkladu 1, ale s použitím dimetylcyklohexylamínu v rovnakom mólovom pomere na IBA ako v príklade 1, sa uskutočnila kondenzácia Fd s IBA. Kondenzácia sa robila za rovnakých podmienok ako v príklade 1.In the apparatus of Example 1, but using dimethylcyclohexylamine in the same molar ratio to IBA as in Example 1, condensation of Fd with IBA was performed. Condensation was carried out under the same conditions as in Example 1.
Následne sa robila oxidácia s peroxidom vodíka za prítomnosti 2,2,6,6-tetrametyl-4hydroxypiperidínu v množstve 10 mmólu v prepočte na 1 mól IBA za rovnakých podmienok oxidácie, ako aj spracovanie roztoku ako v príklade 1.Subsequently, oxidation was carried out with hydrogen peroxide in the presence of 2,2,6,6-tetramethyl-4-hydroxypiperidine in an amount of 10 mmol per 1 mole of IBA under the same oxidation conditions as well as treatment of the solution as in Example 1.
Za uvedených podmienok sa získalo 0,65 kg HPA na 1 kg IBA.Under these conditions, 0.65 kg HPA per kg IBA was obtained.
Priemyselná využiteľnosťIndustrial usability
Kyselina hydroxypivalová je vhodná na výrobu esterov, polyesterov, polyuretánov, pre využitie ako regulátor viskozity pre vodné suspenzie detergentov, pre výrobu práškov, v kozmetike, výrobe mazacích olejov, pre výrobu farieb, riedidiel náterových látok alebo samotná ako oplachovadlo riadov - pre zabránenie vzniku škvŕn na riadoch v automatických umývačkách, prídavok do pracích práškov a podobne.Hydroxypivalic acid is suitable for the production of esters, polyesters, polyurethanes, for use as a viscosity regulator for aqueous detergent suspensions, for the manufacture of powders, cosmetics, the production of lubricating oils, paints, paint thinners or as a rinse aid alone on dishwashers, detergent additive and the like.
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CN105753683A (en) * | 2016-01-18 | 2016-07-13 | 吉林市吉化江城油脂化工有限责任公司 | Method for preparing hydroxypivalic acid by catalytic oxidation of phosphotungstic acid |
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CN105753683A (en) * | 2016-01-18 | 2016-07-13 | 吉林市吉化江城油脂化工有限责任公司 | Method for preparing hydroxypivalic acid by catalytic oxidation of phosphotungstic acid |
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