NO147641B - PROCEDURE FOR THE PREPARATION OF 2,6-DITERATED BUTYLPHENOL BY ALKYLING OF PHENOL WITH ISOBUTYLEN IN THE PRESENT OF ALUMINUM PHENOLATE CATALYST - Google Patents
PROCEDURE FOR THE PREPARATION OF 2,6-DITERATED BUTYLPHENOL BY ALKYLING OF PHENOL WITH ISOBUTYLEN IN THE PRESENT OF ALUMINUM PHENOLATE CATALYST Download PDFInfo
- Publication number
- NO147641B NO147641B NO770987A NO770987A NO147641B NO 147641 B NO147641 B NO 147641B NO 770987 A NO770987 A NO 770987A NO 770987 A NO770987 A NO 770987A NO 147641 B NO147641 B NO 147641B
- Authority
- NO
- Norway
- Prior art keywords
- butylphenol
- tert
- phenol
- catalyst
- procedure
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims description 20
- 238000000034 method Methods 0.000 title claims description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims description 13
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims description 10
- OPSWAWSNPREEFQ-UHFFFAOYSA-K triphenoxyalumane Chemical compound [Al+3].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 OPSWAWSNPREEFQ-UHFFFAOYSA-K 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 title 2
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims description 16
- 238000005804 alkylation reaction Methods 0.000 claims description 10
- 230000029936 alkylation Effects 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 3
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 2
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000001030 gas--liquid chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Foreliggende oppfinnelse angår fremstilling av 2,6-di-tert.-butylfenol ved alkylering av fenol med isobutylen ved for-høyet temperatur i nærvær av en aluminiumfenolatkatalysator. The present invention relates to the production of 2,6-di-tert-butylphenol by alkylation of phenol with isobutylene at an elevated temperature in the presence of an aluminum phenolate catalyst.
2,6-di-tert.butylfenol er brukbart når det gjelder organiske synteser og spesielt for fremstilling av fenoliske stabili-satorer som benyttes for stabilisering av syntetisk gummi, plastikk og syntetiske fibre. 2,6-di-tert.butylphenol is useful when it comes to organic syntheses and especially for the production of phenolic stabilizers which are used to stabilize synthetic rubber, plastics and synthetic fibres.
En kjent fremgangsmåte for fremstilling av 2,6-di-tert.butyl-fenol omfatter alkylering av fenol med et olefin i nærvær av aluminiumfenolat. Denne fremgangsmåte er beskrevet av G.N. Harlampovich og GU.V. Churkin i "Phenols", s. 226, A known method for the production of 2,6-di-tert.butyl-phenol comprises the alkylation of phenol with an olefin in the presence of aluminum phenolate. This procedure is described by G.N. Harlampovich and GU.V. Churkin in "Phenols", p. 226,
1974 . 1974.
Denne kjente fremgangsmåte gjør det mulig å oppnå 2,6-di-tert . butylfenol i et utbytte på 75-78 vekt-%, mens 22-25% utgjør biprodukter, nemlig para-tert.butylfenol, 2,4-di-tert.butylfenol og tri-tert.butylfenol. This known method makes it possible to obtain 2,6-di-tert. butylphenol in a yield of 75-78% by weight, while 22-25% are by-products, namely para-tert.butylphenol, 2,4-di-tert.butylphenol and tri-tert.butylphenol.
Videre er det kjent en fremgangsmåte for fremstilling av 2,6-di-tert.butylfenol ved alkylering av fenol med isobutylen i nærvær av aluminiumklorid under et trykk på 7 0 atmosfærer (se US patent nr. 2.923.745). Ved denne fremgangsmåte er produktutbyttet 56-60 vekt-%. Furthermore, a method is known for the production of 2,6-di-tert.butylphenol by alkylating phenol with isobutylene in the presence of aluminum chloride under a pressure of 70 atmospheres (see US patent no. 2,923,745). In this method, the product yield is 56-60% by weight.
Også kjent fra den ovenfor nevnt bok er en fremgangsmåte Also known from the above-mentioned book is a procedure
for fremstilling av 2,6-di-tert.butylfenol ved alkylering av fenol med isobutylen i nærvær av aluminiumfenolat ved en temperatur på 150°C under et trykk fra 45-50 atmosfærer. for the production of 2,6-di-tert.butylphenol by alkylation of phenol with isobutylene in the presence of aluminum phenolate at a temperature of 150°C under a pressure of 45-50 atmospheres.
Utbyttet av 2,6-di-tert.butylfenol er 76-79 vekt-%. På tross av det høye produktutbyttet har denne fremgangsmåte mangler som ligger i nødvendigheten av å benytte et kompli-sert prosessutstyr på grunn av anvendelsen av høye trykk og temperaturer. The yield of 2,6-di-tert.butylphenol is 76-79% by weight. Despite the high product yield, this method has shortcomings which lie in the necessity of using a complicated process equipment due to the application of high pressures and temperatures.
Det skal videre henvises til US-PS 3.426.082 og de eksempler i beskrivelsen i dette patent der det anvendes katalysator uten halogenider. Spesielt under henvisning til kolonne 9, tabell VIII og IX, angis sammensetningen av alkylfenoler fremstilt i disse eksempler og det fremgår at det gjennom-føres en praktisk talt fullstendig alkylering av fenol (spesielt i henhold til tabell IX) for å oppnå det ønskede produkt 2,6-di-tert.butylfenol samt biproduktene, 2,4-di-tert.butylfenol og 2,4,6-tri-tert.butylfenol, noe som viser at anvendelse av slike katalysatorer for fremstilling av 2,6-di-tert.butylfenol er problematisk. Further reference should be made to US-PS 3,426,082 and the examples in the description in this patent where a catalyst without halides is used. In particular with reference to column 9, tables VIII and IX, the composition of alkylphenols produced in these examples is indicated and it appears that a practically complete alkylation of phenol is carried out (especially according to table IX) to obtain the desired product 2 ,6-di-tert.butylphenol as well as the by-products, 2,4-di-tert.butylphenol and 2,4,6-tri-tert.butylphenol, which shows that the use of such catalysts for the production of 2,6-di- tert.butylphenol is problematic.
Gjenstand for foreliggende oppfinnelse er å forbedre fremgangsmåten for fremstilling av 2,6-di-tert.butylfenol for' The object of the present invention is to improve the process for the production of 2,6-di-tert.butylphenol for
å øke produktutbyttet med en samtidig forenkling av prosess-teknologien . to increase the product yield with a simultaneous simplification of the process technology.
Oppfinnelsen angår i henhold til dette en fremgangsmåte for fremstilling av 2,6-di-tert.butylfenol ved alkylering av fenol med isobutylen ved forhøyet temperatur i nærvær av en aluminiumfenolatkatalysator, og denne fremgangsmåte karakteriseres ved at det som aluminiumfenolatkatalysator anvendes fenoksyorto-tert.butylfenoksyhydroaluminiumsyre med formelen: Accordingly, the invention relates to a method for the production of 2,6-di-tert.butylphenol by alkylating phenol with isobutylene at elevated temperature in the presence of an aluminum phenolate catalyst, and this method is characterized by the fact that phenoxyortho-tert.butylphenoxyhydroaluminum acid is used as the aluminum phenolate catalyst with the formula:
hvor n er 1-3, m er 1-3, under forutsetning av at n + m = 4. where n is 1-3, m is 1-3, provided that n + m = 4.
Fortrinnsvis gjennomføres alkyleringen ved en temperatur innen området 100-110°C. The alkylation is preferably carried out at a temperature in the range 100-110°C.
Denne katalysator gjør det mulig å gjennomføre prosessen under milde betingelser, f.eks. under atmosfæriske trykk, og å øke produktselektiviteten for det ønskede produkt til • opptil 90-95% og som et resultat et produktutbytte på This catalyst makes it possible to carry out the process under mild conditions, e.g. under atmospheric pressure, and to increase the product selectivity for the desired product to • up to 90-95% and as a result a product yield of
80% (vekt-%). 80% (weight %).
Fremgangsmåten ifølge oppfinnelsen gjennomføres på følgende måte. The method according to the invention is carried out in the following way.
Fenol og den ovenfor angitte katalysator tilføres en reak-tor, blandingen oppvarmes til 100-110°C og isobutylenet føres gjennom i 8 timer. Det resulterende alkylat underkastes en vakuum-rektifisering. Etter omkrystallisering av produktet fra alifatiske hydrokarboner oppnås et 100% rent 2,6-di-tert.butylfenol. Phenol and the above-mentioned catalyst are fed into a reactor, the mixture is heated to 100-110°C and the isobutylene is passed through for 8 hours. The resulting alkylate is subjected to a vacuum rectification. After recrystallization of the product from aliphatic hydrocarbons, a 100% pure 2,6-di-tert.butylphenol is obtained.
Alkyleringskatalysatoren kan fremstilles ved å omsette aluminiumfenolat med orto-tert.butylfenol fra alkylat-rektifiseringen. Katalysatormengden ved alkyleringspro-sessen kan varieres innen området 0,5 til 1 vekt-% beregnet på aluminium. The alkylation catalyst can be prepared by reacting aluminum phenolate with ortho-tert-butylphenol from the alkylate rectification. The amount of catalyst in the alkylation process can be varied within the range of 0.5 to 1% by weight calculated on aluminium.
Fremgangsmåten gjennomføres slik som nevnt ovenfor ved en temperatur innen området 100-110°C. Alkylering ved en temperatur under 100°C resulterer i et redusert utbytte av 2,6-di-tert.butylfenol, mens alkylering ved en temperatur over 110°C resulterer i en uønsket forandring i sammensetningen av alkylfenoler og en øket mengde av biprodukter. The procedure is carried out as mentioned above at a temperature within the range of 100-110°C. Alkylation at a temperature below 100°C results in a reduced yield of 2,6-di-tert.butylphenol, while alkylation at a temperature above 110°C results in an undesirable change in the composition of alkylphenols and an increased amount of by-products.
For bedre forståelse av oppfinnelsen gis nedenfor illu-strerende eksempeler. Trykket i eksemplene var omgivelses-trykk. For a better understanding of the invention, illustrative examples are given below. The pressure in the examples was ambient pressure.
Eksempel 1 Example 1
74,98 g av en katalysator med en sammensetning tilsvarende formelen [(C,HcO)_(orto-tert. C.HnCrH.0)_Al]H tilsettes en blanding av 172,4 g fenol og 156 g orto-tert.butylfenol, det hele oppvarmes til 110°C og isobutylen føres gjennom i 8 timer og man oppnår 697 g av et alkylat med følgende sammensetning i vekt-%: 74.98 g of a catalyst with a composition corresponding to the formula [(C,HcO)_(ortho-tert. C.HnCrH.0)_Al]H is added to a mixture of 172.4 g of phenol and 156 g of ortho-tert.butylphenol , the whole is heated to 110°C and the isobutylene is passed through for 8 hours and 697 g of an alkylate with the following composition in % by weight is obtained:
Alkylatet befris for katalysatoren ved hydrolyse med vann og underkastes rektifisering under vakuum. Den gjenvunne 2,6-di-tert.butylfenol smelter ved 35°C. Produktutbyttet er 80,1 vekt-% av den teoretiske verdi. For å oppnå 2,6-di-tert . butylfenol med en renhet på 100% underkastes det en rektifisering og omkrystallisering fra n hydrokarboner. Renheten i produktet ifølge gassvæske-kromatografi er The alkylate is freed from the catalyst by hydrolysis with water and subjected to rectification under vacuum. The recovered 2,6-di-tert.butylphenol melts at 35°C. The product yield is 80.1% by weight of the theoretical value. To obtain 2,6-di-tert. butylphenol with a purity of 100% is subjected to a rectification and recrystallization from n hydrocarbons. The purity of the product according to gas liquid chromatography is
100% og smeltepunktet er 35,2°C. 100% and the melting point is 35.2°C.
Eksempel 2 Example 2
25,0 g av en katalysator med formelen: 25.0 g of a catalyst with the formula:
[(/CgH5)3(orto-tert. C^HgC^O)^Al]H blandes med 100 g fenol og 40 g orto-tert.butylfenol. Blandingen oppvarmes til en temperatur på 105°C og isobutylen føres gjennom i 8 timer. Det resulterende alkylat befris for katalysator og man oppnår en blanding av alkylfenoler med følgende sammensetning i vekt-%: [(/CgH5)3(ortho-tert. C^HgC^O)^Al]H is mixed with 100 g of phenol and 40 g of ortho-tert.butylphenol. The mixture is heated to a temperature of 105°C and the isobutylene is passed through for 8 hours. The resulting alkylate is freed of catalyst and a mixture of alkylphenols with the following composition in % by weight is obtained:
Selektiviteten er 94,47%. The selectivity is 94.47%.
Eksempel 3 Example 3
37,49 g av en katalysator med formelen: 37.49 g of a catalyst with the formula:
[(OC6H5) 1(orto-tert. C^HgCgH^O)^Al]H blandes med 86,2 g fenol. Blandingen oppvarmes til 110 C og isobutylen føres gjennom i 8 timer. Katalysatoren fjernes deretter fra det resulterende alkylat og man oppnår en blanding av alkylfenoler med følgende sammensetning i vekt-%: [(OC6H5)1(ortho-tert. C^HgCgH^O)^Al]H is mixed with 86.2 g of phenol. The mixture is heated to 110 C and the isobutylene is passed through for 8 hours. The catalyst is then removed from the resulting alkylate and a mixture of alkylphenols with the following composition in % by weight is obtained:
Selektiviteten er 90,5%. The selectivity is 90.5%.
Eksempel 4 Example 4
Dette eksempel viser katalysatorfremstillingen (sammensetningen er den samme som i eksempel 1 ovenfor). This example shows the catalyst preparation (the composition is the same as in example 1 above).
30,6 g aluminiumfenolat oppløses i et aiifatisk oppløsnings-middel slik som heptan og blandes med 30 g orto-tert.butyl-fenol. Blandingen omrøres i en time ved romtemperatur og etter fjerning av oppløsningsmidlet oppnås det 51,2 g av en katalysator med følgende sammensetning: 30.6 g of aluminum phenolate is dissolved in an aliphatic solvent such as heptane and mixed with 30 g of ortho-tert-butyl-phenol. The mixture is stirred for one hour at room temperature and after removal of the solvent, 51.2 g of a catalyst with the following composition is obtained:
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SU762344577A SU632681A1 (en) | 1976-03-22 | 1976-03-22 | Method of obtaining 2,6-di-tret-butylphenol |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO770987L NO770987L (en) | 1977-09-23 |
| NO147641B true NO147641B (en) | 1983-02-07 |
| NO147641C NO147641C (en) | 1983-06-01 |
Family
ID=20655833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO770987A NO147641C (en) | 1976-03-22 | 1977-03-21 | PROCEDURE FOR THE PREPARATION OF 2,6-DITERATED BUTYLPHENOL BY ALKYLING OF PHENOL WITH ISOBUTYLEN IN THE PRESENT OF ALUMINUM PHENOLATE CATALYST |
Country Status (4)
| Country | Link |
|---|---|
| ES (1) | ES457045A1 (en) |
| IT (1) | IT1114768B (en) |
| NO (1) | NO147641C (en) |
| SU (1) | SU632681A1 (en) |
-
1976
- 1976-03-22 SU SU762344577A patent/SU632681A1/en active
-
1977
- 1977-03-21 NO NO770987A patent/NO147641C/en unknown
- 1977-03-21 ES ES457045A patent/ES457045A1/en not_active Expired
- 1977-03-22 IT IT2155077A patent/IT1114768B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| IT1114768B (en) | 1986-01-27 |
| SU632681A1 (en) | 1978-11-15 |
| ES457045A1 (en) | 1978-03-01 |
| NO770987L (en) | 1977-09-23 |
| NO147641C (en) | 1983-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4487847A (en) | Ethylene dimerization | |
| US4154969A (en) | Production of dihydroxydiphenyl alkanes | |
| US3865814A (en) | Process for preparing n-substituted lactams | |
| EP0206241A1 (en) | Process for the preparation of cis-5-fluoro-2-methyl-1-(4-methylthiobenzylidene)-indene-3-acetic acid | |
| Milas et al. | Studies in Organic Peroxides. XXIV. Preparation, Separation and Identification of Peroxides Derived from Diethyl Ketone and Hydrogen Peroxide | |
| US4113976A (en) | Method of preparing 2,6-di-tert.butylphenol | |
| US5387718A (en) | Method of manufacturing alkylphenyl alkyl ethers or alkylphenyl alkyl thioethers | |
| NO147641B (en) | PROCEDURE FOR THE PREPARATION OF 2,6-DITERATED BUTYLPHENOL BY ALKYLING OF PHENOL WITH ISOBUTYLEN IN THE PRESENT OF ALUMINUM PHENOLATE CATALYST | |
| EP0331173B1 (en) | Process for preparing 4,4'-dihydroxydiphenylmethane | |
| US4141920A (en) | Process for the preparation of trimethylsulfoxonium bromide | |
| US4092367A (en) | Alkylation of phenols | |
| US2332555A (en) | Process for producing tertiary alkyl phenols | |
| Ichikawa et al. | The Reaction of Olefins with Aromatic Substances in the Presence of Mercury Salts and Catalyst. II. Synthesis of β-Arylethyl Alcohols and sym-Diarylethanes | |
| US4118586A (en) | Process for preparing dihydroxytoluene | |
| US4560809A (en) | Alkylation process | |
| CA1093101A (en) | Method of preparing 2,6-di-tert. butylphenol | |
| US4956505A (en) | Process for the preparation of 4,4-dimethyl-1-(p-chlorophenyl)pentan-3-one | |
| CA1310018C (en) | Process for cleaving aliphatic ether compounds | |
| US3532713A (en) | Process for the production of ethylene episulfide | |
| US3689580A (en) | Preparation of halodienes | |
| EP0460111B1 (en) | Preparation of 4-substituted aryl olefins | |
| US4073815A (en) | Process for the preparation of 2,2-bis(3,5-di-t-butyl-4-hydroxyphenyl)propane | |
| KR890005300B1 (en) | Process for the preparation of 4,4-bis(4-hydroxyphenyl)cycolohexane carobxylic acid derivatives | |
| US6388160B1 (en) | Method for producing of 2,3-dimethylbutene-1 and 2,3-dimethylbutene-2 | |
| US4845301A (en) | Process for the preparation of α-hdroxyketones |