CA1093101A - Method of preparing 2,6-di-tert. butylphenol - Google Patents
Method of preparing 2,6-di-tert. butylphenolInfo
- Publication number
- CA1093101A CA1093101A CA274,611A CA274611A CA1093101A CA 1093101 A CA1093101 A CA 1093101A CA 274611 A CA274611 A CA 274611A CA 1093101 A CA1093101 A CA 1093101A
- Authority
- CA
- Canada
- Prior art keywords
- tert
- butylphenol
- preparing
- catalyst
- tertbutylphenol
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims abstract description 19
- 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 title abstract description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 230000029936 alkylation Effects 0.000 claims abstract description 9
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 9
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 3
- SKDGWNHUETZZCS-UHFFFAOYSA-N 2,3-ditert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(O)=C1C(C)(C)C SKDGWNHUETZZCS-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 9
- 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 6
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 5
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
- PFEFOYRSMXVNEL-UHFFFAOYSA-N 2,4,6-tritert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PFEFOYRSMXVNEL-UHFFFAOYSA-N 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001030 gas--liquid chromatography Methods 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000000446 fuel Substances 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
- 238000004519 manufacturing process 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
- 239000003921 oil Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 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
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 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)
Abstract
METHOD OF PREPARING 2,6-DI-TERT.BUTYLPHENOL
Abstract of the Disclosure A method of preparing 2,6-di-tert.butylphenol comprises alkylation of phenol with isobutylene at a temperature within the range of from 100 to 110°C in the presence, as a catalyst, of phenyloxyorthotertbutylphenoxyhydroaluminium acid of the formula:
[(OC6H5)n(ortho-tert.C4H9C6H4O)mA1] H
wherein n = 1 to 3;
n = 1 to 3;
n + m = 4.
The method of the present invention makes it possible to increase the product yield to 80% by weight and to con-duct the process under atmospheric pressure.
Abstract of the Disclosure A method of preparing 2,6-di-tert.butylphenol comprises alkylation of phenol with isobutylene at a temperature within the range of from 100 to 110°C in the presence, as a catalyst, of phenyloxyorthotertbutylphenoxyhydroaluminium acid of the formula:
[(OC6H5)n(ortho-tert.C4H9C6H4O)mA1] H
wherein n = 1 to 3;
n = 1 to 3;
n + m = 4.
The method of the present invention makes it possible to increase the product yield to 80% by weight and to con-duct the process under atmospheric pressure.
Description
10~3~LO~L
The present invention relates to the art of petro-chemical synthesis and, more specifically, to substituted phe-nols, in particular, it relates to methods of preparing 2,6-di-tert.butylphenol.
The present invention relates to the art of petro-chemical synthesis and, more specifically, to substituted phe-nols, in particular, it relates to methods of preparing 2,6-di-tert.butylphenol.
2,6-di-tertbutylphenol is useful in the field of orga-nic synthesis and, in particular, for the production of phe-nolic stabilizers employed for stabilization of synthetic rub-ber, plastics, synthetic fibres. Phenolic stabilizers such as 4-methyl-2,6-ditertbutylphenol ~ionol) is also useful as an antioxidant additive -for oils, fuels and other petroleum pro-ducts.
A prior art process for the preparation of 2,6-di-tert.
butylphenol comprises alkylation of phenol with an olefine in the presence of aluminium phenolate.
This prior art method makes it possible to obtain 2,6-di-tertbutylphenol with a yield of 75-87% by weight, while 22-25% by weight constitute by-products, namely para-tert.-butylphenol, 2,4-di-tertbutylphenol and tri-tert.butylphenol.
Known in the art is a method of preparing 2,6-ditert.- `
butylphenol by alkylation of phenol with isobutylene in the `
presence of aluminium chloride under the pressure of 70 atm.
(cf. U.S. Patent ~o. 2,923,745). In this method the product yield is 56 to 60% by weight.
Also known is another method of preparing 2,6-di-tert.
butylphenol by alkylation of phenol with isobutylene in the presence of aluminium phenolate at the temperature of 150C
under a pressure of from 45 to S0 atm.
me yield of 2,6-ditertbutylphenol is 76-79% by weight.
Despite the high product yield this method has disadvantages which reside in the necessity of employing sophisticated pro- ~-cess equipment due to the use of high pressures.
'~
F~
, , .. , , ,j .. , , ;.. . .. ., ... ; . , .. , .,, , .. , . , ; . . .
93~
It is an object of the present invention to improve the method of preparing 2,6-di-tert.butylphenol so as to increase the product yield with a simultaneous simplification of the process technology.
The object of the present invention is accomplished by a method of preparing 2,6-di-tert.butylphenol which comprises alkylation of phenol with isobutylene at a temperature of 100 to 110C in the presence of phenyloxyorthotertbutylphenoxy-hydroaluminium acid of the formula: ;
(OC6H5)ntortho-tert.C4~ C6H40)mAl H, wherein n = 1 to 3, m = 1 to 3; n + m = 4, as a catalyst.
This catalyst makes it possible to perform the process under mild conditions, i.e. under atmospheric preseure, and ;
to increase the product selectivity relative to the desired product up to 90-95% and, consequently, the product yield up to 80% by weight. ';
Phenol and the above-mentioned catalyst are charged into a reactor: the mixture is heated to 100-110C and isobu- ;
tylene is passed thereinto for 8 hours. The resulting alkylate ~ ;
is subjected to a vacuum-rectification. After recrystalliza-tion of t,he product from aliphatic hydrocarbons a 100% pure ~`
2,6-di-tertbutylphenol is obtained. ,' The starting alkylation catalyst can be prepared by re-acting aluminium phenolate with ortho-tertbut,ylphenol result-ing from the alkylate rectification. The catalyst amount in the alXylation process can be varied within the range of from 0.5 to 1% by weight as calculated for aluminium.
The process is conducted, as it has been mentioned hereinbefore, at a temperature within the range cf from 100 to 110C. Alkylation at a temperature below 100CC results in ',.
~ ~ ~ -2- ~
A prior art process for the preparation of 2,6-di-tert.
butylphenol comprises alkylation of phenol with an olefine in the presence of aluminium phenolate.
This prior art method makes it possible to obtain 2,6-di-tertbutylphenol with a yield of 75-87% by weight, while 22-25% by weight constitute by-products, namely para-tert.-butylphenol, 2,4-di-tertbutylphenol and tri-tert.butylphenol.
Known in the art is a method of preparing 2,6-ditert.- `
butylphenol by alkylation of phenol with isobutylene in the `
presence of aluminium chloride under the pressure of 70 atm.
(cf. U.S. Patent ~o. 2,923,745). In this method the product yield is 56 to 60% by weight.
Also known is another method of preparing 2,6-di-tert.
butylphenol by alkylation of phenol with isobutylene in the presence of aluminium phenolate at the temperature of 150C
under a pressure of from 45 to S0 atm.
me yield of 2,6-ditertbutylphenol is 76-79% by weight.
Despite the high product yield this method has disadvantages which reside in the necessity of employing sophisticated pro- ~-cess equipment due to the use of high pressures.
'~
F~
, , .. , , ,j .. , , ;.. . .. ., ... ; . , .. , .,, , .. , . , ; . . .
93~
It is an object of the present invention to improve the method of preparing 2,6-di-tert.butylphenol so as to increase the product yield with a simultaneous simplification of the process technology.
The object of the present invention is accomplished by a method of preparing 2,6-di-tert.butylphenol which comprises alkylation of phenol with isobutylene at a temperature of 100 to 110C in the presence of phenyloxyorthotertbutylphenoxy-hydroaluminium acid of the formula: ;
(OC6H5)ntortho-tert.C4~ C6H40)mAl H, wherein n = 1 to 3, m = 1 to 3; n + m = 4, as a catalyst.
This catalyst makes it possible to perform the process under mild conditions, i.e. under atmospheric preseure, and ;
to increase the product selectivity relative to the desired product up to 90-95% and, consequently, the product yield up to 80% by weight. ';
Phenol and the above-mentioned catalyst are charged into a reactor: the mixture is heated to 100-110C and isobu- ;
tylene is passed thereinto for 8 hours. The resulting alkylate ~ ;
is subjected to a vacuum-rectification. After recrystalliza-tion of t,he product from aliphatic hydrocarbons a 100% pure ~`
2,6-di-tertbutylphenol is obtained. ,' The starting alkylation catalyst can be prepared by re-acting aluminium phenolate with ortho-tertbut,ylphenol result-ing from the alkylate rectification. The catalyst amount in the alXylation process can be varied within the range of from 0.5 to 1% by weight as calculated for aluminium.
The process is conducted, as it has been mentioned hereinbefore, at a temperature within the range cf from 100 to 110C. Alkylation at a temperature below 100CC results in ',.
~ ~ ~ -2- ~
3~
a decreased yield of 2,6-di-tertbutylphenol, whereas alkyla-tion at a temperature above 110C results in undesirable chan-~es in composition of alkylphenols and an increased amount of the by-products.
For a better understanding of the present invention some specific Examples are given hereinbelow by way of illus-tration.
74.98 g of a catalyst having the composition correspond-ing to the formula [(C6H50)2(ortho-tert.c4H9c6H40)2Al] H are added into a mixture of 172.4 g of phenol and 156 g of ortho-tert.butylphenol; the mixture is heated to the temperature of llO~C and isobutylene is passed therethrough for a 8 hours to give 697 g of an alkylate with the following composition, per cent by weight: phenol 0.2, ortho-tertbutylphenol 10.5, 2,6-ditertbutylphenol 80.1, 2,4-diter~butylphenol 0.2, 2,4,6-tri-tertbutylphenol 9. me alkylate is exempted of t~e catalyst by hydrolysis with water and subjected to rectification under va-cuum. The recovered 2,6-di-tertbutylphenol melts at 35C.
me product yield is 80.1% by weight of the theoretical value.
To obtain 2,6-ditertbutylphenol of a 100% purity grade, it is subjected to rectification and recrystallization from normal-structure hydrocarbons, Purity of the product, according to the data of gas-liquid chromatography (GLC) is 100%, melting point is 35.2C.
25.0 g of a catalyst of the formula:
[(OC6H5)3(ortho-tert.C~HgC~O)lAl] H are mixed with 100 g of phenol and 40 g of ortho-tertbutylphenol. The mixture is heated to the temperature of 10~C and isobutylene is passed thereinto for 8 hours. The resulting alkylate is exempted of 93~
the catalyst to give a mixture of alkylphenols of the follow-ing composition, per cent by weight: phenol 0.6, ortho-tert-butylphenol 16.2; 2,6-di-tertbutylphenol 76: 2,4-di-tert-butylphenol 0.2, 2,4,6-tri-tertbutylphenol 5. Selectivity is 94.47%.
37.49 g of a catalyst of the formula:
[~0C6H5)1(ortho-tert.C4~ C6H4O)3Al] H are mixed wi~h 86.2 g of phenol. The mixture is heated to the temperature of 110C
and isobutylene is passed therethrough for 8 hours. Ihe cata-lyst is then removed from the resulting alkylate to give a mix-ture of alkylphenols having the following composition, per cent by weight: phenol 0.2; ortho-tertbutylphenol 10.6, 2,6-ditert-butylphenol 80.0, 2,4-di-tertbutylphenol 0.4, 2,4,6-tri-tertbutylphenol 9~/~. Selectivity is 9005%. ``
This example illustrates the catalyst preparation (thecomposition is the same as in Example 1 hereinbefore).
30.6 g aluminium phenolate dissolved in an aliphatic solvent tsuch as heptane) are mixed with 30 g of ortho-tert-butylphenol. Ihe mixture is stirred for 1 hour at room temper-ature, after the removal of the solvent there are obtained 51.2 g of a catalyst having the following composition:
~oC6H5)2(ortho-tertc4H9c6H40)2Al] H-
a decreased yield of 2,6-di-tertbutylphenol, whereas alkyla-tion at a temperature above 110C results in undesirable chan-~es in composition of alkylphenols and an increased amount of the by-products.
For a better understanding of the present invention some specific Examples are given hereinbelow by way of illus-tration.
74.98 g of a catalyst having the composition correspond-ing to the formula [(C6H50)2(ortho-tert.c4H9c6H40)2Al] H are added into a mixture of 172.4 g of phenol and 156 g of ortho-tert.butylphenol; the mixture is heated to the temperature of llO~C and isobutylene is passed therethrough for a 8 hours to give 697 g of an alkylate with the following composition, per cent by weight: phenol 0.2, ortho-tertbutylphenol 10.5, 2,6-ditertbutylphenol 80.1, 2,4-diter~butylphenol 0.2, 2,4,6-tri-tertbutylphenol 9. me alkylate is exempted of t~e catalyst by hydrolysis with water and subjected to rectification under va-cuum. The recovered 2,6-di-tertbutylphenol melts at 35C.
me product yield is 80.1% by weight of the theoretical value.
To obtain 2,6-ditertbutylphenol of a 100% purity grade, it is subjected to rectification and recrystallization from normal-structure hydrocarbons, Purity of the product, according to the data of gas-liquid chromatography (GLC) is 100%, melting point is 35.2C.
25.0 g of a catalyst of the formula:
[(OC6H5)3(ortho-tert.C~HgC~O)lAl] H are mixed with 100 g of phenol and 40 g of ortho-tertbutylphenol. The mixture is heated to the temperature of 10~C and isobutylene is passed thereinto for 8 hours. The resulting alkylate is exempted of 93~
the catalyst to give a mixture of alkylphenols of the follow-ing composition, per cent by weight: phenol 0.6, ortho-tert-butylphenol 16.2; 2,6-di-tertbutylphenol 76: 2,4-di-tert-butylphenol 0.2, 2,4,6-tri-tertbutylphenol 5. Selectivity is 94.47%.
37.49 g of a catalyst of the formula:
[~0C6H5)1(ortho-tert.C4~ C6H4O)3Al] H are mixed wi~h 86.2 g of phenol. The mixture is heated to the temperature of 110C
and isobutylene is passed therethrough for 8 hours. Ihe cata-lyst is then removed from the resulting alkylate to give a mix-ture of alkylphenols having the following composition, per cent by weight: phenol 0.2; ortho-tertbutylphenol 10.6, 2,6-ditert-butylphenol 80.0, 2,4-di-tertbutylphenol 0.4, 2,4,6-tri-tertbutylphenol 9~/~. Selectivity is 9005%. ``
This example illustrates the catalyst preparation (thecomposition is the same as in Example 1 hereinbefore).
30.6 g aluminium phenolate dissolved in an aliphatic solvent tsuch as heptane) are mixed with 30 g of ortho-tert-butylphenol. Ihe mixture is stirred for 1 hour at room temper-ature, after the removal of the solvent there are obtained 51.2 g of a catalyst having the following composition:
~oC6H5)2(ortho-tertc4H9c6H40)2Al] H-
-4-
Claims
1. A method of preparing 2,6~di-tertbutylphenol compris-ing alkylation of phenol with isobutylene at a temperature within the range of from 100 to 110°C in the presence of a catalyst, viz. phenyloxyorthotertbutylphenoxyhydroaluminium acid of the formula:
[(OC6H5)n(ortho-tert.C4H9C6H4O)mAl] H
wherein n = 1 to 3;
m = 1 to 3;
n + m = 4.
[(OC6H5)n(ortho-tert.C4H9C6H4O)mAl] H
wherein n = 1 to 3;
m = 1 to 3;
n + m = 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA274,611A CA1093101A (en) | 1977-03-23 | 1977-03-23 | Method of preparing 2,6-di-tert. butylphenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA274,611A CA1093101A (en) | 1977-03-23 | 1977-03-23 | Method of preparing 2,6-di-tert. butylphenol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1093101A true CA1093101A (en) | 1981-01-06 |
Family
ID=4108226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA274,611A Expired CA1093101A (en) | 1977-03-23 | 1977-03-23 | Method of preparing 2,6-di-tert. butylphenol |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1093101A (en) |
-
1977
- 1977-03-23 CA CA274,611A patent/CA1093101A/en not_active Expired
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |