GB2129011A - Improvements in or relating to organic compounds - Google Patents
Improvements in or relating to organic compounds Download PDFInfo
- Publication number
- GB2129011A GB2129011A GB08328239A GB8328239A GB2129011A GB 2129011 A GB2129011 A GB 2129011A GB 08328239 A GB08328239 A GB 08328239A GB 8328239 A GB8328239 A GB 8328239A GB 2129011 A GB2129011 A GB 2129011A
- Authority
- GB
- United Kingdom
- Prior art keywords
- mixture
- technical grade
- butylphenol
- composition
- butyl
- 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.)
- Granted
Links
- 150000002894 organic compounds Chemical class 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims abstract description 48
- 239000000446 fuel Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 26
- 238000007710 freezing Methods 0.000 claims description 13
- 230000008014 freezing Effects 0.000 claims description 13
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 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 claims description 4
- 150000002431 hydrogen Chemical group 0.000 claims description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000003963 antioxidant agent Substances 0.000 abstract description 6
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical class CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002883 o-cresols Chemical class 0.000 abstract description 2
- 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 4
- 230000006208 butylation Effects 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- ZZZRZBIPCKQDQR-UHFFFAOYSA-N 2,4-ditert-butyl-6-methylphenol Chemical compound CC1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O ZZZRZBIPCKQDQR-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- MNVMYTVDDOXZLS-UHFFFAOYSA-N 4-methoxyguaiacol Natural products COC1=CC=C(O)C(OC)=C1 MNVMYTVDDOXZLS-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
- C10L1/1826—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms poly-hydroxy
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
- C07C39/06—Alkylated phenols
Abstract
Mixtures of certain 2-t- butylphenols and 2-methyl phenols are useful as antioxidants for hydrocarbon fuels, and have the advantageous property of remaining liquid at low temperatures.
Description
SPECIFICATION
Improvements in or-relating to organic compounds
This invention relates to mixtures of sterically hindered phenols, which are liquid at low temperatures.
It is known to use sterically hindered phenols, e.g. 2,6-di-t-butylphenol, 2,6-t-butyl-4-methylphenol or 2,4-dimethyl-6-t-butylphenol as antioxidants in plastics and other organic materials, including hydrocarbon fuels. When these antioxidants are used in liquid substrates such as fuels (petrol, diesel fuel, jet turbine fuel, etc).it is advantageous to add the antioxidants in liquid form, which allows the correct quantity to be added exactly and gives rapid mixing and solution in the fuel.
it has been suggested therefore to employ mixtures, in specific proportions, of 2,6-di-t-butylphenoi, 2-t-butyiphenol and 2,4,6-tri-t-butylphenol. Such mixtures are liquid at room temperature, but at lower temperatures it is necessary to dilute with a solvent such as toluene in order to avoid solidification.
It has now been found that specific mixtures of 2-t-butylphenol compounds and 2-methylphenol compounds can have freezing points below 1000 and even well below 0 C, without the addition of solvent, and that such mixtures are effective antioxidants in hydrocarbon fuels.
Accordingly the present invention provides a composition comprising a mixture of-A) at least one compound of formula a)
and B) at least one compound of formula b)
in which R1 is hydrogen, methyl or t-butyl each R2, independently, is hydrogen or t-butyl and R3 is hydrogen, methyl or t-butyl, the ratio of components A) to B) being such that the freezing point of the mixture lies below 10"C.
In these compounds, R1 is preferably R; where R; is hydrogen or methyl, R2 is preferably t-butyl and R3 is preferably R3 where R3 is methyl or t-butyl.
Specific compounds or formula a) include the following:
a1) 2,6-di-t-butylphenol
a2) 2,4,6-tri-t-butylphenol
a3) 2,6-di-t-butyl-4-methylphenol
a4) 2-t-butylphenol
a5) 2-t-butyl-4-methylphenol of which compounds a1) and a3) are preferred. Mixtures of two or more of any of these may also be used as component A) of the mixture.
Preferred compounds of formula b) are:
b1) 2,4-dimethyl-6-t-butylphenol
b2) 2-methyl-4,6-di-t-butylphenol or mixtures of these compounds.
Mixtures of components A) and B) can readily be selected which have a freezing point below 1 0 C, preferably below 0 C, and the choice of such mixtures will be a routine matter for the man skilled in the art. In general, mixtures of A) and B) in the range of A):B) ratios 1 :4to 4:1, will give freezing points below 1000. In this specification, all ratios and percentages are on a weight basis.
The freezing point of the mixture may be determined experimentally by the following method, and all numerical values given in this specification refer to values determined by this method. The mixture to be tested (50 g) is placed in a small flask and cooled slowly in a dry ice cooling bath while the contents are stirred and small seed crystals are added. When crystals first begin to form the temperature of the mixture is noted and the flask is removed from the cooling bath. Crystallisation proceeds until the entire mixture is solid, while the temperature rises by approx. 1 - 2"C due to the latent heat of crystallisation. The temperature at which the entire mixture becomes solid is noted and is taken as the freezing point.
In practice, crude products as obtained directly from the preparation of compounds A) and B) may be used without further purification. Technical grade products obtained industrially may consist of mixtures of various compounds, for example technical grade 2,6-di-t-butylphenol (a1T) obtained by butylation of phenol contains a mixture of a1), a2) and a4) in average ratio of a1):a2):a4) = 78:18:4, and technical grade 2,6-di-t-butyl-4-methylphenol (a3T) obtained by butylation of p-cresol contains 90-94% a3) and 6-10% a5).
Similarly technical grade 2,4-dimethyl-6-t-butylphenol (b1T) produced by butylation of crude 2,4dimethylphenol will contain approx. 72% b1) and 28% of t-butylated products of o-cresol and 2,5dimethylphenol.
Suitable mixtures of technical grade products are for example 50-75% a1T) with 25-50% b1T); or 50% a1T with 5-15% a3T) and 45-35% b1T).
Such technical grade products may contain minor amounts of unbutylated starting material which will not interfere with the properties of the end products.
It will also be appreciated that by butylation of a suitable mixture of starting materials 3.9. phenol + o-cresol or o- + p-cresol, it may be possible to obtain a suitable mixture of compounds A) and B) which can be used directly without further mixing operations.
Compositions according to the invention remain liquid at low temperatures without loss of antioxidative efficacy on a weight basis (in contrast to systems containing solvent). They can also be prepared cheaply.
The preparation of compounds A) and B) and their use as antioxidants is well described in the literature.
The use of many of these compounds in jet turbine fuel for military aircraft is approved according to
MIL-T-5624J (USAF/NATO).
The following Examples illustrate the invention.
Example 1
500 g of compound a) is mixed with 500 g of compound b1), both components being approx. 98% pure.
The mixture has a freezing point of -5 C to -7"C.
Example 2
250 g of compound a3) is mixed with 750 g of compound b1), both components being approx. 98% pure.
The mixture has a freezing point of - 1 20C to - 14 C.
Example 3
750 g of technical grade compounds a1T) is mixed with 250 g of 98% pure compound b1). The mixture has a freezing point of -1 C to -3 C.
Example 4
500 g of technical grade compound a1T) is mixed with 500 g of technical grade b1T). The mixture has a freezing point of -14"C to -16"C.
Example 5 500 g of technical grade compound a1T) is mixed with 75 g technical grade compound a3T) and 425 g technical grade compound b1T). On cooling, the mixture becomes very viscous, but does not crystallise even at very low temperatures, so that no freezing point can be measured by the given method. However, the mixture remains liquid indefinitely on storage at -10"C and isireadily miscible with liquid hydrocarbon fuels at this temperature.
Claims (9)
1. A composition comprising a mixture of A) at least one compound of formula a)
and B) at least one compound of formula b)
in which R1 is hydrogen, methyl or t-butyl each.R2, independently, is hydrogen or t-butyl and R3 is hydrogen, methyl or t-butyl, the ratio of components A) to B) being such that the freezing point of the mixture lies below 10"C.
2. A composition comprising a mixture of A) at least one compound of formula
and B) at least one compound of formula
in which R1 is hydrogen or methyl and R3, is methyl or t-butyl.
3. A composition as claimed in Claim 1 or Claim 2 in which the weight ratio component A) to component
B) is from 1:4to4:1.
4. A composition as claimed in any one of the preceding claims in which the ratio of components A) to B) is such that the freezing point of the mixture lies below 0 C.
5. A composition as claimed in any one of the preceding claims in which component A) is technical grade 2,6-di-t-butylphenol, component B) is technical grade 2,4-dimethyl-6-t-butylphenol, and the proportions of A) and B) in the mixture are 50-75% wt. A) and 25-50% wt. B).
6. A composition as claimed in any one of Claims 1-4 in which the mixture of A) and B) contains 45-55%wt. technical grade 2,6-di-t-butylphenol, 5-1 5%wt. technical grade 2,6-di-t-butyl-4-methylphenol and 45-35% wt. technical grade 2,4-dimethyl-6-t-butylphenol.
7. A composition as claimed in Claim 6 in which the mixture contains 50% wt. technical grade 2,6-di-t-butylphenol, 7.5% wt. technical grade 2,6-di-t-butyl-4-methylphenol and 42.5% wt. technical grade 2,4-dimethyl-6-t-butylphenol.
8. A composition as described in any one of the Examples.
9. Liquid hydrocarbon fuel contining an antioxidative effective amount of a composition as claimed in any one of the preceding claims.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3239458 | 1982-10-25 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8328239D0 GB8328239D0 (en) | 1983-11-23 |
| GB2129011A true GB2129011A (en) | 1984-05-10 |
| GB2129011B GB2129011B (en) | 1986-11-05 |
Family
ID=6176544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08328239A Expired GB2129011B (en) | 1982-10-25 | 1983-10-21 | Improvements in or relating to organic compounds |
Country Status (4)
| Country | Link |
|---|---|
| CH (1) | CH656118A5 (en) |
| GB (1) | GB2129011B (en) |
| IT (1) | IT1237342B (en) |
| NL (1) | NL8303632A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7479168B2 (en) * | 2003-01-31 | 2009-01-20 | Chevron U.S.A. Inc. | Stable low-sulfur diesel blend of an olefinic blend component, a low-sulfur blend component, and a sulfur-free antioxidant |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB796603A (en) * | 1955-05-18 | 1958-06-18 | Ici Ltd | Improvements in and relating to inhibitors of oxidation, peroxidation and polymerisation |
| GB828910A (en) * | 1955-03-21 | 1960-02-24 | Ethyl Corp | Antioxidant compositions |
| GB1309995A (en) * | 1970-04-13 | 1973-03-14 | Ciba Geigy Ag | Stabilizing compositions comprising dialkylphenothiazines and phenolic antioxidants |
| GB1391716A (en) * | 1971-08-19 | 1975-04-23 | Basf Ag | Colour-stable oxidation inhibitors |
| GB1410788A (en) * | 1972-12-18 | 1975-10-22 | Basf Ag | Gasoline fuels for internal combustion engines |
| GB1587949A (en) * | 1976-10-09 | 1981-04-15 | Basf Ag | Gasoline fuels for internal combustion engines |
-
1983
- 1983-10-13 CH CH5584/83A patent/CH656118A5/en not_active IP Right Cessation
- 1983-10-20 IT IT8349184A patent/IT1237342B/en active
- 1983-10-21 NL NL8303632A patent/NL8303632A/en not_active Application Discontinuation
- 1983-10-21 GB GB08328239A patent/GB2129011B/en not_active Expired
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB828910A (en) * | 1955-03-21 | 1960-02-24 | Ethyl Corp | Antioxidant compositions |
| GB796603A (en) * | 1955-05-18 | 1958-06-18 | Ici Ltd | Improvements in and relating to inhibitors of oxidation, peroxidation and polymerisation |
| GB1309995A (en) * | 1970-04-13 | 1973-03-14 | Ciba Geigy Ag | Stabilizing compositions comprising dialkylphenothiazines and phenolic antioxidants |
| GB1391716A (en) * | 1971-08-19 | 1975-04-23 | Basf Ag | Colour-stable oxidation inhibitors |
| GB1410788A (en) * | 1972-12-18 | 1975-10-22 | Basf Ag | Gasoline fuels for internal combustion engines |
| GB1587949A (en) * | 1976-10-09 | 1981-04-15 | Basf Ag | Gasoline fuels for internal combustion engines |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7479168B2 (en) * | 2003-01-31 | 2009-01-20 | Chevron U.S.A. Inc. | Stable low-sulfur diesel blend of an olefinic blend component, a low-sulfur blend component, and a sulfur-free antioxidant |
Also Published As
| Publication number | Publication date |
|---|---|
| NL8303632A (en) | 1984-05-16 |
| GB2129011B (en) | 1986-11-05 |
| IT1237342B (en) | 1993-05-31 |
| CH656118A5 (en) | 1986-06-13 |
| IT8349184A0 (en) | 1983-10-20 |
| GB8328239D0 (en) | 1983-11-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |