CN1223254A - Tertiary alkyl primary amines and process for preparing the same - Google Patents
Tertiary alkyl primary amines and process for preparing the same Download PDFInfo
- Publication number
- CN1223254A CN1223254A CN 98115925 CN98115925A CN1223254A CN 1223254 A CN1223254 A CN 1223254A CN 98115925 CN98115925 CN 98115925 CN 98115925 A CN98115925 A CN 98115925A CN 1223254 A CN1223254 A CN 1223254A
- Authority
- CN
- China
- Prior art keywords
- amine
- alkyl
- fuel oil
- acid
- mixture
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A C8-C10 branched tertiary alkyl primary amine mixture is disclosed which is useful as a multi-functional additive in fuels, lubricants, and dyes. The subject amines are prepared by reacting an acid, a nitrile, a C8-C10 substrate in the presence of water to form a first intermediate product; further reacting the first intermediate with an acid in the presence of water to form a second intermediate product and neutralizing the second intermediate with a basic compound to form the product.
Description
The present invention relates to branching primary t-alkyl-amine, its preparation method and contain the composition of this amine.This amine is used as multifunction additive in fuel oil, lubricant and dyestuff.
Alkylamine is as fuel oil and lubricant additive, oneself is proposed various primary amine, secondary amine, tertiary amine with other material as the colour stabilizer and/or the plugging inhibitor that distillate fuel oil, for example see american documentation literature 2672408,2684292 and No. 2758086, primary t-alkyl-amine is especially suitable, particularly contains C
4, C
7, C
8The primary t-alkyl-amine of carbochain, its C
12-C
15Mixture, C
16-C
18Mixture and C
16-C
22Mixture all is proposed and as the fuel oil stablizer, for example sees american documentation literature No. 2945749.
But, in these disclosed documents, obviously lack C
8-C
10The primary t-alkyl-amine mixture of scope.General aliphatic amide, particularly fat primary amine be by widespread production and application, sees the 369th page of " Kirk-Othmer chemistry encyclopedia " the 2nd volume (the 4th edition, 1992, John Wiley NY publishes).Aliphatic amide is divided into two classes traditionally: (1) lower aliphatic primary amine, it is C that a length is arranged usually
1-C
6Carbochain, the amine of (2) higher molecular weight is often referred to aliphatic amide, generally at C
12-C
18In the scope.Low-grade amine is generally prepared by petrochemical materials, as the methyl alcohol in the alcohols, ethanol, propyl alcohol and butanols, the aliphatic amide that provides on the market is made by the lipid acid that nature exists on the other hand, and these lipid acid are derived by fatty oil such as Tallow, beef, Oleum Cocois, soybean oil and plam oil.Yet partly cause is the cause that lacks suitable raw material, in the amine of being supplied, at C
9There is a blank in the environs.In addition, more common primary amine have specific characteristics can primary t-alkyl-amine at C
9A blank is also arranged near the scope, and commercial this blank is very important, because people wish that obtained performance comprises the well balanced of flowing property, hydrophilic-lipophilic balance and molecular weight optimization.
The invention provides C
8-C
10The branching primary t-alkyl-amine mixture of scope has been filled up this blank, and this class amine is coming from molecular weight C
8-C
10Get up with the properties of combination of side chain tertiary alkyl.As the result of this combination, C of the present invention
8-C
10The branching primary t-alkyl-amine of scope has following several respects outstanding feature:
(1) demonstrates good and compatibility non-polar hydrocarbon (low-grade amine and aliphatic amide solvability in non-polar solvents such as mineral oil, kerosene, petroleum naphtha is very poor or insoluble fully);
(2) can obtain ideal oil soluble and water miscible equilibrium (aliphatic amide can be dissolved in oil slightly, but water-insoluble almost, and low-grade amine can be water-soluble, but is dissolved in oil hardly).
(3) broad is mobile interval, even promptly also show flowability in quite low temperature, and under free air temperature, have low volatility (solid normally under the aliphatic amide free air temperature, and low-grade aliphatic amine often has strong volatility, therefore has operational issue) and
(4) compare with aliphatic amide, every pound contains more amine nitrogen.
(5) have than aliphatic amide and the stronger alkalescence of low-grade aliphatic amine, promptly its pKa value is 11.5 pairs 10.
Branching primary t-alkyl-amine mixture of the present invention is used for fuel oil, lubricant and dyestuff as multifunction additive.
As a first aspect of the present invention, a kind of branching primary t-alkyl-amine mixture is provided, contain the C of at least a formula (1) expression
8, C
9And C
10Isomer.
R wherein
1, R
2And R
3Be C independently of one another
1-C
6Alkyl or substituted alkyl, C
1-C
6Alkenyl or substituted alkenyl base, and the R of at least 50% isomer wherein
1, R
2And R
3At least one is a side chain.
As a second aspect of the present invention, provide C
8-C
10The primary t-alkyl-amine preparation process of mixture may further comprise the steps: (A) at 0-120 ℃ of temperature range internal heating reaction mixture, reach the C that can generate carbon ion with acid-respons comprising acid, nitrile, water
8-C
10Response matrix generates first reaction intermediate in reaction mixture; (B) in the presence of water, make first reaction intermediate in the reaction mixture form second reaction intermediate with the acid effect; (C), form amine mixt with second reaction intermediate of alkali cpd neutralization.
Term " the C of Shi Yonging in this article
1-C
6" or " C
1-C
5" be meant that the straight or branched alkyl of 1-6 or 1-5 carbon atom, term " alkene oligomer " are meant by the olefinic monomer polymerization and form the compound that the straight chain of repeating unit or loop chain, side chain are formed.
Term " more amount " is interpreted as that greater than 50% (weight), term " more a small amount of " then is interpreted as less than 50% (weight) herein.
Ramose carbon takes place herein be called secondary carbon, promptly with two other carbon atom key carbon even, the carbon that connects with other three carbon atom keys is called tertiary carbon, generally see Morrison, R.T. and Boyd, " organic chemistry " (Prentice Hall of R.N., Inc. the 6th edition, 1992, the 92 pages), term " primary amine tertiary carbon " means the tertiary carbon that connects with amine nitrogen key.
Term " highly basic " is meant that pKa is more than or equal to 8 alkali herein.
In this specification sheets and claims, unless other explanation is arranged, related per-cent is weight percent, and all temperature are centigradetemperature, and all pressure all are normal atmosphere.
Should be understood that, cited scope and ratio, being limited to meaning in specification sheets and the claim and being can bonded, and the scope of certain parameter is 1-20 and 5-15 as described, then is interpreted as scope 1-15 and 5-20 and also allows.
The total of branching primary t-alkyl-amine of the present invention is characterised in that it is to contain at least a C
8, C
9And C
10The complex mixture of primary amine isomer, this isomer contain a tertiary alkyl that is connected with amine nitrogen atom, and the carbochain that is connected on the primary amine tertiary carbon is arranged, and promptly this branching primary t-alkyl-amine can be regarded as C
8Or C
9Or C
10Or C
8With C
9Or C
9With C
10Or C
10With C
8And C
8, C
9With C
10Isomer mixture, usually in these isomer, the carbochain that connects the primary amine tertiary carbon has at least one to be side chain, promptly connects on the carbochain of primary amine tertiary carbon and can contain secondary carbon and tertiary carbon, this structure explanation is in above-mentioned formula (1).In one embodiment, at least 50%, preferably at least 75%, more preferably at least 90% the isomer, R
1, R
2And R
3At least one is a side chain.In another embodiment, at least 50% of mixture, preferably at least 75%, more preferably at least 90% is C
9Isomer is no more than 50%, preferably is no more than 25%, is C more preferably no more than 10%
8Isomer and be no more than 50% preferably is no more than 25%, is C more preferably no more than 10%
10Isomer.
Contained C in the amine mixt of the present invention
9The example of isomer includes but not limited to 3,4-dimethyl-heptane-4-amine, 3,4 dimethyl-heptane-3-amine, 2,3-dimethyl-heptane-2-amine, 2,3-dimethyl heptane-3-amine, 2,5-dimethyl-heptane-2-amine, 3,6-dimethyl heptane-3-amine, 2,4-dimethyl-heptane-2-amine, 2,4-dimethyl-heptane 4 amine, 3,5-dimethyl-heptane-3-amine, 2,6-dimethyl-heptane-2 amine, 3-methyl-octane-3-amine, 4-methyl-octane-4-amine, 2-methyloctane-2-amine, 2,3,5-trimethylammonium-hexane-2-amine, 2,3,5-trimethylammonium-hexane-3-amine, 2,4,5-trimethylammonium-hexane-3-amine, 2,3,4 trimethylammoniums-hexane-2-amine, 2,3,4-trimethylammonium-hexane-3-amine, 3,4,5-trimethylammonium-hexane-3-amine, 2,5,5-trimethylammonium-hexane-2-amine, 3,4,4-trimethylammonium-hexane-3-amine and 3,5,5-trimethylammonium-hexane-3-amine also can contain formula (1) C in addition
9Isomer, its example include but not limited to positive nonyl amine, different nonyl amine.
Contained C in the amine mixt of the present invention
8The example of isomer includes but not limited to 2,3-dimethyl-hexane-3 amine, 2,3-dimethyl-hexane-2 amine, 2,4-dimethyl-hexane-2 amine, 2,4-dimethyl-hexane-4 amine, 2,5-dimethyl-hexane-2 amine, 2-methyl-heptane-2-amine, 3-methyl-heptane-3-amine, 4-methyl-heptane-4-amine also can contain formula (1) C in addition
8Isomer, its example includes but not limited to n-octyl amine and octodrine.
Contained C in the amine mixt of the present invention
10The example of isomer includes but not limited to 2,3-dimethyl-octane-2-amine, 2,3-dimethyl-octane-3-amine, 2,4-dimethyl-octane-2-amine, 2,4-dimethyl-octane-4-amine, 2,5-dimethyl-octane-2-amine, 2,5-dimethyl-octane-5-amine, 2,6-dimethyl-octane-2-amine, 2,6-dimethyl-octane-6-amine, 2,7-dimethyl-octane-2-amine, 3,4-dimethyl-octane-3-amine, 3,4-dimethyl-octane-4-amine, 3,5-dimethyl-octane-3-amine, 3,5-dimethyl-octane-5-amine, 3,6-dimethyl-octane-3-amine, 3,7-dimethyl-octane-7-amine, 4,5-dimethyl-octane-4-amine, 4,6-dimethyl-octane-4-amine, 4,6-dimethyl-octane-6-amine, 4,7-dimethyl-octane-4-amine, 4,7-dimethyl-octane-7-amine, 2-methylnonane-2-amine, 3-methyl-nonane-3-amine, 4-methyl-nonane-4-amine and 5-methylnonane-5-amine also can contain formula (1) C in addition
10Isomer, its example includes but not limited to n-Decylamine and isodecyl amine.
Amine mixt of the present invention is a highly basic, particularly in nonpolar organic medium.The common C of the pKa value that this amine mixt has greater than other type
8-C
10The pKa value of amine, generally speaking, the pKa of this scope primary amine commonly used is 9-11, is 10 as the pKa of positive nonyl amine, different nonyl amine, the pKa value of amine mixt of the present invention is generally 10.5-12, preferably 10.8-12, more preferably 11.0-12.0.
Preferred amine mixt is prepared by Propylene trimers.
As mentioned above, C is also disclosed
8-C
10The primary t-alkyl-amine preparation process of mixture.The matrix compounds that method of the present invention is used be well-known in the reaction substrate of special (Ritter) reaction, comprise as alcohol, alkene, aldehyde, ketone, ether, generally see " Ritter reaction " (1969, the 213-325 page or leaf) in " organic reaction " the 17th volume of L.I.Krimen and D.J.Cota.
In one embodiment, response matrix is an alkene, preferred C
8-C
10Alkene or the C of structural formula (2) expression
8-C
10Alkene mixture:
R wherein
aAnd R
bBe C independently of one another
1-C
6The C of alkyl, replacement
1-C
6Alkenyl, R
cAnd R
dBe H or C independently of one another
1-C
6The C of alkyl, replacement
1-C
6Alkyl, C
1-C
6The C of alkenyl, replacement
1-C
6Alkene.
C
1-C
6The example that alkyl is fit to includes but not limited to methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl etc., C
1-C
6The example that is fit to of substituted alkyl include but not limited to methyl that hydroxyl, halogen and nitro replace, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl etc.
C
1-C
6The example that alkenyl is fit to includes but not limited to vinyl, positive propenyl, pseudoallyl, n-butene base, isobutenyl, uncle's butenyl, positive pentenyl, isopentene group, new pentenyl, n-hexylene base etc., C
1-C
6The example that is fit to of substituted alkenyl base include but not limited to the vinyl that hydroxyl, halogen and nitro replace, positive propenyl, pseudoallyl, n-butene base, isobutenyl, uncle's butenyl, positive pentenyl, isopentene group, new pentenyl, n-hexylene base etc.
According to the present invention, employed alkene example includes but not limited to 3,4-dimethyl-heptene, 2,3-dimethyl-heptene, 2,5-dimethyl-heptene, 2,4-dimethyl-heptene, 3,5-dimethyl-heptene, 2,6-dimethyl heptene, 2-methyl-octene, 3-methyl-octene, 4 methyl-octene, 2,3,5-trimethylammonium-hexene, 2,3,4-trimethylammonium-hexene, 2,5,5-trimethylammonium-hexene, 3,5,5-trimethylammonium-hexene, 2,3-dimethyl-hexene, 2,4-dimethyl-hexene, 2,5-dimethyl-hexene, 2-methyl-heptene, 3-methyl-heptene, 4-methyl-heptene, 2,3-dimethyl-octene, 2,4-dimethyl-octene, 2,5-dimethyl-octene, 2,6-dimethyl-octene, 2,7-dimethyl-octene, 3,4-dimethyl-octene, 3,5-dimethyl-octene, 3,7-dimethyl-octene, 4,5-dimethyl-octene, 4,6-dimethyl-octene, 4,7-dimethyl-octene, 2-methyl-nonene, 3-methyl-nonene, 4 methyl-nonene, 5-methyl-nonene, alkene oligomer and their mixture, suitable alkene oligomer includes but not limited to Propylene trimers, the butene dimerization body, with the iso-butylene dimer.
In preferred embodiments, matrix compounds is alkene oligomer, more preferably Propylene trimers.
In one embodiment, used strong acid (HA) be the pKa value less than 5, preferably less than 3, be more preferably less than 2 strong acid, the example of the strong acid that uses among the preparation method of the present invention includes but not limited to mineral acid example hydrochloric acid, phosphoric acid, perchloric acid, sulfuric acid; Organic acid such as formic acid, methylsulphonic acid, p-methyl benzenesulfonic acid and highly acid ion exchange resin such as Amberlist
15 resins (Rohm and HaasCompany of Philadelphia, Pa).
In particularly preferred embodiments, used acid is dense aqueous sulfuric acid, and it comprises the sulfuric acid of 60-100% (weight).
In one embodiment, the chain carrier of matrix compounds with respect to every mole, contained acid is the 0.2-4 mole in the reaction mixture, preferred 0.5-3 mole, more preferably 1-2 mole, wherein the mole number of the chain carrier of matrix compounds equals the product of chain carrier number in the mole number of matrix compounds and each the matrix compounds molecule.
Used nitrile is in the presence of water, can form any nitrile compound of first reaction intermediate with acid and substrate reaction, and nitrile in one embodiment as the formula (3)
R-C ≡ N (3) wherein R is H, C
1-C
5Alkyl or substituted alkyl, vinyl, phenyl or substituted-phenyl, suitable examples of alkyl groups includes but not limited to methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl.
The example that is used for preparation method's of the present invention nitrile includes but not limited to prussic acid, acetonitrile, vinyl cyanide, butyronitrile, benzonitrile, to the methyl benzonitrile, preferred prussic acid.Nitrile directly can be added in the reaction mixture, also can add the compound that can form nitrile in addition and make its original position generation nitrile under reaction conditions of the present invention enter the first step reaction mixture.
In preferred embodiments, prussic acid directly joins reaction mixture as nitrile.In the embodiment of alternative, be added in the compound that produces prussic acid under present method reaction conditions, the prussic acid original position is generated, the example that produces the compound of prussic acid includes but not limited to hydrocyanide such as sodium cyanide and potassium cyanide.
In one embodiment, the reactive site of the matrix with respect to every mole contains the 1-10 mole in the reaction mixture, preferred 1-5 mole, the more preferably compound of the generation nitrile of the nitrile of 1-1.5 mole or a great deal of.
The chain carrier of the matrix with respect to every mole, the aqueous amount of reaction mixture is the 0.8-10 mole in first preparation process, preferred 1-5 mole, more preferably 1-3 mole.
First preparation process is with the temperature of reaction mixture at 0-120 ℃, preferred 25-90 ℃, and more preferably 30-60 ℃ of heating down.In one embodiment, matrix compounds is placed reaction vessel, acid and nitrile by certain feed rate distribute (profile) join reaction vessel, make reaction heat be heated to selected temperature to reaction mixture, promptly, make temperature of reaction remain on desired temperature range by the adding speed of control acid and nitrile.
In first preparation process, usually reaction mixture is remained on 1-10 normal atmosphere, preferred 1-5 normal atmosphere, more preferably 1 normal atmosphere.
Second preparation process is that first reaction intermediate is used acid treatment in the presence of water, the reactive site of matrix with respect to every mole, and the aqueous amount of the second step reaction mixture is the 0.5-20 mole, preferred 1-15 mole, more preferably 1-10 mole.
Second reaction intermediate do not separate from reaction mixture, do not arrest the constraint in theory, and in preferred embodiments, matrix is the alkene of formula (2) expression, it is believed that second reaction intermediate is the ammonium salt with formula (4):
Wherein A is the residue of used acid (HA) in first preparation process, R
a, R
b, R
cAnd R
dAs above-mentioned definition.
The acid that is used for second preparation process is the above-mentioned acid that is suitable for first preparation process, and the vitriol oil is preferred as (HA).
In second preparation process, reaction mixture is heated to 40-150 ℃ temperature, preferred 50-130 ℃, more preferably 60-110 ℃, the pressure that reaction mixture keeps is 0.1-2 normal atmosphere, preferably 0.5-1.5 normal atmosphere, more preferably 1 normal atmosphere.
In the 3rd preparation process, neutralize second reaction intermediate to pH=9 or higher with alkali cpd usually, form the amine compound shown in the formula (1).In one embodiment, alkali cpd is a highly basic.These alkali include but not limited to ammonium hydroxide, sodium hydroxide, potassium hydroxide and ammoniacal liquor.In preferred embodiments, used highly basic is sodium hydroxide or ammoniacal liquor, and more preferably pKa is not less than 8 ammonia soln.
In preferred embodiments, the organic layer of reaction mixture is separated, distilled, thereby reclaim and purifying amine product.In another embodiment, can be chosen in when finishing for second step, carry out separating of organic layer and water layer.
In an optional step, can be by distillation or method well known in the art, with C
8, C
9Or C
10One or more isomer separation, such amine compound that generates can be C
8Or C
9Or C
10Or C
8With C
9Or C
9With C
10Or C
10With C
8Or C
8, C
9With C
10Isomer mixture.
Amine mixt of the present invention is as the multifunction additive of fuel oil, lubricant and dyestuff, and its multifunctionality makes them be especially suitable for use as the stablizer of fuel oil, and therefore, amine mixt of the present invention can add and produces stabilization in the fuel oil.Wish to be not limited to theoretical constraint, the generation that it is believed that stabilization is because the multi-functional character that the branching primary t-alkyl-amine is given.The dispersiveness that amine mixt of the present invention is given and the demulsibility of improvement and stop oxidation and the corrosive nature stable fuel oil that combines.Amine mixt of the present invention not only plays slowing oil generation oxidation, as decompose hydroperoxide, and can form the salt be dissolved in fuel oil with the tart oxidized byproduct, or with metal and other material complexing, form the suspension liquid of these by products, thereby reduce the formation of color and slag thing.Can stop it rotten in the fuel oil so amine mixt of the present invention adds, also can solve the problem that produces behind the oil deterioration.
In one embodiment, disclosed fuel composition comprises the fuel oil of (A) more amount and (B) amine mixt of more a spot of formula (1) expression, the significant quantity of its amount for giving fuel oil multifunctional.
Usually in fuel composition, use the fuel oil of more amount, in preferred embodiments, the usage quantity of fuel oil is for being no less than 75% (weight), more preferably be no less than 90% weight, the general use of the amine mixt of formula (1) expression is more a small amount of, the significant quantity of its amount for giving fuel oil multifunctional, in embodiments, the concentration that amine mixt uses is 1-300 pound in per 1000 barrels of fuel oils, preferred 5-100 pound, more preferably 10-50 pound.
The used fuel oil of the present invention generally is meant rotten fuel oil takes place in the storage process, in preferred embodiments, used fuel oil is that initial boiling point is not less than 100 final boiling point and is not higher than 750 hydrocarbon fraction, keeps boiling continuously at this boiling range, and this fuel oil is commonly referred to as the middle distillate fuel oil.The example that is used for middle distillate fuel oil of the present invention includes but not limited to distilled oil, furnace oil, diesel oil, jet engine fuel oil and residual fuel oil such as ship's boiler fuel oil, marine internal combustion engine fuel oil and train fuel of internal combustion engine etc.
Amine mixt shown in the formula (1) preferably adopts from the amine mixt of Propylene trimers preparation.
In addition, also designed the method for stable fuel oil, be included in the described fuel oil and add significant quantity and stablize the amine mixt shown in the formula (1) of fuel oil.Fuel oil and formula (1) amine mixt is middle distillate fuel oil and preferred amine mixt by the Propylene trimers preparation.In one embodiment, add formula (1) amine mixt concentration be per 1000 barrels of fuel oil 1-300 pounds, preferred 5-100 pound, more preferably 10-50 pound.
The embodiment that below provides is to explanation of the present invention.Embodiment 1
C
1-C
10The preparation of branching primary t-alkyl-amine mixture
Rise at a 1-and to assemble heating jacket, thermometer, mechanical stirrer, reflux condensing tube, prussic acid and sour dropper on the four neck reaction vessels, add 126 gram Propylene trimers, 122.5 gram sulfuric acid, 22.5 Ke Shui and 33.2 gram prussic acid, temperature is remained on 25-50 ℃, stirred reaction mixture 2 hours.After two hours, remove the dropper on the reaction vessel, load onto the Dean-Stark couch water trap that matches with prolong, add 183 gram water, add under stirring and refluxed 3.5 hours, after 3.5 hours, reaction mixture is cooled to room temperature changes Dean-Stark couch water trap and condensing works with the ammoniacal liquor dropping funnel, cool off a following ammoniacal liquor and slowly join in the reaction mixture, with its neutralization.Stop to stir, make reaction mixture be divided into organic layer and water layer, obtain organic layer 122.9 grams after the separation, distillation is also collected 160-174 ℃ cut, obtain 118.2 gram product amine (theoretical yield 81.4%), its pKa is 11.5, boiling point is 170 ℃, zero pour is 103 ℃, adopt the composition of this material of gas Chromatographic Determination, used instrument is the HP5990 Series II GC of Hewlett-Packard Co., in the long 30m of RTX-5 type * diameter 0.53mm * 1 μ film capillary column of flame ionization detector and Restek Company is housed, the stratographic analysis display result is for containing 96.01%C
9Amine isomer, 0.02%C
8Amine isomer and 3.97%C
10The complex mixture of amine isomer.
Embodiment 2-10
The preparation of other branching primary t-alkyl-amine mixture
According to the method for embodiment 1, difference is that the alkene of use formula (2) and table 1 definition as matrix, has also prepared other branching primary t-alkyl-amine mixture.
Table 1
| Embodiment | ????R a | ????R b | ????R c | ????R d |
| ????2 | Methyl | Isobutyl- | ????H | N-propyl |
| ????3 | ?H | Isobutyl- | Methyl | Ethyl |
| ????4 | Ethyl | Methyl | ????H | N-pentyl |
| ????5 | Methyl | Methyl | ????H | Isopentyl |
| ????6 | Methyl | N-propyl | ????H | Isobutyl- |
| ????7 | Methyl | Methyl | ????H | The 2-hexyl |
| ????8 | Ethyl | Methyl | ????H | Normal-butyl |
| ????9 | N-propyl | Methyl | ????H | N-pentyl |
| ????10 | ??H | 3,3-dimethyl-butyl | Methyl | Methyl |
Embodiment 11-14 fuel oil shelf test
Be prepared into the fuel composition sample that contains the different concns additive shown in the table II with catalytic pyrolysis furnace oil (No. 2 fuel oils).The fuel oil shelf test is carried out as follows, and the fuel composition of preparation is placed the fuel oil sample bottle of 4-ounce, leaves in 43 ℃ the big thermostat container.At regular intervals, carry out spectrodensitometry one time.After sample firmly shaken up, leach a little sample with Corbing 30F sintered glass filter crucible, Lambda 2 UV/ visible light light-splitting instrument with Perkin Elmer Corp. carry out spectrodensitometry to the sample before and after filtering respectively, and it is further aging that all the other do not use part to put back in the thermostat container again.According to the pairing fate of optical density value of a certain regulation, determine the out-of-service time of sample with diagram or other interpolation technique.Two values being quoted are: (1) does not filter and the optical density(OD) difference Δ OD of filtered sample is 0.12, and (2) not the optical density value TOD of filtered sample are 1.00.Ask during inefficacy that gained the results are shown in Table II than being doping sample and the undressed base stock ratio of out-of-service time under controlled conditions.
The table II
| Embodiment | Additive | Concentration (pound/1000 barrels) | The inefficacy fate (the 1.0mg insolubles/100ml) |
| ????11 | Do not have | ????- | ????29 |
| ????12 | ?Primene 81-R 1 | ????15 | ????70 |
| ????13 | ?Primene TOA 2 | ????15 | ????70 |
| ????14 | Embodiment 1 amine mixt | ????15 | ????90 |
1Rohm and Haas Company of Philadelphia, the C of Pa supply
12-C
14The primary t-alkyl-amine compound.
2Rohm and Haas Company of Philadelphia, uncle's octyl group primary amine of Pa supply.
The table II shows that branching primary t-alkyl-amine of the present invention is better than amine commonly used well known in the art to the stabilization of fuel oil.
Embodiment 15-23
The diesel oil oxidation stability test
Preparation diesel oil (Gulf Coast0.4% sulphur Howell) fuel composition, the additive of contained different concns is shown in the table III.The diesel oil oxidation stability test is undertaken by improved ASTM2274 test method, and duration of test runs was changed into 40 hours from 16 hours to improve the ASTM2274 method, and the fuel composition oxidative stability is shown in the table III with the scale that generates insolubles.
The table III
| Embodiment | Additive | Concentration (ppm) | Insolubles (mg/100ml) |
| ????15 | Do not have | ????- | ????2.5 |
| ????16 | Primene 81-R 1+????Acryloid 91?7T(70/30) 2 | ????20 | ????1.3 |
| ????17 | Embodiment 1 amine mixt | ????15 | ????＜0.1 |
| ????18 | ?Primene 81-R 1 | ????15 | ????1.2 |
| ????19 | ?Primene JM-T 3 | ????15 | ????1.4 |
| ????20 | ?Primene TOA 4 | ????15 | ????0.4 |
| ????21 | 2 ethyl hexylamine | ????15 | ????2.2 |
| ????22 | Positive nonyl amine | ????15 | ????1.9 |
| ????23 | Different nonyl amine | ????15 | ????2.1 |
1Rohm and Haas Company of Philadelphia, the C of Pa supply
12-C
14The primary t-alkyl-amine compound.
2Rohm and Haas Company of Philadelphia, the methylacrylic acid alkyl ester copolymer that is dissolved in treated neutrals of Pa supply.
30Rohm and Haas Company of Philadelphia, the C of Pa supply
16-C
22The primary t-alkyl-amine compound.
4Rohm and Haas Company of Philadelphia, uncle's octyl group primary amine of Pa supply.
The table III shows amine commonly used and the amine mixt that branching primary t-alkyl-amine of the present invention is better than knowing to the oxidation-stabilized effect of fuel oil.
Claims (10)
1. the mixture of a branching primary t-alkyl-amine comprises the C that at least a following formula is represented
8, C
9And C
10Isomer
R wherein
1, R
2And R
3Be C independently of one another
1-C
6Alkyl or substituted alkyl, C
1-C
6Alkenyl or substituted alkenyl base, and the R of at least 50% isomer wherein
1, R
2And R
3At least one is a side chain.
2. the mixture of claim 1 contains at least 50% C
9Isomer is no more than 50% C
8Isomer and be no more than 50% C
10Isomer.
3. the mixture of claim 1 has the pKa value of 10.5-12.
4.C
8-C
10Branching primary t-alkyl-amine preparation process of mixture may further comprise the steps: (A) at 0-120 ℃ of temperature range internal heating reaction mixture, reach the C that can generate carbon ion with acid-respons comprising acid, nitrile, water
8-C
10Matrix compounds generates first reaction intermediate in reaction mixture; (B) in the presence of water, make first reaction intermediate in the reaction mixture form second reaction intermediate with the acid effect; (C), form amine mixt with second reaction intermediate of alkali cpd neutralization.
5. according to the method for claim 4, its mesostroma is formula (a 2) compound
R wherein
aAnd R
bBe C independently of one another
1-C
6The C of alkyl, replacement
1-C
6Alkenyl, R
cAnd R
dBe H or C independently of one another
1-C
6The C of alkyl, replacement
1-C
6Alkyl, C
1-C
6The C of alkenyl, replacement
1-C
6Alkene.
6. according to the method for claim 4, its mesostroma is a Propylene trimers, and nitrile is a prussic acid, and acid is dense aqueous sulfuric acid, comprises the sulfuric acid of 60-100% (weight), and alkali cpd is that the pKa value is not less than 8 ammonia soln.
7. fuel composition comprises:
(A) fuel oil of more amount; With
(B) amine mixt of more a spot of claim 1, its usage quantity are the significant quantity of giving fuel oil multifunctional character.
8. according to the fuel composition of claim 7, wherein the working concentration of amine mixt is per 1000 barrels of fuel oil 1-300 pounds.
9. the method for a stable fuel oil is included in the amine mixt of the claim 1 of the stable fuel oil that adds significant quantity in the fuel oil.
10. according to the method for claim 9, the amount that wherein adds amine mixt is per 1000 barrels of fuel oil 1-300 pounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98115925 CN1223254A (en) | 1997-07-07 | 1998-07-06 | Tertiary alkyl primary amines and process for preparing the same |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US051867 | 1997-07-07 | ||
| CN 98115925 CN1223254A (en) | 1997-07-07 | 1998-07-06 | Tertiary alkyl primary amines and process for preparing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1223254A true CN1223254A (en) | 1999-07-21 |
Family
ID=5224857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98115925 Pending CN1223254A (en) | 1997-07-07 | 1998-07-06 | Tertiary alkyl primary amines and process for preparing the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1223254A (en) |
-
1998
- 1998-07-06 CN CN 98115925 patent/CN1223254A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1295306C (en) | Fuel composition additive used for reducing sediment formed in combustion chamber | |
| US6194361B1 (en) | Lubricant composition | |
| EP0488747B1 (en) | Composition and method relating to diesel powered vehicles | |
| US3779905A (en) | Adding corrosion inhibitor to top of crude oil still | |
| CN100519515C (en) | Method of making hydroxyalkyl amide containing reduced level of unreacted alkanolamine | |
| EP1569923A1 (en) | Use of a mixture of esters of fatty acids as fuel or solvent | |
| AU2014339149A1 (en) | Use of a complex ester in a fuel | |
| EP2844630B1 (en) | Tritylated ethers | |
| CN101205489A (en) | Fuel oil additive composition, preparation and use thereof | |
| US4380498A (en) | Sulfurized, transesterified oil additives and their use in a lubricating oil and a fuel | |
| CN1223254A (en) | Tertiary alkyl primary amines and process for preparing the same | |
| CA2242658A1 (en) | Tertiary alkyl primary amines and process for preparing the same | |
| US2261227A (en) | Compression ignition engine fuels | |
| US3429812A (en) | Method of preparing lubricating oil concentrate containing calcium salt of alkylphenol - formaldehyde - diaminoalkane condensation product | |
| EP0185477A1 (en) | Production of ether/ether-alcohol compositions | |
| DE69908975T2 (en) | LUBRICANT ADDITIVE, METHOD FOR PRODUCING LUBRICANT ADDITIVES, AND MEDIUM DISTILLATE FUEL COMPOSITIONS CONTAINING THEM | |
| CA1154786A (en) | Preparation of alkoxysilane cluster compounds useful as functional fluids | |
| CN113462442B (en) | Diesel antiwear agent composition, preparation method thereof and diesel oil composition | |
| US2912458A (en) | Bis-2-methyl-2-norcamphanemethanol alkane-dioates as synthetic ester lubricants | |
| CN100457717C (en) | Method of purifying hydroxyalkyl amide | |
| US3377377A (en) | Complex ester lubricant | |
| CN103060029B (en) | Diesel additive composition containing alkyl ethylene glycol acetic acid polyol ester and application thereof | |
| US2699385A (en) | Hydrocarbon fuel oil compositions | |
| EP0919537B1 (en) | Process for producing aliphatic amine derivative | |
| US3218137A (en) | Stabilization of thermally unstable liquid hydrocarbon fuels |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |