CN101528664A - Process for making long chain internal fatty tertiary amines - Google Patents
Process for making long chain internal fatty tertiary amines Download PDFInfo
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- CN101528664A CN101528664A CNA2005800387668A CN200580038766A CN101528664A CN 101528664 A CN101528664 A CN 101528664A CN A2005800387668 A CNA2005800387668 A CN A2005800387668A CN 200580038766 A CN200580038766 A CN 200580038766A CN 101528664 A CN101528664 A CN 101528664A
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- C07—ORGANIC CHEMISTRY
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
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Abstract
The invention relates to a process for preparing long chain internal fatty amines, quaternized amines and amine oxides and selected amine oxides having a symmetric alkyl portion.
Description
Invention field
The present invention relates to a kind of aminomethylation method that is used to prepare long chain internal fatty tertiary amines, quaternised amine and corresponding oxidation amine.
Background of invention
The straight chain tertiary amine of chain length between 8 and 24 carbon atoms is generally known as aliphatic tertiary amine.According to " Ullman ' s Encyclopedia of Chemical Technology ", the 5th edition, the A2 volume, these materials and their derivative (as corresponding quaternary ammonium compound) extensively use in as fabric softener, drilling mud, tensio-active agent, asphalt emulsifier and sterilant/Application of disinfectants.
For fabric softener, the most effectively aliphatic quaternary ammonium compounds dialkyl dimethyl ammonium chloride or methyl esters vitriol accordingly.For drilling mud, the methyl or the benzyl ammonium chloride that derive from dialkyl methyl amines are useful.For tensio-active agent, use based on C usually
12Or C
14The dimethyl alkyl amine oxide.For sterilant and sterilizing agent, alkyl (benzyl) dimethyl and alkyl trimethyl compound (wherein aliphatic alkyl comprises 12 to 14 carbon atoms) can tackle most of organisms most effectively.Alternatively, when aliphatic alkyl comprised 8 to 10 carbon atoms, the dialkyl dimethyl compound was the most effective.
Aliphatic amide originates from natural fat and oil or traditional petrochemical material usually.Use three kinds of main feeds to prepare aliphatic tertiary amine: fatty nitrile, Fatty Alcohol(C12-C14 and C12-C18) or aldehyde and long-chain olefin.
Fatty nitrile (it is being formed by dehydration catalyst in Liquid-phase reactor or liquid and gas reactor under 280 ℃ to 360 ℃ by lipid acid and ammonia) is reacted to produce N with dimethylamine or with formaldehyde and formic acid, and the N-dimethyl alkylamine is (referring to authorizing Lion Fat ﹠amp; The US 4,248,801 of Oil Co. and the US 3,444,205 that authorizes Hoechst).
Can 230 ℃ under the barometric point (0.1MPa to 0.5MPa) in the presence of dimethylamine or other primary amine or secondary amine, use copper chromite catalyst (for pure feed) or precious metal, copper chelate or copper carboxylate catalyzer (for aldehyde), by direct amination fatty alcohols and aldehydes is changed into same product (referring to authorizing Gulf Research and Development the US 4 of Co., 251,465, authorize the US 4 of Hoechst, 138,437, and the US4 that authorizes Kao, 254,060 and US 4,210,605).
Yet these methods produce high-load terminal amine, are typically 91 weight % or higher." terminal amine " used herein is meant that amine moiety is connected on the α or β carbon of chain alkyl chain of described amine.
For the situation of amine oxide surfactant, cleaning effect that this can provide really and high froth stability.Yet, need to produce the interior amine of high-content (10 weight % or higher) sometimes.This branched chain surfactant for the wettability of the cold water cleaning effect with improvement, moderate froth stability and improvement will be useful.
Therefore, need a kind of hydrocarbon that use multiple source to prepare the method for the viable commercial of long-chain fat family tertiary amine and amine oxide (it provides the interior amine of desired content).Second target be by cheaply, economic method produces these amine.
Summary of the invention
The method that the present invention relates to may further comprise the steps:
(a) provide long-chain internal olefin source, described alkene source is selected from the group of being made up of following material: oligomeric C
2To C
11The C of alkene, replacement(metathesis)reaction
5To C
10Alkene, Fischer-Tropsch alkene, dehydrogenation long-chain paraffinic hydrocarbon, hot tearing chloroflo or dimerization vinyl olefins and their mixture;
(b) by aminomethylation with internal olefin source and primary amine or secondary amine reaction to produce long chain internal fatty tertiary amines;
(c) randomly isolate all unconverted hydrocarbon and part colored or odorous, obtain the long-chain fat family tertiary amine product of purifying from described long-chain fat family tertiary amine;
(d) randomly (have or do not have step (c)) described long-chain fat family tertiary amine is oxidized to corresponding amine oxide; With
(e) randomly (have or do not have step (c) and/or (d)) changes into quaternised long chain internal fatty tertiary amines product with described long-chain fat family tertiary amine quaternary ammonium.
Detailed Description Of The Invention
" long-chain internal olefin " used herein is meant the alkene that has 8 to 22 carbon atoms and be positioned at non-end (α and/or the β carbon) position on the alkene above 10% carbon-to-carbon double bond.Preferably surpass 50%, 70%, 90% and maximum 100% carbon-to-carbon double bond and be positioned at non-end (α and/or β carbon) position on the alkene.Described long-chain internal olefin can be straight chain or side chain.If the long-chain internal olefin is a side chain, C
1-C
5The side chain of carbon is preferred.
" interior amine " used herein is meant that amine moiety is connected the amine on the moieties, and the described amine moiety above 10%, 50%, 70%, 90% and maximum 100% is positioned at non-end (α and/or the β carbon) position on the moieties.
When with the formal representation of " X to Y " or " about X to about Y ", the number average in all scopes involved be included in herein, as clearly having write out in this article.Should be appreciated that each limit value that provides will comprise all lower limits or the upper limit in whole specification sheets, be determined on a case-by-case basis, clearly write out in this article as this lower limit or the upper limit.Each scope that in whole specification sheets, provides will comprise be included in this relative broad range all than close limit, write out fully clearly at this paper than close limit as this.
Be not bound by theory, it is believed that the low cost production that reaches long chain internal fatty tertiary amines by the method for using low-cost feed best, this is because in a large number, the manufacturing cost of chemical production processes is subjected to the domination of raw materials cost usually efficiently.Alkene, as the feed that can be used for producing long-chain fat family tertiary amine, one of raw material that cost is minimum normally.But alpha-olefin is used for making terminal tertiary amine, and amine needs long-chain internal olefin source in the long-chain.
Long-chain internal olefin source can derive from multiple diverse ways, comprises C
2To C
11Olefin oligomerization method, C
5To C
10The catalytic dehydrogenation of olefin metathesis reaction method, fischer-tropsch process, long-chain paraffinic hydrocarbon, the hot tearing of chloroflo and vinyl olefins dimerization method.
Can use the method such as the aminomethylation of viable commercial then, will derive from the reaction of the long-chain internal olefin of above-mentioned any method and primary amine or secondary amine to generate long-chain fat family tertiary amine.Use distillation or other commercial technology subsequently, isolate all unconverted hydrocarbon and part colored or odorous from described long chain internal fatty tertiary amines.
In the final step that present method is chosen wantonly, described long chain internal fatty tertiary amines is changed into corresponding amine oxide by oxidation.
The process of this paper and method comprise many other modification.Process of the present invention and method are described in greater detail in hereinafter.
Present method relates to the long-chain internal olefin is changed into long chain internal fatty tertiary amines, and optionally changes into amine oxide in the long-chain.
Long-chain internal olefin source
Oligomeric C
2
-C
11
Alkene
Derive from oligomeric C
2To C
11The long-chain internal olefin source of alkene can easily derive from multiple source, comprises Sweet natural gas, petroleum naphtha, and diesel oil distillate.Oligomerisation of ethylene can be available from supplier such as Shell Chemicals, Exxon Chemicals, BP Amoco and ChevronPhillips.
Described oligomeric C
2To C
11Alkene can be derived from C
2To C
11Alkene, described alkene produce the chain length of wide region in the presence of organo-aluminium compound, transition-metal catalyst or acid zeolite, it preferably distills by various known method and is further purified (referring to the US 3 that authorizes Shell OilCo., 647,906,4,727,203 and 4,895,997, authorize the US 5,849,974 of Amoco Corp., and the US 6 that authorizes Chevron Chemicals, 281,404, it discloses catalyzer and the treatment condition that are applicable to ethylene oligomerizationization).
Low dimerization reaction package is drawn together and is used catalyzer (as acid zeolite, nickel oxide or metallocene catalyst) to carry out the production of dipolymer, trimer or tetramer.For example, US 5,026, and 933 disclose the use of the ZSM-23 zeolite that is used for oligomeric acrylamideization.Other appropriate catalyst comprises
And acid zeolite (comprising the mordenite, offretite and the H-ZSM-12 that exist with acid form to small part) (also be illustrated in " Comprehensive OrganicTransformation ", the 2nd edition, Larock, Richard C., the 633rd to 636 page; " Vogel ' s Textbook of Practical Organic Chemistry ", the 5th edition, Furniss, Brian S., Hannaford, Antony J., Smith, Peter W.G. and Tatchell, AustinR., the 574th to 579 page).
The alpha-olefin or the internal olefin that depend on supplier and institute's using method are generated by low dimerization method.For the situation of alpha-olefin feed or blended alpha-olefin and internal olefin feed, need isomerization steps to produce required long-chain internal olefin.Isomerization steps causes two keys to be in the random site of carbochain.Suitable isomerization catalyst comprises homogeneous phase or heterogeneous acid catalyst, supporting metal oxide (as cobalt oxide, ferric oxide or manganese oxide), and carbonyl metal compound (as cobalt-carbonyl and iron carbonyl), referring to the US 3 that authorizes Shell Oil Co., 647,906, US4,727,203 and US 4,895,997, authorize the US 5,849,974 of Amoco Corp., and the US 6 that authorizes Chevron Chemi-cals, 281,404, it discloses catalyzer and the treatment condition that are applicable to double-bond isomerization.
C
5
-C
10
The replacement(metathesis)reaction of alkene
Can use C
5-C
10Alkene and other alkene or even produce the suitable long-chain internal olefin be used for present method with the replacement(metathesis)reaction of intersecting of grease chemical article.For example, two octene molecules can react and form tetradecene and ethene.Perhaps oleic methyl esters can react to form dodecylene and lauric methyl esters with hexene.Common homogeneous catalyst comprises based on Grubb ' the s catalyzer of ruthenium and Schrock catalyzer.The replacement(metathesis)reaction of intersecting also is described in the textbook " Olefin Metathesis and Metathesis Polymerization " (1997) of Ivin and Mol, and also has magazine " Chemical and Engineering News ", the 80th volume, the 51st phase, on December 23rd, 2002, the 29th to 33 page.
Other internal olefin
The alternative method that is used for alkene comes from the isomerization/disproportionation process of alkene and/or Shell Chemical's
Method.These are can trade(brand)name
Commercially available material.
Fischer-Tropsch alkene and paraffin
The long-chain internal olefin source that derives from Fischer-Tropsch relates to the hydrocarbon that carbon source such as coal, methane or conversion of natural gas is become the carbon chain length distribution broad, and use technology is isolated narrow hydrocarbon-fraction as distillation or liquid-liquid extraction then.
Two kinds of different catalyzer of commercial use: iron and cobalt, wherein Tie Tong often produces the alkene of higher yields and cobalt produces the paraffin of higher yields.The hydrocarbon that is obtained by fischer-tropsch reaction may be the mixture of straight chain and branched-chain hydrocarbon, alkene and paraffin, and it has terminal double link and internal double bond.Directly Fischer-Tropsch alkene and the paraffin that is come out by nozzle and/or diesel oil distillate can be used in the inventive method.
As mentioned above, can use double bond isomerizing catalyst that alpha-olefin is changed into internal olefin.Can stay until amination with internal olefin and finish being present in paraffin in the internal olefin incoming flow.
For fischer-tropsch reaction product, before amination, may need oxidation so that it is separated from hydrocarbon based on iron.Oxide compound relates to carboxylic acid, alcohol, aldehyde and ketone, and its chain length is C
1To C
18Oxide compound is given the worthless color of tertiary amine, smell and is formed impurity, and must remove from hydrocarbon before amination or remove from thick tertiary amine after amination.
Several method separating oxide from the Fischer-Tropsch crude product was arranged before amination.Liquid-liquid extraction is the preferred method that is used for from the hydrocarbon separating oxide.Liquid-liquid extraction is effectively remove alcohol and carboxylic acid from hydrocarbon aspect, and can realize than distillation or the more rational fund input of absorption.Alkaline purification, centrifugal subsequently, washing or filter neutralization with separates carboxylic acid aspect be effective, but invalid for alcohol.
Using liquid-liquid extraction to remove oxide compound can utilize multiple solvent to carry out.For example, it is reported that glycol ether is to be used for solvent that aromatic substance is removed from reformate, and it is reported that propane is to be used for solvent that lipid acid is removed from natural oil.Referring to " Packed Tower Design andApplications ", the 2nd edition, Strigle, the 294th page.Selecting must to consider multiple factor aspect the suitable solvent, comprise difference, viscosity, corrodibility between solvability, interfacial tension, phase density, and cost.The solvent polarity index is the solvability of oxide compound and the insoluble important indication of hydrocarbon.For the description of polarity index, referring to " the Practical HPLC Development " of Snyder, Kirkland and Glajch, the 2nd edition, the 723rd page; With " the Introduction to Modern LiquidChromatography " of Snyder and Kirkland, the 2nd edition, the 258th to 260 page.The applicant finds, and preferably using polarity index for Fischer-Tropsch product is 5.6 to 6.0 solvent.A kind of suitable solvent is the ethanol/water mixture of 80/20 weight %.The service temperature of liquid-phase extraction is 20 ℃ and extremely just is positioned under the boiling point of selected solvent.The ratio of solvent and feed is 0.1 to 3 to be preferred.
Extraction can be carried out in three class devices: mixer-settler, contact tower or centrifuge contactor.When only needing flash trapping stage, can use mixer-settler for extraction step.When the density variation between the phase is big, can use spray column.When needs surpassed three grades separation, packing tower or tray column with adverse current were preferred devices.If liquid phase has little density variation and needs many equilibrium stages, also can use centrifuge contactor.When ten to 12 balance joints of needs, usually use mechanical contact device, because these have the efficient higher than filler contactor with rotating disk or impeller.Preferred balance joint number order is one to 12.
Can use distillation separating oxide from hydrocarbon in theory, but the boiling point of oxide compound and hydrocarbon may be overlapping, so distillation is not preferred.By using molecular sieve adsorption to carry out separating in batches also is possible, but is expensive from fund input.
The dehydrogenation of long chain hydrocarbon
Long-chain internal olefin source also can derive from the catalytic dehydrogenation of long-chain paraffin or paraffin/alkene mixture, and its generation has the long-chain olefin of same carbon atoms number and the random site that two key is in carbochain.As mentioned above, can use double bond isomerizing catalyst that alpha-olefin is changed into internal olefin.Can stay until amination with internal olefin and finish being present in paraffin in the internal olefin incoming flow.
The source comprises kerosene(oil)fraction and Fischer-Tropsch paraffin or the paraffin/alkene mixture from oil refinery.Referring to the US 3,531,543 that authorizes Chevron Research and the US 3,745,112, the US 3,909,451 and 4,608,360 that authorize UOP, it discloses catalyzer and the treatment condition that are applicable to the paraffin dehydrogenation.Directly Fischer-Tropsch alkene and the paraffin that is come out by nozzle and/or diesel oil distillate can be used in the catalytic dehydrogenation method.Described UOP
Method uses the carrying alumina platinum catalyst to operate under 450 ℃ to 510 ℃ and 0.3MPa, and this method is promoted by lithium, arsenic or germanium.In order farthest to reduce by product, use the low-conversion of 10% to 15 weight %.Use low-conversion to cause paraffin-alkene mixture can pass through UOP
Method by further separation and purifying or carry out paraffin separates before and amine one react.
The hot tearing chloroflo
The long-chain internal olefin also can be derived from the hot tearing from the chloroflo (comprising Fischer-Tropsch paraffin) of oil industry or fischer-tropsch reaction.The chain length of these waxes is usually greater than C
22Hot tearing is non-catalytic, the free radical proceed that at high temperature causes in the presence of steam, and it distills subsequently to isolate unreacted wax and unreacted wax is recycled in the cracking furnace.
The preferred tube furnace that uses carries out cracking reaction.The temperature range of hot tearing is 400 to 600 ℃.Do not need to select higher temperature, because higher temperature causes forming the more alkene (chain length＜C of short chain
5), more high-load polyolefine, and more gas products.Do not need to select lower temperature, because lower temperature has reduced the conversion of each long-chain internal olefin, it stands in that fund cost puts is worthless.
Pressure in the hot tearing conversion zone is 0.1 to 1MPa.Higher pressure causes the increase of liquid yield usually, and the minimizing of corresponding alpha-olefin content.Space velocity be 1.25 to 5.0 volumes feed/volume reactor/hour.This roughly is consistent with residence time of 2.5 to 10 seconds in the reactor.Do not need the longer residence time, because it causes decomposing the increase with the secondary by product relative with required long-chain internal olefin.The transformation efficiency of each reaction is 10% to 25 weight %.
The gas that derives from the hot tearing reactor separates with 100 ℃ to 280 ℃ temperature with the pressure of liquid product by distilation steps use 10 to 2500Pa.Any unreacted wax is taken out from distilation steps as end cut, and recirculation is back to the hot tearing stove and mixes with fresh chloroflo.As mentioned above, all alpha-olefins that can use double bond isomerizing catalyst to exist change into the long-chain internal olefin.
Interior vinylidene
Vinylidene is as the long-chain internal olefin source of present method in also can utilizing.Can produce vinylidene by a kind of method, described method comprises vinyl olefins and at least a trialkyl aluminium compound dimerization.The condition that also has can be at US 5,625, finds in 105.Also can be by as US4, described in 973,788 in the presence of the trialkylaluminium catalyzer with the method production vinylidene of vinyl olefins monomer dimerization.
The long-chain internal olefin under the use aminomethylation condition and the reaction of primary amine or secondary amine
By the required long-chain fat family tertiary amine of the reaction production present method between aforesaid long-chain internal olefin and primary alkyl amine or the secondary alkylamine.If use primary alkyl amine such as Monomethylamine, then two kinds of long-chain internal olefin molecules added to this primary alkyl amine to produce two uncle of long-chain fat family monoalkylamine products.If use secondary alkylamine such as dimethylamine, then a kind of long-chain internal olefin molecule is added to this alkylamine with the manufacture order long-chain fat uncle of family dialkylamine product second month in a season.
The interior amine content that the tertiary amine product of producing by the inventive method has is 10 weight % to 100 weight %, and normal olefine content is about 1 weight % to 100 weight %, and paraffinicity is that 0 weight % is to about 90 weight %.
The embodiment of required tertiary amine product includes but not limited to trioctylphosphine amine, three decyl amine, tridodecylamine, two (dodecyl) methylamine, two (tetradecyl) methylamine, two (hexadecyl) methylamine, two (octadecyl) methylamine, decyl dimethyl amine, dodecyl dimethyl amine, tetradecyl dimethyl amine, hexadecyldimethyl benzyl ammonium amine, and the octadecyl dimethyl amine.The amine moiety of these materials is positioned on the interior location of chain alkyl.The α of the non-chain alkyl of carbon that interior location relates to or β carbon.The internal olefin that amination is used for present method comprises hydrocarbonylation, and is further described in hereinafter.
In an embodiment of present method, react the tertiary amine that generation has following structure with the aminomethylation of long-chain internal olefin (those feeds as previously discussed):
R wherein
1And R
2Be the hydrocarbon of straight chain or half straight chain, the chain length that this hydrocarbon comprises is 1 to 19 carbon atom." half straight chain " used herein is meant R
1And/or R
2Comprise stochastic distribution or the consistent C that distributes between 1 and 4
1To C
3Alkyl branches.Described amine structure is such: the carbon summation that moieties has is 8 to 22 carbon atoms.Moieties used herein be in the above institute reference structure between nitrogen and R
1And R
2Between R
1+ R
2+ 2 carbon atoms.
In a preferred embodiment, moieties (R
1+ R
2+ 2 carbon) summation of carbon is 10 to 22 in, and is preferred 12 to 20, more preferably 10 to 14 carbon atoms.R
1Carbonatoms can be approximated to be and R
2Identical carbonatoms is so that R
1And R
2Be symmetric." symmetric " used herein be meant for carbon atom, at least 50 weight %, and more preferably in the long-chain fat family that produces of this paper of at least 75 weight % to 100 weight % in the amine, | R
1-R
2| be less than or equal to 5 carbon atoms.In another embodiment, | R
1-R
2| less than 4.
Be not bound by theory, it is believed that the symmetrical structure of amine oxide in the long-chain fat family has improved the surface wettability of amine oxide, compare it with asymmetric side chain amine oxide and help under lower wash temperature to remove the precipitation of grease thing from the surface." asymmetric " used herein is meant | R
1-R
2| greater than 5 carbon atoms.Yet, comprise the mixture of amine oxide in the asymmetric and symmetrical structure long-chain fat family, for described purpose may also need, but not preferred.
According to the preferred embodiments of the invention, described method is included in catalyzer (preferred heterogeneous catalysts) and exists the alkene (preferably with stoichiometric ratio) that will contain synthetic gas (H2 and CO) down to react to form the step of tertiary amine product with primary amine or secondary amine.Preferred treatment condition are the pressure of 60 to 200 ℃ temperature, 2.8 to 21MPa (400 to 3000 pounds/square inch), 0.5 to 3.0 H2: CO mol ratio, and 0.1 to 10.0 hour reaction times.The catalyzer that is applicable to present method comprises noble metal catalyst such as rhodium oxide, rhodium chloride or ruthenium chloride, catalyst content for by the weight 50 of described alkene to 1000ppm.Randomly, can use part such as triphenylphosphine to stablize preferred heterogeneous noble metal catalyst.The preferred content of triphenylphosphine for by the weight 100 of described alkene to 5000ppm.
The optional thermal Release Technology purifying internal fatty tertiary amines that uses
Method of the present invention is further comprising the steps of: purifying derives from the long chain internal fatty tertiary amines product of preceding step to form the long chain internal fatty tertiary amines product of purifying.After purification step, the preferred purity of the long chain internal fatty tertiary amines product of purifying is counted about 95 weight % or higher by the weight of the long chain internal fatty tertiary amines product of described purifying, 97 weight % or higher more preferably from about, most preferably from about 98 weight % are to about 100 weight %.
Described long chain internal fatty tertiary amines product may be mixed with paraffin, unreacted alkene, material coloured and odorous, and the oxide compound of a small amount of in other impurity such as alcohol or carboxylic acid.
Above listed each impurity can be removed by thermal Release Technology.Preferred purification step can be undertaken by flash distillation still and/or topping tower.The equipment of flash distillation still and topping tower comprises falling-film evaporator, luwa evaporator, heavily boil unit and multistage distillation tower fast.All equipment it is known to those skilled in the art that, and can be available from supplier such as Pfaudler, Lewa and Koch.Heavy seeds as poly-alkylamine, salt and coloured moiety can be under the temperature of the pressure of 10 to 2500Pa (0.1 to 20mmHg) and 90 ℃ to 205 ℃ operation and in by the bottom of shift-in flash distillation still stream.Light impurity such as residual hydrocarbon (alkene or paraffin) and coloured moiety can be under the temperature of the pressure of 10 to 2500Pa (0.1 to 20mmHg) and 150 ℃ to 250 ℃ operation and in by the overhead product of shift-in topping tower stream.
The oxidation step that the internal fatty tertiary amines of purifying is optional
Method of the present invention also comprises following optional step: the long chain internal fatty tertiary amines of oxidative purification is to provide the oxygenated products of aliphatics amine oxide in the corresponding long-chain.Can randomly use material to transform as the hydrogen peroxide of 5% to 70 weight % long chain internal fatty tertiary amines with purifying.As authorize Procter ﹠amp; The US 6 of Gamble Co., 294, described in 514, typically the long chain internal fatty tertiary amines of purifying can be mixed with the hydrogen peroxide of 5% to 70 weight %, 0.3% to 2.5% supercarbonate material (as sodium bicarbonate or saleratus) and optional water, obtaining oxidation products, it is the oxidation products of fatty amine in the corresponding long-chain of 30% to 38 weight % by weight.The amount of hydrogen peroxide is to stoichiometric 100% to 115% of the amount that has amine.The target temperature of oxidation step is about 40 to 100 ℃ (preferred 60 ℃ to 70 ℃), and pressure is 0.1MPa.
When the amount of residual hydrogen peroxide is to be lower than 1% of the finished product composition, when preferably being lower than 0.1 weight %, oxidation step is finished.Reaction times is generally 4 to 24 hours.The typical case is by maintaining temperature of reaction with residual hydrogen peroxide decomposition with described material.If desired, the carrying alumina platinum reagent that can use 0.1% to 5 weight % by weight as sorbent material from oxidation products, to remove residual hydrogen peroxide.
The quaternized step that the internal fatty tertiary amines of purifying is optional
Method of the present invention also can may further comprise the steps: the long chain internal fatty tertiary amines of quaternized purifying is to provide quaternised long chain internal fatty tertiary amines product.Quaternized can the realization by the long chain internal fatty tertiary amines of purifying and the reaction of methyl chloride or methyl-sulfate.Quaternized with methyl chloride by under the nitrogen pressure of 101 to 10100kPa (1 to 100atm), in autoclave, realizing to 80 ℃ the temperature range with methyl chloride reaction with respect to long chain internal fatty tertiary amines 1.0 to 1.3 molar equivalents of purifying in room temperature (20 ℃).
Methyl-sulfate can 10 ℃ to 70 ℃ in the flask under the nitrogen protection with molar equivalent reaction, to form required quaternised long chain internal fatty tertiary amines product with respect to the long chain internal fatty tertiary amines 1.0 to 1.1 of purifying.
Embodiment
Following examples have further described and have proved the embodiment in the scope of the invention.Providing these embodiment only is to illustrate for example, but not to be interpreted as be limitation of the present invention, because do not deviating under the prerequisite of the present invention and can carry out many changes to it.
Embodiment 1The hot tearing of-paraffin, isomerization and aminomethylation
Step 1
In the glass beaker of 800mL, be that 52 ℃ to 58 ℃ paraffin and chain length is C with melting range
21To C
36Straight chain hydrocarbon fusing.The equipment that is used for the hot tearing reaction below the use:
-FMI piston pump (model QSY-1) is to be conducted to the metering of fused paraffin in the tubular reactor
-length is that 3.35m (11 feet) diameter is the stainless steel coil pipe of 4.57mm (0.18 inch), heating (preheater) in retort furnace
-length is that 3.66m (12 feet) diameter is the coil pipe of 4.57mm (0.18 inch), places second retort furnace (reactor)
-length is that 9.14m (30 feet) diameter is the coil pipe of 4.57mm (0.18 inch), places one 2 liters the beaker of filling water (quencher)
-be used to comprise 1 liter beaker of quench liquid product
The stainless steel pipeline of-electric tracing had thermopair before or after the reactor coil pipe
With 3.4 volume of liquid feed/volume reactor/hour the residence time and 575 ℃ temperature of reactor, use the mass velocity cracking fused paraffin of 0.04g/s (2.6g/min).652 gram fused paraffin meterings are conducted in the tubular reactor, and receive to such an extent that comprise the product of about 579 gram product liquids, this product liquid and incompressible steam and gaseous product balance.
Collect product from reactor, described product comprises cracked olefin and unreacted paraffin.Temperature with 667Pa (5mmHg) and 200 ℃ in the flash distillation still is isolated alkene from unreacted paraffin, uses Hewlett Packard 6890 serial gas-chromatographies to analyze then.Can obtain the distillate of about 67 grams.
Described distillate composed as follows:
C
10-C
20Alpha-olefin 93.1 weight %
C
10-C
20Diolefine 2.5 weight %
C
10-C
20Paraffin 2.8 weight %
C
10-C
20Other material 1.6 weight %
Internal olefin 0 weight %
Branched-chain alkene 0 weight %
Aromatic substance 0 weight %
Carbonyl value (being expressed as C=O) is 32ppm, and it illustrates that few hydrocarbon is oxidized.
Step 2
50 grams are derived from the C of above step 1
10To C
20The distillate composition places the Parr autoclave of 300mL, and with 0.025 the gram iron carbonyl Fe
2(CO)
9Any pair of key that mixing exists with isomerization and obtain internal olefin.With this reactor of nitrogen purging of 349.35kPa (50 pounds/square inch), under agitation heat distillate composition and iron carbonyl to 180 then ℃ one hour.
Cooling reactor to 40 ℃ also adds the rhodium oxide of 0.052 gram and the triphenylphosphine ligand of 0.131 gram.With this reactor of nitrogen purging of 349.35kPa (50 pounds/square inch) ten times, use the synthesis gas (synthetic gas) of 3493.5kPa (500 pounds/square inch) to purge this reactor twice then.The dimethylamine of 13.5 grams is added in this reactor.(use H with synthetic gas
2: CO is 0.5 mol ratio) reactor is forced into 7685.7kPa (1100 pounds/square inch).Control be reflected at 150 ℃ 3 hours, be cooled to 40 ℃ and make reactor decompression then to obtain crude product.GC-MS analyzes and should show to such an extent that the major part of crude product of autoreactor is mono-alkyl dimethyl amine straight chain and side chain.
Embodiment 2The isomerization of-alpha-olefin, aminomethylation subsequently and oxidation.
Step 1
C with 18.6kg (41 pounds)
10The C of alpha-olefin and 7.71kg (17 pounds)
12Alpha-olefin adds in the stirred reactor of 75.7L (20 gallons) together with the iron carbonyl of 25 grams as isomerization catalyst.With nitrogen reactor is forced into 139.74kPa (20 pounds/square inch), reactor heating to 180 ℃ a hour is so that double bond isomerization reaction carries out then.
Alternative step 1:
With 15.1g
10,136.6g
12 and the mixture of 109.1g 1-tridecylene together with 70g shape-selective catalyst (acidic beta zeolite catalyzer ZEOCAT
TMPB/H) add to the stainless steel agitated autoclave of a 7.57L (2 gallons) from a container.
10 and 12 is can be by the commercially available alkene of Shell Chemical Company.With the 200mL normal hexane alkene residual in the container and catalyst wash are advanced in the autoclave and with autoclave to seal.With nitrogen blow-off's purification reactor twice of 1724.25kPa (250 pounds/square inch), fill the nitrogen of 413.82kPa (60 pounds/square inch) then.Stir and heated mixt to 170 ℃ was cooled to 70 ℃ to 80 ℃ in about 18 hours then to 175 ℃.Open the valve that is connected to benzene condenser and holding tank from autoclave.The heating high-pressure still continues to be heated to 120 ℃ then to about 60 ℃, continues hexane is collected in the holding tank.Should no longer include hexane when reactor reaches 120 ℃ can collect.Cooling reactor to 40 ℃ and extract the 1kg normal hexane with pump and mix to autoclave.Drain autoclave so that the reaction mixture product is shifted out.The filter reaction mixture product is to remove catalyzer and boil off normal hexane under rough vacuum.High vacuum (133Pa to 667Pa[1 is to 5mm Hg post]) down the distillation reaction mix product to provide mixtures of internal olefins.Collect about 210g mixtures of internal olefins 85 ℃ to 150 ℃ temperature.
Cooling reactor to 50 ℃ with the reactor decompression, adds following composition to reactor then: 26 gram rhodium oxides, 65 restrain triphenylphosphine and 7.71kg (17.6 pounds) dimethylamine.With the synthetic gas (CO that described synthetic gas has: H
2Mol ratio is 1: 1) reactor is forced into 6987kPa (1000 pounds/square inch), be heated to then 150 ℃ three hours, obtain mixing prod, this product contain unreacted dimethylamine mutually with tertiary amine mutually.GC analyzes and shows that described mixing prod is the tertiary amine of 61 weight % and the unreacting olefin of 39 weight %.Cooling reactor also inclines mixing prod to the plastic tank of 18.0L (5 gallons).Any unreacted dimethylamine (DMA) is sunk in the separation mutually mutually, and from top decantation tertiary amine to provide thick tertiary amine product.
In 7.62cm (3 inches) glass batch still, use batch distillation to remove DMA and any unreacted alkene from the thick product of tertiary amine with 7 grades of separation and backflow.The thick tertiary amine of 31.1kg (68.5 pounds) is added to still kettle and uses following condition to distill under vacuum:
Distillation begins distillation and finishes
Tower top pressure 1.51kPa (11.3mmHg) 1.15kPa (8.6mmHg)
Tower bottom pressure 1.96kPa (14.7mmHg) 1.83kPa (13.7mmHg)
60 ℃ 132 ℃ of tower top temperatures
85 ℃ 144 ℃ of column bottom temperatures
" reflux ratio " used herein is defined as the mass rate of the mass rate of the distillate that is back to rectifying tower divided by the distillate that comes out from rectifying tower.Reflux ratio can be changed to 4.0 from 1.0.Obtain many cuts with various unreacting olefins and unreacted amine content.Stop rectifying tower steaming and stop the distillation and the cooling.Obtain about 2.13kg (4.7 pounds) bottoms.
The tertiary amine of cut and highest purity is mixed into blend, and this blend has the C greater than 99 weight %
11And C
13Amine and less than the C of 1 weight %
10And C
12Alkene.The glass Older-shaw rectifying column that use has the 5.08mm (2 inches) of 10 column plates utilizes the laboratory distillation to obtain pure C
11Amine.Here used " pure C
11Amine " be meant C
11The weight percent of amine is greater than 99 weight %.2230 gram distillates are added to still kettle and use following condition to distill under vacuum:
Distillation begins distillation and finishes
Tower top pressure 667Pa (5mmHg) 800Pa (6mmHg)
The tower bottom pressure nothing
82 ℃ 88 ℃ of tower top temperatures
125 ℃ 131 ℃ of column bottom temperatures
It is 6.0 that reflux ratio is set in whole distillation.There is C having collected
11After several cuts of tertiary amine, stop distillation.Collect about 600 gram distillates and restrain bottomss and stay in the still kettle about 1630.
Can in one 3 liters stirred flask, carry out oxidation step.Under agitation with 600 gram C
11The hydrogen peroxide of tertiary amine, 506 grams, 50 weight %, 1049 gram water, and 0.44 gram
2066 sequestrants add in the glass flask and are heated to 65 ℃.After mixing 10 hours, the composition of gained mixture should be the residual peroxide of about 1.1 weight %, the ligroin extraction of 2.1 weight % and the active oxidation amine of 28 weight %, detects less than unhindered amina is arranged.
Adsorb residual superoxide with 0.5% carrying alumina platinum sorbent material with continuous portion-wise addition, and use B and filter paper filtering above five times.With 32 restraining the about altogether 2150 gram amine oxides of sorbent treatment altogether.The finished product of gained should be the residual peroxide of about 0.09 weight %, the ligroin extraction of 2.1 weight % and the active oxidation amine of 28 weight %, detect less than unhindered amina is arranged.Use spectrophotometer and 1mm cuvette to be the reference measurement color with water, the percent transmission that obtains at 470nm is 96.4%.
Embodiment 3The replacement(metathesis)reaction of-alpha-olefin, aminomethylation subsequently.
Step 1
Use Grubbs catalyzer [first-generation, benzylidene-two (tricyclohexyl phosphine) ruthenous chloride] to prepare the 6-dodecylene by the replacement(metathesis)reaction of 1-heptene.Use vacuum fractionation from reaction mixture purifying 6-dodecylene.
Step 2
Use of the 6-dodecylene aminomethylation of following experimental procedure with generation in the step 1:
Rh
2O
3 (0.525mM) 10.25mg
TPP (P∶Rh＝1.2∶1) 26mg
6-dodecylene 13mL
Me
2NH 3.0g
At nitrogen (～0.1MPa (1 crust)) under with Rh
2O
3, TPP and alkene is heated to 150 ℃.Use the synthetic gas (H of 7.6MPa (76 crust)
2: CO2: 1) inject Me
2NH, and with this pressure supply synthetic gas 20h.
GC and GCMS analyze and show following products distribution:
Olefin conversion 90%
Aldehyde 17.2%
Enamine 11.4%
Alcohol 8.3%
Amine 63%
The amine products distribution is as follows:
A 2-amyl group octyl group dimethylamine 32.7%
B 2-butyl nonyl dimethylamine 27.3%
C 2-propyl group decyl dimethylamine 12.2%
D 2-ethyl undecyl dimethylamine 9.5%
E 2-methyl domiphen 13.6%
F straight chain-tridecyl dimethylamine 4.8
Embodiment 4The dehydrogenation of-long-chain paraffinic hydrocarbon, aminomethylation subsequently.
Use the following experimental procedure will be derived from C
11C
12Mineral wax mixture (form: C by alkene
11～44.5%, C
12～55.5%) the commercially available C of Pacol dehydrogenation
11C
12Feed olefin changes into amine:
Rh
2O
3 (0.525mM) 10.2mg
TPP (P∶Rh＝1.2∶1) 26mg
C11C12 Pacol alkene 13mL
Me
2NH 3.43g
At nitrogen (～0.1MPa (1 crust)) under with Rh
2O
3, TPP and alkene is heated to 150 ℃.Use the synthetic gas (H of 7.6MPa (76 crust)
2: CO 2: 1) inject Me
2NH, and with this pressure supply synthetic gas 20h.GC analyzes demonstration: (ignoring the product that derives from C10 and C13 alkene and aromatic substance in the feed in a small amount herein).
Transformation efficiency 82%
Alcohol～5%
Aldehyde～38.5%
Enamine～21.4%
Amine～35.1%
Amine distributes as follows:
Derive from the C13 amine of C12-alkene
A 2-amyl group octyl group dimethylamine 13.2%
B 2-butyl nonyl dimethylamine 16.6%
C 2-propyl group decyl dimethylamine 2.5%
D 2-ethyl undecyl dimethylamine 3.0%
E 2-methyl domiphen 5.3%
F straight chain-tridecyl dimethylamine 7.4%
Derive from the C12 amine of C11-alkene
G 2-amyl group heptyl dimethylamine 1.2%
H 2-butyl octyl dimethylamine 2.3%
I 2-propyl group nonyl dimethylamine 9.5%
J 2-ethyl decyl dimethylamine 17.6%
K 2-methyl undecyl dimethylamine 13.1%
L straight chain-domiphen 8.3%
Embodiment 5The dimerization of-alpha-olefin and vinylidene alkene, aminomethylation subsequently.
Step 1
Use bis cyclopentadienyl zirconium dichloride (Cp
2ZrCl
2) and methylaluminoxane (Al: Zr: alkene 50: 1: 1000) with 1-hexene dimerization, and by the vacuum fractionation purifying.Principal product is 2-butyl-1-octene (a C12-vinylidene).
Use following experimental procedure to carry out the hydrogen aminomethylation of 2-butyl-1-octene (C12-vinylidene):
Rh
2O
3 (0.525mM) 10.2mg
TPP (P∶Rh＝1.2∶1) 26mg
2-butyl-1-octene 13mL
Me
2NH 3.38g
At nitrogen (～0.1MPa (1 crust)) under with Rh
2O
3, TPP and alkene is heated to 150 ℃.Use the synthetic gas (H of 7.6MPa (76 crust)
2: CO 2: 1) annotate Me
2NH, and with this pressure supply synthetic gas 20h.
GC analyzes demonstration:
Transformation efficiency 83%
Paraffin 5%
Enamine 38%
Aldehyde 18%
Amine 39%
＞97% amine is dispensed to required 3-butyl nonyl dimethylamine isomer.
The relevant portion of all documents of quoting in detailed Description Of The Invention is incorporated herein by reference, and it is to its approval as prior art of the present invention that the quoting of any document not can be regarded as.
Although illustrated and described the present invention with specific embodiments, it will be apparent to those skilled in the art that many other variations and modifications may be made in the case of without departing from the spirit and scope of protection of the present invention.Therefore, in additional claims, comprise all such changes and modifications that belong in the scope of the invention consciously.
Claims (34)
1. method said method comprising the steps of:
A) provide long-chain internal olefin source;
B) by aminomethylation with internal olefin source and primary amine or secondary amine reaction to produce aliphatic tertiary amine;
C) randomly isolate all unconverted hydrocarbon from long-chain fat family tertiary amine, obtain the long-chain fat family tertiary amine product of purifying, described unconverted hydrocarbon randomly comprises part colored or odorous.
2. the method for claim 1, wherein said method is further comprising the steps of:
D) the long-chain fat family tertiary amine product with purifying changes into long-chain fat family amine oxide product.
3. the method for claim 1, wherein said method is further comprising the steps of:
E) long-chain fat family tertiary amine quaternary ammonium is changed into quaternised long chain internal fatty tertiary amines product.
4. at least one described method of claim as described above, wherein said long-chain internal olefin source is selected from the group of being made up of following material: oligomeric C
2To C
11The C of alkene, replacement(metathesis)reaction
5To C
10Alkene, Fischer-Tropsch alkene and paraffin, dehydrogenation long-chain paraffinic hydrocarbon, hot tearing chloroflo or dimerization vinyl olefins and their mixture.
5. at least one described method of claim as described above, wherein said long-chain internal olefin source is selected from oligomeric C
2To C
11Alkene, wherein said oligomeric C
2To C
11Alkene derives from low dimerization step, and described low dimerization step utilizes organo-aluminium compound, transition-metal catalyst, acid zeolite, nickel oxide or metallocene catalyst to produce long-chain internal olefin source.
6. at least one described method of claim as described above, wherein said long-chain internal olefin source derives from isomerization steps, and described isomerization steps utilizes an acidic catalyst, metal oxide or metallic carbonyls catalyzer to transform alpha-olefin feed or blended alpha-olefin and internal olefin feed.
7. at least one described method of claim as described above, wherein said long-chain internal olefin source is selected from Fischer-Tropsch alkene, paraffin and their mixture.
8. at least one described method of claim as described above, wherein said long-chain internal olefin source derives from isomerization steps, and described isomerization steps utilizes an acidic catalyst, metal oxide or metallic carbonyls catalyzer to transform alpha-olefin feed or blended alpha-olefin and internal olefin feed.
9. at least one described method of claim as described above, wherein in step (b) before, described method is further comprising the steps of: remove C by liquid-liquid extraction, alkaline purification, distillation, molecular sieve or their combination
1To C
18Oxide compound.
10. method as claimed in claim 9, the wherein selected step of removing is the liquid-liquid extraction by the use solvent, described solvent has 5.6 to 6.0 polarity index.
11. method as claimed in claim 10, the wherein said step of removing is carried out under about 20 ℃ of temperature to the boiling point that just is positioned at selected solvent; The ratio in wherein said solvent and long-chain internal olefin source is 0.1 to 3.
12. method as claimed in claim 9, wherein said oxide compound are selected from carboxylic acid, alcohol, aldehyde, ketone and their mixture.
13. method as claimed in claim 10, the wherein said step of removing is utilized mixer-settler, contact tower or centrifuge contactor.
14., wherein comprise 1 to 12 equilibrium stage in the step described removing as at least one described method in the claim 9 to 13.
15. method as claimed in claim 14, the wherein said step of removing comprises 10 to 12 equilibrium stages and utilizes contact tower; Wherein said contact tower is packing tower or the tray column with adverse current.
16. at least one described method of claim as described above, wherein said long-chain internal olefin source is selected from dehydrogenation long-chain paraffin or long-chain paraffin/alkene mixture.
17. as at least one described method in the claim 1 to 15, wherein said long-chain internal olefin source is selected from the hot tearing chloroflo, described chloroflo is from oil industry or fischer-tropsch reaction, wherein said long-chain internal olefin source is produced by the step of heating chloroflo in tube furnace, described step 400 ℃ to 600 ℃, 0.1 to 1MPa, 1.25 feed/volume reactor to about 5.0 volumes/hour space velocity under carry out, and each transformation efficiency is 10% to 25 weight % in the described reaction.
18. as at least one described method in the claim 1 to 15, wherein said long-chain internal olefin source comprises alpha-olefin, described alpha-olefin becomes the corresponding long chain internal olefin by isomerisation of alpha-conversion of olefines in the presence of isomerization catalyst.
19. as at least one described method in the claim 1 to 15, wherein said long-chain internal olefin source is selected from the interior vinylidene that is produced by the vinyl olefins dimerization.
20. at least one described method of claim as described above, wherein step (b) comprises the use of primary alkyl amine, make primary alkyl amine for each molecule, add two molecules from the long-chain internal olefin in long-chain internal olefin source to produce two-long-chain fat family tertiary amine product.
21. as at least one described method in the claim 1 to 19, wherein step (b) comprises the use of secondary alkylamine, make secondary alkylamine for each molecule, add a part from the long-chain internal olefin in long-chain internal olefin source to produce mono-long chain aliphatic tertiary amine product.
22. at least one described method of claim as described above, the content of the paraffin that wherein said long-chain fat family tertiary amine product comprises is counted 0 weight % to about 90 weight % by the weight of described long-chain fat family tertiary amine product.
23. at least one described method of claim as described above, wherein said long-chain fat family tertiary amine product is selected from the group of being made up of following material: trioctylphosphine amine, three decyl amine, tridodecylamine, two (dodecyl) methylamine, two (tetradecyl) methylamine, two (hexadecyl) methylamine, two (octadecyl) methylamine, decyl dimethyl amine, dodecyl dimethyl amine, tetradecyl dimethyl amine, hexadecyldimethyl benzyl ammonium amine, octadecyl dimethyl amine and their mixture.
24. as at least one described method in the claim 1 to 22, wherein said long-chain fat family tertiary amine comprises following structure:
R wherein
1And R
2Be the hydrocarbon of straight chain or half straight chain, and have the chain length of 1 to 19 carbon atom.
25. at least one described method of claim as described above, wherein method described in the step (b) be included in primary amine or secondary amine and catalyzer, preferred heterogeneous catalysts in the presence of with the step of alkene and synthesis gas reaction.
26. at least one described method of claim as described above, wherein step (b) is at 60 ℃ to 200 ℃ temperature, 2.8 to 21MPa pressure, 0.5 to 3.0 H
2: the CO mol ratio, and carry out under 0.1 to 10 hour reaction times.
27. as claim 25 or 26 described methods, wherein said catalyzer is made up of rhodium oxide, rhodium chloride or ruthenium chloride, the content of described catalyzer counts 50 to 1000ppm by the weight of described alkene.
28. as claim 25,26 or 27 described methods, the triaryl phosphine that wherein adds triphenylphosphine or replacement is with rugged catalyst, the content of the triaryl phosphine of described triphenylphosphine or replacement counts 100 to 5000ppm by the weight of described alkene.
29. at least one described method of claim as described above, wherein the long-chain fat amine product of the purifying of step (c) comprises the long-chain fat amine to about 100% by the about 95 weight % of weight of the tertiary amine product of described purifying.
30. as at least one described method in the claim 2 to 29, wherein step (d) comprises that the long-chain fat amine product that mixes hydrogen peroxide, water and purifying is to produce amine oxide product in the long-chain.
31. as at least one described method in the claim 2 to 29, wherein step (d) has about 40 ℃ to 100 ℃ temperature and the pressure of about 0.1Mpa.
32., wherein continue step (d) until the 1 weight % of hydrogen peroxide less than adding hydrogen peroxide original vol as at least one described method in the claim 2 to 29.
33., wherein continue step (d) until the 0.1 weight % of hydrogen peroxide less than adding hydrogen peroxide original vol as at least one described method in the claim 2 to 29.
34. as at least one described method in the claim 2 to 29, wherein step (d) also comprises the carrying alumina platinum reagent of 5 weight % by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US62795904P | 2004-11-15 | 2004-11-15 | |
| US60/627,959 | 2004-11-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101528664A true CN101528664A (en) | 2009-09-09 |
Family
ID=35811680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800387668A Pending CN101528664A (en) | 2004-11-15 | 2005-11-15 | Process for making long chain internal fatty tertiary amines |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1812376A1 (en) |
| JP (1) | JP2008519802A (en) |
| CN (1) | CN101528664A (en) |
| BR (1) | BRPI0518005A (en) |
| CA (1) | CA2586592A1 (en) |
| WO (1) | WO2006050994A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110172109A (en) * | 2019-06-18 | 2019-08-27 | 青岛科技大学 | A kind of method of continuous synthesis oxidized polyethylene wax |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR112013004585B1 (en) * | 2010-09-20 | 2021-09-08 | Merck Sharp & Dohme Corp | CATIONIC LIPIDIUM, LNP COMPOSITION, E, USE OF A CATIONIC LIPIDE |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4138437A (en) * | 1975-08-06 | 1979-02-06 | Hoechst Aktiengesellschaft | Process for the preparation of tertiary aliphatic amines |
| US4179469A (en) * | 1978-12-20 | 1979-12-18 | Uop Inc. | Preparation of amines |
| JPS58183648A (en) * | 1982-04-22 | 1983-10-26 | Mitsubishi Petrochem Co Ltd | Preparation of tertiary amine |
| JPS60258145A (en) * | 1984-06-02 | 1985-12-20 | Mitsubishi Petrochem Co Ltd | Production of tertiary amine |
| DE19737053A1 (en) * | 1997-08-26 | 1999-03-04 | Hoechst Ag | One-step process for the production of amines |
| US6294514B1 (en) * | 1998-11-24 | 2001-09-25 | The Procter & Gamble Company | Process for preparing mono-long chain amine oxide surfactants with low nitrite, nitrosamine and low residual peroxide |
| DE10321421A1 (en) * | 2003-05-12 | 2004-12-02 | Degussa Ag | Hydroaminomethylating terminal alkenes, to prepare amines useful e.g. as pharmaceuticals, by reacting with amine, hydrogen and carbon monoxide over catalyst containing rhodium and bidentate phosphorus ligand |
-
2005
- 2005-11-15 JP JP2007540611A patent/JP2008519802A/en active Pending
- 2005-11-15 BR BRPI0518005-8A patent/BRPI0518005A/en not_active IP Right Cessation
- 2005-11-15 CA CA002586592A patent/CA2586592A1/en not_active Abandoned
- 2005-11-15 CN CNA2005800387668A patent/CN101528664A/en active Pending
- 2005-11-15 WO PCT/EP2005/012243 patent/WO2006050994A1/en active Application Filing
- 2005-11-15 EP EP05810966A patent/EP1812376A1/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110172109A (en) * | 2019-06-18 | 2019-08-27 | 青岛科技大学 | A kind of method of continuous synthesis oxidized polyethylene wax |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008519802A (en) | 2008-06-12 |
| BRPI0518005A (en) | 2008-10-21 |
| EP1812376A1 (en) | 2007-08-01 |
| WO2006050994A1 (en) | 2006-05-18 |
| CA2586592A1 (en) | 2006-05-18 |
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