CN101223128A - Process for synthesizing alkylated arylamines - Google Patents
Process for synthesizing alkylated arylamines Download PDFInfo
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- CN101223128A CN101223128A CNA2006800195037A CN200680019503A CN101223128A CN 101223128 A CN101223128 A CN 101223128A CN A2006800195037 A CNA2006800195037 A CN A2006800195037A CN 200680019503 A CN200680019503 A CN 200680019503A CN 101223128 A CN101223128 A CN 101223128A
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- arylamines
- alkylating
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- reaction
- pentanoic
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- 150000004982 aromatic amines Chemical class 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 57
- 230000008569 process Effects 0.000 title claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- 239000002168 alkylating agent Substances 0.000 claims abstract description 38
- 229940100198 alkylating agent Drugs 0.000 claims abstract description 38
- 230000002152 alkylating effect Effects 0.000 claims abstract description 35
- 229910000039 hydrogen halide Inorganic materials 0.000 claims abstract description 22
- 239000012433 hydrogen halide Substances 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 97
- 239000000203 mixture Substances 0.000 claims description 65
- 150000001336 alkenes Chemical class 0.000 claims description 49
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 48
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 24
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 18
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 230000005587 bubbling Effects 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 4
- 238000005755 formation reaction Methods 0.000 claims 7
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- 238000006467 substitution reaction Methods 0.000 abstract description 10
- -1 aluminum compound Chemical class 0.000 abstract description 8
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 24
- 230000009466 transformation Effects 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 12
- YLKFDHTUAUWZPQ-UHFFFAOYSA-N N-Nitrosodi-n-propylamine Chemical compound CCCN(N=O)CCC YLKFDHTUAUWZPQ-UHFFFAOYSA-N 0.000 description 11
- 238000005804 alkylation reaction Methods 0.000 description 10
- 150000001399 aluminium compounds Chemical class 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000029936 alkylation Effects 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 5
- 235000011089 carbon dioxide Nutrition 0.000 description 5
- 239000003518 caustics Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- LVZUNTGFCXNQAF-UHFFFAOYSA-N n-nonyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCCC)C1=CC=CC=C1 LVZUNTGFCXNQAF-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- QVXGKJYMVLJYCL-UHFFFAOYSA-N 2,3-di(nonyl)-N-phenylaniline Chemical compound C(CCCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCCC QVXGKJYMVLJYCL-UHFFFAOYSA-N 0.000 description 1
- 238000006418 Brown reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012858 resilient material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
-
- B01J35/19—
Abstract
An improved process and novel catalyst system for alkylating arylamines generally comprising the combination of an arylamine and an alkylating agent in the presence of a trialkyl aluminum compound and a hydrogen halide. The improved process and new catalyst system allows for higher total conversion of the arylamine feedstock without sacrificing substitution product selectivity and also allows for the reaction of recycled alkylene feedstock.
Description
Related application
The application based on and require the U.S. Provisional Application 60/687,182 submitted on June 2nd, 2005 and the right of priority of the U.S. Provisional Application 60/717,322 submitted on September 14th, 2005.
Technical field
The present invention relates generally to a kind of improving one's methods of synthesizing alkylated arylamines that be used for, and it generally includes the catalyst system that method that service routine heats up or relatively mild reaction conditions and utilization comprise trialkyl aluminium compound and hydrogen halide reacts the blended alkene and the arylamines of material fresh or fresh and recirculation.
Background technology
Alkylating arylamines has many different application.Wherein one of application is to be used for motor vehicle and industrial lubricants as a kind of antioxidant addn, synthetic, semisynthetic or natural polymkeric substance, particularly thermoplastic material and resilient material, hydraulic fluid, metal working fluids, fuel, circulation oils, gear oils and engine oils.In this class is used, alkylating arylamines usually with about 0.05wt% extremely the additive of about 2wt% concentration exist.Alkylating arylamines has anti-oxidant, heat resistanceheat resistant and/or photolytic stabilization for organic materials.A kind of special alkylating arylamines, promptly the pentanoic of nonylated is as the additive of the organic products of stablizing easy oxidative degradation.The pentanoic nonene of the synthetic nonylated of nonene and diphenylamine reaction is called as tripropylene sometimes, and it is the C of isomery
9The mixture of alkene.It and diphenylamine reaction form substitution product, promptly monoalkylation, dialkyl groupization and mixture trialkylated pentanoic, and this mixture and any unreacted pentanoic remain in the solution.Often, for the pentanoic of nonylated, a kind of concrete substitution product is desirable.The arylamines of dialkyl groupization is desirable.
The method of the alkylating arylamines of known many preparations, great majority relate to alkene and arylamines reacts in the presence of catalyzer, efforts be made so that the consumption of raw material (arylamines) and the maximum production of concrete substitution product.
Using aluminum chloride is used for a long time as the catalyzer in the pentanoic alkylation in the art.For example, United States Patent (USP) 3,496,230 have described the production method of using aluminum trichloride catalyst to prepare the pentanoic (nDPA) of nonylated.In addition referring to United States Patent (USP) 2,776,994 and United States Patent (USP) 4,739,121.Yet because aluminum chloride is a kind of solid, it is difficult to use in technical scale.
Similarly, the use of clay catalyst in the pentanoic alkylation is well known in the art.For example, United States Patent (USP) 6,315,925 have described the method for use acidic white earth catalyzer (particularly acid clay) diphenylamine compound of production nonylated (the especially pentanoic of dinonylization) under the situation that does not have free proton acid.Referring to United States Patent (USP) 6,204,412 and United States Patent (USP) 4,824,601.Yet, use acid clay low and need high temperature as the common efficient of solid catalyst.
Summary of the invention
The route of traditional synthesizing alkylated arylamines is devoted to maximize the transformation efficiency of arylamines raw material to required substitution product.Yet the maximization transformation efficiency is a cost with desirable product selectivity often.For example, for alkylating pentanoic, higher transformation efficiency generally produces the trialkyl substitution product of higher concentration.Can under the situation of not sacrificing product selectivity, obtain the total conversion rate of higher arylamines raw material with new catalyst system this disclosed improving one's methods.
Except these advantages, described improved method and novel catalyst system also can make the olefin feedstock of recirculation react.Olefin feedstock generally includes the mixture of isomeric olefine.The determining positions of two keys in isomeric olefine its reactive behavior.For example, in vinyl (2,2-is dibasic) type and 1,2, in the mixture of 3-three substituted type alkene, vinyl olefins is estimated with the arylamines reaction faster.Because the olefin feedstock charging is excessive, the non-reacted parts of olefin feedstock has the low reactivity 1,2 of greater concn than fresh feed, 3-three substituted type alkene.Therefore, when excessive alkene accumulated recirculation, its low reactivity needed the longer time, and this causes the increase of undesirable substitution product.
Of the present invention improving one's methods generally includes the olefin feedstock of packing into, and described olefin feedstock is the mixture of the alkene of fully fresh raw material or fresh alkene and recirculation; When adding trialkyl aluminium compound and hydrogen halide, make the reaction of olefin feedstock and arylamines.Make fresh fully olefin feedstock total conversion rate maximization for the selectivity of not sacrificing substitution product, use the trialkylaluminium loading capacity of relatively mild temperature of reaction, reduction and excessive hydrogen halide.Excessive hydrogen halide has increased the lewis acidity of catalyst system.For comprising fresh and olefin feedstock recirculation alkene, reach similar result by the raw material sectional feeding.At first, the trialkylaluminium loading capacity of reduction and excessive hydrogen halide are used in the charging under initial higher temperature of reaction of the alkene of recirculation, to increase the lewis acidity of catalyst system.After the initial charging of recirculation alkene, add fresh olefin feedstock, this permission is reacted under the initial charge temperature of reaction at first, is reduced to relatively mild temperature of reaction subsequently to suppress undesirable substitution product.
Novel catalyst system of the present invention mainly comprises add trialkyl aluminium compound ((Al (alkyl) in reaction mass
3) and hydrogen halide.Selectively, sodium halide or similar compounds can be used as halide source, still, and preferred hydrogen halide.Suitable trialkyl aluminium compound comprises having the C that selects alone
1-C
8The compound of straight or branched alkyl (alkyl group that is concrete trialkyl aluminium compound needn't be identical); Yet, preferably have C
2-C
4The trialkyl aluminium compound of alkyl is because they are easy to handle.Preferred novel catalyst system and the olefin feedstock with 4-28 carbon atom of using reacts.
Embodiment
Although following detailed description mainly provides the alkylated reaction of pentanoic, method described herein to those skilled in the art and catalyst system can be used for other arylamines, for example alkylation of aniline and other similar compounds.
The alkylating total reaction flow process of pentanoic the figure illustrates that pentanoic reacts to obtain alkylating pentanoic with alkylating agent (alkene) when adding trialkyl aluminium compound and HCl as shown in Figure 1.Catalyst system of the present invention and method cause main forming 4,4 '-dialkyl diphenylamine, and only a spot of neighbour-alkylating product.Right-alkylation degree height according to the present invention in the formed product demonstrates that processing property improves under oxidation, heat and/or photoinduced degradation condition.Except the product of dialkyl groupization, also formed the pentanoic of a spot of trialkylization and monoalkylation.
The advantage that forms para-isomeride is considered to based on the tridimensional electronic field.Formed active catalyst species is considered to one or more chloro-hexichol acid amides (chloro-dianilide) type structures in reaction mixture.The mechanism of the ortho-alkylating of its mechanism and aniline similar (people such as G.Ecke, J.Org.Chem., the 639th page, the 22nd phase, nineteen fifty-seven).
Fig. 1. adding Al (alkyl)
3Prepare alkylation DPA down with HCl
Usually, alkylating pentanoic prepares by pentanoic and alkylating agent (alkene) reaction under adding trialkylaluminium and hydrogenchloride situation, and wherein the mol ratio of muriate and aluminium is at least about 3: 1, preferably at least about 4: 1.The mol ratio of alkylating agent and pentanoic also can change, but preferred about 2: 1 to about 4: 1.Al (alkyl)
3Also can change in reaction with the mol ratio of pentanoic, but preferred about 0.05: 1 to about 0.25: 1.R, R ' and R " can for the corresponding any direct-connected or branched alkyl group of the olefin isomer of alkylating agent, preferably have 4-28 carbon atom.
Reactant is stirred under 100 ℃ of-180 ℃ of temperature.Pentanoic transformation efficiency greater than about 95% can be observed down at about 150 ℃ in about one hour.When the dialkyl group production concentration increases, consume the reaction that pentanoic generates the trialkyl product and have more competitiveness, in time and/or the rising of temperature and become especially remarkable.
As mentioned above, when use comprised fresh and recirculation olefin alkylation agent, because long reaction times and/or the high necessary temperature of total conversion rate, the alkene of recirculation had lower reactivity, and trend produces a large amount of undesirable substitution products.Therefore, in order to guarantee to keep suitable product specification, the alkene of recirculation preferably is confined to account for 40% of total olefin raw material.Before adding fresh alkene, make recirculation alkene and diphenylamine reaction, this mode forces the alkene of aromatic ring and relatively poor reactive behavior to react.
A preferred embodiment of catalyst system is by obtaining to pentanoic adding trialkyl aluminium compound and gas HCl.Gas HCl bubbling produces heat release by aluminum compound and diphenylamine compound.Like this, blended alkyl chloride catalyzer derivative is on-the-spot to be generated, and it contains one or more following material: AlCl
3, Al (alkyl) Cl
2, Al (alkyl)
2Cl, Al
2(alkyl)
2Cl
4, [Al (alkyl) Cl
3]
-, [Al
2(alkyl)
2Cl
5]
-, [Al
3(alkyl)
3Cl
7]
-[Al
2(alkyl) Cl
6]
-The existence of ionic species is accelerated reaction speed by improving lewis acidity, especially under the situation that excessively HCl exists.Because above-mentioned listed material is very important in reaction mechanism, monoalkyl and/or dialkyl group/halogenated aluminum compound can be as the alternative of trialkyl aluminium compound in this catalyst system.
Embodiment
Embodiment 1
Use following general procedure to prepare the pentanoic of nonylated.
The glass reaction container purged with nitrogen before using, and was reflected under the condition of nitrogen gas and carried out.Conventional raw materials components mole ratio is: C
9: DPA=2.89; TEA: DPA=0.157; Cl: Al (catalyzer)=～3.3-3.5.
The pentanoic (DPA) that in the 500mL Kjeldahl flask, adds 85g.Flask purged 5 minutes with nitrogen, was heated to 60 ℃ with fusing DPA.Nonene (the C that in the adding tower that is connected in flask, adds 183g
9).Use suitable measure and transfer techniques that the triethyl aluminum (TEA) of 9g is transferred in the reaction flask, then, add nonene by adding tower immediately.After the violent stirring, the HCl bubbling of aim parameter is by the reaction mixture in the container.This is reflected at 150 ℃ of heating 3 hours, at t=0, and sampling in 1.5 and 3 hours.Cooling reactor is then poured out raw product and is weighed.Embodiment 1A-1L carries out according to general procedure, uses TEA+HCl as catalyst system, has summarized reactant quantity and reaction times in the table 1 and has gone up noticeable change.Each reaction is all carried out under 150 ℃, positive a little nitrogen pressure.
The illustrative preparation of the alkylating pentanoic of table 1 and products distribution
| Sample | 1A 1/23 | 1B 1/28 | 1C 2/3 | ID 2/4 | 1E 2/9 | IF 2/10 | 1G 2/13 | 1H 2/14 | 1I 2/16 | 1J 2/18 | 1K 4/20 | 1L 4/21 | |
| Reaction conditions | Time (hour) | 21.0 | 9.0 | 3.0 | 3.0 | 3.0 | 2.5 | 3.0 | 3.0 | 3.0 | 3.0 | 3.3 | 3.5 |
| Wt％Al | 0.79 | 0.92 | 1.23 | 1.00 | 1.44 | 1.18 | 1.33 | 1.32 | 1.30 | 1.18 | 1.41 | 1.38 | |
| Wt％Cl | 3.17 | 3.49 | 5.34 | 4.23 | 5.60 | 5.2 | 5.60 | 6.26 | 5.90 | 5.59 | 6.20 | 6.44 | |
| Cl∶Al | 3.1 | 2.9 | 3.3 | 3.2 | 3.0 | 3.4 | 3.3 | 3.6 | 3.5 | 3.6 | 3.3 | 3.6 | |
| Goal response thing group is to area %) | DPA | 3.2 | 1.4 | 1.4 | 1.3 | 1.3 | 1.0 | 0.9 | 1.0 | 0.9 | 1.6 | 1.2 | |
| MONO | 27.9 | 21.4 | 21.7 | 21.3 | 21.3 | 19.1 | 18.4 | 18.3 | 18.2 | 21.2 | 19.9 | ||
| DI | 64.6 | 71.1 | 71.6 | 70.8 | 71.0 | 72.1 | 72.2 | 72.4 | 72.8 | 71.7 | 71.0 | ||
| TRI | 4.2 | 6.1 | 6.3 | 6.5 | 6.4 | 7.8 | 8.5 | 8.4 | 8.0 | 5.2 | 7.7 | ||
| Final product is formed (area %) | C9 | 34.8 | 3.8 | 1.8 | 1.9 | 0.2 | 0.3 | 0.2 | 0.2 | 0.3 | 0.3 | 0.7 | 0.3 |
| DPA | 0.8 | 3.1 | 1.2 | 1.3 | 1.2 | 1.2 | 0.9 | 0.9 | 0.9 | 0.8 | 1.4 | 1.1 | |
| MONO | 12.0 | 26.8 | 20.0 | 20.6 | 20.0 | 20.3 | 18.5 | 17.8 | 17.5 | 16.4 | 20.7 | 18.8 | |
| DI | 47.3 | 62.1 | 70.1 | 69.7 | 71.2 | 71.0 | 72.0 | 71.7 | 71.9 | 73.4 | 70.4 | 71.1 | |
| TRI | 4.6 | 4.1 | 6.7 | 6.3 | 7.1 | 7.0 | 8.2 | 9.1 | 9.0 | 8.8 | 5.6 | 8.5 | |
| Viscosity (cSt) | n/a | 220 | 315 | 300 | 483 | 482 | n/a | n/a | n/a | n/a | n/a | 529 | |
| Colourity (Gardner) | n/a | n/a | n/a | n/a | 3.2 | n/a | n/a | n/a | n/a | n/a | n/a | 3.8 | |
The single nonyl diphenylamine of MONO=
The DI=dinonyldiphenylamine
TRI=three nonyl diphenylamine
The DPA=pentanoic
The C9=nonene
Embodiment 2
In loft drier, (10g 0.088mol) packs in the 1-L round-bottomed flask of mixture of the nonene that contains 36.0g (0.28mol, required total nonene about 20%) recirculation and the fresh alkene of 42.0g (0.33mol) (78g, about 0.62mol) altogether with TEA.Flask transferred in the stink cupboard add DPA rapidly (85.0g 0.50mol), stirs under the HCl bubbling in nitrogen atmosphere.This reactor is equipped with stirring rod, thermopair and is connected with condenser.
Approximately the HCl (0.82mol, Cl/Al is than about 9.3) of feeding 30g is 10 minutes, observes heat release (136 ℃).Heating is set to 150 ℃.When temperature of reaction arrived 150 ℃, the DPA of GC analytical table express contract 67% changed into the mixture that is mainly single nonyl thing.Do not form the trialkyl product.
Then, in 17 minutes, add required 2.9 equivalent nonenes (the fresh alkene of 105g, 0.83mol, the about 183g of combined feed total feed nonene, about 2.9 equivalents).Added behind all nonenes 1 hour, GC analyzes and shows that about 98%DPA changes into product.Heat after 2 hours the DPA transformation efficiency and increase to approximately 98.4% a little, stop heating.
Reaction mixture is by pouring into the 25wt% caustic solution quencher of 150g.Exert oneself to separate organic phase after the jolting with the aqueous solution, be transferred to then in the round-bottomed flask that is connected with receptor and outfit thermopair and magnetic stirring bar.Crude mixture by heating jacket device vacuum heat gradually about 0.5 hour 150 ℃ to remove excessive nonene and residuary water.Collect the dry nonene (MgSO of about 56g in the dry ice cooling receptor
4).
NDPA obtains the light brown oily NDPA of 172g by the active alkaline bed of aluminium oxide filtration of 20g while hot under vacuum.Nitrogen analysis to NDPA (nonylated diphenylamine) is measured as 3.86% weight.
Separated product is carried out GC to be analyzed.Product in the table 2 distributes and shows when using catalyst system of the present invention and method, obtains the contraposition alkylation of height.
Table 2: the GC of separated product analyzes
| Component | Area % |
| DPA | 1.53 |
| O-list-alkylation DPA | 0.28 |
| P-list-alkylation-DPA | 21.91 |
| O-two-alkylation DPA | 3.05 |
| P-two-alkylation-DPA | 65.35 |
| Three-alkylation DPA | 7.70 |
Embodiment 3
(7.0g 61mmol) adds in the 1L round-bottomed flask (being equipped with magnetic stirrer, thermopair and cooler condenser) that contains 120g (0.95mol) nonene with TEA.
(85g 0.50mol) joins in nonene/TEA mixture, and the HCl bubbling stirs these slurries down under the condition of nitrogen gas with solid DPA.Heating temperature is set to 125 ℃, adds the HCl (0.32mol, Cl/Al is than being about 5.2) of about 11.7g in 15 minutes.The GC analysis revealed heating transformation efficiency that DPA is converted into product during less than 2 hours is 88%.Add the 3rd normal nonene (61g, 181g altogether), the monitoring reaction process is summarized as shown in table 3.Adding transformation efficiency＞99% that heats 15 hours DPA after all nonenes altogether is inevitable.
In the 1-L round-bottomed flask of independent outfit mechanical stirrer, slowly the crude reaction material is poured into 125g 25wt% caustic solution, firmly mix (320rpm, 25 minutes), and make it be separated into two-phase (30 minutes).
Organic phase is transferred to be equipped with magnetic stirrer and to be connected dry ice cools off receptor and lack in the round-bottomed flask of condenser.Under 15mm Hg vacuum with light brown reaction raw materials heating (heating gradually) to 150 ℃ about 0.5 hour to remove excessive nonene and residuary water.Collect the dry (MgSO of 43 (43) grams
4) nonene.
Table 3: reaction process (@125 ℃ of GC area %)
| Reaction times (h) | The DPA transformation efficiency |
| 1 4 7 15 | 95.7 97.9 98.0 99.2 |
Under the vacuum NDPA is filtered the removal traces of solids through active alkali alumina (20g) heat (130 ℃).The NDPA that the GC analytical separation obtains (179g), its result is presented in the table 4.
The GC area % that table 4:NDPA analyzes
| Component | GC area % |
| DPA list-alkyl-DPA two-alkyl-DPA three-alkyl-DPA | 0.72 15.8 77.9 5.4 |
Embodiment 4
(7.0g 61mmol) joins in the 1L round-bottomed flask that contains 70.0g (0.55mol) distillation circulation nonene with TEA.(85g 0.50mol), stirs slurries under the condition of nitrogen gas to add DPA.This reactor is equipped with stirring rod, thermopair and connects cooler condenser.
Approximately 17.0g HCl (0.466mol, Cl/Al is than being about 7.6) is sparging in the slurries 22 minutes, observes heat release (101 ℃).Heating be provided with at first 150 ℃ about 0.5 hour to guarantee that recycled olefins reaction adds fresh nonene (113g, 183g alkene altogether) in 14 minutes then in the reaction mixture that refluxes.It is 92.1% that GC analysis revealed nonene adds fashionable DPA transformation efficiency fully.Heating at once is set to 125 ℃, and as above-mentioned embodiment, by GC monitoring reaction process, its result is presented in the table 5.Add and heat 15 hours DPA transformation efficiencys behind all nonenes altogether greater than 99% be inevitable.
Table 5: reaction process GC area %
| Reaction times (h) | The DPA transformation efficiency |
| 0 1 | 92.1 95.9 |
| 3 7 15 | ～98 98.3 ～99.3 |
In the 1L round-bottomed flask of independent outfit mechanical stirrer, crude reaction product is slowly added the 25wt% caustic solution of 125g, firmly mix (320rpm, 40 minutes).Kept two-phase 30 minutes before separating.Organic phase is transferred to be equipped with magnetic stirrer and to be connected dry ice to be cooled off receptor and lacks in the 1L round-bottomed flask of condenser.Under the 12mm Hg vacuum reactant is heated to 150 ℃ about 0.5 hour to remove excessive nonene and residuary water.Collect the dry (MgSO of 43 (43) grams
4) nonene.
By active alkali alumina (20g) NDPA vacuum heat (125 ℃) is filtered to remove traces of solids salt.The NDPA of GC analytical separation (182g) is in the data presentation table 6 below.
The GC of table 6:NDPA analyzes area %
| Component | GC area % |
| DPA list-alkyl-DPA two-alkyl-DPA three-alkyl-DPA | 0.68 15.7 75.2 8.3 |
Embodiment 5
(10.0g 61mmol) joins in the 1L round-bottomed flask (being equipped with magnetic stirrer, thermopair and cooler condenser) that contains 61g (0.48mol) nonene with TEA.(85g 0.50mol) joins in nonene/TEA mixture, stirs when intermittence blasts gas HCl under condition of nitrogen gas with DPA.
The initial HCl (0.32mol, Cl/Al is than being about 3.7) that in 30 minutes, adds about 11.9g.Originally Heating temperature is set to 150 ℃, and heating is about 11 minutes under this temperature.Add the second equivalent nonene (61g, 122g altogether) in 10 minutes, continue heating 1 hour at 150 ℃.The HCl total amount that add this moment is 13.5g, (Cl/Al about 4.2).The GC analysis revealed DPA transformation efficiency of crude product mixture is about 94%.Add third part nonene (61g, 183g altogether) rapidly, temperature resets to 140 ℃ of heating 1 hour.The GC analysis revealed forms a small amount of trialkylated DPA, and the transformation efficiency of DPA is about 98.1%.140 ℃ continue heating the second hour when blasting extra 2.1g HCl (altogether 15.6, Cl/Al about 4.9) again, and the DPA transformation efficiency is increased to 98.6%.Adding the 4th in 8 minutes is last part nonene (61g, 244g altogether, about 3.86 equivalents).Temperature of reaction reset be changed to about two hours of 130 ℃ of heating to transformation efficiency greater than 99% (heating was less than 6 hours).
In the 1L round-bottomed flask of independent outfit mechanical stirrer, the slow impouring 125g of crude reaction thing 25wt.% caustic solution firmly mixes (320rpm, 30 minutes).Make it be separated into two-phase.Organic phase is transferred to be equipped with magnetic stirrer and to be connected dry ice to be cooled off receptor and lacks in the 1L round-bottomed flask of condenser.
Under the 11mm Hg vacuum with browning reaction material heating (heating gradually) to 150 ℃ of about 0.5h to remove excessive nonene and residuary water.By active alkali alumina (20g) thick NDPA being carried out vacuum heat (85 ℃) filters to remove traces of solids salt.The NDPA of GC analytical separation (178g).DPA concentration is 0.49wt.%, and trialkylated-DPA concentration is 9.56%.。
Embodiment 6
Under the condition of nitrogen gas with the 85g pentanoic (DPA, 0.50mol), 210g tetrapropylene (C12 alkene) (about 1.25mol), the n-heptane solution of 80ml 1.0M TEA (0.08mol) joins in the three-necked flask.(6g 0.16mol) blasts in the mixture HCl gas, and reaction raw materials heated 4 hours down at 150 ℃.GC analyzes and records the DPA transformation efficiency is about 90%.(4g, 0.11mol), reaction mass heated 3 hours in addition to blast extra HCl.GC analysis revealed DPA transformation efficiency is about 94%.Add the excessive tetrapropylene of 40g, mixture heating up 8 hours.About 3% unreacted DPA still is present in the reaction mixture.
By pouring into 25%NaOH aqueous solution quencher reaction mass, wash (3 * 400ml) then with water.The heating organic phase is heated to 180 ℃ gradually by decompression and removes moisture, heptane and excessive alkene to obtain 219g heavy-gravity brown oil.
Mainly, remove most DPA with the oil of steam flushing heating under the vacuum by intaking lentamente (0.2) to the surface of the oil (150 ℃) of heating with the speed of 0.5ml/min with the wriggling fresh feed pump.In dry ice cooling receiving flask, collect DPA and condensed steam.GC analyzes tetrapropylene-DPA, in the data presentation table 7 below.
Table 7: the GC area % that tetrapropylene-DPA analyzes
| Component | GC area % |
| DPA list-alkyl-DPA two-alkyl-DPA three-alkyl-DPA | ＜0.1 21.35 66.74 11.88 |
Embodiment 7
Under the condition of nitrogen gas with the 85g pentanoic (DPA, 0.50mol), 217g tetrapropylene, Et
2AlCl (the 50mL1.0M n-heptane solution, 0.05mol) and AlCl
3(7.0g, 0.05mol) mixture joins in the three-necked flask.The reaction mixture heating did not detect product in two hours.HCl gas (14g altogether, 0.38mol) bubbling is gone in the mixture, and reaction mass heated 9 hours altogether at 150 ℃.Vacuum is removed excessive alkene after adding caustic alkali, and the oily matter of gained passes through diatomite filtration.The result that gained brown oil GC analyzes is presented in the following table 8.
The GC area % that table 8 polypropylene-DPA analyzes
| Component | GC area % |
| DPA list-alkyl-DPA two-alkyl-DPA three-alkyl-DPA | 2.86 29.78 59.17 6.14 |
The foregoing description does not constitute qualification, only is the explanation of all respects of the present invention and embodiment.The present invention carries out according to physical condition and obtains mentioned result and advantage, and institute's inherent characteristics is apparent to those skilled in the art.Some changes and other utilizations can take place to those skilled in the art, and it is contained in spirit of the present invention, as the defined scope of claim.
Claims (65)
1. a method that is used for alkylated aryl amine comprises step: by the raw material formation reaction material that comprises arylamines, alkylating agent, trialkylaluminium and hydrogen halide; And formation alkylated aryl amine.
2. the process of claim 1 wherein that the mol ratio of halogenide and aluminium was at least about 3: 1.
3. the process of claim 1 wherein that the mol ratio of alkylating agent and arylamines is about 2: about 4: 1 of 1-.
4. the process of claim 1 wherein that the mol ratio of trialkylaluminium and arylamines is about 0.05: about 0.25: 1 of 1-.
5. the process of claim 1 wherein that described arylamines is a pentanoic.
6. the process of claim 1 wherein that described alkylating agent is the alkene with 4-28 carbon atom.
7. the process of claim 1 wherein that described alkylating agent is the mixture with isomeric olefine of 4-28 carbon atom.
8. the method for claim 7, wherein, described alkylating agent is the isomer mixture of nonene.
9. the method for claim 8, wherein, described arylamines is a pentanoic.
10. the process of claim 1 wherein that the alkyl of described trialkylaluminium comprises 1-8 carbon atom.
11. the method for claim 10, wherein, described trialkylaluminium is a triethyl aluminum.
12. the process of claim 1 wherein that described hydrogen halide is a hydrogenchloride.
13. a method that is used for alkylated aryl amine comprises step:
By the raw material formation reaction material that comprises arylamines, alkylating agent, trialkylaluminium and hydrogen halide;
Reaction mass was mixed at least about one hour, be heated to the temperature between about 100 ℃-Yue 180 ℃ simultaneously;
Basically remove all unreacted alkylating agents; And
The alkylating arylamines of resulting separation.
14. the method for claim 13, wherein, described alkylating agent is fresh unreacted alkene.
15. the method for claim 14 wherein, is mixed the part of described trialkylaluminium and total alkylating agent at first, adds arylamines then, makes the hydrogen halide bubbling pass through reaction mass subsequently.
16. the method for claim 14, wherein, described arylamines combines with alkylating agent and trialkylaluminium, makes the hydrogen halide bubbling pass through reaction raw materials then.
17. the method for claim 14, wherein, described reaction mass is heated to initial reaction temperature, is cooled to lower temperature of reaction subsequently.
18. the method for claim 17, wherein, described reaction mass is heated to the initial reaction temperature between about 140 ℃-Yue 180 ℃.
19. the method for claim 18, wherein, described reaction mass be cooled to subsequently between about 120 ℃-Yue 140 ℃ than low reaction temperatures.
20. the method for claim 19, wherein, described arylamines is a pentanoic.
21. the method for claim 20, wherein, described alkylating agent is the isomer mixture of nonene.
22. the method for claim 13, wherein, the alkyl of described trialkylaluminium comprises 1-8 carbon atom.
23. the method for claim 22, wherein, described trialkylaluminium is a triethyl aluminum.
24. the method for claim 13, wherein, described hydrogen halide is a hydrogenchloride.
25. the method for claim 13, wherein, described alkylating agent comprises the fresh unreacted alkene and the alkene of recirculation.
26. the method for claim 25 wherein, is mixed the part of described trialkylaluminium and total alkylating agent at first, adds arylamines then, makes the hydrogen halide bubbling pass through reaction mass subsequently.
27. the method for claim 25, wherein, described alkylating agent and trialkylaluminium combine with arylamines, make the hydrogen halide bubbling pass through reaction mass then.
28. the method for claim 26, wherein, the some of the initial total alkylating agent of bonded comprises the alkene of recirculation.
29. the method for claim 28 wherein, in conjunction with recirculation alkene the time, is heated to initial reaction temperature with reaction mass.
30. the method for claim 29 wherein, is heated to initial reaction temperature between about 140 ℃-Yue 180 ℃ with reaction raw materials.
31. the method for claim 29, wherein, described fresh unreacted alkene is heated to after the initial reaction temperature, and it combines with reaction mass.
32. the method for claim 31 wherein, when fresh unreacting olefin combines, is cooled to lower temperature of reaction with reaction mass.
33. the method for claim 32, wherein, with reaction mass be cooled to about 120 ℃-Yue 140 ℃ than low reaction temperatures.
34. the composition of the alkylated reaction that arylamines and alkylating agent carried out in the catalyzed reaction material, said composition comprises trialkylaluminium and hydrogen halide.
35. the composition of claim 34, wherein, the mol ratio of halogenide and aluminium is at least about 3: 1.
36. the composition of claim 34, wherein, the mol ratio of trialkylaluminium and arylamines is about 0.05: about 0.25: 1 of 1-.
37. the composition of claim 34, wherein, described arylamines is a pentanoic.
38. the composition of claim 34, wherein, the alkyl of described trialkylaluminium comprises 1-8 carbon atom.
39. the composition of claim 38, wherein, described trialkylaluminium is a triethyl aluminum.
40. the composition of claim 34, wherein, described hydrogen halide is a hydrogenchloride.
41. an alkylating arylamines mixture, it prepares by following steps: by the raw material formation reaction material that comprises arylamines, alkylating agent, trialkylaluminium and hydrogen halide; Reaction mass was mixed at least about one hour, and be heated to the temperature between about 100 ℃-180 ℃ simultaneously; Basically remove all unreacted alkylating agents; And the alkylating arylamines mixture of resulting separation, this alkylating arylamines mixture comprises monoalkylation, dialkyl groupization, trialkylated arylamines component, wherein, the alkyl group of the arylamines component of monoalkylation is mainly in the 4-position, the alkyl group of the arylamines component of dialkyl groupization mainly pounds 4,4 '-position.
42. the alkylating arylamines mixture of claim 41, wherein, the halogenide in the reaction mass and the mol ratio of aluminium are at least about 3: 1.
43. the alkylating arylamines mixture of claim 41, wherein, the alkylating agent in the reaction mass and the mol ratio of arylamines are about 2: about 4: 1 of 1-.
44. the alkylating arylamines mixture of claim 41, wherein, the trialkylaluminium in the reaction mass and the mol ratio of arylamines are about 0.05: about 0.25: 1 of 1-.
45. the alkylating arylamines mixture of claim 41, wherein, described arylamines is a pentanoic.
46. the alkylating arylamines mixture of claim 41, wherein, described alkylating agent is the alkene with 4-28 carbon atom.
47. the alkylating arylamines mixture of claim 41, wherein, described alkylating agent is the mixture with isomeric olefine of 4-28 carbon atom.
48. the alkylating arylamines mixture of claim 41, wherein, described alkylating agent is the isomer mixture of nonene.
49. the alkylating arylamines mixture of claim 48, wherein, described arylamines is a pentanoic.
50. method that makes the fluid stable of easily oxidated, hot and/or photoinduced degraded, comprise the step of the alkylating arylamines mixture that in this fluid adding is an amount of, described alkylating arylamines mixture is to prepare by following steps: the reaction mass that is generated by the raw material that comprises arylamines, alkylating agent, trialkylaluminium and hydrogen halide; This reaction mass was mixed at least about one hour, be heated to the temperature between about 100 ℃-Yue 180 ℃ simultaneously; Basically remove all unreacted alkylating agents; The alkylating arylamines mixture of resulting separation, this alkylating arylamines mixture comprises monoalkylation, dialkyl groupization and trialkylated arylamines component, wherein, the alkyl group of the arylamines component of described monoalkylation is mainly in the 4-position, the alkyl group of the arylamines component of dialkyl groupization mainly 4,4 '-position.
51. the method for claim 50, wherein, described arylamines is a pentanoic.
52. the alkylating arylamines mixture of claim 50, wherein, described alkylating agent is the alkene with 4-28 carbon atom.
53. the alkylating arylamines mixture of claim 50, wherein, described alkylating agent is the mixture with isomeric olefine of 4-28 carbon atom.
54. the alkylating alkylating agent mixture of claim 50, wherein, described alkylating agent is the isomer mixture of nonene.
55. the alkylating arylamines mixture of claim 54, wherein, described arylamines is a pentanoic.
56. composition, comprise the liquid and the alkylating arylamines mixture of easily oxidated, hot and/or photoinduced degraded, described alkylating arylamines mixture is to prepare by following steps: by the raw material formation reaction material that comprises arylamines, alkylating agent, trialkylaluminium and hydrogen halide; This reaction mass was mixed at least about one hour, be heated to the temperature between about 100 ℃-180 ℃ simultaneously; Basically remove all unreacted alkylating agents; And the alkylating arylamines mixture of resulting separation, this alkylating arylamines mixture comprises monoalkylation, dialkyl groupization, trialkylated arylamines component, wherein, the alkyl group of the arylamines component of described monoalkylation is mainly in the 4-position, the alkyl group of the arylamines component of dialkyl groupization mainly 4,4 '-position.
57. the composition of claim 56, wherein, described arylamines is a pentanoic.
58. the composition of claim 56, wherein, described alkylating agent is the alkene with 4-28 carbon atom.
59. the composition of claim 56, wherein, described alkylating agent is the mixture with isomeric olefine of 4-28 carbon atom.
60. the composition of claim 56, wherein, described alkylating agent is the isomer mixture of nonene.
61. the composition of claim 60, wherein, described arylamines is a pentanoic.
62. method that is used to make the pentanoic nonylization, comprise step: by the raw material formation reaction material that comprises pentanoic, nonene, triethyl aluminum and hydrogen halide, wherein, the mol ratio of nonene and pentanoic is about 2: 1 to about 4: 1, the mol ratio of triethyl aluminum and pentanoic is about 0.05: 1 to about 0.25: 1, and the mol ratio of muriate and aluminium is at least about 3: 1; And the pentanoic that forms nonylated.
63. the method for claim 62, wherein, described nonene is fresh nonene.
64. the method for claim 62, wherein, described nonene comprises the fresh nonene and the nonene of recirculation.
65. a method that is used to make the pentanoic nonylated comprises step:
By the raw material formation reaction material of the nonene that comprises pentanoic, recirculation, triethyl aluminum and hydrogenchloride, wherein, the mol ratio of triethyl aluminum and pentanoic is about 0.05: about 0.25: 1 of 1-, and the mol ratio of muriate and aluminium is at least about 3: 1;
Reaction mass was mixed at least about one hour, be heated to the initial reaction temperature between about 140 ℃-Yue 180 ℃ simultaneously;
In described reaction mass, add fresh nonene, make that the mol ratio of total nonene and pentanoic is about 2: 1 to about 4: 1, and mix this reaction mass, simultaneously temperature of reaction is reduced to about 120 ℃ to about 140 ℃ at least about one hour;
Basically remove all unreacted nonenes;
The pentanoic of the nonylated of resulting separation.
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