CN1181021C - Oligomerization of alpha-olefine - Google Patents
Oligomerization of alpha-olefine Download PDFInfo
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- CN1181021C CN1181021C CNB02116911XA CN02116911A CN1181021C CN 1181021 C CN1181021 C CN 1181021C CN B02116911X A CNB02116911X A CN B02116911XA CN 02116911 A CN02116911 A CN 02116911A CN 1181021 C CN1181021 C CN 1181021C
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Abstract
The present invention discloses an oligomerization method of C5 to C20 straight chain alpha-alkene. The alpha-alkene contacts a catalytic system with the following components under an oligomerization condition for reaction: loading transition metal compounds and catalytic components of aluminum alkyl, wherein the carrier is selected from silicon dioxide, aluminum oxide or the mixture of the silicon dioxide and the aluminum oxide; the general formula of the transition metal compounds is M(OR<1>)nX<4-n>, M is selected from IVB group metal, R<1> is selected from alkyl from C1 to C10, X is halogen, n is an integer number from 0 to 4, the content of the IVB group metal is from 0.5 to 8.0 wt%, and the aluminum content is from 1.0 to 40.0 wt%; halogenating alkane whose the general formula is R'X, wherein R' is selected from alkyl from C2 to C6, and X is halogen; the molar ratio of halogenating alkane to aluminium in the catalytic system is from 1 to 50. The oligomerization product prepared by the method of the present invention has the advantages of small chlorinity content and high stability.
Description
Technical field
The present invention is a kind of C
5～C
20The oligomerization of linear alpha-olefin specifically, is the method that a kind of working load type catalyzer carries out the alpha-olefin oligomerisation.
Background technology
Ucon oil is C
6～C
20The oligopolymer of linear alpha-olefins.It is compared with natural lubricating oil, have high viscosity, high viscosity index (HVI), low-freezing, Heat stability is good, band press that cutting performance is stable, corrodibility is low, with advantages such as the mutual capacitive of mineral oil is good, nontoxic.
The catalyst system that is used for the alpha-olefin oligomerisation mainly contains: BF
3System, Cr compound system, Al compound system and metallocene compound system.Because BF
3Poison big with the Cr compound to human body and environmental pollution serious, the existing Primary Catalystss that adopt Al compounds and transition metal as olefin oligomerization more.
US4,642,410 disclose a kind of alpha-olefin oligomerization, and this method check weighing is in the addition sequence of reacting middle catalyst, i.e. during oligomerisation, alpha-olefin is contacted with Organohalogen compounds with transition metal halide, and then the adding alkylaluminium cpd, the ratio of its reactive halogen and aluminium is 2.5～25, the alpha-olefin oligomerisation molecular weight that makes is 500～5000, wherein make solvent, make oligopolymer viscosity index that the oligomerisation of decylene-1 homogeneous phase makes greater than 140 with hexane.Its used transition metal halide is TiCl
4, Organohalogen compounds are chloropropene or tert-butyl chloride, aluminum alkyls is a diethyl aluminum chloride.The catalyzer that this method is used is homogeneous catalyst, and catalytic active component is not carried out load, and reaction can only intermittently be carried out.
USP5,922,636 disclose a kind of loading type catalyst for oligomerization, and this catalyzer is carrier with silicon-dioxide, and the active ingredient of load is AlCl
3, promotor is an organoaluminum.Promotor can be carried in the carrier, also it can be dissolved in the hydrocarbon solvent, when oligomerisation and supported catalyst together add reactor.The advantage of supported catalyst is to carry out oligomerisation reaction in fixed-bed reactor, the renewable use of catalyzer, and can avoid containing in the oligopolymer excessive chlorine.Because of too much cl content will influence the use properties of oligopolymer, its aging speed is accelerated.This patent catalyzer uses AlCl
3Be active ingredient,, will cause corrosion, and reaction back depleted aluminum chloride is more difficult, easily causes environmental pollution equipment because aluminum chloride is acid strong.
Summary of the invention
The oligomerization that the purpose of this invention is to provide a kind of alpha-olefin, this method working load type catalyzer, the activity of such catalysts component is easy to load and processing, and available fixed-bed process carries out the alpha-olefin oligomerisation.
We find, the Ziegler-Natta catalyst of routine is carried on the porous inorganic matter carrier, and in the presence of halogenated alkane, carry out the alpha-olefin oligomerisation, oligomerisation transformation efficiency height not only, and the selectivity of two～pentamer is higher, and product can be used as lubricant base, edible oil or foodstuff additive.The decylene-1 oligopolymer of a preferred embodiment preparation of the present invention, 40 ℃ viscosity index reaches 41.69, and pour point is-42 ℃.
Be that the method for the supported catalyst preparation oligopolymer of active ingredient is compared with aluminum chloride in the prior art, the loaded catalyst that the present invention uses is easy to preparation, and is pollution-free substantially to environment, and can overcome AlCl
3The shortcoming that aftertreatment is loaded down with trivial details, cl content is less in the products obtained therefrom, and product stability strengthens.
Embodiment
C provided by the invention
5～C
20The oligomerization of linear alpha-alkene, comprise with described alpha-olefin under the oligomerisation condition with have the catalyst system contact reacts of following component,
(1) catalyst component of a kind of carrying transition metal compound and aluminum alkyls, wherein carrier is selected from silicon-dioxide, aluminum oxide or the mixture of the two; The transistion metal compound general formula is M (OR
1)
nX
4-n, M is selected from IVB family metal, R in the formula
1Be selected from C
1～C
10Alkyl, X be halogen, n is selected from 0～4 integer, the general formula of aluminum alkyls is R
m 2AlX
3-m, R in this formula
2Be selected from C
2～C
4Alkyl, m is 0～3 integer; X is a halogen, and IVB family metal content is 0.5～8.0 heavy % in the described component, and aluminium content is 1～40 heavy %;
(2) general formula is the halogenated alkane of R ' X, and R ' is selected from C
2～C
6Alkyl, X is a halogen;
The mol ratio of halogenated alkane and aluminium is 1～50 in this catalyst system, preferred 1～20.
IVB family metal in the above-mentioned catalyst component in the transistion metal compound general formula is selected from titanium or zirconium, preferred titanium, R
1Preferred C
2～C
4Alkyl, the preferred chlorine of X, the value of n preferred 0 or 4 that is to say, comparatively preferred transistion metal compound is titanium tetrachloride, dichloro titanium butoxide, dichloro ethanolato-titanium, purity titanium tetraethoxide or four titanium butoxide, more preferably titanium tetrachloride.
R in the described aluminum alkyls general formula
2Be selected from C
2～C
4Alkyl, as ethyl, propyl group, sec.-propyl, butyl or isobutyl-, the m value is preferred 2, the preferred chlorine of X.Comparatively preferred aluminum alkyls is diethyl aluminum chloride, di-n-butyl aluminum chloride.
Among described halogenated alkane R ' X, preferred propyl group of R ' or butyl, the preferred chlorine of X.Preferred halogenated alkane is a n-propylcarbinyl chloride, a chloro-iso-butane, a chloro n-propane, a chloroisopropane.
The content of IVB family metal preferred 2.0～8.0 heavy % in the described catalyst component, aluminium content preferred 10～40 heavy %, more preferably 20～40 heavy %.Aluminium and IVB transition metal mol ratio are 10～500: 1, preferred 10～100: 1, more preferably 10～50: 1.Carrier is silicon-dioxide, aluminum oxide or the mixture of the two, and when carrier was mixture, silicon-dioxide was 1～9: 1 with the mixed weight ratio of aluminum oxide.
The preparation method of the catalyst component of carrying transition metal compound (1) and aluminum alkyls comprises: in the presence of organic medium, carrier is fully contacted with transistion metal compound, add aluminum alkyls again and stir, filtration, drying.
In the above-mentioned preparation process, the time that carrier contacts with transistion metal compound is 5～12 hours, and preferred 6～10 hours, temperature was 20～60 ℃, preferred 30～50 ℃.The transition metal of preferred every gram carrier 0.1～1.0 mmole of the add-on of transistion metal compound.The temperature that adds aluminum alkyls is 20～60 ℃, and preferred 30～50 ℃, churning time is 5～10 hours, preferred 5～8 hours, and the aluminium of preferred every gram carrier 1.0～5.0 mmoles of the add-on of aluminum alkyls.The used organic medium of preparation process is selected from C
6～C
10Saturated alkane, also can be sherwood oil, preferred hexane, heptane, the add-on of organic medium should be 5～15 times of vehicle weight.Reaction finishes, and solid is at 30～80 ℃, preferred 30～50 ℃ of dryings, preferred 2～10 hours of time of drying.
The temperature that the present invention carries out the alpha-olefin oligomerisation is 30～200 ℃, preferred 30～150 ℃, and pressure is 0.1～3.0MPa, preferred 0.1～1.0MPa.Preferred alpha-olefin is C
6～C
12Linear alpha-alkene, as hexene-1, octene-1 or decylene-1.Can be with an organic solvent in the oligomerisation process, also can be not with an organic solvent.Organic solvent is selected from C
6～C
10Saturated alkane or aromatic hydrocarbons, preferred hexane, heptane or toluene.The consumption of organic solvent should be 0.5～2.0 times of alpha-olefin quality.
Before oligomerisation, the alpha-olefin of use and solvent must purify and be dry, to remove the micro-detrimental impurity and the micro-moisture that make catalytic activity reduction even inactivation that exists in monomer and the solvent.
Oligomerization product of the present invention is dimer, tripolymer, the tetramer, the pentamer of 'alpha '-olefin monomers and the mixture that is higher than pentamer.The key joint structure of oligomerization product is made up of 'alpha '-olefin monomers head-tail, head-head and tail-tail inserted mode, has isomers in the oligomerization product.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
The used oligomerization solid catalyst component of preparation the present invention.
Restrain silica gel (U.S., Grace company) and 80 milliliters of hexanes that trade names are Davison 955 with 5.0 and add in the volumetric flask, stir adding down 0.56 and restrain TiCl
4(3.0mmol), 30 ℃ were reacted 6 hours.Add 2.0 gram (22mmol) diethyl aluminum chloride (Et afterwards again
2AlCl) stirring reaction is 6 hours.Filter, the gained solid washs respectively 3 times with 40 milliliters of hexanes, and 30 ℃ of dryings 10 hours must solid catalytic component A.Titaniferous 5.6 heavy % among the A contain aluminium 36.0 heavy %, and titanium, aluminium content adopt analyses, down together.
Example 2
Method according to example 1 prepares solid catalytic component B, and different is with 5.0 gram γ-Al
2O
3(Nanjing petro-chemical corporation) replaces silica supports, TiCl
4Add-on be 0.56 the gram (3.0mmol), Et
2The add-on of AlCl is 2.0 grams (22mmol).Titaniferous 6.0 heavy % among the B contain aluminium 38.7 heavy %.
Example 3
Method according to example 1 prepares solid catalytic component C, and different is to add 4.0 gram silica gel and 1.0 gram γ-Al in volumetric flask
2O
3, titaniferous 4.8 heavy % among the C contain aluminium 36.2 heavy %.
Example 4
Method according to example 1 prepares solid catalytic component D, and different is to add 1.0 gram silica gel and 4.0 gram γ-Al in volumetric flask
2O
3, titaniferous 5.2 heavy % among the D contain aluminium 39.7 heavy %.
Example 5
Method according to example 1 prepares solid catalytic component E, and different is to add 0.5 gram dichloro titanium butoxide to replace TiCl
4React, titaniferous 4.7 heavy % among the solid catalytic component E that makes contain aluminium 29.9 heavy %.
Example 6～10
Following example carries out oligomerisation reaction by the inventive method.
Raise to press in the glass still 0.3, add 0.5 gram ingredient of solid catalyst and 20 milliliters of hexanes, warming while stirring to 70 ℃ adds 20 milliliters of decylene-1s and 5 milliliter of one chlorine normal butane again, and feeding high pure nitrogen, to make pressure be 0.3MPa, reacted 3 hours.Use the deionized water stopped reaction, oligomerization product is washed 3～4 times with deionized water, filters, removes catalyzer.Air distillation removes desolvates, and removes unreacted decylene-1 and volatile component under 90 ℃, 0.01MPa pressure.Get 14.5 gram oligopolymers, the transformation efficiency of decylene-1 is 98 heavy %, and oligopolymer distributes and sees Table 1, and character sees Table 2.Oligomerization product viscosity is pressed the standard test of ASTM-D-45 in the table 2, and measuring temperature is 40 ℃ and 100 ℃.Pour point is pressed the standard test of ASTM-D-97.The calculation formula of viscosity index is: VI=156.8+4.94 * (V
100 ℃)
0.5
Example 11
Press the method for example 6, use solid catalytic component A to carry out oligomerisation reaction, different is to carry out oligomerisation with hexene-1.Get 26 gram oligopolymers, the transformation efficiency of hexene-1 is 98 heavy %.
Example 12
Press the method for example 6, use solid catalytic component A C
9～C
13Alkene carries out oligomerisation, wherein C
9Alkene content is 19.1 heavy %, C
10Alkene content is 20.8 heavy %, C
11Alkene content is 18.7 heavy %, C
12Alkene content is 21.0 heavy %, C
13Alkene content is 20.4 heavy %.Get 28.1 gram oligopolymers, the oligomerisation transformation efficiency is 97 heavy %.
Table 1
| Instance number | Catalyst component | Oligopolymer distributes, heavy % | Transformation efficiency, heavy % | ||||
| Dimer | Tripolymer | The tetramer | Pentamer | Six aggressiveness + | |||
| 6 | A | 9.6 | 23 | 20 | 9.1 | 29.3 | 98 |
| 7 | B | 9.7 | 23 | 18 | 7.4 | 29.4 | 93 |
| 8 | C | 6.2 | 12 | 22 | 16 | 32.8 | 89 |
| 9 | D | 7.1 | 14 | 11 | 7.5 | 60.4 | 82 |
| 10 | E | 8.6 | 23 | 20 | 9.1 | 29.3 | 90 |
Table 2
| Instance number | Viscosity, unit | Viscosity index | Pour point, ℃ | |
| 100℃ | 40℃ | |||
| 6 | 41.69 | 398.31 | 157.8 | -42 |
| 7 | 41.50 | 392.68 | 151.7 | -43 |
| 8 | 42.78 | 400.67 | 159.1 | -40 |
| 9 | 40.91 | 396.35 | 158.9. | -38 |
| 10 | 41.03 | 397.60 | 161.00 | -40 |
Claims (8)
1, a kind of C
5～C
20The oligomerization of linear alpha-olefin, comprise with described alpha-olefin under the oligomerisation condition with the catalyst system contact reacts with following component,
(1) catalyst component of a kind of carrying transition metal compound and aluminum alkyls, wherein carrier is selected from silicon-dioxide, aluminum oxide or the mixture of the two, and the transistion metal compound general formula is M (OR
1)
nX
4-n, M is selected from IVB family metal, R in the formula
1Be selected from C
1～C
10Alkyl, X be halogen, n is selected from 0～4 integer; The general formula of aluminum alkyls is R
m 2AlX
3-m, R in this formula
2Be selected from C
2～C
4Alkyl, m is 0～3 integer, X is a halogen; IVB family metal content is 0.5～8.0 heavy % in the described component, and aluminium content is 1.0～40.0 heavy %;
(2) general formula is the halogenated alkane of R ' X, and R ' is selected from C
2～C
6Alkyl, X is a halogen; The mol ratio of halogenated alkane and aluminium is 1～50 in this catalyst system.
2, in accordance with the method for claim 1, it is characterized in that described IVB family metal is selected from titanium or zirconium, R
1Be selected from C
2～C
4Alkyl, m is 2, X is a chlorine.
3, in accordance with the method for claim 1, it is characterized in that described transistion metal compound is a titanium tetrachloride, R
2Be selected from C
2～C
4Alkyl, n is 2, X is a chlorine; Among halogenated alkane R ' X, R ' is propyl group or butyl, and X is a chlorine.
4, according to described any one method of claim 1～3, when it is characterized in that carrier is the mixture of silicon-dioxide and aluminum oxide, silicon-dioxide is 1～9: 1 with the mixed weight ratio of aluminum oxide.
5, in accordance with the method for claim 1, it is characterized in that the oligomerisation temperature is that 30～200 ℃, pressure are 0.1～3.0MPa.
6, in accordance with the method for claim 1, it is characterized in that described alpha-olefin is C
6～C
12Linear alpha-alkene, oligomerisation is carried out in the presence of organic solvent.
7, in accordance with the method for claim 1, the preparation that it is characterized in that the catalyst component of carrying transition metal compound described in (1) and aluminum alkyls comprises, in the presence of organic medium, carrier is fully contacted with transistion metal compound, add aluminum alkyls again and stir, filtration, drying.
8, in accordance with the method for claim 7, it is characterized in that the time that carrier contacts with transistion metal compound is 5～12 hours, temperature is 20～60 ℃, and the temperature that adds aluminum alkyls is 20～60 ℃, and stirring is 5～10 hours.
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|---|---|---|---|
| CNB02116911XA CN1181021C (en) | 2002-04-26 | 2002-04-26 | Oligomerization of alpha-olefine |
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