CN1021220C - Catalyst for preparation of straight chain low carbon alpha olefine by use of vinyl oligomerization - Google Patents

Catalyst for preparation of straight chain low carbon alpha olefine by use of vinyl oligomerization Download PDF

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CN1021220C
CN1021220C CN89106141A CN89106141A CN1021220C CN 1021220 C CN1021220 C CN 1021220C CN 89106141 A CN89106141 A CN 89106141A CN 89106141 A CN89106141 A CN 89106141A CN 1021220 C CN1021220 C CN 1021220C
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何仁
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China Petrochemical Corp
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Abstract

The present invention relates to a composite catalyst for preparing straight chain low carbon alpha olefine by ethylene oligomerization. The present invention is composed of a zirconium compound, an organic aluminium compound, an alkali metal organic oxygen containing compound and (or) a phosphorus compound. The catalyst carries out pre-reaction at the temperature of 30 to 120 DEG C, preferably 60 to 90 DEG C by an organic solvent. Reaction time is from 15 minutes to 9 hours, preferably 0.5 to 3 hours. Then, the catalyst carries out ethylene oligomerization reaction at the pressure of 0.6 to 1.4 megapascal at the temperature of 40 to 130 DEG C, preferably 70 to 100 DEG C. Catalytic activity can reach 1141.0 gram / gram zirconium /hour, and the selectivity of the alpha olefine of which the carbon content is smaller than 10 can reach 88.6%, wherein the selectivity of the straight chain alpha olefine is 95.5%.

Description

Catalyst for preparation of straight chain low carbon alpha olefine by use of vinyl oligomerization
The present invention adopts ethylene oligomerization production straight chain low carbon alpha olefine in the presence of Zr catalyst, the straight chain C of generation 4-C 10Alhpa olefin is the important modified copolymer monomer of polyolefin industry, also can be used as the raw material of fine chemical products such as synthetic senior lubricant, higher alcohols.
The method that the ethylene oligomerization that more existing patent reports adopt nickel complex to make catalyzer is produced alhpa olefin, as German Patent 2062293, United States Patent (USP) 3647906, but they are to produce C 10-C 10The high-carbon alhpa olefin is a purpose.Though European patent 0241596 uses zirconium-based catalyst, is the 3rd component and adopt organic compound nitrogenous, sulphur, the molecular weight distribution of oligomerization product is also very wide, from C 4-C 10Alkene is until wax.The Primary Catalysts of United States Patent (USP) 3855341 is methyl ethyl diketone zirconiums, is applicable to propylene polymerization.The catalyzer of United States Patent (USP) 4486615 is simple zirconium-aluminum binary catalyst system, and the oligomerization product molecular weight distribution is very wide, from C 4-C 20Alkene is until wax.3947507 of United States Patent (USP)s adopt Titanium series catalyst, are suitable for C 4-C 14The oligomerisation of alhpa olefin, purpose are to produce lubricating oil.It is Primary Catalysts that the clear 58-701729 of Japanese Patent has reported with the zirconium, and ethylene oligomerization is produced C 4-C 9-alhpa olefin, but the zirconium complex complex structure that it adopted, the preparation difficulty.Though the clear 62-59225 of Japanese Patent has simplified Primary Catalysts, its activity is relatively poor.Catalyzer each component of the present invention is simple and easy to, and cost is lower, and catalytic activity can reach 1141.0 gram/gram zirconiums, and the alhpa olefin selectivity of carbon below 10 can reach 88.6%, and wherein the selectivity of straight can be up to 95.5%.
The inventive method
The present invention adopts the quaternary system catalyzer, promptly is Primary Catalysts with the zirconium compounds, and organo-aluminium compound is a promotor, and basic metal organic oxygen-containing compound and phosphine compound are as conditioning agent.
The organic acid of zirconium or inorganic acid salt all can be used as effective catalyzer, wherein ZrCl 4With zirconate Zr(OR ') 4Better, (R ' is propyl group, butyl etc. in the formula), the solubleness of this compounds in organic solvent is bigger.
Organo-aluminium compound such as Et 2Al, Et 2AlCl, EtAlCl 2, Et 3Al 2Cl 3And Et 2AlCl and EtAlCl 2Mixture all can be used as promotor.Et 2Al has higher alkylation ability, stronger reductibility, and lower lewis acidity, it generates in the reaction of alkene the ethylene catalyst oligomerisation, is easy to obtain the high-carbon alhpa olefin, and easily forms superpolymer.EtAlCl 2Acidity stronger, can suppress the generation of high-carbon alhpa olefin, but its alkylation ability is lower, makes catalyst activity reduction.Et 2AlCl has more moderate alkylation ability and lewis acidity, and the selectivity of higher straight can be arranged.
The basic metal organic oxygen-containing compound is with R 2ONa is representative, R in the formula 2Can be propyl group, butyl,
Figure 89106141X_IMG3
Figure 89106141X_IMG4
Deng.
Phosphine compound is R 3 3P is the tertiary phosphine of representative, R in the formula 2Can be propyl group, butyl, phenyl, phenoxy group etc.
Basic metal organic oxygen-containing compound and phosphine compound play regulating effect to the zirconium catalyst system.From ZrCl 4Show with n-BuONa or PhONa system infrared spectroscopic study, zirconium-oxygen key absorption peak is arranged in this system, mean the concentricity metallographic phase combination of-oxyl, this has not only improved the solubleness of catalyzer in organic solvent, and the thermostability of catalyzer and selectivity are improved greatly.
Primary Catalysts ZrCl 4Solubleness in organic solvent is very low, ZrCl 4Molecule is to be present in the solvent with the association state.According to surveying and determination 10 -3Mole is stagnation point (ZrCl 4In chlorobenzene), be lower than this concentration, catalytic activity is higher, selectivity is also better, and when being higher than this concentration, catalyst performance descends rapidly.
The consumption of promotor aluminum alkyls is represented with Al/Zr, and the interior in a big way of Al/Zr=10-80 changes usually, and the scope of Al/Zr=20-30 is then better, and too high Al/Zr can make catalytic activity and linear rate descend.
Change in the Na/Zr=1-4 scope, improve Na/Zr catalytic activity is descended, but the selectivity of carbon 10 following alhpa olefins and their linear rate raising, so should be controlled at suitable proportion, both make catalyzer that higher activity is arranged, had the selectivity of higher straight chain low carbon alpha olefine simultaneously.
The method of the synthetic straight chain low carbon alpha olefine of ethylene oligomerization:
1. catalyzer gives reaction (ageing)
Each component should be mixed by certain way in the catalyzer of the present invention, and gives reaction under certain condition.Primary Catalysts should at first mix with organic oxygen-containing thing sodium salt and phosphine compound, adds the promotor aluminum alkyls then.Ageing temperature of reaction and time have direct influence and temperature of reaction and reaction times to exist the relation of mutual restriction to catalyst performance.The ageing temperature is low, then needs long digestion time, and ageing temperature height can shorten digestion time, and the ageing temperature can be carried out between 30-120 ℃ usually, and 60-90 ℃ then better, and digestion time is generally between 15 minutes to 9 hours, and 0.5-3 hour then better.
2, catalyzed reaction
Under the purity nitrogen protection; with Primary Catalysts and organic oxygen-containing thing sodium salt; join in the Schlenk bottle of crossing with nitrogen replacement; add organic solvent; at room temperature stirred 10 minutes; add the promotor aluminum alkyls then; stir; transfer to immediately in the stainless steel autoclave of replacing with purity nitrogen; under 30-120 ℃ of (60-90 ℃ then better) temperature, carry out the ageing reaction; reaction times is 15 minutes to 9 hours (0.5-3 hour then better); that finishes catalyzer gives the reaction response still under 40-130 ℃ of (being preferably 70-100 ℃) temperature, and the pressure of 1.4 MPas feeds polymer grade ethylene down, carries out the ethylene oligomerization catalysis reaction; after 0.5-6 hour (1-2 hour is then better) reaction, immediately with cold water or ice-cooled autoclave to room temperature.Collect unreacted ethene and gas oligomerization product, liquid phase adds the ethanolic soln of saturated sodium hydroxide, the terminated oligomer reaction.Wash with aqueous sodium hydroxide washes earlier, wash with water again, carry out drying, fractionation then, obtain the low carbon alpha olefine product.
Temperature of reaction is low, and catalyst activity is low, but selectivity and linear rate height.Reaction times shot-catalyst agent activity, selectivity and linear rate height, but catalyst production is low.In order to improve the productive rate of catalyzer, should keep the suitable reaction times.Oligomerisation reaction is to carry out under constant voltage, improves reaction pressure, and is all favourable to improving catalyst activity, selectivity and linear rate.
Organic solvent adopts the inert varsol, as alkane, naphthenic hydrocarbon, halohydrocarbon etc., is better especially with the halogenated aryl hydrocarbon.
Embodiment 1
Under purity nitrogen protection with 0.05 * 10 -3Mole ZlCl 4Place the Schlenk bottle of replacing, add 30 milliliters of anhydrous chlorobenzenes, add Et again with pure ammonia 2AlCl0.1 * 10 -3Mole changes this solution in the autoclave over to after the stirring, gives reaction 1 hour under 90 ℃.Under 1.4 MPa pressure, feed ethene then, reacted 2 hours down at 90 ℃.Record reaction result, catalytic activity is 1765.0 gram/gram zirconiums hour, and the selectivity of carbon 10 following alhpa olefins is 63.5%, and wherein the selectivity of straight is 85.6%.
Embodiment 2
Method similarly to Example 1 is with Et 3Al 2C 3L0.15 * 10 -3Mole replaces Et 2AlCl adopts the cyclohexane give solvent, gives reaction 0.5 hour, under reaction conditions similarly to Example 1, record reaction result, catalytic activity is 101.4 gram/gram zirconiums hour, the selectivity of carbon 10 following alhpa olefins is 72.6%, and wherein the selectivity of straight is 85.5%.
Embodiment 3
Method adds Zr(OPr similarly to Example 1 i) 40.05 * 10 -3Mole, Et 3Al 2Cl 30.15 * 10 -3Mole, reaction conditions is similarly to Example 1 adopted in 60 ℃ of following ageings 0.5 hour then.Record reaction result, catalytic activity is 1643.0 gram/gram zirconiums hour, and the selectivity of carbon 10 following alhpa olefins is 60.0%, and wherein the selectivity of straight is 86.9%.
Embodiment 4
Method adds Zr(OBu similarly to Example 1 n) 40.05 * 10 -3Mole, Et 3Al 2Cl 20.15 * 10 -3Mole, reaction conditions is similarly to Example 1 adopted in 60 ℃ of following ageings 0.5 hour then, records reaction result, and catalytic activity is 2598.1 gram/gram zirconiums hour, and the selectivity of carbon 10 following alhpa olefins is 54.0%, and wherein the selectivity of straight is 77.3%.
Embodiment 5
Under purity nitrogen keeps, with 0.05 * 10 -3Mole ZrCl 4With 0.05 * 10 -3Mole Pr iONa joins in the Schlenk bottle of replacing with purity nitrogen, adds 30 milliliters of anhydrous chlorobenzenes, at room temperature stirs 10 minutes, adds 0.15 * 10 again -3Mole Et 2AlCl, catalyst solution is transferred in the autoclave, give reaction 0.5 hour under 60 ℃, temperature is brought up to 70 ℃ subsequently, fed ethene, reaction is 2 hours under 1.4 MPa pressure, record reaction result, catalytic activity is 1458.0 gram/gram zirconiums hour, and the selectivity of carbon 10 following alhpa olefins is 84.2%, and wherein the selectivity of straight is 92.6%.
Embodiment 6
Method adds ZrCl similarly to Example 5 40.1 * 10 -3Mole, PhONa0.1 * 10 -3Mole, Et 2AlCl3.0 * 10 -2Mole, 60 milliliters of anhydrous chlorobenzenes give reaction 1 hour under 70 ℃, adopt reaction conditions similarly to Example 5 then, record reaction result, catalytic activity is 3086.0 gram/gram zirconiums hour, the selectivity of carbon 10 following alhpa olefins is 77.1%, and wherein the selectivity of straight is 90.0%.
Embodiment 7
Method adds BuONa0.15 * 10 similarly to Example 5 -3Mole, Et 3Al 2Cl 30.15 * 10 -3Mole, 90 ℃ are given reaction 0.5 hour, adopt reaction conditions similarly to Example 5 then, record reaction result, and catalytic activity is 1042.4 gram/gram zirconiums hour, and the selectivity of carbon 10 following alhpa olefins is 88.4%, and wherein the selectivity of straight is 89.2%.
Embodiment 8
Method adds ZrCl similarly to Example 5 40.1 * 10 -2Mole, Et 2AlCl3.0 * 10 -2Mole, Ph 3P0.075 * 10 -2Mole, 90 milliliters of anhydrous chlorobenzenes give reaction 1 hour under 50 ℃, adopt reaction conditions similarly to Example 5 then, record reaction result, catalytic activity is 1141.0 gram/gram zirconiums hour, the selectivity of carbon 10 following alhpa olefins is 88.6%, and wherein the selectivity of straight is 95.6%.
Embodiment 9
Method adds Zr(OPr similarly to Example 5 i) 40.05 * 10 -3Mole, Et 2AlCl0.15 * 10 -3Mole Ph 3P0.15 * 10 -3Mole gives reaction 0.5 hour under 60 ℃, temperature is brought up to 90 ℃ then, adopt reaction conditions similarly to Example 5, record reaction result, catalytic activity is 1006.7 gram/gram zirconiums hour, the selectivity of bowl 10 following alhpa olefins is 62.2%, and wherein the selectivity of straight is 90.1%.
Embodiment 10
Method adds ZrCl similarly to Example 5 40.1 * 10 -3Mole, PhONa0.1 * 10 -3Mole, Ph 3P0.75 * 10 -2Mole, 90 milliliters of anhydrous chlorobenzenes stirred 10 minutes under the room temperature, added Et then 2AlCl10.3 * 10 -3Mole gives reaction 1 hour under 50 ℃ of temperature, temperature is brought up to 90 ℃ then, adopt the reaction conditions same with example 5, record reaction result, catalytic activity is 879.0 gram/gram zirconiums hour, the selectivity of carbon 10 following alhpa olefins is 92.6%, and wherein the selectivity of straight is 94.0%.
Subordinate list is listed the reaction result of embodiment 1 to 10.
Figure 89106141X_IMG5

Claims (1)

1, a kind ofly is used for the composite catalyst that ethylene oligomerization prepares straight-chain low-carbon alpha-alkene, this catalyzer comprises zirconium-containing compound, organo-aluminium compound, basic metal organic oxygen-containing compound or basic metal oxygenatedchemicals and phosphine compound, it is characterized in that: (1) zirconium-containing compound is a zirconates, ZrCl 4, or zirconate, Zr (OR ') 4, R ' in the formula=Pr i, Bu n, the concentration of zirconium is 3 * 10 -5～2 * 10 -3Mole, 3 * 10 -4～1 * 10 -3Mole is better; (2) organo-aluminium compound is aluminum alkyls or aluminum alkyl halide, Et 3Al, Et 2AlCl, EtAlCl 2, Et 3Al 2Cl 3And their mixture, aluminium/zirconium=10～80, and aluminium/zirconium=20～30 are better; (3) the basic metal organic oxygen-containing compound is R 2ONa, R in the formula 2=Pr i, Bu n,
Figure 89106141X_IMG1
,
Figure 89106141X_IMG2
Sodium/zirconium=1～4; (4) phosphine compound is R 3 3P, R in the formula 3=Pr i, Bu n,-Ph ,-OPh.
CN89106141A 1989-08-04 1989-08-04 Catalyst for preparation of straight chain low carbon alpha olefine by use of vinyl oligomerization Expired - Lifetime CN1021220C (en)

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