CN109092367B - Phosphine group modification type metal catalyst and method for producing 1-hexene-1-dodecene by catalyzing ethylene oligomerization - Google Patents

Phosphine group modification type metal catalyst and method for producing 1-hexene-1-dodecene by catalyzing ethylene oligomerization Download PDF

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CN109092367B
CN109092367B CN201810795723.3A CN201810795723A CN109092367B CN 109092367 B CN109092367 B CN 109092367B CN 201810795723 A CN201810795723 A CN 201810795723A CN 109092367 B CN109092367 B CN 109092367B
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朱红平
刘睿
陈志康
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Xiamen University
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2495—Ligands comprising a phosphine-P atom and one or more further complexing phosphorus atoms covered by groups B01J31/1845 - B01J31/1885, e.g. phosphine/phosphinate or phospholyl/phosphonate ligands
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    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
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Abstract

A phosphine-based modified metal catalyst and a method for producing 1-hexene-1-dodecene by catalyzing ethylene oligomerization, which relate to metal catalysts. Phosphine-based modified metal catalyst and PC3NP is main skeleton and has the chemical general formula of [ R1R2PCH2CH2CH2N(R5)PR3R4]MXnThe phosphine group modulation type metal catalyst is applied to the preparation of 1-hexene-1-dodecene through ethylene oligomerization, the phosphine group modulation type metal catalyst is subjected to ethylene oligomerization in an organic solvent to obtain 1-hexene-1-dodecene coupled carbon linear α -olefin, the phosphine group modulation type metal catalyst can be used for synthesizing the 1-hexene-1-dodecene with high selectivity, and the mass fraction of the linear α -olefin is up to 76%.

Description

Phosphine group modification type metal catalyst and method for producing 1-hexene-1-dodecene by catalyzing ethylene oligomerization
Technical Field
The invention relates to a metal catalyst, in particular to a phosphine group modulation type metal catalyst and a method for producing 1-hexene-1-dodecene by catalyzing ethylene oligomerization.
Background
In the α -olefin application field, 1-hexene-1-dodecene occupies about 45% of the market, the demand is large, the added value is high, α -olefin can be used as comonomer raw material to produce high-quality polyolefin plastomer and elastomer, as oligomerization monomer raw material to produce base synthetic oil, as hydroformylation raw material to prepare medium-long chain alcohol, acid and ester, as epoxidation raw material to produce medium-long chain dihydric alcohol, and also as organic solvent, etc. α -olefin is mainly produced by ethylene oligomerization catalysis method in the market at present, which is cleaner and more efficient than the traditional wax cracking, alkane catalytic cracking, alkane dehydrogenation, coal extraction, extraction separation, fatty alcohol dehydrogenation, olefin dimerization and disproportionation, internal olefin isomerization, etc., and the product quality is high.
The ethylene oligomerization catalysis method comprises a selective oligomerization method and a nonselective oligomerization method, and the selective oligomerization method can only produce 1-C4、1-C6And 1-C8One or two of them, and 1-C10And 1-C12Cannot be produced, and the non-selective oligomerization method can produce α -olefin with higher carbon number, but the product often presents Schulz-Flory or Poisson distribution,wherein 1-C6～1-C12The low mass fraction of olefins early, Chevron ethylene oligomerization process used trialkylaluminum catalysts to produce Poisson's distribution of α -olefins, C6～C1250-58% and a linearity of 96% (Chem Systems, Inc, New York, 1986). The BP Amoco ethylene oligomerization process is improved, and the product still has Poisson distribution and C6～C12Over 50%, but the linearity decreases with increasing carbon number (Linear Alpha-Olefins, Chemical Economics Handbook, 2017). The ethylene oligomerization process by the SHOP (Shell highher Olifin process) uses a metallic nickel compound catalyst with a nitrogen-phosphorus coordination framework, and a product obtained by the catalysis of the catalyst is in Schulz-Flory distribution C6～C12About 47%, linearity is 98% (Linear Alpha-Olefins, Chemical Economics Handbook, 2017). The UOP company and UCC company adopt a homogeneous catalyst system consisting of nickel chloride, sodium borohydride and ligand 2-dibenzoyl-1-naphthalene sulfonic acid, the product composition also follows Schulz-Flory distribution, wherein only C is given4～C8The contents, although they are close to 100% in linearity, vary in the range of 45% to 70% (Eur Chem News,1998, Chemcopy May: 24). Brookhart, Bennett and Gibson independently found that catalyst systems consisting of iron (or cobalt) pyridinediimine with methylaluminoxane also gave a product with a Schulz-Flory distribution in which C is6～C12About 52% to 57%, and a linearity of more than 96% (J.Am.chem.Soc.1998,120, 7143; WO 1998027124; J.Am.chem.Soc.1999,121, 8728).
In recent years, several metal chromium-based catalysts have also been reported for the synthesis of α -olefins with a broad carbon number distribution, such as the chromium catalyst system reported by Overett et al of Sasol corporation for the non-selective oligomerization of ethylene with a product composition that follows the Schulz-Flory distribution (α ═ 0.55) (J.mol.Catal.A: chem.2008,283, 114.) Gambarotta et al reported a pyridine backbone ligand-derived N, P coordinated chromium catalyst that catalyzes ethylene oligomerization under methylalumoxane activation, but with a product distribution that is different from the Schulz-Flory distribution and thus C, and P coordination6～C12The mass fraction of the compound reaches 60 to 75 percent, and the linearity is 100 percent (Organometallic)s 2013,32, 7107; 2014,33,1602). Danopoulos et al also subsequently reported that a chromium-based catalyst of similar structure catalyzed oligomerization of ethylene under activation by methylaluminoxane to yield C6～C12The mass fraction of (A) is up to 71% (Organometallics 2016,35, 4044).
The above results show that the mass fraction of 1-hexene to 1-dodecene produced is gradually increased with the improvement of the catalyst, but the reports of the catalyst are not many and the structure is relatively single. The development of a catalyst with a novel structure and the realization of the high-selectivity synthesis of 1-hexene-1-dodecene are still the problems to be solved in the technical field.
Disclosure of Invention
One object of the present invention is to provide a phosphine-based modulated metal catalyst.
The second purpose of the invention is to provide the application of the phosphine-based modified metal catalyst.
The invention also aims to provide a method for preparing 1-hexene-1-dodecene by using the phosphine group modulation type metal catalyst in ethylene oligomerization.
The phosphine-based modified metal catalyst is PC3NP is main skeleton and has the chemical general formula of [ R1R2PCH2CH2CH2N(R5)PR3R4]MXnThe characteristic structural formula is as follows:
Figure BDA0001735845110000021
wherein R is5Represents hydrogen, alkyl containing heteroatoms, cycloalkyl, heterocycloalkyl, aryl, substituted aryl and derivatives thereof, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2, 6-dimethylcyclohexyl, adamantyl, vinyl, allyl, phenyl, naphthyl, 2-methylphenyl, 3, 5-dimethylphenyl, 3, 5-dimethoxyphenyl, 3, 5-di-tert-butylphenyl, 2-thienyl, 2-furyl, 2-pyridyl, 3-pyridoPyridine group, trimethylsilyl group, or the like;
R1、R2、R3、R4each independently represents one of straight-chain alkyl, branched-chain alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, substituted aryl and derivatives thereof, amino, alkoxy, alkylthio, oxygen aryl, sulfur aryl and the like;
R1、R2、R3、R4has adjustable denaturation, and can be completely the same, partially the same or completely different.
When the phosphine group modulation type metal catalyst is used for producing 1-hexene-1-dodecene, R1、R2、R3、R4At least one of the groups is a heteroatom-containing group, preferably n-propylamino, isopropylamino, n-butylamino, isobutylamino, tert-butylamino, anilino, 2-methylanilino, 3-methylanilino, 4-methylanilino, 2, 6-dimethylanilino, 2, 6-diethylanilino, 2, 6-diisopropylanilino, 2,4, 6-trimethylanilino, dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-n-butylamino, diisobutylamino, di-tert-butylamino, dicyclohexylamino, dianilino, dibenzylamino, bis (trimethylsilyl) amino, methylphenylamino, ethylphenylamino, pyrrolyl, piperidinyl, bis (2-methylphenyl) amino, bis (3-methylphenyl) amino, bis (4-methylphenyl) amino, Bis (2, 6-dimethylphenyl) amino, bis (2, 6-diethylphenyl) amino, bis (2, 6-diisopropylphenyl) amino, bis (2,4, 6-trimethylphenyl) amino, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, phenolic, 2, 6-di (tert-butyl) phenolic, trimethylsiloxy, triethylsiloxy, triphenylsiloxy; methylmercapto, ethylmercapto, n-propylmercapto, isopropylmercapto, n-butylmercapto, isobutylmercapto, tert-butylmercapto, n-pentylmercapto, n-hexylmercapto, n-heptylmercapto, n-octylmercapto, cyclopropylmercapto, cyclobutylmercapto, in alkylmercapto or arylmercapto groupPentylmercapto group, cyclohexylmercapto group, thiophenol group, trimethylsilmercapto group, triethylsilylmercapto group, triphenylsilylmercapto group, 2-thienyl group, 2-furyl group, 2-pyridyl group, 3-pyridyl group, etc.
The phosphine-based modified metal catalyst consists of a ligand R1R2PCH2CH2CH2N(R5)PR3R4With metal compounds MXnThe two can be directly used for catalytic reaction after in-situ mixing.
Said metal compound MXnIs selected from metal inorganic substance and metal organic compound, wherein the metal M comprises fourth, fifth and sixth period transition metal elements including Sc, Y, Fe, Ni, Co, Ti, Zr, Cr, Hf and Mo, preferably one of Fe, Ni and Cr; metal compound MXnPreferably, the chromium chloride is one of chromium dichloride, chromium trichloride, a tetrahydrofuran complex of chromium dichloride, a toluene tetrahydrofuran complex of chromium dichloride, a tetrahydrofuran complex of chromium trichloride, a carbon carbene complex of chromium dichloride, a carbon carbene complex of chromium trichloride, chromium acetylacetonate, chromium tris (2-ethylhexanoate), a methyl chromium dichloride tetrahydrofuran complex, a triphenyl chromium tetrahydrofuran complex, a dimethyl chromium carbon carbene complex, a diethyl chromium carbon carbene complex, a diphenyl chromium carbon carbene complex, chromium carbonyl, ferrous chloride, cobalt chloride, nickel chloride, alkyl iron, alkyl cobalt, alkyl nickel and the like.
The phosphine group modulation type metal catalyst is applied to the preparation of 1-hexene-1-dodecene by ethylene oligomerization.
The method for preparing 1-hexene-1-dodecene coupled carbon number linear α -olefin by using the phosphine group modulation type metal catalyst in ethylene oligomerization comprises the following steps:
the phosphine group modulation type metal catalyst is subjected to ethylene oligomerization reaction in an organic solvent to obtain 1-hexene-1-dodecene couple carbon number linear α -olefin.
The temperature of the ethylene oligomerization reaction can be 0-200 ℃, the pressure of the reaction is 0.1-20 MPa, the reaction time is 0.01-50 h, the molar concentration of the phosphine group modulation type metal catalyst can be 0.001-100 mmol/L, and the molar concentration of the activating agent can be 0.1-1000 mmol/L.
The organic solvent may be one selected from benzene, toluene, xylene, mesitylene, butane, pentane, cyclopentane, methylcyclopentane, hexane, cyclohexane, methylcyclohexane, heptane, octane, nonane, decane, hendecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, dichloromethane, dichloroethane, chlorobenzene, bromobenzene, iodobenzene, etc.
The activator may be selected from the group consisting of alkylaluminum compounds, organoboron compounds, and the like, preferably one of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and modified aluminoxanes thereof, diethylaluminum chloride, diethylaluminum hydride, tris (pentafluorophenyl) aluminum, tris (pentafluorophenyl) boron, tetrafluoroborate ether, epoxyborane, triethylboron, tetrakis (pentafluorophenyl) borate, trisperfluoroarylborane, tetraperfluoroarylborate, tributylborate, and the like.
When the phosphine group is changed in the phosphine group-modulated metal catalyst, different 1-C can be obtained6/1-C8/1-C10/1-C12And (4) proportion.
In the invention, when one catalyst is selected for ethylene oligomerization reaction, different 1-C can be obtained by temperature regulation6/1-C8/1-C10/1-C12And (4) proportion.
The phosphine-based modified metal catalyst can synthesize 1-hexene-1-dodecene with high selectivity, and the mass fraction of the linear α -olefin is up to 76%.
The present invention provides a PC3The catalyst is characterized in that phosphine groups are transformed, high-selectivity preparation of 1-hexene-1-dodecene can be realized, the mass fraction of linear α -olefin is more than 67 percent and can reach 76 percent at most, and different output can be realized by modulating the phosphine groupsSpecific ethylene oligomerization product 1-C6、1-C8、1-C10And 1-C12And (4) synthesizing.
Drawings
FIG. 1 is a gas chromatographic analysis of the oligomeric product of example 2 (internal standard n-heptane).
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
The method for producing 1-hexene-1-dodecene by ethylene oligomerization is as follows, and the catalyst shown below is used for catalyzing ethylene oligomerization reaction.
Figure BDA0001735845110000041
Preparing 1mmol/L of catalyst toluene solution in a glove box, measuring 10mL of catalyst solution for later use, loading the catalyst solution into a reaction kettle, preheating to 100 ℃, cooling to room temperature after vacuum drying, replacing to ethylene atmosphere, sequentially adding 10mL of catalyst toluene solution, 1mL of methylaluminoxane toluene solution with the concentration of 1.5mol/L and 50mL of toluene, rapidly heating to 60 ℃, simultaneously increasing the ethylene pressure to 4MPa, stirring at the speed of 500rpm, keeping for 60min, rapidly cooling the reaction system to 0 ℃, decompressing, adding 100mL of anhydrous ethanol and 5mL of 10% hydrochloric acid for quenching, oscillating, standing, adding 5g of n-heptane internal standard substance, taking organic phase liquid for gas chromatography analysis, and obtaining the catalyst with the activity of 8.8 × 10 by utilizing the internal standard method6g/mol Cr. h, the product composition is reported in Table 1.
Example 2
The reaction temperature in example 1 was adjusted from 60 ℃ to 50 ℃ and the other operating conditions were unchanged, and the catalyst activity was calculated by the internal standard method to be 4.6 × 106g/mol Cr. h, the product composition is reported in Table 1.
Example 3
The reaction temperature in example 1 was adjusted from 60 ℃ to 40 ℃ and the other operating conditions were unchanged, and the catalyst activity was found to be 6.5 × 10 by calculation using the internal standard method6g/mol Cr. h, product composition is reported in the Table1。
Example 4
The reaction temperature of 60 ℃ in example 1 was adjusted to 30 ℃ and other operating conditions were unchanged, and the catalyst activity was 8.5 × 10 as calculated by the internal standard method6g/mol Cr. h, the product composition is reported in Table 1.
Example 5
The reaction temperature of 60 ℃ in example 1 was adjusted to 20 ℃ and other operating conditions were unchanged, and the catalyst activity was 3.1 × 10 as calculated by the internal standard method6g/mol Cr. h, the product composition is reported in Table 1.
Example 6
The ethylene pressure in example 1 was changed from 4MPa to 3MPa, and the other operating conditions were unchanged, and the catalyst activity was found to be 6.8 × 10 by calculation using the internal standard method6g/mol Cr. h, the product composition is reported in Table 1.
Example 7
The ethylene pressure in example 1 was changed from 4MPa to 2MPa, and the other operating conditions were not changed, and the catalyst activity was 5.6 × 10 by calculation using the internal standard method6g/mol Cr. h, the product composition is reported in Table 1.
Example 8
The ethylene pressure of 4MPa in example 1 was changed to 1MPa, and the other operating conditions were not changed, and the catalyst activity was 4.8 × 10 by calculation using the internal standard method6g/mol Cr. h, the product composition is reported in Table 1.
Example 9
The reaction time in example 1 was changed from 60min to 120min, and the other operating conditions were unchanged, and the catalyst activity calculated by the internal standard method was 7.6 × 106g/mol Cr. h, the product composition is reported in Table 1.
Example 10
The reaction time in example 1 was changed from 60min to 180min, and the other operating conditions were unchanged, and the catalyst activity calculated by the internal standard method was 7.2 × 106g/mol Cr. h, the product composition is reported in Table 1.
Example 11
The method for producing 1-hexene-1-dodecene by ethylene oligomerization is as follows, and the catalyst shown below is used for catalyzing ethylene oligomerization by adopting a method of in-situ mixing of a ligand and a metal compound.
Figure BDA0001735845110000061
1mmol/L ligand toluene solution is prepared in a glove box, and 10mL solution is measured for standby. Loading into a reaction kettle, preheating to 100 ℃, vacuum drying, cooling to room temperature, replacing with ethylene atmosphere, and sequentially adding 10mL of ligand toluene solution and 0.01mmol of CrCl3(THF)31mL of methylaluminoxane toluene solution with the concentration of 1.5mol/L and 50mL of toluene are quickly heated to 60 ℃, the ethylene pressure is simultaneously increased to 4MPa, the stirring speed is 500rpm, the reaction system is quickly cooled to 0 ℃, the pressure is released, 100mL of absolute ethyl alcohol and 5mL of 10% hydrochloric acid are added for quenching, the mixture is vibrated and kept stand, 5g of n-heptane internal standard substance is added, organic phase liquid is used for gas chromatography analysis, and the activity of the catalyst obtained by calculation by the internal standard method is 8.1 × 106g/molCr. h, product composition is reported in Table 1.
TABLE 1 results of catalytic reactions in examples 1 to 11
Figure BDA0001735845110000062
Example 12
The method for producing 1-hexene-1-dodecene by ethylene oligomerization is as follows, and the catalyst shown below is used for catalyzing ethylene oligomerization reaction.
Figure BDA0001735845110000071
1mmol/L of catalyst toluene solution is freshly prepared in a glove box, and 10mL of catalyst solution is measured for standby. Loading the mixture into a reaction kettle, preheating the mixture to 100 ℃, cooling the mixture to room temperature after vacuum drying, replacing the atmosphere with ethylene, adding 50mL of toluene solution, 10mL of catalyst toluene solution and 1mL (1.5mol/L) of methyl aluminoxane toluene solution, rapidly heating the mixture to 60 ℃, simultaneously increasing the ethylene pressure to 4MPa, stirring the mixture at the speed of 500rpm, and keeping the mixture for 60 min. Quickly cooling the reaction system to 0 ℃, decompressing,adding 100mL of absolute ethyl alcohol and 5mL of 10% hydrochloric acid for quenching, shaking, standing, adding 5g of n-heptane internal standard for gas phase analysis, and obtaining the catalyst with the activity of 7.6 × 10 by calculation of an internal standard method6g/mol Cr. h, the product composition is reported in Table 2.
Example 13
The method for producing 1-hexene-1-dodecene by ethylene oligomerization is as follows, and the catalyst shown below is used for catalyzing ethylene oligomerization reaction.
Figure BDA0001735845110000072
Preparing 1mmol/L of catalyst toluene solution in a glove box, measuring 10mL of catalyst solution for standby, loading the catalyst solution into a reaction kettle, preheating to 100 ℃, cooling to room temperature after vacuum drying, replacing to ethylene atmosphere, adding 50mL of toluene solution, 10mL of catalyst toluene solution and 1mL (1.5mol/L) of methylaluminoxane toluene solution, rapidly heating to 60 ℃, simultaneously increasing the ethylene pressure to 4MPa, stirring at the speed of 500rpm, keeping for 60min, rapidly cooling the reaction system to 0 ℃, decompressing, adding 100mL of anhydrous ethanol and 5mL of 10% hydrochloric acid for quenching, oscillating, standing, adding 5g of n-heptane internal standard for gas phase analysis, and obtaining the catalyst with the activity of 6.5 × 10 by utilizing the internal standard method6g/mol Cr. h, the product composition is reported in Table 2.
Example 14
The method for producing 1-hexene-1-dodecene by ethylene oligomerization is as follows, and the catalyst shown below is used for catalyzing ethylene oligomerization reaction.
Figure BDA0001735845110000073
1mmol/L of catalyst toluene solution is freshly prepared in a glove box, and 10mL of catalyst solution is measured for standby. Loading the mixture into a reaction kettle, preheating the mixture to 100 ℃, cooling the mixture to room temperature after vacuum drying, replacing the atmosphere with ethylene, adding 50mL of toluene solution, 10mL of catalyst toluene solution and 1mL (1.5mol/L) of methyl aluminoxane toluene solution, rapidly heating the mixture to 60 ℃, simultaneously increasing the ethylene pressure to 4MPa, stirring the mixture at the speed of 500rpm, and keeping the mixture for 60 min. Fast cooling reactionThe system is decompressed to 0 ℃, 100mL of absolute ethyl alcohol and 5mL of 10% hydrochloric acid are added for quenching, shaking and standing are carried out, 5g of normal heptane internal standard is added for gas phase analysis, and the activity of the catalyst is 5.8 × 10 calculated by an internal standard method6g/mol Cr. h, the product composition is reported in Table 2.
Example 15
The method for producing 1-hexene-1-dodecene by ethylene oligomerization is as follows, and the catalyst shown below is used for catalyzing ethylene oligomerization reaction.
Figure BDA0001735845110000081
Preparing 1mmol/L of catalyst toluene solution in a glove box, measuring 10mL of catalyst solution for standby, loading the catalyst solution into a reaction kettle, preheating to 100 ℃, cooling to room temperature after vacuum drying, replacing to ethylene atmosphere, adding 50mL of toluene solution, 10mL of catalyst toluene solution and 1mL (1.5mol/L) of methylaluminoxane toluene solution, rapidly heating to 60 ℃, simultaneously increasing the ethylene pressure to 4MPa, stirring at the speed of 500rpm, keeping for 60min, rapidly cooling the reaction system to 0 ℃, decompressing, adding 100mL of anhydrous ethanol and 5mL of 10% hydrochloric acid for quenching, oscillating, standing, adding 5g of n-heptane internal standard for gas phase analysis, and obtaining the catalyst with the activity of 4.7 × 10 by utilizing the internal standard method6g/mol Cr. h, the product composition is reported in Table 2.
Example 16
The method for producing 1-hexene-1-dodecene by ethylene oligomerization is as follows, and the catalyst shown below is used for catalyzing ethylene oligomerization reaction.
Figure BDA0001735845110000082
1mmol/L of catalyst toluene solution is freshly prepared in a glove box, and 10mL of catalyst solution is measured for standby. Loading into a reaction kettle, preheating to 100 ℃, vacuum drying, cooling to room temperature, replacing with ethylene atmosphere, adding 50mL of toluene solution, 10mL of catalyst toluene solution and 1mL (1.5mol/L) of methyl aluminoxane toluene solution, rapidly heating to 60 ℃, simultaneously increasing the ethylene pressure to 4MPa, stirring at 500rpm, and keeping the ethylene pressure constantHolding for 60min, rapidly cooling the reaction system to 0 ℃, decompressing, adding 100mL of absolute ethyl alcohol and 5mL of 10% hydrochloric acid for quenching, oscillating, standing, adding 5g of n-heptane internal standard for gas phase analysis, and obtaining the catalyst with the activity of 8.0 × 10 by utilizing the calculation of an internal standard method6g/mol Cr. h, the product composition is reported in Table 2.
Example 17
The method for producing 1-hexene-1-dodecene by ethylene oligomerization is as follows, and the catalyst shown below is used for catalyzing ethylene oligomerization reaction.
Figure BDA0001735845110000091
Preparing 1mmol/L of catalyst toluene solution in a glove box, measuring 10mL of catalyst solution for standby, loading the catalyst solution into a reaction kettle, preheating to 100 ℃, cooling to room temperature after vacuum drying, replacing to ethylene atmosphere, adding 50mL of toluene solution, 10mL of catalyst toluene solution and 1mL (1.5mol/L) of methylaluminoxane toluene solution, rapidly heating to 60 ℃, simultaneously increasing the ethylene pressure to 4MPa, stirring at the speed of 500rpm, keeping for 60min, rapidly cooling the reaction system to 0 ℃, decompressing, adding 100mL of anhydrous ethanol and 5mL of 10% hydrochloric acid for quenching, oscillating, standing, adding 5g of n-heptane internal standard for gas phase analysis, and obtaining the catalyst with the activity of 7.8 × 10 by utilizing the internal standard method6g/mol Cr. h, the product composition is reported in Table 2.
Example 18
The method for producing 1-hexene-1-dodecene by ethylene oligomerization is as follows, and the catalyst shown below is used for catalyzing ethylene oligomerization reaction.
Figure BDA0001735845110000092
1mmol/L of catalyst toluene solution is freshly prepared in a glove box, and 10mL of catalyst solution is measured for standby. Loading into a reaction kettle, preheating to 100 deg.C, vacuum drying, cooling to room temperature, replacing with ethylene atmosphere, adding 50mL of toluene solution, 10mL of catalyst toluene solution, 1mL (1.5mol/L) of methyl aluminoxane toluene solution, rapidly heating to 60 deg.C, and simultaneously increasing ethylene pressure to 4 deg.CMPa, stirring speed of 500rpm, keeping for 60min, rapidly cooling the reaction system to 0 ℃, decompressing, adding 100mL of absolute ethyl alcohol and 5mL of 10% hydrochloric acid for quenching, oscillating, standing, adding 5g of normal heptane internal standard for gas phase analysis, and obtaining the catalyst with activity of 7.2 × 10 by calculation of an internal standard method6g/mol Cr. h, the product composition is reported in Table 2.
Example 19
The method for producing 1-hexene-1-dodecene by ethylene oligomerization is as follows, and the catalyst shown below is used for catalyzing ethylene oligomerization reaction.
Figure BDA0001735845110000101
Preparing 1mmol/L of catalyst toluene solution in a glove box, measuring 10mL of catalyst solution for standby, loading the catalyst solution into a reaction kettle, preheating to 100 ℃, cooling to room temperature after vacuum drying, replacing to ethylene atmosphere, adding 50mL of toluene solution, 10mL of catalyst toluene solution and 1mL (1.5mol/L) of methylaluminoxane toluene solution, rapidly heating to 60 ℃, simultaneously increasing the ethylene pressure to 4MPa, stirring at the speed of 500rpm, keeping for 60min, rapidly cooling the reaction system to 0 ℃, decompressing, adding 100mL of anhydrous ethanol and 5mL of 10% hydrochloric acid for quenching, oscillating, standing, adding 5g of n-heptane internal standard for gas phase analysis, and obtaining the catalyst with the activity of 1.05 × 10 by utilizing the internal standard method7g/mol Cr. h, the product composition is reported in Table 2.
Example 20
The method for producing 1-hexene-1-dodecene by ethylene oligomerization is as follows, and the catalyst shown below is used for catalyzing ethylene oligomerization reaction.
Figure BDA0001735845110000102
1mmol/L of catalyst toluene solution is freshly prepared in a glove box, and 10mL of catalyst solution is measured for standby. Loading into a reaction kettle, preheating to 100 deg.C, vacuum drying, cooling to room temperature, replacing with ethylene atmosphere, adding toluene solution 50mL, catalyst toluene solution 10mL, and methyl aluminoxane toluene solution 1mL (1.5mol/L), rapidly heating to 60 deg.CSimultaneously increasing the ethylene pressure to 4MPa, stirring at the speed of 500rpm, keeping the stirring speed for 60min, rapidly cooling the reaction system to 0 ℃, decompressing, adding 100mL of absolute ethyl alcohol and 5mL of 10% hydrochloric acid for quenching, oscillating, standing, adding 5g of n-heptane internal standard for gas phase analysis, and obtaining the catalyst with the activity of 6.3 × 10 by calculation of an internal standard method6g/mol Cr. h, the product composition is reported in Table 2.
Example 21
The method for producing 1-hexene-1-dodecene by ethylene oligomerization is as follows, and the catalyst shown below is used for catalyzing ethylene oligomerization reaction.
Figure BDA0001735845110000103
Preparing 1mmol/L of catalyst toluene solution in a glove box, measuring 10mL of catalyst solution for standby, loading the catalyst solution into a reaction kettle, preheating to 100 ℃, cooling to room temperature after vacuum drying, replacing to ethylene atmosphere, adding 50mL of toluene solution, 10mL of catalyst toluene solution and 1mL (1.5mol/L) of methylaluminoxane toluene solution, rapidly heating to 60 ℃, simultaneously increasing the ethylene pressure to 4MPa, stirring at the speed of 500rpm, keeping for 60min, rapidly cooling the reaction system to 0 ℃, decompressing, adding 100mL of anhydrous ethanol and 5mL of 10% hydrochloric acid for quenching, oscillating, standing, adding 5g of n-heptane internal standard for gas phase analysis, and calculating by using an internal standard method to obtain the catalyst with the activity of 5.5 × 10 10.106g/mol Cr. h, the product composition is reported in Table 2.
Example 22
The method for producing 1-hexene-1-dodecene by ethylene oligomerization is as follows, and the catalyst shown below is used for catalyzing ethylene oligomerization reaction.
Figure BDA0001735845110000111
1mmol/L of catalyst toluene solution is freshly prepared in a glove box, and 10mL of catalyst solution is measured for standby. The reaction kettle is filled, preheated to 100 ℃, and cooled to room temperature after vacuum drying, and after the atmosphere is replaced by ethylene, 50mL of toluene solution, 10mL of catalyst toluene solution and 1mL (1) of methylaluminoxane toluene solution are added.5mol/L), rapidly heating to 60 ℃, simultaneously increasing the ethylene pressure to 4MPa, stirring at the speed of 500rpm, keeping for 60min, rapidly cooling the reaction system to 0 ℃, decompressing, adding 100mL of absolute ethanol and 5mL of 10% hydrochloric acid for quenching, oscillating, standing, adding 5g of n-heptane internal standard for gas phase analysis, and obtaining the catalyst with the activity of 4.6 × 10 by utilizing the internal standard method6g/mol Cr. h, the product composition is reported in Table 2.
Example 23
The method for producing 1-hexene-1-dodecene by ethylene oligomerization is as follows, and the catalyst shown below is used for catalyzing ethylene oligomerization reaction.
Figure BDA0001735845110000112
Preparing 1mmol/L of catalyst toluene solution in a glove box, measuring 10mL of catalyst solution for standby, loading the catalyst solution into a reaction kettle, preheating to 100 ℃, cooling to room temperature after vacuum drying, replacing to ethylene atmosphere, adding 50mL of toluene solution, 10mL of catalyst toluene solution and 1mL (1.5mol/L) of methylaluminoxane toluene solution, rapidly heating to 60 ℃, simultaneously increasing the ethylene pressure to 4MPa, stirring at the speed of 500rpm, keeping for 60min, rapidly cooling the reaction system to 0 ℃, decompressing, adding 100mL of anhydrous ethanol and 5mL of 10% hydrochloric acid for quenching, oscillating, standing, adding 5g of n-heptane internal standard for gas phase analysis, and calculating by using an internal standard method to obtain the catalyst with the activity of 5.2 × 106g/mol Cr. h, the product composition is reported in Table 2.
Example 24
The method for producing 1-hexene-1-dodecene by ethylene oligomerization is as follows, and the catalyst shown below is used for catalyzing ethylene oligomerization reaction.
Figure BDA0001735845110000121
1mmol/L of catalyst toluene solution is freshly prepared in a glove box, and 10mL of catalyst solution is measured for standby. Loading into a reaction kettle, preheating to 100 ℃, vacuum drying, cooling to room temperature, replacing with ethylene atmosphere, adding 50mL of toluene solution, 10mL of catalyst toluene solution and methyl aluminum1mL (1.5mol/L) of siloxane toluene solution, rapidly heating to 60 ℃, simultaneously increasing the ethylene pressure to 4MPa, stirring at the speed of 500rpm, keeping for 60min, rapidly cooling the reaction system to 0 ℃, decompressing, adding 100mL of absolute ethyl alcohol and 5mL of 10% hydrochloric acid for quenching, oscillating, standing, adding 5g of normal heptane internal standard for gas phase analysis, and obtaining the catalyst with the activity of 6.6 × 10 by utilizing the internal standard method6g/mol Cr. h, the product composition is reported in Table 2.
Example 25
The method for producing 1-hexene-1-dodecene by ethylene oligomerization is as follows, and the catalyst shown below is used for catalyzing ethylene oligomerization reaction.
Figure BDA0001735845110000122
Preparing 1mmol/L of catalyst toluene solution in a glove box, measuring 10mL of catalyst solution for standby, loading the catalyst solution into a reaction kettle, preheating to 100 ℃, cooling to room temperature after vacuum drying, replacing to ethylene atmosphere, adding 50mL of toluene solution, 10mL of catalyst toluene solution and 1mL (1.5mol/L) of methylaluminoxane toluene solution, rapidly heating to 60 ℃, simultaneously increasing the ethylene pressure to 4MPa, stirring at the speed of 500rpm, keeping for 60min, rapidly cooling the reaction system to 0 ℃, decompressing, adding 100mL of anhydrous ethanol and 5mL of 10% hydrochloric acid for quenching, oscillating, standing, adding 5g of n-heptane internal standard for gas phase analysis, and obtaining the catalyst with the activity of 4.5 × 10 by utilizing the internal standard method6g/mol Cr. h, the product composition is reported in Table 2.
Example 26
The method for producing 1-hexene-1-dodecene by ethylene oligomerization is as follows, and the catalyst shown below is used for catalyzing ethylene oligomerization reaction.
Figure BDA0001735845110000123
1mmol/L of catalyst toluene solution is freshly prepared in a glove box, and 10mL of catalyst solution is measured for standby. Loading into a reaction kettle, preheating to 100 ℃, vacuum drying, cooling to room temperature, replacing with ethylene atmosphere, adding 50mL of toluene solution and catalyst10mL of toluene solution and 1mL (1.5mol/L) of methylaluminoxane toluene solution, quickly heating to 60 ℃, simultaneously increasing the ethylene pressure to 4MPa, stirring at the speed of 500rpm, keeping the reaction system for 60min, quickly cooling the reaction system to 0 ℃, relieving the pressure, adding 100mL of absolute ethyl alcohol and 5mL of 10% hydrochloric acid for quenching, oscillating, standing, adding 5g of n-heptane internal standard for gas phase analysis, and obtaining the catalyst with the activity of 8.1 × 10 by utilizing the internal standard method6g/mol Cr. h, the product composition is reported in Table 2.
Example 27
The method for producing 1-hexene-1-dodecene by ethylene oligomerization is as follows, and the catalyst shown below is used for catalyzing ethylene oligomerization reaction.
Figure BDA0001735845110000131
Preparing 1mmol/L of catalyst toluene solution in a glove box, measuring 10mL of catalyst solution for standby, loading the catalyst solution into a reaction kettle, preheating to 100 ℃, cooling to room temperature after vacuum drying, replacing to ethylene atmosphere, adding 50mL of toluene solution, 10mL of catalyst toluene solution and 1mL (1.5mol/L) of methylaluminoxane toluene solution, rapidly heating to 60 ℃, simultaneously increasing the ethylene pressure to 4MPa, stirring at the speed of 500rpm, keeping for 60min, rapidly cooling the reaction system to 0 ℃, decompressing, adding 100mL of anhydrous ethanol and 5mL of 10% hydrochloric acid for quenching, oscillating, standing, adding 5g of n-heptane internal standard for gas phase analysis, and obtaining the catalyst with the activity of 8.5 × 10 by utilizing the internal standard method6g/mol Cr. h, the product composition is reported in Table 2.
Example 28
The method for producing 1-hexene-1-dodecene by ethylene oligomerization is as follows, and the catalyst shown below is used for catalyzing ethylene oligomerization reaction.
Figure BDA0001735845110000132
1mmol/L of catalyst toluene solution is freshly prepared in a glove box, and 10mL of catalyst solution is measured for standby. Loading into reaction kettle, preheating to 100 deg.C, vacuum drying, cooling to room temperature, replacing with ethylene atmosphere, adding50mL of toluene solution, 10mL of catalyst toluene solution and 1mL (1.5mol/L) of methylaluminoxane toluene solution, rapidly heating to 60 ℃, simultaneously increasing the ethylene pressure to 4MPa, stirring at a speed of 500rpm, keeping for 60min, rapidly cooling the reaction system to 0 ℃, relieving pressure, adding 100mL of absolute ethanol and 5mL of 10% hydrochloric acid for quenching, oscillating, standing, adding 5g of n-heptane internal standard for gas phase analysis, and obtaining the catalyst with the activity of 3.3 × 10 by utilizing the internal standard method6g/mol Cr. h, the product composition is reported in Table 2.
TABLE 2 results of catalytic reactions in examples 12 to 28
Figure BDA0001735845110000141
Example 29
Using the catalyst of example 17, the coordinated metal was exchanged for CrCl2The catalyst has the following structure, and is used for ethylene oligomerization under the same other conditions, and the activity of the catalyst is calculated to be 1.2 × 10 by using an internal standard method6g/mol Cr. h, the product composition is reported in Table 3.
Figure BDA0001735845110000142
Example 30
Using the catalyst of example 17, the coordinated metal was replaced by FeCl2The catalyst has the following structure, and is used for ethylene oligomerization under the same other conditions, and the activity of the catalyst is calculated to be 1.5 × 10 by using an internal standard method6g/mol Fe. h, the product composition is reported in Table 3.
Figure BDA0001735845110000143
Example 31
Using the catalyst of example 17, the coordinated metal was changed to CoCl2The catalyst has the following structure, and is used for ethylene oligomerization under the same other conditions, and the activity of the catalyst is calculated by an internal standard method to be 0.6 × 106g/mol Co. h, the product composition is reported in Table 3.
Figure BDA0001735845110000151
Example 32
Using the catalyst of example 17, the coordination metal was exchanged for NiCl2The catalyst has the following structure, and is used for ethylene oligomerization under the same other conditions, and the activity of the catalyst is calculated by an internal standard method to be 0.5 × 106g/mol Ni. h, the product composition is shown in Table 3.
Figure BDA0001735845110000152
TABLE 3 results of catalytic reactions of examples 29 to 32
Figure BDA0001735845110000153
Example 33
The amount of the methylaluminoxane toluene solution obtained in example 13 was changed from 1mL to 3mL, and the catalyst activity was calculated to be 1.56 × 10 by the internal standard method without changing other operating conditions7g/mol Cr. h, the product composition is reported in Table 4.
Example 34
The amount of methylaluminoxane toluene solution added in example 13 was changed from 1mL to 3mL, the reaction temperature was changed from 60 ℃ to 20 ℃, other operating conditions were not changed, and the catalyst activity was calculated by the internal standard method to be 1.01 × 107g/mol Cr. h, the product composition is reported in Table 4.
Example 35
The methylaluminoxane toluene solution in example 13 was changed to a triethylaluminum/tetrakis (pentafluorophenyl) borate toluene solution, and other operating conditions were unchanged, and the catalyst activity calculated by the internal standard method was 6.2 × 106g/mol Cr. h, the product composition is reported in Table 4.
Example 36
The methylaluminoxane toluene solution in example 13 was changed to a tri-n-butylaluminum/tetrakis (pentafluorophenyl) borate toluene solution, and the catalyst activity was calculated by the internal standard method without changing other operating conditionsThe sex was 5.3 × 106g/mol Cr. h, the product composition is reported in Table 4.
Example 37
The methylaluminoxane toluene solution in example 13 was changed to a triisobutylaluminum/tetrakis (pentafluorophenyl) borate toluene solution, and other operating conditions were not changed, and the catalyst activity obtained by calculation using an internal standard method was 1.2 × 106g/mol Cr. h, the product composition is reported in Table 4.
Example 38
The toluene solution in example 13 was changed to an n-pentane solution, and the catalyst activity calculated by the internal standard method was 5.6 × 10 without changing other operating conditions6g/mol Cr. h, the product composition is reported in Table 4.
Example 39
The reaction pressure in example 13 was changed from 4MPa to 5MPa, and the other operating conditions were not changed, and the catalyst activity was 1.20 × 10 by calculation using the internal standard method7g/mol Cr. h, the product composition is reported in Table 4.
Example 40
The catalyst activity of 3.5 × 10 was calculated by the internal standard method with the amount of the catalyst solution added in example 13 changed from 10mL to 50mL and the other operating conditions were not changed6g/mol Cr. h, the product composition is reported in Table 4.
TABLE 2 results of catalytic reactions of examples 33 to 40
Figure BDA0001735845110000161
FIG. 1 shows the GC analysis of the oligomeric products of example 2 (internal standard n-heptane).

Claims (10)

1. Phosphine-based modified metal catalyst, characterized in that it is based on PC3NP is main skeleton and has the chemical general formula of [ R1R2PCH2CH2CH2N(R5)PR3R4]MXnThe characteristic structural formula is as follows:
Figure 932995DEST_PATH_IMAGE002
wherein R is5Represents hydrogen, alkyl containing heteroatoms, cycloalkyl, heterocycloalkyl, aryl, substituted aryl and derivatives thereof;
R1、R2、R3、R4each independently represents one of straight-chain alkyl, branched-chain alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, substituted aryl and derivatives thereof, amino, alkoxy, alkylthio, oxygen aryl and sulfur aryl;
R1、R2、R3、R4have adjustable denaturation, are completely identical or partially identical or completely different;
when the phosphine-based modulated metal catalyst is used for producing 1-hexene-1-dodecene, R1、R2、R3、R4At least one of the groups is a heteroatom-containing group.
2. The phosphine-mediated metal catalyst of claim 1, wherein the heteroatom-containing group is selected from the group consisting of n-propylamino, isopropylamino, n-butylamino, isobutylamino, tert-butylamino, anilino, 2-methylanilino, 3-methylanilino, 4-methylanilino, 2, 6-dimethylanilino, 2, 6-diethylanilino, 2, 6-diisopropylanilino, 2,4, 6-trimethylanilino, dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-n-butylamino, diisobutylamino, di-tert-butylamino, dicyclohexylamino, dianilino, dibenzylamino, bistrimethylsilyl-amino, methylphenylamino, ethylphenylamino, pyrrolyl, piperidinyl, bis (2-methylphenylamino), bis (3-methylphenylamino), di-t-butylamino, di-cyclohexylamino, dianilino, dibenzylamino, bis (trimethylsilyl) amino, methylphenylamino, ethylphenylamino, pyrrolyl, piperidinyl, bis (2-methylphenylamino), di, Bis (4-methylphenyl) amino, bis (2, 6-dimethylphenyl) amino, bis (2, 6-diethylphenyl) amino, bis (2, 6-diisopropylphenyl) amino, bis (2,4, 6-trimethylphenyl) amino, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, phenolic, 2, 6-di (tert-butyl) phenolic, trimethylsiloxy, triethylsiloxy, triphenylsiloxy; one of methylmercapto, ethylmercapto, n-propylmercapto, isopropylmercapto, n-butylmercapto, isobutylmercapto, tert-butylmercapto, n-pentylmercapto, n-hexylmercapto, n-heptylmercapto, n-octylmercapto, cyclopropylmercapto, cyclobutylmercapto, cyclopentylmercapto, cyclohexylmercapto, thiophenol, trimethylsilylthio, triethylsilylmercapto, triphenylsilylmercapto, 2-thienyl, 2-furyl, 2-pyridyl and 3-pyridyl in alkylmercapto or arylmercapto.
3. The phosphine-modulated metal catalyst of claim 1, characterized in that the phosphine-modulated metal catalyst is formed from a ligand R1R2PCH2CH2CH2N(R5)PR3R4With metal compounds MXnReaction synthesis, or reaction synthesis of ligand R1R2PCH2CH2CH2N(R5)PR3R4With metal compounds MXnDirectly used for catalytic reaction after in-situ mixing.
4. The phosphine-regulated metal catalyst according to claim 3, wherein said metal compound MX is selected from the group consisting ofnIs selected from metal inorganic substance and metal organic compound, wherein the metal M comprises fourth, fifth and sixth period transition metal elements, and the transition metal elements comprise Sc, Y, Fe, Ni, Co, Ti, Zr, Cr, Hf and Mo.
5. The phosphine-regulated metal catalyst according to claim 4, wherein said metal compound MX is selected from the group consisting ofnIs selected from metal inorganic substance and metal organic compound, wherein the metal M comprises fourth, fifth and sixth period transition metal elements; the transition metal element comprises one of Fe, Ni and Cr.
6. The phosphine-regulated metal catalyst according to claim 3, wherein said metal compound MX is selected from the group consisting ofnSelected from chromium dichloride, chromium trichloride, dichloroChromium-removing tetrahydrofuran compound, chromium-removing toluene tetrahydrofuran compound, chromium-removing carbon carbene compound, chromium acetylacetonate, chromium tris (2-ethylhexanoate), chromium-removing methyl tetrahydrofuran compound, chromium-removing triphenyl tetrahydrofuran compound, chromium-removing dimethyl compound, chromium-removing diethyl compound, chromium-removing diphenyl compound, chromium carbonyl, ferrous chloride, cobalt chloride, nickel chloride, alkyl iron, alkyl cobalt and alkyl nickel.
7. The phosphine-based modified metal catalyst as claimed in any one of claims 1 to 6, which is used for oligomerization of ethylene to produce 1-hexene-1-dodecene.
8. The method of claim 7, wherein the phosphine based modulated metal catalyst is used for the oligomerization of ethylene to produce 1-hexene to 1-dodecene coupled linear α -olefin, and the method comprises the following steps:
performing ethylene oligomerization reaction on the phosphine group modulation type metal catalyst in an organic solvent to obtain 1-hexene-1-dodecene coupled carbon number linear α -olefin.
9. The method of claim 8, wherein the temperature of the oligomerization reaction of ethylene is 0 to 200%oC, the reaction pressure is 0.1-20 MPa, the reaction time is 0.01-50 h, the molar concentration of the phosphine group modulation type metal catalyst is 0.001-100 mmol/L, and the molar concentration of the activating agent is 0.1-1000 mmol/L;
the organic solvent is selected from one of benzene, toluene, xylene, mesitylene, butane, pentane, cyclopentane, methyl cyclopentane, hexane, cyclohexane, methyl cyclohexane, heptane, octane, nonane, decane, carbon undecane, carbon dodecane, carbon tridecane, carbon tetradecane, carbon pentadecane, carbon hexadecane, dichloromethane, dichloroethane, chlorobenzene, bromobenzene and iodobenzene;
the activator is selected from alkyl aluminum compounds and organic boron compounds.
10. The use of claim 9 wherein the activator is selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, diethylaluminum chloride, diethylaluminum hydride, tris (pentafluorophenyl) aluminum, tris (pentafluorophenyl) boron, tetrafluoroborate ethertetrafluoroborate, epoxyborane, triethylboron, tetrakis (pentafluorophenyl) borate, trisperfluoroarylborane, tetraperfluoroarylborate, tributylborate.
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