A supported ethylene polymerization main catalyst and ethylene polymerization catalyst composition and application thereof

Abstract

The present invention discloses a supported ethylene polymerization main catalyst and an ethylene polymerization catalyst composition and application. The supported ethylene polymerization main catalyst comprises a molecular sieve and a metal complex supported on the molecular sieve, wherein the metal complex is a metal complex of AMBn of general formula (I); wherein A is an organic ligand of general formula (II), and general formula (II) is (Ar1)(Ar2)PN(R)P(Ar3)(Ar4), wherein Ar1, Ar2, Ar3, Ar4 are each independently a phenyl group or a halogen-substituted phenyl group; wherein M is selected from a transition metal of chromium, molybdenum or tungsten; wherein B is selected from acetylacetone, tetrahydrofuran, isooctanoic acid; wherein n=1 to 3. The present invention can combine the high activity and high selectivity of homogeneous catalysts with the advantages of easy regeneration and easy separation of heterogeneous catalysts by adopting a suitable carrier, thereby realizing the heterogeneity of homogeneous catalysts, and can also prolong the life of the catalyst, reduce the amount of co-catalyst, and steadily release the catalytic activity of the reaction system.

Description

Technical Field

[0001] The present invention relates to the field of ethylene polymerization, specifically to the field of ethylene oligomerization, ethylene trimerization or ethylene tetramerization, and more specifically to a supported ethylene oligomerization main catalyst, and an ethylene oligomerization catalyst composition containing the supported ethylene oligomerization main catalyst and its application. Background Art

[0002] α-Olefins are important organic raw materials and chemical intermediates, mainly used in the production of high-quality polyethylene (PE), lubricant base oils, plasticizers, detergents and other fields. Ethylene oligomerization is one of the most important reactions in the olefin polymerization industry. Through oligomerization, cheap small molecule ethylene can be converted into high value-added products, namely α-olefins of different length chains. Since the 1970s, the research on olefin polymerization and oligomerization catalyzed by transition metal complexes has gradually attracted the attention of scientists. People have begun to work hard to study new catalysts and improve existing catalysts to improve the activity of catalysts and the selectivity of catalytic products. Among the many explorations, the earliest, fastest-growing and most concentrated one is the nickel-based cationic catalytic system, such as the long-reported US patents US3686351A and US3676523A, and the Shell SHOP process based on this patented technology. The OP bridging ligand is involved in the Shell SHOP process, but the catalyst contains toxic organic phosphorus groups, and the synthesis steps are complicated and the stability is poor. Later, many patents were developed for OO, PN, PP and NN type coordinated nickel catalysts, such as JP11060627, WO9923096A1, CN1401666A, CN1769270A, etc. However, the catalysts obtained from the above patents generally have the disadvantage of relatively complicated preparation methods.

[0003] Sasol's patent WO2004056478A1 discloses a PNP skeleton catalyst. In the ethylene tetramerization reaction, the C8 component selectivity is about 66wt%, the C6 component selectivity is about 21wt%, of which the content of 1-hexene in the C6 component is only 82%, and the total selectivity of 1-hexene and 1-octene is about 84%. The US20100137669A1 patent discloses a PCCP symmetric skeleton catalyst. In the ethylene tetramerization reaction, the catalyst is more stable than the PNP system, and the total selectivity of 1-hexene and 1-octene does not exceed 85%. The prior art also attempts to increase the reaction temperature to increase the content of 1-hexene in the C6 component, but it often leads to a rapid decrease in the content of the most important target product 1-octene.

[0004] In the above reaction systems, although the byproducts such as cycloolefins and cyclized products in the C6 product can be removed by separation and purification, it is not conducive to the economic efficiency of the entire process. Therefore, how to increase the content of 1-hexene in the C6 component while maintaining a high 1-octene content in the reaction product, thereby improving the economic efficiency of the process, is of certain challenge.

[0005] On the other hand, the above reaction systems are basically homogeneous catalysis, while there are few technologies related to supported ethylene polymerization catalysts, mainly because the selection of carriers is very difficult. The acidity and alkalinity, particle size, particle size, pore size and pore distribution, specific surface area, etc. of the carrier determine its bonding ability with the active components of the catalyst. Summary of the invention

[0006] In view of the above problems existing in the prior art, the present invention provides a new supported ethylene oligomerization main catalyst, and an ethylene oligomerization catalyst composition and application containing the supported ethylene oligomerization main catalyst. The present invention can combine the high activity and high selectivity of homogeneous catalysts with the advantages of easy regeneration and easy separation of heterogeneous catalysts by adopting a suitable carrier, thereby realizing heterogeneity of homogeneous catalysts, prolonging the life of catalysts, reducing the amount of co-catalysts used, and stably releasing the catalytic activity of the reaction system.

[0007] The first aspect of the present invention provides a supported ethylene polymerization main catalyst, comprising a molecular sieve and a metal complex supported on the molecular sieve, wherein the metal complex is a metal complex of AMBn of general formula (I),

[0008] Wherein A is an organic ligand of general formula (II), and general formula (II) is (Ar 1 )(Ar 2 )PN(R)P(Ar 3 )(Ar 4 ), where Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 Each is independently phenyl or halogen-substituted phenyl;

[0009] wherein M is a transition metal selected from chromium, molybdenum or tungsten;

[0010] Wherein B is selected from acetylacetone, tetrahydrofuran, and isooctanoic acid;

[0011] Where n=1~3.

[0012] According to some embodiments of the present invention, the molecular sieve is selected from SAPO molecular sieves, preferably at least one selected from SAPO-5 molecular sieve, SAPO-11 molecular sieve, SAPO-31 molecular sieve, SAPO-34 molecular sieve and SAPO-41 molecular sieve.

[0013] According to some embodiments of the present invention, in the general formula (II), Ar connected to P 1 ,Ar 2 ,Ar 3 ,Ar 4 wherein the phenyl group has one or more fluorine atoms or fluorinated substituents at the ortho position.

[0014] According to some embodiments of the present invention, in the general formula (II), R is selected from substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 3 -C 20 Cycloalkyl and substituted or unsubstituted C 6 -C 30 Preferably, R is selected from substituted or unsubstituted C 1 -C 10 Alkyl, substituted or unsubstituted C 3 -C 10 Cycloalkyl and substituted or unsubstituted C 6 -C 20 More preferably, R is selected from at least one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl and substituted phenyl.

[0015] According to some embodiments of the present invention, preferably, the general formula (II) is selected from (Ph) 2 PN( i Pr)P(Ph)(2-F-Ph), (Ph) 2 PN( i Pr)P(2-F-Ph) 2 、(2-F-Ph)(Ph)PN( i Pr)P(Ph)(2-F-Ph), (2-F-Ph)(Ph)PN( i Pr)P(2-F-Ph) 2 、(Ph) 2 PN( t Bu)P(Ph)(2-F-Ph) 、(Ph) 2 PN(C y )P(Ph)(2-F-Ph), (Ph) 2At least one of PN(Ph)P(Ph)(2-F-Ph).

[0016] According to some embodiments of the present invention, in the general formula (I), M is selected from transition metals of chromium.

[0017] According to some embodiments of the present invention, in the general formula (I), B is selected from acetylacetone.

[0018] According to some embodiments of the present invention, in the general formula (I), n represents the number of valence states of M, for example, n is selected from 1, 2 or 3, preferably, n is 3.

[0019] According to some embodiments of the present invention, the weight ratio of the metal complex to the molecular sieve is 1:1-3000, preferably 1:10-2000, and more preferably 1:100-1000.

[0020] The second aspect of the present invention provides an ethylene oligomerization catalyst composition, comprising the above-mentioned main catalyst and an organic aluminum co-catalyst.

[0021] According to some embodiments of the present invention, the organoaluminum co-catalyst is selected from at least one of alkylaluminum compounds, alkoxyaluminum compounds and alkylaluminum chloride compounds, more preferably selected from at least one of methylaluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, ethylaluminumoxane and modified methylaluminoxane. In the present invention, the modified methylaluminoxane can be an alkyl-modified methylaluminoxane, such as the conventional alkyl-modified methylaluminoxane MMAO in the art.

[0022] According to some embodiments of the present invention, the molar ratio of the main catalyst to the co-catalyst calculated as metal M is 1:1-2000, preferably 1:10-1000, and more preferably 1:100-600.

[0023] The third aspect of the present invention provides a method for ethylene oligomerization, comprising: carrying out an ethylene oligomerization reaction in an organic solvent in the presence of the above-mentioned main catalyst or the above-mentioned ethylene oligomerization catalyst composition.

[0024] According to some embodiments of the present invention, based on the volume of the organic solvent, the concentration of the catalyst composition is 0.1-10 μmol / L in terms of metal.

[0025] According to some embodiments of the present invention, the reaction conditions may be the reaction conditions commonly used in the art. Preferably, the reaction temperature of the ethylene oligomerization reaction is 0-75° C., preferably the reaction temperature is 30-75° C., and more preferably 40-65° C. The supported ethylene oligomerization main catalyst of the present invention or the ethylene oligomerization catalyst composition of the present invention can be used to carry out the oligomerization reaction at a relatively low temperature, and the effect is good.

[0026] According to some embodiments of the present invention, the reaction conditions may be the reaction conditions commonly used in the art. Preferably, the ethylene pressure of the ethylene oligomerization reaction is 0.1-20.0 MPa, preferably 0.5-5.0 MPa, more preferably 2.0-5.0 MPa.

[0027] According to some embodiments of the present invention, the organic solvent includes aliphatic hydrocarbon compounds and / or aromatic hydrocarbon compounds.

[0028] According to some embodiments of the present invention, the aliphatic hydrocarbon compound is selected from at least one of straight-chain alkanes, branched-chain alkanes and cycloalkanes; more preferably at least one of pentane, heptane, hexane, cyclohexane and methylcyclohexane.

[0029] According to some embodiments of the present invention, the aromatic hydrocarbon compound is selected from at least one of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorotoluene and derivatives thereof.

[0030] According to some embodiments of the present invention, in the above reaction, the supported main catalyst and the co-catalyst can be pre-mixed and then added to the reaction system together, or the two components of the supported main catalyst and the co-catalyst can be added to the reaction system separately.

[0031] The fourth aspect of the present invention provides a method for ethylene trimerization or ethylene tetramerization, comprising: carrying out ethylene trimerization or ethylene tetramerization reaction in an organic solvent in the presence of the above-mentioned main catalyst or the above-mentioned ethylene oligomerization catalyst composition.

[0032] According to some embodiments of the present invention, based on the volume of the organic solvent, the concentration of the catalyst composition is 0.1-10 μmol / L in terms of metal.

[0033] According to some embodiments of the present invention, the reaction conditions may be the reaction conditions commonly used in the art. Preferably, the reaction temperature of the ethylene trimerization or ethylene tetramerization reaction is 0-75°C, preferably the reaction temperature is 30-75°C, and more preferably 40-65°C. The supported ethylene oligomerization main catalyst of the present invention or the ethylene oligomerization catalyst composition of the present invention can be used to carry out the ethylene trimerization or ethylene tetramerization reaction at a relatively low temperature, and the effect is good.

[0034] According to some embodiments of the present invention, the reaction conditions may be commonly used reaction conditions in the art. Preferably, the ethylene pressure of the ethylene trimerization or ethylene tetramerization reaction is 0.1-20.0 MPa, preferably 0.5-5.0 MPa, more preferably 2.0-5.0 MPa.

[0035] According to some embodiments of the present invention, the organic solvent includes aliphatic hydrocarbon compounds and / or aromatic hydrocarbon compounds.

[0036] According to some embodiments of the present invention, the aliphatic hydrocarbon compound is selected from at least one of straight-chain alkanes, branched-chain alkanes and cycloalkanes; more preferably at least one of pentane, heptane, hexane, cyclohexane and methylcyclohexane.

[0037] According to some embodiments of the present invention, the aromatic hydrocarbon compound is selected from at least one of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorotoluene and derivatives thereof.

[0038] According to some embodiments of the present invention, in the above reaction, the supported main catalyst and the co-catalyst can be pre-mixed and then added to the reaction system together, or the two components of the supported main catalyst and the co-catalyst can be added to the reaction system separately.

[0039] Beneficial effects of the present invention:

[0040] (1) The supported ethylene polymerization catalyst and catalyst composition of the present invention improve the stability of the catalyst by supporting the metal complex on the weakly acidic SAPO molecular sieve, and the economic efficiency of industrial application is better and the cost is lower. When the catalyst composition provided by the present invention is used, the catalytic activity exceeds 2×10 8 g·mol(Cr) -1 ·h -1 , up to 6×10 8 g·mol(Cr) -1 ·h -1 Under different conditions, the total selectivity of 1-hexene and 1-octene is above 93% by weight, and can be as high as 96% by weight. Byproducts such as cycloolefins and cyclized products are significantly reduced, the polymerization reaction can last for more than 2 hours, and the amount of co-catalyst used is also significantly reduced. Therefore, the catalyst composition of the present invention has the characteristics of high catalytic activity, high selectivity, high stability, etc., and has good industrial application prospects and economic value.

[0041] (2) The supported main catalyst of the present invention has better stability, novel structure, simple preparation and low cost. The catalyst activity lasts for a long time and the amount of co-catalyst is low.

[0042] (3) The catalyst composition of the present invention can effectively catalyze ethylene polymerization, especially ethylene polymerization, ethylene trimerization and ethylene tetramerization, with high catalyst activity and good product selectivity; and by-products such as cycloolefins and cyclized products in the C6 product are significantly reduced.

[0043] (4) The catalyst composition described in the present invention has the characteristics of high catalytic activity and high selectivity, and has good industrial application prospects and economic value. DETAILED DESCRIPTION

[0044] In order to make the present invention more easily understood, the present invention will be described in detail below in conjunction with embodiments. These embodiments are only for illustration and are not intended to limit the application scope of the present invention.

[0045] The test method of the present invention and the equipment used in the test are as follows:

[0046] (1) In the embodiments of the present invention, nuclear magnetic resonance is detected using a Bruker AV400 nuclear magnetic resonance instrument, wherein the detection conditions of the nuclear magnetic resonance are: deuterated chloroform is used as the solvent.

[0047] (2) Room temperature test The gas chromatography was tested using an Agilent 7890 chromatograph. The detection conditions of the gas chromatography were: chromatographic column SE-54, high-purity nitrogen carrier gas, FID detector; and the column temperature was raised using a two-step program.

[0048] In the present invention, t Bu is tert-butyl, i Pr is isopropyl, Cy is cyclohexyl, Ph is phenyl, Ar is substituted aryl, acac is acetylacetone, 2-EHA is isooctanoic acid, and THF is tetrahydrofuran.

[0049] [Preparation Example 1]

[0050] Preparation of organic ligand A 1 :(Ph) 2 PN( i Pr)P(Ph)(2-F-Ph)

[0051] At 0°C, (o-fluorophenyl)phenylphosphonium chloride (10 mmol) was added dropwise to a solution of isopropylamine (12.5 mmol) and triethylamine (5 mL) in dichloromethane (10 mL), and the mixture was stirred for 30 minutes. The mixture was then heated to room temperature and stirred overnight. The solvent was drained from the mixture, and anhydrous ether (20 mL) was added to form a suspension. The filtrate was filtered and dried under reduced pressure to obtain an oily substance. The oily substance (2.0 g) was dissolved in dichloromethane (10 mL), triethylamine (0.5 mL) was added, and then diphenylphosphonium chloride (3.3 g, 15.2 mmol) was added dropwise. After the addition was complete, the mixture was heated to room temperature and stirred overnight. The solvent of the mixture was drained, and a white solid powder A was obtained by basic alumina column chromatography. 1 . 1 H NMR (400 MHz, CDCl 3 ) δ = 7.52-7.41 (m, 1H), 7.42-7.22 (m,16H), 7.11 (t, 1H), 6.99 (td, 1H), 3.87-3.69 (m, 1H), 1.30 (d, 3H), 1.02 (d,3H).

[0052] [Preparation Example 2]

[0053] Preparation of organic ligand A 2 :(Ph) 2 PN( i Pr)P(2-F-Ph) 2

[0054] Di(o-fluorophenyl)phosphine chloride (10 mmol) was added dropwise to a solution of isopropylamine (12.5 mmol) and triethylamine (5 mL) in dichloromethane (10 mL) at 0°C and stirred for 30 minutes, then heated to room temperature and stirred overnight. The mixture was drained of solvent, and then anhydrous ether (20 mL) was added to form a suspension. The filtrate was filtered and vacuum-dried to obtain an oily crude product. 0.5 g of the crude product was dissolved in dichloromethane (10 mL), triethylamine (0.5 mL) was added, and then diphenylphosphine chloride (0.8 g, 3.6 mmol) was added dropwise. After the addition was complete, the mixture was heated to room temperature and stirred overnight. The mixture solvent was drained and a white solid powder A was obtained by basic alumina column chromatography. 2 . 1 H NMR (400 MHz, CDCl 3 ) δ = 7.42-7.27 (m, 14H), 7.09 (t, 2H), 6.99 (td, 2H), 3.93-3.77 (m, 1H), 1.18 (d, 6H).

[0055] [Preparation Example 3]

[0056] Preparation of organic ligand A 3 :(2-F-Ph)(Ph)PN( i Pr)P(Ph)(2-F-Ph)

[0057] (o-Fluorophenyl)phenylphosphonium chloride (10 mmol) was added dropwise to a solution of isopropylamine (4 mmol) and triethylamine (5 mL) in dichloromethane (10 mL) at 0°C and stirred for 30 minutes. The mixture was then heated to room temperature and stirred overnight. The solvent was drained from the mixture and a white solid powder ligand A was obtained by basic alumina column chromatography. 3 . 1 H NMR (400 MHz, CDCl 3 ) δ 7.45 (m,1H), 7.39-7.20 (m, 13H), 7.10 (m, 2H), 6.97 (m, 2H), 3.91 -3.70 (m, 1H), 1.40(d, 1.5H), 1.17 (d, 3H), 0.90 (d, 1.5H).

[0058] [Preparation Example 4]

[0059] Preparation of organic ligand A 4 :(2-F-Ph)(Ph)PN( i Pr)P(2-F-Ph) 2

[0060] Di(o-fluorophenyl)phosphonium chloride (10 mmol) was added dropwise to a solution of isopropylamine (12.5 mmol) and triethylamine (5 mL) in dichloromethane (10 mL) at 0°C and stirred for 30 minutes, then heated to room temperature and stirred overnight. The mixture was drained of solvent, and then anhydrous ether (20 mL) was added to form a suspension. The filtrate was filtered and vacuum-dried to obtain an oily substance. The oily substance (1.8 g) was dissolved in n-hexane, cooled to -60°C, and n-butyl lithium (6.3 mmol) was added. After the addition, the mixture was slowly heated to room temperature and stirred for 30 minutes. The mixture was cooled to -60°C again, and (o-fluorophenyl)phenylphosphonium chloride (1.7 g, 7.0 mmol) was added dropwise. After stirring for 30 minutes, the mixture was moved to room temperature and reacted overnight. The mixture solvent was drained and a white solid powder A was obtained by basic alumina column chromatography. 4 . 1 HNMR (400 MHz, CDCl 3 ) δ 7.33 (m, 11H), 7.18-7.04 (m, 3H), 7.05-6.87 (m, 3H), 3.86 (m, 1H), 1.33 (d, 6H).

[0061] [Preparation Example 5]

[0062] Preparation of organic ligand A 5 :(Ph) 2 PN( t Bu)P(Ph)(2-F-Ph)

[0063] The preparation method is the same as that of Preparation Example 1, except that isopropylamine is replaced by tert-butylamine. 1 H NMR (400 MHz, CDCl 3 ) δ = 7.49-7.40 (m, 1H), 7.38-7.20 (m, 16H), 7.09 (t, 1H), 6.98 (td,1H), 1.20 (s, 9H).

[0064] [Preparation Example 6]

[0065] Preparation of organic ligand A 6 :(Ph) 2 PN(C y )P(Ph)(2-F-Ph)

[0066] The preparation method is the same as that of Preparation Example 1, except that isopropylamine is replaced by cyclohexylamine. 1 H NMR (400 MHz, CDCl 3 ) δ = 7.50-7.43 (m, 1H), 7.40-7.25 (m, 16H), 7.11 (t, 1H), 7.00 (td,1H), 2.90 (m, 1H), 1.60-1.40 (m, 10H).

[0067] [Preparation Example 7]

[0068] Preparation of organic ligand A 7 :(Ph) 2 PN(Ph)P(Ph)(2-F-Ph)

[0069] The preparation method is the same as that of Preparation Example 1, except that isopropylamine is replaced by aniline. 1 H NMR (400 MHz, CDCl 3 )δ = 7.35-6.90 (m, 24H).

[0070] [Preparation Example 8]

[0071] Preparation of organic ligand A 8 :(Ph) 2 PN(Ph)P(Ph) 2, (i.e., a phenyl group having no fluorine atom or fluorinated substituent at the ortho position)

[0072] Diphenylphosphine chloride (10 mmol) was added dropwise to a solution of aniline (5 mmol) and triethylamine (5 mL) in dichloromethane (10 mL) at 0°C and stirred for 30 minutes, then heated to room temperature and stirred overnight. The mixture was drained of solvent, and then anhydrous ether (20 mL) was added to form a suspension. The filtrate was filtered and dried under reduced pressure to obtain an oily substance. The oily substance was subjected to basic alumina column chromatography to obtain a white solid powder A. 8 . 1 H NMR (400 MHz, CDCl 3 ) δ = 7.40-6.85 (m, 25H).

[0073]

Synthesis Example 1-9

[0074] The preparation method of the metal complex AMBn is as follows: 5 mmol of organic ligand A 1 -A 7 (prepared in Preparation Examples 1-7, respectively) and 5 mmol of chromium acetylacetonate were transferred to a Schlenk tube, 50 mL of toluene solution was added, and then the temperature was raised to 80°C and stirred for 8 hours. The reaction solution was cooled to room temperature and filtered, and the obtained solid was washed with toluene and n-hexane, respectively, and vacuum dried to obtain the corresponding metal complex AMBn, i.e., C 1 -C 7 .

[0075] Metal Complex C 8 The preparation method is the same as that of Synthesis Example 7, except that chromium acetylacetonate is replaced by chromium isooctanoate.

[0076] Metal Complex C 9 The preparation method is the same as that of Synthesis Example 1, except that chromium acetylacetonate is replaced by tetrahydrofuran chromium chloride.

[0077]

Synthesis Example 10

[0078] The preparation method of the metal complex AMBn is as follows: 5 mmol of organic ligand A 8 (prepared in Preparation Example 8) and 5 mmol of chromium acetylacetonate were transferred to a Schlenk tube, 50 mL of toluene solution was added, and then the temperature was raised to 80°C and stirred for 8 hours. The reaction solution was cooled to room temperature and filtered, and the obtained solid was washed with toluene and n-hexane respectively, and vacuum dried to obtain the corresponding metal complex AMBn, i.e., C 10 .

[0079] [Preparation Example 1 of Supported Main Catalyst]

[0080] Preparation of supported main catalyst S5-1:

[0081] Under nitrogen protection, 50 g of SAPO-5 molecular sieve was added to the reaction bottle, 200 mL of cyclohexane was added, and 0.05 g of metal complex C was added under stirring. 1 The temperature was raised from room temperature to 60°C and stirred overnight. The reaction was stopped and the solvent was removed from the reaction solution by a rotary evaporator to obtain a solid powder, namely the supported main catalyst S5-1.

[0082] [Preparation Example 2 of Supported Main Catalyst]

[0083] Preparation of supported main catalyst S11-1.

[0084] The same as the supported main catalyst preparation example 1, the difference is that the SAPO-5 molecular sieve is replaced by SAPO-11 molecular sieve.

[0085] [Preparation Example 3 of Supported Main Catalyst]

[0086] Preparation of supported main catalyst S34-2.

[0087] The same as the preparation example 1 of the supported main catalyst, except that the SAPO-5 molecular sieve is replaced by SAPO-34 molecular sieve, and the metal complex C 1 Replaced by metal complex C 2 .

[0088] [Preparation Example 4 of Supported Main Catalyst]

[0089] Preparation of supported main catalyst S41-3.

[0090] The same as the preparation example 1 of the supported main catalyst, except that the SAPO-5 molecular sieve is replaced by SAPO-41 molecular sieve, and the metal complex C 1 Replaced by metal complex C 3 .

[0091] [Preparation Example 5-12 of Supported Main Catalyst]

[0092] Preparation of supported main catalysts S5-2 to S5-9.

[0093] The same as the preparation example 1 of the supported main catalyst, except that the metal complex C 1 Replaced by metal complex C 2 -C 9 .

[0094] [Preparation Example 13 of Supported Main Catalyst]

[0095] Preparation of supported main catalyst S5-10.

[0096] The same as the preparation example 1 of the supported main catalyst, except that the metal complex C 1 Replaced by metal complex C 10 .

[0097] [Example 1]

[0098] The supported main catalyst S5-1 was used for ethylene polymerization.

[0099] A 300mL stainless steel polymerization autoclave was used. The autoclave was heated to 100°C, evacuated and replaced with nitrogen several times, then filled with ethylene for replacement, and then cooled to the set temperature. Methylcyclohexane was then added at 70°C, and 0.1μmol of the main catalyst S5-1 (in terms of chromium metal) and the co-catalyst modified methylaluminoxane (MMAO) were added at the same time. The total volume of the mixed liquid was 100mL, in which the molar ratio of the main catalyst S5-1 (in terms of chromium metal) to the co-catalyst was 1:600. The reaction pressure was controlled at 3MPa, and ethylene was introduced at 70°C to carry out ethylene polymerization.

[0100] After the reaction lasted for 2 hours, the reaction was completed, the system was cooled to room temperature, the gas phase product was collected in a gas measuring tank, the liquid phase product was collected in a conical flask, and 1 mL of ethanol was added as a terminator to terminate the reaction. The gas and liquid phase products were measured and analyzed by gas chromatography (the chromatograph was HP 5890). The data results are shown in Table 1.

[0101] [Example 2]

[0102] The supported main catalyst S11-1 was used for ethylene polymerization.

[0103] Same as Example 1, except that the main catalyst S5-1 is replaced by the main catalyst S11-1. The data results are shown in Table 1.

[0104] [Example 3]

[0105] The supported main catalyst S34-2 was used for ethylene polymerization.

[0106] Same as Example 1, except that the main catalyst S5-1 is replaced by the main catalyst S34-2. The data results are shown in Table 1.

[0107] [Example 4]

[0108] The supported main catalyst S41-3 was used for ethylene polymerization.

[0109] Same as Example 1, except that the main catalyst S5-1 is replaced by the main catalyst S41-3. The data results are shown in Table 1.

[0110] [Example 5]

[0111] The supported main catalyst S5-1 was used for ethylene polymerization.

[0112] Same as Example 1, except that the modified methylaluminoxane is replaced by triethylaluminum. The data results are shown in Table 1.

[0113] [Example 6]

[0114] The supported main catalyst S5-1 was used for ethylene polymerization.

[0115] Same as Example 1, except that the reaction temperature was changed from 70° C. to 30° C. The data results are shown in Table 1.

[0116] [Example 7]

[0117] The supported main catalyst S5-1 was used for ethylene polymerization.

[0118] Same as Example 1, except that the reaction temperature was changed from 70° C. to 40° C. The data results are shown in Table 1.

[0119] [Example 8]

[0120] The supported main catalyst S5-1 was used for ethylene polymerization.

[0121] Same as Example 1, except that the reaction temperature was changed from 70° C. to 75° C. The data results are shown in Table 1.

[0122] [Example 9]

[0123] The supported main catalyst S5-1 was used for ethylene polymerization.

[0124] Same as Example 1, except that the reaction pressure was changed from 3 MPa to 5 MPa. The data results are shown in Table 1.

[0125] [Example 10]

[0126] The supported main catalyst S5-1 was used for ethylene polymerization.

[0127] Same as Example 1, except that the molar ratio of the main catalyst S5-1 to the co-catalyst is changed from 1:600 ​​to 1:100. The data results are shown in Table 1.

[0128] [Examples 11-18]

[0129] The supported main catalysts S5-2 to S5-9 were respectively used to carry out ethylene polymerization reaction.

[0130] Same as Example 1, except that the main catalyst S5-1 is replaced by S5-2 to S5-9 respectively. The data results are shown in Table 1.

[0131] [Example 19]

[0132] Same as Example 1, except that the molar ratio of the main catalyst S5-1 to the co-catalyst is 1:1000. The data results are shown in Table 1.

[0133] [Example 20]

[0134] The supported main catalyst S5-1 was used for ethylene polymerization.

[0135] Same as Example 1, except that the molar ratio of the main catalyst S5-1 to the co-catalyst is 1:2000. The data results are shown in Table 1.

[0136] [Example 21]

[0137] The supported main catalyst S5-1 was used for ethylene polymerization.

[0138] Same as Example 1, except that the reaction temperature was changed from 40° C. to 100° C. The data results are shown in Table 1.

[0139] [Example 22]

[0140] The supported main catalyst S5-1 was used for ethylene polymerization.

[0141] Same as Example 1, except that the reaction temperature was changed from 40° C. to 80° C. The data results are shown in Table 1.

[0142] [Example 23]

[0143] The supported main catalyst S5-10 was used for ethylene polymerization.

[0144] Same as Example 1, except that S5-1 is replaced by metal complex S5-10. The data results are shown in Table 1.

[0145] [Comparative Example 1]

[0146] The compound bis[(S, S)-(phenyl) 2 PCH(Me)CH(Me)P(phenyl) 2 Dichloro(μ-chloro)chromium] for ethylene polymerization.

[0147] The implementation method is as described in Comparative Example 2 in CN104169003A. The data results are shown in Table 1.

[0148] [Comparative Example 2]

[0149] The compound bis[(S, S)-(o-fluoro-phenyl) 2 PCH(Me)CH(Me)P(o-Fluoro-phenyl) 2Dichloro(μ-chloro)chromium] for ethylene polymerization.

[0150] The implementation method is as described in Example 4 of CN104169003A. The data results are shown in Table 1.

[0151] [Comparative Example 3]

[0152] The compound bis[(S, S)-(o-fluoro-phenyl) 2 PCH(Me)CH(Me)P(o-Fluoro-phenyl) 2 [μ-chloro] chromium dichloride was loaded on SAPO-5 molecular sieve in the same manner as in Preparation Example 1 of the loaded main catalyst to obtain the loaded main catalyst S5-D1.

[0153] The supported main catalyst S5-D1 was used to carry out ethylene polymerization reaction in the same manner as in Example 1. The data results are shown in Table 1.

[0154] Table 1

[0155]

[0156] From the data in Table 1, it can be seen that the preferred supported catalyst composition provided by the present invention has a catalytic activity of more than 2×10 8 g·mol(Cr) -1 ·h -1 , up to 6.4×10 8 g·mol(Cr) -1 ·h -1 , under different conditions, the total selectivity of 1-hexene and 1-octene is above 92% by weight, and the highest can exceed 96% by weight. Compared with Example 21 and Example 22, the catalyst composition provided by the present invention has significantly higher catalyst activity and selectivity of 1-octene at a moderate reaction temperature (below 75°C). Compared with the homogeneous catalyst of Comparative Example 1, the SAPO molecular sieve-supported catalyst composition provided by the present invention has a catalyst activity several times or even more than 10 times higher. While maintaining a high selectivity for 1-octene, the content of 1-hexene in C6 is greatly increased, and by-products such as cycloolefins and cyclized products are significantly reduced. The stability of the catalyst after molecular sieve loading is improved, the catalytic activity can be maintained for more than 2 hours, the amount of co-catalyst used is also significantly reduced, and it can react even at a very low amount of co-catalyst. It shows that the catalyst composition described in the present invention has better performance, and the SAPO molecular sieve can improve the dispersion of the metal complex, increase the specific surface area of ​​the metal, and improve the activity and stability of the catalyst composition.

[0157] The selectivity of 1-octene in the present invention is significantly improved. Since the polyolefin field, especially POE, C8-LLDPE, PAO new materials, etc., urgently needs copolymerization grade high-purity 1-octene, which is in short supply in the market and is completely dependent on imports in China, and its price is significantly higher than other long-chain α-olefins; therefore, the process technology with higher 1-octene selectivity has obvious economic benefits and social value.

[0158] The supported ethylene oligomerization catalyst composition of the present invention can effectively catalyze ethylene polymerization reaction, has high catalyst activity, rapid reaction initiation, stable operation, good repeatability, strong practicability and broad industrial prospect.

[0159] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this field, under the technical enlightenment provided by the present invention, as common knowledge in the field, other equivalent variations and improvements can also be made, which should also be regarded as the protection scope of the present invention.

Claims

1. A supported ethylene polymerization main catalyst, comprising a molecular sieve and a metal complex supported on the molecular sieve, wherein: The metal complex is a metal complex of AMBn of general formula (I); Where A is (Ph)2PN(C y )P(Ph)(2-F-Ph); wherein M is a transition metal selected from chromium, molybdenum or tungsten; Wherein B is selected from acetylacetone, tetrahydrofuran, and isooctanoic acid; Where n=1~3; The molecular sieve is selected from SAPO molecular sieves.

2. The main catalyst according to claim 1, characterized in that The molecular sieve is at least one selected from SAPO-5 molecular sieve, SAPO-11 molecular sieve, SAPO-31 molecular sieve, SAPO-34 molecular sieve and SAPO-41 molecular sieve.

3. The main catalyst according to claim 1 or 2, characterized in that In the general formula (I), M is selected from a chromium transition metal; and / or B is selected from acetylacetonate or tetrahydrofuran chromium chloride; and / or n is selected from 1, 2 or 3.

4. The main catalyst according to claim 3, characterized in that In the general formula (I), n is 3.

5. The main catalyst according to claim 1 or 2, characterized in that: The weight ratio of the metal complex to the molecular sieve is 1:1-3000.

6. The main catalyst according to claim 5, characterized in that The weight ratio of the metal complex to the molecular sieve is 1:10-2000.

7. The main catalyst according to claim 6, characterized in that The weight ratio of the metal complex to the molecular sieve is 1:100-1000.

8. An ethylene oligomerization catalyst composition comprising the main catalyst according to any one of claims 1 to 7 and an organic aluminum co-catalyst.

9. The catalyst composition according to claim 8, characterized in that The organoaluminum co-catalyst is selected from at least one of alkylaluminum compounds, alkoxyaluminum compounds and alkylaluminum chloride compounds; and / or the molar ratio of the main catalyst to the co-catalyst calculated on the basis of metal M is 1:1-2000.

10. The catalyst composition according to claim 9, characterized in that The organoaluminum co-catalyst is selected from at least one of methylaluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, ethylaluminumoxane and alkyl-modified methylaluminoxane; and / or the molar ratio of the main catalyst to the co-catalyst calculated on the basis of metal M is 1:10-1000.

11. The catalyst composition according to claim 10, characterized in that The molar ratio of the main catalyst to the co-catalyst calculated on the basis of metal M is 1:100-600.

12. A method for the polymerization of ethylene, comprising: In the presence of the procatalyst according to any one of claims 1 to 7 or the ethylene oligomerization catalyst composition according to any one of claims 8 to 11, an ethylene oligomerization reaction is carried out in an organic solvent.

13. The method according to claim 12, characterized in that Based on the volume of the organic solvent, the concentration of the main catalyst or catalyst combination is 0.1-10 μmol / L in terms of metal M; And / or, the reaction temperature of the ethylene oligomerization reaction is 0-75°C; And / or, the ethylene pressure of the ethylene oligomerization reaction is 0.1-20.0 MPa.

14. The method according to claim 13, characterized in that The reaction temperature of the ethylene polymerization reaction is 30-75°C; And / or, the ethylene pressure of the ethylene oligomerization reaction is 0.5-5.0 MPa.

15. The method according to claim 14, characterized in that The reaction temperature of the ethylene oligomerization reaction is 40-65°C; And / or, the ethylene pressure of the ethylene oligomerization reaction is 2.0-5.0 MPa.

16. A method for ethylene trimerization or ethylene tetramerization, comprising: In the presence of the procatalyst according to any one of claims 1 to 7 or the ethylene oligomerization catalyst composition according to any one of claims 8 to 11, an ethylene trimerization or ethylene tetramerization reaction is carried out in an organic solvent.

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