CN105344381A - Dual-core chromium catalyst for ethylene oligomerization and preparation method thereof - Google Patents
Dual-core chromium catalyst for ethylene oligomerization and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a dual-core chromium catalyst for ethylene oligomerization and a preparation method thereof; the dual-core chromium catalyst contains a transition metal chromium complex with a dual-core structure and an organic metal compound activator, the transition metal chromium complex with the dual-core structure is a compound having the general formula (I) defined in the specification, wherein R1, R2, R3 and R4 are connection groups and can be arbitrarily selected from alkyl, naphthenic group, aryl or heteroatomic groups containing O and S having a chain base structure with 1-6 atoms, R4, R5 and R6 are arbitrarily arene or alkane substituents, and CrX is CrCl2, CrCl3, Cr(acac)3, chromium 2-ethylhexanoate or Cr(CO)6. The catalyst has the catalytic activity of greater than 4.92*10<6> g polymerization product*mol<-1> Cr*h<-1>, and the selectivity of linear alpha-olefin in products is more than 98%. The catalyst composition has the characteristics of simple preparation method, high catalytic activity, and fewer C1-C4 alkanes and high-polymerized products in the products.
Description
Technical field
The invention belongs to ethylene oligomerization catalysis field, especially a kind of double-core chrome catalysts of ethylene oligomerization, preparation method and its preparing the application in linear alpha-alkene.
Background technology
Linear alpha-alkene has a wide range of applications in fields such as ethylene comonomer, synthesis of surfactant intermediate, plasticizer alcohol, synthetic lubricant fluid and oil dopes.In recent years, along with the development of polyolefin industry, the demand rapid development to higher linear alpha olefins in world wide.Ethylene oligomerization is the main method preparing higher linear alpha olefins, by oligomerisation reaction, the ethene of cheapness can be transformed into and have high value-added product.
The research that transient metal complex homogeneous catalyst is used for olefinic polymerization and oligomerisation is subject to people's attention always, and researcher makes great efforts research new catalyst and improves existing catalyst, improves the activity of catalyst and the selective of catalysate.Current research is more, develop ethylene oligomerisation catalyst faster mainly contains nickel system, iron system and chromium system etc.As US Patent No. 368635l and US3676523 discloses a kind of O-P bridging type part Raney nickel for ethylene oligomerization, be developed into SHOP (ShellHigherOlefinProcess) technical process of shell (SHOP) company based on this patented technology.
1996, Brookhart group (people such as Brookhart, M, J.Am.Chem.Soc., 1998,120,7143 ~ 7144; W099/02472,1999), Gibson group (people such as Gibson, V.C., Chem.Commun., 1998,849 ~ 850; Chem.Eur.J., 2000,222l ~ 2231) find that the trident pyridinimine complex of a class Fe (II) and Co (II) can catalyzed ethylene oligomerisation respectively, not only the catalytic activity of catalyst is very high, and product linear alpha-alkene is selective also very high.Chinese patent CN101074244A, CN1364818A, CN1463799, CN1453069 and CN1850339A report the catalyst of a class for ethylene oligomerization, this catalyst is the complex compound of late transition metal Fe or Co of coordination, under the effect of co-catalyst MAO, this catalyst has good ethylene oligomerization catalysis performance as major catalyst, and wherein iron (II) complex shows very high oligomerization activity to ethene.Oligomerization product comprises C4 ~ C32 etc., linear alpha-alkene selective up to more than 98%; But obtain a certain amount of polymer in oligomerization, research shows that the polymer obtained is low-molecular-weight polyolefin and wax-like polyolefin.This low-molecular-weight polyolefin there will be the problem such as wall built-up and blocking pipeline in continuous polymerization process.
Chrome catalysts is used for ethylene oligomerization, mainly ethylene selectivity trimerization or four poly-preparation 1-hexenes, 1-octene.The four-way catalyst composition be made up of pyrrole ligand, chromium compound, co-catalyst alkyl aluminum and promoter as CN102407159A, CN103102237A and CN102107146A etc. are disclosed is used for ethylene trimer high selectivity and prepares 1-hexene, and Phillips company, CNPC and Sinopec etc. all develop the catalyst of ethylene trimerization composition of oneself and achieve suitability for industrialized production.Patent WO04/056479, US20090118117, US7906681, US7829749, US7511183, US7381857, US7297832 etc. disclose by using chromium-based catalysts to make ethylene tetramerization prepare 1-octene.Wherein said chromium-based catalysts contains phosphorus and nitrogen as heteroatomic part.Patent CN101720253, CN101606605, CN101600722, CN101351424, CN101291734, CN1993180A, CN1741850A and CN1741849A etc. disclose the poly-method of alkene four, and described carbon monoxide-olefin polymeric all comprises heteroatom ligand, transistion metal compound and co-catalyst.
Disclosed in science and patent document, chrome catalysts is used for ethylene trimer or four and poly-usually has one or more lower column defects up to now: 1. product purity is low; 2. form polymer, this causes reactor plugs, is difficult to continuous long-term operation; 3. poor catalyst activity, co-catalyst cost are high; 4. severe reaction conditions, need high pressure, cause drop into, safeguard and energy cost high; 5. to the sensitive of co-catalyst quality.
The object of this invention is to provide the carbon monoxide-olefin polymeric for ethylene oligomerization and method that overcome prior art defect.Especially regardless of process conditions, higher linear alpha-alkene can all be obtained selective and avoid the formation of a large amount of wax and polymer.Under the appropriate reaction conditions, carbon monoxide-olefin polymeric of the present invention is used for ethylene oligomerization, and have the selective height of low-carbon alkene, product carbon number is adjustable, and catalytic activity is high, the selective high of linear alpha-alkene.
Summary of the invention
The object of this invention is to provide a kind of preparation method of double-core chromium transition metal complex ethylene oligomerisation catalyst, the synthesis of this binuclear transition metal complex is simple, yield is high.The catalyst system and catalyzing that this double-core chromium transition metal complex and alkyl aluminum or alumina alkane activator form is used for ethylene oligomerization, and the linear alpha-alkene having higher ethylene oligomerization active and higher is selective.
Object of the present invention also provides a kind of above-mentioned double-core chromium transition metal complex to be the method for the ethylene oligomerization of major catalyst.
Object of the present invention can be achieved by the following measures: for the carbon monoxide-olefin polymeric of ethylene oligomerization, the catalyst system and catalyzing that transition metal chromium complex (a) comprising a kind of dual-core architecture forms with a kind of organo-metallic compound activator (b), transition metal chromium complex (a) of described dual-core architecture meets the compound shown in following general formula (I):
Wherein R1, R2, R3, R4 are linking group, can be identical, also can be different.R1, R2, R3 and R4 are selected from the alkyl of C1 ~ C6, cycloalkyl and aryl respectively, also can be selected from-O-and-S-; R5, R6 are aromatic hydrocarbons, alkane substituting group, can be identical, also can be different; CrX is CrCl
2, CrCl
3, Cr (acac)
3, isooctyl acid chromium, Cr (CO)
6.The synthetic route of the transition metal complex (a) of dual-core architecture is as follows:
Described organo-metallic compound activator (b) is alkyl aluminum compound, aluminium alkoxide compound, organoboron compound, organic salt, inorganic acid and inorganic salts, also can be the mixture of one or more in them;
In described carbon monoxide-olefin polymeric, the mol ratio of the component (a) comprised and (b) is (a): (b)=1:0.1 ~ 5000;
By (a) and (b) two components, be pre-mixed; Or directly can join in reaction system and carry out fabricated in situ;
Described catalytic component is used for ethylene oligomerization, and react and carry out in atent solvent, atent solvent can be selected from alkane, cycloalkane, aromatic hydrocarbons, alkene and ionic liquid; The temperature of reaction is 0 DEG C ~ 200 DEG C, and reaction pressure is 0.1MPa ~ 20MPa, obtained ethylene oligomerization product.
Describe the product that carbon monoxide-olefin polymeric contains following component in detail:
(1) at least one be selected from shown in general formula (I) containing heteroatomic part (a)
Wherein R
1, R
2, R
3, R
4for linking group, can be identical, also can be different.R
1, R
2, R
3, R
4be selected from the alkyl of C1 ~ C6, cycloalkyl, aryl etc. respectively; Also-O-and-S-can be selected from; R
5, R
6for aromatic hydrocarbons, alkane substituting group, can be identical, also can be different; CrX is CrCl
2, CrCl
3, Cr (acac)
3, isooctyl acid chromium, Cr (CO)
6.Preferred: R
1, R
2, R
3, R
4for there is the straight chained alkyl of 2 ~ 4 C atoms, R
5, R
6for aryl.Preferred: R
5, R
6for phenyl.
(2) a kind of organo-metallic compound activating agent (b)
Selectable organo-metallic compound comprises alkyl aluminum compound, aluminium alkoxide compound, organic-magnesium, organic zinc, organoboron compound, organic salt, inorganic acid and inorganic salts.Specifically be selected from various trialkylaluminium and aluminium alkoxide compound, as the aikyiaiurnirsoxan beta etc. of triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, three just base aluminium, tri-n-octylaluminium, MAO, ethylaluminoxane, isobutyl aluminium alkoxide and modification.Also aluminum alkyl halide, alkyl aluminum hydride or alkylaluminium sesquichloride can be used, as AlEt
2cl and A1
2et
3c1
3, also can be the mixture with above-mentioned one or more alkyl aluminums of mentioning or aikyiaiurnirsoxan beta.Organic salt activator is as lithium methide, methyl-magnesium-bromide, diethyl zinc etc.; Inorganic acid and inorganic salts activator are as tetrafluoro boric acid etherate, tetrafluoroborate, hexafluoro antimonate etc.Organoboron compound comprises boroxin, sodium borohydride, boron triethyl, three (pentafluorophenyl group) boron, tri butyl boron hydrochlorate etc.
(I) reactive mode of the double-core chromium transition metal complex described in and metal organic activator, can pass through liquid phase reactor, as reacted under the action of the solvent, selectable solvent is as alkane, cycloalkane, toluene, benzene and its derivative etc.; Also solid phase reaction can be passed through; Also catalyst can be generated by carrying out reaction in-situ in oligomerisation reaction process.
Ethylene oligomerization reaction is mainly carried out in atent solvent.Selectable solvent comprises alkane, cycloalkane, aromatic hydrocarbons, halogenated hydrocarbons, alkene etc.Typical solvent includes, but are not limited to benzene,toluene,xylene, isopropylbenzene, normal heptane, n-hexane, hexahydrotoluene, cyclohexane, 1-hexene, 1-octene, ionic liquid etc.
The preparation of catalyst is that double-core chromium transition metal complex (a) and organo-metallic compound activator (b) are pre-mixed; Also double-core chromium transition metal complex (a) and organo-metallic compound activator (b) directly can be joined in reaction system and carry out fabricated in situ;
The temperature of ethylene oligomerization reaction can be carried out in 0 DEG C ~ 200 DEG C, preferably 50 DEG C ~ 150 DEG C.The pressure of ethylene oligomerization reaction can carry out under the pressure of 0.1MPa ~ 20MPa, preferred 1.0MPa ~ 10MPa.In reaction system, the concentration of catalyst can from 0.01mol metal/L ~ 1000mol metal/L, preferred 0.1mol metal/L ~ 10mol metal/L.
Advantage of the present invention and good effect:
1, dinuclear catalyst of the present invention is by different connected modes by metal center bridging, and the catalyst making metal center close, compared with corresponding monokaryon catalyst, has cooperative effect significantly.Dinuclear catalyst has higher catalytic activity than corresponding monokaryon catalyst; Dinuclear catalyst changes chain tra nsfer dynamics, if β-H is to the transfer of metal or monomer.
2, dinuclear catalyst system of the present invention is used for ethylene oligomerization, and compared with prior art tool has the following advantages: catalyst activity is high, the selective height of linear alpha-alkene, 1-C4 and polymerizate content is low, catalyst life is long.
Detailed description of the invention
The embodiment enumerated below, is further illustrated the present invention, instead of is used for limiting the scope of the invention.
Embodiment 1
1, Isosorbide-5-Nitrae is prepared, 7,10-tetra-(diphenylphosphine amine)-Isosorbide-5-Nitrae, 7,10-tetra-azo-cycle dodecane part (C
56h
56n
4p
4)
Ligand 1,4,7,10-tetra-(diphenylphosphine amine)-Isosorbide-5-Nitrae, shown in the following structural formula of structure of 7,10-tetra-azo-cycle dodecane:
Preparation method is as follows:
Through N
2the carrene (20mL) through processed is added in the 100mL reactor of the band stirring of abundant displacement, triethylamine (3.75mL), diphenyl phosphorus chloride (1.326mL, 7.2mmol), be cooled to 0 DEG C, slowly add Isosorbide-5-Nitrae, 7,10-tetra-azo-cycle dodecane (1.75mmol).Rise to room temperature after stirring reaction 30min and continue reaction 12 hours.Filtration, drying obtain product (1.18g, 74.2%).
1HNMR(400MHz,CDCl
3):d＝2.935-2.951(m,16H,(CH
2)
2),7.132-7.249(m,40H,P(Ph)
2)；
13C{
1H}NMR(100MHz,CDCl
3):d＝139.82,139.68,131.88,131.68,128.42-128.12,77.33-76.70.31PNMR(121MHz,CDCl
3)δ:66.496.
2, the preparation of catalyst
Through N
2the toluene (10mL) through processed is added in the 100mL reactor of the band stirring of abundant displacement, MAO (MAO) toluene solution (2.4mL of 1.4mol/L, 3.4mmol), Isosorbide-5-Nitrae, 7,10-tetra-(diphenylphosphine amine)-Isosorbide-5-Nitrae, 7,10-tetra-azo-cycle dodecane part (2.2mg) (2.4 μm of ol), CrCl
3(THF)
3(1.8mg, 4.8 μm of ol), for subsequent use after room temperature reaction 5min.
3, ethylene oligomerization
The autoclave heating of 500mL vacuumizes 2 hours, is filled with ethene, cools to 90 DEG C, add the toluene (200mL) through processed and above-mentioned catalyst after nitrogen displacement for several times.90 DEG C, carry out oligomerisation reaction under the pressure of 4.0MPa, with ice bath cooling, release after reaction 30min, be the acidic ethanol cessation reaction of 10% with mass fraction.Catalyst activity is 8.9 × 10
5g oligomer/molCrh.The distribution of oligomerization product is in table 1.
Embodiment 2
With embodiment 1, difference is that the addition of the toluene solution of the MAO of 1.4mol/L is 1.7mL.(2.4mmol),70℃。Catalyst activity is 2.28 × 10
6g oligomer/molCrh.The distribution of oligomerization product is in table 1.
Embodiment 3
1,1,5,8,12-tetra-(diphenylphosphine amine)-1,5,8,12-tetra-azo-cycle tetradecane part (C is prepared
58h
60n
4p
4)
Ligand 1, shown in the following structural formula of structure of 5,8,12-tetra-(diphenylphosphine amine)-1,5,8, the 12-tetra-azo-cycle tetradecane:
Preparation method is as follows:
The carrene (20mL) through processed is added in the 100mL reactor that the band of fully replacing through N2 stirs, triethylamine (3.75mL), diphenyl phosphorus chloride (1.33mL, 7.2mmol), be cooled to 0 DEG C, slowly add 1,5,8,12-tetra-azo-cycle dodecane (1.75mmol).Rise to room temperature after stirring reaction 30min and continue reaction 12 hours.Filtration, drying obtain product (1.40g, 85.5%).
1HNMR(400MHz,CDCl
3):d＝1.436(s,4H,CH
2),2.711-2.728(d,8H,NCH
2CH
2CH
2N),3.009-3.035(d,8H,NCH
2CH
2N),7.096-7.290(m,40H,P(Ph)
2)；
13C{
1H}NMR(100MHz,CDCl
3):d＝139.52,139.37,132.08,131.88,128.41-128.12,77.34-76.70,49.27-48.78,27.03.
31PNMR(121MHz,CDCl
3)δ:64.63.
2, the preparation of catalyst
The toluene (10mL) through processed is added in the 100mL reactor that the band of fully replacing through N2 stirs, MAO (MAO) toluene solution (2.1mL of 1.4mol/L, 2.9mmol), 1,5,8,12-tetra-(diphenylphosphine amine)-1,5,8,12-tetra-azo-cycle dodecane part (4.5mg) (4.8 μm of ol), Cr (acac)
3(3.4mg, 9.6 μm of ol), for subsequent use after room temperature reaction 5min.
3, ethylene oligomerization
The autoclave of 500mL is heated to and vacuumizes 2 hours, is filled with ethene, cools to predetermined temperature, add the toluene (200mL) through processed and above-mentioned catalyst after nitrogen displacement for several times.80 DEG C, carry out oligomerisation reaction under the pressure of 1.0MPa, with ice bath cooling, release after reaction 30min, be the acidic ethanol cessation reaction of 10% with mass fraction.Catalyst activity is 0.7 × 10
6g oligomer/molCrh.The distribution of oligomerization product is in table 1.
Embodiment 4
With embodiment 3, difference is that the addition of the toluene solution of the MAO of 1.4mol/L is 2.4mL (3.4mmol), 40 DEG C.Catalyst activity is 2.74 × 10
6g oligomer/molCrh.The distribution of oligomerization product is in table 1.
Embodiment 5
1, Isosorbide-5-Nitrae is prepared, 9,12-tetra-(diphenylphosphine amine)-Isosorbide-5-Nitrae, 9,12-tetra-azo-cycle hexadecane part (C
60h
64n
4p
4)
Ligand 1,4,9,12-tetra-(diphenylphosphine amine)-Isosorbide-5-Nitrae, shown in the following structural formula of structure of 9, the 12-tetra-azo-cycle tetradecane:
Preparation method is as follows:
The carrene (20mL) through processed is added in the 100mL reactor that the band of fully replacing through N2 stirs, triethylamine (3.75mL), diphenyl phosphorus chloride (1.33mL, 7.2mmol), be cooled to 0 DEG C, slowly add Isosorbide-5-Nitrae, 9,12-tetra-azo-cycle dodecane (1.75mmol).Rise to room temperature after stirring reaction 30min and continue reaction 12 hours.Filtration, drying obtain product (1.35g, 80.2%).
1HNMR(400MHz,CDCl
3):d＝1.171(s,8H,(CH
2)
2),2.854-2.876(d,16H,CH
2NCH
2),7.239-7.324(m,40H,P(Ph)
2)；
13C{
1H}NMR(100MHz,CDCl
3):d＝77.33-76.69,36.50,36.36,31.58,29.69-29.33,27.24-26.09,22.64,14.10.
31PNMR(121MHz,CDCl
3)δ:63.05.
2, the preparation of catalyst
The toluene (10mL) through processed is added, MAO (MAO) toluene solution (3.4mL, 4.8mmol) of 1.4mol/L in the 100mL reactor that the band of fully replacing through N2 stirs, 1,4,9,12-tetra-(diphenylphosphine amine)-1,4,9,12-tetra-azo-cycle dodecane part (4.5mg) (4.8 μm of ol), isooctyl acid chromium (4.6mg, 9.6 μm of ol), for subsequent use after room temperature reaction 5min.
3, ethylene oligomerization
The autoclave of 100mL is heated to and vacuumizes 2 hours, is filled with ethene, cools to predetermined temperature, add the toluene (20mL) through processed and above-mentioned catalyst after nitrogen displacement for several times.50 DEG C, carry out oligomerisation reaction under the pressure of 2.0MPa, with ice bath cooling, release after reaction 30min, be the acidic ethanol cessation reaction of 10% with mass fraction.Catalyst activity is 1.8 × 10
5g oligomer/molCrh.The distribution of oligomerization product is in table 1.
Embodiment 6
With embodiment 5, difference is that the addition of the toluene solution of the MAO of 1.4mol/L is 4.8mL (6.7mmol), 40 DEG C, 1.0MPa.Catalyst activity is 2.04 × 10
6g oligomer/molCrh.The distribution of oligomerization product is in table 1.
Embodiment 7
1,1,5,8,12-tetra-(diphenylphosphine amine)-1,5,8,12-cyclal part (C is prepared
59h
62n
4p
4)
Ligand 1, shown in the following structural formula of structure of 5,8,12-tetra-(diphenylphosphine amine)-1,5,8, the 12-cyclal:
Preparation method is as follows:
Through N
2the carrene (20mL) through processed is added in the 100mL reactor of the band stirring of abundant displacement, triethylamine (3.75mL), diphenyl phosphorus chloride (1.326mL, 7.2mmol), be cooled to 0 DEG C, slowly add 1,5,8, the 12-cyclal (1.75mmol).Rise to room temperature after stirring reaction 30min and continue reaction 12 hours.Filtration, drying obtain product (1.30g, 78.2%).
1HNMR(400MHz,CDCl
3)δ:7.510(m,40H),2.861-2.886(d,4H)2.575-2.831(m,16H)0.835-0.898(d,6H)；
31PNMR(400MHz,CDCl
3)δ:65.44,64.48.
2, the preparation of catalyst
Through N
2the toluene (10mL) through processed is added in the 100mL reactor of the band stirring of abundant displacement, MAO (MAO) toluene solution (3.4mL of 1.4mol/L, 4.8mmol), 1,5,8,12-tetra-(diphenylphosphine amine)-1,5,8,12-cyclal part (4.6mg) (4.8 μm of ol), CrCl
3(THF)
3(3.6mg, 9.6 μm of ol), for subsequent use after room temperature reaction 5min.
3, ethylene oligomerization
The autoclave heating of 100mL vacuumizes 2 hours, is filled with ethene, cools to 90 DEG C, add the toluene (20mL) through processed and above-mentioned catalyst after nitrogen displacement for several times.60 DEG C, carry out oligomerisation reaction under the pressure of 1.0MPa, with ice bath cooling, release after reaction 30min, be the acidic ethanol cessation reaction of 10% with mass fraction.Catalyst activity is 1.84 × 10
6g oligomer/molCrh.The distribution of oligomerization product is in table 1.
Embodiment 8
1,1,5,10,13-tetra-(diphenylphosphine amine)-1,5,10,13-tetra-azo-cycle heptadecane part (C is prepared
59h
62n
4p
4)
Ligand 1, shown in the following structural formula of 5,10,13-tetra-(diphenylphosphine amine) the margaric structure of-1,5,10,13-tetra-azo-cycle:
Preparation method is as follows:
Through N
2the carrene (20mL) through processed is added in the 100mL reactor of the band stirring of abundant displacement, triethylamine (3.75mL), diphenyl phosphorus chloride (1.326mL, 7.2mmol), be cooled to 0 DEG C, slowly add 1,5,10,13-tetra-azo-cycle heptadecane (1.75mmol).Rise to room temperature after stirring reaction 30min and continue reaction 12 hours.Filtration, drying obtain product (1.26g, 73.6%).
1HNMR(400MHz,CDCl
3)δ:7.13-7.25(m，40H)，2.946-2.969(m，4H)；2.831-2.852(d，4H)，2.652-2.711(m，8H),1.041-1.139(m,8H)，
31PNMR(400MHz,CDCl
3)δ:64.05，63.07，36.57，35.17(s).
2, the preparation of catalyst
Through N
2the toluene (10mL) through processed is added in the 100mL reactor of the band stirring of abundant displacement, MAO (MAO) toluene solution (4.8mL of 1.4mol/L, 6.7mmol), 1,5,10,13-tetra-(diphenylphosphine amine)-1,5,10,13-tetra-azo-cycle heptadecane part (4.7mg) (4.8 μm of ol), CrCl
2(THF)
2(2.6mg, 9.6 μm of ol), for subsequent use after room temperature reaction 5min.
3, ethylene oligomerization
The autoclave heating of 100mL vacuumizes 2 hours, is filled with ethene, cools to 60 DEG C, add the toluene (20mL) through processed and above-mentioned catalyst after nitrogen displacement for several times.60 DEG C, carry out oligomerisation reaction under the pressure of 1.0MPa, with ice bath cooling, release after reaction 30min, be the acidic ethanol cessation reaction of 10% with mass fraction.Catalyst activity is 1.76 × 10
6g oligomer/molCrh.The distribution of oligomerization product is in table 1.
Embodiment 9
With embodiment 8, difference is that the addition of the toluene solution of the MAO of 1.4mol/L is 3.4mL (4.8mmol), 40 DEG C, 1.0MPa.Catalyst activity is 1.52 × 10
6g oligomer/molCrh.The distribution of oligomerization product is in table 1.
Table 1 ethylene oligomerization experimental result
Above-described is only the preferred embodiment of the present invention, it should be pointed out that for the person of ordinary skill of the art, and under the prerequisite not departing from inventive concept, can also make some distortion and improvement, these all belong to protection scope of the present invention.
Claims (10)
1. the double-core chrome catalysts for ethylene oligomerization, comprising and a kind of there is the transition metal chromium complex of dual-core architecture and a kind of organo-metallic compound activator, it is characterized in that: the described transition metal chromium complex with dual-core architecture is for meeting the compound shown in following general formula (I):
Wherein R
1, R
2, R
3, R
4for there is straight or branched alkyl, cycloalkyl, the aryl of 1 ~ 6 C atom and containing O or S heteroatom group; R
5, R
6for aromatic hydrocarbons, alkane substituting group; CrX is CrCl
2, CrCl
3, Cr (acac)
3, isooctyl acid chromium, Cr (CO)
6.
2. the double-core chrome catalysts for ethylene oligomerization according to claim 1, is characterized in that: R
1, R
2, R
3, R
4for having the straight chained alkyl of 2 ~ 4 C atoms.
3. the double-core chrome catalysts for ethylene oligomerization according to claim 1, is characterized in that: R
5, R
6for phenyl.
4. the double-core chrome catalysts for ethylene oligomerization according to claim 1, is characterized in that: described organo-metallic compound activator is one or more the mixture in alkyl aluminum compound, aluminium alkoxide compound, organoboron compound, organic salt, inorganic acid or inorganic salts.
5. the double-core chrome catalysts for ethylene oligomerization according to claim 1, is characterized in that: the mol ratio of the transition metal chromium complex and organo-metallic compound activator with dual-core architecture is 1:0.1 ~ 5000.
6. the double-core chrome catalysts for ethylene oligomerization according to claim 1, is characterized in that: the described synthetic route with the transition metal chromium complex of dual-core architecture is as follows:
7. the double-core chrome catalysts for ethylene oligomerization according to claim 1, is characterized in that: the preparation method of described catalyst is: will have transition metal chromium complex and organo-metallic compound activator two components of dual-core architecture, and be pre-mixed; Or directly join in reaction system and carry out fabricated in situ.
8. the application of transition metal chromium complex in olefinic polyreaction of a catalyst according to claim 1 or dual-core architecture.
9. the application of transition metal chromium complex in ethylene selectivity trimerization or four poly-reactions of a catalyst according to claim 1 or dual-core architecture.
10. application according to claim 9, is characterized in that: in ethylene selectivity trimerization or four poly-reactions, react and carry out in atent solvent, the temperature of reaction is 0 DEG C ~ 200 DEG C, and reaction pressure is 0.1MPa ~ 20MPa.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN108607613A (en) * | 2018-04-16 | 2018-10-02 | 天津科技大学 | It is a kind of for the catalyst system of ethylene selectivity oligomerisation, preparation method and ethylene oligomerization reaction method |
| CN108607612A (en) * | 2018-04-16 | 2018-10-02 | 天津科技大学 | It is a kind of for the catalyst system of ethylene selectivity oligomerisation, preparation method and ethylene oligomerization reaction method |
| RU2781515C1 (en) * | 2021-07-19 | 2022-10-12 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Иркутский государственный университет" (ФГБОУ ВО "ИГУ") | METHOD FOR PRODUCING COMPLEX COMPOUNDS OF CHROMIUM(III) WITH TRIDENTATE SULPHUR-CONTAINING LIGANDS BY THE GENERAL FORMULA [CrCl3{(RSCH2CH2)2S}] |
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| CN108607613A (en) * | 2018-04-16 | 2018-10-02 | 天津科技大学 | It is a kind of for the catalyst system of ethylene selectivity oligomerisation, preparation method and ethylene oligomerization reaction method |
| CN108607612A (en) * | 2018-04-16 | 2018-10-02 | 天津科技大学 | It is a kind of for the catalyst system of ethylene selectivity oligomerisation, preparation method and ethylene oligomerization reaction method |
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| RU2781515C1 (en) * | 2021-07-19 | 2022-10-12 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Иркутский государственный университет" (ФГБОУ ВО "ИГУ") | METHOD FOR PRODUCING COMPLEX COMPOUNDS OF CHROMIUM(III) WITH TRIDENTATE SULPHUR-CONTAINING LIGANDS BY THE GENERAL FORMULA [CrCl3{(RSCH2CH2)2S}] |
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