CN104059105B - Ligand compound containing pyridine radicals, the catalyst containing this compound and application thereof - Google Patents
Ligand compound containing pyridine radicals, the catalyst containing this compound and application thereof Download PDFInfo
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Abstract
The invention provides a kind of ligand compound containing pyridine radicals, the catalyst containing this compound and application thereof.As shown in the formula (I), wherein R is selected from alkyl, hydrogen or halogen to the structure of the described ligand compound containing pyridine radicals, and R is preferably the alkyl of C1～C6, fluorine, chlorine or bromine.The carbon monoxide-olefin polymeric of described ethylene tetramerization, this carbon monoxide-olefin polymeric includes the ligand compound containing pyridine radicals of structure such as formula (I), transistion metal compound and promoter.Present invention also offers the application in ethylene tetramerization or oligomerization process of the described carbon monoxide-olefin polymeric.Carbon monoxide-olefin polymeric preparation method of the present invention is simple, and it is used for ethylene tetramerization, it is possible to highly selective produces 1-octene, and the selectivity of 1-octene reaches as high as 76%, and the overall selectivity of 1-octene and 1-hexene is up to more than 80%.
Description
Technical field
The present invention relates to catalyst field, be specifically related to a kind of ligand compound containing pyridine radicals, the catalyst containing this compound；The invention still further relates to the application in ethylene tetramerization or oligomerization process of the above-mentioned catalyst.
Background technology
1-octene, as important Organic Ingredients and chemical intermediate, is mainly used in production high-quality polyethylene (PE) field.The linear low density polyethylene (LLDPE) produced by 1-octene and ethylene copolymer can significantly improve the properties of PE, particularly to significantly improve the mechanical performance of polyethylene, optical property and tear strength and impact strength, product is very suitable for packaging film and the fields such as agricultural mulch films such as greenhouse, canopy room.It addition, 1-octene is also widely used in the intermediate etc. of plasticizer, fatty acid, detergent alcohols and lube oil additive.
There is no to produce with high selectivity the industrial technology of 1-octene as ethylene trimerization production 1-hexene at ethylene oligomerization domain variability at present.Traditional 1-production of octenes method is ethylene oligomerization method, and ethylene oligomerization technology is distributed according to Schulz-Flory, not only obtains 1-octene product, also has other alpha-olefins and a small amount of solid superpolymer simultaneously, and the selectivity of purpose product 1-octene is less than 30%.The SHOP method (US3676523) adopted such as Shell company uses nickel-metal catalyst system to carry out ethylene oligomerization reaction, can obtain the 1-octene of 11%；United States Patent (USP) (US6184428) reports a kind of nickel compound of use as catalyst, and the yield of 1-octene is 19%.Japan Patent JP2002121157 reports use zirconium metal catalyzer and carries out ethylene oligomerization reaction, and wherein the content of 1-octene is approximately 15%.Person skilled develops a series of catalyst for ethylene tetramerization system in recent years, 1-octene can be synthesized by highly selective, as patent application CN1741850A, CN1741849A, CN101032695A, CN101351424A, CN101415494A, CN1651142A, CN101291734A and patent application US2006/0128910A1 disclose the use of containing Phosphine ligands and chromium coordination, catalyzed ethylene four gathers, 1-octene, the content of 1-octene about 50～70% in product can be produced by highly selective.
In most cases employing double; two phosphine type part in existing catalyst for ethylene tetramerization system, two phosphorus atoms are connected by groups such as C, N or O.As patent application CN101605605A discloses the chromium-based catalysts utilized containing P-C-C-P backbone structure ligand for ethylene tetramerization, thus highly selective is prepared for 1-octene, selectivity about 70%.But above-mentioned technology only limitedly discloses the substituent structure containing P-N-P, P-C-C-P or similar backbone structure ligand and such ligand structure relative complex, and preparation process is loaded down with trivial details, and relatively costly.
Summary of the invention
Present inventor is found that a kind of novel containing pyridinyl catalysis agent part when research is containing phosphorous ethylene oligomerisation catalyst, the preparation of this part is simple, less costly, the carbon monoxide-olefin polymeric being made up of this part can carry out the poly-reaction of ethylene selectivity four, wherein the content of 1-octene reaches as high as 76%, the overall selectivity of 1-octene and 1-hexene, up to more than 80%, has the feature such as high activity, high selectivity
An object of the present invention is to provide the carbon monoxide-olefin polymeric of a kind of ethylene oligomerization, and this carbon monoxide-olefin polymeric comprises pyridyl ligands, transistion metal compound and promoter.
A kind of ligand compound containing pyridine radicals, its structure shown in formula I:
Wherein, X is H or alkyl or the group as shown in Formula II；
R is selected from alkyl, hydrogen or halogen, it is preferred to the alkyl of C1～C6, fluorine, chlorine or bromine.
The described ligand compound containing pyridine radicals is preferably the compound shown in structure such as Formula II or formula III:
Wherein, R is selected from alkyl, hydrogen or halogen, it is preferred to the alkyl of C1～C6, fluorine, chlorine or bromine.
Present invention also offers a kind of carbon monoxide-olefin polymeric, including the ligand compound containing pyridine radicals shown in such as Formulas I, formula III or Formulas I V, transistion metal compound and promoter.
In the carbon monoxide-olefin polymeric of the present invention, described transistion metal compound can be transistion metal compound commonly used in the art, it is selected from least one in the compound of chromium, molybdenum, ferrum, titanium, zirconium or nickel, it is preferred at least one in chromium acetylacetonate, isooctyl acid chromium, three (oxolane) chromium trichlorides and two (oxolane) chromium dichloride.
In the carbon monoxide-olefin polymeric of the present invention, described promoter can be organo-aluminum compound commonly used in the art, it is selected from alkyl aluminum compound and/or aluminium alkoxide compound, at least one in preferred following compound: at least one in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, ethyl aluminum dichloride, MAO, ethylaluminoxane or modified methylaluminoxane, more preferably MAO.
In above-mentioned carbon monoxide-olefin polymeric, the mol ratio of described part, transistion metal compound and promoter is 1:0.1～10:1～1000, it is preferred to 1:0.25～2:10～700, more preferably 1:0.5～2:100～500.
The concrete preparation method of structure in the present invention such as part shown in Formulas I, II or IV as: the phosphorus chloride that propanol yl pyridines and aromatic group replace can be reacted at low temperatures with triethylamine for catalyst about 1 hour in absolute ether, mixture filters, crude material is obtained after filtrate decompression being distilled, then this crude material purifies with column chromatography, eluant is petroleum ether and dichloromethane, target product is obtained, the structure such as part shown in Formulas I, II or IV namely limited in the present invention after removing solvent.The structure of part is characterized by nuclear magnetic resonance, NMR chromatograph.
The present invention also provides for the carbon monoxide-olefin polymeric of a kind of any of the above-described kind application in ethylene tetramerization technique, carries out four poly-reactions including ethylene, organic solvent and carbon monoxide-olefin polymeric of the present invention being added in reactor.
In the ethylene tetramerization technique of the present invention, reaction condition condition is as follows: ethylene, organic solvent and carbon monoxide-olefin polymeric of the present invention are added in reactor, and then controlling ethylene pressure is 0.1～6.0Mpa, it is preferable that 0.5～5.0MPa；Reaction temperature is 0～100 DEG C, it is preferable that 0～80 DEG C；Catalyst concn is 0.05～0.3mmolCr/L；Reacting, reaction is cooled to room temperature after terminating.Then take gas, liquid product and carry out chromatography.
Described carbon monoxide-olefin polymeric adds the method for reactor for be pre-mixed in part, transistion metal compound and promoter in carbon monoxide-olefin polymeric any two kinds, then joins in reaction system together with another kind again；Or part, transistion metal compound and promoter these three component are added directly in reaction system and carry out fabricated in situ；Or after part, transistion metal compound and promoter premix, directly add as a mixture in reaction system.
In the ethylene tetramerization technique of the present invention, described solvent includes arene compounds or aliphatic hydrocarbon compound, and described arene compounds includes benzene,toluene,xylene, monochlor-benzene, dichlorobenzene, trichloro-benzene or monochlorotoluene and derivant thereof；Described aliphatic hydrocarbon compound includes linear paraffin, branched paraffin or cycloalkane, it is preferable that pentane, heptane, hexamethylene or hexane.Solvent load is to ensure that reactant fully dissolves or disperses.
Beneficial effects of the present invention:
The carbon monoxide-olefin polymeric comprising pyridyl ligands provided by the invention, when using this catalyst system to carry out ethylene tetramerization reaction, it is possible to high selectivity produces 1-octene, 1-Octenes selectivity is close to 60%, and ligand structure is simple, synthesis step is easy, and ethylene tetramerization synthesizes the less costly of 1-octene.
Detailed description of the invention
The following example is only for the present invention is described in detail, it will be appreciated that the scope of the present invention is not limited to these embodiments.
Part synthetic example
Embodiment 1
The synthesis of part A, part A is part shown in formula III, wherein R=H.
Part preparation method is: under nitrogen protection; round-bottomed flask adds 0.01mol diphenyl phosphorus chloride and 100mL absolute ether and 1mL triethylamine; stirring, ice bath is cooled to 0 DEG C, adds 0.01mol2-propanol yl pyridines; stirring reaction 1 hours; filter, by filtrate with vacuum pump decompression (10mm mercury column) distillation, obtain white oil thing; purify (eluant is petroleum ether and dichloromethane) with column chromatography, obtain target product part A.Productivity 65%.1H-NMR (δ, ppm, CDCl3, TMS): 7.1～8.4 (m, 14H, Ar-HandPy-H), 3.5 (t, 2H, CH2-O), 2.8 (t, 2H, CH2), 1.8 (m, 2H, CH2)。
Embodiment 2
The synthesis of part B, part B is part shown in formula III, wherein R=2-F.
Preparation method, with part synthetic example 1, is different in that and diphenyl phosphorus chloride replaces with two (adjacent fluorophenyl) phosphorus chloride, and other conditions are constant.Productivity 59%.1H-NMR (δ, ppm, CDCl3, TMS): 7.0～8.4 (m, 12H, Ar-HandPy-H), 3.5 (t, 2H, CH2-O), 2.8 (t, 2H, CH2), 1.8 (m, 2H, CH2)。
Embodiment 3
The synthesis of part C, part C is part shown in Formulas I V, wherein R=H.
Preparation method, with part synthetic example 1, is different in that and 2-propanol yl pyridines replaces with 2,6-dipropyl alcohol yl pyridines, and diphenyl phosphorus chloride consumption is changed into 0.02mol by 0.01mol, and other conditions are constant.Productivity 55%.1H-NMR (δ, ppm, CDCl3, TMS): 7.1～7.6 (m, 23H, Ar-HandPy-H), 3.6 (t, 4H, CH2-O), 2.9 (t, 4H, CH2), 1.8 (m, 4H, CH2)。
Embodiment 4
The synthesis of part D, part D is part shown in Formulas I V, wherein R=4-CH3。
Preparation method, with part synthetic example 3, is different in that and diphenyl phosphorus chloride replaces with two (4-aminomethyl phenyl) phosphorus chloride, and diphenyl phosphorus chloride consumption is changed into 0.02mol by 0.01mol, and other conditions are constant.Productivity 53%.1H-NMR (δ, ppm, CDCl3, TMS): 7.1～7.6 (m, 19H, Ar-HandPy-H), 3.6 (t, 4H, CH2-O), 2.9 (t, 4H, CH2), 2.4 (s, 12H, CH3), 1.8 (m, 4H, CH2)。
Polymerization Example
Embodiment 5
Adopt 300ml rustless steel polymeric kettle.Autoclave is heated to 80 DEG C, replaces for several times with nitrogen after evacuation, be then charged with being down to room temperature when ethylene is 3MPa to ethylene pressure.Then at 30 DEG C, add dehydrated toluene, be simultaneously introduced the part (part A) in 20 μm of ol embodiments 1 and chromium acetylacetonate (Cr (acac)3) and promoter MAO (MAO), the cumulative volume of mixed liquor is 100mL, wherein the mol ratio of part, chromium acetylacetonate and promoter is 2:1:300, namely chromium acetylacetonate addition is 10 μm of ol, MAO additions is 3mmol, control reaction pressure 2.0MPa, pass into ethylene, carry out ethylene tetramerization reaction.
After having reacted, system is cooled to room temperature, gaseous products is collected in aerometer measuring tank, and liquid-phase product is collected in conical flask, adds 1mL ethanol as terminator, terminates ethylene tetramerization reaction.The laggard circulation of qi promoting analysis of hplc of liquid phase gauging of products (chromatograph is Hewlett-Packard 5890).
Record reaction result as follows: catalysis activity is 38600g/molCr h, 1-Octenes selectivity is 69.8%, and the selectivity of 1-hexene is 15.2%.Result is as shown in table 1.
Embodiment 6
The pressure of polyreaction is replaced with 1.0MPa, and other conditions are with embodiment 5；Record reaction result as follows: catalysis activity is 21700g/molCr h, 1-Octenes selectivity is 60.5%, and the selectivity of 1-hexene is 22.5%.Result is as shown in table 1.
Embodiment 7
The pressure of polyreaction is replaced with 5.0MPa, and other conditions are with embodiment 5；Record reaction result as follows: catalysis activity is 62200g/molCr h, 1-Octenes selectivity is 76.3%, and the selectivity of 1-hexene is 13.2%.Result is as shown in table 1.
Embodiment 8
The temperature of polyreaction is replaced with 10 DEG C, and other conditions are with embodiment 5；Record reaction result as follows: catalysis activity is 15000g/molCr h, 1-Octenes selectivity is 59.4%, and the selectivity of 1-hexene is 18.7%.Result is as shown in table 1.
Embodiment 9
The temperature of polyreaction is replaced with 80 DEG C, and other conditions are with embodiment 5；Record reaction result as follows: catalysis activity is 29100g/molCr h, 1-Octenes selectivity is 55.1%, and the selectivity of 1-hexene is 23.1%.Result is as shown in table 1.
Embodiment 10
Changing Al/Cr mol ratio into 50, namely MAO addition changes 500 μm of ol into, and other conditions are with embodiment 5；Record reaction result as follows: catalysis activity is 8300g/molCr h, 1-Octenes selectivity is 46.4%, and the selectivity of 1-hexene is 21.8%.Result is as shown in table 1.
Embodiment 11
Changing Al/Cr mol ratio into 1000, namely MAO addition changes 10mmol into, and other conditions are with embodiment 5；Record reaction result as follows: catalysis activity is 52100g/molCr h, 1-Octenes selectivity is 61.9%, and the selectivity of 1-hexene is 21.3%.Result is as shown in table 1.
Embodiment 12
Being changed by chromium acetylacetonate in embodiment 5 is three-(oxolane) chromium trichloride (Cr (THF)3Cl3), other conditions are with embodiment 5；Record reaction result as follows: catalysis activity is 34300g/molCr h, 1-Octenes selectivity is 57.5%, and the selectivity of 1-hexene is 19.6%.Result is as shown in table 1.
Embodiment 13
MAO in embodiment 5 changes into triethyl aluminum (AlEt3), and other conditions are with embodiment 5；Record reaction result as follows: catalysis activity is 11700g/molCr h, 1-Octenes selectivity is 41.1%, and the selectivity of 1-hexene is 28.5%.Result is as shown in table 1.
Embodiment 14
Part A changes into the part (part B) in part synthetic example 2, and other conditions are with embodiment 5；Record reaction result as follows: catalysis activity is 36600g/molCr h, 1-Octenes selectivity is 60.8%, and the selectivity of 1-hexene is 21.8%.Result is as shown in table 1.
Embodiment 15
Part A changes into the part (part C) in embodiment 3, and other conditions are with embodiment 5；Record reaction result as follows: catalysis activity is 32300g/molCr h, 1-Octenes selectivity is 56.6%, and the selectivity of 1-hexene is 20.7%.Result is as shown in table 1.
Embodiment 16
Part A changes into the part (part D) in embodiment 4, and other conditions are with embodiment 5；Record reaction result as follows: catalysis activity is 30900g/molCr h, 1-Octenes selectivity is 57.2%, and the selectivity of 1-hexene is 19.4%.Result is as shown in table 1.
Table 1
Claims (18)
1. a carbon monoxide-olefin polymeric, including the structure ligand compound containing pyridine radicals shown in formula I, transistion metal compound and promoter；
Wherein, X is H, alkyl or the group as shown in Formula II；
R is selected from the alkyl of C1～C6, hydrogen or halogen, and * represents the decorating site of the group shown in Formula II；
Described transistion metal compound is selected from containing chromium compound；
Described promoter is selected from organo-aluminum compound.
2. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that the described ligand compound containing pyridine radicals is the compound shown in structure such as formula III or Formulas I V:
Wherein, R is selected from the alkyl of C1～C6, hydrogen or halogen.
3. carbon monoxide-olefin polymeric according to claim 1, the R in Formulas I is fluorine, chlorine or bromine.
4. carbon monoxide-olefin polymeric according to claim 2, formula III or the R in Formulas I V are fluorine, chlorine or bromine.
5. the carbon monoxide-olefin polymeric according to any one of claim 1-4, it is characterized in that, described transistion metal compound is at least one in chromium acetylacetonate, isooctyl acid chromium, three (oxolane) chromium trichlorides or two (oxolane) chromium dichloride.
6. the carbon monoxide-olefin polymeric according to any one of claim 1-4, it is characterised in that described promoter is selected from alkyl aluminum compound and/or aluminium alkoxide compound.
7. carbon monoxide-olefin polymeric according to claim 6, it is characterized in that, described promoter at least one in following compound: trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, ethyl aluminum dichloride, MAO, ethylaluminoxane or modified methylaluminoxane.
8. carbon monoxide-olefin polymeric according to claim 7, it is characterised in that described promoter is MAO.
9. the carbon monoxide-olefin polymeric according to any one of claim 1-4, it is characterised in that described part: transistion metal compound: the mol ratio of promoter is 1:(0.1～10): (1～1000).
10. carbon monoxide-olefin polymeric according to claim 9, it is characterised in that described part: transistion metal compound: the mol ratio of promoter is 1:(0.25～2): (10～700).
11. carbon monoxide-olefin polymeric according to claim 10, it is characterised in that described part: transistion metal compound: the mol ratio of promoter is 1:(0.5～2): (100～500).
12. the application process that the carbon monoxide-olefin polymeric according to any one of claim 1-11 is in ethylene tetramerization technique, including ethylene, organic solvent and described carbon monoxide-olefin polymeric being added in the presence of the solvent, reactor carries out four poly-reactions.
13. application process according to claim 12, it is characterised in that comprise the steps of: ethylene, organic solvent and described carbon monoxide-olefin polymeric are added in reactor, then controlling ethylene pressure is 0.1～6.0Mpa；Reaction temperature is 0～100 DEG C, and catalyst concn is 0.05～0.3mmolCr/L；Reacting, reaction is cooled to room temperature after terminating.
14. application process according to claim 13, it is characterised in that control ethylene pressure is 0.5～5.0MPa.
15. application process according to claim 13, it is characterised in that reaction temperature is 0～80 DEG C.
16. the application process according to any one of claim 12-15, it is characterized in that, described method includes being pre-mixed in part, transistion metal compound and promoter in described carbon monoxide-olefin polymeric any two kinds, then joins in reactor together with another kind again；Or described part, transistion metal compound and promoter these three component are added directly in reactor and carry out fabricated in situ；Or after described part, transistion metal compound and promoter premix, directly add as a mixture in reactor.
17. the application process according to any one of claim 12-15, it is characterized in that, described solvent includes arene compounds or aliphatic hydrocarbon compound, and described arene compounds includes benzene,toluene,xylene, monochlor-benzene, dichlorobenzene, trichloro-benzene or monochlorotoluene and derivant thereof；Described aliphatic hydrocarbon compound includes linear paraffin, branched paraffin or cycloalkane.
18. application process according to claim 17, it is characterised in that described aliphatic hydrocarbon compound includes pentane, heptane, hexamethylene or hexane.
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| CN105562101B (en) * | 2014-10-13 | 2017-12-19 | 中国石油化工股份有限公司 | A kind of catalyst for ethylene tetramerization composition and ethylene tetramerization method |
| CN105562090B (en) * | 2014-10-15 | 2017-12-19 | 中国石油化工股份有限公司 | A kind of catalyst for ethylene tetramerization composition and ethylene tetramerization method |
| CN107233919B (en) * | 2016-03-28 | 2020-10-20 | 中国石油化工股份有限公司 | Oligomerization catalyst composition and application thereof |
| CN107282128B (en) * | 2016-03-31 | 2020-02-18 | 中国石油化工股份有限公司 | Ethylene tetramerization catalyst composition and ethylene tetramerization method |
| CN109701663B (en) * | 2017-10-26 | 2021-12-21 | 中国石油化工股份有限公司 | Catalyst composition and application thereof |
| CN109701652B (en) * | 2017-10-26 | 2021-12-21 | 中国石油化工股份有限公司 | Catalyst composition and application thereof |
| CN109796498A (en) * | 2019-03-13 | 2019-05-24 | 东北石油大学 | A kind of hyperbranched pyridines bidentate chromium compound and its synthetic method and application |
| CN114163475B (en) * | 2021-12-01 | 2023-07-28 | 浙江智英石化技术有限公司 | Catalyst system containing pyrrole rigid structure multi-site ligand, preparation method and application |
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| CN1741850A (en) * | 2002-12-20 | 2006-03-01 | Sasol技术股份有限公司 | Tetramerization of olefins |
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| CN1741850A (en) * | 2002-12-20 | 2006-03-01 | Sasol技术股份有限公司 | Tetramerization of olefins |
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| "Bite angle effect of bidentate P–N ligands in palladium catalysed allylic alkylation";Richard. J Et al,;《J. Chem. Soc., Dalton Trans》;20000428;第10卷;第1550页Fig.2 * |
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