CN104059105A - Ligand compound containing pyridyl group, and catalyst containing ligand compound and application thereof - Google Patents
Ligand compound containing pyridyl group, and catalyst containing ligand compound and application thereof Download PDFInfo
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Abstract
The invention provides a ligand compound containing a pyridyl group, and a catalyst containing the ligand compound and application thereof. The structure of the ligand compound containing the pyridyl group is shown in a formula (I) as described in the specification, and in the formula, R is selected from an alkyl group, hydrogen or halogen, preferably, a C1-C6 alkyl group, fluorine, chlorine or bromine. The catalyst composition for ethylene tetramerization comprises the pyridyl group-containing ligand compound as shown in the formula (I), a transition metal compound and a cocatalyst. The invention further provides application of the catalyst composition in ethylene tetramerization or oligomerization. A preparation method for the catalyst composition is simple; when used for ethylene tetramerization, the catalyst composition can highly selectively produce 1-octylene, selectivity of 1-octylene is as high as 76%, and the total selectivity of 1-octylene and 1-hexylene 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 pyridyl, the catalyzer that contains this compound; The invention still further relates to the application in poly-or oligomerization process at ethene four of above-mentioned catalyzer.
Background technology
1-octene, as important organic raw material and chemical intermediate, is mainly used in high-quality polyethylene (PE) field that produces.The linear low density polyethylene (LLDPE) of being produced by 1-octene and ethylene copolymer can significantly improve the properties of PE, particularly can significantly improve poly mechanical property, optical property and tearing strength and resistance to impact shock, product is very suitable for the fields such as agricultural mulch films such as packing film and greenhouse, canopy chamber.In addition, 1-octene is also widely used in the intermediate of softening agent, lipid acid, detergent alcohols and lubricating oil additive etc.
In ethylene oligomerization field, as producing 1-hexene, do not produce ethylene trimerization at present the industrial technology of 1-octene with highly selective.Traditional 1-production of octenes method is ethylene oligomerization method, and ethylene oligomerization technology distributes according to Schulz-Flory, not only obtains 1-octene product, also have other alpha-olefins and a small amount of solid superpolymer, and the selectivity of object product 1-octene is no more than 30% simultaneously.As the SHOP method (US3676523) that Shell company adopts, use nickel-metal catalyst system to carry out ethylene oligomerization reaction, can obtain 11% 1-octene; United States Patent (USP) (US6184428) has reported that a kind of nickel compound of use is as catalyzer, and the yield of 1-octene is 19%.Japanese Patent JP2002121157 has reported that use zirconium metal catalyzer carries out ethylene oligomerization reaction, and wherein the content of 1-octene is approximately 15%.Person skilled has been developed the poly-catalyst system of a series of ethene four in recent years, can synthesize 1-octene by highly selective, as disclosing, patent application CN1741850A, CN1741849A, CN101032695A, CN101351424A, CN101415494A, CN1651142A, CN101291734A and patent application US2006/0128910A1 use containing phosphine part and chromium coordination, catalyzed ethylene four is poly-, can produce 1-octene by highly selective, in product, the content of 1-octene approximately 50～70%.
In the poly-catalyst system of existing ethene four, in most cases used two phosphine type parts, two phosphorus atom are connected by groups such as C, N or O.As patent application CN101605605A discloses the chromium-based catalysts utilizing containing P-C-C-P skeleton structure part, for ethene four, gather, thereby highly selective has been prepared 1-octene, selectivity approximately 70%.But above-mentioned technology has only limitedly disclosed the substituent structure containing P-N-P, P-C-C-P or similar skeleton structure part, and such ligand structure relative complex, and preparation process is loaded down with trivial details, and cost is higher.
Summary of the invention
Present inventor has found during phosphorous type ethylene oligomerization catalyst a kind of novel containing pyridyl catalyst ligand in research, this part preparation is simple, cost is lower, the catalyst composition being comprised 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 can reach more than 80%, has the features such as high reactivity, highly selective
One of object of the present invention is to provide a kind of catalyst composition of ethylene oligomerization, and this catalyst composition comprises pyridyl ligands, transistion metal compound and promotor.
Containing a ligand compound for pyridyl, its structure is suc as formula shown in I:
Wherein, X is H or alkyl or suc as formula the group shown in II;
R is selected from alkyl, hydrogen or halogen, is preferably alkyl, fluorine, the chlorine or bromine of C1～C6.
The described ligand compound containing pyridyl is preferably structure suc as formula the compound shown in II or formula III:
Wherein, R is selected from alkyl, hydrogen or halogen, is preferably alkyl, fluorine, the chlorine or bromine of C1～C6.
The present invention also provides a kind of catalyst composition, comprises suc as formula ligand compound, transistion metal compound and the promotor containing pyridyl shown in I, formula III or formula IV.
In catalyst composition of the present invention, described transistion metal compound can be the conventional transistion metal compound in this area, can be selected from least one in the compound of chromium, molybdenum, iron, titanium, zirconium or nickel, be preferably at least one in chromium acetylacetonate, isocaprylic acid chromium, three (tetrahydrofuran (THF)) chromium trichloride and two (tetrahydrofuran (THF)) chromium dichloride.
In catalyst composition of the present invention, described promotor can be the conventional organo-aluminium compound in this area, can be selected from alkylaluminium cpd 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, methylaluminoxane, ethylaluminoxane or modified methylaluminoxane, more preferably methylaluminoxane.
In above-mentioned catalyst composition, the mol ratio of described part, transistion metal compound and promotor is 1:0.1～10:1～1000, is preferably 1:0.25～2:10～700, more preferably 1:0.5～2:100～500.
Structure in the present invention be take triethylamine suc as formula the concrete preparation method of the part shown in I, II or IV as: the phosphorus chloride that propyl alcohol yl pyridines and aromatic group can be replaced and reacted at low temperatures approximately 1 hour as catalyzer in anhydrous diethyl ether, mixture filters, to after filtrate decompression distillation, obtain crude product product, then this crude product product purifies with column chromatography, eluent is sherwood oil and methylene dichloride, except after desolventizing, obtain target product, the structure limiting in the present invention is suc as formula part shown in I, II or IV.The structure of part characterizes by nucleus magnetic resonance chromatogram.
The present invention also provides the application of a kind of above-mentioned any catalyst composition in ethene four polymerizing technologies, comprises ethene, organic solvent and catalyst composition of the present invention are added and in reactor, carry out four poly-reactions.
In ethene four polymerizing technologies of the present invention, reaction conditions condition is as follows: ethene, organic solvent and catalyst composition of the present invention are added in reactor, and then controlling ethylene pressure is 0.1～6.0Mpa, preferably 0.5～5.0MPa; Temperature of reaction is 0～100 ℃, preferably 0～80 ℃; Catalyst concn is 0.05～0.3mmol Cr/L; React, after reaction finishes, be cooled to room temperature.Then get gas, liquid product and carry out stratographic analysis.
The method that described catalyst composition adds reactor for by part, transistion metal compound and promotor in catalyst composition any two kinds be pre-mixed, and then join in reaction system together with another kind; Or these three kinds of components of part, transistion metal compound and promotor are directly joined in reaction system, to carry out original position synthetic; Or by after part, transistion metal compound and promotor premix, directly with form of mixtures, add in reaction system.
In ethene four polymerizing technologies of the present invention, described solvent comprises arene compounds or aliphatic hydrocarbon compound, and described arene compounds comprises benzene,toluene,xylene, monochloro-benzene, dichlorobenzene, trichloro-benzene or monochlorotoluene and derivative thereof; Described aliphatic hydrocarbon compound comprises straight-chain paraffin, branched paraffin or naphthenic hydrocarbon, preferably pentane, heptane, hexanaphthene or hexane.Solvent load is to guarantee that reactant fully dissolves or disperses.
Beneficial effect of the present invention:
The catalyst composition that comprises pyridyl ligands provided by the invention, when using this catalyst system to carry out ethene four poly-reaction, can highly selective produce 1-octene, 1-octene selectivity approaches 60%, and ligand structure is simple, synthesis step is easy, and the cost that ethene four aggregates into 1-octene is lower.
Embodiment
The following example is only for the present invention is described in detail, but is understood that scope of the present invention is not limited to these embodiment.
Part synthetic example
Embodiment 1
Part A's is synthetic, and part A is part shown in formula III, wherein R=H.
Part preparation method is: under nitrogen protection; in round-bottomed flask, add 0.01mol diphenyl phosphorus chloride and 100mL anhydrous diethyl ether and 1mL triethylamine; stir, ice bath is cooled to 0 ℃, adds 0.01mol2-propyl alcohol yl pyridines; about stirring reaction 1 hour; filter, filtrate, with vacuum pump decompression (10mm mercury column) distillation, is obtained to white oily matter; with column chromatography, purify (eluent is sherwood oil and methylene dichloride), obtain target product part A.Productive rate 65%.
1H-NMR(δ，ppm，CDCl
3，TMS)：7.1～8.4(m，14H，Ar-H and Py-H)，3.5(t，2H，CH
2-O)，2.8(t，2H，CH
2)，1.8(m，2H，CH
2)。
Embodiment 2
Part B's is synthetic, and part B is part shown in formula III, wherein R=2-F.
Preparation method is with part synthetic example 1, and difference is diphenyl phosphorus chloride to replace with two (adjacent fluorophenyl) phosphorus chloride, and other conditions are constant.Productive rate 59%.
1H-NMR(δ，ppm，CDCl
3，TMS)：7.0～8.4(m，12H，Ar-H and Py-H)，3.5(t，2H，CH
2-O)，2.8(t，2H，CH
2)，1.8(m，2H，CH
2)。
Embodiment 3
Part C's is synthetic, and part C is part shown in formula IV, wherein R=H.
Preparation method is with part synthetic example 1, and difference is 2-propyl alcohol yl pyridines to replace with 2,6-dipropyl alcohol yl pyridines, and diphenyl phosphorus chloride consumption changes 0.02mol into by 0.01mol, and other conditions are constant.Productive rate 55%.
1H-NMR(δ，ppm，CDCl
3，TMS)：7.1～7.6(m，23H，Ar-H and Py-H)，3.6(t，4H，CH
2-O)，2.9(t，4H，CH
2)，1.8(m，4H，CH
2)。
Embodiment 4
Part D's is synthetic, and part D is part shown in formula IV, wherein R=4-CH
3.
Preparation method is with part synthetic example 3, and difference is diphenyl phosphorus chloride to replace with two (4-aminomethyl phenyl) phosphorus chloride, and diphenyl phosphorus chloride consumption changes 0.02mol into by 0.01mol, and other conditions are constant.Productive rate 53%.
1H-NMR(δ，ppm，CDCl
3，TMS)：7.1～7.6(m，19H，Ar-H and Py-H)，3.6(t，4H，CH
2-O)，2.9(t，4H，CH
2)，2.4(s，12H，CH
3)，1.8(m，4H，CH
2)。
Polymerization embodiment
Embodiment 5
Adopt 300ml stainless steel polymeric kettle.Autoclave is heated to 80 ℃, vacuumize rear with nitrogen replacement for several times, be then filled with ethene and when ethylene pressure is 3MPa, be down to room temperature.Then at 30 ℃, add dehydrated toluene, add part (part A) and chromium acetylacetonate (Cr (acac) in 20 μ mol embodiment 1 simultaneously
3) and promotor methylaluminoxane (MAO), the cumulative volume of mixed solution is 100mL, wherein the mol ratio of part, chromium acetylacetonate and promotor is 2:1:300, be that chromium acetylacetonate add-on is that 10 μ mol, MAO add-on are 3mmol, control reaction pressure 2.0MPa, pass into ethene, carry out the poly-reaction of ethene four.
After having reacted, system is cooled to room temperature, and gaseous products is collected in aerometer measuring tank, and liquid-phase product is collected in Erlenmeyer flask, adds 1mL ethanol as terminator, stops the poly-reaction of ethene four.The laggard promoting the circulation of qi analysis of hplc of liquid phase ganging of products (chromatographic instrument is Hewlett-Packard 5890).
Record reaction result as follows: catalytic activity is 38600g/mol Crh, 1-octene selectivity is that the selectivity of 69.8%, 1-hexene is 15.2%.Result is as shown in table 1.
Embodiment 6
The pressure of polyreaction is replaced with to 1.0MPa, and other conditions are with embodiment 5; Record reaction result as follows: catalytic activity is 21700g/mol Crh, 1-octene selectivity is that the selectivity of 60.5%, 1-hexene is 22.5%.Result is as shown in table 1.
Embodiment 7
The pressure of polyreaction is replaced with to 5.0MPa, and other conditions are with embodiment 5; Record reaction result as follows: catalytic activity is 62200g/mol Crh, 1-octene selectivity is that the selectivity of 76.3%, 1-hexene is 13.2%.Result is as shown in table 1.
Embodiment 8
The temperature of polyreaction is replaced with to 10 ℃, and other conditions are with embodiment 5; Record reaction result as follows: catalytic activity is 15000g/mol Crh, 1-octene selectivity is that the selectivity of 59.4%, 1-hexene is 18.7%.Result is as shown in table 1.
Embodiment 9
The temperature of polyreaction is replaced with to 80 ℃, and other conditions are with embodiment 5; Record reaction result as follows: catalytic activity is 29100g/mol Crh, 1-octene selectivity is that the selectivity of 55.1%, 1-hexene is 23.1%.Result is as shown in table 1.
Embodiment 10
Change Al/Cr mol ratio into 50, MAO add-on changes 500 μ mol into, and other conditions are with embodiment 5; Record reaction result as follows: catalytic activity is 8300g/mol Crh, 1-octene selectivity is that the selectivity of 46.4%, 1-hexene is 21.8%.Result is as shown in table 1.
Embodiment 11
Change Al/Cr mol ratio into 1000, MAO add-on changes 10mmol into, and other conditions are with embodiment 5; Record reaction result as follows: catalytic activity is 52100g/mol Crh, 1-octene selectivity is that the selectivity of 61.9%, 1-hexene is 21.3%.Result is as shown in table 1.
Embodiment 12
It is three-(tetrahydrofuran (THF)) chromium trichloride (Cr (THF) that chromium acetylacetonate in embodiment 5 is changed
3cl
3), other conditions are with embodiment 5; Record reaction result as follows: catalytic activity is 34300g/mol Crh, 1-octene selectivity is that the selectivity of 57.5%, 1-hexene is 19.6%.Result is as shown in table 1.
Embodiment 13
Change the methylaluminoxane in embodiment 5 into triethyl aluminum (AlEt3), other conditions are with embodiment 5; Record reaction result as follows: catalytic activity is 11700g/mol Crh, 1-octene selectivity is that the selectivity of 41.1%, 1-hexene is 28.5%.Result is as shown in table 1.
Embodiment 14
Change part A into part (part B) in part synthetic example 2, other conditions are with embodiment 5; Record reaction result as follows: catalytic activity is 36600g/mol Crh, 1-octene selectivity is that the selectivity of 60.8%, 1-hexene is 21.8%.Result is as shown in table 1.
Embodiment 15
Change part A into part (part C) in embodiment 3, other conditions are with embodiment 5; Record reaction result as follows: catalytic activity is 32300g/mol Crh, 1-octene selectivity is that the selectivity of 56.6%, 1-hexene is 20.7%.Result is as shown in table 1.
Embodiment 16
Change part A into part (part D) in embodiment 4, other conditions are with embodiment 5; Record reaction result as follows: catalytic activity is 30900g/mol Crh, 1-octene selectivity is that the selectivity of 57.2%, 1-hexene is 19.4%.Result is as shown in table 1.
Table 1
Claims (10)
1. containing a ligand compound for pyridyl, its structure is suc as formula shown in I:
Wherein, X is H, alkyl or suc as formula the group shown in II;
R is selected from alkyl, hydrogen or halogen, is preferably alkyl, fluorine, the chlorine or bromine of C1～C6.
2. ligand compound according to claim 1, is characterized in that, the described ligand compound containing pyridyl is the compound of structure as shown in formula III or formula IV:
Wherein, R is selected from alkyl, hydrogen or halogen, is preferably alkyl, fluorine, the chlorine or bromine of C1～C6.
3. a catalyst composition, comprises that structure is suc as formula ligand compound, transistion metal compound and the promotor containing pyridyl shown in I, formula III or formula IV.
4. catalyst composition according to claim 3, it is characterized in that, described transistion metal compound is selected from least one in the compound of chromium, molybdenum, iron, titanium, zirconium or nickel, is preferably at least one in chromium acetylacetonate, isocaprylic acid chromium, three (tetrahydrofuran (THF)) chromium trichloride or two (tetrahydrofuran (THF)) chromium dichloride.
5. according to the catalyst composition described in claim 3 or 4, it is characterized in that, described promotor is selected from alkylaluminium cpd and/or aluminium alkoxide compound, preferably 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, methylaluminoxane, ethylaluminoxane or modified methylaluminoxane; Methylaluminoxane more preferably.
6. according to the catalyst composition described in any one in claim 3 or 4, it is characterized in that, described part: transistion metal compound: the mol ratio of promotor is 1:0.1～10:1～1000, is preferably 1:0.25～2:10～700, more preferably 1:0.5～2:100～500.
7. the application method in ethene four polymerizing technologies according to the catalyst composition described in any one in claim 3-6, comprises during ethene, organic solvent and described catalyst composition are added to reactor under the existence of solvent and carries out four poly-reactions.
8. method according to claim 7, is characterized in that, comprises following steps: ethene, organic solvent and described catalyst composition are added in reactor, and then controlling ethylene pressure is 0.1～6.0Mpa, preferably 0.5～5.0MPa; Temperature of reaction is 0～100 ℃, and preferably 0～80 ℃, catalyst concn is 0.05～0.3mmol Cr/L; React, after reaction finishes, be cooled to room temperature.
9. according to the method described in claim 7 or 8, it is characterized in that, described method comprise by part, transistion metal compound and promotor in described catalyst composition any two kinds be pre-mixed, and then join in reactor together with another kind; Or these three kinds of components of described part, transistion metal compound and promotor are directly joined in reactor, to carry out original position synthetic; Or by after described part, transistion metal compound and promotor premix, directly with form of mixtures, add in reactor.
10. according to the method described in any one in claim 7-9, it is characterized in that, described solvent comprises arene compounds or aliphatic hydrocarbon compound, and described arene compounds comprises benzene,toluene,xylene, monochloro-benzene, dichlorobenzene, trichloro-benzene or monochlorotoluene and derivative thereof; Described aliphatic hydrocarbon compound comprises straight-chain paraffin, branched paraffin or naphthenic hydrocarbon, preferably pentane, heptane, hexanaphthene or hexane.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105562090A (en) * | 2014-10-15 | 2016-05-11 | 中国石油化工股份有限公司 | Ethylene tetramerization catalyst composition and ethylene tetramerization method |
| CN105562101A (en) * | 2014-10-13 | 2016-05-11 | 中国石油化工股份有限公司 | Catalyst composition for ethylene tetramerization and ethylene tetramerization method |
| CN107233919A (en) * | 2016-03-28 | 2017-10-10 | 中国石油化工股份有限公司 | A kind of catalyst for oligomerization composition and its application |
| CN107282128A (en) * | 2016-03-31 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of catalyst for ethylene tetramerization composition and ethylene tetramerization method |
| CN109701652A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | A kind of carbon monoxide-olefin polymeric and its application |
| CN109701663A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | A kind of carbon monoxide-olefin polymeric and its application |
| 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 |
| CN114163475A (en) * | 2021-12-01 | 2022-03-11 | 浙江智英石化技术有限公司 | Catalyst system containing pyrrole-based rigid structure multi-site ligand, preparation method and application |
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| CN105562101A (en) * | 2014-10-13 | 2016-05-11 | 中国石油化工股份有限公司 | Catalyst composition for ethylene tetramerization and ethylene tetramerization method |
| 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 |
| CN105562090A (en) * | 2014-10-15 | 2016-05-11 | 中国石油化工股份有限公司 | Ethylene tetramerization catalyst 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 |
| CN107233919A (en) * | 2016-03-28 | 2017-10-10 | 中国石油化工股份有限公司 | A kind of catalyst for oligomerization composition and its application |
| 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 |
| CN107282128A (en) * | 2016-03-31 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of catalyst for ethylene tetramerization composition and ethylene tetramerization method |
| CN109701663A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | A kind of carbon monoxide-olefin polymeric and its application |
| CN109701652A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | A kind of carbon monoxide-olefin polymeric and its application |
| 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 |
| CN114163475A (en) * | 2021-12-01 | 2022-03-11 | 浙江智英石化技术有限公司 | Catalyst system containing pyrrole-based rigid structure multi-site ligand, preparation method and application |
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