CN107235885B - Ligand compound and preparation method and application thereof - Google Patents
Ligand compound and preparation method and application thereof Download PDFInfo
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- CN107235885B CN107235885B CN201610182076.XA CN201610182076A CN107235885B CN 107235885 B CN107235885 B CN 107235885B CN 201610182076 A CN201610182076 A CN 201610182076A CN 107235885 B CN107235885 B CN 107235885B
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/36—Oxygen or sulfur atoms
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
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- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
- B01J2531/002—Materials
- B01J2531/004—Ligands
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
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Abstract
The invention relates to a ligand compound, which is shown as a general formula I: wherein R is1And R is the same or different and is independently selected from alkyl and cycloalkyl. The invention also relates to a preparation method and application of the ligand compound.
Description
Technical Field
The invention relates to a ligand compound, in particular to a ligand compound of an ethylene oligomerization catalyst, especially a ligand compound of an ethylene dimerization, trimerization or tetramerization catalyst, and also relates to a preparation method of the catalyst ligand compound and application of the catalyst ligand compound in an ethylene oligomerization process.
Background
The use of chromium-based catalysts for the oligomerization of olefins, primarily alpha-olefins, has been extensively studied. More specifically, a number of chromium-based catalysts have been developed and used for the oligomerization of olefins to produce alpha-olefins. Among them, the trimerization of ethylene to 1-hexene and the tetramerization of ethylene to 1-octene are of particular significance. Compared with the copolymer of 1-butene, the LLDPE resin copolymerized by 1-hexene and 1-octene has obviously excellent tensile strength, impact strength, tear resistance and durability, and is particularly suitable for packaging films, agricultural covering films for greenhouses, sheds and the like. In the context of alpha-olefins as comonomers, 1-hexene and 1-octene have been gradually substituted for 1-butene to produce high performance PE products.
The production method of alpha-olefin mainly includes wax cracking method, ethylene oligomerization method, extraction separation method, fatty alcohol dehydrogenation method and internal olefin isomerization method. Among them, the ethylene oligomerization method is one of the important ways of producing alpha-olefin because of its characteristics of high purity, good selectivity, high utilization rate of raw material, etc.
After a way of selectively preparing 1-hexene by ethylene trimerization by using a homogeneous ternary chromium-based catalyst is reported by John R.Briggs in J.chem.Soc., chem.Commun.,1989,674-675, a 1-hexene production technology is greatly developed. In order to make more rational use of petroleum feedstocks, efforts have been made to develop highly efficient oligomerization catalysts, with the expectation of obtaining high purity higher alpha-olefins. In many explorations, the interaction of heteroatom ligands with chromium-based compounds and their use for the oligomerization of olefins has become a new area of research in this field. CN1606539A discloses a coordination compound of multidentate ligand phosphine, arsenic and/or antimony containing aluminoxane and chromium salt, and the coordination compound is used in the ethylene oligomerization reaction process; WO2003053890 reports that a novel sulfur-nitrogen heteroatom ligand is used for olefin oligomerization, olefin oligomerization occurs under the action of a chromium compound and alkylaluminoxane, and the catalyst composition has the characteristics of high catalytic activity and high purity of 1-hexene as a product. The alkoxy aluminum (including methylaluminoxane, modified methylaluminoxane) and the like serving as cocatalysts have the problems of high cost, large using amount and the like, and the problem of high production cost is bound to be caused when the alkoxy aluminum is used for ethylene trimerization reaction on a large scale.
There is no doubt that there is still a need for a novel catalyst with excellent comprehensive performance in the field of olefin oligomerization. Attention is paid to the fact that novel ligand compounds for ethylene oligomerization catalysts are obtained, and therefore ethylene oligomerization catalysts with high activity and selectivity are developed.
Disclosure of Invention
The inventor of the application discovers a novel ethylene oligomerization catalyst ligand when researching a phosphorus-containing ethylene oligomerization catalyst, and the ligand compound contains S and N heteroatoms, has a novel structure, is simple to prepare and has low cost. The composition formed by the ligand compound can effectively catalyze ethylene oligomerization reaction, especially ethylene trimerization reaction. Has the characteristics of high activity, high selectivity and the like, and has better industrial application prospect and economic value.
In a first aspect, the present invention relates to a ligand compound represented by formula I:
wherein R is1And R is the same or different and is independently selected from alkyl and cycloalkyl.
In a preferred embodiment of the present invention, R is1And R is independently selected from C1-C15Alkyl or C3-C12Cycloalkyl of (2), preferably C1-C12Alkyl or C3-C8A cycloalkyl group of (a). In a specific example, the R is1And R is selected from the group consisting of methyl, ethyl, isopropyl, hexyl, octyl, dodecyl, cyclopropyl, cyclopentyl, and cyclohexyl. In a preferred embodiment, R and R1The same is true.
The ligand with the novel structure provided by the invention has the advantages of novel structure, simple preparation and lower cost. The composition formed by the ligand compound can effectively catalyze ethylene oligomerization reaction, especially ethylene trimerization reaction, and has the characteristics of high activity, high selectivity and the like
A second aspect of the present invention provides a method for preparing the ligand compound, comprising:
a) dissolving substituted pyrrole shown in a general formula II in an organic solvent, adding methyl iodide, and reacting to obtain a compound shown in a general formula III;
b) adding catalyst to mercaptans (RSH and R)1SH), then adding into an organic solvent solution containing a compound shown in a general formula III, and reacting to obtain a ligand compound shown in a general formula I, wherein R is1And R is as defined above. It is clear that when R is1When R is different, mercaptans RSH and R1SH is RSH and R1A mixture of SH; when R is1When R is the same, thiol RSH and R1SH is the same substance.
In a preferred embodiment of the production process of the present invention, the molar ratio of the substituted pyrrole to methyl iodide is 1 (0.8-3.0).
In a preferred embodiment of the preparation process according to the invention, the molar ratio of the total amount of the compound III, the catalyst and the thiol is 1 (0.8-1.2) to (0.4-0.6).
In a preferred embodiment of the preparation process according to the invention, when R is1And when R is different: addition of catalyst to mercaptans RSH and R1Mixture of SH (molar ratio RSH: R)1SH ═ 1:1), then slowly dropwise adding the compound into an organic solvent solution containing the compound shown in the general formula III, and separating the product after reaction to obtain the ligand compound shown in the general formula I.
In a preferred embodiment of the production method of the present invention, the organic solvent is selected from at least one of aromatic hydrocarbon compounds and aliphatic hydrocarbon compounds, preferably at least one selected from toluene, tetrahydrofuran, hexane and dichloromethane. The organic solvent in the step a) and the organic solvent in the step b) can be the same or different.
In a preferred embodiment of the preparation method of the present invention, the reaction temperature in the step a) is 0 to 30 ℃ and the reaction time is 3 to 10 hours.
In a preferred embodiment of the preparation method of the present invention, the reaction temperature in the step b) is-10 to 100 ℃ and the reaction time is 3 to 10 hours. In said step b), said catalyst is an organolithium compound, preferably selected from the group consisting of N-butyllithium, methyllithium, ethyllithium and lithium N, N-diisopropylamide.
According to the preparation method provided by the invention, the preparation process is simple, the process flow is short, and the ligand compound can be efficiently prepared.
The third aspect of the invention relates to the application of the ligand compound in preparing the catalyst composition for ethylene oligomerization.
The invention also provides the application of the ligand compound in ethylene dimerization, trimerization or tetramerization reaction, and has the advantages of high activity and high selectivity.
The catalyst composition provided by the invention has the advantages of novel ligand compound structure, simple preparation and lower cost, and the catalyst composition consisting of the ligand compound can be used for ethylene oligomerization. The product obtained is mainly C6The content is more than 95 percent, and the others are small amount of C4、C8、C10、C12And the like. The activity of the catalyst can be more than 300kg of oligomerization products g (Cr)-1·h-1. The ethylene trimerization reaction carried out by the method has few high molecular polymers. Has the characteristics of high activity, high selectivity and the like, and has better industrial application prospect and economic value.
Detailed Description
The following examples are merely illustrative of the present invention in detail, but it should be understood that the scope of the present invention is not limited to these examples.
In the examples of the present invention, nmr was measured using a Bruker AV400 nmr apparatus; the gas chromatography was performed using a Hewlett packard 5890 chromatograph.
Wherein, the detection conditions of the nuclear magnetic resonance are as follows: deuterated chloroform is used as a solvent, and the test is carried out at room temperature.
Wherein, the detection conditions of the gas chromatography are as follows: chromatographic column SE-54, high-purity nitrogen carrier gas and FID detector; the column temperature adopts two-step temperature programming.
Example 1
Ligand Compound 1 (R)1And R is n-octyl) comprising:
at room temperature, methyl iodide (30mmol) is added dropwise into a tetrahydrofuran solution (20mL) containing substituted pyrrole II (10mmol), after the addition, the reaction is stirred at room temperature for 8 hours, and the solvent is drained to obtain light yellow powder, namely the compound III, with the yield of 93.2%.
N-butyllithium (10mmol) was added to n-C at 0 deg.C8H17SH (10 mmol). Half an hour later, the reaction mixture was transferred to a tetrahydrofuran solution (10mL) containing Compound III (5mmol), and then the reaction mixture was stirred for 5 hours while gradually increasing the temperature to 70 ℃. After the reaction is completed, the solvent is removed under reduced pressure, and column chromatography purification is carried out to obtain brown liquid, namely ligand compound 1. The yield was 63.5%.
Nuclear magnetic data for ligand compound 1:
1H NMR(400MHz,CDCl3)δ＝8.34(m,1H),5.88(s,2H),3.35(s,4H),2.38(t,4H),1.58-1.49(m,4H),1.32-1.31(m,20H),0.88(t,6H)。
example 2
Ligand Compound 2 (R)1And R is ethyl) is prepared as in ligand Compound 1, except that C is used2H5SH (10mmol), yield of ligand compound 2 was 71.9%.
1H NMR(400MHz,CDCl3)δ＝8.21(m,1H),5.62(s,2H),3.60(s,4H),2.48(m,4H),1.32-1.31(m,20H),1.20(t,6H)。
Example 3
Ligand Compound 3 (R)1And R is cyclopentyl) was prepared as for ligand compound 1, except that C was used5H9SH(10mmol), the yield of ligand compound 3 was 66.0%.
1H NMR(400MHz,CDCl3)δ＝8.29(m,1H),5.62(s,2H),3.58(s,4H),2.51(m,2H),2.01-1.45(m,16H)。
Example 4
Ligand Compound 4 (R)1Is n-octyl and R is cyclohexyl) comprises the following steps:
at room temperature, methyl iodide (30mmol) is added dropwise into a tetrahydrofuran solution (20mL) containing substituted pyrrole II (10mmol), after the addition, the reaction is stirred at room temperature for 8 hours, and the solvent is drained to obtain light yellow powder, namely the compound III, with the yield of 93.2%.
N-butyllithium (10mmol) was added to nC at 0 deg.C8H17SH (5mmol) and cyclohexyl mercaptan (5 mmol). After half an hour, the above mixture was slowly added dropwise to a tetrahydrofuran solution (10mL) containing Compound III (5mmol), and then the reaction was stirred for 5 hours while gradually warming to 70 ℃. After the reaction is completed, the solvent is removed under reduced pressure, and column chromatography purification is carried out to obtain brown liquid, namely ligand compound 4. The yield was 36.1%.
Nuclear magnetic data for ligand compound 4:
1H NMR(400MHz,CDCl3)δ＝8.30(m,1H),5.62(s,2H),3.51(s,4H),2.52(m,1H),2.41(t,2H),1.20-1.68(m,22H),0.90(t,3H)。
example 5
Ligand Compound 5 (R)1Butyl, R is cyclohexyl) was prepared as described for ligand compound 1, except that: n-butyllithium (10mmol) was added to n-C at 0 deg.C4H9In a mixture of SH (5mmol) and cyclohexyl thiol (5mmol), the yield of ligand compound 5 was 45.5%.
1H NMR(400MHz,CDCl3)δ＝8.29(m,1H),5.71(s,2H),3.70(s,4H),2.51(m,3H),1.30-1.90(m,14H),1.09(t,3H)。
Example 6 (polymerization example)
A stainless steel polymerizer is used. The autoclave was heated to 80 ℃, evacuated, replaced with nitrogen several times, then replaced with ethylene and cooled to the reaction temperature. Then adding at 60 deg.CAdding heptane, 10 μmol of tetrahydrofuran chromium trichloride, ligand compound 1(R is n-octyl) and cocatalyst triethylaluminum (AlEt)3) And the total volume of the mixed solution is 100mL, wherein the molar ratio of the tetrahydrofuran chromium trichloride, the ligand compound 1 and the cocatalyst is 1: 2: 100, controlling the reaction pressure to be 1MPa, and introducing ethylene to carry out ethylene oligomerization.
And after the reaction is finished, cooling the system to room temperature, collecting the gas-phase product in a gas metering tank, collecting the liquid-phase product in a conical flask, and adding 1mL of ethanol as a terminator to terminate the ethylene oligomerization reaction. And (4) carrying out gas chromatographic analysis after the gas-liquid phase product is measured. The results show that the obtained product is mainly C6, the content of which is more than 95 percent, and the others are small amount of alpha-olefin such as C4, C8, C10, C12 and the like. The catalyst activity was about 305kg of oligomerization product g (Cr)-1·h-1. The ethylene trimerization reaction carried out by the method has few high molecular polymers.
Example 7
The same as example 6, except that the ligand Compound 1 was changed to the ligand Compound 2 (R)1R, is ethyl). The data results are shown in table 1.
Example 8
The same as example 6, except that the ligand Compound 1 was changed to the ligand Compound 5 (R)1Is butyl and R is cyclohexyl). The data results are shown in table 1.
Comparative example 1
The difference from example 6 is that the ligand is 2, 5-dimethylpyrrole. The data results are shown in table 1.
TABLE 1
From the above data, it can be seen that the method of the present invention has a simple preparation process and a short process flow, and can efficiently prepare the ligand compound of the present invention. The ligand compound provided by the invention has the advantages of novel structure, simple preparation and low cost. The ligand compound can be used for catalyzing ethylene oligomerization reaction, particularly ethylene trimerization reaction, and has the characteristics of high activity, high selectivity and the like. The content of C4 with low economic added value is low, while the content of other oligomerization products with high economic added value is high, in particular, the selectivity of C6 is high.
It should be noted that the above-mentioned embodiments are used for explaining the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to the exemplary embodiments illustrated above, but it is understood that all words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (11)
1. A ligand compound of formula I:
wherein R is1And R is octyl.
2. A method for preparing the ligand compound according to claim 1, comprising:
a) dissolving substituted pyrrole shown in a general formula II in an organic solvent, adding methyl iodide, and reacting to obtain a compound shown in a general formula III;
b) addition of catalyst to mercaptans RSH and R1SH, then adding into an organic solvent solution containing a compound shown in a general formula III, and reacting to obtain a ligand compound shown in a general formula I, wherein R and R1Is as defined in claim 1.
3. The method of claim 2, wherein the molar ratio of substituted pyrrole to methyl iodide is 1 (0.8-3.0).
4. The method as claimed in claim 2 or 3, wherein the molar ratio of the total amount of the compound of the formula III, the catalyst and the thiol is 1 (0.8-1.2) to (0.4-0.6).
5. The method according to claim 2 or 3, wherein the organic solvent is at least one selected from aromatic hydrocarbon compounds and aliphatic hydrocarbon compounds.
6. The method according to claim 5, wherein the organic solvent is at least one selected from the group consisting of toluene, tetrahydrofuran, hexane, and dichloromethane.
7. The process according to claim 2 or 3, wherein the reaction temperature in step a) is 0-30 ℃ and the reaction time is 3-10 hours; and/or the reaction temperature in the step b) is-10 to 100 ℃, and the reaction time is 3 to 10 hours.
8. The process according to claim 2 or 3, characterized in that in step b) the catalyst is an organolithium compound.
9. The process according to claim 8, wherein in step b) the catalyst is N-butyllithium, methyllithium, ethyllithium and lithium N, N-diisopropylamide.
10. Use of the ligand compound according to claim 1 or the ligand compound prepared by the method according to any one of claims 2 to 9 in ethylene oligomerization.
11. Use of a ligand compound according to claim 1 or a ligand compound prepared by a process according to any one of claims 2 to 9 in ethylene dimerization, trimerization or tetramerization.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102164672A (en) * | 2008-10-31 | 2011-08-24 | 切弗朗菲利浦化学公司 | Oligomerization catalyst system and process for oligomerizing olefins |
| CN102407159A (en) * | 2001-12-20 | 2012-04-11 | Sasol技术股份有限公司 | Trimerisation And Oligomerisation Of Olefins Using A Chromium Based Catalyst |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102407159A (en) * | 2001-12-20 | 2012-04-11 | Sasol技术股份有限公司 | Trimerisation And Oligomerisation Of Olefins Using A Chromium Based Catalyst |
| CN102164672A (en) * | 2008-10-31 | 2011-08-24 | 切弗朗菲利浦化学公司 | Oligomerization catalyst system and process for oligomerizing olefins |
Non-Patent Citations (1)
| Title |
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| Isocytosine H2-receptor histamine antagonists.III. The synthesis and biological activity of lupitidine (SK&F 93479) and related compounds;TH Brownl，et al.;《Eur J Med Chem》;19901231;第25卷;217-226 * |
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