CN104415790A - Ethylene tetramerization catalyst composition and application thereof - Google Patents
Ethylene tetramerization catalyst composition and application thereof Download PDFInfo
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Abstract
The invention provides an ethylene tetramerization catalyst composition. The catalyst composition includes a ligand represented by formula (I), a transition metal compound and a cocatalyst. The invention also provides a method using the catalyst composition to carry out ethylene tetramerization. The catalyst composition is used in ethylene tetramerization in order to produce 1-octene in a high selectivity manner, the selectivity of 1-octene in products exceeds 70%, the total selectivity of 1-octene and 1-hexene can exceed 80%, and the catalyst composition has a high activity.
Description
Technical field
The present invention relates to ethylene oligomerization field, be specifically related to a kind of carbon monoxide-olefin polymeric for ethylene tetramerization.The invention still further relates to the application in this carbon monoxide-olefin polymeric.
Background technology
1-octene as important Organic Ingredients and chemical intermediate, mainly for the production of high-quality polyethylene (PE).The LLDPE (LLDPE) produced by 1-octene and ethylene copolymer significantly can improve the properties of PE, particularly poly mechanical performance, optical property and tear strength and impact strength are all significantly increased, be very suitable for packaging film and the agricultural mulch films etc. such as greenhouse, canopy room, 1-octene is also used as the intermediate of plasticizer, aliphatic acid, detergent alcohols and lube oil additive simultaneously.
Although the value of 1-octene is well-known, this area does not produce 1-octene with high selectivity at present as ethylene trimer produces 1-hexene.Traditional 1-production of octenes method is ethylene oligomerization method, ethylene oligomerization technology distributes according to Schulz-Flory, not only obtains 1-octene product, also has other alpha-olefins and a small amount of solid superpolymer simultaneously, and object product 1-octene is selective very low, is no more than 30%.The SHOP method (US3676523) that such as Shell company adopts uses nickel-metal catalyst system to carry out ethylene oligomerization reaction, can obtain the 1-octene of 11%; United States Patent (USP) (US6184428) report uses a kind of nickel compound as catalyst ethylene oligomerization, and the yield of 1-octene is 19%.Japan Patent JP2002121157 reports and uses zirconium metal catalyzer to carry out ethylene oligomerization reaction, and wherein the content of 1-octene is approximately 15%.The ethylene tetramerization ternary catalyst systems of nearest report can synthesize 1-octene by highly selective, as patent application CN1741850A(WO2004/056478A1), CN1741849A(WO2004/056479A1), CN101032695A, CN101351424A, CN101415494A, CN1651142A, CN101291734A and patent application US2006/0128910A1 all disclose and use P-N-P part and chromium coordination catalysis ethylene tetramerization, can produce 1-octene by highly selective, in product, the content of 1-octene even can be greater than 70%.Patent application CN101605605A discloses and utilizes containing the chromium-based catalysts of P-C-C-P backbone structure ligand for ethylene tetramerization, thus highly selective has prepared 1-octene, is selectively the highlyest greater than 70%.
In view of containing the application of Phosphine ligands in ethylene tetramerization, present inventor has found a kind of novel catalyst for ethylene tetramerization, and this system comprises asymmetric P-C (R)-C-P matrix type part, transistion metal compound and co-catalyst.Use this catalyst system and catalyzing effectively can gather reaction by catalyzed ethylene four, catalyst has the feature such as high activity and high selectivity, and wherein 1-octene is selective more than 70%.
Summary of the invention
The object of the present invention is to provide the catalyst for ethylene tetramerization system comprising Novel Ligands, when using this catalyst system to carry out ethylene tetramerization reaction, high selectivity can obtain 1-octene.
The invention provides a kind of carbon monoxide-olefin polymeric of ethylene tetramerization, comprise such as formula the diphosphine ligand shown in I, transistion metal compound and co-catalyst three components;
Wherein, in formula I, R and R ' is selected from alkyl, cycloalkyl, monocycle and polyaromatic independently of one another.
In a preferred embodiment of the present invention, described alkyl is C
1~ C
20straight chain or branching saturated alkyl, preferred C
1~ C
10straight chain or branching saturated alkyl, more preferably C
1~ C
6straight chain or branching saturated alkyl.
In further preferred embodiment of the present invention, described alkyl can be selected from following group: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, sec-amyl, isopentyl, n-hexyl, Sec-Hexyl, isohesyl, n-heptyl and isomers thereof etc.; Preferable methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl or isobutyl group.
In a preferred embodiment of the present invention, described cycloalkyl is C
3~ C
10cycloalkyl, preferred C
3~ C
6cycloalkyl.
In further preferred embodiment of the present invention, described cycloalkyl can be selected from cyclopropyl, cyclopenta or cyclohexyl.
In a preferred embodiment of the present invention, described monocycle and polyaromatic are C
6~ C
20monocycle or polycyclic aromatic group, the carbon atom preferably on wherein one or more rings is by the hybrid atom MCM-41 of oxygen, nitrogen and/or sulphur, and described monocycle and polyaromatic also can by halogen and/or C
1~ C
20alkyl replaces.
In further preferred embodiment of the present invention, described monocycle and polyaromatic are selected from phenyl or substituted-phenyl, naphthyl or pyridine radicals, more preferably phenyl or substituted-phenyl.
In carbon monoxide-olefin polymeric of the present invention, described transistion metal compound can be the transistion metal compound that this area is commonly used, be selected from the compound of chromium, molybdenum, iron, titanium, zirconium or nickel as can be, be preferably chromium chloride, chromium acetylacetonate, isooctyl acid chromium or three (oxolane) chromium trichloride.
In inventive catalyst composition, described co-catalyst can be the organo-aluminum compound that this area is commonly used, as can be alkyl aluminum compound or aluminium alkoxide compound, one or more in preferred trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, ethyl aluminum dichloride, MAO, ethylaluminoxane or modified methylaluminoxane, most preferably modified methylaluminoxane, MAO and/or triethyl aluminum.
In a preferred embodiment of carbon monoxide-olefin polymeric of the present invention, the mol ratio of described part, transistion metal compound and co-catalyst is 1:0.1 ~ 10:1 ~ 1000, be preferably 1:0.25 ~ 2:50 ~ 700, be more preferably 1:0.5 ~ 2:100 ~ 500.
Present invention also offers a kind of method using above-mentioned carbon monoxide-olefin polymeric to carry out ethylene tetramerization, under being included in the existence of described carbon monoxide-olefin polymeric and organic solvent, ethene is carried out four poly-reactions.
In the method for ethylene tetramerization of the present invention, the reaction temperature of described ethylene tetramerization is 0 ~ 200 DEG C; Reaction pressure 0.1 ~ 20MPa.
Ethylene tetramerization organic solvent is the organic solvent being selected from aliphatic hydrocarbon or aromatic hydrocarbons, wherein, arene compounds is selected from least one in following compound: benzene,toluene,xylene, monochlor-benzene, dichlorobenzene, trichloro-benzene or monochlorotoluene and derivative thereof; Aliphatic hydrocarbon compound is selected from least one in following compound: linear paraffin, branched paraffin or cycloalkane, preferred pentane, heptane, cyclohexane or hexane.Solvent load is to ensure that reactant fully dissolves or disperses.
In above-mentioned ethylene tetramerization technique, can by part, transistion metal compound and co-catalyst in carbon monoxide-olefin polymeric any two kinds be pre-mixed, and then to join together with another kind in reaction system; Or these three kinds of components of part, transistion metal compound and co-catalyst are directly joined in reaction system and carries out fabricated in situ; Or after component part, transistion metal compound and co-catalyst premix, directly add as a mixture in reaction system.
In above-mentioned ethylene tetramerization technique, the reaction condition that reaction condition can be commonly used for this area.Optimal conditions is as follows: add in reactor by ethene, organic solvent and described carbon monoxide-olefin polymeric, then ethylene pressure be 1 ~ 6Mpa, reaction temperature be 0 ~ 100 DEG C at reaction, catalyst concn is 0.05 ~ 0.3mmol Cr/L.After reaction terminates, be cooled to room temperature, get gas, liquid product and carry out chromatography.
Beneficial effect of the present invention:
When using carbon monoxide-olefin polymeric provided by the invention to carry out ethylene tetramerization reaction, high selectivity can produce 1-octene, 1-Octenes selectivity can more than 70%, and in product, the overall selectivity of 1-octene and 1-hexene can more than 80%, and the activity of catalyst is high.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.But the present invention is not limited to following examples.
In an embodiment of the present invention:
Nuclear magnetic resonance adopts Switzerland Bruker company AV400MHz nuclear magnetic resonance chemical analyser to detect.
Gas-chromatography adopts Hewlett-Packard 5890 chromatograph to detect.
The synthesis of part:
Embodiment 1: ligand L
1(the R=CH in formula I
3, R '=Ph) synthesis
The part used in the present embodiment synthesizes by following synthesis path.
Wherein:
By MsCl(2.15mL, 55.2mmol) be dissolved in 5mL carrene, at 0 DEG C, slowly dropwise add in the carrene mixed solution of triethylamine (4mL) and propane diols (26.3mmol), react after 1 hour, rise to room temperature and continue stirring 2 hours.After reaction terminates, add 1M aqueous hydrochloric acid solution, aqueous phase dichloromethane extraction, by organic phase except desolventizing, obtain intermediate.At-78 DEG C, by LiPPh2(10mmol) THF (5mL) solution slowly instill the THF(5mL of above-mentioned intermediate (10mmol)) in solution.After 10min, rise to room temperature reaction and spend the night.After reaction terminates, except desolventizing, add suitable quantity of water, have a large amount of precipitation, filtering-depositing.Column chromatography is purified and is obtained ligand L 1.1H NMR(400MHz,CDCl3):δ=7.41～7.21(m,25H,Ph-H),2.38～2.23(m,2H,CHH,CHMe),1.94～1.81(m,2H,CH2),1.28(dd,3H,CH3);31P NMR(CDCl3)δ=1.7;-20.6.
Embodiment 2: ligand L
2the synthesis of (R=R ' in formula I=Ph)
Preparation method is with embodiment 1, and difference is propane diols to replace with styrene glycol, and other conditions are constant.Productive rate 75%.
1H NMR(400MHz,CDCl
3):δ=7.4～7.0(m,25H,Ph-H),3.3～3.4(m,1H,CH),2.4～2.5(m,2H,CH
2);
31P NMR(CDCl
3)δ=22.2;-2.3.
Part synthetic example 3: ligand L
3the synthesis of (R=Cy, R '=Ph)
Preparation method is with embodiment 1, and difference is propane diols to replace with cyclohexyl ethylene glycol, and other conditions are constant.Productive rate 75%.
1H NMR(400MHz,CDCl
3):δ=7.24～7.15(m,20H),2.20-2.16(m,1H),2.02-1.98(m,2H),1.83-1.79(m,1H),1.60-1.03(m,10H);
31P NMR(CDCl
3)δ=2.7;–22.1.
Embodiment 3: complex C
1synthesis
The part that the present embodiment uses synthesizes by following synthetic route:
By CrCl
3(THF)
3(1.5mmol) ligand L is added
1(1.5mmol) CH
2cl
2(3mL) in solution.Stir after 4 hours, concentrated solvent, add n-hexane and be namely settled out a large amount of blue solid.After n-hexane, drain solvent and obtain blue Cr complex C
1, productive rate 95%.
Polymerization experiment:
Embodiment 4
Adopt 300mL stainless steel polymeric kettle.Autoclave is heated to 80 DEG C, vacuumizes the displacement of rear nitrogen for several times, be then filled with ethene displacement once, be down to design temperature.Hexahydrotoluene is added at 40 DEG C, add part in 3.3 μm of ol part synthetic examples 1 and chromium trichloride 3.3 μm of ol and co-catalyst modified methylaluminoxane (MMAO) simultaneously, the cumulative volume of mixed liquor is 100mL, wherein the mol ratio of part, chromic salts and co-catalyst is 1:1:500, control reaction pressure 4.0MPa, pass into ethene, carry out ethylene tetramerization reaction.
React after 0.5 hour, system is cooled to room temperature, and gaseous products be collected in aerometer measuring tank, liquid-phase product is collected in conical flask, adds 1mL ethanol as terminator, stops ethylene tetramerization reaction.The laggard promoting the circulation of qi analysis of hplc of liquid phase gauging of products.
Record reaction result as shown in table 1: catalytic activity is 1577kg/gCrh, 1-Octenes selectivity be the selective of 68.7%, 1-hexene is 14.6%.
Embodiment 5
The pressure of polymerisation is replaced with 1.0MPa, and other conditions are with Polymerization Example 1; Record reaction result as shown in table 1: catalytic activity is 899kg/gCrh, 1-Octenes selectivity be the selective of 60.6%, 1-hexene is 16.8%.
Embodiment 6
The pressure of polymerisation is replaced with 6.0MPa, and other conditions are with Polymerization Example 1; Record reaction result as shown in table 1: catalytic activity is 1903kg/gCrh, 1-Octenes selectivity be the selective of 71.5%, 1-hexene is 12.9%.
Embodiment 7
The temperature of polymerisation is replaced with 0 DEG C, and other conditions are with Polymerization Example 1; Record reaction result as shown in table 1: catalytic activity is 652kg/gCrh, 1-Octenes selectivity be the selective of 48.3%, 1-hexene is 26.3%.
Embodiment 8
The temperature of polymerisation is replaced with 80 DEG C, and other conditions are with Polymerization Example 1; Record reaction result as shown in table 1: catalytic activity is 1150kg/gCrh, 1-Octenes selectivity be the selective of 63.4%, 1-hexene is 17.0%.
Embodiment 9
The addition of Cr is identical with embodiment 1, and change Al/Cr mol ratio into 100 by the addition changing aluminium, other conditions are with Polymerization Example 1; Record reaction result as shown in table 1: catalytic activity is 708kg/gCrh, 1-Octenes selectivity be the selective of 55.1%, 1-hexene is 15.4%.
Embodiment 10
Being changed by chromium trichloride in Polymerization Example 1 is three-(oxolane) chromium trichloride (Cr (THF)
3cl
3), other conditions are with Polymerization Example 1; Record reaction result as shown in table 1: catalytic activity is 1836kg/gCrh, 1-Octenes selectivity be the selective of 70.2%, 1-hexene is 19.7%.
Embodiment 11
Chromium trichloride in Polymerization Example 1 is changed as chromium acetylacetonate (Cr (acac)
3), other conditions are with Polymerization Example 1; Record reaction result as shown in table 1: catalytic activity is 1697kg/gCrh, 1-Octenes selectivity be the selective of 69.8%, 1-hexene is 20.4%.
Embodiment 12
Change the modified methylaluminoxane in Polymerization Example 1 for MAO (MAO), other conditions are with Polymerization Example 1; Record reaction result as shown in table 1: catalytic activity is 1344kg/gCrh, 1-Octenes selectivity be the selective of 66.0%, 1-hexene is 18.6%.
Embodiment 13
MAO in Polymerization Example 1 is changed as triethyl aluminum (AlEt
3), other conditions are with Polymerization Example 1; Record reaction result as shown in table 1: catalytic activity is 438kg/gCrh, 1-Octenes selectivity be the selective of 61.5%, 1-hexene is 16.5%.
Embodiment 14
Change the part of part synthetic example 1 into part in part synthetic example 2, other conditions are with Polymerization Example 1; Record reaction result as shown in table 1: catalytic activity is 937kg/gCrh, 1-Octenes selectivity be the selective of 70.8%, 1-hexene is 19.8%.
Embodiment 15
Change the part of part synthetic example 1 into part in part synthetic example 3, other conditions are with Polymerization Example 1; Record reaction result as shown in table 1: catalytic activity is 1097kg/gCrh, 1-Octenes selectivity be the selective of 72.2%, 1-hexene is 20.5%.
Embodiment 16
Adopt 300mL stainless steel polymeric kettle.Autoclave is heated to 80 DEG C, vacuumizes the displacement of rear nitrogen for several times, be then filled with ethene displacement once, be down to design temperature.At 40 DEG C, add hexahydrotoluene, add the complex C in 3.3 μm of ol complex synthetic examples simultaneously
1and co-catalyst modified methylaluminoxane (MMAO), the cumulative volume of mixed liquor is 100mL, and wherein the mol ratio of complex and co-catalyst is 1:500, controls reaction pressure 4.0MPa, passes into ethene, carry out ethylene tetramerization reaction.
React after 0.5 hour, system is cooled to room temperature, and gaseous products be collected in aerometer measuring tank, liquid-phase product is collected in conical flask, adds 1mL ethanol as terminator, stops ethylene tetramerization reaction.The laggard promoting the circulation of qi analysis of hplc of liquid phase gauging of products.
Record reaction result as shown in table 1: catalytic activity is 1720kg/gCrh, 1-Octenes selectivity be the selective of 70.1%, 1-hexene is 21.3%.
Table 1
Claims (10)
1., for a catalyst for ethylene tetramerization composition, comprise such as formula the diphosphine ligand shown in I, transistion metal compound and co-catalyst;
Wherein, in formula I, R and R ' is selected from alkyl, cycloalkyl, monocycle and polyaromatic independently of one another.
2. carbon monoxide-olefin polymeric according to claim 1, is characterized in that, described alkyl is C
1~ C
20straight chain or branching saturated alkyl, preferred C
1~ C
10straight chain or branching saturated alkyl, more preferably C
1~ C
6straight chain or branching saturated alkyl, preferred from following group further: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, sec-amyl, isopentyl, n-hexyl, Sec-Hexyl, isohesyl, n-heptyl and isomers thereof; Most preferable, ethyl, n-pro-pyl, isopropyl, normal-butyl or isobutyl group.
3. carbon monoxide-olefin polymeric according to claim 1 and 2, is characterized in that, described cycloalkyl is C
3~ C
10cycloalkyl, preferred C
3~ C
6cycloalkyl, further preferred cyclopropyl, cyclopenta or cyclohexyl.
4. the carbon monoxide-olefin polymeric according to any one of claim 1-3, is characterized in that, described monocycle and polyaromatic are C
6~ C
20monocycle or polycyclic aromatic group, the carbon atom preferably on wherein one or more rings by the hybrid atom MCM-41 of oxygen, nitrogen and/or sulphur, or by halogen and/or C
1~ C
20alkyl replaces; Preferred phenyl or substituted-phenyl, naphthyl or pyridine radicals, most preferably phenyl or substituted-phenyl further.
5. the carbon monoxide-olefin polymeric according to any one of claim 1-4, it is characterized in that, described transistion metal compound is selected from the compound of chromium, molybdenum, iron, titanium, zirconium or nickel, is preferably chromium chloride, chromium acetylacetonate, isooctyl acid chromium or three (oxolane) chromium trichloride.
6. the carbon monoxide-olefin polymeric according to any one of claim 1-4, it is characterized in that, described co-catalyst is selected from alkyl aluminum compound or aluminium alkoxide compound, one or more in preferred trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, ethyl aluminum dichloride, MAO, ethylaluminoxane or modified methylaluminoxane, most preferably modified methylaluminoxane, MAO and/or triethyl aluminum.
7. the carbon monoxide-olefin polymeric according to any one of claim 1-6, it is characterized in that, the mol ratio of described part, transistion metal compound and co-catalyst is 1:0.1 ~ 10:1 ~ 1000, is preferably 1:0.25 ~ 2:50 ~ 700, is more preferably 1:0.5 ~ 2:100 ~ 500.
8. use the carbon monoxide-olefin polymeric according to any one of claim 1-7 to carry out a method for ethylene tetramerization, under being included in the existence of described carbon monoxide-olefin polymeric and organic solvent, ethene is carried out four poly-reactions.
9. method according to claim 8, is characterized in that, the reaction temperature of described ethylene tetramerization is 0 ~ 200 DEG C; Reaction pressure 0.1 ~ 20MPa.
10. method according to claim 8 or claim 9, it is characterized in that, described organic solvent is the organic solvent being selected from aliphatic hydrocarbon or aromatic hydrocarbons, wherein, the at least one of aliphatic hydrocarbon compound preferably in following compound: linear paraffin, branched paraffin or cycloalkane, preferred pentane, heptane, cyclohexane or hexane; At least one of arene compounds preferably in following compound: benzene,toluene,xylene, monochlor-benzene, dichlorobenzene, trichloro-benzene or monochlorotoluene and derivative thereof.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107282133A (en) * | 2016-03-31 | 2017-10-24 | 中国石油化工股份有限公司 | Catalyst for ethylene tetramerization composition and application |
| CN107282125A (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 its application |
| CN109701660A (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 |
| CN113583053A (en) * | 2020-04-30 | 2021-11-02 | 中国石油化工股份有限公司 | Metal complex, catalyst for ethylene oligomerization and application thereof |
| CN113600244A (en) * | 2021-08-06 | 2021-11-05 | 山东京博石油化工有限公司 | Catalyst for synthesizing 1-octene and application thereof |
| CN116328832A (en) * | 2021-12-24 | 2023-06-27 | 中国石油化工股份有限公司 | Organic polymer carrier, main catalyst, ethylene polymerization catalyst composition and application thereof |
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| CN1741849A (en) * | 2002-12-20 | 2006-03-01 | Sasol技术股份有限公司 | Tetramerization of olefins |
| US20060128910A1 (en) * | 2002-12-20 | 2006-06-15 | Kevin Blann | Tandem tetramerisation-polymerisation of olefins |
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Patent Citations (2)
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| CN1741849A (en) * | 2002-12-20 | 2006-03-01 | Sasol技术股份有限公司 | Tetramerization of olefins |
| US20060128910A1 (en) * | 2002-12-20 | 2006-06-15 | Kevin Blann | Tandem tetramerisation-polymerisation of olefins |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107282133A (en) * | 2016-03-31 | 2017-10-24 | 中国石油化工股份有限公司 | Catalyst for ethylene tetramerization composition and application |
| CN107282125A (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 its application |
| CN107282133B (en) * | 2016-03-31 | 2020-02-18 | 中国石油化工股份有限公司 | Ethylene tetramerization catalyst composition and application |
| CN107282125B (en) * | 2016-03-31 | 2020-05-12 | 中国石油化工股份有限公司 | Ethylene tetramerization catalyst composition and application thereof |
| CN109701660A (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 |
| CN109701660B (en) * | 2017-10-26 | 2021-12-21 | 中国石油化工股份有限公司 | Catalyst composition and application thereof |
| CN113583053A (en) * | 2020-04-30 | 2021-11-02 | 中国石油化工股份有限公司 | Metal complex, catalyst for ethylene oligomerization and application thereof |
| CN113583053B (en) * | 2020-04-30 | 2023-12-08 | 中国石油化工股份有限公司 | Metal complex, catalyst for ethylene oligomerization and application thereof |
| CN113600244A (en) * | 2021-08-06 | 2021-11-05 | 山东京博石油化工有限公司 | Catalyst for synthesizing 1-octene and application thereof |
| CN116328832A (en) * | 2021-12-24 | 2023-06-27 | 中国石油化工股份有限公司 | Organic polymer carrier, main catalyst, ethylene polymerization catalyst composition and application thereof |
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