CN103100420A - Catalyst composition for ethylene tetramerization and preparation method of ligand thereof - Google Patents
Catalyst composition for ethylene tetramerization and preparation method of ligand thereof Download PDFInfo
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- CN103100420A CN103100420A CN2011103517764A CN201110351776A CN103100420A CN 103100420 A CN103100420 A CN 103100420A CN 2011103517764 A CN2011103517764 A CN 2011103517764A CN 201110351776 A CN201110351776 A CN 201110351776A CN 103100420 A CN103100420 A CN 103100420A
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Abstract
The invention provides a catalyst composition for ethylene tetramerization. The catalyst composition comprises a ligand shown as a formula (I), a transition metal compound and a catalyst promoter. The invention also provides a preparation method of the ligand and an ethylene tetramerization process. The catalyst composition for ethylene tetramerization provided by the invention can produce 1-hexene in high selectivity, and selectivity of 1-octene is higher than 70%.
Description
Technical field
The present invention relates to the ethylene oligomerization field, be specifically related to a kind of for the poly-carbon monoxide-olefin polymeric of ethene four.The invention still further relates to the preparation method of part in this carbon monoxide-olefin polymeric and the application of composition.
Background technology
The 1-octene is as important Organic Ingredients and chemical intermediate, mainly for the production of high-quality polyethylene (PE).Can significantly be improved the properties of PE by the LLDPE (LLDPE) of 1-octene and ethylene copolymer production, particularly poly mechanical performance, optical property and tear strength and impact strength all are significantly increased, be very suitable for the agricultural mulch films such as packaging film and greenhouse, canopy chamber etc., the 1-octene is also 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 the 1-octene with high selectivity at present as ethylene trimer is produced the 1-hexene.Traditional 1-production of octenes method is the ethylene oligomerization method, the ethylene oligomerization technology distributes according to Schulz-Flory, not only obtains 1-octene product, also has simultaneously other alpha-olefins and a small amount of solid superpolymer, and purpose product 1-octene is selectively very low, is no more than 30%.For example the SHOP method (US3676523) that adopts of Shell company uses the nickel-metal catalyst system to carry out the ethylene oligomerization reaction, can obtain 11% 1-octene; United States Patent (USP) (US6184428) report uses a kind of nickel compound as the catalyst ethylene oligomerization, and the yield of 1-octene is 19%.Japan Patent JP2002121157 has reported that the use zirconium metal catalyzer carries out the ethylene oligomerization reaction, and wherein the content of 1-octene is approximately 15%.The poly-three-way catalyst system of ethene four of report can be synthesized the 1-octene by highly selective recently, it is poly-as patent application CN1741850A (WO2004/056478A1), CN1741849A (WO2004/056479A1), CN101032695A, CN101351424A, CN101415494A, CN1651142A, CN101291734A and patent application US2006/0128910A1, use P-N-P part and chromium coordination catalysis ethene four to be disclosed all, but highly selective is produced the 1-octene, and in product, the content of 1-octene even can be greater than 70%.Patent application CN101605605A discloses that to utilize the chromium-based catalysts that contains P-C-C-P skeleton structure part to be used for ethene four poly-, thereby highly selective has prepared the 1-octene, selectively the highest can be greater than 70%.
In view of containing the application of phosphine part in ethene four is poly-, the present inventor has found a kind of for the poly-novel catalyst of ethene four, this system bag P-N-P-N-P matrix type part, transistion metal compound and co-catalyst.Further found to prepare the method for this catalyst ligand.Use the effectively poly-reaction of catalyzed ethylene four of this catalyst system and catalyzing, catalyst has the characteristics such as high activity and high selectivity, and wherein the 1-octene selectively can surpass 70%.
Summary of the invention
The invention provides the poly-catalyst system of ethene four that comprises Novel Ligands, when using this catalyst system to carry out ethene four poly-reaction, can high selectivity obtain the 1-octene.
One of purpose of the present invention is to provide the poly-carbon monoxide-olefin polymeric of a kind of ethene four, comprises heteroatom ligand, transistion metal compound and three components of co-catalyst, and the structural formula of described heteroatom ligand is as follows:
R in formula
1, R
2Identical or different, be selected from replacement or unsubstituted monocycle and polyaromatic; R
3Be selected from alkyl, cycloalkyl, monocycle and polyaromatic.
In the present invention, term " alkyl " refers to 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.Described alkyl can relate to 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 the present invention, term " monocycle and polyaromatic " refers to C
6~C
20Monocycle or polycyclic aromatic group, and the carbon atom on optional wherein one or more rings is selected from the hetero atom replacement of oxygen, nitrogen and sulphur.Described
" monocycle and polyaromatic " also can be by halogen or C
1-C
20Alkyl replaces.Described " monocycle and polyaromatic " preferred phenyl, naphthyl or pyridine radicals, more preferably phenyl.
In the preferred embodiment of above-mentioned carbon monoxide-olefin polymeric, R in described part
1, R
2Identical or different, be selected from C
6-C
20Aryl is preferably selected from C
6-C
12Aryl more preferably is selected from C
6-C
10Aryl, most preferably phenyl or substituted-phenyl.R
3Be selected from C
1-C
10Alkyl, C
3-C
10Cycloalkyl, monocycle and polyaromatic are preferably selected from C
1-C
6Alkyl, C
3-C
6Cycloalkyl, phenyl or substituted-phenyl, more preferably isopropyl, cyclohexyl, cyclopenta, cyclopropyl, phenyl.
In above-mentioned carbon monoxide-olefin polymeric, transistion metal compound can be this area transistion metal compound commonly used, as the compound of chromium, molybdenum, iron, titanium, zirconium or nickel, be preferably chromium acetylacetonate, isooctyl acid chromium or three (oxolane) chromium trichloride etc.
In above-mentioned carbon monoxide-olefin polymeric, co-catalyst can be this area organo-aluminum compound commonly used, as 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 preferable aikyiaiurnirsoxan beta and triethyl aluminum.
In above-mentioned carbon monoxide-olefin polymeric, 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: 10~and 700, more preferably 1: 0.5~2: 100~500.
The present invention also provides the preparation method of a kind of above-mentioned part (I), comprises the steps:
Steps A: in organic solvent, with R
1-PCl
2With R
3-NH
2Hybrid reaction is reacted complete desolventizing, obtains compound (II);
Step B: in organic solvent, make compound (II) and (R
2)
2Complete desolventizing is reacted in-PCl reaction, namely obtains heteroatom ligand (I).
R wherein
1, R
2, R
3With the definition in the ligand structure of carbon monoxide-olefin polymeric.Wherein in steps A and B, operable organic solvent comprises aliphatic hydrocarbon compound or arene compounds, is preferably carrene, chloroform, ether, toluene, benzene or monochlor-benzene, most preferably carrene or ether.Solvent load gets final product to guarantee that reactant fully dissolves or disperses.
In part preparation method of the present invention, the reaction in steps A and B is-30 ℃ to 100 ℃ in temperature, preferred-10 ℃ to 80 ℃, and most preferably-5 ℃ to 50 ℃; Reaction time is 0.5-20 hour, preferred 5-10 hour.
In preparation method of the present invention, R in steps A
1-PCl
2With R
3-NH
2Mol ratio be 1: 0.5-10, preferred 1: 1-5.Compound in step B (II) and (R
2)
2The mol ratio of-PCl is 1: 0.5-10, preferred 1: 1-5.
Another object of the present invention is to provide a kind of ethene four polymerizing technologies, comprises adopting above-mentioned carbon monoxide-olefin polymeric, comprises the part shown in following formula (I) in wherein said carbon monoxide-olefin polymeric; And ethene four poly-reaction temperatures are 0~200 ℃; Reaction pressure 0.1~20MPa; Ethene four is poly-is the organic solvent that is selected from aliphatic hydrocarbon or aromatic hydrocarbons with solvent.
Wherein, arene compounds comprises benzene,toluene,xylene, monochlor-benzene, dichlorobenzene, trichloro-benzene or monochlorotoluene and derivative thereof; The aliphatic hydrocarbon compound comprises linear paraffin, branched paraffin or cycloalkane, as pentane, heptane, cyclohexane or hexane etc.Solvent load gets final product to guarantee that reactant fully dissolves or disperses.
Described reaction temperature is preferably 0~100 ℃; Preferred 1~the 6MPa of reaction pressure; Described organic solvent is preferably benzene, toluene, monochlor-benzene, pentane, hexane, heptane or cyclohexane.
In above-mentioned ethene four polymerizing technologies, can with in part, transistion metal compound and co-catalyst in carbon monoxide-olefin polymeric any two kinds be pre-mixed, and then join in reaction system together with another kind; Perhaps these three kinds of components of part, transistion metal compound and co-catalyst are joined directly that to carry out original position in reaction system synthetic; Perhaps with after component part, transistion metal compound and co-catalyst premix, directly add in reaction system with form of mixtures.
In above-mentioned ethene four polymerizing technologies, reaction condition can be this area reaction condition commonly used.Optimal conditions is as follows: ethene, organic solvent and described carbon monoxide-olefin polymeric are added in reactor, are then that 1~6Mpa, reaction temperature are reaction under 0~100 ℃ at ethylene pressure, and catalyst concn is 0.05~0.3mmolCr/L.Reaction is cooled to room temperature after finishing, and gets the gas, liquid product and carries out chromatography.
When using carbon monoxide-olefin polymeric provided by the invention to carry out ethene four poly-reaction, can high selectivity produce the 1-octene, the 1-octene selectively can surpass 70%, and in product, the overall selectivity of 1-octene and 1-hexene can surpass 90%.
The specific embodiment
The following example only is used for that 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 1: ligand L
1(R
1=R
2=Ph, R
3=iPr) synthetic
1, under nitrogen protection; add 0.05mol dichlorophenyl phosphine and 200mL anhydrous methylene chloride in round-bottomed flask; stir; ice bath is cooled to 0 ℃; add the 0.1mol isopropylamine, stirring reaction removed by filter insoluble impurities about 10 hours; filtrate is distilled with vacuum pump decompression (10mm mercury column), and obtaining grease is compound (II).
2, under nitrogen protection, add 0.02mol diphenyl phosphine chloride and 50mL anhydrous methylene chloride in round-bottomed flask, stir; ice bath is cooled to 0 ℃, slowly adds the grease in 0.01mol step 1, approximately adds in 1 hour; remove ice bath and rise to room temperature, continue stirring reaction about 10 hours.Remove by filter insoluble impurities, filtrate with vacuum pump decompression (10mm mercury column) distillation desolventizing, is obtained ligand L
1
Productive rate 80%.
1H-NMR(δ,ppm,CDCl
3,TMS):7.1~7.9(m,25H,Ar-H),3.1(m,2H,CH),1.2(d,12H,CH
3)。
Part synthetic example 2: ligand L
2(R
1=R
2=Ph, R
3=Ph) synthetic
The preparation method is with embodiment 1, and difference is isopropylamine is replaced with aniline, and other conditions are constant.Productive rate 75%.
1H-NMR(δ,ppm,CDCl
3,TMS):7.1~7.9(m,35H,Ar-H)。
Part synthetic example 3: ligand L
3(R
1=R
2=Ph, R
3=Cy) synthetic
The preparation method is with embodiment 1, and difference is isopropylamine is replaced with cyclohexylamine, and other conditions are constant.Productive rate 81%.
1H-NMR(δ,ppm,CDCl
3,TMS):7.1~7.9(m,25H,Ar-H),0.7~2.6(m,22H,Cy-H)。
Polymerization embodiment 1
Adopt 300ml stainless steel polymeric kettle.Autoclave is heated to 80 ℃, vacuumize rear with nitrogen replacement for several times, then be filled with ethene and be down to room temperature when ethylene pressure be 2MPa.Then add dehydrated toluene under 30 ℃, add simultaneously part and chromium acetylacetonate 10 μ mol and co-catalyst MAO (MAO) in 10 μ mol part synthetic examples 1, the cumulative volume of mixed liquor is 100mL, wherein the mol ratio of part, chromium acetylacetonate and co-catalyst is 1: 1: 300, control reaction pressure 2.0MPa, pass into ethene, carry out the poly-reaction of ethene four.
React after 1 hour, system is cooled to room temperature, and gaseous products is collected in the aerometer measuring tank, and liquid-phase product is collected in conical 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 gauging of products (chromatograph is Hewlett-Packard 5890).
Record reaction result as follows: catalytic activity is 3150000g/mol Crh, the 1-octene be selectively 71.6%, 1-hexene be selectively 20.9%.
Polymerization embodiment 2
The pressure of polymerisation is replaced with 1.0MPa, and other conditions are with polymerization embodiment 1; Record reaction result as follows: catalytic activity is 2070000g/mol Crh, the 1-octene be selectively 70.5%, 1-hexene be selectively 19.1%.
Polymerization embodiment 3
The pressure of polymerisation is replaced with 5.0MPa, and other conditions are with polymerization embodiment 1; Record reaction result as follows: catalytic activity is 4330000g/mol Crh, the 1-octene be selectively 73.2%, 1-hexene be selectively 21.0%.
Polymerization embodiment 4
The pressure of polymerisation is replaced with 6.0MPa, and other conditions are with polymerization embodiment 1; Record reaction result as follows: catalytic activity is 4590000g/mol Crh, the 1-octene be selectively 73.3%, 1-hexene be selectively 20.8%.
Polymerization embodiment 5
The temperature of polymerisation is replaced with 0 ℃, and other conditions are with polymerization embodiment 1; Record reaction result as follows: catalytic activity is 870000g/mol Crh, the 1-octene be selectively 68.1%, 1-hexene be selectively 19.8%.
Polymerization embodiment 6
The temperature of polymerisation is replaced with 50 ℃, and other conditions are with polymerization embodiment 1; Record reaction result as follows: catalytic activity is 2970000g/mol Crh, the 1-octene be selectively 71.9%, 1-hexene be selectively 21.2%.
Polymerization embodiment 7
The temperature of polymerisation is replaced with 100 ℃, and other conditions are with polymerization embodiment 1; Record reaction result as follows: catalytic activity is 2130000g/mol Crh, the 1-octene be selectively 66.7%, 1-hexene be selectively 19.5%.
Polymerization embodiment 8
The addition of Cr is identical with embodiment 1, changes the Al/Cr mol ratio into 50 by the addition that changes aluminium, and other conditions are with polymerization embodiment 1; Record reaction result as follows: catalytic activity is 620000g/mol Crh, the 1-octene be selectively 67.8%, 1-hexene be selectively 20.4%.
Polymerization embodiment 9
The addition of Cr is identical with embodiment 1, changes the Al/Cr mol ratio into 150 by the addition that changes aluminium, and other conditions are with polymerization embodiment 1; Record reaction result as follows: catalytic activity is 2280000g/mol Crh, the 1-octene be selectively 70.9%, 1-hexene be selectively 20.5%.
Polymerization embodiment 10
The addition of Cr is identical with embodiment 1, changes the Al/Cr mol ratio into 500 by the addition that changes aluminium, and other conditions are with polymerization embodiment 1; Record reaction result as follows: catalytic activity is 4610000g/mol Crh, the 1-octene be selectively 71.5%, 1-hexene be selectively 21.1%.
Polymerization embodiment 11
The addition of Cr is identical with embodiment 1, changes the Al/Cr mol ratio into 1000 by the addition that changes aluminium, and other conditions are with polymerization embodiment 1; Record reaction result as follows: catalytic activity is 4700000g/mol Crh, the 1-octene be selectively 71.8%, 1-hexene be selectively 22.0%.
Polymerization embodiment 12
It is three-(oxolane) chromium trichloride (Cr (THF) that chromium acetylacetonate in polymerization embodiment 1 is changed
3Cl
3), other conditions are with polymerization embodiment 1; Record reaction result as follows: catalytic activity is 2870000g/mol Crh, the 1-octene be selectively 67.6%, 1-hexene be selectively 20.3%.
Polymerization embodiment 13
MAO in polymerization embodiment 1 is changed be triethyl aluminum (AlEt
3), other conditions are with polymerization embodiment 1; Record reaction result as follows: catalytic activity is 990000g/mol Crh, the 1-octene be selectively 65.5%, 1-hexene be selectively 25.7%.
Polymerization embodiment 14
Change the part of part synthetic example 1 in part synthetic example 2 part, other conditions are with polymerization embodiment 1; Record reaction result as follows: catalytic activity is 2910000g/mol Crh, the 1-octene be selectively 71.2%, 1-hexene be selectively 21.7%.
Polymerization embodiment 15
Change the part of part synthetic example 1 in part synthetic example 3 part, other conditions are with polymerization embodiment 1; Record reaction result as follows: catalytic activity is 2850000g/mol Crh, the 1-octene be selectively 71.3%, 1-hexene be selectively 21.2%.
Table 1
Claims (10)
1. one kind is used for the poly-carbon monoxide-olefin polymeric of ethene four, comprises heteroatom ligand, transistion metal compound and three components of co-catalyst, and the structural formula of described heteroatom ligand is as follows:
R wherein
1, R
2Identical or different, be selected from replacement or unsubstituted monocycle and polyaromatic; R
3Be selected from alkyl, cycloalkyl, monocycle and polyaromatic.
2. carbon monoxide-olefin polymeric according to claim 1, is characterized in that: R
1And R
2Be selected from C
6-C
10Aryl; R
3Be selected from C
1-C
10Alkyl, C
3-C
10Cycloalkyl, monocycle and polyaromatic.
3. carbon monoxide-olefin polymeric according to claim 2, is characterized in that: R
1And R
2Be selected from phenyl or substituted-phenyl; R
3Be selected from isopropyl, cyclohexyl, cyclopenta, cyclopropyl, phenyl.
4. the described carbon monoxide-olefin polymeric of any one according to claim 1 to 3, it is characterized in that: described transistion metal compound is chromium acetylacetonate, isooctyl acid chromium or three (oxolane) chromium trichloride.
5. the described carbon monoxide-olefin polymeric of any one according to claim 1 to 3, it is characterized in that: described co-catalyst is organo-aluminum compound, specifically is selected from one or more in MAO, ethylaluminoxane, modified methylaluminoxane, triethyl aluminum and trimethyl aluminium.
6. the described carbon monoxide-olefin polymeric of any one according to claim 1 to 3, it is characterized in that: the mol ratio of described part, transistion metal compound and co-catalyst is 1: 0.5~2: 100~500.
7. the preparation method of a part as described in any one in claim 1 to 6 (I), comprise the steps:
Steps A: in organic solvent, with R
1-PCl
2With R
3-NH
2Hybrid reaction is reacted complete desolventizing, obtains compound (II);
Step B: in organic solvent, make compound (II) and (R
2)
2Complete desolventizing is reacted in-PCl reaction, namely obtains heteroatom ligand (I).
8. preparation method according to claim 7 is characterized in that: the reaction temperature in steps A and B is-5-50 ℃, and the reaction time is 5-10 hour; R in steps A
1-PCl
2With R
3-NH
2Mol ratio be 1: 1-5, compound in step B (II) and (R
2)
2The mol ratio of-PCl is 1: 1-5; Organic solvent described in steps A and B is carrene, chloroform, ether, toluene, benzene or monochlor-benzene.
9. ethene four polymerizing technologies that the described carbon monoxide-olefin polymeric of any one carries out under existing in claim 1~6, wherein, ethene four poly-reaction temperatures are 0~200 ℃; Reaction pressure 0.1~20MPa; Ethene four is poly-is the organic solvent that is selected from aliphatic hydrocarbon or aromatic hydrocarbons with solvent.
10. ethene four polymerizing technologies according to claim 10, described reaction temperature is 0~100 ℃; Reaction pressure 1~6MPa; Described organic solvent is benzene, toluene, monochlor-benzene, pentane, hexane, heptane or cyclohexane.
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JP2016505073A (en) * | 2013-02-11 | 2016-02-18 | サウディ ベーシック インダストリーズ コーポレイション | Process for purifying crude PNPNH compounds |
CN107282126A (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 |
CN108097322A (en) * | 2017-12-11 | 2018-06-01 | 天津科技大学 | It is a kind of for the catalyst system of ethylene selectivity oligomerisation and ethylene oligomerization reaction method |
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CN105080612A (en) * | 2014-05-08 | 2015-11-25 | 中国石油化工股份有限公司 | Aromatic alkylation catalyst composition and application thereof |
CN105080612B (en) * | 2014-05-08 | 2017-12-19 | 中国石油化工股份有限公司 | A kind of aromatic alkylation catalysts composition and application |
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