CN106117396A - Three-dimensional porous organic polymer part list cyclopentadienyl chromic compound and application thereof - Google Patents
Three-dimensional porous organic polymer part list cyclopentadienyl chromic compound and application thereof Download PDFInfo
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- CN106117396A CN106117396A CN201610464477.4A CN201610464477A CN106117396A CN 106117396 A CN106117396 A CN 106117396A CN 201610464477 A CN201610464477 A CN 201610464477A CN 106117396 A CN106117396 A CN 106117396A
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- Prior art keywords
- organic polymer
- porous organic
- cyclopentadienyl
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- dimensional porous
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- 229920000620 organic polymer Polymers 0.000 title claims abstract description 37
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 title claims abstract description 36
- 150000001875 compounds Chemical class 0.000 title claims abstract description 35
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005977 Ethylene Substances 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 11
- -1 alkyl aluminium halide Chemical class 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- 125000001424 substituent group Chemical group 0.000 claims description 18
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 239000002585 base Substances 0.000 claims description 13
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 13
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical group 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical group CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002685 polymerization catalyst Substances 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000012968 metallocene catalyst Substances 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- 241001191009 Gymnomyza Species 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001638 boron Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NVKDFGCILHNHRS-UHFFFAOYSA-N C1(C=CC=C1)[Au] Chemical compound C1(C=CC=C1)[Au] NVKDFGCILHNHRS-UHFFFAOYSA-N 0.000 description 1
- TZSUMGXYCFAANX-UHFFFAOYSA-N C1(C=CC=C1)[Cr] Chemical class C1(C=CC=C1)[Cr] TZSUMGXYCFAANX-UHFFFAOYSA-N 0.000 description 1
- LWMKDBLYUJZWJX-UHFFFAOYSA-N C[Cr](C)(C)(C)(C)C1C=CC=C1.Br.Br Chemical compound C[Cr](C)(C)(C)(C)C1C=CC=C1.Br.Br LWMKDBLYUJZWJX-UHFFFAOYSA-N 0.000 description 1
- LGOJDFAQYHGBAM-UHFFFAOYSA-N C[Cr](C)(C)(C)(C)C1C=CC=C1.Cl.Cl Chemical compound C[Cr](C)(C)(C)(C)C1C=CC=C1.Cl.Cl LGOJDFAQYHGBAM-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LLXJSERYGGMIJY-UHFFFAOYSA-L Cl[Cr](C1C=CC=C1)Cl Chemical compound Cl[Cr](C1C=CC=C1)Cl LLXJSERYGGMIJY-UHFFFAOYSA-L 0.000 description 1
- 241001443715 Fusarium oxysporum f. sp. conglutinans Species 0.000 description 1
- GULNLELHSGQSKR-UHFFFAOYSA-L [Cl-].[Cl-].[Cr++]C1C=Cc2ccccc12 Chemical compound [Cl-].[Cl-].[Cr++]C1C=Cc2ccccc12 GULNLELHSGQSKR-UHFFFAOYSA-L 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002469 indenes Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- BPELEZSCHIEMAE-UHFFFAOYSA-N salicylaldehyde imine Chemical compound OC1=CC=CC=C1C=N BPELEZSCHIEMAE-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63912—Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/6392—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/63922—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/63925—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2420/00—Metallocene catalysts
- C08F2420/04—Cp or analog not bridged to a non-Cp X ancillary anionic donor
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Three-dimensional porous organic polymer part list cyclopentadienyl chromic compound of the present invention and application thereof, belongs to the technical field of porous organic polymer material.Described three-dimensional porous organic polymer part list cyclopentadienyl chromic compound has a following general structure:
Description
Technical field
The invention belongs to the technical field of porous organic polymer material, particularly to a kind of three-dimensional porous organic polymer
The preparation of part list cyclopentadienyl chromic compound and answering in terms of catalysed olefin polymerization, particularly catalyzed ethylene polymerization reaction thereof
With.
Background technology
Polyolefin products due to have cheap, be easily worked, the advantage such as good mechanical property, application are wide, by extensively
The general every field being applied to human being's production and life, has become as the synthesis macromolecular material that human society usage amount is maximum.
Along with development and the progress of technology of society, people are also improving constantly for the kind of polyolefin products and the requirement of quality,
It is thus desirable to continually develop new polyolefin products.The technical merit producing polyolefin products depends primarily on used catalyst,
Currently used catalyst can be divided into three major types: traditional Ziegler-Natta catalyst, metallocene catalyst and Nonmetallocene
Catalyst.Wherein metallocene catalyst belongs to single centre olefin polymerization catalysis, has that catalysis activity is high, polymer architecture is equal
One, molecular weight distribution is narrow, can design the advantages such as catalyst structure as required, has been the world since eighties of last century nineties
In the range of the emphasis of main oil company's developmental research, had multiple metallocene-polyolefin launch products.But, cyclopentadienyl gold
Metal catalyst also has the shortcoming that it is intrinsic, and one is that most metallocene catalyst is required for a large amount of MAOs (MAO)
Or four (phenyl-pentafluoride base) boron salt of costliness/alkyl aluminum composite catalyst activation so that the cost of metallocene-polyolefin product
High;Two be metallocene catalyst be homogeneous catalyst, it is impossible to directly apply on commercial plant, need supported after
Can apply to commercial plant, the supported challenge brought of homogeneous catalyst is that catalysis activity is decreased obviously, it will usually decline
An order of magnitude.Another shortcoming using above-mentioned carrier loadedization catalyst is to introduce a large amount of ash in polymeric articles
Point.If synthesis one can be designed from solid-carrying type (need not carrier) and can only use alkane as Ziegler-Natta catalyst
The catalyst of base aluminum activation [not using MAO and four (phenyl-pentafluoride base) boron salt] just energy highly active catalytic olefinic polyreaction, just
It is expected to overcome the disadvantages mentioned above of metallocene catalyst.
In recent years, applicant seminar is devoted to develop this kind of olefin polymerization catalysis always, and it is gratifying to achieve some
Progress.Applicant seminar in 2007 develop a class only with the activation of a small amount of alkyl aluminum can highly active catalytic vinyl polymerization anti-
The mono-metallocene chrome catalysts (Chinese invention patent CN 101029096A) answered, its concrete structure is shown below:
As it was previously stated, this type of catalyst is homogeneous single chromium catalyst, need supported after just can apply to commercial production
Device.In order to find the solution substituting conventional load, within 2015, applicant seminar develops a kind of many containing plane
The mono-metallocene chrome catalysts (Chinese invention patent publication number CN 104892801A) of hole organic polymer part, it is specifically tied
Structure is shown below:
This kind single chromium catalyst containing plane porous organic polymer part is existing skill immediate with the present invention
Art, this kind of catalyst limits due to its inherent structure, and its pore passage structure is mainly polymer plane fold, overlapping generates, and does not has
Standby regular 3 D stereo duct, catalyst form, strength and stability are relatively poor.In order to develop performance preferably this type of from
Immobilized AlCl_3 catalyst, needs to transform the structure of porous organic polymer part, to obtaining form, strength and stability
Preferably from solid-carrying type metallocene catalyst.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes deficiency present in background technology, it is provided that a kind of available alkyl aluminum
Activating catalytic olefinic polymerization, form, strength and stability are preferable, have the porous organic polymer part list of 3-D solid structure
Cyclopentadienyl chromic compound, and the preparation method of this coordination compound and its in catalysed olefin polymerization particularly ethylene polymerization
Application.
In order to solve above-mentioned technical problem, the present invention by the following technical solutions:
A kind of three-dimensional porous organic polymer part list cyclopentadienyl chromic compound, has a following general structure:
Wherein, cyclopentadienyl ring is non-substituted, monosubstituted or polysubstituted cyclopentadienyl group, or by polysubstituted cyclopentadiene
Base group is interconnected to condensed ring by two adjacent substituents, generates indenyl, substituted indenyl, fluorenyl or replaces fluorenyl groups,
Substituent R1~R5Selected from hydrogen, alkyl, aryl, alkenyl, aIkylsilyl groups or alkenyl silyl group;Substituent R6
It is alkyl, aryl, substituted aryl, aryl alkyl or silyl group;X is halogen, alkoxyl, amido, alkyl, aryl, alkene
Base, aryl alkyl or silyl group;N is the natural number more than 1.
In the one three-dimensional porous organic polymer part list cyclopentadienyl chromic compound of the present invention, described substituent R1~R5Excellent
Hydrogen, methyl, phenyl or aIkylsilyl groups group, described substituted indenyl preferred methyl substituted indenyl or phenyl is selected to replace indenes
Base;The described preferred methyl of replacement fluorenyl replaces fluorenyl or phenyl replaces fluorenyl;Substituent R6Preferably alkyl, aryl or replacement virtue
Base group;The preferred halogen of X, methyl, phenyl, benzyl, trimethyl silicane ylmethyl or neopentyl group.
In the one three-dimensional porous organic polymer part list cyclopentadienyl chromic compound of the present invention, described substituent R1~R5Enter
The one preferred hydrogen of step, methyl or phenyl group, described substituted indenyl further preferred methyl substituted indenyl;Described replacement fluorenyl
Further preferably methyl replaces fluorenyl;Substituent R6Further preferably alkyl or aryl group;The further preferred halogen of X, methyl,
Benzyl group.
In the one three-dimensional porous organic polymer part list cyclopentadienyl chromic compound of the present invention, described substituent R1~R5More
Further preferably hydrogen or methyl group;Substituent R6The further preferably tert-butyl group, adamantyl or phenyl group;X more enters one
Walk preferred halogen.
Three-dimensional porous organic polymer part and single cyclopentadienyl chromic compound thereof of the present invention can with those skilled in the art
The various synthesis known have the method for the porous organic polymer of similar structures unit and synthesize containing salicylaldimine ligand list
The method synthesis of cyclopentadienyl chromium class coordination compound, it is possible to reference to embodiments of the invention 1~2-in-1 one-tenth.
The purposes of a kind of three-dimensional porous organic polymer part list cyclopentadienyl chromic compound, it is characterised in that with described three-dimensional
Porous organic polymer part list cyclopentadienyl chromic compound is major catalyst, urges with alkyl aluminum, alkyl aluminium halide or its mixture for helping
Agent, reacts for catalyzed ethylene polymerization;Described alkyl aluminum is trimethyl aluminium, triethyl aluminum or triisobutyl aluminium, described
Alkyl aluminium halide is diethyl aluminum chloride or sesquialter aluminium ethide;In promoter in aluminum and major catalyst the mol ratio of chromium be 5~
10000:1;Concretely comprise the following steps: under vinyl monomer existence condition, add major catalyst and promoter to polymeric kettle ,-20
DEG C~the ethylene pressure of the reaction temperature of 200 DEG C and 1~200 atmospheric pressure under the conditions of react 30~720 minutes, polyreaction tie
Shu Hou, the polymer acid solution washing that will obtain, dry to constant weight in 60 DEG C in vacuum drying oven.
In the purposes of a kind of three-dimensional porous organic polymer part list cyclopentadienyl chromic compound of the present invention, in promoter aluminum with
The mol ratio of chromium preferably 50~500:1 in major catalyst.
In the purposes of a kind of three-dimensional porous organic polymer part list cyclopentadienyl chromic compound of the present invention, described reaction temperature
Preferably 0 DEG C~80 DEG C, preferably 5 atmospheric pressure of described ethylene pressure.
The present invention has a following beneficial effect:
1, the three-dimensional porous organic polymer part list cyclopentadienyl chromic compound of the present invention is as from solid-carrying type olefinic polymerization catalysis
Agent has that form is good, intensity big, good stability, feature without inorganic impurity (carrier).
2, the three-dimensional porous organic polymer part list cyclopentadienyl chromic compound of the present invention is as olefin polymerization catalyst, only
Need to activate with alkyl aluminum, it is not necessary to use expensive MAO and four (phenyl-pentafluoride base) boron salt promoter, can effectively reduce catalysis alkene
The cost of polymerized hydrocarbon.
3, the three-dimensional porous organic polymer part list cyclopentadienyl chromic compound of the present invention is as olefin polymerization catalyst, tool
There are catalysis activity height, life-span length, feature that polymer molecular weight is high.
Detailed description of the invention
Further illustrate the present invention below by embodiment, but the scope of the present invention is not limited to listed embodiment.
The synthesis of embodiment 1 three-dimensional porous organic polymer part
300mg (0.79mmol) four (4-aminophenyl) methane, 1.58mmol3,3 '-two formyl is added in 25ml flask
Base-5,5 '-two replacement (R6)-4,4 '-dihydroxybiphenyl, the anhydrous DMSO of 25mL (with front warp newly activate 4A molecular sieve soak 3 days with
On).Reactant mixture reacts 12 hours respectively through procedural intensification in 70 DEG C of oil baths, 100 DEG C of reactions one day, then
React two days at 120 DEG C.Yellow solid reaction obtained filters, with THF, DMF, CH3After the washing of OH equal solvent, gained solid
With THF, CH3The each surname extraction of OH 6 hours, then at 120 DEG C, vacuum drains solvent, obtains yellow solid powdery product.
Wherein substituent R 6 takes the tert-butyl group respectivelytBu, adamantyl Ad and phenyl Ph, obtain three kinds of parts and be designated as respectively: ligand 1 (R6=
The tert-butyl grouptBu), productivity 96%;Part 2 (R6=adamantyl Ad), productivity 92%;Part 3 (R6=phenyl Ph), productivity 89%.
The synthesis of embodiment 2 three-dimensional porous organic polymer part list cyclopentadienyl chromic compound
In a nitrogen atmosphere, 120mg ligand 1,157mg part 2 or 129mg part 3 (all containing 0.47mmol OH) are dissolved in
In 20mL dry toluene, at-60 DEG C, add 0.47mmol n-BuLi, be warmed to room temperature and stir 2 hours.By reactant mixture
Being cooled to-60 DEG C, addition pentamethyl cyclopentadienyl chromium dichloride Han 0.47mmol (being designated as A), pentamethyl cyclopentadienyl chromium dibromide (are designated as
B), the oxolane of cyclopentadienyl chromium dichloride (being designated as C), indenyl chromium dichloride (being designated as D) or fluorenyl chromium dichloride (being designated as E) is molten
Liquid, rises to assigned temperature (20,40,60 or 80 DEG C) and stirs reaction certain time (20,48 or 96 hours) afterwards, be filtered to remove molten
Agent.The solid product oxolane washing being dried, the lower 140 DEG C of heating of vacuum condition remove solvent in 4 hours, obtain porous organo polysilica
Compound ligand-complexes product.Cr weight/mass percentage composition in coordination compound is recorded by icp analysis.Pass through specific surface area analysis
Record the specific surface area of coordination compound.13 coordination compound samples of synthesis altogether, experimental result is shown in Table 1.
Table 1 single cyclopentadienyl chromic compound compound experiment result summary sheet
Embodiment 3 catalyzed ethylene polymerization reacts
Polyreaction is carried out in 250mL autoclave, uses the porous organic polymer of preparation in above-described embodiment 2
Part list cyclopentadienyl chromic compound 1~13 is promoter as major catalyst, alkyl aluminum and haloalkyl aluminum.React before polyreaction
Still under vacuo 120 DEG C toast 1 hour, be filled with an atmospheric pressure ethylene gas.Under ethylene atmosphere, first by 50mL containing co-catalysis
The toluene solution of agent adds in reactor, and the toluene solution that 10mL contains major catalyst (Cr content 3umol) the most again adds anti-
Answer in device, ethylene pressure is risen to 5 atmospheric pressure, and starts timing.Reaction is vented ethylene gas in reactor after terminating, and uses
HCI/ methanol solution terminates polyreaction.Being leached by polymer and fully wash the removal of impurity with water and methanol, 60 DEG C of vacuum are done
Dry to constant weight.Ubbelohde capillary viscosimeter is utilized to measure polymer intrinsic viscosity also in 135 scholar 0.1 DEG C in decahydro Cai
Calculate polymer viscosity-average molecular weight.Reaction result is shown in Table 2.
Table 2 catalyzed ethylene polymerization experimental result summary sheet
Claims (7)
1. a three-dimensional porous organic polymer part list cyclopentadienyl chromic compound, has a following general structure:
Wherein, cyclopentadienyl ring is non-substituted, monosubstituted or polysubstituted cyclopentadienyl group, or by polysubstituted cyclopentadienyl group base
Group is interconnected to condensed ring by two adjacent substituents, generates indenyl, substituted indenyl, fluorenyl or replaces fluorenyl groups, replacing
Base R1~R5Selected from hydrogen, alkyl, aryl, alkenyl, aIkylsilyl groups or alkenyl silyl group;Substituent R6It is alkane
Base, aryl, substituted aryl, aryl alkyl or silyl group;X is halogen, alkoxyl, amido, alkyl, aryl, alkenyl, virtue
Base alkyl or silyl group;N is the natural number more than 1.
One the most according to claim 1 three-dimensional porous organic polymer part list cyclopentadienyl chromic compound, it is characterised in that institute
The substituent R stated1~R5Selected from hydrogen, methyl, phenyl or aIkylsilyl groups group, described substituted indenyl is that methyl replaces indenes
Base or phenyl substituted indenyl;Described replacement fluorenyl is that methyl replaces fluorenyl or phenyl replaces fluorenyl;Substituent R6It is alkyl, virtue
Base or substituted aryl group;X is halogen, methyl, phenyl, benzyl, trimethyl silicane ylmethyl or neopentyl group.
One the most according to claim 1 three-dimensional porous organic polymer part list cyclopentadienyl chromic compound, it is characterised in that institute
The substituent R stated1~R5Selected from hydrogen, methyl or phenyl group, described substituted indenyl is methyl substituted indenyl;Described replacement
Fluorenyl is that methyl replaces fluorenyl;Substituent R6It it is alkyl or aryl group;X is halogen, methyl, benzyl group.
4. according to the arbitrary described one three-dimensional porous organic polymer part list cyclopentadienyl chromic compound of claims 1 to 3, its feature
It is, described substituent R1~R5Selected from hydrogen or methyl group;Substituent R6It is the tert-butyl group, adamantyl or phenyl group;X
It it is halogen.
5. the purposes of the three-dimensional porous organic polymer part list cyclopentadienyl chromic compound of a claim 1, it is characterised in that with power
Profit requires that the three-dimensional porous organic polymer part list cyclopentadienyl chromic compound described in 1 is major catalyst, with alkyl aluminum, alkyl aluminium halide
Or its mixture is promoter, react for catalyzed ethylene polymerization;Described alkyl aluminum is trimethyl aluminium, triethyl aluminum or three
Aluminium isobutyl, described alkyl aluminium halide is diethyl aluminum chloride or sesquialter aluminium ethide;In promoter in aluminum and major catalyst
The mol ratio of chromium is 5~10000:1;Concretely comprise the following steps: under vinyl monomer existence condition, to polymeric kettle add major catalyst and
Promoter, reacts 30~720 under the conditions of the ethylene pressure of-20 DEG C~the reaction temperature of 200 DEG C and 1~200 atmospheric pressure
Minute, after polyreaction terminates, the polymer acid solution washing that will obtain, dry to permanent in 60 DEG C in vacuum drying oven
Weight.
The purposes of a kind of three-dimensional porous organic polymer part list cyclopentadienyl chromic compound the most according to claim 5, its feature
Being, in promoter, aluminum is 50~500:1 with the mol ratio of chromium in major catalyst.
7., according to the purposes of a kind of three-dimensional porous organic polymer part list cyclopentadienyl chromic compound described in claim 5 or 6, it is special
Levying and be, described reaction temperature is 0 DEG C~80 DEG C, and described ethylene pressure is 5 atmospheric pressure.
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