CN106117396B - Three-dimensional porous organic polymer ligand list cyclopentadienyl chromic compound and application thereof - Google Patents
Three-dimensional porous organic polymer ligand list cyclopentadienyl chromic compound and application thereof Download PDFInfo
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- CN106117396B CN106117396B CN201610464477.4A CN201610464477A CN106117396B CN 106117396 B CN106117396 B CN 106117396B CN 201610464477 A CN201610464477 A CN 201610464477A CN 106117396 B CN106117396 B CN 106117396B
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- 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
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- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic System
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- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic System
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic System compounds without a metal-carbon linkage
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
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- 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
Abstract
The three-dimensional porous organic polymer ligand list cyclopentadienyl chromic compound and application thereof of the present invention, belongs to the technical field of porous organic polymer material.The three-dimensional porous organic polymer ligand list cyclopentadienyl chromic compound has the following structure general formula：
Description
Technical field
The invention belongs to the technical field of porous organic polymer material, more particularly to a kind of three-dimensional porous organic polymer
The preparation of ligand list cyclopentadienyl chromic compound and its answering in terms of catalysed olefin polymerization, particularly catalyzed ethylene polymerization reaction
With.
Background technology
Polyolefin products due to have many advantages, such as it is cheap, be easily worked, good mechanical property, application field it is wide, it is wide
The general every field applied to human being's production and life has become the maximum synthesis high molecular material of human society usage amount.
With the development of society and advancement of technology, requirement of the people for the kind and quality of polyolefin products is also being continuously improved,
Therefore it needs to continually develop new polyolefin products.The technical merit of production polyolefin products depends primarily on used catalyst,
Catalyst used at present can be divided into three categories：Traditional Ziegler-Natta catalyst, metallocene catalyst and Nonmetallocene
Catalyst.Wherein metallocene catalyst belongs to single centre olefin polymerization catalysis, has catalytic activity height, polymer architecture equal
One, molecular weight distribution is narrow, can design the advantages that catalyst structure as needed, has been the world since the last century 90's
The emphasis of main oil company's developmental research in range, there are many metallocene-polyolefin launch products.However, cyclopentadienyl gold
Metal catalyst also has the shortcomings that its is intrinsic, first, most metallocene catalysts are required for a large amount of methylaluminoxane (MAO)
Or four expensive (phenyl-pentafluoride base) boron salts/alkyl aluminum composite catalyst activation so that the cost of metallocene-polyolefin product
It is high；Second is that metallocene catalyst is homogeneous catalyst, cannot directly be applied on commercial plant, need it is supported after
Commercial plant is can apply to, supported bring the challenge of homogeneous catalyst is that catalytic activity is decreased obviously, it will usually be declined
An order of magnitude.Using above-mentioned carrier loadedization catalyst another disadvantage is that a large amount of ashes can be introduced in polymeric articles
Point.If synthesis one kind can be designed from solid-carrying type (not needing carrier) and can only use alkane as Ziegler-Natta catalyst
The catalyst of the activation of base aluminium [without using MAO and four (phenyl-pentafluoride base) boron salts] energy highly active catalytic olefinic polyreaction, just
It is expected to overcome the disadvantages mentioned above of metallocene catalyst.
In recent years, applicant seminar has been devoted to develop this kind of olefin polymerization catalysis, and it is gratifying to achieve some
Progress.Applicant seminar in 2007 develop it is a kind of only with a small amount of alkyl aluminum activate can highly active catalytic vinyl polymerization it is anti-
The mono-metallocene chrome catalysts (Chinese invention patent CN 101029096A) answered, concrete structure is shown below：
As previously mentioned, such catalyst is homogeneous single chromium catalyst, need it is supported after just can apply to industrial production
Device.In order to find the solution for substituting conventional load, applicant seminar in 2015 develops a kind of more containing plane
The mono-metallocene chrome catalysts (Chinese invention patent publication number CN 104892801A) of hole organic polymer ligand, it is specific to tie
Structure is shown below：
Single chromium catalyst of such ligand of porous organic polymer containing plane is and the immediate existing skill of the present invention
Art, for such catalyst since its inherent structure limits, pore passage structure is mainly polymer plane fold, overlapping generation, is not had
Standby regular 3 D stereo duct, catalyst form, strength and stability are relatively poor.In order to develop performance preferably it is such from
Immobilized AlCl_3 catalyst needs the structure to porous organic polymer ligand to be transformed, to obtain form, strength and stability
Preferably from solid-carrying type metallocene catalyst.
Invention content
The technical problem to be solved by the present invention is to overcome deficiency present in background technology, alkyl aluminum can be used by providing one kind
Activating catalytic olefinic polymerization, form, strength and stability are preferable, the porous organic polymer ligand list with three-dimensional structure
The preparation method of luxuriant chromic compound and the complex is with it in catalysed olefin polymerization especially ethylene polymerization
Using.
In order to solve the above-mentioned technical problem, the present invention uses following technical scheme：
A kind of three-dimensional porous organic polymer ligand list cyclopentadienyl chromic compound, has the following structure general formula：
Wherein, luxuriant 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 substitution 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, alkoxy, amido, alkyl, aryl, alkene
Base, aryl alkyl or silyl group；N is the natural number more than 1.
In a kind of three-dimensional porous organic polymer ligand list cyclopentadienyl chromic compound of the present invention, the substituent R1~R5It is excellent
Hydrogen, methyl, phenyl or aIkylsilyl groups group, the preferred methyl substituted indenyl of the substituted indenyl or phenyl is selected to replace indenes
Base；The preferred methyl substitution fluorenyl of the substitution fluorenyl or phenyl replace fluorenyl；Substituent R6Optimizing alkyl, aryl or substitution virtue
Base group；The preferred halogens of X, methyl, phenyl, benzyl, trimethyl silicane ylmethyl or neopentyl group.
In a kind of three-dimensional porous organic polymer ligand list cyclopentadienyl chromic compound of the present invention, the substituent R1~R5Into
The preferred hydrogen of one step, methyl or phenyl group, the further preferred methyl substituted indenyl of the substituted indenyl；The substitution fluorenyl
Further preferred methyl replaces fluorenyl；Substituent R6Further preferred alkyl or aryl group；The further preferred halogens of X, methyl,
Benzyl group.
In a kind of three-dimensional porous organic polymer ligand list cyclopentadienyl chromic compound of the present invention, the substituent R1~R5More
Further preferred hydrogen or methyl group；Substituent R6Still more preferably tertiary butyl, adamantyl or phenyl group；X is more into one
Walk preferred halogen.
The three-dimensional porous organic polymer ligand of the present invention and its single luxuriant chromic compound can be with those skilled in the art
There is the method for the porous organic polymer of similar structures unit and synthesis to contain salicylaldimine ligand list for the various synthesis known
The method of luxuriant chromium class complex synthesizes, and also can refer to the synthesis of the embodiment of the present invention 1~2.
A kind of purposes of three-dimensional porous organic polymer ligand list cyclopentadienyl chromic compound, which is characterized in that with the three-dimensional
Porous organic polymer ligand list cyclopentadienyl chromic compound is major catalyst, is to help to urge with or mixtures thereof alkyl aluminum, alkyl aluminium halide
Agent is reacted for catalyzed ethylene polymerization；The alkyl aluminum is trimethyl aluminium, triethyl aluminum or triisobutyl aluminium, described
Alkyl aluminium halide is diethyl aluminum chloride or sesquialter aluminium ethide；In co-catalyst in aluminium and major catalyst the molar ratio of chromium be 5~
10000:1；The specific steps are：Under vinyl monomer existence condition, major catalyst and co-catalyst is added to polymeric kettle, -20
DEG C~200 DEG C of reaction temperature and the ethylene pressure of 1~200 atmospheric pressure under the conditions of react 30~720 minutes, polymerisation knot
Shu Hou washs obtained polymer with acid solution, and drying to constant weight in 60 DEG C in vacuum drying oven.
The present invention a kind of three-dimensional porous organic polymer ligand list cyclopentadienyl chromic compound use on the way, in co-catalyst aluminium with
The molar ratio of chromium preferably 50~500 in major catalyst:1.
The present invention a kind of three-dimensional porous organic polymer ligand list cyclopentadienyl chromic compound use on the way, the reaction temperature
It is preferred that 0 DEG C~80 DEG C, the ethylene pressure preferably 5 atmospheric pressure.
The present invention has following advantageous effect：
1, three-dimensional porous organic polymer ligand list cyclopentadienyl chromic compound of the invention is used as from solid-carrying type olefinic polymerization catalysis
Agent has the characteristics that form is good, intensity is big, stability is good, is free of inorganic impurity (carrier).
2, three-dimensional porous organic polymer ligand list cyclopentadienyl chromic compound of the invention is as olefin polymerization catalyst, only
It need to be activated with alkyl aluminum, without using expensive MAO and four (phenyl-pentafluoride base) boron salt co-catalysts, can effectively reduce catalysis alkene
The cost of polymerized hydrocarbon.
3, three-dimensional porous organic polymer ligand list cyclopentadienyl chromic compound of the invention is as olefin polymerization catalyst, tool
Have the characteristics that catalytic activity height, long lifespan, polymer molecular weight are high.
Specific implementation mode
It is further illustrated the present invention below by embodiment, but the scope of the present invention is not limited to listed embodiment.
The synthesis of 1 three-dimensional porous organic polymer ligand of embodiment
300mg (0.79mmol) four (4- aminophenyls) methane ,-two formyls of 1.58mmol3,3 ' are added in 25ml flasks
Base -5,5 '-two replaces (R6The anhydrous DMSO of) -4,4 '-dihydroxybiphenyl, 25mL (with it is preceding through new activation 4A molecular sieves impregnate 3 days with
On).Reaction mixture reacts 12 hours in 70 DEG C of oil baths respectively through procedural heating, reacts one day at 100 DEG C, then
It is reacted two days at 120 DEG C.Yellow solid obtained by the reaction is filtered, with THF, DMF, CH3After the washing of OH equal solvents, obtained solid
With THF, CH3Each Soxhlet extractions of OH 6 hours, then vacuum drains solvent at 120 DEG C, obtains yellow solid powdery product.
Wherein substituent R 6 takes tertiary butyl respectivelytBu, adamantyl Ad and phenyl Ph obtain three kinds of ligands and are denoted as respectively：Ligand 1 (R6=
Tertiary butyltBu), yield 96%；2 (R of ligand6=adamantyl Ad), yield 92%；3 (R of ligand6=phenyl Ph), yield 89%.
The synthesis of 2 three-dimensional porous organic polymer ligand list cyclopentadienyl chromic compound of embodiment
In a nitrogen atmosphere, 120mg ligand 1s, 157mg ligands 2 or 129mg ligands 3 (OH containing 0.47mmol) are dissolved in
In 20mL dry toluenes, 0.47mmol n-BuLis are added at -60 DEG C, is warmed to room temperature and stirs 2 hours.By reaction mixture
- 60 DEG C are cooled to, the cyclopentadienyl chromium dichloride of pentamethyl containing 0.47mmol (being denoted as A) is added, pentamethyl cyclopentadienyl chromium dibromide (is denoted as
B), the tetrahydrofuran of cyclopentadienyl chromium dichloride (being denoted as C), indenyl chromium dichloride (being denoted as D) or fluorenyl chromium dichloride (being denoted as E) is molten
Liquid is stirred to react certain time (20,48 or 96 hours) after rising to assigned temperature (20,40,60 or 80 DEG C), is filtered to remove molten
Agent.The tetrahydrofuran of solid product drying washs, and the lower 140 DEG C of heating of vacuum condition remove solvent in 4 hours, obtain porous organo polysilica
Close object ligand-complexes product.Mass percentages of the Cr in complex is measured by icp analysis.Pass through specific surface area analysis
Measure the specific surface area of complex.13 complex samples are synthesized altogether, and experimental result is shown in Table 1.
The single luxuriant chromic compound compound experiment result summary sheet of table 1
3 catalyzed ethylene polymerization of embodiment reacts
Polymerisation carries out in 250mL autoclaves, uses the porous organic polymer prepared in above-described embodiment 2
It is co-catalyst that ligand list cyclopentadienyl chromic compound 1~13, which is used as major catalyst, alkyl aluminum and halogenated alkyl aluminium,.It is reacted before polymerisation
Kettle toasts 1 hour for 120 DEG C under vacuum, is filled with an atmospheric pressure ethylene gas.Under ethylene atmosphere, 50mL is first contained into co-catalysis
The toluene solution of agent is added in reaction kettle, then toluene solutions of the 10mL containing major catalyst (Cr content 3umol) is added again anti-
It answers in device, ethylene pressure is risen into 5 atmospheric pressure, and start timing.It is vented ethylene gas in reaction kettle after reaction, uses
HCI/ methanol solutions terminate polymerisation.Polymer is filtered out and is used water and methanol fully wash removal impurity, 60 DEG C of vacuum are dry
It is dry to constant weight.Using Ubbelohde capillary viscometers in decahydro Cai polymer intrinsic viscosity is measured in 0.1 DEG C of 135 scholar simultaneously
Calculate polymer viscosity average molecular weigh.Reaction result is shown in Table 2.
2 catalyzed ethylene polymerization experimental result summary sheet of table
Claims (5)
1. a kind of three-dimensional porous organic polymer ligand list cyclopentadienyl chromic compound, has the following structure general formula：
Wherein, luxuriant 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 substitution fluorenyl groups, substitution
Base R1~R5Selected from hydrogen, alkyl；Substituent R6It is alkyl, aryl；X is halogen；N is the natural number more than 1.
2. a kind of three-dimensional porous organic polymer ligand list cyclopentadienyl chromic compound according to claim 1, which is characterized in that institute
The substituent R stated1~R5Selected from hydrogen, methyl；Substituent R6It is tertiary butyl, adamantyl or phenyl；X is halogen.
3. a kind of purposes of three-dimensional porous organic polymer ligand list cyclopentadienyl chromic compound described in claim 1, which is characterized in that
Using three-dimensional porous organic polymer ligand list cyclopentadienyl chromic compound described in claim 1 as major catalyst, with alkyl aluminum, alkyl halide
Or mixtures thereof base aluminium is co-catalyst, is reacted for catalyzed ethylene polymerization；The alkyl aluminum is trimethyl aluminium, triethyl aluminum
Or triisobutyl aluminium, the alkyl aluminium halide are diethyl aluminum chloride or sesquialter aluminium ethide；Aluminium and main catalytic in co-catalyst
The molar ratio of chromium is 5~10000 in agent:1；The specific steps are：Under vinyl monomer existence condition, main catalytic is added to polymeric kettle
Agent and co-catalyst, under the conditions of the ethylene pressure of -20 DEG C~200 DEG C of reaction temperatures and 1~200 atmospheric pressure react 30~
720 minutes, after polymerisation, obtained polymer is washed with acid solution, be dried in 60 DEG C in vacuum drying oven
Constant weight.
4. a kind of purposes of three-dimensional porous organic polymer ligand list cyclopentadienyl chromic compound according to claim 3, feature
It is, the molar ratio of aluminium and chromium in major catalyst is 50~500 in co-catalyst:1.
5. a kind of purposes of three-dimensional porous organic polymer ligand list cyclopentadienyl chromic compound according to claim 3 or 4, special
Sign is that the reaction temperature is 0 DEG C~80 DEG C, and the ethylene pressure is 5 atmospheric pressure.
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