CN109776620A - A kind of metallocene complex and its preparation and application - Google Patents
A kind of metallocene complex and its preparation and application Download PDFInfo
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Abstract
The present invention relates to metallocene compound technical fields, more particularly to metallocene complex and its preparation and application, metallocene complex cyclopentadienyl ring of the present invention is to the bond distance of central metal hafnium and hafnium metal and increases the σ bond energy between chain carbon atom conducive to the intercalation reaction of generation alkene, stability is good, hanging nitrogen-atoms or oxygen atom are introduced on replacing luxuriant ring, the molecular structure of constrained geometry configuration can be formed with central metal hafnium atom, improve catalytic activity and polymer molecular weight, metallocene complex preparation method is simple, practicability is good, metallocene catalyst compositions are made with co-catalyst using it, with high catalytic activity, the olefin polymer for participating in polymerization preparation has 1000000 or more weight average molecular weight, coefficient of friction is small, wearability is good, it is ideal lubriation material.
Description
Technical field
The present invention relates to metallocene compound technical fields, and in particular to a kind of metallocene complex and its preparation and answers
With.
Background technique
Metallocene catalyst refers to IV B group 4 transition metal, if Ti, Zr, Hf element complexes are as major catalyst, and with
Alkylaluminoxane or organoboron compound are mainly used for the polymerization reaction mistake of alkene as catalyst system composed by co-catalyst
Cheng Zhong, in the molecular structure of the catalyst, at least containing a Cp for the ligand of transition metal element, (cyclopentadienyl group is negative
Ion) or Cp derivative, activity decades of times higher than Ziegler catalyst, for example, most representative metalloscene catalyst is claimed
For " Kaminsky " Cp2ZrCl2, which has high activity at low temperature, olefin polymer can be produced with higher efficiency,
But since it is not suitable for high temperature solution polymerization technique, the polymer of low relative molecular mass can only obtain, and be catalyzed
The co-catalysis dosage of agent system consumption is big, improves cost, development is subject to certain restrictions.
In early 1990s by the Dow Co. constrained geometry catalyst proposed and relevant Insite technique skill
Art has obtained the long chain branching that structure novel, catalytic activity are high, have both excellent processing characteristics and physical mechanical property, opposite point narrow
The polyethylene of branch Mass Distribution；Existing patent document CN105273010A provides a kind of limitation configuration binuclear metallocene chemical combination
Object has double center CGC, it is poly- can easily to regulate and control alkene by the modification of substituent group on abutment C and the length of adjusting carbon bridge
The molecular weight distribution of polymer in conjunction, but polyolefin molecular weight wider distribution, affect effect.
In the polymerization of alkene, the linear polyolefin for producing the super high molecular weight of narrow molecular weight distribution has important meaning
Justice, it is very widely used because the polyolefin of made has preferable intensity and mechanical performance, it is existing frequently-used
The production technology of made polyolefin is complicated, and obtained product property also needs to improve, comparatively, such as formula (a) institute
The metallocene catalyst of the constrained geometry configuration shown with good application prospect, makes catalyst active center from steric configuration
It can only be opened to direction, and this catalyst is almost without stereoselectivity, polymerizeing species co-monomer content can be
Variation in very wide range；It is suitable for the olefin polymer of the long-chain of the copolymerization such as ethylene and the alpha-olefin of C3-C20 generation, and helps and urge
Agent dosage is seldom.
The factor for influencing the catalyst is more, the electron of Cp ring substituents or pushes away electronic effect to will affect polymerization special
Property, melt index (MI) becomes smaller, and density increases；Cloud density on the activated centre metal (M) increases lives with catalysis
Property and comonomer insertion rate it is closely linked；The length of abutment group (L) determines the size of opening direction angle, and the angle controls
The long-chain comonomer that is formed in polymerization process can be inserted into；Therefore, it adjusts and urges by adjusting the structure of the catalyst
Agent produces the olefin polymer with special long chain branched molecules structure during olefin polymerization, needed for generating it
The property wanted, has great importance.
Summary of the invention
Therefore, metal hafnium is used to hang down for coordinating metal and introducing on replacing luxuriant ring the purpose of the present invention is to provide a kind of
The new metallocene complex of outstanding nitrogen-atoms or oxygen atom, and cooperate co-catalyst to obtain a kind of high urge according to its catalytic performance
Change active metallocene catalyst compositions.
The technical problem to be solved in the present invention also resides in overcome extrahigh-molecular weight polyolefins in the prior art to synthesize after, be
Obtaining target capabilities also needs the defect of many and diverse subsequent processing, a kind of has using catalyst preparation of the present invention to provide
There is the method for the extrahigh-molecular weight polyolefins of wear-resisting property, and obtains the linear superelevation that a kind of molecular weight coefficient of friction is small, wear-resisting
Molecular weight polyolefins.
For this purpose, the present invention provides a kind of metallocene complex, the molecule with structural formula shown in formula (1):
Wherein, R1, R2, R3 are independently selected from hydrogen, the substituted or unsubstituted alkyl of C1~C4, substituted or unsubstituted benzene
Base, halogen, nitro；
R4 is selected from hydrogen, the alkyl of C1~C4, halogen；
M is metal hafnium；
X is selected from O or N (Me)2。
Preferably, the metallocene complex has molecular formula as shown below:
The present invention also provides a kind of preparation methods of above-mentioned metallocene complex, include the following steps:
Synthetic ligands:nIn the presence of BuLi, will have the compound of formula (A) structure and the compound with formula (B) structure
It is reacted in the first solvent, the extracted purification process of the solution reacted obtains the ligand compound with formula (C)；
Initiator is added: initiator is added dropwise in the solution of ligand compound, stirs evenly and mixture is made；
It forms complex: mixture being mixed with hafnium compound, obtains complex solution；
It purifies complex: by complex solution filtering, removing solvent, then recrystallize through the second solvent and match to get metallocene
Close object.
Wherein, the formula (A), formula (B) and formula (C) are as follows:
Wherein, R1, R2, R3 independently selected from hydrogen, the substituted or unsubstituted alkyl of C1~C4, halogen, nitro, phenyl,
Substituted phenyl；
R4 is selected from hydrogen, the alkyl of C1~C4, halogen；
X ' is selected from OMe or N (Me)2。
Preferably, in the synthetic ligands step, first solvent be selected from tetrahydrofuran, ether, ethyl alcohol, methanol,
At least one of propyl alcohol, ethylene glycol, toluene, benzene, dimethylbenzene, hexane.
Preferably, the extraction purification operation includes that reaction product is hydrolyzed liquid separation through saturated ammonium chloride solution, is obtained
Organic layer is successively handled through concentrated hydrochloric acid, is neutralized, is dry, chromatographing up to the ligand compound with formula (C).
Preferably, in the addition initiator step, the initiator is usednBuLi solution.
Preferably, in the formation complex step, the hafnium compound is selected from hafnium dichloride or hafnium tetrachloride；It is described mixed
Close the mode that object is mixed with the hafnium compound are as follows: hafnium compound is added drop-wise in mixture or mixture is added drop-wise to hafnium
It closes in object.
Preferably, in the purifying complex step, second solvent is CH2Cl2It is described with the mixed solvent of hexane
CH2Cl2Volume ratio with the hexane is 1:(0.25~4).
The present invention also provides a kind of metallocene catalyst compositions, including above-mentioned metallocene complex or above-mentioned metallocene
The metallocene complex of complex preparation method preparation.
It preferably, further include co-catalyst, the co-catalyst includes alkylaluminoxane；Aluminium in the alkylaluminoxane
The molar ratio of hafnium element is (100~5000) in element and the metallocene catalyst: 1；The alkylaluminoxane is selected from first
Base aikyiaiurnirsoxan beta or the methylaluminoxane of modification.
The present invention also provides a kind of preparation methods of extrahigh-molecular weight polyolefins comprising according to above-mentioned catalyst group
The step of making alkene that polymerization reaction occur in the presence of conjunction object.
Preferably, polymeric reaction temperature is 30~60 DEG C, and reaction pressure is 50~200psi；The polymerization reaction includes second
The copolymerization of polyamino alkenyl or/and ethylene and alpha-olefin；Wherein, the purity of the olefinic monomer is not less than 99.95% volume fraction.
The present invention also provides a kind of extrahigh-molecular weight polyolefins powders, pass through the preparation of above-mentioned extrahigh-molecular weight polyolefins
Method is made.
The present invention also provides a kind of polymer compositions, comprising according to above-mentioned extrahigh-molecular weight polyolefins preparation method system
Standby extrahigh-molecular weight polyolefins or above-mentioned extrahigh-molecular weight polyolefins powder.
The present invention also provides a kind of polymer moulded bodies, by according to above-mentioned extrahigh-molecular weight polyolefins preparation method system
Standby extrahigh-molecular weight polyolefins or the manufacture of above-mentioned extrahigh-molecular weight polyolefins powder or above-mentioned polymer composition.
The present invention also provides a kind of answering in manufacture tubing, plate, bar, film, microporous barrier, microwell plate or fiber
With using the extrahigh-molecular weight polyolefins or above-mentioned supra polymer prepared according to above-mentioned extrahigh-molecular weight polyolefins preparation method
Weight polyolefin powder or above-mentioned polymer composition or above-mentioned polymer moulded bodies.
Technical solution of the present invention has the advantages that
1. the derivative of metallocene complex provided by the invention, a cyclopentadienyl group or cyclopentadienyl group shields metal
The other side of the side of atom, metallic atom has very large space, allows the insertion of various monomers, increases olefinic monomer
Insertion activity；Moreover, in olefin polymerization process, on the one hand, the bond distance of luxuriant ring to central metal hafnium and hafnium metal and growing chain
σ bond energy suitable size between carbon atom is between zirconium and titanium, not only improves the insertion of olefinic monomer, and is had preferable
Stability reduces the probability of β-H migration, is conducive to the increase of weight of otefi pi polymer；On the other hand, on replacing luxuriant ring
Hanging nitrogen-atoms or oxygen atom are introduced, the molecular structure of constrained geometry configuration can be formed with central metal hafnium atom, raising is urged
The catalyst activity of the polymer molecular weight changing activity and catalyzing and synthesizing, metallocene complex preparation of the present invention reaches
7.8kg PE/g catalyst 2 hours.
2. the crosslinking of branch will not occur for extrahigh-molecular weight polyolefins of the present invention, and due to of the present invention
The metallocene complex of constrained geometry configuration, catalytic activity is high, is conducive to molecular polyolefin increase, and even molecular weight distribution is divided
Subchain is long, and coefficient of friction is small between molecule and molecule, is similar to tetrafluoroethene, and wearability is ten times of common polyolefin or more,
It is ideal lubriation material；Meanwhile longer strand hampers the progress of crystallization, causes to exist in long-chain polymer
Big amorphous region is to reduce density, essence impact resistant strength with higher and resistance to washability, impact resistance ratio
The impact resistance of polycarbonate is 3~5 times high.
3. can be used for slurry using metallocene complex of the present invention as catalyst and gas phase polymerization technique be raw
Extrahigh-molecular weight polyolefins are produced, the olefin polymer property of preparation is stablized；The temperature of preparation process is 30~60 DEG C, reaction pressure
For 50-200psi, preparation process mild condition, simple process, practicability is good.
4. extrahigh-molecular weight polyolefins of the present invention can prepare polymer composition, polymer moulded bodies, it is applied to
The manufacture of tubing, plate, bar, microporous barrier, microwell plate or microporous fibre, is widely used, and practicability is good.
Specific embodiment
There is provided following embodiments is to preferably further understand the present invention, it is not limited to the best embodiment party
Formula is not construed as limiting the contents of the present invention and protection scope, anyone under the inspiration of the present invention or by the present invention and its
The feature of his prior art is combined and any and identical or similar product of the present invention for obtaining, all falls within of the invention
Within protection scope.
Specific experiment step or condition person are not specified in embodiment, according to the literature in the art described routine experiment
The operation of step or condition can carry out.Reagents or instruments used without specified manufacturer, being can be by commercially available acquisition
Conventional reagent product.
Hereinafter, the present invention will be described in more detail.
1, metallocene complex
The metallocene complex has the molecule of structural formula shown in formula (1):
Wherein, R1, R2, R3 are independently selected from hydrogen, the substituted or unsubstituted alkyl of C1~C4, substituted or unsubstituted benzene
Base, halogen, nitro；
R4 is selected from hydrogen, the alkyl of C1~C4, halogen；
M is metal hafnium；
X is selected from O or N (Me)2。
Preferably, the metallocene complex has one of molecular formula as shown below:
2, metallocene complex is prepared
Step 1 synthetic ligands
?nIn the presence of BuLi, will have the compound of formula (A) structure and the compound with formula (B) structure molten first
It is reacted in agent, the extracted purification process of the solution reacted, obtains the ligand compound with formula (C), the formula (A), institute
It states formula (B) and the formula (C) is as follows.
Preferably, the X ' is selected from OMe or N (Me)2, it is preferred that it can by the specific embodiment of formula (A) compound indicated
To be one of the compound indicated by following structural formula；However, its is without being limited thereto；
Preferably, the R1, R2, R3 is independently selected from hydrogen, the substituted or unsubstituted alkyl of C1-C4, substitution or does not take
Phenyl, halogen, the nitro in generation；R4 is selected from hydrogen, the alkyl of C1-C4, halogen；
Specifically, can be the compound indicated by following structural formula by the specific embodiment of formula (B) compound indicated
One of, however, its is without being limited thereto.
Preferably, first solvent is selected from tetrahydrofuran, ether, ethyl alcohol, methanol, propyl alcohol, ethylene glycol, toluene, benzene, two
At least one of toluene, hexane, however, its is without being limited thereto；
Preferably, the extraction purification operation includes that reaction product is hydrolyzed liquid separation through saturated ammonium chloride solution, is obtained
Organic layer is successively handled through concentrated hydrochloric acid, is neutralized, is dry, chromatographing up to the ligand compound with formula (C)；
One of the compound indicated by following structural formula can be by the specific embodiment of formula (C) compound indicated, so
And it is without being limited thereto.
Initiator is added in step 2
Initiator is added dropwise in the solution of ligand compound, stirs evenly and mixture is made；
Preferably, the initiator usesnBuLi solution, it is describednThe molar ratio of BuLi and ligand compound is 1:1.
Step 3 forms complex
Mixture is mixed with hafnium compound, obtains complex solution.
Preferably, the hafnium compound is selected from hafnium oxide or hafnium tetrachloride, however, its is without being limited thereto；
Preferably, the mode that the mixture is mixed with the hafnium compound are as follows: hafnium compound is added drop-wise in mixture
Or mixture is added drop-wise in hafnium compound.
Step 4 purifies complex
By complex solution filtering, solvent is removed, then is recrystallized through the second solvent to get metallocene complex.
Preferably, second solvent is CH2Cl2With the mixture of hexane, CH2Cl2Volume ratio with hexane is 1:
(0.25~4), however, its is without being limited thereto.
3, metallocene catalyst compositions
Metallocene catalyst compositions described in the specific embodiment of the invention include being previously mentioned in specific embodiment
Metallocene complex further includes co-catalyst, and the co-catalyst includes alkylaluminoxane, the aluminium member in the alkylaluminoxane
The plain molar ratio with hafnium element in the metallocene catalyst is (100~5000): 1.
Methylaluminoxane
The preferred methylaluminoxane of the alkylaluminoxane or the methylaluminoxane of modification, acid stronger, activity is preferably；
Main function in metallocene catalyst compositions is to make metallocene alkylation and dehalogenation, forms cation activity center, this
The K of a balanced reaction is very small, thus in aluminium element and the metallocene catalyst molar ratio of hafnium element be (100~
5000): 1, the presence of the co-catalyst makes the metallocene catalyst compositions in embodiment with higher to alpha-olefin poly-
Close activity.
Alkylaluminoxane
In addition to methylaluminoxane or the methylaluminoxane of modification, the promoter aluminium alkyl oxygen alkane in specific embodiment is also
Ethylaluminoxane, isobutyl aluminium alkoxide or t-butyl-aluminoxane can be selected, however, its is without being limited thereto.
4, extrahigh-molecular weight polyolefins are prepared
Reaction condition
The polymeric reaction temperature for preparing of extrahigh-molecular weight polyolefins is 30~60 DEG C in the specific embodiment of the invention, reaction
Pressure is 50-200psi.
Olefinic monomer
The olefinic monomer includes ethylene, alpha-olefin；The purity of the olefinic monomer volume not less than 99.95% point
Number；Hydrocarbon impurities be not higher than 10ppm, CO content be not higher than 1ppm, CO2 content be not higher than 5ppm, methanol be not higher than 5ppm, CO,
The impurity such as CO2 or methanol are catalyst toxicity agent, and hydrocarbon impurities influence polymer architecture.
Less due to forming branch, the longer linear structure of length, the intermolecular coefficient of friction of olefin polymer is smaller, closely
It is similar to tetrafluoroethene, it is ideal lubriation material that wearability, which is ten times of common polyolefin or more,.
5, extrahigh-molecular weight polyolefins
In the specific embodiment of the invention, extrahigh-molecular weight polyolefins are carried out using the metallocene catalyst compositions
Preparation obtains the extrahigh-molecular weight polyolefins that weight average molecular weight is 1000000g/mol or more, superelevation as be shown in the examples
Molecular weight polyethylene and ultrahigh molecular weight polypropylene, average grain diameter 50-200um, heap density are 0.15-0.45g/cm3, because
This, it may have preferable impact resistance and resistance to flushing performance.
Embodiment 1
It is catalyzed present embodiment discloses a kind of specific embodiment of metallocene complex and using the metallocene complex
The specific embodiment of synthesizing super high molecular weight polyethylene.
Take 1.0molnThe hexane solution of BuLi, is removed in vacuum solvent, and methyl phenyl ethers anisole 8.5ml is added at -10 DEG C, and system is slow
Slowly 80 DEG C of heating are risen to for 24 hours, solid matter is then collected by filtration, are washed with dry hexane to white；The white powder is dissolved in
In 100ml toluene, the toluene solution (17.8g, 0.076mol) of 2,3,4,5- tetramethyl-ring pentenones is added dropwise at -10 DEG C, stirs
It mixes overnight, then 65 DEG C of heating 4h；NH is saturated with 20ml4Cl aqueous hydrolysis and liquid separation, organic layer are handled with 20ml concentrated hydrochloric acid
Twice, the concentrated hydrochloric acid concentration is 12mol/L.Then neutrality, liquid separation, organic layer sulphur are neutralized to sodium hydroxide and sodium carbonate
Sour magnesium is dry, by silica gel column chromatography, the CH that mobile phase is 3:2 using volume ratio2Cl2With hexane mixed liquor, ligand 1-is obtained
(2- methoxyphenyl) -2,3,4,5- tetramethyl-ring pentadiene (as shown in formula 1-1)；
At-78 DEG C, to dissolved with-2,3,4,5- tetramethyl-ring pentadiene of 4.4mmol ligand 1-(2- methoxyphenyl)
Equivalent is slowly dropped into 100ml diethyl ether solutionnBuLi is then slowly increased to room temperature, is stirred overnight, and solvent is evacuated under vacuum, molten
Enter in 150ml toluene solution；
At -78 DEG C, 50ml is slowly dropped into above-mentioned system dissolved with the toluene solution of 4.4mmol hafnium tetrachloride, then
It is slowly heated to 65 DEG C of holding 12h；
The insoluble matter in reaction system is filtered out, the solvent in filtrate is removed in vacuum, obtains solid, is then 1 with volume ratio:
4 CH2Cl2Required compound, test result are recrystallized to give with hexane mixed solvent are as follows: elemental analysis C15H16Cl2OHf
(461.39): measured value (theoretical value) %:C 39.10 (39.01)；H 3.53(3.47)；O 3.53(3.47)；Cl 15.28
(15.37)；Hf 38.56(38.69).
1H NMR (CDC13,300MHz, 298K): δ 7.30 (t, 1H, Ph), 7.27 (d, 1H, Ph) 7.16 (t, 1H, Ph)
6.65(d,1H,Ph)2.44(s,6H,C5Me4),2.08(s,6H,C5Me4).13C NMR (CDC13,100.5MHz, 298K): δ
175.51,146.34,143.45,131.09,130.15,129.04,128.58,123.86,114.25,13.75,13.39；Really
Recognizing the compound is [2- (2,3,4,5- tetramethyl-ring pentadienyl)-phenoxy group] hafnium dichloride (shown in formula 1-2)；
The metallocene complex and methylaluminoxane that the present embodiment is obtained form carbon monoxide-olefin polymeric, wherein the methyl
The molar ratio of hafnium element is 100:1 in aluminium element and metallocene complex in aikyiaiurnirsoxan beta, the volume point for being 99.95% with purity
Several ethylene is polymerized monomer, prepares ultra-high molecular weight polyethylene.
Embodiment 2
It is catalyzed present embodiment discloses a kind of specific embodiment of metallocene complex and using the metallocene complex
The polyacrylic specific embodiment of synthesizing super high molecular weight.
The present embodiment synthesis step is substantially the same manner as Example 1, and difference is: ligand synthesis phase has put into 2,4- diformazan
The toluene solution (17.8g, 0.076mol) of base-3- chloro tert-butyl cyclopentenone is reacted with methyl phenyl ethers anisole, obtains ligand 1-(2- first
Phenyl) -2,4- dimethyl -3- chloro tert-butylcyclopentadiene；(as shown in formula 2-1)；
Using the ligand according to embodiment described in embodiment 1, the hafnium compound used has obtained cyclopentadienyl for hafnium dichloride
Metal complex [2- (2,4- dimethyl -3- chloro t-butyl cyclopentadienyl)-phenoxy group] hafnium dichloride, elemental analysis
C17H19Cl3OHf (523.84): measured value (theoretical value) %:C 38.90 (38.94)；H 3.68(3.63)；O 3.03(3.05)；
Cl 20.34(20.30)；Hf 34.05(34.07).
1H NMR (CDC13,300MHz, 298K): δ 7.17 (d, 1H, Ph), 7.10 (t, 1H, Ph) 6.93 (t, 1H, Ph)
6.76(d,1H,Ph)3.12-3.37(m,2H,CH2)1.79(s,6H,CH3)0.99(s,6H,CH3)。13C NMR(CDC13,
100.5MHz, 298K): δ 155.0 146.0 133.2 130.1 129.4 129.3 121.5 121.2 120.7 115.8
56.6 51.7 32.2 24.7 23.3 23.3 17.8.Confirm that the compound is [2- (2,4- dimethyl -3- chloro tert-butyl
Cyclopentadienyl group)-phenoxy group] hafnium dichloride.(as shown in formula 2-2)；
The metallocene complex and BCl that the present embodiment is obtained3Modified methylaluminoxane forms carbon monoxide-olefin polymeric,
Described in aluminium element and metallocene complex in methylaluminoxane the molar ratio of hafnium element be 5000:1, in 1 institute of embodiment
Vinyl polymerization is carried out under the conditions of stating prepares ultra-high molecular weight polyethylene.
Embodiment 3
It is catalyzed present embodiment discloses a kind of specific embodiment of metallocene complex and using the metallocene complex
The specific embodiment of synthesizing super high molecular weight polyethylene.
Take 1.5molnThe hexane solution of BuLi, is removed in vacuum solvent, and n,N-Dimethylaniline 20ml is added at -15 DEG C,
System slowly rises to 60 DEG C of heating 8h.Solid matter then is collected by filtration, is washed with dry hexane to white.By the 2g white powder
End is dissolved in 100ml toluene, and the toluene solution (3.7g, 15.7mmol) of 3,4- diphenyl cyclopentenone is added dropwise at -15 DEG C, stirs
It mixes overnight, then 65 DEG C of heating 4h.NH is saturated with 20ml4Cl aqueous hydrolysis and liquid separation, organic layer are with 20ml concentration
The concentrated hydrochloric acid processing of 16mol/L is twice.Then neutrality, liquid separation, organic layer magnesium sulfate are neutralized to sodium hydroxide and sodium carbonate
It is dry, by silica gel column chromatography, the CH that mobile phase is 4:1 using volume ratio2Cl2With hexane mixed liquor, obtain ligand 1-(2-N,
N- 3,5-dimethylphenyl) -3,4- hexichol butylcyclopentadiene (as shown in formula 3-1)；
At-70 DEG C, to dissolved with 1.5mmol ligand 1-(2-N, N- 3,5-dimethylphenyl)-3,4- hexichol butylcyclopentadiene
Equivalent is slowly dropped into 15ml tetrahydrofuran solutionnBuLi is then slowly increased to room temperature, is stirred overnight.
At -70 DEG C, above-mentioned solution is slowly dropped in the tetrahydrofuran solution dissolved with 1.5mmol hafnium dichloride, with
After be heated to room temperature, be stirred overnight.The insoluble matter in reaction system is filtered out, the solvent in filtrate is removed in vacuum, obtains solid, with
The CH for being afterwards 1:1 with volume ratio2Cl2With the mixed solvent of hexane be recrystallized to give [2- (3,4- hexichol cyclopentadienyl group)-N,
N- 3,5-dimethylphenyl] hafnium dichloride, elemental analysis C25H22Cl2HfN (585.39): measured value (theoretical value) %:C 51.17
(51.25)；H 3.71(3.76)；N 2.44(2.39)；Cl 12.05(12.11)；Hf 30.53(30.49).1H NMR
(CDC13,300MHz, 298K): δ 8.46 (dd, 1H, Ph), 7.22 (m, 1H, Ph) 7.14-7.19 (m, 6H, Ph) 7.03-7.08
(m,2H,Ph)6.83(t,2H,Ph)6.68(t,1H,Ph)6.58(m,1H,Ph)6.60(m,1H,C5)4.35(d,1H,C5)
3.01(m,6H,CH3).13C NMR (CDC13,100.5MHz, 298K): δ 148.0 142.2 142.0 138.2 133.6
128.8 128.6 128.6 128.6 128.6 127.9 127.7 126.4 125.7 123.9 119.5 118.5 118.1
117.0 114.7 45.8 45.8 45.7.Confirm that the compound is [2- (3,4- hexichol cyclopentadienyl group)-N, N- dimethyl
Phenyl] hafnium dichloride.(as shown in formula 3-2)；
The metallocene complex methylaluminoxane that the present embodiment is obtained forms carbon monoxide-olefin polymeric, wherein the aluminium methyl
The molar ratio of hafnium element is 3000:1 in aluminium element and metallocene complex in oxygen alkane, the volume point for being 99.95% with purity
Several ethylene is polymerized monomer, prepares ultra-high molecular weight polyethylene.
Embodiment 4
It is catalyzed present embodiment discloses a kind of specific embodiment of metallocene complex and using the metallocene complex
The specific embodiment of synthesizing super high molecular weight polyethylene.
The present embodiment synthesis step and 3 ligand synthesis step of embodiment are essentially identical, and difference is: ligand synthesis phase is thrown
The toluene solution (3.7g, 15.7mmol) for having entered the bromo- cyclopentenone of 2- is reacted with n,N-Dimethylaniline, obtains ligand 1-(2-
N, N- 3,5-dimethylphenyl) the bromo- cyclopentadiene of -2- (as shown in formula 8-1)；
Then [2- (2- bromine cyclopentadienyl group)-N, N- 3,5-dimethylphenyl] dichloro is synthesized according to the synthesis step of embodiment 2
Change hafnium, elemental analysis C13H13NCl2BrHf (592.19): measured value (theoretical value) %:C 26.36 (26.34)；H 2.31
(2.20)；Br 26.88(26.98)；Cl 11.98(11.97)；N 2.39(2.36)；Hf 30.08(30.14).
1H NMR (CDC13,300MHz, 298K): δ 8.46 (dd, 1H, Ph), 7.03 (t, 1H, Ph) 6.68 (d, 1H, Ph)
6.58(t,1H,Ph)6.40(t,1H,C5)2.90(d,2H,C5)3.01(s,6H,CH3)。13C NMR(CDC13,100.5MHz,
298K): δ 148.0 141.1 130.4 130 128.8 123.9 119.5 118.1 117.0 105.1 45.8 45.8
38.Confirm that the compound is [2- (2- bromine cyclopentadienyl group)-N, N- 3,5-dimethylphenyl] hafnium dichloride.(as shown in formula 4-2)；
The metallocene complex and methylaluminoxane that the present embodiment is obtained form carbon monoxide-olefin polymeric, wherein the methyl
The molar ratio of hafnium element is 4000:1, the volume for being 99.95% with purity in aluminium element and metallocene complex in aikyiaiurnirsoxan beta
The ethylene of score is polymerized monomer, prepares ultra-high molecular weight polyethylene.
Embodiment 5
It is catalyzed present embodiment discloses a kind of specific embodiment of metallocene complex and using the metallocene complex
The specific embodiment of synthesizing super high molecular weight polyethylene.
Take 1.5molnThe hexane solution of BuLi, is removed in vacuum solvent, and n,N-Dimethylaniline 20ml is added at -15 DEG C,
System slowly rises to 60 DEG C of heating 8h.Solid matter then is collected by filtration, is washed with dry hexane to white.By the 2g white powder
End is dissolved in 100ml toluene, and the toluene that 3- (3,5- difluorophenyl) -4- nitro -2- cyclopentene-1-one is added dropwise at -15 DEG C is molten
Liquid (3.7g, 15.7mmol), is stirred overnight, then 65 DEG C of heating 4h.NH is saturated with 20ml4Cl aqueous hydrolysis and liquid separation, have
Machine layer is handled twice with 20ml concentrated hydrochloric acid.Then neutrality, liquid separation, organic layer magnesium sulfate are neutralized to sodium hydroxide and sodium carbonate
It is dry, by silica gel column chromatography, the CH that mobile phase is 4:1 using volume ratio2Cl2With hexane mixed liquor, obtain ligand 1-(2-N,
N- 3,5-dimethylphenyl) -3- (3,5- difluorophenyl) -4- nitro cyclopentadiene (being shown below)；
Then, at-80 DEG C, to dissolved with 2.4mmol ligand 1-(2-N, N- 3,5-dimethylphenyl)-3,4- hexichol basic ring penta 2
Equivalent is slowly dropped into the 100ml diethyl ether solution of alkenenBuLi is then slowly increased to room temperature, is stirred overnight；
At -70 DEG C, above-mentioned solution is slowly dropped in the tetrahydrofuran solution dissolved with 2.4mmol hafnium dichloride, with
After be heated to room temperature, be stirred overnight.The insoluble matter in reaction system is filtered out, the solvent in filtrate is removed in vacuum, obtains solid, with
The CH for being afterwards 1:3 with volume ratio2Cl2[1- (2-N, N- diphenyl methyl) -3- (3,5- bis- is recrystallized to give with hexane mixed solvent
Fluorophenyl) -4- nitro cyclopentadienyl group] hafnium dichloride, elemental analysis C19H15F2Cl2N2O2Hf (590.39): measured value is (theoretical
Value) %:C 38.56 (38.62)；H 2.58(2.54)；Cl 12.07(12.01)；N 4.65(4.74)；O 5.46(5.42)；F
6.36(6.44)；Hf 30.32(30.23).
1H NMR (CDC13,300MHz, 298K): δ 8.46 (dd, 1H, Ph) 7.13 (m, 1H, Ph) 7.03-7.09 (t, 2H,
Ph)6.94(d,1H,Ph)6.68(d,1H,Ph)6.58(t,1H,Ph)6.60(t,1H,C5)5.20(d,1H,C5)3.01(s,
6H,CH3).13C NMR (CDC13,100.5MHz, 298K): δ 149.4 148.7 148.0 142.9 142.0 136.6
128.8 125.1 123.9 123.6 119.5 119.0 118.1 117.0 114.7 112.8 91.0 45.8 45.8.Really
Recognizing the compound is [1- (2-N, N- diphenyl methyl) -3- (3,5- difluorophenyl) -4- nitro cyclopentadienyl group] hafnium dichloride.
(being shown below)；
The metallocene complex and methylaluminoxane that the present embodiment is obtained form carbon monoxide-olefin polymeric, wherein the methyl
The molar ratio of hafnium element is 2000:1, the volume for being 99.95% with purity in aluminium element and metallocene complex in aikyiaiurnirsoxan beta
The ethylene of score is polymerized monomer, prepares polymer.
Embodiment 6
It is catalyzed present embodiment discloses a kind of specific embodiment of metallocene complex and using the metallocene complex
The specific embodiment of synthesizing super high molecular weight polyethylene.
The present embodiment synthesis step is essentially identical with 5 synthesis step of embodiment, and difference is: ligand synthesis phase is put into
The toluene solution (17.8g, 0.076mol) and methyl phenyl ethers anisole of 2- methyl -3- (4- (methylsulfonyl) phenyl) -2- cyclopentene-1-one are anti-
It answers, obtains ligand 1-(2- methoxyphenyl)-2- methyl-3- (4- (methylsulfonyl) phenyl) cyclopentadiene (as shown in formula 6-1)；
Then 2- [2- methyl -3- (4- (methylsulfonyl) phenyl)]-phenoxy group dichloro is synthesized according to the synthesis step of embodiment 1
Change hafnium, elemental analysis C19H16Cl2O3SHf (573.46): measured value (theoretical value) %:C 39.79 (39.76)；H 2.88
(2.79)；O 8.27(8.37)；S 5.53(5.59)；Cl 12.38(12.36)；Hf 31.15(31.13).
1H NMR (CDC13,300MHz, 298K): δ 7.75 (d, 2H, Ph) 7.69 (d, 2H, Ph) 7.17 (d, 1H, Ph)
7.10(t,1H,Ph)6.93(t,1H,Ph)6.76(d,1H,Ph)3.39(s,3H,CH3)2.90(s,2H,C5)2.12(s,3H,
CH3).13C NMR (CDC13,100.5MHz, 298K): δ 155.0 144.4 143.0 140.2 135.7 132.5 130.1
129.3 128.2 127.4 121.5 121.2 115.0 47.7 16.0 7.3.Confirm that the compound is 2- [2- methyl -3-
(4- (methylsulfonyl) phenyl)]-phenoxy group hafnium dichloride.(as shown in formula 6-2)；
The metallocene complex and methylaluminoxane that the present embodiment is obtained form carbon monoxide-olefin polymeric, wherein the methyl
The molar ratio of hafnium element is 1000:1, the volume for being 99.95% with purity in aluminium element and metallocene complex in aikyiaiurnirsoxan beta
The ethylene of score is polymerized monomer, prepares ultra-high molecular weight polyethylene.
Embodiment 7
It is catalyzed present embodiment discloses a kind of specific embodiment of metallocene complex and using the metallocene complex
The specific embodiment of synthesizing super high molecular weight polyethylene.
The present embodiment synthesis step and 3 synthesis step of embodiment are essentially identical, and difference is: ligand synthesis phase is put into
The toluene solution (17.8g, 0.076mol) of the fluoro- 3- phenyl-cyclopentenone of 2- methyl-2- is reacted with methyl phenyl ethers anisole, obtains ligand 1-
The fluoro- 3- phenyl cyclopentadiene of (2- methoxyphenyl) -2- methyl -2- (as shown in formula 7-1)；
2- [the fluoro- 3- phenyl of 2- methyl -2-]-phenoxy group hafnium dichloride, member are then synthesized using the synthesis step of embodiment 1
Element analysis C20H19NCl2FHf (541.39): measured value (theoretical value) %:C44.28 (44.25)；H 3.73(3.69)；F 3.56
(3.50)；Cl 12.99(13.07)；N 2.63(2.58)；Hf 32.81(32.91).
1H NMR (CDC13,300MHz, 298K): δ 8.46 (dd, 1H, Ph) 7.22 (m, 1H, Ph) 7.14 (t, 2H, Ph)
7.03(t,1H,Ph)6.83(d,2H,Ph)6.68(dd,1H,Ph)6.58(m,1H,Ph)6.60(t,1H,C5)3.01(s,6H,
CH3)1.31(d,3H,CH3).13C NMR (CDC13,100.5MHz, 298K): δ 148.0 147.5 141.2 139.4
128.6 128.6 127.9 126.4 126.4 123.9 119.5 119.3 118.1 118.0 117.0 103.0 45.8
45.8 30.7.Confirm that the compound is 2- [the fluoro- 3- phenyl of 2- methyl -2-]-phenoxy group hafnium dichloride.(as shown in formula 7-2)；
The metallocene complex and methylaluminoxane that the present embodiment is obtained form carbon monoxide-olefin polymeric, wherein the methyl
The molar ratio of hafnium element is 4000:1, the volume for being 99.95% with purity in aluminium element and metallocene complex in aikyiaiurnirsoxan beta
The ethylene of score is polymerized monomer, prepares ultra-high molecular weight polyethylene.
Comparative example 1
This comparative example is disclosed a kind of specific embodiment of metallocene complex and is catalyzed using the metallocene complex
The specific embodiment of synthesizing super high molecular weight polyethylene.
This comparative example ligand synthesis step is identical with 3 ligand synthesis step of embodiment.
Then, at-80 DEG C, to dissolved with 2.4mmol ligand 1-(2-N, N- 3,5-dimethylphenyl)-3,4- hexichol basic ring penta 2
It is slowly dropped into equivalent nBuLi in the 100ml diethyl ether solution of alkene, room temperature is then slowly increased to, is stirred overnight；
At -70 DEG C, above-mentioned solution is slowly dropped in the tetrahydrofuran solution dissolved with 2.4mmol zirconium chloride, with
After be heated to room temperature, be stirred overnight.The insoluble matter in reaction system is filtered out, the solvent in filtrate is removed in vacuum, obtains solid, with
The CH for being afterwards 1:3 with volume ratio2Cl2[1- (2-N, N- diphenyl methyl) -3,4- two is recrystallized to give with the mixed solvent of hexane
Phenyl cyclopentadienyl group] zirconium dichloride, elemental analysis C25H22Cl2NZr (498.58): measured value (theoretical value) %:C 60.25
(60.23)；H 4.37(4.45)；Cl 14.19(14.22)；N 2.73(2.81)；Zr 18.46(18.30).
1H NMR (CDC13,300MHz, 298K): δ 8.46 (dd, 1H, Ph), 7.22 (m, 1H, Ph) 7.14-7.19 (m,
6H,Ph)7.03-7.08(m,2H,Ph)6.83(t,2H,Ph)6.68(t,1H,Ph)6.58(m,1H,Ph)6.60(m,1H,C5)
4.35(d,1H,C5)3.01(m,6H,CH3).13C NMR (CDC13,100.5MHz, 298K): δ 148.0 142.9 142.2
142.0 139.4 128.8 128.6 128.6 128.6 128.6 127.9 127.7 127.7 126.4 126.4 125.7
123.9 119.5 119.0 118.1 117.0 114.7 47.0 45.8 45.8.Confirm compound [1- (2-N, the N- hexichol
Ylmethyl) -3,4- hexichol cyclopentadienyl group] zirconium dichloride.(as shown in formula 8-2)；
The metallocene complex and methylaluminoxane that the present embodiment is obtained form carbon monoxide-olefin polymeric, wherein the methyl
The molar ratio of hafnium element is 1000:1, the volume for being 99.95% with purity in aluminium element and metallocene complex in aikyiaiurnirsoxan beta
The ethylene of score is polymerized monomer, prepares polymer.
Evaluate example 1
Evaluating catalyst method: reaction kettle and pipeline vacuum/nitrogen are replaced at least 3 times before experiment, remove air.?
Under nitrogen protection, 500ml toluene is added, then 50mg metallocene catalyst is stored in catalyst shot tank, by 2ml
The toluene solution of 10wt% methylaluminoxane (co-catalyst) is stored in feeding gun.Under constant stirring, above-mentioned methyl is added
Aikyiaiurnirsoxan beta then makes the temperature in polymeric kettle rise to 40 DEG C, stirs 10min；It under inert gas protection, will with 150ml toluene
Carried metallocene catalyst brings polymeric kettle into, and temperature is increased to 80 DEG C, is passed through polymer grade ethylene monomer, maintains pressure in kettle
Stop reaction after 1.0MPa, 2h, drying to constant weight by polymer, and weighing obtains polyethylene.
Active characterization meaning are as follows: in 2h, the quality for the polyethylene that can be prepared under the action of 1g catalyst is single
Position is kg PE/g catalyst 2 hours.
1 embodiment 1-7 of table, 1 catalytic activity characterization result of comparative example
Evaluate example 2
The solvent type in 1 ligand synthesis step of embodiment is adjusted, uses tetrahydrofuran, ethyl alcohol, methanol, propyl alcohol, second respectively
Glycol, benzene and hexane replace toluene, and ligand compound is made, and metallocene is made according still further to embodiment described in embodiment 1 and matches
Object is closed, its catalytic activity is tested.
Wherein: compound NMR spectrum is tested using Varian Unitu-400 Nuclear Magnetic Resonance；
Using the molecular chain conformation of GPC (Alliance GPCV2000) test polymer；
Using the dynamic friction coefficient of Labthink MXD-02 type friction coefficient instrument measurement polymer；
Using the simple beam impact strength of U.S. Atlas company API type Apparatus for Impacting at low-temp test material；
Polymer particles size and distribution is measured using 2000 type laser particle analyzer of Mastersizer；
Using the apparent density of ASTM-D-1895 method measurement material；
Using the water absorption rate of ASTM D-570-98 method measurement material.
2 embodiment 1-7 of table, the performance test results of the comparative example 1 as the olefin polymerization of catalyst preparation
Table 2 is continuous
| Embodiment | Dynamic friction coefficient | Impact strength (KJ/m2) | Water absorption rate (%) |
| Embodiment 1 | 0.18 | 236 | <0.01 |
| Embodiment 2 | 0.20 | 125 | <0.01 |
| Embodiment 3 | 0.20 | 211 | <0.01 |
| Embodiment 4 | 0.19 | 192 | <0.01 |
| Embodiment 5 | 0.22 | 188 | <0.01 |
| Embodiment 6 | 0.18 | 248 | <0.01 |
| Embodiment 7 | 0.20 | 221 | <0.01 |
| Comparative example 1 | 0.56 | 10 | <0.01 |
Evaluate example 3
The solvent type in 1 ligand synthesis step of embodiment is adjusted, uses tetrahydrofuran, ethyl alcohol, methanol, propyl alcohol, second respectively
Glycol, benzene and hexane replace toluene, and ligand compound is made, and metallocene is made according still further to embodiment described in embodiment 1 and matches
Object is closed, tests its catalytic activity according to method described in evaluation example 1, as shown in table 3；
Carbon monoxide-olefin polymeric is made with co-catalyst, and according to the preparation method of High molecular weight polyethylene described in embodiment 1
High molecular weight polyethylene is prepared, according to the performance of method test High molecular weight polyethylene described in evaluation example 2, such as 4 institute of table
Show.
The active testing result of the metallocene catalyst synthesized under 3 different solvents of table
The performance test of the lower alkene synthesized of the metallocene catalyst effect synthesized under 4 different solvents of table
Table 4 is continuous
| Embodiment | Dynamic friction coefficient | Impact strength (KJ/m2) | Water absorption rate (%) |
| Embodiment 1- tetrahydrofuran | 0.18 | 236 | <0.01 |
| Embodiment 1- ethyl alcohol | 0.17 | 245 | <0.01 |
| Embodiment 1- methanol | 0.19 | 251 | <0.01 |
| Embodiment 1- propyl alcohol | 0.18 | 239 | <0.01 |
| Embodiment 1- ethylene glycol | 0.18 | 235 | <0.01 |
| Embodiment 1- benzene | 0.16 | 241 | <0.01 |
| Embodiment 1- hexane | 0.17 | 251 | <0.01 |
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (14)
1. a kind of metallocene complex, which is characterized in that the molecule with structural formula shown in formula (1):
Wherein, R1, R2, R3 independently selected from hydrogen, the substituted or unsubstituted alkyl of C1~C4, substituted or unsubstituted phenyl,
Halogen, nitro；
R4 is selected from hydrogen, the alkyl of C1~C4, halogen；
M is metal hafnium；
X is selected from O or N (Me)2。
2. metallocene complex according to claim 1, which is characterized in that the metallocene complex has as shown below
Molecular formula:
3. a kind of preparation method of metallocene complex as claimed in claim 1 or 2, which comprises the steps of:
Synthetic ligands:nIn the presence of BuLi, will have the compound of formula (A) structure and the compound with formula (B) structure the
It is reacted in one solvent, the extracted purification process of the solution reacted obtains the ligand compound with formula (C)；
Initiator is added: initiator is added dropwise in the solution of ligand compound, stirs evenly and mixture is made；
It forms complex: mixture being mixed with hafnium compound, obtains complex solution；
It purifies complex: by complex solution filtering, removing solvent, then recrystallize through the second solvent to get metallocene complex.
Wherein, the formula (A), formula (B) and formula (C) are as follows:
Wherein, R1, R2, R3 are independently selected from hydrogen, the substituted or unsubstituted alkyl of C1~C4, halogen, nitro, phenyl, substitution
Phenyl；
R4 is selected from hydrogen, the alkyl of C1~C4, halogen；
X ' is selected from OMe or N (Me)2。
4. the preparation method of metallocene complex according to claim 3, which is characterized in that in the synthetic ligands step
In,
First solvent is in tetrahydrofuran, ether, ethyl alcohol, methanol, propyl alcohol, ethylene glycol, toluene, benzene, dimethylbenzene, hexane
At least one；
The extraction purification operation includes that reaction product is hydrolyzed liquid separation through saturated ammonium chloride solution, and obtained organic layer successively passes through
Concentrated hydrochloric acid processing neutralizes, is dry, chromatographing up to the ligand compound with formula (C).
5. the preparation method of metallocene complex according to claim 3 or 4, which is characterized in that the addition initiator
In step, the initiator is usednBuLi solution.
6. according to the preparation method of the described in any item metallocene complexes of claim 3-5, which is characterized in that the formation is matched
It closes in object step, the hafnium compound is selected from hafnium dichloride or hafnium tetrachloride；The mixture is mixed with the hafnium compound
Mode are as follows: hafnium compound is added drop-wise in mixture or mixture is added drop-wise in hafnium compound.
7. according to the preparation method of the described in any item metallocene complexes of claim 3-6, which is characterized in that the purifying is matched
It closes in object step, second solvent is CH2Cl2With the mixed solvent of hexane, the CH2Cl2Volume ratio with the hexane is
1:(0.25~4).
8. a kind of metallocene catalyst compositions, which is characterized in that including metallocene complex of any of claims 1 or 2 or
The metallocene complex of any one of the claim 3-7 metallocene complex preparation method preparation.
9. metallocene catalyst compositions according to claim 8, which is characterized in that further include co-catalyst, described help is urged
Agent includes alkylaluminoxane；Mole of hafnium element in aluminium element and the metallocene catalyst in the alkylaluminoxane
Than for (100~5000): 1；The alkylaluminoxane is selected from the methylaluminoxane of methylaluminoxane or modification.
10. a kind of preparation method of extrahigh-molecular weight polyolefins, which is characterized in that it is included according to claim 8 or claim 9
The step of making alkene that polymerization reaction occur in the presence of carbon monoxide-olefin polymeric.
11. a kind of extrahigh-molecular weight polyolefins powder, which is characterized in that poly- by super high molecular weight according to claim 10
The preparation method of alkene is made.
12. a kind of polymer composition, which is characterized in that include the super high molecular weight prepared according to claim 10 the method
Extrahigh-molecular weight polyolefins powder described in polyolefin or claim 11.
13. a kind of polymer moulded bodies, which is characterized in that pass through the super high molecular weight prepared according to claim 10 the method
The manufacture of polymer composition described in extrahigh-molecular weight polyolefins powder or claim 12 described in polyolefin or claim 11.
14. super high molecular weight described in the extrahigh-molecular weight polyolefins or claim 11 of the preparation of claim 10 the method is poly-
Polymer moulded bodies described in polymer composition described in alkene powder or claim 12 or claim 13 manufacture tubing,
Application in plate, bar, film, microporous barrier, microwell plate or fiber.
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