CN100549017C - A kind of benzene oxygen Monodentate compound and its production and application that contains - Google Patents
A kind of benzene oxygen Monodentate compound and its production and application that contains Download PDFInfo
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- CN100549017C CN100549017C CNB2006100811596A CN200610081159A CN100549017C CN 100549017 C CN100549017 C CN 100549017C CN B2006100811596 A CNB2006100811596 A CN B2006100811596A CN 200610081159 A CN200610081159 A CN 200610081159A CN 100549017 C CN100549017 C CN 100549017C
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Abstract
The present invention relates to a kind of application that contains benzene oxygen Monodentate compound; Compound is (1-a phenyl-2,3,4,5-tetramethyl-ring pentadienyl) (2,4, the 6-tri-butyl-phenoxy) titanium dichloride is used for catalyzing propone polymeric catalyzer, charges into an atmospheric propylene, the toluene solution that adds 90mL trityl five fluoro tetraphenyl borates, the transition metal mol ratio of boron and Primary Catalysts is 1.2, and temperature of reaction is 70 ℃, flows down the toluene solution 10mL that will contain 1mg catalyzer and triisobutyl aluminium at propylene gas and injects, the mol ratio of the aluminium in the triisobutyl aluminium and the transition metal of Primary Catalysts is 200, propylene pressure is risen to 5 normal atmosphere, and the reaction times is 30min, with 5%HCl/ methanol solution termination reaction; Polymerization activity reaches 1.0 * 10
6GPP (molTih)
-1More than, the weight-average molecular weight of polymkeric substance is between 10,000～350,000.
Description
Technical field
The present invention relates to the application of the luxuriant benzene oxygen of a kind of list substituted cyclopentadienyl metallocene compound, be specially adapted to catalysis synthetic macromolecule amount Atactic Polypropelene as olefin polymerization catalysis.
Background technology
More Atactic Polypropelene (APP) is used as fuel or is used to make waterproof paper, paper interlayer or coating etc. at first as the byproduct of isotatic polypropylene.The purposes of APP has had new development now, with APP and other macromolecular material blending, can make tackiness agent, seal gum, insulating board and communication cable.APP and pitch blending are used to pave the way and can improve shock-resistance and thermotolerance.High-molecular weight APP can also be used for the additive of rubber, plastics, lubricating oil and paraffin, low-voltage cable material and strippable coatings.APP is carried out the chlorination modified polypropylene film printing-ink of making.Just because of increasing of APP purposes, make its demand constantly increase, direct synthetic necessity has been arranged.At present, existing patent disclosure directly synthesize the Zigle-Natta Catalysts and its preparation method of APP, a kind of catalyzer is disclosed as WO8809348, this catalyzer with chlorine or hydrogenchloride with the organo-magnesium compound chlorination as carrier, again this carrier and titanium tetrachloride reaction are made.CN1146461A discloses a kind of preparation method who prepares low grade polypropylene catalyst, and this method generates homogeneous solution with silicoorganic compound with aluminum chloride in toluene, again with Mg (OC
2H
5)
2Chlorobenzene suspension reaction generate MgCl
2, and then with this carrier and TiCl
4Reaction makes catalyzer.Above catalyzer all will carry out chloridized in preparation process, thereby has increased to the corrodibility of equipment with to the pollution of environment.
CN1124740A discloses a kind of atactic polypropylene catalyst, and this catalyzer is a carrier with magnesium chloride and silicon-dioxide composite bicomponent, and this carrier adds earlier alcoholic solvent reaction for some time after being pre-mixed, and handles with lithium alkylide, then with TiCl again
4Reaction makes catalyzer.Use this catalyzer and carry out propylene polymerization as promotor, can obtain degree of isotacticity and be 20%～40% Atactic Polypropelene with triethyl aluminum.CN1262283A discloses a kind of atactic polypropylene catalyst, this catalyzer be with magnesium halide in varsol with C
1～C
8Monohydroxy-alcohol reaction form clear solution after, add the clay of 1～10 times of magnesium halide weight again, after the stirring reaction, add aluminum alkyls and continue reaction and obtain catalyzer.With this Preparation of Catalyst Atactic Polypropelene, its degree of isotacticity reaches 25%～40%.
Compare with traditional Zigle-Natta catalyzer, metallocene catalyst has high handiness at polyolefinic synthesis and structure controlling party mask.By the ligand structure of design catalyzer, structure and properties that can controlling polymers can obtain the Atactic Polypropelene product of different molecular weight.
Kotohiro Nomura in 1998 has synthesized single luxuriant benzene oxygen type metallocene catalyst (structure such as Fig. 1 a), but the patent of not seeing this type catalyzer so far first.Such catalyzer can the synthetic Atactic Polypropelene of catalyzing propone, but this catalyst stability can be poor, forms easily that oxo bridge connects metallocene compound and its overall activity is lower.Same year, reports such as Jonathan S.Vilardo synthesized the identical compound (as c) of structure, but do not see the report of relevant olefinic polymerization.People such as Alastair J.Nielson report in 1999 has synthesized the synthetic Atactic Polypropelene of the luxuriant phenol oxygen of non-list type catalyst (structure is as figure b) catalyzing propone, and this type of compound for catalysis activity is all lower.Polymer institute of domestic Zhongshan University synthesizes the catalyst system catalyzing propone polymerization of pentamethyl-cyclopentadiene tribenzyl titanium and methylaluminoxane composition, the Atactic Polypropelene of synthetic macromolecule amount.
Summary of the invention
The purpose of this invention is to provide the luxuriant benzene oxygen of a kind of list substituted cyclopentadienyl metallocene compound and its production and application as olefin polymerization catalysis.
It is specifically, of the present invention that to contain the structure expression that benzene oxygen Monodentate compound has as follows:
In said structure, wherein cyclopentadienyl group is single the replacement or polysubstituted group, and substituent R is that hydrogen, alkyl are or/and aryl; M is an IVB family metal; Two X are identical or different halogen, alkyl group, aromatic yl alkenyl group, the aromatic yl alkyl group that does not comprise benzyl or silylation groups; R1, R3 are phenoxy group adjacent substituting groups, and R2 is the substituted radical in the phenoxy group contraposition, are the hydrogen or the tertiary butyl;
Cyclopentadiene substituting group preferred alkyl in the described structural formula is or/and aryl, and wherein R can be that methyl is or/and phenyl, more preferably tetramethyl-one phenyl or phenylbenzene or pentamethyl-, most preferably tetramethyl-one phenyl; Preferred titanium of M or zirconium; Preferred chlorine of X or trimethyl silicane methyl; R1, R3 preferred tertiary butyl, R2 preferred tertiary butyl.
The comparatively preferred catalyzer of the present invention comprises: 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,4, the 6-tri-butyl-phenoxy)-titanium dichloride; 1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,4,6-tri-butyl-phenoxy titanium dichloride; 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,6-di-t-butyl phenoxy group)-titanium dichloride; 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,4-di-t-butyl phenoxy group)-titanium dichloride; 1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,6-di-t-butyl phenoxy group titanium dichloride; 1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,4-di-t-butyl phenoxy group titanium dichloride; 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,4, the 6-tri-butyl-phenoxy)-zirconium dichloride; 1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,4,6-tri-butyl-phenoxy zirconium dichloride; 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,6-di-t-butyl phenoxy group)-zirconium dichloride; 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,4-di-t-butyl phenoxy group)-zirconium dichloride; 1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,6-di-t-butyl phenoxy group zirconium dichloride; 1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,4-di-t-butyl phenoxy group zirconium dichloride; 1,2,3,4,5-
Methyl cyclopentadienyl-(2,4, the 6-tri-butyl-phenoxy)-titanium dichloride; 1,2,3,4,5-
Methyl cyclopentadienyl-(2,4, the 6-tri-butyl-phenoxy)-zirconium dichloride; 1,2,3,4,5-
Methyl cyclopentadienyl-(2, the 6-tri-butyl-phenoxy)-titanium dichloride; 1,2,3,4,5-pentamethyl-cyclopentadienyl-(2,6-di-t-butyl phenoxy group)-zirconium dichloride; 1,2,3,4,5-pentamethyl-cyclopentadienyl-(2,4-di-t-butyl phenoxy group)-zirconium dichloride; 1,2,3,4,5-pentamethyl-cyclopentadienyl-(2, the 4-tri-butyl-phenoxy)-titanium dichloride.
Catalyzer of the present invention can comprise the steps: with following method preparation
(1) in ether solvent, makes cyclopentadienyl derivative and MCl
4Be reaction in 2: 1 in molar ratio, obtain the cyclopentadiene metal chloride, temperature of reaction is-80～180 ℃, and the reaction times is 1～48 hour, and wherein cyclopentadienyl derivative can be tetramethyl-one benzyl ring pentadiene, monomethyl phenylbenzene cyclopentadiene, pentamethyl-cyclopentadiene.
(2) in ether solvent, make strongly alkaline compound and a kind of ligand derivatives that contains the phenoxy group side chain by etc. the mol ratio stirring reaction, remove and desolvate, obtain the metal-salt of part; Earlier strongly alkaline compound is dissolved in the ether during operation, adds the ethereal solution of ligand derivatives again, or opposite, and the add-on of ether solvent should be controlled at 20～100 times of reactant gross weight;
(3) in toluene solvant, make the ligand derivatives that contains the phenoxy group side chain and cyclopentadiene metal chloride by reaction with same mole, filter, gained filtrate is concentrated into solid separates out, collect solid and obtain containing benzene oxygen Monodentate compound;
(4) the benzene oxygen Monodentate compound that contains that aforesaid method is obtained at last carries out purifying, and the solvent that is used for purifying is the alkane of C1～C10, halogenated alkane or their mixture;
(1) step of aforesaid method, suitable temperature of reaction was-80～180 ℃, and preferred-80～80 ℃, the reaction times is 1～48 hour, preferred 1～12 hour; (2) step, described strongly alkaline compound was selected from basic metal, alkalimetal hydride, alkali metal alkyl compound, alkali metal amino compound or alkyl halide magnesium, preferred lithium, sodium, potassium, sodium hydride, potassium hydride KH, butyllithium, sodium amide, lithium methide, methylmagnesium-chloride or benzylmagnesium chloride, described ether solvent is selected from ether or tetrahydrofuran (THF).Can earlier strongly alkaline compound be dissolved in the ether during operation, add the ethereal solution of ligand derivatives again, also can be opposite, the add-on of ether solvent should be controlled at 20～100 times of reactant gross weight, preferred 40～50 times.
The present invention contains the mono-metallocene compound of phenoxy group, can cooperate with suitable promotor and be used for ethene, propylene, iso-butylene, 1-butylene, 1-hexene, 1-octene, 1-decene, end alkene, conjugation or unconjugated diene or polyenoid, vinylbenzene, norbornylene greater than 10 carbon, the tetrahydrobenzene monomer carries out polymerization, ethene or propylene and iso-butylene, 1-butylene, 1-hexene, 1-octene, 1-decene, greater than the end alkene of 10 carbon, the copolymerization of conjugation or unconjugated diene or polyenoid, vinylbenzene, norbornylene or cyclopentenes, polymerization activity reaches 1.0 * 10
6GPP (molTih)
-1More than, the weight-average molecular weight of polymkeric substance is between 10,000～350,000.
Embodiment
Embodiment 1
1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,4, the 6-tri-butyl-phenoxy)-titanium dichloride catalyzer
(1) 1-phenyl-2,3,4,5-tetramethyl-ring pentenyl titanous chloride synthetic
In the dry peace bottle of 50ml, take by weighing 1.61g (8.13mmol) 1-phenyl-2,3,4,5-tetramethyl--cyclopentadiene adds the 20ml anhydrous tetrahydro furan, under-78 ℃, slowly drips 7.5ml n-BuLi (9.00mmol).After one hour, reaction system rises to room temperature gradually, reacts after 8 hours, and solution becomes white pasty state, and the trimethylchlorosilane of 2.06ml is slowly added in the reaction soln in-78 ℃, at room temperature reacts thereafter 2 hours, and solution becomes glassy yellow gradually.Remaining trimethylchlorosilane and tetrahydrofuran solvent are under reduced pressure steamed, use hexane extraction, get yellow oil.
In exsiccant peace bottle, under nitrogen atmosphere, above-mentioned trimethyl silicon based substituent is dissolved in 15ml toluene, under-78 ℃, slowly add the toluene solution (5ml) of 1.8ml (4.06mmol) titanium tetrachloride, keep low temperature to react 1 hour down, slowly rise to room temperature, react after 24 hours the concentration response system, separate out the crystalline thing 1.67g of scarlet, productive rate 58.52%.
(2) 1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,4, the 6-tri-butyl-phenoxy)-titanium dichloride synthetic
In the dry peace bottle of 50ml, under-78 ℃, to 3g 2,4, the diethyl ether solution of 6-tri-butyl-phenol (15ml) slowly adds 1.2mmoln-BuLi (10.30ml), reacts after 4 hours, steam solvent, get white powder 2.8g with dry hexane wash resistates, productive rate 92.9%.
In the dry peace bottle of 100ml, add 0.66g1-phenyl-2,3,4,5-tetramethyl-ring pentenyl titanous chloride and 30ml dry toluene are with 0.50g 2,4, the toluene solution (5ml) of 6-tri-butyl-phenol lithium salts slowly adds above-mentioned system at-78 ℃, slowly rises to room temperature, seal and be heated to 60 ℃, react system clarification after a day, steam solvent, and use the hexane wash resistates, get dark red solid powder catalyst 0.72g, productive rate 66.36%.
(3) with this catalyst propylene polymerization (boron additive and triisobutyl aluminium are promotor)
Be aggregated in the 250mL autoclave and carry out, reactor 110 ℃ of bakings 1 hour under vacuum charge into an atmospheric propylene before the polymerization, and 90mL is contained a certain amount of Ph
3CB (C
6F
5)
4Toluene solution add in the reactor, the boron in the promotor and the mol ratio of the transition metal in the Primary Catalysts are 1.2, temperature of reaction is, under agitation condition, reaction system is heated to 70 ℃, then, flow down and to contain in toluene solution (10mL) injecting reactor of 1mg catalyzer and certain proportion triisobutyl aluminium at propylene gas by a special feeder, the aluminium in the triisobutyl aluminium and the mol ratio of the transition metal in the Primary Catalysts are 200, propylene pressure is risen to 5 normal atmosphere, and pick up counting.Reaction times is generally 30min.Reaction finishes back emptying reactor, stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings obtain polymerisate 4.24g to constant weight, and catalyst activity is 1.41 * 10
6GPP (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 96000.
Embodiment 2
1-phenyl-2,3,4, the building-up process of 5-tetramethyl-ring pentenyl titanous chloride is reacted under the ice-water bath condition, and other operation is identical with embodiment 1, gets catalyst prod 0.78g, productive rate 71.80%.
Method catalyzed ethylene polymerization according among the embodiment 1 obtains polymerisate 5.24g, and catalyst activity is 2.21 * 10
6GPE (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 270000.
Embodiment 3
1-phenyl-2,3,4, the building-up process of 5-tetramethyl-ring pentenyl titanous chloride is reacted under 40 ℃ of conditions, and other operation is identical with embodiment 1, gets product 0.75g, productive rate 69.15%.
Method catalyzing butene polymerization according among the embodiment 1 obtains polymerisate 3.84g, and catalyst activity is 1.14 * 10
6GPE (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 83000.
Embodiment 4
1-phenyl-2,3,4, the building-up process of 5-tetramethyl-ring pentenyl titanous chloride rises to room temperature gradually and reacted 1 hour under agitation condition.Other operation is identical with embodiment 1, gets product 0.79g, productive rate 72.95%.
According to the method catalyzed ethylene among the embodiment 1 and the mixture of norbornylene, the weight ratio of ethene and norbornylene 10: 1 is carried out polymerization, obtains polymerisate 3.59g, and catalyst activity is 1.22 * 10
6GPE (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 145000.
Embodiment 5
1-phenyl-2,3,4, the building-up process of 5-tetramethyl-ring pentenyl titanous chloride rises to room temperature gradually and reacted 6 hours under agitation condition.Other operation is identical with embodiment 1, gets product 0.82g, productive rate 79.75%.
According to the mixture of method catalyzed ethylene among the embodiment 1 and 1-octene, the weight ratio of ethene and 1-octene 10: 1 is carried out polymerization, obtains polymerisate 4.59g, and catalyst activity is 2.02 * 10
6GPE (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 235000.
Embodiment 6
1-phenyl-2,3,4, the building-up process of 5-tetramethyl-ring pentadienyl-(2,4, the 6-tri-butyl-phenoxy)-titanium dichloride, the add-on of solvent is 50 times of reactant gross weight.Other operation is identical with embodiment 1, gets product 0.80g, productive rate 78.13%.
According to method catalyzed ethylene among the embodiment 1 and cinnamic mixture, ethene and cinnamic weight ratio 8: 1 are carried out polymerization, obtain polymerisate 3.48g, and catalyst activity is 1.68 * 10
6GPE (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 115000.
Embodiment 7
1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,4,6-tri-butyl-phenoxy titanium dichloride catalyzer
Synthesizing of (1) 1,2-phenylbenzene-3-methyl-cyclopentadienyl titanous chloride:
Under nitrogen atmosphere, in 100ml peace bottle, add 2.50g (10.8mmol) 1,2-phenylbenzene-4 methyl-cyclopentadiene and 30ml anhydrous tetrahydro furan under-78 ℃, slowly drip the hexane solution of 20mln-BuLi (11mmol).After one hour, reaction system rises to room temperature gradually, reacts after 8 hours, and solution becomes white pasty state, and tetrahydrofuran (THF) is depressurized and steams, and (3 * 20ml), the unreacted nBuLi of flush away gets white pressed powder to add hexane.The lithium salts that generates is dissolved in the tetrahydrofuran (THF) of 30ml, the 12mmol trimethylchlorosilane is slowly added in the reaction soln in-78 ℃, at room temperature reacted thereafter 2 hours, solution becomes glassy yellow gradually.Remaining trimethylchlorosilane and tetrahydrofuran solvent are under reduced pressure steamed, get yellow oil, use dichloromethane extraction, extract under reduced pressure purifying gets the trimethyl silicon based substituent of 2.63 grams, productive rate 80.1%.
Under nitrogen atmosphere, in exsiccant peace bottle, add 8.7mmol titanium tetrachloride and 40ml toluene, under-78 ℃, the toluene solution of above-mentioned trimethyl silicon based substituent is slowly added, keep low temperature to react 1 hour down, slowly rise to room temperature, react after 24 hours, decompression steams solvent down, gets the scarlet material.With dichloromethane solution extraction, add an amount of hexane (dichloromethane/hexane is about 1: 3), be concentrated into saturatedly, under room temperature, separate out red crystals 2.01g, productive rate 60.2%.
(2) 1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,4,6-tri-butyl-phenoxy titanium dichloride
In the dry peace bottle of 50ml, with 4.0g 2,4, the molten sub-20ml diethyl ether solution of 6-tri-butyl-phenol slowly adds 10.9ml 1.4 M n-BuLi solution at-78 ℃, steams solvent after 2 hours, with dry hexane wash precipitate white powder 3.8g, productive rate 93%.
In the dry peace bottle of 100ml, add 1.5 grams 1,2-phenylbenzene-4-methyl-cyclopentadienyl titanous chloride and 60ml dry toluene, with 1.045 grams 2,4, the toluene solution (8ml) of 6-tri-butyl-phenol lithium salts slowly adds above-mentioned system at-78 ℃, slowly rise to room temperature, seal, be heated to 60 ℃, react that system becomes dark red solution after 8 hours, steam solvent, the solid hexane wash gets dark red solid 1.42g, productive rate 60%.
(3) according to the method catalyzing propone polymerization among the embodiment 1, obtain polymerisate 4.84g, catalyst activity is 2.54 * 10
6GPE (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 253000.
Embodiment 8
Press embodiment 7, solids wash is washed with decane in the step (2), gets dark red solid 1.35g, productive rate 58.2%.
Method catalyzing propone polymerization according among the embodiment 1 obtains polymerisate 4.69g, and catalyst activity is 2.41 * 10
6GPE (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 248000.
Embodiment 9
1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,4, the 6-tri-butyl-phenoxy)-zirconium dichloride catalyzer
Press embodiment 1, change titanium tetrachloride in the step (1) into zirconium tetrachloride, get dark red solid powder catalyst 0.92g, productive rate 84.8%.
Method catalyzing propone polymerization according among the embodiment 1 obtains polymerisate 7.59g, and catalyst activity is 4.10 * 10
6GPE (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 260000.
Embodiment 10
1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,6-di-t-butyl phenoxy group)-zirconium dichloride catalyzer
Press embodiment 9, with in the step (2) 2,4, the 6-tri-butyl-phenol changes 2,6 di t butyl phenol into, dark red solid powder catalyst 0.89g, productive rate 83.4%.
Method catalyzing propone polymerization according among the embodiment 1 obtains polymerisate 7.59g, and catalyst activity is 4.10 * 10
6GPE (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 255000.
Embodiment 11
1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,6-di-t-butyl phenoxy group)-titanium dichloride catalyzer
Press embodiment 1, with in the step (2) 2,4, the 6-tri-butyl-phenol changes 2,6 di t butyl phenol into, dark red solid powder catalyst 0.81g, productive rate 79.3%.
Method catalyzing propone polymerization according among the embodiment 1 obtains polymerisate 4.59g, and catalyst activity is 2.50 * 10
6GPE (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 235000.
Embodiment 12
1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,4-di-t-butyl phenoxy group)-titanium dichloride catalyzer
Press embodiment 1, with in the step (2) 2,4, the 6-tri-butyl-phenol changes 2 into, the 4-DI-tert-butylphenol compounds, dark red solid powder catalyst 0.77g, productive rate 76.9%.
Method catalyzing propone polymerization according among the embodiment 1 obtains polymerisate 3.99g, and catalyst activity is 2.01 * 10
6GPE (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 245000.
Embodiment 13
1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl-(2,4-di-t-butyl phenoxy group)-zirconium dichloride catalyzer
Press embodiment 12, change titanium tetrachloride in the step (1) into zirconium tetrachloride, get dark red solid powder catalyst 0.97g, productive rate 86.8%.
Method catalyzing propone polymerization according among the embodiment 1 obtains polymerisate 3.99g, and catalyst activity is 2.01 * 10
6GPE (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 285000.
Embodiment 14
1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,4,6-tri-butyl-phenoxy zirconium dichloride catalyzer
Press embodiment 7, change titanium tetrachloride in the step (1) into zirconium tetrachloride, get dark red solid powder catalyst 1.37g, productive rate 58.8%.
Method catalyzing propone polymerization according among the embodiment 1 obtains polymerisate 6.89g, and catalyst activity is 3.91 * 10
6GPE (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 315000.
Embodiment 15
1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,6-di-t-butyl phenoxy group zirconium dichloride catalyzer
Press embodiment 14, with in the step (2) 2,4, the 6-tri-butyl-phenol changes 2,6 di t butyl phenol into, dark red solid powder catalyst 1.77g, productive rate 61.8%.
Method catalyzing propone polymerization according among the embodiment 1 obtains polymerisate 6.99g, and catalyst activity is 4.00 * 10
6GPE (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 323000.
Embodiment 16
1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,4-di-t-butyl phenoxy group zirconium dichloride catalyzer
Press embodiment 15, with in the step (2) 2,4, the 6-tri-butyl-phenol changes 2 into, the 4-DI-tert-butylphenol compounds, dark red solid powder catalyst 1.79g, productive rate 62.1%.
Method catalyzing propone polymerization according among the embodiment 1 obtains polymerisate 7.09g, and catalyst activity is 4.08 * 10
6GPE (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 318000.
Embodiment 17
1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,4-di-t-butyl phenoxy group titanium dichloride catalyzer
Press embodiment 16, change zirconium tetrachloride in the step (1) into titanium tetrachloride, get dark red solid powder catalyst 1.79g, productive rate 62.1%.
Method catalyzing propone polymerization according among the embodiment 1 obtains polymerisate 7.09g, and catalyst activity is 4.08 * 10
6GPE (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 318000.
Embodiment 18
1,2-phenylbenzene-3-methyl-cyclopentadienyl-2,6-di-t-butyl phenoxy group titanium dichloride catalyzer
Press embodiment 15, change zirconium tetrachloride in the step (1) into titanium tetrachloride, get dark red solid powder catalyst 1.57g, productive rate 54.8%.
Method catalyzing propone polymerization according among the embodiment 1 obtains polymerisate 4.69g, and catalyst activity is 2.37 * 10
6GPE (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 220000.
Embodiment 19
1,2,3,4,5-pentamethyl-cyclopentadienyl-(2,4, the 6-tri-butyl-phenoxy)-titanium dichloride catalyzer
(1) 1,2,3,4,5-pentamethyl-cyclopentenyl titanous chloride synthetic
In the dry peace bottle of 50ml, take by weighing 1.61g (8.13mmol) 1,2,3,4,5-pentamethyl--cyclopentadiene adds the 20ml anhydrous tetrahydro furan, under-78 ℃, slowly drips 7.5ml n-BuLi (9.00mmol).After one hour, reaction system rises to room temperature gradually, reacts after 8 hours, and solution becomes white pasty state, and the trimethylchlorosilane of 2.06ml is slowly added in the reaction soln in-78 ℃, at room temperature reacts thereafter 2 hours, and solution becomes glassy yellow gradually.Remaining trimethylchlorosilane and tetrahydrofuran solvent are under reduced pressure steamed, use hexane extraction, get yellow oil.
In exsiccant peace bottle, under nitrogen atmosphere, above-mentioned trimethyl silicon based substituent is dissolved in 15ml toluene, under-78 ℃, slowly add the toluene solution (5ml) of 1.8ml (4.06mmol) titanium tetrachloride, keep low temperature to react 1 hour down, slowly rise to room temperature, react after 24 hours the concentration response system, separate out the crystalline thing 1.97g of scarlet, productive rate 67.32%.
(2) 1,2,3,4,5-pentamethyl-cyclopentadienyl-(2,4, the 6-tri-butyl-phenoxy)-titanium dichloride synthetic
In the dry peace bottle of 50ml, under-78 ℃, to 3g 2,4, the diethyl ether solution of 6-tri-butyl-phenol (15ml) slowly adds 1.2mmoln-BuLi (10.30ml), reacts after 4 hours, steam solvent, get white powder 2.8g with dry hexane wash resistates, productive rate 92.9%.
In the dry peace bottle of 100ml, add 0.66g 1-phenyl-2,3,4,5-tetramethyl-ring pentenyl titanous chloride and 30ml dry toluene are with 0.50g 2,4, the toluene solution (5ml) of 6-tri-butyl-phenol lithium salts slowly adds above-mentioned system at-78 ℃, slowly rises to room temperature, seal and be heated to 60 ℃, react system clarification after a day, steam solvent, and use the hexane wash resistates, get dark red solid powder catalyst 0.79g, productive rate 69.56%.
Method catalyzing propone polymerization according among the embodiment 1 obtains polymerisate 4.89g, and catalyst activity is 2.67 * 10
6GPE (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 26000.
Embodiment 20
1,2,3,4,5-pentamethyl-cyclopentadienyl-(2,4, the 6-tri-butyl-phenoxy)-zirconium dichloride catalyzer
Press embodiment 19, change titanium tetrachloride in the step (1) into zirconium tetrachloride, get dark red solid powder catalyst 1.56g, productive rate 54.5%.
Method catalyzing propone polymerization according among the embodiment 1 obtains polymerisate 6.69g, and catalyst activity is 3.77 * 10
6GPE (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 45000.
Embodiment 21
1,2,3,4,5-pentamethyl-cyclopentadienyl-(2,6-di-t-butyl phenoxy group)-zirconium dichloride catalyzer
Press embodiment 20, with in the step (2) 2,4, the 6-tri-butyl-phenol changes 2,6 di t butyl phenol into, dark red solid powder catalyst 1.64g, productive rate 58.7%.
Method catalyzing propone polymerization according among the embodiment 1 obtains polymerisate 5.69g, and catalyst activity is 3.87 * 10
6GPE (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 35000.
Embodiment 22
1,2,3,4,5-pentamethyl-cyclopentadienyl-(2,4-di-t-butyl phenoxy group)-zirconium dichloride catalyzer
Press embodiment 20, with in the step (2) 2,4, the 6-tri-butyl-phenol changes 2 into, the 4-DI-tert-butylphenol compounds, dark red solid powder catalyst 1.54g, productive rate 53.7%.
Method catalyzing propone polymerization according among the embodiment 1 obtains polymerisate 5.89g, and catalyst activity is 3.89 * 10
6GPE (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 38000.
Embodiment 23
1,2,3,4,5-pentamethyl-cyclopentadienyl-(2, the 6-tri-butyl-phenoxy)-titanium dichloride catalyzer
Press embodiment 21, change zirconium tetrachloride in the step (1) into titanium tetrachloride, get dark red solid powder catalyst 1.44g, productive rate 52.1%.
Method catalyzing propone polymerization according among the embodiment 1 obtains polymerisate 3.69g, and catalyst activity is 1.67 * 10
6GPE (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 25000.
Embodiment 24
1,2,3,4,5-pentamethyl-cyclopentadienyl-(2, the 4-tri-butyl-phenoxy)-titanium dichloride catalyzer
Press embodiment 23, with in the step (2) 2,4, the 6-tri-butyl-phenol changes 2 into, the 4-DI-tert-butylphenol compounds, dark red solid powder catalyst 1.41g, productive rate 51.9%.
Method catalyzing propone polymerization according among the embodiment 1 obtains polymerisate 3.89g, and catalyst activity is 1.72 * 10
6GPE (molTih)
-1, the weight-average molecular weight of measuring polymkeric substance with the GPC instrument is 18000.
Molecular structure with the nuclear-magnetism characterize polymers
C
13-NMR
Claims (1)
1. application that contains benzene oxygen Monodentate compound, it is characterized in that: containing benzene oxygen Monodentate compound chemical name is (1-phenyl-2,3,4,5-tetramethyl-ring pentadienyl) (2,4, the 6-tri-butyl-phenoxy) titanium dichloride, this benzene oxygen Monodentate compound is as catalyzing propone polymeric catalyzer, be aggregated in the 250mL autoclave and carry out, reactor 110 ℃ of bakings 1 hour under vacuum before the polymerization, charge into an atmospheric propylene, the toluene solution that 90mL is contained a certain amount of trityl five fluoro tetraphenyl borates adds in the reactor, the boron in the promotor and the mol ratio of the transition metal in the Primary Catalysts are 1.2, temperature of reaction is, under agitation condition, reaction system is heated to 70 ℃, then, flow down and to contain in the toluene solution 10mL injecting reactor of 1mg catalyzer and certain proportion triisobutyl aluminium at propylene gas by a feeder, the aluminium in the triisobutyl aluminium and the mol ratio of the transition metal in the Primary Catalysts are 200, propylene pressure is risen to 5 normal atmosphere, and pick up counting, reaction times is 30min, reaction finishes back emptying reactor, stop polyreaction with the 5%HCl/ methanol solution, leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings obtain polymerisate to constant weight.
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| CN102791746B (en) * | 2010-03-08 | 2015-06-17 | Lg化学株式会社 | Method for preparing supported metallocene catalyst and method for preparing polyolefin using the same |
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| CN104059179B (en) * | 2013-03-21 | 2016-09-21 | 中国石油化工股份有限公司 | A kind of supported single metallocene catalyst for vinyl polymerization |
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| CN105646741B (en) * | 2016-03-18 | 2018-03-13 | 中国科学院长春应用化学研究所 | A kind of preparation method of luxuriant zirconium type olefin polymerization catalysis |
| JP7175426B2 (en) * | 2020-07-31 | 2022-11-18 | ポリプラスチックス株式会社 | Method for producing cyclic olefin copolymer |
| CN114805650B (en) * | 2022-04-02 | 2022-12-30 | 东华工程科技股份有限公司 | Metallocene catalyst for preparing cycloolefin copolymer and preparation method thereof |
| CN114716585B (en) * | 2022-04-13 | 2023-02-28 | 吉林大学 | Catalyst system containing aryloxy side-arm metallocene fourth subgroup metal complex and application thereof |
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