CN117069771A - Metallocene-non-metallocene complex, preparation method thereof and application thereof in preparation of disentangled ultra-high molecular weight polyethylene - Google Patents

Metallocene-non-metallocene complex, preparation method thereof and application thereof in preparation of disentangled ultra-high molecular weight polyethylene Download PDF

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CN117069771A
CN117069771A CN202311032500.9A CN202311032500A CN117069771A CN 117069771 A CN117069771 A CN 117069771A CN 202311032500 A CN202311032500 A CN 202311032500A CN 117069771 A CN117069771 A CN 117069771A
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complex
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unsubstituted
halogen
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王保力
曾玺文
崔冬梅
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • 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
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Abstract

The complex provided by the application has a structure of formula (I), formula (II) or formula (III), and consists of a ligand and a central metal, wherein the ligand is a hetero atom containing an aromatic group, the central metal is Ti, and can be used for catalyzing the synthesis of ultra-high molecular weight polyethylene, the viscosity average molecular weight of the prepared ultra-high molecular weight polyethylene is 100-800 ten thousand, the entanglement degree between molecular chains is lower, the melting point is 130-145 ℃, and the polymerization activity is higher than 10 6 . Moreover, the complex provided by the application is simple to synthesize, and the yield is high and can reach 50% -60%.

Description

Metallocene-non-metallocene complex, preparation method thereof and application thereof in preparation of disentangled ultra-high molecular weight polyethylene
Technical Field
The application relates to the technical field of catalysts and applications thereof, in particular to a metallocene-non-metallocene complex, a preparation method thereof and an application thereof in preparation of disentangled ultra-high molecular weight polyethylene.
Background
Gel spinning (gelspin) was invented in the netherlands in 1975 using decalin as a solvent, and Ultra High Molecular Weight Polyethylene (UHMWPE) fibers were successfully prepared and patented in 1979. Since then, the gel spinning method has been proved to be an effective method for manufacturing high-strength polyethylene fibers through ten years of effort research, and has industrial prospect. The ultra-high molecular weight polyethylene has ultra-strong wear resistance and self-lubricating property, high strength, stable chemical property and strong ageing resistance, and plays a role in the fields of modern war, aviation, aerospace, sea area defense equipment and the like.
The ultra-high molecular weight polyethylene has higher molecular weight, poor fluidity and difficult processing. The realization of the synthesis and performance processing of ultra-high molecular weight polyethylene is of great importance for its industrial application, but few catalysts can be used at present. Moreover, almost all commercially available UHMWPE is produced using a Ziegler-Natta catalyst (Z-N catalyst). The Z-N catalyst is a heterogeneous catalyst, and contains a plurality of active sites, and the active sites show different reactivity, so that the molecular weight distribution of the obtained polymer is wider. Meanwhile, due to the high reaction temperature, the prepared UHMWPE can generate molecular chain entanglement, so that the movement capacity of the polymer chain is inhibited, and the processability of the product is affected. The metallocene catalyst and the non-metallocene catalyst are single-activity catalysts, compared with the Z-N catalyst, the active polymerization can be realized, the polymer with narrower molecular weight distribution is obtained, the polymerization temperature is lower, the condition of entanglement of molecular chains can be effectively avoided, but the metallocene catalyst or the non-metallocene catalyst disclosed in the prior art cannot be used for synthesizing UHMWPE.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present application is to provide a complex, a preparation method and use thereof, wherein the complex provided by the present application is a metallocene-non-metallocene complex, and is composed of a ligand and a central metal, and can be used for catalytic synthesis of UHMWPE, and has the advantages of narrow molecular weight distribution and low entanglement degree between molecular chains.
The application provides a complex shown in a formula (I), a formula (II) or a formula (III):
wherein Z is selected from S, O, (CH) 2 ) n The method comprises the steps of carrying out a first treatment on the surface of the n is an integer of 1 to 5;
R 1 selected from substituted or unsubstitutedC1-C12 alkyl, substituted or unsubstituted phenyl or halogen;
R 2 、R 3 independently selected from hydrogen, substituted or unsubstituted C1-C12 alkyl or halogen;
R 4 、R 5 、R 6 、R 7 、R 8 independently selected from hydrogen, substituted or unsubstituted C1-C12 alkyl or halogen;
R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 each independently selected from hydrogen, substituted or unsubstituted silicon-based, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted aryl, or halogen.
The complex provided by the application is a metallocene-non-metallocene complex, and consists of a ligand and a central metal, wherein the ligand is a hetero atom type containing an aromatic group, the central metal is Ti, the ligand can be used for catalyzing the synthesis of ultra-high molecular weight polyethylene, the viscosity average molecular weight of the prepared ultra-high molecular weight polyethylene is 100-800 ten thousand, the entanglement degree between molecular chains is lower, the melting point is 130-145 ℃, and the polymerization activity is higher than 10 6 . Moreover, the complex provided by the application is simple to synthesize, and the yield is high and can reach 50% -60%.
In some embodiments, Z is selected from S or CH 2 ；
R 1 Selected from substituted or unsubstituted C1-C5 alkyl, halogen;
R 2 、R 3 independently selected from hydrogen, substituted or unsubstituted C1-C5 alkyl;
R 4 、R 5 、R 6 、R 7 、R 8 independently selected from hydrogen, substituted or unsubstituted C1-C12 alkyl or halogen;
R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 each independently selected from hydrogen, alkyl substituted silicon based, substituted or unsubstituted C1-C5 alkyl.
In some specific embodiments, the Z is selected from S, CH 2 ；
The R is 1 Selected from Cl, CH 3 ；
The R is 2 、R 3 Is any one of tertiary butyl, methyl, octyl and halogen;
the R is 4 、R 5 、R 6 、R 7 、R 8 Each independently selected from any one of hydrogen, methyl, tertiary butyl and halogen;
the R is 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 Each independently selected from any one of hydrogen, methyl, ethyl, tertiary butyl, octyl and trimethylsilyl;
in some specific embodiments, the complex is selected from the group consisting of:
complex 1: z=s, R 1 ＝Cl,R 2 ＝C(CH 3 ) 3 ,R 3 ＝C(CH 3 ) 3 ,R 4 ＝H,R 5 ＝H,R 6 ＝H,R 7 ＝H,R 8 ＝H,R 9 ＝H,R 10 ＝H,R 11 ＝H,R 12 ＝H,R 13 ＝H；
Complex 2: z=s, R 1 ＝Cl,R 2 ＝C(CH 3 ) 3 ,R 3 ＝C(CH 3 ) 3 ,R 4 ＝F,R 5 ＝F,R 6 ＝F,R 7 ＝F,R 8 ＝F,R 9 ＝H,R 10 ＝H,R 11 ＝H,R 12 ＝H,R 13 ＝H；
Complex 3: z=s, R 1 ＝CH 3 ,R 2 ＝C(CH 3 ) 3 ,R 3 ＝C(CH 3 ) 3 ,R 4 ＝H,R 5 ＝H,R 6 ＝H,R 7 ＝H,R 8 ＝H,R 9 ＝H,R 10 ＝H,R 11 ＝H,R 12 ＝H,R 13 ＝H；
Complex 4: z=ch 2 ,R 1 ＝Cl,,R 2 ＝C(CH 3 ) 3 ,R 3 ＝C(CH 3 ) 3 ,R 4 ＝H,R 5 ＝H,R 6 ＝H,R 7 ＝H,R 8 ＝H,R 9 ＝H,R 10 ＝H,R 11 ＝H,R 12 ＝H,R 13 ＝H；
Complex 5: z=ch 2 ,R 1 ＝Cl,R 2 ＝H,R 3 ＝H,R 4 ＝H,R 5 ＝H,R 6 ＝H,R 7 ＝H,R 8 ＝H,R 9 ＝H,R 10 ＝H,R 11 ＝H,R 12 ＝H,R 13 ＝H；
Complex 6: z=ch 2 ,R 1 ＝CH 3 ,R 2 ＝C(CH 3 ) 3 ,R 3 ＝C(CH 3 ) 3 ,R 4 ＝F,R 5 ＝F,R 6 ＝F,R 7 ＝F,R 8 ＝F,R 9 ＝H,R 10 ＝H,R 11 ＝H,R 12 ＝H,R 13 ＝H；
Complex 7: z=s, R 1 ＝Cl,R 2 ＝C(CH 3 ) 3 ,R 3 ＝C(CH 3 ) 3 ,R 4 ＝H,R 5 ＝H,R 6 ＝H,R 7 ＝H,R 8 ＝H,R 9 ＝CH 3 ,R 10 ＝CH 3 ,R 11 ＝Si(CH 3 ) 3 ,R 12 ＝CH 3 ,R 13 ＝CH 3 ；
Complex 8: z=s, R 1 ＝Cl,R 2 ＝H,R 3 ＝H,R 4 ＝H,R 5 ＝H,R 6 ＝H,R 7 ＝H,R 8 ＝H,R 9 ＝CH 3 ,R 10 ＝CH 3 ,R 11 ＝Si(CH 3 ) 3 ,R 12 ＝CH 3 ,R 13 ＝CH 3 ；
Complex 9: z=s, R 1 ＝Cl,R 2 ＝H,R 3 ＝H,R 4 ＝H,R 5 ＝H,R 6 ＝H,R 7 ＝H,R 8 ＝H,R 9 ＝H,R 10 ＝H,R 11 ＝Si(CH 3 ) 3 ,R 12 ＝H,R 13 ＝H；
Complex 10: z=ch 2 ,R 1 ＝Cl,R 2 ＝C(CH 3 ) 3 ,R 3 ＝C(CH 3 ) 3 ,R 4 ＝F,R 5 ＝F,R 6 ＝F,R 7 ＝F,R 8 ＝F,R 9 ＝H,R 10 ＝H,R 11 ＝Si(CH 3 ) 3 ,R 12 ＝H,R 13 ＝H；
Complex 11: z=s, R 1 ＝Cl,R 2 ＝C(CH 3 ) 3 ,R 3 ＝C(CH 3 ) 3 ,R 4 ＝H,R 5 ＝H,R 6 ＝H,R 7 ＝H,R 8 ＝H,R 9 ＝H,R 10 ＝H,R 11 ＝H,R 12 ＝H,R 13 ＝H,R 14 ＝H，R 15 ＝H；
Complex 12: z=s, R 1 ＝Cl,R 2 ＝C(CH 3 ) 3 ,R 3 ＝C(CH 3 ) 3 ,R 4 ＝H,R 5 ＝H,R 6 ＝H,R 7 ＝H,R 8 ＝H,R 9 ＝H,R 10 ＝H,R 11 ＝H,R 12 ＝H,R 13 ＝H,R 14 ＝H,R 15 ＝H,R 16 ＝H，R 17 ＝H。
In some specific embodiments, the complex has the structure of formulas (1) through (4):
the application also provides a preparation method of the complex, which comprises the following steps:
combining a ligand of formula (a) with a lithiating agent and CpTiX 3 Mixing and reacting to obtain a complex shown in a formula (I), (II) or (III), wherein R1 is selected from X, and X is halogen;
wherein CpTiX is 3 Wherein Cp is selected from substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, substituted or unsubstituted fluorenyl, and X is halogen;
alternatively, R is 1 The complex of formula (I), formula (II) or formula (III) which is halogen is mixed with an alkyl reagent to obtain R 1 A complex of formula (I), formula (II) or formula (III) which is not halogen.
The synthetic route is as follows:
the source of the compound represented by the formula (a) is not particularly limited, and it may be commercially available or may be prepared according to a method known to those skilled in the art. The following figure shows a process for preparing compound (a).
Firstly, under the nitrogen atmosphere, mixing the compound b and the compound c at 0-150 ℃ to obtain FeCl 3 ，MgCl 2 And the like as a catalyst, reacting for 10-72 h, filtering after the reaction is finished, concentrating a reaction solution, and separating by column chromatography, petroleum ether: ethyl acetate 7-10: 0 to 3 to obtain the compound a.
The method comprises the steps of firstly mixing a compound shown in a formula (a) with a lithiation reagent solution in a nitrogen atmosphere at the temperature of-78 ℃ to 0 ℃ for reaction. In some specific embodiments, the solvent of the lithiation reagent solution is n-hexane and the concentration of the lithiation reagent solution is 1 to 5M, preferably 2 to 4M, more preferably 2.5 to 3.2M. In some specific embodiments, the molar ratio of the compound of formula (a) to lithiating agent is from 1:1 to 5, preferably 1:1. In some specific embodiments, the lithiation agent is selected from the group consisting of alkyllithium, including but not limited to n-butyllithium, and the like. In some specific implementations, the reaction temperature is-78 to 0 ℃, preferably-60 to 0 ℃, for a period of 10 to 24 hours, preferably 12 to 20 hours.
After the reaction is finished, filtering, concentrating and recrystallizing the reaction mixture to obtain a white solid, and then mixing the white solid with CpTiX 3 The reaction is carried out to obtain R 1 Complexes of formula (I), formula (II) or formula (III) which are halogen. The application relates to CpTiX 3 The source of (2) is not particularly limited and may be commercially available or may be prepared according to a method known to those skilled in the art. Wherein Cp is selected from substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, substituted or unsubstituted fluorene; x is halogen, preferably Cl.
Specifically, the application prepares the white solid and CpTiX under the conditions of minus 78 ℃ to 0 ℃ and nitrogen 3 Respectively dissolving, mixing and reacting. In some specific implementations, the dissolved solvent is one or more of aliphatic saturated hydrocarbons, aromatic hydrocarbons, aryl halides, and cycloalkanes, preferably toluene. The concentration of the white solid after dissolution is 0.05-5 mmol/mL, preferably 0.1-4 mmol/mL, more preferably 0.15-2 mmol/mL; the CpTiX is 3 The concentration after dissolution is 0.05 to 5mmol/mL, preferably 0.1 to 4mmol/mL, more preferably 0.15 to 2mmol/mL. In some specific implementations, the CpTiX 3 The molar ratio to the white solid obtained is 1:1 to 5, preferably 1:1. In some specific implementations, the reaction temperature is-78 to 0 ℃, preferably-60 to 0 ℃, for a period of 10 to 24 hours, preferably 12 to 20 hours. After the reaction is finished, filtering, concentrating and recrystallizing the reaction mixture to obtain R 1 Complexes of formula (I), formula (II) or formula (III) which are halogen.
Alternatively, the present application will provide R 1 The complex of formula (I), formula (II) or formula (III) which is halogen is mixed with an alkyl reagent to obtain R 1 A complex of formula (I), formula (II) or formula (III) which is not halogen. In some specific embodiments, the alkylating agent includes, but is not limited to, CH 3 BrMg et al, said alkylating agent and said R 1 Formula (I), formula (II) or formula (II) being halogenThe molar ratio of the complex of formula (III) is 1:2 to 10, preferably 1:2. In some specific implementations, the alkylation reaction is carried out at a temperature of-78 ℃ to 0 ℃, preferably-60 ℃ to 0 ℃, for a time of 1 to 10 hours, preferably 3 to 5 hours. After the reaction is finished, filtering to remove the solvent, extracting with hexane, concentrating to obtain R 1 Complexes of formula (I), formula (II) or formula (III) which are not halogen.
The application also provides application of the metallocene-non-metallocene complex in catalyzing ethylene polymerization. The ultra-high molecular weight polyethylene can be obtained by catalyzing the polymerization of polyethylene by adopting the complex, and in some specific implementation modes, the viscosity average molecular weight of the ultra-high molecular weight polyethylene is 100-800 ten thousand, the entanglement degree among molecular chains is low, and the molecular weight is preferably 100-600 ten thousand, and more preferably 100-500 ten thousand. The ultra-high molecular weight polyethylene has a molecular weight distribution of 1 to 10, preferably 1 to 6, more preferably 1 to 4. In the present application, the ultra-high molecular weight polyethylene has a crystallinity of between 60 and 90% and a melting point of 130 to 150 ℃.
The application also provides a catalyst composition, which comprises the complex, the organoboron salt compound and the organoaluminum compound.
In the present application, the organoboron salt compound may be an ionic compound composed of an organoboron anion and a cation; the organoboron anions are not limited to tetraphenylborate ([ BPh) 4 ] - ) Tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate ([ B (C) 6 F 5 ) 4 ] - ) Tetrakis (tetrafluoromethylphenyl) borate, tetrakis (tolyl) borate, tetrakis (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [ tris (pentafluorophenyl) phenyl ]]Borate or undecahydride-7, 8-dicarbaundecaborate; the cations include, but are not limited to, carbonium cations, oxonium cations, ammonium cations, phosphonium cations, cycloheptatrienyl cations, or transition metal containing ferrocenium cations comprising trisubstituted carbonium cations such as triphenylcarbonium cations ([ Ph ] 3 C] + ) And a tris (substituted phenyl) carbonium cation, and more specific examples of the tris (substituted phenyl) carbonium cation include a tris (tolyl) carbonium cation; ammonium cations include trialkylammonium cations such as trimethylammonium cations, triethylammonium cations ([ NEt ] 3 H] + ) Tripropylammonium cation and tributylammonium cation; n, N-dialkylanilinium cations such as N, N-dimethylanilinium cation ([ PhNMe) 2 H] + ) N, N-diethylanilinium cations and N, N-2,4, 6-pentamethylphenylammonium cations and dialkylammonium cations such as diisopropylammonium cations and dicyclohexylammonium cations; phosphonium cations include triarylphosphonium cations such as triphenyl phosphonium cation, tri (tolyl) phosphonium cation, and tri (xylyl) phosphonium cation.
In one embodiment of the application, the organoboron salt compound is specifically selected from [ Ph ] 3 C][B(C 6 F 5 ) 4 ]、[PhNMe 2 H][BPh 4 ]、[NEt 3 H][BPh 4 ]、B(C 6 F 5 ) 3 And [ PhNMe 2 H][B(C 6 F 5 ) 4 ]One or more of the following.
The molar ratio of organoboron salt to metallocene-non-metallocene heteroleptic metal complex in the catalyst composition of the application is preferably (0.5 to 10): 1, more preferably (1 to 5): 1, more preferably (1 to 3): 1.
in some specific implementations, the organoaluminum compound is selected from one or more of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, and ethyldi (p-tolylaluminum.
The molar ratio of alkylaluminum to metallocene-non-metallocene heteroleptic metal complex in the catalyst composition is preferably (1-200): 1, more preferably (1 to 100): 1, more preferably (1 to 20): 1.
the method for preparing the catalyst composition is not particularly limited, and the complex, the organoboron compound and the organoaluminum compound are mixed and dissolved in a solvent. In some specific implementations, the solvent may be one or more of aliphatic saturated hydrocarbons, aromatic hydrocarbons, aryl halides, and cycloalkanes, preferably toluene. In some specific implementations, the ratio of the volume of the solvent to the number of moles of complex in the catalyst is 100 to 1000L:1mol, preferably 200 to 800L:1mol.
The catalyst composition provided by the application can be used for preparing ultra-high molecular weight polyethylene in a catalytic manner, and comprises the following steps:
ethylene monomers are used as raw materials, and polymerization reaction is carried out under the action of the catalyst composition to obtain the ultra-high molecular weight polyethylene.
Specifically, the ethylene monomer is firstly placed in a reaction kettle for anhydrous and anaerobic treatment, and the catalyst composition solution is added for reaction, namely the polymerization reaction is carried out under the anhydrous and anaerobic condition. In some specific implementations, the vinyl monomers include, but are not limited to, styrene, ethylene, propylene, and the like. In some specific implementations, the pressure of the vinyl monomer is 1 to 20atm. In some specific implementations, the reaction is performed in a hydrocarbon solvent, including but not limited to toluene and the like. In some specific implementations, the molar ratio of the hydrocarbon solvent to the metallocene-non-metallocene is from 100 to 1000:1. The temperature of the polymerization reaction is 0-60 ℃ and the time is 30 s-5 h. And after the polymerization is finished, adding ethanol solution acidified by hydrochloric acid to terminate the polymerization reaction, pouring the reaction solution into ethanol to settle, and drying to obtain the low-entanglement ultra-high molecular weight polyethylene.
The complex provided by the application is a metallocene-non-metallocene complex, and consists of a ligand and a central metal, wherein the ligand is a hetero-type containing aromatic groups, the central metal is Ti, and the ligand can be used for catalyzing the synthesis of ultra-high molecular weight polyethylene, and the prepared ultra-high molecular weight polyethylene has the viscosity average molecular weight of 100-800 ten thousand, the molecular weight distribution of 1-10, the crystallinity of 60-90% and the melting point of 130-150 ℃. Moreover, the complex provided by the application is simple to synthesize, and the yield is high and can reach 50% -60%.
Drawings
FIG. 1 is a chart showing the hydrogen nuclear magnetic resonance spectrum of methyl branching of ultra-high molecular weight polyethylene prepared in example 14 of the present application;
FIG. 2 is a photograph showing cold pressing at room temperature for 3 minutes of ultra high molecular weight polyethylene prepared in example 14 of the present application;
FIG. 3 is a DSC of the ultra high molecular weight polyethylene prepared in example 14 of the present application;
FIG. 4 is a KPIC report of the ultra high molecular weight polyethylene prepared in example 14 of the present application.
Detailed Description
The technical solutions of the present application will be clearly and completely described in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In order to further illustrate the present application, the following examples are provided. The raw materials used in the following examples of the present application are all commercially available.
Example 1: preparation of Complex 1
Under nitrogen, m-xylene-2-sulfonyl chloride (3 mmol,0.52 g) and 2, 4-di-tert-butylphenol (3 mmol,0.62 g) were taken as starting materials and dissolved in methylene chloride, feCl 3 The catalyst reacts for 12 hours at room temperature to obtain a gray green solution, the reaction solution is filtered and concentrated, column chromatography separation is carried out, and petroleum ether is used for: ethyl acetate 10:1, 0.46g of a white solid (compound 1) was obtained in a yield of 51%.
A2.5M solution of n-butyllithium in n-hexane (3 mmol,1.2 ml) was added dropwise to a solution of the heteroatomic ligand (compound 1) (3 mmol,0.94 g) in n-hexane (20 ml) at-30℃under nitrogen, and after reacting for 10 hours, the reaction solution was filtered, concentrated and recrystallized to give a white solid. At-30 ℃ and nitrogenWhite solid (3 mmol,0.96 g) and CpTiCl were taken up under conditions 3 (3 mmol,0.63 g) was dissolved in toluene (20 ml), and the white solid solution was added to CpTiCl 3 In the solution, the reaction is carried out for 10 hours, the filtration and the concentration of the reaction solution are carried out, and the recrystallization is carried out, thus obtaining 1,0.8g of orange-red metallocene-non-metallocene complex with the yield of 53 percent.
Nuclear magnetic hydrogen spectrum: 1 H NMR(500MHz，CDCl 3 )δ1.22(s,9H),1.62(s,9H),δ6.41(s,5H),δ6.98(tt,1H),δ7.08(tt,2H),δ7.34(dt,2H),δ7.54(s,2H)
the molecular formula of the elemental analysis target is C 25 H 29 Cl 2 OSTi(％)
Theoretical analysis value: c,60.50; h,5.89. Actual measurement value: c,60.20; h,6.53.
Example 2: preparation of Complex 2
Under nitrogen, benzyl chloride (3 mmol,0.38 g) and 2, 4-di-tert-butylphenol (3 mmol,0.62 g) were taken as starting materials and dissolved in methylene chloride, feCl 3 The catalyst reacts for 12 hours at room temperature to obtain a gray green solution, the gray green solution is filtered, the reaction solution is concentrated, column chromatography separation is carried out, and petroleum ether is used for: ethyl acetate 10:0, 0.40g of a white solid (compound 2) was obtained in 45% yield.
A2.5M solution of n-butyllithium in n-hexane (3 mmol,1.2 ml) was added dropwise to a solution of ligand (compound 2) (3 mmol,1.21 g) in n-hexane (20 ml) at-30℃under nitrogen, reacted for 10 hours, then filtered, the reaction solution was concentrated, and recrystallized to give a white solid. A white solid (3 mmol,1.23 g) and CpTiCl were reacted at-30℃under nitrogen 3 (3 mmol,0.63 g) was dissolved in toluene (20 ml), and the white solid solution was added to CpTiCl 3 In the solution, the reaction was carried out for 10 hours, the reaction solution was filtered, concentrated and recrystallized to obtain orange-red metallocene-non-metallocene complex 2,1.21g, with a yield of 55%.
The molecular formula of the elemental analysis target is C 25 H 24 Cl 2 F 5 OSTi(％)
Theoretical analysis value: c,51.22; h,4.13. Actual measurement value: c,51.35; h,4.52.
Example 3: preparation of Complex 3
A2.5M solution of n-butyllithium in n-hexane (3 mmol,1.2 ml) was added dropwise to a solution of the heteroatomic ligand (compound 1) (3 mmol,0.94 g) in n-hexane (20 ml) at-30℃under nitrogen, and after reacting for 10 hours, the reaction solution was filtered, concentrated and recrystallized to give a white solid. A white solid (3 mmol,0.96 g) and CpTiCl were reacted at-30℃under nitrogen 3 (3 mmol,0.63 g) was dissolved in toluene (20 ml), and the white solid solution was added to CpTiCl 3 In the solution, the reaction was carried out for 10 hours, filtered, and the reaction solution was concentrated, then (3 mmol,1 ml) of 3.0M methyl magnesium bromide in diethyl ether was added at-30℃and reacted for 1 hour, and the mixture was recrystallized by filtration with celite to give orange-red metallocene-non-metallocene complex 3,0.67g in 49% yield.
The molecular formula of the elemental analysis target is C 27 H 36 OSTi(％)
Theoretical analysis value: c,71.04; h,7.95. Actual measurement value: c,71.01; h,8.02.
Example 4: preparation of Complex 4
A2.5M solution of n-butyllithium in n-hexane (3 mmol,1.2 ml) was added dropwise to a solution of ligand (compound 2) (3 mmol,0.89 g) in n-hexane (20 ml) at-30℃under nitrogen, reacted for 10 hours, then filtered, the reaction solution was concentrated, and recrystallized to give a yellow solid. Yellow solid (3 mmol,0.94 g) and CpTiCl were combined at-30℃under nitrogen 3 (3 mmol,0.63 g) was dissolved in toluene (20 ml) and the yellow solid solution was added to CpTiCl 3 In the solution, the reaction is carried out for 10 hours, the filtration and the concentration of the reaction solution are carried out, and the recrystallization is carried out, thus obtaining the orange-red metallocene-non-metallocene complex 4,0.7g, and the yield is 50%.
Nuclear magnetic hydrogen spectrum: 1 H NMR(500MHz，CDCl 3 )δ1.25(s,9H),1.44(s,9H),δ4.18(s,2H),δ6.54(s,5H),δ6.95(d,1H),δ7.22(q,4H),δ7.34(t,2H)
the molecular formula of the elemental analysis target is C 26 H 31 Cl 2 OTi(％)
Theoretical analysis value: c,65.29; h,6.53. Actual measurement value: c,64.98; h,6.89.
Example 5: preparation of Complex 5
Under nitrogen, benzyl chloride (3 mmol,0.38 g) and phenol (3 mmol,0.30 g) were taken as starting materials, dissolved in methylene chloride, and treated with FeCl 3 The catalyst reacts for 12 hours at room temperature to obtain a gray green solution, the gray green solution is filtered, the reaction solution is concentrated, column chromatography separation is carried out, and petroleum ether is used for: ethyl acetate 10:1, 0.22g of a yellow solid (compound 3) was obtained in 40% yield.
A2.5M solution of n-butyllithium in n-hexane (3 mmol,1.2 ml) was added dropwise to a solution of ligand (compound 3) (3 mmol,0.55 g) in n-hexane (20 ml) at-30℃under nitrogen, reacted for 10 hours, then filtered, the reaction solution was concentrated, and recrystallized to give a yellow solid. Yellow solid (3 mmol,0.57 g) and CpTiCl were combined at-30℃under nitrogen 3 (3 mmol,0.63 g) was dissolved in toluene (20 ml) and the yellow solid solution was added to CpTiCl 3 In the solution, the reaction was carried out for 10 hours, the reaction solution was concentrated and recrystallized to give orange-red metallocene-non-metallocene complex 5,0.52g, with a yield of 47%.
The molecular formula of the elemental analysis target is C 18 H 16 Cl 2 OTi(％)
Theoretical analysis value: c,58.89; h,4.39. Actual measurement value: c,58.85; h,4.44.
Example 6: preparation of Complex 6
Under nitrogen, using pentafluorobenzyl chloride (3 mmol,0.65 g) and phenol (3 mmol,0.30 g) as raw materials, and dissolving with dichloromethane to obtain FeCl 3 The catalyst reacts for 12 hours at room temperature to obtain a gray green solution, the gray green solution is filtered, the reaction solution is concentrated, column chromatography separation is carried out, and petroleum ether is used for: ethyl acetate 10:1, 0.48g of a yellow solid (compound 4) was obtained in 42% yield.
A2.5M solution of n-butyllithium in n-hexane (3 mmol,1.2 ml) was added dropwise to a solution of ligand (compound 4) (3 mmol,1.15 g) in n-hexane (20 ml) at-30℃under nitrogen, reacted for 10 hours, then filtered, the reaction solution was concentrated, and recrystallized to give a white solid. A white solid (3 mmol,1.17 g) and CpTiCl were reacted at-30℃under nitrogen 3 (3 mmol,0.63 g) was dissolved in toluene (20 ml), and the white solid solution was added to CpTiCl 3 In the solution, the reaction was carried out for 10 hours, filtered, and the reaction solution was concentrated, then (3 mmol,1 ml) of 3.0M methyl magnesium bromide in diethyl ether was added at-30℃and reacted for 1 hour, and then recrystallized by filtration with celite to give orange-red metallocene-non-metallocene complex 6,0.81g in 51% yield.
The molecular formula of the elemental analysis target is C 28 H 33 F 5 OTi(％)
Theoretical analysis value: c,63.64; h,6.29. Actual measurement value: c,63.51; h,6.52.
Example 7: preparation of Complex 7
A2.5M solution of n-butyllithium in n-hexane (3 mmol,1.2 ml) was added dropwise to a solution of the heteroatomic ligand (compound 1) (3 mmol,0.94 g) in n-hexane (20 ml) at-78℃under nitrogen, and after reacting for 12 hours, the reaction solution was filtered, concentrated and recrystallized to give a white solid. White solid (3 mmol,0.96 g) and C were combined under nitrogen at-78deg.C 12 H 21 SiTiCl 3 (3 mmol,1.03 g) was dissolved in toluene (20 ml), and the white solid solution was added to C 12 H 21 SiTiCl 3 SolutionIn the reaction, the reaction was carried out for 12 hours, filtered, the reaction solution was concentrated, and recrystallized to obtain 15,0.9g of a reddish orange metallocene-non-metallocene complex with a yield of 45%.
Nuclear magnetic hydrogen spectrum: 1 H NMR(500MHz，C 6 D 6 )δ0.48(s,9H),1.12(s,9H),δ1.56(s,9H),δ1.87(s,6H),δ2.46(d,6H),δ6.88(tt,1H),δ7.00(tt,2H),δ7.28(dt,2H),δ7.44(q,2H)。
the molecular formula of the elemental analysis target is C 33 H 48 Cl 2 OSSiTi(％)
Theoretical analysis value: c,65.23; h,7.96. Actual measurement value: c,65.12; h,8.05.
Example 8: preparation of Complex 8
Under nitrogen, m-xylene-2-sulfonyl chloride (3 mmol,0.52 g) and phenol (3 mmol,0.30 g) were taken as starting materials, dissolved in methylene chloride, and treated with FeCl 3 The catalyst reacts for 12 hours at room temperature to obtain a gray green solution, the gray green solution is filtered, the reaction solution is concentrated, column chromatography separation is carried out, and petroleum ether is used for: ethyl acetate 10:1, 0.10g of a yellow solid (compound 5) was obtained in 40% yield.
A2.5M solution of n-butyllithium in n-hexane (3 mmol,1.2 ml) was added dropwise to a solution of ligand (compound 5) (3 mmol,0.61 g) in n-hexane (20 ml) at-78deg.C under nitrogen, reacted for 12 hours, then filtered, the reaction solution was concentrated, and recrystallized to give a white solid. White solid (3 mmol,0.62 g) and C were combined under nitrogen at-78deg.C 12 H 21 SiTiCl 3 (3 mmol,1.22 g) was dissolved in toluene (20 ml), and the white solid solution was added to C 12 H 21 SiTiCl 3 In the solution, the reaction was carried out for 12 hours, the reaction solution was filtered, concentrated and recrystallized to obtain orange-red metallocene-non-metallocene complex 8,0.72g, with a yield of 47%.
The molecular formula of the elemental analysis target is C 24 H 29 Cl 2 OSSiTi(％)
Theoretical analysis value: c,56.26; h,5.70. Actual measurement value: c,56.03; h,5.92.
Example 9: preparation of Complex 9
A2.5M solution of n-butyllithium in n-hexane (3 mmol,1.2 ml) was added dropwise to a solution of a hetero atom ligand (compound 5) (3 mmol,0.61 g) in n-hexane (20 ml) at-78℃under nitrogen atmosphere, and after reacting for 12 hours, the reaction solution was filtered, concentrated and recrystallized to give a white solid. White solid (3 mmol,0.62 g) and C were combined under nitrogen at-78deg.C 8 H 13 SiTiCl 3 (3 mmol,0.87 g) was dissolved in toluene (20 ml), and the white solid solution was added to C 8 H 13 SiTiCl 3 In the solution, the reaction was carried out for 12 hours, the reaction solution was filtered, concentrated and recrystallized to obtain orange-red metallocene-non-metallocene complex 8,0.68g, with a yield of 50%.
The molecular formula of the elemental analysis target is C 20 H 22 Cl 2 OSSiTi(％)
Theoretical analysis value: c,52.53; h,4.85. Actual measurement value: c,52.39; h,5.13.
Example 10: preparation of Complex 10
A2.5M solution of n-butyllithium in n-hexane (3 mmol,1.2 ml) was added dropwise to a solution of ligand (compound 4) (3 mmol,1.16 g) in n-hexane (20 ml) at-78deg.C under nitrogen, reacted for 12 hours, then filtered, the reaction solution was concentrated, and recrystallized to give a white solid. White solid (3 mmol,1.17 g) and C were combined under nitrogen at-78deg.C 8 H 13 SiTiCl 3 (3 mmol,0.87 g) was dissolved in toluene (20 ml), and the white solid solution was added to C 8 H 13 SiTiCl 3 In the solution, the reaction was carried out for 12 hours, the reaction solution was filtered, concentrated and recrystallized to obtain 10,0.92g of a reddish orange metallocene-non-metallocene complex with a yield of 48%.
Element(s)Analytical target molecular formula C 29 H 35 Cl 2 F 5 OSiTi(％)
Theoretical analysis value: c,54.30; h,5.50. Actual measurement value: c,54.21; h,5.62.
Example 11: preparation of Complex 11
A2.5M solution of n-butyllithium in n-hexane (3 mmol,1.2 ml) was added dropwise to a solution of the heteroatomic ligand (compound 1) (3 mmol,0.94 g) in n-hexane (20 ml) at-78℃under nitrogen, and after reacting for 12 hours, the reaction solution was filtered, concentrated and recrystallized to give a white solid. White solid (3 mmol,0.96 g) and C were combined under nitrogen at-78deg.C 10 H 10 TiCl 3 (3 mmol,0.87 g) was dissolved in toluene (20 ml), and the white solid solution was added to C 10 H 10 TiCl 3 In the solution, the reaction was carried out for 12 hours, filtered, the reaction solution was concentrated, and recrystallized to obtain 12,0.85g of orange-red metallocene-non-metallocene complex with a yield of 51%.
The molecular formula of the elemental analysis target is C 30 H 35 Cl 2 OSTi(％)
Theoretical analysis value: c,64.07; h,6.27. Actual measurement value: c,64.01; h,6.53.
Example 12: preparation of Complex 12
A2.5M solution of n-butyllithium in n-hexane (3 mmol,1.2 ml) was added dropwise to a solution of the heteroatomic ligand (compound 1) (3 mmol,0.94 g) in n-hexane (20 ml) at-78℃under nitrogen, and after reacting for 12 hours, the reaction solution was filtered, concentrated and recrystallized to give a white solid. White solid (3 mmol,0.96 g) and C were combined under nitrogen at-78deg.C 10 H 10 TiCl 3 (3 mmol,0.87 g) was dissolved in toluene (20 ml), and the white solid solution was added to C 10 H 10 TiCl 3 In the solution, the reaction was carried out for 12 hours, filtered, the reaction solution was concentrated, and recrystallized to obtain 12,0.92g of orange-red metallocene-non-metallocene complex with a yield of 51%.
The molecular formula of the elemental analysis target is C 34 H 37 Cl 2 OSTi(％)
Theoretical analysis value: c,66.67; h,6.09. Actual measurement value: c,66.53; h,6.23.
Example 13
In a glove box, 40mL of toluene was added to a 150mL polymerization bottle, and an ethylene apparatus was put to pump out air, ethylene=2 atm; complex 1 (5 mg, 10. Mu. Mol), al i Bu 3 (0.4 ml, 200. Mu. Mol,0.5M toluene solvent) and triphenylcarboborate [ Ph ] 3 C][B(C 6 F 5 ) 4 ](9.2 mg, 10. Mu. Mol) was dissolved in toluene to prepare a catalyst composition; the catalyst composition is quickly injected into a polymerization bottle through a syringe to initiate polymerization, after 20min of polymerization reaction, 2ml of hydrochloric acid ethanol solution (v/v, 1:10) is added to terminate the polymerization reaction, and then the polymerization reaction liquid is poured into 100ml of ethanol to settle, filtered and dried for 24h under vacuum, thus obtaining the ultra-high molecular weight polyethylene with the net weight of 0.43g.
Example 14
In a glove box, 40mL of toluene was added to a 150mL polymerization bottle, and an ethylene apparatus was placed to pump out air, ethylene=4 atm; complex 1 (5 mg, 10. Mu. Mol), al i Bu 3 (0.4 ml, 200. Mu. Mol,0.5M toluene solvent) and triphenylcarboborate [ Ph ] 3 C][B(C 6 F 5 ) 4 ](9.2 mg, 10. Mu. Mol) was dissolved in toluene to prepare a catalyst composition; the catalyst composition is quickly injected into a polymerization and bottle through a syringe to initiate polymerization, after 15min of polymerization reaction, 2ml of hydrochloric acid ethanol solution (v/v, 1:10) is added to terminate the polymerization reaction, and then the polymerization reaction solution is poured into 100ml of ethanol to settle, filtered and dried in vacuum for 24h, thus obtaining the ultra-high molecular weight polyethylene with the net weight of 0.47g.
The product of this example was determined according to the method described in C 2 D 2 Cl 4 Homopolymers of which are measured at 110 DEG C 1 Obtaining HNMR spectrogram; melting Point of Polymer (T) m ) By differential scanning calorimetry(DSC) measurement; polymer viscosity average molecular weight (M n ) Measured by a viscometer at 135℃using decalin as mobile phase.
The ultra high molecular weight polyethylene obtained in example 14 was analyzed by nuclear magnetic resonance to obtain it 1 An H NMR spectrum of the sample,
the test analysis was performed by differential scanning calorimetry to obtain a DSC chart thereof, as shown in FIG. 3. The DSC curve of FIG. 3 shows the resulting polyethylene T g =136.9 ℃ and crystallinity x=74.1%. The viscosity average molecular weight was analyzed by a viscometer to obtain a KPIC chart, as shown in FIG. 4.
Example 15
In a glove box, 40mL of toluene was added to a 150mL polymerization bottle, and an ethylene apparatus was placed to pump out air, ethylene=6 atm; complex 1 (5 mg, 10. Mu. Mol), al i Bu 3 (0.4 ml, 200. Mu. Mol,0.5M toluene solvent) and triphenylcarboborate [ Ph ] 3 C][B(C 6 F 5 ) 4 ](9.2 mg, 10. Mu. Mol) was dissolved in toluene to prepare a catalyst composition; the catalyst composition is quickly injected into a polymerization and bottle through a syringe to initiate polymerization, after 2min of polymerization reaction, 2ml of hydrochloric acid ethanol solution (v/v, 1:10) is added to terminate the polymerization reaction, and then the polymerization reaction solution is poured into 100ml of ethanol to settle, filtered and dried in vacuum for 24h, thus obtaining the ultra-high molecular weight polyethylene with the net weight of 0.53g.
Example 16
In a glove box, 40mL of toluene was added to a 150mL polymerization bottle, and an ethylene apparatus was placed to pump out air, ethylene=6 atm; complex 2 (4.5 mg, 10. Mu. Mol), al i Bu 3 (0.4 ml, 200. Mu. Mol,0.5M toluene solvent) and triphenylcarboborate [ Ph ] 3 C][B(C 6 F 5 ) 4 ](9.2 mg, 10. Mu. Mol) was dissolved in toluene to prepare a catalyst composition; the catalyst composition is quickly injected into a polymerization and bottle through a syringe to initiate polymerization, after the polymerization reaction is carried out for 10min, 2ml of hydrochloric acid ethanol solution (v/v, 1:10) is added to terminate the polymerization reaction, and then the polymerization reaction solution is poured into 100ml of ethanol to be settled, filtered and dried for 24h under vacuum, thus obtaining the ultra-high molecular weight polyethylene with the net weight of 0.18g.
Example 17
In a glove box, 40mL of toluene was added to a 150mL polymerization bottle, and an ethylene apparatus was placed to pump out air, ethylene=6 atm; complex 3 (4 mg, 10. Mu. Mol), al i Bu 3 (0.4 ml, 200. Mu. Mol,0.5M toluene solvent) and triphenylcarboborate [ Ph ] 3 C][B(C 6 F 5 ) 4 ](9.2 mg, 10. Mu. Mol) was dissolved in toluene to prepare a catalyst composition; the catalyst composition is quickly injected into a polymerization and bottle through a syringe to initiate polymerization, after the polymerization reaction is carried out for 10min, 2ml of hydrochloric acid ethanol solution (v/v, 1:10) is added to terminate the polymerization reaction, and then the polymerization reaction solution is poured into 100ml of ethanol to be settled, filtered and dried for 24h under vacuum, thus obtaining the ultra-high molecular weight polyethylene with the net weight of 0.19g.
Example 18
In a glove box, 40mL of toluene was added to a 150mL polymerization bottle, and an ethylene apparatus was placed to pump out air, ethylene=6 atm; complex 4 (4 mg, 10. Mu. Mol), al i Bu 3 (0.4 ml, 200. Mu. Mol,0.5M toluene solvent) and triphenylcarboborate [ Ph ] 3 C][B(C 6 F 5 ) 4 ](9.2 mg, 10. Mu. Mol) was dissolved in toluene to prepare a catalyst composition; the catalyst composition is quickly injected into a polymerization and bottle through a syringe to initiate polymerization, after the polymerization reaction is carried out for 10min, 2ml of hydrochloric acid ethanol solution (v/v, 1:10) is added to terminate the polymerization reaction, then the polymerization reaction solution is poured into 100ml of ethanol to be settled, filtered and dried for 24h under vacuum, and the ultra-high molecular weight polyethylene with the net weight of 0.07g is obtained.
Example 19
In a glove box, 40mL of toluene was added to a 150mL polymerization bottle, and an ethylene apparatus was placed to pump out air, ethylene=6 atm; complex 5 (3.6 mg, 10. Mu. Mol), al i Bu 3 (0.4 ml, 200. Mu. Mol,0.5M toluene solvent) and triphenylcarboborate [ Ph ] 3 C][B(C 6 F 5 ) 4 ](9.2 mg, 10. Mu. Mol) was dissolved in toluene to prepare a catalyst composition; rapidly injecting the catalyst composition into a polymerization and bottle through a syringe to initiate polymerization, adding 2ml of hydrochloric acid ethanol solution (v/v, 1:10) to terminate polymerization after 10min, pouring the polymerization reaction solution into 100ml of ethanol to settle, filtering, and standingAir drying for 24 hours gave a net weight of ultra high molecular weight polyethylene of 0.13g.
Example 20
In a glove box, 40mL of toluene was added to a 150mL polymerization bottle, and an ethylene apparatus was placed to pump out air, ethylene=6 atm; complex 6 (5 mg, 10. Mu. Mol), al i Bu 3 (0.4 ml, 200. Mu. Mol,0.5M toluene solvent) and triphenylcarboborate [ Ph ] 3 C][B(C 6 F 5 ) 4 ](9.2 mg, 10. Mu. Mol) was dissolved in toluene to prepare a catalyst composition; the catalyst composition is quickly injected into a polymerization and bottle through a syringe to initiate polymerization, after the polymerization reaction is carried out for 10min, 2ml of hydrochloric acid ethanol solution (v/v, 1:10) is added to terminate the polymerization reaction, and then the polymerization reaction solution is poured into 100ml of ethanol to be settled, filtered and dried for 24h under vacuum, thus obtaining the ultra-high molecular weight polyethylene with the net weight of 0.24g.
Example 21
In a glove box, 40mL of toluene was added to a 150mL polymerization bottle, and an ethylene apparatus was placed to pump out air, ethylene=6 atm; complex 7 (5 mg, 10. Mu. Mol), al i Bu 3 (0.4 ml, 200. Mu. Mol,0.5M toluene solvent) and triphenylcarboborate [ Ph ] 3 C][B(C 6 F 5 ) 4 ](9.2 mg, 10. Mu. Mol) was dissolved in toluene to prepare a catalyst composition; the catalyst composition is quickly injected into a polymerization and bottle through a syringe to initiate polymerization, after the polymerization reaction is carried out for 10min, 2ml of hydrochloric acid ethanol solution (v/v, 1:10) is added to terminate the polymerization reaction, and then the polymerization reaction solution is poured into 100ml of ethanol to be settled, filtered and dried for 24h under vacuum, thus obtaining the ultra-high molecular weight polyethylene with the net weight of 0.11g.
Example 22
In a glove box, 40mL of toluene was added to a 150mL polymerization bottle, and an ethylene apparatus was placed to pump out air, ethylene=6 atm; complex 8 (5 mg, 10. Mu. Mol), al i Bu 3 (0.4 ml, 200. Mu. Mol,0.5M toluene solvent) and triphenylcarboborate [ Ph ] 3 C][B(C 6 F 5 ) 4 ](9.2 mg, 10. Mu. Mol) was dissolved in toluene to prepare a catalyst composition; the catalyst composition was rapidly injected into a polymerization vessel and a flask by a syringe to initiate polymerization, and after 10 minutes, 2ml of ethyl hydrochloride was addedThe polymerization reaction was terminated with an alcohol solution (v/v, 1:10), and the polymerization reaction solution was poured into 100ml of ethanol to be settled, filtered, and vacuum-dried for 24 hours, to obtain ultra-high molecular weight polyethylene having a net weight of 0.05g.
Example 23
In a glove box, 40mL of toluene was added to a 150mL polymerization bottle, and an ethylene apparatus was placed to pump out air, ethylene=6 atm; complex 9 (4.5 mg, 10. Mu. Mol), al i Bu 3 (0.4 ml, 200. Mu. Mol,0.5M toluene solvent) and triphenylcarboborate [ Ph ] 3 C][B(C 6 F 5 ) 4 ](9.2 mg, 10. Mu. Mol) was dissolved in toluene to prepare a catalyst composition; the catalyst composition is quickly injected into a polymerization and bottle through a syringe to initiate polymerization, after 2min of polymerization reaction, 2ml of hydrochloric acid ethanol solution (v/v, 1:10) is added to terminate the polymerization reaction, and then the polymerization reaction solution is poured into 100ml of ethanol to settle, filtered and dried in vacuum for 24h, thus obtaining the ultra-high molecular weight polyethylene with the net weight of 0.16g.
Example 24
In a glove box, 40mL of toluene was added to a 150mL polymerization bottle, and an ethylene apparatus was placed to pump out air, ethylene=6 atm; complex 10 (6.4 mg, 10. Mu. Mol), al i Bu 3 (0.4 ml, 200. Mu. Mol,0.5M toluene solvent) and triphenylcarboborate [ Ph ] 3 C][B(C 6 F 5 ) 4 ](9.2 mg, 10. Mu. Mol) was dissolved in toluene to prepare a catalyst composition; the catalyst composition is quickly injected into a polymerization and bottle through a syringe to initiate polymerization, after the polymerization reaction is carried out for 10min, 2ml of hydrochloric acid ethanol solution (v/v, 1:10) is added to terminate the polymerization reaction, and then the polymerization reaction solution is poured into 100ml of ethanol to be settled, filtered and dried for 24h under vacuum, thus obtaining the ultra-high molecular weight polyethylene with the net weight of 0.21g.
Example 25
In a glove box, 40mL of toluene was added to a 150mL polymerization bottle, and an ethylene apparatus was placed to pump out air, ethylene=6 atm; complex 11 (5.6 mg, 10. Mu. Mol), al i Bu 3 (0.4 ml, 200. Mu. Mol,0.5M toluene solvent) and triphenylcarboborate [ Ph ] 3 C][B(C 6 F 5 ) 4 ](9.2 mg, 10. Mu. Mol) was dissolved in toluene to prepare a catalyst composition; will promoteThe catalyst composition is rapidly injected into a polymerization and bottle through a syringe to initiate polymerization, after the polymerization reaction is carried out for 10min, 2ml of hydrochloric acid ethanol solution (v/v, 1:10) is added to terminate the polymerization reaction, and then the polymerization reaction solution is poured into 100ml of ethanol to be settled, filtered and dried for 24h under vacuum, thus obtaining the ultra-high molecular weight polyethylene with the net weight of 0.75g.
Example 26
In a glove box, 40mL of toluene was added to a 150mL polymerization bottle, and an ethylene apparatus was placed to pump out air, ethylene=6 atm; complex 12 (6.1 mg, 10. Mu. Mol), al i Bu 3 (0.4 ml, 200. Mu. Mol,0.5M toluene solvent) and triphenylcarboborate [ Ph ] 3 C][B(C 6 F 5 ) 4 ](9.2 mg, 10. Mu. Mol) was dissolved in toluene to prepare a catalyst composition; the catalyst composition is quickly injected into a polymerization and bottle through a syringe to initiate polymerization, after the polymerization reaction is carried out for 10min, 2ml of hydrochloric acid ethanol solution (v/v, 1:10) is added to terminate the polymerization reaction, then the polymerization reaction solution is poured into 100ml of ethanol to be settled, filtered and dried for 24h under vacuum, and the ultra-high molecular weight polyethylene with the net weight of 0.87g is obtained.
Referring to Table 1, table 1 shows conditions and results for preparing ultra high molecular weight polyethylene according to examples 13 to 26 of the present application.
TABLE 1 conditions for ethylene homo-polymerization and results data table
The results show that: the metallocene-non-metallocene complex in the embodiment of the disclosure can catalyze ethylene to polymerize after being activated by using a boron-containing cocatalyst, and the polymerization activity can reach 1.59 multiplied by 10 6 g/mol h, the melting point can reach 136.9 ℃, the crystallinity can reach 74.1 percent, and the viscosity average molecular weight of the ultra-high molecular weight polyethylene is 100 w-500 w.
The foregoing is only a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any person skilled in the art, who is within the scope of the present application, should make equivalent substitutions or modifications according to the technical scheme of the present application and the inventive concept thereof, and should be covered by the scope of the present application.

Claims (10)

1. A complex represented by formula (I), formula (II) or formula (III):
wherein Z is selected from S, O, (CH) 2 ) n The method comprises the steps of carrying out a first treatment on the surface of the n is an integer of 1 to 5;
R 1 selected from substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted phenyl or halogen;
R 2 、R 3 independently selected from hydrogen, substituted or unsubstituted C1-C12 alkyl or halogen;
R 4 、R 5 、R 6 、R 7 、R 8 independently selected from hydrogen, substituted or unsubstituted C1-C12 alkyl or halogen;
R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 each independently selected from hydrogen, substituted or unsubstituted silicon-based, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted aryl, or halogen.
2. The complex of claim 1, wherein Z is selected from S or CH 2 ；
R 1 Selected from substituted or unsubstituted C1-C5 alkyl, halogen;
R 2 、R 3 independently selected from hydrogen, substituted or unsubstituted C1-C5 alkyl;
R 4 、R 5 、R 6 、R 7 、R 8 independently selected from hydrogen, substituted or unsubstituted C1-C12 alkyl or halogen;
R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 each independently selected from hydrogen, alkyl substituted silicon based, substituted or unsubstituted C1-C5 alkyl.
3. The metallocene-non-metallocene complex according to claim 2, wherein Z is selected from S, CH 2 ；
The R is 1 Selected from Cl, CH 3 ；
The R is 2 、R 3 Is any one of tertiary butyl, methyl, octyl and halogen;
the R is 4 、R 5 、R 6 、R 7 、R 8 Each independently selected from any one of hydrogen, methyl, tertiary butyl and halogen;
the R is 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 And each is independently selected from any one of hydrogen, methyl, ethyl, tertiary butyl, octyl and trimethylsilyl.
4. A complex according to any one of claims 1 to 3, wherein the complex is selected from the group consisting of:
complex 1: z=s, R 1 ＝Cl,R 2 ＝C(CH 3 ) 3 ,R 3 ＝C(CH 3 ) 3 ,R 4 ＝H,R 5 ＝H,R 6 ＝H,R 7 ＝H,R 8 ＝H,R 9 ＝H,R 10 ＝H,R 11 ＝H,R 12 ＝H,R 13 ＝H；
Complex 2: z=s, R 1 ＝Cl,R 2 ＝C(CH 3 ) 3 ,R 3 ＝C(CH 3 ) 3 ,R 4 ＝F,R 5 ＝F,R 6 ＝F,R 7 ＝F,R 8 ＝F,R 9 ＝H,R 10 ＝H,R 11 ＝H,R 12 ＝H,R 13 ＝H；
Complex 3: z=s, R 1 ＝CH 3 ,R 2 ＝C(CH 3 ) 3 ,R 3 ＝C(CH 3 ) 3 ,R 4 ＝H,R 5 ＝H,R 6 ＝H,R 7 ＝H,R 8 ＝H,R 9 ＝H,R 10 ＝H,R 11 ＝H,R 12 ＝H,R 13 ＝H；
Complex 4: z=ch 2 ,R 1 ＝Cl,,R 2 ＝C(CH 3 ) 3 ,R 3 ＝C(CH 3 ) 3 ,R 4 ＝H,R 5 ＝H,R 6 ＝H,R 7 ＝H,R 8 ＝H,R 9 ＝H,R 10 ＝H,R 11 ＝H,R 12 ＝H,R 13 ＝H；
Complex 5: z=ch 2 ,R 1 ＝Cl,R 2 ＝H,R 3 ＝H,R 4 ＝H,R 5 ＝H,R 6 ＝H,R 7 ＝H,R 8 ＝H,R 9 ＝H,R 10 ＝H,R 11 ＝H,R 12 ＝H,R 13 ＝H；
Complex 6: z=ch 2 ,R 1 ＝CH 3 ,R 2 ＝C(CH 3 ) 3 ,R 3 ＝C(CH 3 ) 3 ,R 4 ＝F,R 5 ＝F,R 6 ＝F,R 7 ＝F,R 8 ＝F,R 9 ＝H,R 10 ＝H,R 11 ＝H,R 12 ＝H,R 13 ＝H；
Complex 7: z=s, R 1 ＝Cl,R 2 ＝C(CH 3 ) 3 ,R 3 ＝C(CH 3 ) 3 ,R 4 ＝H,R 5 ＝H,R 6 ＝H,R 7 ＝H,R 8 ＝H,R 9 ＝CH 3 ,R 10 ＝CH 3 ,R 11 ＝Si(CH 3 ) 3 ,R 12 ＝CH 3 ,R 13 ＝CH 3 ；
Complex 8: z=s, R 1 ＝Cl,R 2 ＝H,R 3 ＝H,R 4 ＝H,R 5 ＝H,R 6 ＝H,R 7 ＝H,R 8 ＝H,R 9 ＝CH 3 ,R 10 ＝CH 3 ,R 11 ＝Si(CH 3 ) 3 ,R 12 ＝CH 3 ,R 13 ＝CH 3 ；
Complex 9: z=s, R 1 ＝Cl,R 2 ＝H,R 3 ＝H,R 4 ＝H,R 5 ＝H,R 6 ＝H,R 7 ＝H,R 8 ＝H,R 9 ＝H,R 10 ＝H,R 11 ＝Si(CH 3 ) 3 ,R 12 ＝H,R 13 ＝H；
Complex 10: z=ch 2 ,R 1 ＝Cl,R 2 ＝C(CH 3 ) 3 ,R 3 ＝C(CH 3 ) 3 ,R 4 ＝F,R 5 ＝F,R 6 ＝F,R 7 ＝F,R 8 ＝F,R 9 ＝H,R 10 ＝H,R 11 ＝Si(CH 3 ) 3 ,R 12 ＝H,R 13 ＝H；
Complex 11: z=s, R 1 ＝Cl,R 2 ＝C(CH 3 ) 3 ,R 3 ＝C(CH 3 ) 3 ,R 4 ＝H,R 5 ＝H,R 6 ＝H,R 7 ＝H,R 8 ＝H,R 9 ＝H,R 10 ＝H,R 11 ＝H,R 12 ＝H,R 13 ＝H,R 14 ＝H，R 15 ＝H；
Complex 12: z=s, R 1 ＝Cl,R 2 ＝C(CH 3 ) 3 ,R 3 ＝C(CH 3 ) 3 ,R 4 ＝H,R 5 ＝H,R 6 ＝H,R 7 ＝H,R 8 ＝H,R 9 ＝H,R 10 ＝H,R 11 ＝H,R 12 ＝H,R 13 ＝H,R 14 ＝H,R 15 ＝H,R 16 ＝H，R 17 ＝H。
5. The complex according to claim 4, which has the structure of formula (1) to formula (4):
6. the process for producing a complex according to any one of claims 1 to 5, comprising the steps of:
combining a ligand of formula (a) with a lithiating agent and CpTiX 3 Mixing and reacting to obtain R 1 A complex of formula (I), (II) or (III) which is halogen, wherein;
wherein CpTiX is 3 Wherein Cp is selected from substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, substituted or unsubstituted fluorenyl, and X is halogen;
optionally, the R 1 The complex of formula (I), formula (II) or formula (III) which is halogen is mixed with an alkyl reagent to obtain R 1 A complex of formula (I), formula (II) or formula (III) which is not halogen.
7. The method of claim 4, wherein the lithiation reagent is selected from the group consisting of n-butyllithium;
the molar ratio of the compound shown in the formula (a) to the lithiation reagent is 1 (1-5);
compounds of formula (a) and CpTiCl 3 The molar ratio of (2) is 1 (1) to (5).
8. A catalyst composition comprising the complex of any one of claims 1 to 5, an organoboron salt compound, and an organoaluminum compound.
9. The composition of claim 7, wherein the molar ratio of the complex, organoboron salt compound, and organoaluminum compound is from 1:0.5 to 5:1 to 100;
the organoboron salt compound is selected from [ Ph ] 3 C][B(C 6 F 5 ) 4 ]、[PhNMe 2 H][BPh 4 ]、[NEt 3 H][BPh 4 ]、B(C 6 F 5 ) 3 And [ PhNMe 2 H][B(C 6 F 5 ) 4 ]One or more of the following;
the organic aluminum compound is selected from one or more of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum and ethyldi (p-tolylaluminum).
10. A method for preparing ultra-high molecular weight polyethylene, comprising the following steps:
the ultra-high molecular weight polyethylene is obtained by polymerizing ethylene monomers as raw materials under the action of the catalyst composition of claim 8 or 9.
CN202311032500.9A 2023-08-16 2023-08-16 Metallocene-non-metallocene complex, preparation method thereof and application thereof in preparation of disentangled ultra-high molecular weight polyethylene Pending CN117069771A (en)

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