CN111116788B - Polypropylene and preparation method thereof - Google Patents

Polypropylene and preparation method thereof Download PDF

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CN111116788B
CN111116788B CN201811277180.2A CN201811277180A CN111116788B CN 111116788 B CN111116788 B CN 111116788B CN 201811277180 A CN201811277180 A CN 201811277180A CN 111116788 B CN111116788 B CN 111116788B
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CN111116788A (en
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李化毅
胡友良
马良兴
杜建强
李倩
蒋洁
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China Petroleum and Chemical Corp
Institute of Chemistry CAS
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Institute of Chemistry CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to the field of olefin polymerization, and discloses a method for preparing polypropyleneAnd polypropylene produced by the process. The method provided by the invention comprises the following steps: taking propylene as a monomer, and carrying out polymerization reaction in the presence of a dinuclear metallocene supported catalyst; wherein the dinuclear metallocene supported catalyst contains an active component which is a dinuclear metallocene compound having a structure represented by formula (1),

Description

Polypropylene and preparation method thereof
Technical Field
The invention relates to the field of olefin polymerization, in particular to a method for preparing polypropylene and the polypropylene prepared by the method.
Background
The olefin polymer is an important high molecular material and has wide application prospect. Homopolymerization or copolymerization of olefin monomers such as propylene, butene and the like is an important reaction process for obtaining an olefin polymer, wherein a polymerization catalyst used is an important influence factor on catalytic activity of reaction progress and an isotacticity index of the obtained polymer. Increasing the activity of polymerization catalysts for the preparation of olefin polymers and the isotacticity of the resulting polymers have been the focus of attention in the olefin polymerization art.
Metallocene catalysts are an important research hotspot in olefin polymerization processes. Processes for preparing polyolefins using soluble homogeneous catalyst systems comprising a metallocene-type transition metal component and a cocatalyst component, such as alumoxanes, Lewis acids or ionic compounds, are known. These catalysts have high activity and give polymers and copolymers with narrow molecular weight distributions.
The prior art has disclosed some metallocene compounds for preparing catalysts for olefin polymerization, but as the requirements for catalytic activity and polymer product isotacticity for olefin polymerization are continuously increased, the requirements for polymerization production cannot be met, and olefin polymers with proper isotacticity cannot be produced.
Disclosure of Invention
The invention aims to overcome the problems of insufficient catalyst activity and low isotacticity of the prepared polypropylene in the conventional propylene polymerization, and provides a method for preparing polypropylene.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing polypropylene, comprising: taking propylene as a monomer, and carrying out polymerization reaction in the presence of a dinuclear metallocene supported catalyst; wherein the dinuclear metallocene supported catalyst contains an active component which is a dinuclear metallocene compound having a structure represented by formula (1),
Figure BDA0001847259040000021
wherein,
-the two M are the same or different and are each independently a metal element of group IIIB, group IVB or group VB of the periodic table of the elements, or an actinide or lanthanide;
-each X is the same or different and is independently halogen;
-L is a group of formulae
Figure BDA0001847259040000022
A divalent bridging group shown, wherein R1、R2Each independently is H, methyl or ethyl;
in the formula (1), R1、R2、R3、R4、R5、R6、R10、R11、R12、R13、R14、R15、R16、R17、R18And R19Each independently is H, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C2-C20Alkenyl, substituted or unsubstituted C7-C40Aralkyl, or substituted or unsubstituted C6-C40Aryl, and R2And R5Not H at the same time.
Preferably, the active component is a dinuclear metallocene compound represented by formula (3)
Figure BDA0001847259040000031
Preferably, R1、R2Is methyl.
In a second aspect the present invention provides a polypropylene obtainable by the process of the invention.
According to the technical scheme, the active component of the catalyst used in the method is the dinuclear metallocene compound with a binuclear structure, so that the catalytic activity can be effectively improved, and the polypropylene with improved isotacticity can be prepared.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The present invention provides in a first aspect a process for the preparation of polypropylene, which process comprises: taking propylene as a monomer, and carrying out polymerization reaction in the presence of a dinuclear metallocene supported catalyst; wherein the dinuclear metallocene supported catalyst contains an active component which is a dinuclear metallocene compound having a structure represented by formula (1),
Figure BDA0001847259040000041
wherein,
-the two M are the same or different and are each independently a metal element of group IIIB, group IVB or group VB of the periodic table of the elements, or an actinide or lanthanide;
-each X is the same or different and is independently halogen;
-L is a group of formulae
Figure BDA0001847259040000042
A divalent bridging group shown, wherein R1、R2Each independently is H, methyl or ethyl;
in the formula (1), R1、R2、R3、R4、R5、R6、R10、R11、R12、R13、R14、R15、R16、R17、R18And R19Each independently is H, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C2-C20Alkenyl, substituted or unsubstituted C7-C40Aralkyl, or substituted or unsubstituted C6-C40Aryl, and R2And R5Not H at the same time.
The compound shown in the formula (1) can have two metal cores and is used as a catalyst component for olefin polymerization reaction, so that the catalytic reaction activity can be effectively improved, and the isotacticity of the obtained polypropylene can be improved.
According to the invention, in the structure of formula (1), the substituents R1-R19The metal M, halogen X and L groups may be further preferred as long as the dinuclear metallocene compound of the present invention combined can solve the technical problems of the present invention. Preferably, in the formula (1),
-two M are the same or different and are each independently a metal element of group IIIB, group IVB or group VB of the periodic table of the elements;
-each X is the same or different and is independently fluorine, chlorine or bromine;
-R1、R2、R3、R4、R5、R6、R10、R11、R12、R13、R14、R15、R16、R17、R18and R19Each independently is H, substituted or unsubstituted C1-C16Alkyl, substituted or unsubstituted C2-C16Alkenyl, substituted or unsubstituted C7-C20Aralkyl, or substituted or unsubstituted C6-C20Aryl, and R2And R5Not H at the same time.
In the present invention, R1-R19When each group defined in (1) is substituted, the substituent may be C1-C4Alkyl group of (1).
More preferably, in formula (1),
-two M are the same or different, each independently Ti, Zr or Hf;
-each X is the same or different and is independently fluorine, chlorine or bromine;
-R1、R2、R3、R4、R5、R6、R10、R11、R12、R13、R14、R15、R16、R17、R18and R19Each independently is H, substituted or unsubstituted C1-C8Alkyl, substituted or unsubstituted C2-C8Alkenyl, substituted or unsubstituted C7-C20Aralkyl or substituted or unsubstituted C6-C20Aryl radicalsAnd R is2And R5Not H at the same time.
Further preferably, in the formula (1),
-both M are the same and are Ti, Zr or Hf;
-each X is the same and is fluorine, chlorine or bromine;
-R1、R2、R3、R4、R5、R6、R10、R11、R12、R13、R14、R15、R16、R17、R18and R19Each independently is H, substituted or unsubstituted C1-C8Alkyl, substituted or unsubstituted C2-C8Alkenyl, substituted or unsubstituted C7-C20Aralkyl, or substituted or unsubstituted C6-C20Aryl, and R2And R5Not simultaneously being H or R10And R15、R11And R16、R12And R17、R13And R18、R14And R19Respectively corresponding to the same.
Specifically, the active component may be a dinuclear metallocene compound represented by formula (3)
Figure BDA0001847259040000061
Wherein, pair M, L, R1-R4、R11-R14、R16-R19Is as defined above.
According to the present invention, more preferably, the active component may be a dinuclear metallocene compound represented by formula (3)
Figure BDA0001847259040000062
Wherein, two M are the same and are Ti, Zr or Hf; r1、R2Each independently is H, methyl or ethyl. Accordingly, formula (1)In, R1-R4、R11-R14、R16-R19In R1、R11、R16Is methyl, the remainder is H.
The invention particularly provides a compound of formula (3) R1、R2The dinuclear metallocene compound which is methyl is used as an active component of the dinuclear metallocene supported catalyst.
The dinuclear metallocene compound of the present invention can be prepared according to the following method, including:
(i) carrying out precipitation reaction on a compound A shown in a formula (4) and a compound B shown in a formula (5) in the presence of a catalyst to obtain a precipitation mother liquor containing a binuclear ligand shown in a formula (6);
(ii) adding to said mother liquor a compound of formula MXnThe halide shown in the formula is firstly subjected to a first reaction at a temperature below 0 ℃, and then is heated to a temperature above 20 ℃ to be subjected to a second reaction;
(iii) (iii) performing solid-liquid separation on the product obtained in the step (ii), and purifying the solid to obtain the dinuclear metallocene compound; wherein,
Figure BDA0001847259040000071
wherein R is1、R2、R3、R4、R5And R6Each independently is H, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C2-C20Alkenyl, substituted or unsubstituted C7-C40Aralkyl or substituted or unsubstituted C6-C40Aryl, and R2And R5Not H at the same time; wherein R is1、R2Each independently is H, methyl or ethyl;
Figure BDA0001847259040000072
wherein R is10、R11、R12、R13、R14、R15、R16、R17、R18And R19Each independently is H, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C2-C20Alkenyl, substituted or unsubstituted C7-C40Aralkyl or substituted or unsubstituted C6-C40An aryl group;
Figure BDA0001847259040000081
wherein L is a general formula
Figure BDA0001847259040000082
A divalent bridging group as shown;
wherein M is a metal element of group IIIB, IVB or VB of the periodic Table of the elements, or an actinide or lanthanide, n is the valence of the element equal to M, and X is a halogen;
wherein the catalyst is selected from butyl lithium.
In the above-mentioned process for producing a dinuclear metallocene compound, the compounds represented by the formulae (4) to (6) correspond in structure to the structure of the obtained dinuclear metallocene compound represented by the formula (1), wherein each substituent R is defined1-R19The metal M, halogen X and L groups may correspond to those in formula (1). Wherein M, L, substituent R1-R19The definitions of (A) are as described above and will not be described herein.
More preferably, according to the present invention, the compound A has a structure represented by formula (a),
Figure BDA0001847259040000083
the compound B has a structure shown in a formula (B),
Figure BDA0001847259040000091
in the present invention, the compound a can be synthesized from the compound represented by formula (7) as a starting material through a series of reactions.
Figure BDA0001847259040000092
In one embodiment of the present invention, the compound a may be prepared by following steps, starting from the compound represented by formula (7), and performing a series of reactions to synthesize each intermediate until the compound represented by formula (a) is obtained, wherein the reactions are performed under the protection of an inert gas, and the following steps are specifically performed:
1)
Figure BDA0001847259040000093
2-bromotoluene in tetrahydrofuran, and tetrahydrofuran containing Mg powder was added. Gradually heating to reflux state.
After the reaction is cooled to room temperature, a catalytic amount of NiCl is added2Or triphenyl phosphorus nickel chloride, and dripping the mixed solution of bromobenzene and tetrahydrofuran for reflux reaction.
Removing tetrahydrofuran from the product obtained by the reflux reaction, pouring the product into ice water, adjusting the pH value of the solution, extracting the organic matters by using diethyl ether, drying and filtering; the ether was then removed. The resultant organic matter was distilled under reduced pressure, and the distillate was collected at 88 ℃ and 0.1mmHg to obtain a colorless liquid.
The product was determined by mass spectrometry to be 2-phenyl toluene.
2)
Figure BDA0001847259040000101
Slowly heating and refluxing 2-phenyl toluene, N-bromosuccinimide (NBS) and Azobisisobutyronitrile (AIBN) in carbon tetrachloride, and cooling to room temperature.
The reaction product was filtered and the resulting solid was washed with dichloromethane and distilled under reduced pressure to give a pale yellow liquid at 128 ℃ and 0.1 mmHg.
The product was determined by mass spectrometry to be 2-phenylbenzyl bromide.
3)
Figure BDA0001847259040000102
Dissolving Na in absolute ethyl alcohol, dripping a mixed solution of diethyl methylmalonate and absolute ethyl alcohol into the solution, stirring uniformly, and slowly dripping a mixed solution of 2-phenylbenzyl bromide and absolute ethyl alcohol. A white precipitate was produced and heated to reflux. The product was cooled to room temperature, aqueous KOH was added, and heating and refluxing were carried out. The solid gradually dissolved and the solution was orange red or brownish red. After the reaction was completed, the solvent ethanol was removed, water was added to completely dissolve the mixture and the pH was adjusted to 1, and the yellow precipitate was filtered off and dried. The solid obtained is decarboxylated at 130 ℃ and under vacuum conditions to obtain a dark yellow viscous solid. The product was determined by mass spectrometry to be 2- (2-phenylbenzyl) propionic acid.
4)
Figure BDA0001847259040000103
Adding thionyl chloride into 2- (2-phenylbenzyl) propionic acid, stirring for reaction, removing the thionyl chloride under reduced pressure, and replacing the thionyl chloride with toluene to remove residual trace SOCl2. Dissolving the product in toluene containing aluminum trichloride, adding ice while adjusting pH to 1 under heating and stirring, extracting with diethyl ether, washing with saturated aqueous solution of sodium bicarbonate and sodium chloride, drying, and filtering to remove diethyl ether. The product is distilled and purified under reduced pressure, and the product is obtained at about 130 ℃ and 0.1 mmHg. The product was determined by mass spectrometry to be 2-methyl-4-phenylindan-1-one.
5)
Figure BDA0001847259040000111
Dissolving 2-methyl-4-phenyl indan-1-ketone in a mixed solvent of tetrahydrofuran and anhydrous methanol, adding sodium borohydride at low temperature, and stirring at room temperature for reaction.
After completion of the reaction, the solvent was removed, ice water was added thereto, and the pH was adjusted to 1. The product was extracted with ether, washed with saturated aqueous sodium chloride solution, dried, filtered and the ether removed. Toluene and p-toluenesulfonic acid are added for reflux reaction, and after the solution is cooled to room temperature, the solution is washed by a saturated solution of sodium bicarbonate. The solvent was distilled off under reduced pressure to obtain a pale yellow liquid at 148 ℃ and 10 mmHg. The product was determined by mass spectrometry to be 2-methyl-7-phenylindene.
6)
Figure BDA0001847259040000112
2-methyl-7-phenylindene was dissolved in a toluene solvent and a butyllithium/hexane solution was added dropwise at low temperature. Slowly raising the temperature to room temperature for reaction, and a large amount of orange yellow precipitates appear in the reaction. After the reaction is finished, cooling the system to below zero ℃, dripping dichlorodimethylsilane, and slowly heating to room temperature for reaction. The orange-yellow precipitate gradually changed to white precipitate as the reaction proceeded, and the solution appeared orange-yellow. After the reaction was complete, water was added and the organic phase was separated, the solvent was removed and the resulting mixture was separated by column chromatography (hexane/dichloromethane 9:1 solution elution) to give a pale yellow liquid. Crystallization gives orange-yellow crystals. The product was determined by mass spectrometry to be dimethylbis (2-methyl-4-phenylindenyl) silane.
In the present invention, the compound B can be synthesized from the compound represented by the formula (8) as a starting material through a series of reactions.
Figure BDA0001847259040000121
Wherein, the substituent R12-R14、R17-R19As mentioned above, no further description is given. Preferably, the starting material is a compound represented by the formula (9),
Figure BDA0001847259040000122
R12-R14、R17-R19are all H.
In one embodiment of the present invention, the compound B can be prepared by following steps, starting from the compound of formula (9) and performing a series of reactions to obtain the compound of formula (B), wherein the reactions are performed under an inert gas atmosphere, and the following steps are performed:
1)
Figure BDA0001847259040000123
dissolving Na in anhydrous ethanol, and dripping mixed solution of diethyl methylmalonate and anhydrous ethanol into the anhydrous ethanolAfter stirring uniformly, slowly dropping in
Figure BDA0001847259040000124
And absolute ethyl alcohol. A white precipitate was produced and heated to reflux.
The product was cooled to room temperature, aqueous KOH was added, and heating and refluxing were carried out. The solid gradually dissolved and the solution was orange red or brownish red.
After the reaction was completed, the solvent ethanol was removed, water was added to completely dissolve the mixture and the pH was adjusted to 1, and the yellow precipitate was filtered off and dried. The solid obtained is decarboxylated at 130 ℃ and under vacuum conditions to obtain a dark yellow viscous solid.
The product was determined by mass spectrometry to be
Figure BDA0001847259040000131
2)
Figure BDA0001847259040000132
In that
Figure BDA0001847259040000133
Adding thionyl chloride, stirring for reaction, removing thionyl chloride under reduced pressure, and replacing residual trace SOCl with toluene to remove2。
Dissolving the product in toluene containing aluminum trichloride, adding ice while adjusting pH to 1 under heating and stirring, extracting with diethyl ether, washing with saturated aqueous solution of sodium bicarbonate and sodium chloride, drying, and filtering to remove diethyl ether. The product is distilled and purified under reduced pressure, and the product is obtained at about 130 ℃ and 0.1 mmHg.
The product was determined by mass spectrometry to be
Figure BDA0001847259040000141
3)
Figure BDA0001847259040000142
Will be provided with
Figure BDA0001847259040000143
Dissolving in a mixed solvent of tetrahydrofuran and anhydrous methanol, adding sodium borohydride at low temperature, and stirring at room temperature for reaction.
After completion of the reaction, the solvent was removed, ice water was added thereto, and the pH was adjusted to 1. The product was extracted with ether, washed with saturated aqueous sodium chloride solution, dried, filtered and the ether removed. Toluene and p-toluenesulfonic acid are added for reflux reaction, and after the solution is cooled to room temperature, the solution is washed by a saturated solution of sodium bicarbonate. The solvent was distilled off under reduced pressure to obtain a pale yellow liquid at 148 ℃ and 10 mmHg.
The product was determined by mass spectrometry to be
Figure BDA0001847259040000144
4)
Figure BDA0001847259040000151
Will be provided with
Figure BDA0001847259040000152
In toluene solvent and at low temperature, a butyl lithium/hexane solution was added dropwise. Slowly raising the temperature to room temperature for reaction, and a large amount of orange yellow precipitates appear in the reaction. After the reaction is finished, cooling the system to below zero ℃, dripping dichlorodimethylsilane, and slowly heating to room temperature for reaction. The orange-yellow precipitate gradually changed to white precipitate as the reaction proceeded, and the solution appeared orange-yellow. After the reaction was complete, water was added and the organic phase was separated, the solvent was removed and the resulting mixture was separated by column chromatography (hexane/dichloromethane 9:1 solution elution) to give a pale yellow liquid. Crystallization gives orange-yellow crystals. The product was determined by mass spectrometry to be
Figure BDA0001847259040000153
In the invention, the prepared dinuclear metallocene compound can determine the final chemical formula and structure through mass spectrum data.
In step (i) of the present invention, the compound may beA itself through the general formula
Figure BDA0001847259040000154
The silane groups may be bridged by the general formula of the compound A and the compound B
Figure BDA0001847259040000161
The silane groups represented bridge. However, with the present invention, the reaction process conditions carried out in step (i) can be adjusted to favor bridging between the compound a and the compound B through the silane groups. Preferably, step (i) comprises: respectively dissolving the compounds A and B in an organic solvent, mixing, adding an organic solution containing the catalyst into the obtained mixed solution under the protection of inert atmosphere, and carrying out the precipitation reaction at 20-40 ℃. The organic solvent may be at least one of toluene, ethylbenzene, and xylene. The amount of the organic solvent is such that the compounds a and B are completely dissolved. The catalyst is used in a catalytic amount, and the precipitation reaction time can be 10-16 h. The resulting precipitate was an orange-red precipitate.
According to the present invention, a plurality of ligands may be contained in the mother liquor obtained in step (ii). The preferred binuclear ligand of the present invention is a compound represented by formula (10),
Figure BDA0001847259040000162
in the present invention, step (ii) may further achieve ligand formation of the dinuclear metallocene compound. Preferably, in step (ii), the halide is at least one of zirconium tetrachloride, titanium tetrachloride and hafnium tetrachloride; the first reaction temperature is-30 ℃ to-20 ℃, and the first reaction time is 0.1-1 h; the second reaction temperature is 20-40 ℃, and the second reaction time is 20-30 h. Wherein the halide may be used in an amount of 2 to 2.2 times the molar amount of the compound of formula (6).
According to the invention, step (iii) may be effected on the product obtained from step (ii)Obtaining pure dinuclear metallocene compound with the structure provided by the invention, wherein the structure can be shown as a formula (1), and more preferably, the structure is shown as a formula (3), wherein R1、R2Is methyl. The solid-liquid separation may be filtration. The resulting precipitate (filter cake) can be washed with an organic solvent, such as toluene. The filtrates were then combined. Part of the solvent was distilled off under reduced pressure, hexane was added dropwise until precipitation occurred, and a very small amount of toluene was added to dissolve the precipitate. Crystallizing the solution at the temperature of-20 ℃, filtering to obtain orange red crystals, and drying to obtain the dinuclear metallocene compound.
In the present invention, the purity of the obtained dinuclear metallocene compound can be further improved by recrystallization.
In the present invention, in order to further improve the isotacticity of the polypropylene obtained by the preparation, preferably, the catalyst further comprises a cocatalyst and a carrier;
preferably, the cocatalyst is selected from at least one of alkylaluminoxanes, Lewis acids, and ionic compounds capable of reacting with metallocenes to convert them into cationic compounds. More preferably, the cocatalyst is an alkylaluminoxane. In the present invention, the alkylaluminoxane may be C1-C20For example, methylaluminoxane.
Preferably, the support is selected from at least one of silica, alumina, magnesia, zirconia, titania and boria. More preferably, the specific surface area of the support may be 200-400m2Per g, pore volume of 0.8-3mL/g, average particle size of 10-200 μm.
Preferably, the amount of the cocatalyst is 0.1 to 3g based on 1g of the carrier; the amount of the active component is 10-150 mg.
In the present invention, the polymerization reaction may be a reaction for polypropylene that is commonly used in the art. To further improve the isotacticity of the polypropylene obtained, preferably, the polymerization conditions include: the polymerization temperature is 50-200 ℃; the polymerization pressure is 0.1-5MPa gauge pressure; the polymerization time is 1-8 h.
Specifically, the process of olefin polymerization may include: vacuumizing a 1L reaction kettle, removing air, filling propylene gas to atmospheric pressure, adding hexane as a solvent, adding a hexane solution of triethyl aluminum, and adding 50-150mg of a supported catalyst;
and after the polymerization reaction is carried out for 1-8h under the conditions that the polymerization temperature is 50-200 ℃ and the polymerization pressure is 0.1-5MPa gauge pressure, stopping introducing the propylene, and adding ethanol to stop the reaction. Filtering to obtain polypropylene, and washing and drying the polypropylene.
In a second aspect of the invention, there is provided a polypropylene obtainable by the process of the invention.
Preferably, the weight average molecular weight of the polypropylene is 19-39 ten thousand; the isotacticity is 96.8% -98.1%.
The present invention will be described in detail below by way of examples. In the following examples, the prepared dinuclear metallocene compound can be determined by mass spectrometry data to determine the final chemical formula and structure.
Use of13The isotacticity of polypropylene is measured by the C NMR method. Molecular weight and molecular weight distribution (PDI) were measured using GPC.
Preparation example 1
For the preparation of compound A of formula (a).
Using a compound shown as a formula (7) as an initiator,
1)
Figure BDA0001847259040000181
24.55mL (0.20mol) of 2-bromotoluene was slowly dropped into a three-necked flask containing 4.91g (0.20mol) of Mg powder and 10mL of tetrahydrofuran in 40mL of tetrahydrofuran. The reaction system was gradually warmed to reflux and held for 3 h.
After the reaction is cooled to room temperature, a catalytic amount of NiCl is added2(about 0.1g), and a mixed solution of 21.06mL (0.20mol) of bromobenzene and 10mL of tetrahydrofuran was added dropwise thereto, followed by reflux reaction at 50-55 ℃ for 3-5 h.
After removal of the tetrahydrofuran by rotary evaporation, the mixture was poured into 500mL of ice water and the pH of the solution was adjusted to about 1, 3X 60mL of diethyl ether with 6M hydrochloric acid to extract the organics over MgSO4Drying, filtering, and rotary evaporating to remove ether. Is provided withThe organic matter was distilled under reduced pressure, and the distillate was collected at 88 ℃ and 0.1mmHg to obtain 27.62g of a colorless liquid.
The liquid product was subjected to mass spectrometry. The product was 2-phenyl toluene. Yield: 82 percent.
2)
Figure BDA0001847259040000191
5.00g (0.030mol) of 2-phenyl toluene, 6.41g (0.036mol) of N-bromosuccinimide (NBS), and 0.10g of Azobisisobutyronitrile (AIBN) were put in 120mL of carbon tetrachloride, slowly heated to 90 ℃ and refluxed for 5 hours, and then cooled to room temperature.
The solid was filtered and washed with dichloromethane, the filtrates were combined, and after removing the solvent by rotary evaporation, the organic matter was distilled under reduced pressure to give 5.30g of a pale yellow liquid at 128 ℃ and 0.1 mmHg.
The liquid product was subjected to mass spectrometry. The product is 2-phenylbenzyl bromide. Yield: 72 percent.
3)
Figure BDA0001847259040000192
1.86g (0.081mol) of Na was dissolved in 50mL of anhydrous ethanol, and a mixed solution of 14.60mL (0.081mol) of diethyl methylmalonate and 20mL of anhydrous ethanol was added dropwise to the solution, followed by stirring uniformly, and then a mixed solution of 20.00g (0.081mol) of 2-phenylbenzyl bromide and 20mL of anhydrous ethanol was added dropwise slowly. A white precipitate formed over a period of time. The mixture was heated to reflux at 100 ℃ for 3 h.
Cooled to room temperature, aqueous KOH (16g KOH in 45mL water) was added and the mixture heated at 100 ℃ under reflux for 4 h. The solid gradually dissolved and the solution was orange red or brownish red.
After the reaction is complete, the solvent ethanol is removed, water is added to dissolve the mixture completely, the pH is very carefully adjusted to 1 with 6MHCl, the yellow precipitate is filtered off and dried. The solid obtained is decarboxylated at 130 ℃ and evacuated to give 17.61g of a dark yellow, viscous solid.
The product was subjected to mass spectrometry. The product was 2- (2-phenylbenzyl) propionic acid. Yield: 91 percent.
4)
Figure BDA0001847259040000201
52.85g (0.220mol) of 2- (2-phenylbenzyl) propionic acid was added with 56.72mL (0.77mol) of thionyl chloride, and after stirring the reaction at room temperature for 18 hours, the thionyl chloride was removed under reduced pressure, and the remaining trace amount of SOCl was removed by replacing 3 times with 50mL of toluene2。
The product was dissolved in 180mL of toluene, dropped into a reaction flask containing 44.00g (0.33mol) of aluminum trichloride and 700mL of toluene, stirred at 80 ℃ for 1 hour, poured onto 1000g of ice, extracted with diethyl ether adjusted to pH 1 with concentrated hydrochloric acid, 3X 200mL of saturated aqueous solution of sodium bicarbonate and sodium chloride, washed with saturated aqueous solution of sodium chloride, and MgSO4And (5) drying. The ether was removed by filtration. The product is distilled and purified under reduced pressure, and the product is obtained at about 130 ℃ and 0.1 mmHg.
The product was subjected to mass spectrometry. The product is 2-methyl-4-phenyl indan-1-one. The yield thereof was found to be 89%.
5)
Figure BDA0001847259040000202
0.22mol of 2-methyl-4-phenylindan-1-one is dissolved in 300mL of a mixed solvent of 2:1 tetrahydrofuran and anhydrous methanol, 12.50g (0.33mol) of sodium borohydride is carefully added at 0 ℃, and the reaction is stirred at room temperature for 16 h.
After completion of the reaction, the solvent was removed, 300g of ice water was added thereto, the mixture was adjusted to pH 1 with concentrated hydrochloric acid, and the mixture was extracted with 3X 200mL of diethyl ether, washed with saturated aqueous solution of sodium chloride, and MgSO4Drying, filtering and removing the ether. 500mL of toluene and 2g of p-toluenesulfonic acid are added, reflux reaction is carried out for 2h, and after the solution is cooled to room temperature, the solution is washed by a saturated solution of sodium bicarbonate. The solvent was distilled off under reduced pressure, and 13.00g of a pale yellow liquid was obtained at 148 ℃ and 10 mmHg.
The product was subjected to mass spectrometry. The product is 2-methyl-7-phenylindene. Yield: 29 percent.
6)
Figure BDA0001847259040000211
10.00g (0.049mol) of 2-methyl-7-phenylindene was added dropwise to a solution of 16.96mL (0.049mol) of butyllithium/hexane (2.86mol/L) in 150mL of a toluene solvent at 0 ℃ and allowed to slowly warm to room temperature for 12 hours. The reaction showed a large amount of orange-yellow precipitate. After the reaction is finished, cooling the system to-20 ℃, dripping 2.98mL (0.025mol) of dichlorodimethylsilane, slowly raising the temperature to room temperature and reacting for 24 h. The orange-yellow precipitate gradually changed to white precipitate as the reaction proceeded, and the solution appeared orange-yellow. After the reaction was completed, 100mL of water was added and the organic phase was separated, the solvent was removed, and the resulting mixture was subjected to column chromatography (hexane/dichloromethane 9:1 solution elution) to obtain 4.8g of a pale yellow liquid. Crystallization gives orange-yellow crystals.
The product was subjected to mass spectrometry. The product was dimethylbis (2-methyl-4-phenylindenyl) silane, noted as feed A. Yield: 42 percent.
Preparation example 2
For illustrating the preparation of Compound B of formula (B)
Using a compound shown as a formula (9) as a starting material,
1)
Figure BDA0001847259040000212
1.86g (0.081mol) of Na was dissolved in 50mL of absolute ethanol, and 14.60mL (0.081mol) of a mixed solution of diethyl methylmalonate and absolute ethanol was added dropwise to the solution, followed by stirring uniformly and then slowly adding 20.00g (0.081mol)
Figure BDA0001847259040000221
And 20mL of absolute ethanol. A white precipitate formed and the mixture was heated at 100 ℃ under reflux for 3 h.
The product was cooled to room temperature, aqueous KOH (16g KOH in 45mL water) was added and the mixture heated at 100 ℃ under reflux for 4 h. The solid gradually dissolved and the solution was orange red or brownish red.
After the reaction was complete, the solvent ethanol was removed, water was added to dissolve the mixture completely and the pH was adjusted to 1 with 6MHCl, the yellow precipitate was filtered off and dried. The solid obtained is decarboxylated at 130 ℃ and evacuated to give 23.4g of a dark yellow, viscous solid.
The product was subjected to mass spectrometry. The product is
Figure BDA0001847259040000222
The yield was 92%.
2)
Figure BDA0001847259040000223
At 52.85g (0.220mol)
Figure BDA0001847259040000231
Adding 56.72mL (0.77mol) of thionyl chloride, stirring at room temperature for reaction for 18h, removing thionyl chloride under reduced pressure, replacing with 50mL of toluene 3 times to remove residual trace SOCl2。
The product was dissolved in 180mL of toluene, dropped into a reaction flask containing 44.00g (0.33mol) of aluminum trichloride and 700mL of toluene, stirred at 80 ℃ for 1 hour, poured onto 1000g of ice, extracted with diethyl ether adjusted to pH 1 with concentrated hydrochloric acid, 3X 200mL of saturated aqueous solution of sodium bicarbonate and sodium chloride, washed with saturated aqueous solution of sodium chloride, and MgSO4And (5) drying. The ether was removed by filtration. The product is distilled and purified under reduced pressure, and the product is obtained at about 130 ℃ and 0.1 mmHg.
The product was subjected to mass spectrometry. The product is
Figure BDA0001847259040000232
The yield thereof was found to be 59%.
3)
Figure BDA0001847259040000233
0.01mol of
Figure BDA0001847259040000241
Dissolved in 300mL of a mixed solvent of 2:1 tetrahydrofuran and anhydrous methanol, 12.50g (0.33mol) of sodium borohydride was added carefully at 0 ℃ and the reaction was stirred at room temperature for 16 hours.
After completion of the reaction, the solvent was removed, 300g of ice water was added thereto, the pH was adjusted to 1 with concentrated hydrochloric acid, the mixture was extracted with 3X 200mL of diethyl ether, washed with a saturated aqueous solution of sodium chloride, and MgSO4Drying, filtering, and removingDiethyl ether. 500mL of toluene and 2g of p-toluenesulfonic acid are added, reflux reaction is carried out for 2h, and after the solution is cooled to room temperature, the solution is washed by a saturated solution of sodium bicarbonate. The solvent was distilled off under reduced pressure, and 13.00g of a pale yellow liquid was obtained at 148 ℃ and 10 mmHg.
The product was subjected to mass spectrometry. The product is
Figure BDA0001847259040000242
The yield was 79%.
4)
Figure BDA0001847259040000243
0.02mol of
Figure BDA0001847259040000251
16.96mL (0.049mol) of butyllithium/hexane solution (2.86mol/L) was added dropwise to 150mL of toluene solvent at 0 ℃ and the mixture was allowed to slowly warm to room temperature for 12 hours. The reaction showed a large amount of orange-yellow precipitate. After the reaction is finished, cooling the system to-20 ℃, dripping 2.98mL (0.025mol) of dichlorodimethylsilane, slowly raising the temperature to room temperature and reacting for 24 h. The orange-yellow precipitate gradually changed to white precipitate as the reaction proceeded, and the solution appeared orange-yellow. After the reaction was completed, 100mL of water was added and the organic phase was separated, the solvent was removed, and the resulting mixture was subjected to column chromatography (hexane/dichloromethane 9:1 solution elution) to obtain 4.8g of a pale yellow liquid. Crystallization gives orange-yellow crystals.
The product was subjected to mass spectrometry. The product is
Figure BDA0001847259040000252
Denoted as raw material B. The yield was 52%.
Example 1
4.41mL (0.013mol) of a butyllithium/hexane solution (2.86mol/L) was added dropwise to a 100mL toluene solution containing 2.96g (0.0063mol) of the raw material A and 1.48g (0.0063mol) of the raw material B at 0 ℃ and the mixture was slowly warmed to room temperature to react for 12 hours, thereby obtaining a large amount of mother liquor of a precipitate in an orange-red color.
The precipitation mother liquor was cooled to-25 ℃. 2.39g (0.0126mol) of zirconium tetrachloride were carefully added, the reaction stirred, kept at-25 ℃ for 0.5h and slowly warmed to room temperature for 24 h.
The precipitate was filtered, washed with 50mL of toluene and the filtrates combined. Part of the solvent was distilled off under reduced pressure, hexane was added dropwise until precipitation occurred, and a very small amount of toluene was added back to dissolve the precipitate. Crystallizing the solution at-20 deg.C, filtering to obtain orange red crystal, and drying to obtain 3.97g
Figure BDA0001847259040000261
Yield: 70 percent.
The product was subjected to mass spectrometry. The dinuclear metallocene compound represented by the above formula is identified as BU-Zr.
Comparative example 1
The metallocene compound was obtained by subjecting the raw material A obtained in preparation example 1 to the following reaction procedures.
Figure BDA0001847259040000262
4.41mL (0.013mol) of a butyllithium/hexane solution (2.86mol/L) was added dropwise to a 50mL toluene solution containing 2.96g (0.0063mol) of the raw material A at 0 ℃ and the mixture was slowly warmed to room temperature to react for 12 hours, thereby obtaining a large amount of orange-red precipitates.
The system was cooled to-25 ℃. 1.50g (0.0063mol) of zirconium tetrachloride were carefully added, the reaction was stirred, kept at-25 ℃ for 0.5h, and slowly warmed to room temperature for 24 h.
The precipitate was filtered, washed with 50mL of toluene and the filtrates combined. Part of the solvent was distilled off under reduced pressure, hexane was added dropwise until precipitation occurred, and a very small amount of toluene was added to dissolve the precipitate. The solution was crystallized from-20 ℃ and filtered to give orange-red crystals, which were dried to give 3.97g of dimethylsilyl-bis (2-methyl-4-phenylindenyl) zirconium dichloride. Yield: 70 percent.
The product was subjected to mass spectrometry. The dinuclear metallocene compound represented by the above formula was identified and noted as DM-Zr.
Example 2
The procedure of example 1 was followed except that 2.94g (0.0126mol) of zirconium tetrachloride was replaced with 2.94g (0.0126mol) of titanium tetrachloride.
Figure BDA0001847259040000271
The obtained product is determined to be the dinuclear metallocene compound shown in the formula and is marked as BU-Ti.
Example 3
The procedure of example 1 was followed except that 4.04g (0.0126mol) of hafnium tetrachloride was used in place of 2.39g (0.0126mol) of zirconium tetrachloride.
Figure BDA0001847259040000272
The obtained product is determined to be the dinuclear metallocene compound shown in the formula and is marked as BU-Hf.
Examples 4 to 6
For illustrating a supported catalyst prepared using the dinuclear metallocene compound of the present invention as an active component.
1g of silica and 0.5g of methylaluminoxane were reacted at 90 ℃ for 24 h. After precipitation, the supernatant was removed and the precipitate was washed 2 times with toluene. 110mg of metallocene compound (BU-Zr in example 4, BU-Ti in example 5 and BU-Hf in example 6) were dissolved in toluene and reacted with the above precipitate at 40 ℃ for 5 hours. After the reaction and precipitation were complete, the supernatant was removed and washed 2 times with toluene, then 2 times with hexane and dried under vacuum to give the supported catalysts, noted Cat-1, Cat-2 and Cat-3.
Examples 7 to 28
In a 1L reaction kettle, vacuumizing, removing air, charging propylene gas to atmospheric pressure, adding 500mL of hexane as a solvent, adding 1mL of triethylaluminum (30 wt% hexane solution), and 100mg of a catalyst;
and (3) carrying out polymerization reaction for 1h under the conditions that the polymerization temperature is 70 ℃ and the polymerization pressure is 0.5MPa gauge pressure, stopping introducing propylene, and adding ethanol to terminate the reaction. Filtering to obtain polypropylene, and washing and drying the polypropylene.
Wherein, the catalyst in the embodiment 7-11 is Cat-1; the catalyst in examples 12-16 was Cat-2; the catalyst in examples 17-21 was Cat-3.
Use of13The isotacticity of polypropylene is measured by the C NMR method. Molecular weight and molecular weight distribution (PDI) were measured using GPC and the results are listed in table 1.
Comparative example 2
A supported catalyst was prepared by following the procedure of example 4, except that the metallocene compound BU-Zr was replaced with DM-Zr to obtain catalyst Cat-4.
Propylene polymerization was conducted in the same manner as in example 7, except that the catalyst Cat-1 was replaced with Cat-4.
Use of13The isotacticity of polypropylene is measured by the C NMR method. Molecular weight and molecular weight distribution (PDI) were measured using GPC and the results are listed in table 1.
TABLE 1
Figure BDA0001847259040000291
Test example
The polypropylene obtained in examples 7 to 21 and comparative example 2 were measured and the results are shown in Table 1, and the overall results are: the weight average molecular weight of the polypropylene obtained in examples 7 to 21 was 19 to 39 ten thousand; the isotacticity is 96.8% -98.1%. While comparative example 2 produced polypropylene having a weight average molecular weight of 20 ten thousand and an isotacticity of 94.8%.
From the above results, it can be seen that when the dinuclear metallocene compound provided by the present invention is used as an active component of an olefin polymerization catalyst to perform propylene homopolymerization, the catalytic activity can be effectively improved, and compared with a catalyst using the DM-Zr compound provided by the prior art in the comparative example 1 as an active component, the catalytic activity of the supported catalyst provided by the present invention is improved by more than 20%. The isotacticity of the obtained polypropylene is improved by about 2 percentage points compared with that of the polypropylene obtained in the comparative example 2, and reaches over 96.8 percent.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (13)

1. A process for preparing polypropylene, the process comprising: taking propylene as a monomer, and carrying out polymerization reaction in the presence of a dinuclear metallocene supported catalyst; wherein the dinuclear metallocene supported catalyst contains an active component which is a dinuclear metallocene compound having a structure represented by formula (1),
Figure FDA0003439000830000011
wherein,
-both M are the same and are Ti, Zr or Hf;
-each X is the same or different and is independently halogen;
-L is a group of formulae
Figure FDA0003439000830000012
A divalent bridging group shown, wherein R1、R2Each independently is H, methyl or ethyl;
in the formula (1), R1、R2、R3、R4、R5、R6、R10、R11、R12、R13、R14、R15、R16、R17、R18And R19Each independently is H, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C2-C20Alkenyl, substituted or unsubstituted C7-C40Aralkyl, or substituted or unsubstituted C6-C40Aryl, and R2And R5Not H at the same time.
2. The method according to claim 1, wherein, in formula (1),
-each X is the same or different and is independently fluorine, chlorine or bromine;
-R1、R2、R3、R4、R5、R6、R10、R11、R12、R13、R14、R15、R16、R17、R18and R19Each independently is H, substituted or unsubstituted C1-C16Alkyl, substituted or unsubstituted C2-C16Alkenyl, substituted or unsubstituted C7-C20Aralkyl, or substituted or unsubstituted C6-C20Aryl, and R2And R5Not H at the same time.
3. The method according to claim 2, wherein, in formula (1),
-each X is the same or different and is independently fluorine, chlorine or bromine;
-R1、R2、R3、R4、R5、R6、R10、R11、R12、R13、R14、R15、R16、R17、R18and R19Each independently is H, substituted or unsubstituted C1-C8Alkyl, substituted or unsubstituted C2-C8Alkenyl, substituted or unsubstituted C7-C20Aralkyl, or substituted or unsubstituted C6-C20Aryl, and R2And R5Not H at the same time.
4. The method according to claim 3, wherein, in formula (1),
-each X is the same and is fluorine, chlorine or bromine;
-R1、R2、R3、R4、R5、R6、R10、R11、R12、R13、R14、R15、R16、R17、R18and R19Each independently is H, substituted or unsubstituted C1-C8Alkyl, substituted or unsubstituted C2-C8Alkenyl, substituted or unsubstituted C7-C20Aralkyl, or substituted or unsubstituted C6-C20Aryl, and R2And R5Not H at the same time;
-R10and R15、R11And R16、R12And R17、R13And R18、R14And R19Respectively corresponding to the same.
5. The method according to claim 4, wherein the active component is a dinuclear metallocene compound represented by formula (2)
Figure FDA0003439000830000031
6. The method according to claim 5, wherein the active component is a dinuclear metallocene compound represented by formula (3)
Figure FDA0003439000830000032
7. The method of claim 6, wherein R1、R2Is methyl.
8. The process of any one of claims 1-7, wherein the catalyst further comprises a cocatalyst and a support.
9. The process of claim 8, wherein the cocatalyst is selected from alkylaluminoxanes.
10. The method according to claim 8, wherein the carrier is selected from at least one of silica, alumina, magnesia, zirconia, titania, and boria.
11. The process according to claim 8, wherein the amount of the cocatalyst is 0.1 to 3g based on 1g of the carrier; the amount of the active component is 10-150 mg.
12. The process of claim 1, wherein the polymerization conditions comprise: the polymerization temperature is 50-200 ℃; the polymerization pressure is 0.1-5MPa gauge pressure; the polymerization time is 1-8 h.
13. Polypropylene obtainable by a process according to any one of claims 1 to 12.
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