CN108484809B - Olefin polymerization catalyst - Google Patents

Olefin polymerization catalyst Download PDF

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CN108484809B
CN108484809B CN201810128082.6A CN201810128082A CN108484809B CN 108484809 B CN108484809 B CN 108484809B CN 201810128082 A CN201810128082 A CN 201810128082A CN 108484809 B CN108484809 B CN 108484809B
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olefin polymerization
polymerization catalyst
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CN108484809A (en
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胡泓梵
周生远
李新乐
薛山
孙鑫
马树刚
郎笑梅
张雪芹
朱博超
辛世煊
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Petrochina Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
    • C08F4/545—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof rare earths being present, e.g. triethylaluminium + neodymium octanoate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • 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
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/06—Butadiene

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Abstract

The invention relates to an olefin polymerization catalyst, which consists of a main catalyst, a cocatalyst and a third component, wherein the main catalyst is indeno [2,1-b ]]Indole-based rare earth metal complexes of the formula [ I ]]Represents:
Figure DDA0001574027970000011
wherein Ln is a transition metal element of group IIIB of the periodic Table of the elements; z1And Z2Are the same or different from each other; dnIs a neutral ligand coordinated with the rare earth metal, and n is an integer greater than or equal to 0; l is represented by the formula [ II]Removal of Compounds and R6Substituents formed by hydrogen on the attached carbon atom; the cocatalyst is selected from the chemical formula [ III]A compound of the formula [ IV]The compound and the chemical formula [ V]At least one of the compounds shown, the third component being a lewis basic compound. The method is suitable for olefin solution polymerization systems.

Description

Olefin polymerization catalyst
Technical Field
The invention relates to a catalyst for olefin polymerization, a preparation method and application thereof, in particular to an indeno [2,1-b ] indole rare earth metal catalyst composition and a preparation method thereof, and the catalyst composition is particularly suitable for preparing high cis-olefin rubber.
Background
The catalyst system for olefin rubber is a key to the production technology of olefin rubber, and currently used catalyst systems mainly include nickel (Ni) based, titanium (Ti) based, cobalt (Co) based, rare earth neodymium (Nd) based, and lithium (Li) based (zingiber officinale, et al, rare earth butadiene rubber, published by metallurgical industry, 2016, 39). Wherein, the lithium catalyst adopts anion polymerization, and the cis-1, 4 content in the prepared olefin rubber product is usually lower; the cis-1, 4 content of the olefin rubber product prepared by adopting a Ziegler-Natta catalytic system of cobalt, nickel and rare earth can reach more than 95 percent. Among the catalytic systems, the rare earth catalyst is the most distinctive variety with excellent comprehensive performance, and the olefin rubber produced by the rare earth catalyst has high cis-structure content, high linear structure regularity, high molecular weight and narrow distribution. Compared with a titanium catalyst, a cobalt catalyst and a nickel catalyst, the rare earth catalyst has the following advantages in the process of preparing the synthetic rubber by catalyzing the polymerization of the conjugated diene (adv.Polym.Sci.,2006,204; Yangxuhua, etc., rare earth catalysis synthetic rubber culture [ C ] scientific publishing agency, 1980,210; Shenqi, etc., rare earth catalysis synthetic rubber culture [ C ] scientific publishing agency, 1980,238): (1) saturated alkane hexane is used as a solvent, and benzene and toluene are not used, so that the environment is protected; (2) the monomer conversion rate is up to 100 percent, which is higher than titanium (< 95%), cobalt (< 80%) and nickel (< 85%); (3) intermolecular crosslinking reaction is not easy to occur, and almost no gel is generated; (4) the conjugated diene hardly generates a dimer in the polymerization reaction; (5) the polymerization temperature can be increased to 120 ℃ without affecting the polymer structure and properties.
The Changchun acclimatization institute of Chinese academy of sciences in 1970 successfully developed a ternary catalytic system of rare earth carboxylate, alkylaluminum and alkylaluminum chloride for preparing high cis-polybutadiene rubber (rare earth catalytic synthetic rubber article [ C ]. scientific Press, 1980, 25). The industrialization of rare earth polybutadiene rubbers was achieved in the 80 th century in Germany by Bayer (At 133rd meeting of the Rubber Division of ACS,1988,4, 19; At 133rd meeting of Rubber Division of ACS,1988,10,18) and in Enichem, Italy (Kautschuk Gummi Kunststiffe,1993,6, 458). The rare earth catalysts currently used in industry are mainly ternary neodymium catalysts, and the core technology thereof is mainly mastered by Lanxess company in Germany (EP2311889, EP2363303, EP2676968, EP3057998, CN102574955, CN102762613, CN104395351 and CN107254008) and by the research groups of Changchun nationality institute (CN01128284, CN01128287, US7288611, CN01128289, CN03127180 and CN 200610016949). The biggest disadvantages of neodymium based catalyst systems are: (1) the activity of the catalyst is still low, and the prepared olefin rubber product has higher ash content; (2) the molecular weight distribution of the rubber product is relatively wide, and the processing and mechanical properties of the rubber product are influenced. Compared with the homogeneous single-center rare earth metal catalyst, the homogeneous single-center rare earth metal catalyst has higher activity and narrower molecular weight distribution, and is easier to regulate and control polymerization activity, polymer molecular weight and stereoregularity.
Currently, the research on single-site rare earth metal catalysts with specific structures for the directional polymerization of conjugated dienes has been well developed, which have the characteristics of high activity and narrow molecular weight distribution in the catalytic diene polymerization reaction (J.Organomet. chem.,2001,621,327; Macromol. chem. Phys.,2003,204,1747; Macromol. chem. Phys.,2004,205,737; Angew. chem.,2005,117,2649; Angew. chem. int. Ed.,2005,44, 2593; Macromolecules 1999,32, 9078; Macromolecules 2001,34, 1539; Macromolecules 2003,36, 7923; Macromolecules 2004,37, 5860; Macromolecules 2006,39, 1359-containing 1363; Dalton, Trans.,2008,2531; Angew. chem. Int. Ed. 46,1909; Soc. 2008. 4984, 130). The disadvantage is that most homogeneous single-site rare earth metal catalysts need to be cationized by expensive borate reagents; the catalytic polymerization activity is not easy to control, so that the industrial use is difficult; in addition, the stereoregularity of the polymerization reaction is greatly influenced by the temperature, and the cis-1, 4 content under the high-temperature condition is not easy to control. In view of this, the search for homogeneous single-site rare earth metal catalyst systems with more controllable polymerization activity and stereoregularity and the reduction of cocatalyst cost are the key to the realization of industrial applications of these catalysts.
Disclosure of Invention
The invention relates to a novel indeno [2,1-b ] indole rare earth metal catalyst composition for olefin polymerization, a preparation method and application thereof, wherein the catalyst composition is particularly suitable for preparing high cis-olefin rubber.
The invention provides an olefin polymerization catalyst, which consists of a main catalyst, a cocatalyst and a third component, wherein the main catalyst is an indeno [2,1-b ] indolyl rare earth metal complex and is represented by a chemical formula [ I ]:
Figure BDA0001574027960000031
wherein Ln is a transition metal element of group IIIB;
Z1and Z2The same or different, each independently selected from hydrogen, halogen, alkyl-R, silyl-SiR3alkoxy-OR, mercapto-SR, carboxy-OCOR, amino-NR2And phosphino-PR2Wherein R is selected from one of the group consisting of saturated alkyl of C1-C20, unsaturated alkenyl of C2-C20, cycloalkyl of C3-C20, aryl or aralkyl of C6-C30 and derivatives thereof, alkyl, aryl or aralkyl of C1-C30 containing heteroatoms of elements in groups IIIA to VIIA of the periodic Table of the elements and derivatives thereof;
Dnis a neutral ligand coordinated with Ln, and n is an integer greater than or equal to 0;
l is represented by the formula [ II]Removal of Compounds and R6Substituents formed by hydrogen on the attached carbon atom:
Figure BDA0001574027960000041
wherein R is1To R10The same or different, each is independently one selected from the group consisting of hydrogen, halogen, saturated alkyl of C1-C20, unsaturated alkenyl of C2-C20, cycloalkyl of C3-C20, aryl of C6-C30 and derivatives thereof, aralkyl of C7-C30 and derivatives thereof, alkyl, aryl or aralkyl of C1-C30 containing heteroatoms of the elements in groups IIIA to VIIA of the periodic Table of the elements and derivatives thereof, and R is R2To R5To ChineseAnd R7To R10Wherein at least two adjacent groups can be joined together to form a substituted or unsubstituted aliphatic or aromatic ring;
the cocatalyst is selected from at least one of a compound shown in a chemical formula [ III ], a compound shown in a chemical formula [ IV ] and a compound shown in a chemical formula [ V ];
chemical formula [ III]：[EH]+[BA4]-、[E]+[BA4]-Or BA3Wherein E is a nitrogen-or carbon-containing neutral or cationic Lewis acid, B is boron, H is hydrogen, A3And A4Are the same or different and are each independently C6-C20 aryl or haloaryl, C1-C20 alkyl or haloalkyl;
chemical formula [ IV]：-[Al(R11)O]n-, wherein Al is aluminum element, R11Is C1-C20 alkyl or haloalkyl, n is an integer greater than or equal to 2;
chemical formula [ V ]]：Al(R12)3Wherein Al is aluminum element, R12Is hydrogen, halogen, alkyl or haloalkyl of C1-C20;
the third component is a lewis basic compound.
In the olefin polymerization catalyst of the present invention, Ln is preferably one selected from scandium, yttrium, and lanthanoid rare earth elements.
The olefin polymerization catalyst of the invention, wherein Z1And Z2Each independently is preferably one selected from the group consisting of trimethylsilylmethyl, bis (trimethylsilyl) methyl, tris (trimethylsilyl) methyl, o- (N, N-dimethylamino) benzyl, N-bis (trimethylsilyl) amine, but is not limited thereto.
The olefin polymerization catalyst of the invention, wherein the saturated alkyl group having 1-20 is preferably selected from one of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, but is not limited thereto;
the unsaturated alkenyl group of C2-C20 is preferably selected from one of vinyl, propenyl, allyl, butenyl, pentenyl, but is not limited thereto;
the cycloalkyl of C3-C20 is preferably selected from one of cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, but is not limited thereto;
the aryl group and the derivative thereof of C6-C30 are preferably selected from one of phenyl, biphenyl, naphthyl, phenanthryl and fluorenyl, but not limited thereto;
the aralkyl group of C7 to C30 and its derivatives are preferably selected from one of benzyl, p-methylphenyl, o-methylphenyl, m-methylphenyl, o-dimethylphenyl, m-dimethylphenyl, mesityl-trimethylphenyl, o-diisopropylphenyl, p-tert-butylphenyl, but not limited thereto;
the C1-C30 alkyl, aryl, aralkyl and their derivatives containing heteroatoms belonging to groups IIIA to VIIA of the periodic Table of the elements are preferably selected from one of chloromethyl, bromomethyl, iodomethyl, chloroethyl, bromoethyl, iodoethyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, trimethylsilylmethyl, dimethylamino, diethylamino, diisopropylamino, methoxy, ethoxy, cyano, nitro, trifluoromethyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, p-trifluoromethylphenyl, p-methoxyphenyl, p-cyanophenyl, p-nitrophenyl, p-dimethylaminophenyl, but not limited thereto.
The olefin polymerization catalyst of the invention, wherein DnPreferably, the solvent is one selected from tetrahydrofuran, diethyl ether, thiophene, pyridine, pyrrole, imidazole, carbazole, oxazole, and triphenylphosphine, but not limited thereto, and more preferably tetrahydrofuran, diethyl ether, thiophene, or pyridine, and the pyridine is more preferably 2, 6-lutidine, 4-bipyridine.
The olefin polymerization catalyst of the present invention is characterized in that the compound represented by the formula [ iii ] is preferably one selected from the group consisting of a triphenyl (methyl) -tetrakis (pentafluorobenzene) boron salt, a phenyl-dimethylamino-tetraphenylboron salt, a tris (pentafluorobenzene) boron salt, and a triphenyl boron salt, and is more preferably a phenyl-dimethylamino-tetraphenylboron salt.
In the olefin polymerization catalyst of the present invention, the compound represented by the chemical formula [ iv ] is preferably selected from one of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane and n-butylaluminoxane, but is not limited thereto, and is more preferably modified methylaluminoxane. The modified methylaluminoxane is usually commercially available, and can also be prepared by the following method, and the method comprises the following specific steps: triisobutylaluminum was added in a certain proportion to trimethylaluminum and subsequently prepared by a controlled partial hydrolysis process.
In the olefin polymerization catalyst of the present invention, the compound represented by the formula [ v ] is preferably one selected from trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, diethylbenzylaluminum, and ethyl-p-tolylaluminum, but is not limited thereto, and is more preferably triisobutylaluminum.
In the olefin polymerization catalyst of the present invention, it is preferable that the lewis basic compound is a single lewis base or a double lewis base linked via an aliphatic chain or an aromatic hydrocarbon-containing structural unit and does not contain acidic hydrogen therein.
In the olefin polymerization catalyst according to the present invention, the lewis basic compound is preferably one selected from pyridine, 2, 6-lutidine, 4' -bipyridine, 4-dimethylaminopyridine, N ' -tetramethylp-phenylenediamine, N ' -tetramethylethylenediamine, p-dimethoxybenzene, and 4,4' -dimethoxybiphenyl, but is not limited thereto, and more preferably 4,4' -bipyridine. The catalyst of the invention realizes the regulation and control of the catalytic activity of the catalyst composition and the stereoregularity of olefin polymerization products by adding the basic compound. The regulation principle is mainly to control the Lewis acidity of the central metal of the cationic rare earth metal complex to control the catalytic activity; the stereoregularity of the polymerization product is controlled by adjusting the spatial environment of the metal center.
The olefin polymerization catalyst of the invention, wherein the molar ratio of the third component to the main catalyst is preferably 0.1/1 to 10/1, and more preferably 0.5/1 to 2/1; the molar ratio of the compound represented by the formula [ III ] to the main catalyst is preferably 0.1/1 to 10/1, more preferably 0.8/1 to 2.5/1; the molar ratio of the compound represented by the formula [ IV ] to the main catalyst is preferably 0.1/1 to 10000/1, and more preferably 10/1 to 1000/1; the molar ratio of the compound represented by the formula [ V ] to the procatalyst is preferably from 0.1/1 to 100000/1, more preferably from 10/1 to 50000/1.
The olefin polymerization catalyst of the invention can be prepared according to scheme C:
Figure BDA0001574027960000071
the preparation of the catalyst composition is shown in scheme C, and specifically can be prepared by the following 2 methods:
(1) directly mixing a solution of indeno [2,1-b ] indole rare earth metal catalyst represented by a chemical formula [ I ] with a solution (or suspension) of a compound represented by a chemical formula [ III ] or a chemical formula [ IV ] to obtain an activated catalyst composition, and adding a mixed solution of a polymerized olefin monomer and the compound represented by the chemical formula [ V ];
(2) adding the solution of indeno [2,1-b ] indole rare earth metal catalyst represented by the chemical formula [ I ] into the mixed solution of polymerized olefin monomer and compound represented by the chemical formula [ V ], then adding the solution (or suspension) of the compound represented by the chemical formula [ III ] or the chemical formula [ IV ], and generating the activated rare earth metal catalyst composition in situ in a polymerization system.
In the preparation of the olefin polymerization catalyst, the molar ratio of the compound represented by the formula [ IV ] to the main catalyst is preferably from 0.1/1 to 10000/1, more preferably from 10/1 to 1000/1. Since the compound represented by the formula [ IV ] forms clusters by itself and the effective component thereof tends to be lower than the theoretical value, the indeno [2,1-b ] indole rare earth metal catalyst is hardly activated when the molar ratio is lower than 10/1.
In the preparation of the olefin polymerization catalyst, the molar ratio of the compound represented by the formula [ V ] to the indeno [2,1-b ] indole-based rare earth metal catalyst represented by the formula [ I ] is preferably from 0.1/1 to 100000/1, more preferably from 10/1 to 50000/1. The compound represented by the formula [ V ] is mainly used as a chain transfer agent for a polymer, and the amount thereof has a large influence on the molecular weight of the polymer. In addition, the catalyst also serves as a main impurity removal reagent to react with impurities in the polymerized monomers for impurity removal. Therefore, when the molar ratio of the compound of the formula [ V ]/the compound of the formula [ I ] is in the above range, the problem of partial deactivation of the catalyst due to incomplete removal of impurities from the polymerized monomers can be avoided; the polymer molecular weight distribution can also be controlled within a suitable range.
In the olefin polymerization catalyst, the trialkyl aluminum represented by the chemical formula [ V ] can be added into a reaction system in advance and mixed with a monomer in advance; in addition, the borate represented by the formula [ III ] and the alkylaluminoxane compound represented by the formula [ IV ] are not used in the same catalyst composition, and either one of them is used in combination with a main catalyst.
The present invention preferably employs process (2) for the preparation of the catalyst composition.
The olefin polymerization catalyst is used for producing olefin polymers, has remarkable activity, and has better stereoregularity.
In particular, when the olefin polymerization catalyst of the present invention is used, the polymerization activity thereof and the stereoregularity of the polymer can be adjusted by the addition of a Lewis base.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
Indeno [2,1-b ]]Indole derivatives Synthesis reference patent (CN 106905223A), rare earth Metal precursorsCompounds (e.g. rare earth tribenzyl compounds Ln (CH)2C6H4NMe2-o)3) The synthetic reference of (chem. eur. j.2008,14, 2167-2179).
The synthesis of the indeno [2,1-b ] indolyl rare earth metal catalyst composition and the catalytic olefin polymerization reaction are carried out under anhydrous and anaerobic conditions without special description and are realized by an inert gas glove box or Schlenk technology. All solvents used in the experiment are subjected to anhydrous and anaerobic treatment.
Furthermore, nuclear magnetic resonance of rare earth metal complexes1H-NMR spectrum is tested by Bruker Ascend 600MHz, and part of complexes cannot be tested due to paramagnetic property1And H-NMR characterization. Cis-1, 4 selective passage of polymers13C-NMR spectrum determination is carried out, and an inverse gating decoupling mode is adopted; the molecular weight and molecular weight distribution of the polymer were measured by PL-GPC50 gel permeation chromatography.
Example 1
Preparation of the procatalyst 1
Figure BDA0001574027960000091
0.39g of anhydrous YCl was weighed out in a 100mL Schlenk flask3(Fw-195.26, 2mmol), 20mL of tetrahydrofuran (with water removed) was added, and the mixture was stirred at 60 ℃ for 10 hours. The THF was then removed in vacuo to give YCl as a white powder3(THF)3.5And directly used in the next step.
Called N-methylindeno [2,1-b ]]Lithium indolyl salt 0.450g (Fw-225.21, 2mmol) was dissolved in anhydrous THF to prepare a solution. It was then added slowly dropwise to YCl at-25 deg.C3(THF)3.5(2mmol) of THF, after the addition, the reaction mixture was allowed to spontaneously warm to room temperature and stirred at room temperature for a further 12 hours. After the reaction is finished, THF is pumped out in vacuum, the residue is extracted by anhydrous toluene, filtrate is collected after pumping filtration, and the toluene is pumped out in vacuum to obtain a yellow solid which is N-methylindeno [2,1-b ]]Indolyl yttrium dichloride, used directly in the next step.
Dissolving the intermediate product of the N-methyl indeno [2,1-b ] indolyl yttrium dichloride in anhydrous toluene to prepare a solution, and cooling the solution to-25 ℃. Subsequently, a toluene solution of o-dimethylaminobenzyllithium (0.62g, Fw 141.14,4.4mmol) was slowly added dropwise thereto at-25 ℃, allowed to spontaneously warm to room temperature after the addition was completed, and the reaction was stirred at room temperature for 16 hours, whereupon a white precipitate was generated. After completion of the reaction, insoluble matter was removed by filtration, and the obtained filtrate was subjected to solvent removal under vacuum and washed 2 times with anhydrous n-hexane to obtain 0.996g (Fw-575.58) of a bright yellow solid product in 86.5% yield.
Nuclear magnetic data:1H-NMR(600MHz,C6D6):1.74(s,4H),2.21(s,12H,N-Me),3.10(s,3H,N-Me),5.02(s,1H),6.62(m,2H),6.69(t,2H,J＝6Hz),6.86(m,2H),6.92(m,1H),7.06(m,1H),7.28(m,5H),7.42(d,1H,J＝6Hz),7.73(d,1H,J＝6Hz),7.89(d,1H,J＝6Hz).
example 2
Preparation of procatalyst 2
Figure BDA0001574027960000111
1.15g N-methylindeno [2,1-b ] were weighed out in 2 100mL Schlenk bottles, respectively]Indole (Fw ═ 219.28,5.25mmol) and 2.80g Gd (CH)2C6H4NMe2-o)3(Fw-559.84, 5mmol) was dissolved in 30mL of toluene to prepare solutions. At room temperature, adding N-methylindeno [2,1-b ]]Indole in toluene (light brown) was slowly added dropwise to Gd (CH)2C6H4NMe2-o)3Then stirring was continued at room temperature for 1 hour. Subsequently, the reaction flask was placed in an oil bath and heated to 50 ℃ and the reaction was continued for 12 hours, and the reaction solution gradually changed from pale yellow to orange yellow. After the reaction was completed, the solvent was removed under vacuum to obtain a dark brown oil, 20mL of n-hexane was added to precipitate a solid, and the solid was filtered with suction and washed with a small amount of n-hexane for 2 times to obtain 2.24g (Fw-643.92) of a dark yellow powdery solid with a yield of 69.6%.
Example 3
Preparation of the procatalyst 3
Figure BDA0001574027960000112
0.39g of anhydrous YCl was weighed out in a 100mL Schlenk flask3(Fw-195.26, 2mmol), 20mL of tetrahydrofuran (with water removed) was added, and the mixture was stirred at 60 ℃ for 10 hours. The THF was then removed in vacuo to give YCl as a white powder3(THF)3.5And directly used in the next step.
Weighing N-phenyl indeno [2,1-b ]]Lithium indolyl salt 0.574g (Fw-287.28, 2mmol) was dissolved in anhydrous THF to prepare a solution. It was then slowly added dropwise to 0.96g GdCl at-25 deg.C3(THF)n(2mmol) of THF, after the addition, the reaction mixture was allowed to spontaneously warm to room temperature and stirred at room temperature for a further 12 hours. After the reaction is finished, THF is pumped out in vacuum, the residue is extracted by anhydrous toluene, filtrate is collected after pumping filtration, and the toluene is pumped out in vacuum to obtain a yellow solid which is N-phenyl indeno [2,1-b ]]Indolyl yttrium dichloride, used directly in the next step.
Dissolving the intermediate product of the N-phenyl indeno [2,1-b ] indolyl yttrium dichloride in anhydrous toluene to prepare a solution, and cooling the solution to-25 ℃. Subsequently, a toluene solution of o-dimethylaminobenzyllithium (0.62g, Fw 141.14,4.4mmol) was slowly added dropwise thereto at-25 ℃, allowed to spontaneously warm to room temperature after the addition was completed, and the reaction was stirred at room temperature for 16 hours, whereupon a white precipitate was generated. After completion of the reaction, insoluble matter was removed by filtration, and the obtained filtrate was subjected to solvent removal under vacuum and washed 2 times with anhydrous n-hexane to obtain 1.06g (Fw-637.64) of a bright yellow solid product in 83.1% yield.
Nuclear magnetic data:1H-NMR(600MHz,C6D6):1.85(s,4H),2.10(s,12H,N-Me),5.19(s,1H),6.56(m,2H),6.68(m,2H),6.80(m,1H),6.91(m,1H),7.04(m,2H),7.22(m,7H),7.55(m,4H),7.83(m,2H).
example 4
Preparation of the procatalyst 4
Figure BDA0001574027960000131
0.526g of anhydrous GdCl was weighed into a 100mL Schlenk bottle3(Fw-263.61, 2mmol), 30mL of tetrahydrofuran (with water removed) was added, and the mixture was stirred at 70 ℃ for 10 hours. THF was then removed in vacuo to give GdCl as a white powdery solid3(THF)3And directly used in the next step.
N-phenylindeno [2,1-b ]]Lithium indolyl salt 0.574g (Fw-287.28, 2mmol) was dissolved in anhydrous THF to prepare a solution. It was then slowly added dropwise to 0.96g GdCl at-25 deg.C3(THF)3(2mmol) of THF, after the addition, the reaction mixture was allowed to spontaneously warm to room temperature and stirred at room temperature for a further 12 hours. After the reaction is finished, THF is pumped out in vacuum, the residue is extracted by anhydrous toluene, filtrate is collected after pumping filtration, and the toluene is pumped out in vacuum to obtain a yellow oily substance which is N-phenyl indeno [2,1-b ]]Indolyl gadolinium dichloride, used directly in the next step.
Dissolving the intermediate product of the N-phenyl indeno [2,1-b ] indolyl gadolinium dichloride in anhydrous toluene to prepare a solution, and cooling the solution to-25 ℃. Subsequently, a toluene solution of o-dimethylaminobenzyllithium (0.62g, Fw 141.14,4.4mmol) was slowly added dropwise thereto at-25 ℃, allowed to spontaneously warm to room temperature after the addition was completed, and the reaction was stirred at room temperature for 16 hours, whereupon a white precipitate was generated. After the reaction was completed, insoluble matter was removed by filtration, and the obtained filtrate was subjected to solvent removal under vacuum and washed 2 times with anhydrous n-hexane to obtain 1.088g (Fw-705.99) of a bright yellow solid product in a yield of 77.1%.
Examples 5 to 8
Figure BDA0001574027960000141
0.02mmol of N-substituted indeno [2,1-b ] was weighed into a 25mL Schlenk flask]An indolyl rare earth dibenzyl compound (the compound respectively selects a main catalyst 1, a main catalyst 2, a main catalyst 3 and a main catalyst 4 in turn to obtain examples 5-8 correspondingly) is dissolved in anhydrous toluene to prepare a solution; then, under room temperature conditions, rapidly add [ PhNHMe2][B(C6F5)4](16mg,0.02mmol) in toluene was added to the polymerization system after 1min of rapid stirring before an oil was formed.
Examples 9 to 11
Figure BDA0001574027960000142
12mg of N-methylindeno [2,1-b ] are weighed into a 25mL Schlenk flask]An indolyl dibenzyl yttrium compound (i.e., main catalyst 1) (Fw ═ 575.58,0.02mmol) was dissolved in anhydrous toluene to prepare a solution; then adding a toluene solution of Lewis base (0.02mmol) at room temperature, stirring for 15min, and rapidly adding the mixed solution into the PhNHMe2][B(C6F5)4](16mg,0.02mmol) in toluene was added to the polymerization system after 1min of rapid stirring before an oil was formed. Lewis bases used in examples 9 to 11 were 4, 4-bipyridine, 2, 6-lutidine and p-dimethoxybenzene, respectively.
Example 12
Catalyst evaluation
In an inert gas glove box, 14.4g (2.16g,40mmol) of a hexane solution (mass fraction 15%) of 1, 3-butadiene was weighed into a 100mL round-bottomed flask, 0.2mL (1M,0.2mmol) of a hexane solution of triisobutylaluminum was added, and stirred at room temperature for 30min, and a toluene solution of the catalyst composition (0.02mmol) of example 5 was added to the polymerization solution. After polymerization for 15min at room temperature, the polymerization system became viscous and the polymerized monomers were completely consumed. After the polymerization was completed, the reaction flask was taken out of the inert gas glove box, anhydrous methanol was slowly added with stirring until the polymer was completely precipitated, 0.02g of BHT antioxidant (1% of the polymer mass) was added, the polymer was washed with anhydrous methanol 3 times, placed in a vacuum oven to dry at 70 ℃ for 5 hours, and weighed.
The polymerization results are shown in Table 1.
Examples 13 to 15
Catalyst evaluation
Ethylene polymerization was conducted in accordance with the same procedures as in example 12 except that the catalyst compositions of examples 5 to 8 were used in this order, respectively.
The polymerization results are shown in Table 1.
TABLE 1 examples 12-15
Figure BDA0001574027960000151
Figure BDA0001574027960000161
Description of the drawings: (1) [ B ]]N＝[PhNHMe2][B(C6F5)4],[B]N/[Ln]＝1.2
As can be seen from the data in the table, the overall performance of the catalyst composition is best when Ph substitution is on N and the central metal is Y.
Examples 16 to 18
Ethylene polymerization was carried out in the same manner as in example 12 except that the catalyst of example 7 was used in each case and the molar ratio of 1, 3-butadiene monomer to the central metal of the catalyst was varied, and the amount of triisobutylaluminum was adjusted, and the specific amounts and polymerization results thereof are shown in Table 2.
TABLE 2 examples 16 to 18
Figure BDA0001574027960000162
Description of the drawings: (1) [ B ]]N＝[PhNHMe2][B(C6F5)4],[B]N/[Ln]＝1.2
As can be seen from the data in the table, when the central metal is Y and borate is used as a cocatalyst, the catalyst system shows higher polymerization activity, the molecular weight can be adjusted by changing the using amount of triisobutylaluminum, and the molecular weight distribution is narrower.
Examples 19 to 21
Ethylene polymerization was carried out in the same manner as in example 12 except that the amount of the cocatalyst was used, and the specific amount of the cocatalyst used and the polymerization results were as shown in Table 3. (polymerization Activity is represented by TOF)
TABLE 3 examples 19 to 21
Figure BDA0001574027960000171
Description of the drawings: (1) [ B ]]N＝[PhNHMe2][B(C6F5)4]
As can be seen from the data in the table, when the cocatalyst to catalyst molar ratio is below 1, the catalytic activity decreases due to incomplete activation; when the molar ratio of the cocatalyst to the catalyst is between 1 and 2, the activation is thorough, and the catalytic activity is highest; when the molar ratio of promoter to catalyst is too large, catalyst deactivation may result.
Examples 22 to 24
Ethylene polymerization was conducted in accordance with the same procedures as in example 12 except that the olefin catalysts of examples 9 to 11 were used in this order, respectively, and the Lewis bases used were 4, 4-bipyridine, 2, 6-dimethylpyridine and p-dimethoxybenzene, respectively, in this order. The polymerization results are shown in Table 4. (polymerization Activity is represented by TOF)
TABLE 4 examples 22 to 24
Figure BDA0001574027960000181
Description of the drawings: (1) [ B ]]N＝[PhNHMe2][B(C6F5)4],[B]N/[Ln]＝1.2
(2)[Lewis Base]/[Ln]＝1:1
As can be seen from the data in the table, the catalytic activity of the catalyst system containing the Lewis base is related to the coordination ability of the Lewis base, and the stronger the coordination ability of the Lewis base is, the lower the catalytic activity thereof is; in addition, the addition of Lewis base changes the steric hindrance of the metal center of the catalyst, and the cis-1, 4 content of the polymerization product is obviously improved.
As described above, the activity and stereoregularity of the olefin polymerization reaction can be controlled by the Lewis base contained in the catalyst composition.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (9)

1. The olefin polymerization catalyst is characterized by comprising a main catalyst, a cocatalyst and a third component, wherein the main catalyst is an indeno [2,1-b ] indolyl rare earth metal complex and is represented by a chemical formula [ VI ]:
Figure FDA0002742317320000011
wherein Ln is a transition metal element of group IIIB;
R1selected from hydrogen, halogen, saturated alkyl of C1-C20, aryl of C6-C30, and aralkyl of C7-C30;
the cocatalyst is selected from at least one of a compound shown in a chemical formula [ III ], a compound shown in a chemical formula [ IV ] and a compound shown in a chemical formula [ V ];
chemical formula [ III]：[EH]+[BA4]-、[E]+[BA4]-Or BA3Wherein E is a nitrogen-or carbon-containing neutral or cationic Lewis acid, B is boron, H is hydrogen, A3And A4Are the same or different and are each independently C6-C20 aryl or haloaryl, C1-C20 alkyl or haloalkyl;
chemical formula [ IV]：-[Al(R11)O]n-, wherein Al is aluminum element, R11Is C1-C20 alkyl or haloalkyl, n is an integer greater than or equal to 2;
chemical formula [ V ]]：Al(R12)3Wherein Al is aluminum element, R12Is hydrogen, halogen, alkyl or haloalkyl of C1-C20;
the third component is a lewis basic compound.
2. The olefin polymerization catalyst of claim 1, wherein Ln is selected from one of scandium, yttrium, and a lanthanide rare earth element.
3. The olefin polymerization catalyst according to claim 1, wherein the saturated alkyl group having from C1 to C20 is selected from one of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl; the aryl of C6-C30 is selected from one of phenyl, biphenyl, naphthyl, phenanthryl and fluorenyl; the aralkyl of C7-C30 is selected from one of benzyl, p-methylphenyl, o-methylphenyl, m-methylphenyl, o-dimethylphenyl, m-dimethylphenyl, mesityl, o-diisopropylphenyl and p-tert-butylphenyl.
4. The olefin polymerization catalyst according to claim 1, wherein the compound represented by the formula [ III ] is one selected from the group consisting of a triphenyl (methyl) -tetrakis (pentafluorobenzene) boron salt, a phenyl-dimethylamino-tetraphenylboron salt, a tris (pentafluorobenzene) boron salt, and a triphenyl boron salt.
5. The olefin polymerization catalyst according to claim 1, wherein the compound represented by the formula [ IV ] is one selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane and n-butylaluminoxane.
6. The olefin polymerization catalyst according to claim 1, wherein the compound represented by the formula [ V ] is one selected from trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, diethylbenzylaluminum, and ethyl-p-tolylaluminum.
7. The olefin polymerization catalyst according to claim 1, wherein the Lewis basic compound is one selected from the group consisting of 4,4 '-bipyridine, 4-dimethylaminopyridine, N, N, N', N '-tetramethylp-phenylenediamine, p-dimethoxybenzene, and 4,4' -dimethoxybiphenyl.
8. The olefin polymerization catalyst according to claim 1, wherein the molar ratio of the third component to the procatalyst is from 0.1/1 to 10/1, the molar ratio of the compound of formula [ III ] to the procatalyst is from 0.1/1 to 10/1, the molar ratio of the compound of formula [ IV ] to the procatalyst is from 0.1/1 to 10000/1, and the molar ratio of the compound of formula [ V ] to the procatalyst is from 0.1/1 to 100000/1.
9. The olefin polymerization catalyst according to claim 1, wherein the molar ratio of the third component to the procatalyst is from 0.5/1 to 2/1, the molar ratio of the compound of formula [ III ] to the procatalyst is from 0.8/1 to 2.5/1, the molar ratio of the compound of formula [ IV ] to the procatalyst is from 10/1 to 1000/1, and the molar ratio of the compound of formula [ V ] to the procatalyst is from 10/1 to 50000/1.
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