CN108383862B - Indeno [2,1-b ] indolyl rare earth metal complex and preparation method thereof - Google Patents

Indeno [2,1-b ] indolyl rare earth metal complex and preparation method thereof Download PDF

Info

Publication number
CN108383862B
CN108383862B CN201810127233.6A CN201810127233A CN108383862B CN 108383862 B CN108383862 B CN 108383862B CN 201810127233 A CN201810127233 A CN 201810127233A CN 108383862 B CN108383862 B CN 108383862B
Authority
CN
China
Prior art keywords
rare earth
earth metal
indeno
indolyl
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810127233.6A
Other languages
Chinese (zh)
Other versions
CN108383862A (en
Inventor
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
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Petrochina Co Ltd
Original Assignee
Petrochina Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Petrochina Co Ltd filed Critical Petrochina Co Ltd
Priority to CN201810127233.6A priority Critical patent/CN108383862B/en
Publication of CN108383862A publication Critical patent/CN108383862A/en
Application granted granted Critical
Publication of CN108383862B publication Critical patent/CN108383862B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates

Abstract

The invention relates to an indeno [2,1-b ]]Indole-based rare earth metal complexes and preparation method thereof, wherein the rare earth metal complexes are shown as chemical formula [ I]Shown in the figure:
Figure DDA0001573867660000011
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:
Figure DDA0001573867660000012
wherein R is1To R10Are the same or different, and R2To R5In and R7To R10At least two adjacent groups can be joined together to form a substituted or unsubstituted aliphatic or aromatic ring.

Description

Indeno [2,1-b ] indolyl rare earth metal complex and preparation method thereof
Technical Field
The invention relates to a new catalyst for olefin polymerization and a preparation method thereof, in particular to an indeno [2,1-b ] indolyl rare earth metal complex and a preparation method thereof, and the complex is particularly suitable for preparing high cis-olefin rubber.
Background
The catalyst system for olefin rubber is the key of the olefin rubber production technology, and the catalyst systems adopted at present mainly comprise nickel (Ni) systems, titanium (Ti) systems, cobalt (Co) systems, rare earth neodymium (Nd) systems, lithium (Li) systems and the like. Among them, rare earth catalysts are the most distinctive species in these catalytic systems and have excellent comprehensive properties, and the olefin rubber produced by using them has high cis-structure content, high linear structure regularity, high molecular weight and narrow distribution. At present, the more rare earth catalysts used are ternary neodymium catalysts which are multi-center Ziegler-Natta catalyst systems.
Compared with a multi-center Ziegler-Natta rare earth catalyst system, the homogeneous single-center rare earth metal catalyst has higher activity, less dosage, easy dispersion and easier regulation and control of polymerization activity, polymer molecular weight and regularity. At present, the research on single-site rare earth metal catalysts (including metallocene rare earth metal catalysts and non-metallocene rare earth metal catalysts) with specific structures for the directional polymerization of conjugated dienes is well developed.
Taube et al found that neodymium allyl metallocenes with a suitable lewis acid can constitute highly active catalysts (j. organometat. chem.,2001,621,327.) Boisson and Monteil et al reported silicon-bridged neodymium metallocenes and neodymium bifluorenes complex catalysts that effect the copolymerization of butadiene with an olefin (macromol. chem. phys.,2003,204,1747; macromol. chem. phys.,2004,205,737; angelw.chem., 2005,117,2649; angelw.chem. int.ed.,2005,44, 2593.). Kaita uses bis (pentamethylcyclopentadienyl) stabilized complexes of gadolinium and samarium to catalyze the cis-1, 4 polymerization of butadiene or isoprene with high activity in the presence of Modified Methylaluminoxane (MMAO) or borate (Macromolecules 1999,32, 9078-. In addition, the bis-indenyl-stabilized gadolinium amine compound also shows excellent polymerization performance under the activation of borate (Dalton trans.,2008, 2531-. Non-metallocene PNP rare earth metal compounds (Angew. chem. int. Ed.2007,46, 1909-.
The search for ligands suitable for rare earth metals is one of the main research directions in rare earth organic chemistry. Indeno [2,1-b ]]Indole is a kind of electron-rich cyclopentadiene derivative, and is widely applied to synthesis of group IV transition metal organic compounds. Conventional indeno [2,1-b ]]The synthesis method of indole derivatives (US6232260, US6908972, US6559251, US5554775, US5539124, US 567660 and US5902866) uses a large amount of concentrated sulfuric acid as a catalyst, has low synthesis yield, is only suitable for small-scale preparation in a laboratory and is not suitable for large-scale ligand preparation. Indeno [2,1-b ] is disclosed in the patent (CN106905223A) and the literature (Chinese Chemical Letters 2017,28(3),569-]The new synthesis method of indolyl derivative uses aryl substituted hydrazine ammonium salt and may be used in synthesizing indeno [2,1-b ] successfully in single organic solvent without needing any foreign acid catalyst]Indole, yield is close to 100%; can carry out abundant substitution reaction on indole N atom in the presence of nickel catalyst to prepare a plurality of kinds of N-alkyl and aryl substituted indeno [2,1-b ] groups]Indole derivatives and very high yields. Indeno [2,1-b ]]Indolyl derivative stabilized group IV transition metal organic compounds (e.g. KR2015015791, KR 2015015789, WO 2015016423, WO 2015016422, WO 2002092647, WO9924446, CN1249756A, CN1805980A, WO2009/032048A1, WO2009/032051A1, WO2015/016423A1) having C2Symmetry or CsThe symmetrical structure, the catalytic system of which is used for ethylene or propylene polymerization, can synthesize polyolefin products with different properties. Indeno [2,1-b ] for patent (CN 105985368, CN 105985383, PCT CN2016073644)]An organic compound of an indolyl derivative and a transition metal of group IV having a quasi-C2The catalyst has a symmetrical structure, shows good catalytic performance to ethylene or propylene, and can regulate and control the structure of a homopolymerized block polymer. However, in the field of rare earth metal organic chemistry, the application of the compounds as ligands is less. Accordingly, indeno [2,1-b ]]The synthesis of rare earth metal complexes with indole as ligand and the application of the rare earth metal complexes in catalyzing olefin polymerization are yet to be researched.
Disclosure of Invention
In order to solve the above problems, the present invention aims to develop an indeno [2,1-b ] indolyl rare earth metal complex which can be used as a catalyst for preparing a high cis-olefin rubber, and a preparation method thereof.
To this end, the present invention provides an indeno [2,1-b ] indolyl rare earth metal complex represented by the following chemical formula [ I ]:
Figure BDA0001573867650000031
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 a substituent formed by removing hydrogen from the carbon atom to which R6 is bonded by a compound of the formula [ II ]:
Figure BDA0001573867650000041
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 R5In and R7To R10At least two adjacent groups can be joined together to form a substituted or unsubstituted aliphatic or aromatic ring.
The indeno [2,1-b ] indolyl rare earth metal complex of the present invention, wherein Ln is preferably one selected from scandium, yttrium and lanthanide rare earth elements.
The indeno [2,1-b ] of the invention]Indolyl rare earth metal complex 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 indeno [2,1-b ] indolyl rare earth metal complex of the present invention, wherein the saturated alkyl group of C1-C20 is preferably selected from one of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, and 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 indeno [2,1-b ] of the invention]Indolyl rare earth metal complexes of which 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 invention also provides a preparation method of the indeno [2,1-b ] indolyl rare earth metal complex, which is the preparation method of the complex and comprises the following steps:
will be of the chemical formula [ II]Compound LnZ with homoleptic trisubstituted rare earth metal compound3Heating, and performing acid-base reaction to obtain the indeno [2,1-b ] of the metallocene]Indolyl rare earth metal complexes;
the acid-base reaction is carried out in a reaction solvent;
LnZ3in, Ln is a transition metal element of group IIIB;
z is selected from the group consisting of 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;
the compound of the formula [ II ] is shown below:
Figure BDA0001573867650000061
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 hetero atom of transition metal element in IIIB group of periodic Table and derivatives thereof, and R is2To R5In and R7To R10Can form a substituted or unsubstituted aliphatic or aromatic ring by linking together.
The preparation method of the indeno [2,1-b ] indolyl rare earth metal complex, disclosed by the invention, has the advantages that the reaction temperature of the acid-base reaction is preferably 0-120 ℃, and further preferably 40-80 ℃.
The preparation method of the indeno [2,1-b ] indolyl rare earth metal complex provided by the invention is characterized in that Z is preferably selected from one of trimethylsilylmethyl, bis (trimethylsilyl) methyl, tris (trimethylsilyl) methyl, o- (N, N-dimethylamino) benzyl and N, N-bis (trimethylsilyl) amino.
The preparation method of the indeno [2,1-b ] indolyl rare earth metal complex, provided by the invention, is characterized in that the reaction solvent is preferably at least one selected from toluene, hexane, diethyl ether and tetrahydrofuran.
The invention also provides a preparation method of the indeno [2,1-b ] indolyl rare earth metal complex, which is the preparation method of the complex and comprises the following steps:
s1 carrying out lithiation reaction on alkyl lithium reagent and compound of chemical formula [ II ] to obtain lithiation product;
s2 reaction of lithiated product with LnX3Salt elimination reaction to obtain the monocyclopentadienyl indeno [2,1-b]Indolyl rare earth metal dihalides;
s3, carrying out elimination reaction on the mono-metallocene indeno [2,1-b ] indolyl rare earth metal double halide and a nucleophilic substitution reagent to prepare the indeno [2,1-b ] indolyl rare earth metal complex;
the above S1, S2 and S3 are all carried out in an organic solvent;
wherein the compound of the formula [ II ] is as follows:
Figure BDA0001573867650000071
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 hetero atom of transition metal element in IIIB group of periodic Table and derivatives thereof, and R is2To R5In and R7To R10Can form a substituted or unsubstituted aliphatic or aromatic ring by linking together adjacent groups of at least two of;
LnX3wherein Ln is a transition metal element of group IIIB; x is a halogen element.
The preparation method of the indeno [2,1-b ] indolyl rare earth metal complex, provided by the invention, is characterized in that X is preferably chlorine, bromine or iodine.
The indeno [2,1-b ] indolyl rare earth metal complex of the present invention has a reaction temperature of preferably-80 ℃ to 25 ℃, and more preferably-40 ℃ to 0 ℃ in the lithiation reaction; the reaction temperature of the salt elimination reaction is preferably-80-25 ℃, and more preferably-40-0 ℃; the reaction temperature of the elimination reaction is preferably-80 ℃ to 25 ℃, and more preferably-40 ℃ to 0 ℃.
The indeno [2,1-b ] indolyl rare earth metal complex of the present invention, wherein the alkyl lithium reagent is preferably at least one selected from the group consisting of methyl lithium, n-butyl lithium, t-butyl lithium, and lithium diisopropylamide.
The indeno [2,1-b ] indolyl rare earth metal complex of the present invention, wherein the nucleophilic substitution reagent is preferably at least one selected from the group consisting of trimethylsilylmethyl lithium, bis (trimethylsilyl) methyl lithium, tris (trimethylsilyl) methyl lithium, o- (N, N-dimethylamino) benzyl lithium, and N, N-bis (trimethylsilyl) amido lithium.
The indeno [2,1-b ] indolyl rare earth metal complex of the present invention, wherein the organic solvent is preferably at least one selected from toluene, hexane, diethyl ether, and tetrahydrofuran.
The specific structural diagram of the compound of formula [ II ] is as follows, but not limited thereto:
Figure BDA0001573867650000081
Figure BDA0001573867650000091
Figure BDA0001573867650000101
chemical formula [ I]The specific structure of the complex is shown below, but not limited thereto. Wherein Ln ═ Sc, Y and lanthanoid rare earth metal element, R ═ CH2SiMe3Or CH2C6H4(NMe2) -o, when R ═ CH2SiMe3When D isnWhere D ═ THF, n is an integer greater than or equal to 1 (depending on the rare earth central metal ion radius):
Figure BDA0001573867650000102
Figure BDA0001573867650000111
Figure BDA0001573867650000121
the preparation method of the indeno [2,1-B ] indolyl rare earth metal complex provided by the invention can be represented by the following preparation route A and route B:
Figure BDA0001573867650000131
wherein, X can be halogen elements, preferably chlorine, bromine and iodine;
preparation route A is to prepare the mono-metallocene indeno [2,1-b ] indolyl rare earth metal complex by the acid-base reaction between an indeno [2,1-b ] indole derivative and an homoleptic tri-substituted rare earth metal compound. The reaction temperature can be selected from 0-120 ℃, preferably 40-80 ℃, and is preferably selected according to different types of substituent groups and rare earth metals; the reaction solvent can be selected from toluene, hexane, diethyl ether, tetrahydrofuran, preferably toluene.
In the preparation route B, the indeno [2,1-B ] indole derivative is lithiated by an alkyl lithium reagent, and then undergoes a salt elimination reaction with a rare earth metal trihalide to prepare a single-metallocene indeno [2,1-B ] indolyl rare earth metal dihalide, and finally undergoes an elimination reaction with 2 molecules of a nucleophilic substitution reagent to prepare the indeno [2,1-B ] indolyl rare earth metal complex. The reaction temperature is-78-room temperature, preferably-30-room temperature; the reaction solvent can be selected from toluene, hexane, diethyl ether, tetrahydrofuran, preferably tetrahydrofuran.
The indeno [2,1-b ] indolyl rare earth metal complex of the present invention may be used in producing olefin polymer with obvious activity and high stereo regularity.
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 patent (CN106905223A), rare earth metal precursor compounds (e.g. rare earth metal tribenzyl compound 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 complex is carried out under anhydrous and oxygen-free conditions without special description and is 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 Ascend600MHz, 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
Figure BDA0001573867650000141
1.15g N-methylindeno [2,1-b ] were weighed out in 2 100mL Schlenk bottles, respectively]Indole (Fw ═ 219.28,5.25mmol) and 2.46g Y (CH)2C6H4NMe2-o)3(Fw-491.50, 5mmol) was dissolved in 30mL of toluene to prepare solutions. At room temperature, adding N-phenyl indeno [2,1-b ]]Indole in toluene (light brown) was slowly added dropwise to Y (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 70 ℃ and the reaction was continued for 12 hours, and the reaction solution gradually changed from pale yellow to dark yellow. After the reaction was completed, the solvent was removed under vacuum to obtain a brown-yellow oil, 20mL of n-hexane was added to precipitate a solid, and the solid was filtered off with suction and washed with a small amount of n-hexane for 2 times to obtain 2.05g of a brown-yellow powdery solid (Fw: 575.58) with a yield of 71.3%.
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
Figure BDA0001573867650000151
In a 200mL Schlenk bottle, 4.38g N-methylindeno [2,1-b ] indole (Fw 219.28,20mmol) was weighed and added to 100mL of dehydrated ether to prepare a solution. It was cooled to-25 ℃ and then a solution of n-BuLi in hexane (2.4M,9.2mL,22mmol) was slowly added dropwise, the solution gradually turned bright yellow with the formation of yellow insoluble material. After the completion of the dropwise addition, the reaction mixture was allowed to spontaneously warm to room temperature and stirred at room temperature for 2 hours, and after the completion of the reaction, the solvent was removed under vacuum and washed with anhydrous n-hexane for 2 times to obtain 4.46g (Fw ═ 225.21) of a pale yellow solid powder as a lithium salt intermediate product in a yield of 99%.
Example 3
Figure BDA0001573867650000152
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 4
Figure BDA0001573867650000171
The synthesis of the objective compound was carried out according to the same method as in preparation example 3, except that the synthesis of the intermediate product of N-methylindeno [2,1-b ] indolyl yttrium dichloride was carried out in a toluene solvent, thereby eliminating the steps of draining THF and extracting with toluene, simplifying the preparation process, and also avoiding the use of a large amount of THF solvent.
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 5
Figure BDA0001573867650000172
0.527g 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)nAnd 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 slowly added dropwise to 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 toluene is pumped out in vacuum to obtain a deep yellow oily substance which is N-methyl indeno [2,1-b ]]Indolyl gadolinium dichloride, used directly in the next step.
Dissolving the intermediate product of the N-methyl 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 completion of the reaction, insoluble matter was removed by filtration, and the obtained filtrate was subjected to solvent extraction under vacuum and washed 2 times with anhydrous n-hexane to obtain 0.970g (Fw-643.92) of a pale yellow solid product in a yield of 75.3%.
Example 6
Figure BDA0001573867650000181
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 7
Figure BDA0001573867650000191
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,filtering, collecting filtrate, and removing toluene in vacuum to obtain yellow solid 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 8
Figure BDA0001573867650000201
1.48g N-Phenylindeno [2,1-b ] were weighed in 2 100mL Schlenk bottles, respectively]Indole (Fw ═ 281.35,5.25mmol) and 2.46g Y (CH)2C6H4NMe2-o)3(Fw-491.50, 5mmol) was dissolved in 30mL of toluene to prepare solutions. At room temperature, adding N-phenyl indeno [2,1-b ]]Indole in toluene (colorless) was slowly added dropwise to Y (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 80 ℃ 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 yellow 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 2.607g (Fw: 637.64) of a bright yellow powdery solid in a yield of 81.8%.
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 9
Figure BDA0001573867650000211
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%.
Example 10
Figure BDA0001573867650000221
0.768g of anhydrous NdBr was weighed into a 100mL Schlenk flask3(Fw-383.95, 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 NdBr as a white powdery solid3(THF)nAnd 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 subsequently slowly added dropwise to NdBr at-25 ℃3(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 toluene is pumped out in vacuum to obtain a brown oily substance which is N-phenyl indeno [2,1-b ]]Indolyldiserzino dibromide, used directly in the next step.
Dissolving the intermediate product of the neodymium N-phenylindeno [2,1-b ] indolyl dibromide 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 1.048g (Fw-692.98) of a yellowish brown solid product in a yield of 75.6%.
Example 11
Figure BDA0001573867650000222
0.513g of anhydrous SmCl was weighed into a 100mL Schlenk bottle3(Fw-256.72, 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 SmCl as a white powder3(THF)nAnd directly used in the next step.
Weighing N-phenyl indeno [2,1-b ]]Preparation of indolyl lithium salt 0.574g (Fw ═ 287.28,2mmol) in anhydrous THFForming a solution. It was then slowly added dropwise to SmCl 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 toluene is pumped out in vacuum to obtain a brown oily substance which is N-phenyl indeno [2,1-b ]]Indole-dichlorinated sweaters, used directly in the next step.
Dissolving the N-phenyl indeno [2,1-b ] indolyl dichloride sweater intermediate product in anhydrous toluene to prepare solution, and cooling 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 1.237g (Fw-699.10) of a brown solid product in 88.5% yield.
Example 12
Figure BDA0001573867650000231
0.495g of anhydrous PrCl was weighed into a 100mL Schlenk flask3(Fw-247.27, 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 yield PrCl as a white powdery solid3(THF)nAnd 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 PrCl 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 toluene is pumped out in vacuum to obtain a brown oily substance which is N-phenyl indeno [2,1-b ]]Indolyl praseodymium dichloride, directly used in the next step.
Dissolving the intermediate product of the N-phenyl indeno [2,1-b ] indolyl praseodymium 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 1.117g (Fw-689.65) of a bright yellow solid product in a yield of 81.0%.
Example 13
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, a toluene solution of the complex of example 4 (12mg, Fw ═ 575.58,0.02mmol) was added to the polymerization solution and stirred for 1min, and finally [ PhNHMe ] was added2][B(C6F5)4](19mg, Fw-801.22, 0.024mmol) in toluene. After 1 hour of polymerization 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 number of conversion per unit Time (TOF) was 2667/h-1The cis-1, 4 content was 92%.
Example 14
Ethylene polymerization was carried out according to the same method as in example 13 except that the complex of example 6 was used. The number of conversions per unit Time (TOF) was 1013/h-1The cis-1, 4 content was 91%.
Example 15
Ethylene polymerization was carried out in accordance with the same method as in example 13 except that the molar ratio of the monomer to the catalyst was 10000. The number of conversion per unit Time (TOF) was 4000/h-1The cis-1, 4 content was 93%.
As mentioned above, the indeno [2,1-b ] indolyl rare earth metal complex prepared by the method provided by the invention is suitable for preparing high cis-olefin rubber.
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. An indeno [2,1-b ] indolyl rare earth metal complex characterized by being represented by the following chemical formula [ I ]:
Figure FDA0002764499530000011
wherein Ln is selected from one of scandium, yttrium and lanthanide rare earth elements;
Z1and Z2Same, Z1And Z2One selected from the group consisting of trimethylsilylmethyl, bis (trimethylsilyl) methyl, tris (trimethylsilyl) methyl, o- (N, N-dimethylamino) benzyl, and N, N-bis (trimethylsilyl) amino;
Dnis a neutral ligand coordinated to Ln and n is an integer equal to 0;
l is represented by the formula [ II]Removal of Compounds and R6Substituents formed by hydrogen on the attached carbon atom:
Figure FDA0002764499530000012
wherein R is1Is methyl, R2To R10Is hydrogen.
2. A process for preparing an indeno [2,1-b ] indolyl rare earth metal complex of claim 1, comprising the steps of:
will be of the chemical formula [ II]Compound LnZ with homoleptic trisubstituted rare earth metal compound3Heating, and performing acid-base reaction to obtain the indeno [2,1-b ] of the metallocene]Indolyl rare earth metal complexes;
the acid-base reaction is carried out in a reaction solvent;
LnZ3in the formula (I), Ln is one of scandium, yttrium and lanthanide rare earth metal elements;
z is selected from one of trimethylsilylmethyl, bis (trimethylsilyl) methyl, tris (trimethylsilyl) methyl, o- (N, N-dimethylamino) benzyl, N-bis (trimethylsilyl) amino.
3. The method for preparing the indeno [2,1-b ] indolyl rare earth metal complex according to claim 2, wherein the reaction temperature of the acid-base reaction is 0 ℃ to 120 ℃.
4. The method for preparing an indeno [2,1-b ] indolyl rare earth metal complex according to claim 2, wherein the reaction solvent is at least one selected from the group consisting of toluene, hexane, diethyl ether, and tetrahydrofuran.
5. A process for preparing an indeno [2,1-b ] indolyl rare earth metal complex of claim 1, comprising the steps of:
s1 carrying out lithiation reaction on alkyl lithium reagent and compound of chemical formula [ II ] to obtain lithiation product;
s2 reaction of lithiated product with LnX3Salt elimination reaction to obtain the monocyclopentadienyl indeno [2,1-b]Indolyl rare earth metal dihalides;
s3, carrying out elimination reaction on the mono-metallocene indeno [2,1-b ] indolyl rare earth metal double halide and a nucleophilic substitution reagent to prepare the indeno [2,1-b ] indolyl rare earth metal complex;
the above S1, S2 and S3 are all carried out in an organic solvent;
LnX3wherein Ln is one of scandium, yttrium and lanthanide rare earth elements;x is a halogen element;
the nucleophilic substitution reagent is selected from at least one of trimethylsilyl methyl lithium, bis (trimethylsilyl) methyl lithium, tris (trimethylsilyl) methyl lithium, o- (N, N-dimethylamino) benzyl lithium and N, N-bis (trimethylsilyl) amido lithium.
6. The method of preparing an indeno [2,1-b ] indolyl rare earth metal complex according to claim 5, wherein X is chlorine, bromine, or iodine.
7. The method for preparing an indeno [2,1-b ] indolyl rare earth metal complex according to claim 5, wherein the reaction temperature of the lithiation reaction is from-80 ℃ to 25 ℃; the reaction temperature of the salt elimination reaction is-80 ℃ to 25 ℃; the reaction temperature of the elimination reaction is-80 ℃ to 25 ℃.
8. The method of making an indeno [2,1-b ] indolyl rare earth metal complex according to claim 5, wherein the alkyllithium reagent is selected from at least one of methyllithium, n-butyllithium, t-butyllithium, and diisopropylaminolithium.
9. The method of claim 5, wherein the organic solvent is at least one selected from the group consisting of toluene, hexane, diethyl ether, and tetrahydrofuran.
CN201810127233.6A 2018-02-08 2018-02-08 Indeno [2,1-b ] indolyl rare earth metal complex and preparation method thereof Active CN108383862B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810127233.6A CN108383862B (en) 2018-02-08 2018-02-08 Indeno [2,1-b ] indolyl rare earth metal complex and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810127233.6A CN108383862B (en) 2018-02-08 2018-02-08 Indeno [2,1-b ] indolyl rare earth metal complex and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108383862A CN108383862A (en) 2018-08-10
CN108383862B true CN108383862B (en) 2021-03-30

Family

ID=63074562

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810127233.6A Active CN108383862B (en) 2018-02-08 2018-02-08 Indeno [2,1-b ] indolyl rare earth metal complex and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108383862B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1409718A (en) * 1999-12-03 2003-04-09 波利玛利欧洲股份公司 Bridged metallocene compounds as olefin-polymerization catalysts
CN1646583A (en) * 2002-04-16 2005-07-27 伊奎斯塔化学有限公司 Method for polymerisation of olefins with indeno-indolyl catalysts
CN101238154A (en) * 2005-08-03 2008-08-06 伊奎斯塔化学有限公司 Olefin polymerization methods
CN102143999A (en) * 2008-09-03 2011-08-03 伊奎斯塔化学有限公司 Polyethylene thick film and process for preparing polyethylene
WO2012081529A1 (en) * 2010-12-16 2012-06-21 東レ株式会社 Polyester composition for solar battery and method for producing same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1409718A (en) * 1999-12-03 2003-04-09 波利玛利欧洲股份公司 Bridged metallocene compounds as olefin-polymerization catalysts
CN1646583A (en) * 2002-04-16 2005-07-27 伊奎斯塔化学有限公司 Method for polymerisation of olefins with indeno-indolyl catalysts
CN101238154A (en) * 2005-08-03 2008-08-06 伊奎斯塔化学有限公司 Olefin polymerization methods
CN102143999A (en) * 2008-09-03 2011-08-03 伊奎斯塔化学有限公司 Polyethylene thick film and process for preparing polyethylene
WO2012081529A1 (en) * 2010-12-16 2012-06-21 東レ株式会社 Polyester composition for solar battery and method for producing same

Also Published As

Publication number Publication date
CN108383862A (en) 2018-08-10

Similar Documents

Publication Publication Date Title
CN106062012B (en) Support type mixed catalyst and the method for preparing the polymer based on alkene using it
CN109942638A (en) Asymmetric alpha-diimine nickel (II) complex that methylbenzyl is replaced containing ortho position two for vinyl polymerization
CN108484809B (en) Olefin polymerization catalyst
CN108191907A (en) Non- cyclopentadienyl class bidentate bis vanadium complex and preparation method and purposes
CN107406546A (en) The manufacture method and catalyst of oligomer
Li et al. Controlled iso-specific polymerization of 2-vinylpyridine catalyzed by arylamide-ligated rare-earth metal aminobenzyl complexes
CN109957049B (en) Asymmetric (alpha-diimine) nickel olefin catalyst and preparation method and application thereof
CN109956979B (en) Heat-resistant asymmetric alpha-diimine nickel olefin catalyst and preparation method and application thereof
CN103242353A (en) Pincer-like rare earth complex, and synthesis method and application thereof
CN103717303B (en) Comprise the transition-metal catalyst composition of transistion metal compound and use this carbon monoxide-olefin polymeric to prepare polyolefinic method
CN111848669A (en) Vanadium complex catalyst containing phenoxy ligand and preparation method and application thereof
CN108383862B (en) Indeno [2,1-b ] indolyl rare earth metal complex and preparation method thereof
CN104592425B (en) A kind of cycloheptatriene base rare-earth metal catalyst, preparation method and application
CN108218901B (en) Indeno [1,2-b ] indolyl rare earth metal complex and preparation method thereof
CN111715296A (en) Ethylene tetramerization catalytic system, preparation method and application thereof
EP2245035A1 (en) Post-metallocene complexes based on bis(naphtoxy)pyridine and bis(naphtoxy)thiophene ligands for the polymerisation of ethylene and alpha-olefins
CN101607934B (en) 2-ammonia methyl-pyridine nickel complex, preparation method and application thereof
CN108341903B (en) Olefin polymerization catalyst
Zhang et al. Substituent effects of pyridyl-methylene cyclopentadienyl rare-earth metal complexes on styrene polymerization
Diether et al. Rare-earth metal-promoted (double) C–H-bond activation of a lutidinyl-functionalized alkoxy ligand: formation of [ONC] pincer-type ligands and implications for isoprene polymerization
CN104151454A (en) Cobalt catalyst and application thereof in polymerization reaction of 1, 3-butadiene
KR100440480B1 (en) Catalyst for olefin polymerization and method for preparing polyolefins
CN111620975B (en) Binuclear rare earth olefin polymerization catalyst and application thereof
KR20100129330A (en) Sterically emcumbered bidentate and tridentate naphthoxy-imine metallic complexes
JP2750145B2 (en) Method for producing vinyl polymer

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant