CN111747981A - Transition metal compound and preparation method and application thereof - Google Patents
Transition metal compound and preparation method and application thereof Download PDFInfo
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- CN111747981A CN111747981A CN202010707983.8A CN202010707983A CN111747981A CN 111747981 A CN111747981 A CN 111747981A CN 202010707983 A CN202010707983 A CN 202010707983A CN 111747981 A CN111747981 A CN 111747981A
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- 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
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic System without C-Metal linkages
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
Abstract
The invention discloses a transition metal compound shown as a formula (I): ln1MXn2(I) Wherein, L is C1-C20 alkyl substituted or unsubstituted N heteroatom-containing aryl or cycloalkyl or C1-C20 alkyl substituted or unsubstituted amine; m is a group IVB-IIB transition metal atom; n is1Is the coordination number of M, and takes an integer ranging from 1 to 3; x is halogen or hydrogen atom, or halogen substituted or unsubstituted C1-C20 hydrocarbon group; n is2Is the coordination number of M, and takes an integer ranging from 1 to 3. The preparation method of the transition metal compound provided by the invention is simple and canLow consumption and high yield. It is used in ethylene polymer and has the features of high activity, high heat resistance and excellent copolymerization performance.
Description
Technical Field
The invention belongs to the field of polyolefin catalysts, and particularly relates to a transition metal compound and a preparation method and application thereof.
Background
The advent of single site catalysts has become a breakthrough in the development of polyolefin catalysts in the fifties of the last century. Compared with the traditional heterogeneous Ziegler-Natta catalyst, the single-active-site catalyst has higher catalytic activity, the obtained polymer has narrow relative molecular mass distribution, shows more excellent copolymerization performance of ethylene, alpha-olefin, diolefin and cycloolefin, can even realize copolymerization reaction with polar monomers, can accurately control the content and the distribution of the comonomer on a polymer molecular chain, is used for preparing improved and novel polyolefin materials, and has greater development potential than that of the heterogeneous catalyst. Of the single-site catalyst systems of primary interest are the fourth subgroup of metallocene catalysts, including bridged or unbridged mono-and bis-metallocene catalysts, the fourth subgroup of non-metallocene catalysts without metallocene-type ligands, and the late transition metal catalysts represented by the nickel palladium and iron cobalt systems.
In the polymerization of ethylene, EP0277004 discloses bridged bis-metallocene catalysts which have good heat resistance and a polymerization activity of up to 10 at a high temperature of 170 ℃8g.Polymer/(mol.h), and the copolymerization performance for ethylene and α -olefin is general.
The bridged mono-metallocene catalysts disclosed in US758654, US5272236, US5272272, U5064802, EP0420436 are linked by a cyclopentadienyl ring or a substituted cyclopentadienyl ring through a bridging group and another heteroatom group, have excellent copolymerization performance, can prepare ethylene/alpha-olefin copolymers with high comonomer content, but have general heat resistance, more synthesis steps and lower yield.
CN1096303A, CN1322763A and TW284769B disclose olefin polymerization catalysts having multidentate ligands comprising the combination of (1) a phosphoheteroatom group and a ligand having a sigma bond and at least one pi bond or lone pair donor bond; combining (2) a 5-membered heterocyclic ligand and a ligand having a sigma bond and at least one pi bond or lone pair of donor bonds; combining (3) a tripyrazolyl tridentate ligand and an alkapolyenyl ligand having a sigma bond and two or more pi bonds; the catalyst has high activity for ethylene polymerization, but does not relate to the copolymerization performance of ethylene/alpha-olefin.
CN1145370A discloses a transition metal compound containing at least one cyclopentadienyl or substituted cyclopentadienyl and at least one cyclic ligand containing hetero atom, its compound activator is used for ethylene/1-hexene copolymerization reaction, its copolymerization property is good, polymerization activity can be up to 10 at 60 deg.C7g.Polymer/(mol.h), but the catalyst yield was less than 10%, and the heat resistance at high temperature was examined.
EP0874005 provides a non-metallocene catalyst containing phenoxyimine ligand, the polymerization activity of which can reach the level of that of metallocene catalyst, but the ability to catalyze the copolymerization of ethylene and alpha-olefin at high temperature is inferior to that of metallocene catalyst.
It follows that in the field of olefin polymerization catalysts, there is a constant search for catalyst performance. In particular, in the prior art, particularly in the field of ethylene/α -olefin copolymerization catalysts, transition metal catalysts having high activity, heat resistance and excellent copolymerization properties are hot spots of research, and only satisfactory products are emerging.
Disclosure of Invention
In view of the above-mentioned problems in the prior art, particularly the problems of insufficient heat resistance and copolymerization performance of an ethylene/α -olefin copolymerization catalyst, the present invention provides a transition metal compound. The preparation method of the transition metal compound is simple, low in energy consumption and high in yield. It is used in ethylene polymer and has the features of high activity, high heat resistance and excellent copolymerization performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
one aspect of the present invention provides a transition metal compound represented by the formula (I):
Ln1MXn2(I)
wherein L is one or more, for example two, of C1-C20 alkyl substituted or unsubstituted N heteroatom-containing aryl or cycloalkyl groups or C1-C20 alkyl substituted or unsubstituted amine groups; n is1Is the coordination number of M, and is an integer in the range of 1 to 3, for example 2;
m is a group IVB-IIB transition metal atom, preferably titanium, zirconium or hafnium;
x is halogen (preferably chlorine) or hydrogen atom, or halogen substituted or unsubstituted C1-C20 hydrocarbon group; n is2Is the coordination number of M and is an integer in the range of 1 to 3, for example 2.
In a preferred embodiment of the present invention, in the above formula (I), L is one or more, for example two, of methyl, ethyl or tert-butyl substituted or unsubstituted indazolyl, indolyl, benzindolyl, carbazolyl, piperidinyl, tetrahydropyrrolyl, cyclohexylamino, cyclopentylamino or anilino groups.
In a further preferred embodiment of the present invention, in the above formula (I), L is preferably one or more, for example two, of 7-methylindazolyl, 7-tert-butylindazolyl, 5, 7-dimethylindazolyl, 7-ethylindazolyl, 5, 7-diethylindazolyl, 2, 3-dimethylindolyl, 5-tert-butylindolyl, 3-ethylindolyl, 5-ethylindolyl, 2, 3-dimethylbenzoindolyl, 2-ethylbenzindolyl, 5-tert-butylbenzoindolyl, 1,2,3, 4-tetrahydrocarbazolyl, piperidinyl, cyclohexylamino, cyclopentylamino, anilino and tetrahydropyrrolyl.
In a preferred embodiment of the invention, the transition metal compound is selected from the following compounds:
7-methylindazolyl titanium trichloride, 7-tert-butylindazolyl titanium trichloride, 5, 7-dimethylindazolyl titanium trichloride, 7-ethylindazolyl zirconium trichloride, 7-tert-butylindazolyl zirconium trichloride, 5, 7-dimethylindazolyl zirconium trichloride, or 5, 7-diethylindazolyl hafnium trichloride; or
2, 3-dimethylindolytittanium trichloride, 5-tert-butylindolytittanium trichloride, 3-ethylindolyzirconiumtrichloride, 5-ethylindolyzirconiumtrichloride, 2, 3-dimethylindolyhafnium trichloride or 5-tert-butylindolyhafnium trichloride; or
2, 3-dimethylbenzoindolyltitanium trichloride, 2-ethylbenzindolyl zirconium trichloride, or 5-tert-butylbenzoindolyl hafnium trichloride; or
1,2,3, 4-tetrahydrocarbazolyltium trichloride, 1,2,3, 4-tetrahydrocarbazolyzirconium trichloride or 1,2,3, 4-tetrahydrocarbazolyhafnium trichloride; or
Bis (5, 7-dimethylindazolyl) titanium dichloride, bis (7-tert-butylindazolyl) titanium dichloride, bis (7-methylindazolyl) titanium dichloride, 5, 7-dimethylindazolyl (5-tert-butylindolyl) titanium dichloride, 7-methylindazolyl (2, 3-dimethylindolyl) titanium dichloride, bis (5, 7-dimethylindazolyl) zirconium dichloride, bis (7-tert-butylindazolyl) zirconium dichloride, 7-tert-butylindazolyl (5-tert-butylindolyl) zirconium dichloride, 7-methylindolyl (2, 3-dimethylindolyl) hafnium dichloride, or 5, 7-dimethylindazolyl (5-tert-butylindolyl) hafnium dichloride; or
5, 7-dimethylindazolyl (2, 3-dimethylbenzindoliyl) titanium dichloride, 7-tert-butylindazolyl (2, 3-dimethylbenzindoliyl) titanium dichloride, 7-methylindolyl (2, 3-dimethylbenzindoliyl) titanium dichloride, 5, 7-dimethylindazolyl (2, 3-dimethylbenzindoliyl) zirconium dichloride or 5, 7-dimethylindazolyl (2, 3-dimethylbenzindoliyl) hafnium dichloride; or
5, 7-dimethylindazolyl (1,2,3, 4-tetrahydrocarbazolyl) titanium dichloride, 7-tert-butylindazolyl (1,2,3, 4-tetrahydrocarbazolyl) titanium dichloride, 7-methylindazolyl (1,2,3, 4-tetrahydrocarbazolyl) titanium dichloride, 5, 7-dimethylindazolyl (1,2,3, 4-tetrahydrocarbazolyl) zirconium dichloride, 5, 7-dimethylindazolyl (1,2,3, 4-tetrahydrocarbazolyl) hafnium dichloride, or 7-methylindazolyl (1,2,3, 4-tetrahydrocarbazolyl) hafnium dichloride; or
5, 7-dimethylindazolyl (piperidinyl) titanium dichloride, 7-methylindazolyl (cyclopentylamino) titanium dichloride, 5, 7-dimethylindazolyl (anilino) zirconium dichloride, 5, 7-diethylindazolyl (tetrahydropyrrolyl) hafnium dichloride, 7-ethylindazolyl (cyclohexylamino) hafnium dichloride, 7-tert-butylindazolyl (4-tert-butylcyclohexylamino) titanium dichloride, 2, 3-dimethylbenzindolinyl (anilino) zirconium dichloride or 1,2,3, 4-tetrahydrocarbazolyl (tetrahydropyrrolyl) hafnium dichloride.
Another aspect of the present invention provides a method for preparing the transition metal compound as described above, comprising the steps of:
1) one or more C1-C20 alkyl substituted or unsubstituted aromatic ring compounds or aliphatic ring compounds containing N heteroatoms or C1-C20 alkyl substituted or unsubstituted amine compounds are contacted with alkyl lithium to react to obtain a solution component 1 of amino lithium salt;
2) reacting the solution component 1 in the step 1) with IVB-IIB group transition metal halide or a complex thereof and a metal salt reducing agent to obtain a suspension component 2;
3) evaporating the solvent in the suspension component 2 in the step 2) to dryness, then adding an inert solvent for washing treatment, filtering solid residues, adding an alkane solvent for washing treatment again, filtering, and carrying out vacuum drying on the collected solid to obtain a transition metal compound component 3.
In a preferred embodiment of the present invention, in step 1) of the method for preparing the transition metal compound as described above, the alkyl substituted or unsubstituted N heteroatom-containing aromatic ring compound or aliphatic ring compound of C1 to C20 or the alkyl substituted or unsubstituted amine compound of C1 to C20 includes the following groups: methyl-, ethyl-or tert-butyl-substituted or unsubstituted indazolyl, indolyl, benzindolyl, carbazolyl, piperidinyl, tetrahydropyrrolyl, cyclohexylamino, cyclopentylamino or anilino groups, for example two.
In a further preferred embodiment of the present invention, in step 1) of the method for preparing the transition metal compound as described above, the alkyl substituted or unsubstituted N-heteroatom-containing aromatic ring compound or aliphatic ring compound of C1 to C20 or the alkyl substituted or unsubstituted amine compound of C1 to C20 preferably includes the following groups: one or more, for example two, of 7-methylindazolyl, 7-tert-butylindazolyl, 5, 7-dimethylindazolyl, 7-ethylindazolyl, 5, 7-diethylindazolyl, 2, 3-dimethylindolyl, 5-tert-butylindolyl, 3-ethylindolyl, 5-ethylindolyl, 2, 3-dimethylbenzoindolyl, 2-ethylbenzindolyl, 5-tert-butylbenzoindolyl, 1,2,3, 4-tetrahydrocarbazolyl, piperidinyl, cyclohexylamino, cyclopentylamino, anilino, and tetrahydropyrrolyl.
In a preferred embodiment of the present invention, in step 1) of the process for preparing the transition metal compound as described above, the alkyllithium is selected from one or more of methyllithium, ethyllithium, isopropyllithium, n-butyllithium and t-butyllithium, preferably n-butyllithium.
In a preferred embodiment of the present invention, in step 2) of the method for preparing the transition metal compound as described above, the transition metal halide or the complex thereof is selected from the group consisting of: complexes of titanium halides with tetrahydrofuran, preferably [ TiCl3(THF)3]Or [ TiCl4(THF)2](ii) a Complexes of zirconium halides with tetrahydrofuran, preferably [ ZrCl ]3(THF)3]Or [ ZrCl ]4(THF)2](ii) a Hafnium halide, preferably HfCl4(ii) a The transition metal halide or the complex thereof is more preferably [ TiCl3(THF)3]、[ZrCl3(THF)3]Or HfCl4。
In a preferred embodiment of the present invention, in step 2) of the method for preparing a transition metal compound as described above, the metal salt reducing agent is selected from lead chloride or silver chloride, preferably lead chloride.
In a preferred embodiment of the present invention, in step 3) of the method for preparing the transition metal compound as described above, the inert solvent is selected from one or more of dichloromethane, chloroform, trichloroethane, chloropropane, benzene, toluene and xylene, preferably toluene; the alkane solvent is selected from aliphatic alkanes of C6-C10, and n-hexane is preferred.
In a preferred embodiment of the present invention, in step 1) of the method for preparing the transition metal compound as described above, the alkyl substituted or unsubstituted N heteroatom-containing aromatic ring compound or aliphatic ring compound of C1 to C20 or alkyl substituted or unsubstituted amine compound of C1 to C20 is contacted with an alkyllithium under the conditions: the initial contact reaction temperature is-100 ℃ to 0 ℃, preferably-80 ℃ to-30 ℃, such as-90 ℃, 70 ℃, 60 ℃, 50 ℃, 40 ℃, 20 ℃ or-10 ℃ and the like; the reaction temperature is 0 ℃ to 60 ℃, for example, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃ or 50 ℃ and the like; the reaction time is 0.5h to 12h, such as 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or 11 h; step 1) is preferably carried out in the presence of a solvent, preferably one or more of diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, 2-methylfuran, 2, 5-dimethylfuran and 2, 3-benzofuran, more preferably diethyl ether and/or tetrahydrofuran.
In a preferred embodiment of the present invention, in step 2) of the method for preparing the transition metal compound as described above, the conditions for contact reaction of the solution component 1 with the group IVB-IIB transition metal halide or the complex thereof are: the initial contact reaction temperature is-100 ℃ to 0 ℃, preferably-80 ℃ to-30 ℃, such as-90 ℃, 70 ℃, 60 ℃, 50 ℃, 40 ℃, 20 ℃ or-10 ℃ and the like; the reaction temperature is 0 ℃ to 60 ℃, for example, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃ or 50 ℃ and the like; the reaction time is 0.5h to 12h, such as 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or 11 h; the conditions of the contact reaction with the metal salt reducing agent are as follows: the reaction temperature is 0 ℃ to 60 ℃, for example, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃ or 50 ℃ and the like; the reaction time is 0.5h to 12h, for example, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or 11 h.
In the method for preparing the transition metal compound of the present invention, one skilled in the art can appropriately prepare the raw materials according to the reaction formula and the conventional techniques in the art. For example, in step 1), the molar ratio of the alkyl substituted or unsubstituted N-heteroatom-containing aromatic ring compound or aliphatic ring compound of C1-C20 or the alkyl substituted or unsubstituted amine compound of C1-C20 to the alkyl lithium may be about 1: 1; in the step 2), the molar ratio of the solution component 1 to the transition metal halide or the complex thereof and the metal salt reducing agent can be 1:1: 2-6. Although the molar ratio of each raw material in the process for producing the transition metal compound represented by the formula (I) is exemplified, those skilled in the art can reasonably adjust the molar ratio within a reasonable range according to actual needs, and such adjustment is within the scope of the present invention.
In still another aspect of the present invention, there is provided a process for olefin polymerization, wherein the homopolymerization or copolymerization of ethylene is carried out in the presence of the transition metal compound as described above or the transition metal compound obtained by the process for preparing a transition metal compound as described above and an activating cocatalyst. The polymerization of olefins (homopolymerization and copolymerization) is a technique well known in the art, and a person skilled in the art can select suitable conditions according to actual needs.
In a preferred embodiment of the present invention, in the process for the polymerization of olefins, the cocatalyst is selected from one or more of alkylaluminoxane, alkylaluminum, tris (pentafluorophenyl) boron or borate; preferably methylaluminoxane and/or tris (pentafluorophenyl) boron, wherein the molar ratio of methylaluminoxane to the transition metal compound is 10 to 1000:1, preferably 50 to 200:1, such as 20:1, 30:1, 40:1, 60:1, 70:1, 80:1, 90:1, 100:1, 300:1, 400:1, 500:1, 600:1, 700:1, 800:1 or 900:1, etc., and the molar ratio of tris (pentafluorophenyl) boron to the transition metal compound is 0 to 15:1, preferably 0 to 5:1, such as 1:1, 2:1, 3:1, 4:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1 or 14:1, etc.
In a preferred embodiment of the present invention, in the process for the polymerization of olefins, the comonomer in the copolymerization is selected from one or more of propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene and styrene, preferably 1-octene and/or 1-hexene.
Compared with the prior art, the beneficial effects of the invention are mainly embodied in the following aspects:
the transition metal compound of the invention has simple preparation method, low energy consumption and high yield, and compared with other single-active-center catalysts, the catalyst has excellent temperature resistance and excellent copolymerization performance at high temperature.
Detailed Description
The present invention is described in further detail below, but the present invention is not limited thereto.
Raw materials
TABLE 1 Source and Specifications of raw materials
Test method
The structural characterization of the transition metal compound was carried out by 1H-NMR (Bruker ADVANCE III 400M) in deuterated chloroform with a nitrogen reflux in calcium hydride.
The polymerization activity is calculated as the ratio of the weight of the dried polymer product obtained by the polymerization reaction to the number of moles of the transition metal compound added during the reaction.
Polymer molecular weight (Mw) and molecular weight distribution (PDI) were determined by high temperature gel permeation chromatography (PL-GPC220) using 1,2, 4-trichlorobenzene as the mobile phase and polystyrene as the standard at 150 ℃, with a standard concentration of 0.1mg/mL, a solvent flow rate of 1.0mL/min, standard use parameters of K59.1, α 0.69, sample parameters of K14.1, α 0.70.
The comonomer insertion in the ethylene/alpha-olefin copolymer was measured by 13C-NMR (Bruker ADVANCE III 400M). The polymer was formulated in a solution of deuterated 1, 2-orthodichlorobenzene at about 100mg/mL at 130 ℃. The instrument parameters are pulse angle 30 degrees, whole decoupling is carried out, pulse delay time is 3s, and a sample is continuously scanned more than 3000 times to obtain a high-temperature nuclear magnetic spectrum. The carbon spectrum of the copolymer is assigned by adopting an ASTM D5017-96 method, and the sequence distribution and the average comonomer composition of the copolymer are calculated.
Examples
Preparation of transition metal compound:
example 1: preparation of 5, 7-dimethyl indazolyl titanium trichloride
1) Preparation of component 1
Adding 5, 7-dimethylindazole (0.439g, 3mmol) into 40mL of THF solvent, slowly stirring and dropwise adding 1.2mL of 2.5M n-BuLi in hexane at the temperature of-78 ℃, heating to room temperature after dropwise adding, and stirring for reaction for 10h to obtain a brown yellow transparent solution component 1;
2) preparation of component 2
The temperature of the above clear solution component 1 was cooled to-78 ℃ and slowly added dropwise to the solution containing TiCl3(THF)3(1.112g, 3mmol) in 40mL THF solvent, after the dropwise addition, raising the temperature to about 25 ℃, and stirring for reaction for 12h to obtain a brown suspension; rapidly adding 1.67g of lead chloride, stirring and reacting for 2 hours to obtain a dark green suspension component 2 after the reaction is finished;
3) preparation of component 3
Removing the solvent by reduced pressure distillation to obtain a dark green solid, then adding 50mL of toluene solvent for washing, filtering out the solid, concentrating the obtained filtrate to a very small amount, then adding 20mL of n-hexane, finding that a large amount of yellow crystals are separated out, and finally washing the filtered solid by n-hexane for multiple times to obtain 0.509g of yellow transition metal compound component 3 with the yield of 57%.
1H-NMR(400MHz,CHCl3,TMS,in ppm):1.90(s,3H,Indozole-CH3),2.32(s,3H,Indozole-CH3),7.26(m,H,Indozole-CH),7.68(m,H,Indozole-CH),8.10(m,H,NCH).
Example 2: preparation of 5-tert-butylbenzindolinyl hafnium trichloride
1) Preparation of component 1
The procedure is followed for the preparation of component 1 of example 1, with the difference that: replacement of 5, 7-dimethylindazole (0.439g, 3mmol) with 5-tert-butylbenzoindole (0.669g, 3mmol) gave component 1 as a pale yellow clear solution;
2) preparation of component 2
The procedure is followed for the preparation of component 2 of example 1, with the difference that: with HfCl4(0.961g, 3mmol) instead of TiCl3(THF)3(1.112g, 3mmol) to give a greenish black suspension component 2;
3) preparation of component 3
According to the preparation method of component 3 of example 1, 0.943g of white transition metal compound component 3 was obtained in a yield of 62%.
1H-NMR(400MHz,CHCl3,TMS,in ppm):1.45(s,9H,Benzopyrene-CC3H9),5.34(m,H,Benzopyrene-NCH3),6.80-7.90(m,H,Benzopyrene-CH).
Example 3: preparation of bis (5, 7-dimethylindazolyl) zirconium dichloride
1) Preparation of component 1
The procedure is followed for the preparation of component 1 of example 1, with the difference that: replacement of 5, 7-dimethylindazole (0.439g, 3mmol) with 5, 7-dimethylindazole (0.877g, 6mmol) gave component 1 as a pale yellow clear solution;
2) preparation of component 2
The procedure is followed for the preparation of component 2 of example 1, with the difference that: with ZrCl3(THF)3(1.242g, 3mmol) instead of TiCl3(THF)3(1.112g, 3mmol) to give a greenish black suspension component 2;
3) preparation of component 3
According to the preparation method of component 3 of example 1, 0.621g of white transition metal compound component 3 was obtained in a yield of 46%.
1H-NMR(400MHz,CHCl3,TMS,in ppm):1.95(s,6H,Indozole-CH3),2.30(s,6H,Indozole-CH3),7.31(m,2H,Indozole-CH),7.77(m,2H,Indozole-CH),8.63(m,2H,NCH).
Example 4: preparation of 7-methylindazolyl (2, 3-dimethylindolyl) hafnium dichloride
1) Preparation of component 1
The procedure is followed for the preparation of component 1 of example 1, with the difference that: replacement of 5, 7-dimethylindazole (0.439g, 3mmol) with 7-methylindazole (0.396g, 3mmol) and 2, 3-dimethylindole (0.435g, 3mmol) gave component 1 as a pale yellow transparent solution;
2) preparation of component 2
The procedure is followed for the preparation of component 2 of example 1, with the difference that: with HfCl4(0.961g, 3mmol) instead of TiCl3(THF)3(1.112g, 3mmol) to give a greenish black suspension component 2;
3) preparation of component 3
According to the production method of component 3 of example 1, 0.882g of a white transition metal compound component 4 was obtained in a yield of 56%.
1H-NMR(400MHz,CHCl3,TMS,in ppm):1.92(s,3H,Indozole-CH3),2.28(s,6H,Indole-CH3),7.36-7.73(m,3H,Indozole-CH),6.93-7.46(m,4H,Indole-CH),8.13(m,H,NCH).
Example 5: preparation of 5, 7-dimethylindazolyl (2, 3-dimethylbenzindolinyl) zirconium dichloride
1) Preparation of component 1
The procedure is followed for the preparation of component 1 of example 1, with the difference that: replacement of 5, 7-dimethylindazole (0.439g, 3mmol) with 5, 7-dimethylindazole (0.439g, 3mmol) and 2, 3-dimethylbenzoindole (0.585g, 3mmol) gave brown clear solution component 1;
2) preparation of component 2
The procedure is followed for the preparation of component 2 of example 1, with the difference that: with ZrCl3(THF)3(1.242g, 3mmol) instead of TiCl3(THF)3(1.112g, 3mmol) to give a greenish black suspension component 2;
3) preparation of component 3
According to the production method of component 3 of example 1, 0.584g of yellow transition metal compound component 5 was obtained in 39% yield.
1H-NMR(400MHz,CHCl3,TMS,in ppm):1.91(s,3H,Indozole-CH3),2.34(s,6H,Benzopyrene-CH3),2.39(s,6H,Indozole-CH3),7.22-7.74(m,2H,Indozole-CH),7.40-8.16(m,6H,Benzopyrene-CH),8.33(m,H,NCH).
Example 6: preparation of 5, 7-dimethylindazolyl (2, 3-dimethylbenzindolinyl) titanium dichloride
1) Preparation of component 1
The procedure is followed for the preparation of component 1 of example 1, with the difference that: replacement of 5, 7-dimethylindazole (0.439g, 3mmol) with 5, 7-dimethylindazole (0.439g, 3mmol) and 2, 3-dimethylbenzoindole (0.585g, 3mmol) gave component 1 as a yellow, transparent solution;
2) preparation of component 2
Following the procedure for the preparation of component 2 of example 1, a greenish black suspension component 2 was obtained;
3) preparation of component 3
According to the production method of component 3 of example 1, 0.713g of yellow transition metal compound component 6 was obtained in a yield of 52%.
1H-NMR(400MHz,CHCl3,TMS,in ppm):1.96(s,3H,Indozole-CH3),2.28(s,6H,Benzopyrene-CH3),2.33(s,6H,Indozole-CH3),7.22-7.74(m,2H,Indozole-CH),7.40-8.16(m,6H,Benzopyrene-CH),8.17(m,H,NCH).
Example 7: preparation of 7-tert-butylindazolyl (1,2,3, 4-tetrahydrocarbazolyl) titanium dichloride
1) Preparation of component 1
The procedure is followed for the preparation of component 1 of example 1, with the difference that: replacement of 5, 7-dimethylindazole (0.439g, 3mmol) with 7-tert-butylindazole (0.522g, 3mmol) and 1,2,3, 4-tetrahydrocarbazole (0.513g, 3mmol) gave component 1 as a yellow transparent solution;
2) preparation of component 2
Following the procedure for the preparation of component 2 of example 1, a greenish black suspension component 2 was obtained;
3) preparation of component 3
According to the production method of component 3 of example 1, 0.913g of yellow transition metal compound component 6 was obtained in a yield of 66%.
1H-NMR(400MHz,CHCl3,TMS,in ppm):1.32(s,9H,CC3H9),1.79-2.77(s,8H,Tetrahydrocarbazole-CH2),7.40-8.34(m,4H,Indozole-CH),6.91-7.55(m,4H,Tetrahydrocarbazole-CH).
Example 8: preparation of 7-tert-butylindazolyl (4-tert-butylcyclohexylamino) titanium dichloride
1) Preparation of component 1
The procedure is followed for the preparation of component 1 of example 1, with the difference that: replacement of 5, 7-dimethylindazole (0.439g, 3mmol) with 7-tert-butylindazole (0.522g, 3mmol) and 4-tert-butylcyclohexylamine (0.466g, 3mmol) gave component 1 as a yellow, transparent solution;
2) preparation of component 2
Following the procedure for the preparation of component 2 of example 1, a greenish black suspension component 2 was obtained;
3) preparation of component 3
According to the preparation method of component 3 of example 1, 0.841g of yellow transition metal compound component 6 was obtained in a yield of 63%.
1H-NMR(400MHz,CHCl3,TMS,in ppm):0.92(s,9H,CC3H9),1.22-1.52(s,10H,Cyclohexane-CH),7.45-8.64(m,4H,Indozole-CH),5.15(m,H,NH).
Comparative example 1: preparation of comparative transition Metal Compound
0.802g of cyclopentadienyl tetramethylpyrrolylzirconium dichloride, a transition metal compound, was prepared according to the method disclosed in patent application CN1145370A and used in the subsequent comparative example 2.
The transition metal compounds obtained in examples 1 to 8 were used in subsequent polymerization examples 9 to 16.
Polymerization of ethylene
Example 9
The ethylene/alpha-olefin solution copolymerization was carried out in a 2L stainless steel batch reactor with magnetic stirring.
Under the protection of inert gas, 1000mL of toluene solvent and 5mL of 1.1M triisobutylaluminum hexane solution were added to the reaction kettle, water oxygen impurities in the reaction kettle were treated by rapid stirring, and then the reaction kettle was vacuum-dried at high temperature and replaced with ethylene gas three times. Keeping the micro-positive pressure in the kettle, sequentially adding 1000mL of toluene solvent, 250mL of 1-octene and 0.1mL of 1.5M Methyl Aluminoxane (MAO) toluene solution into the reaction kettle at the stirring speed of 500rpm, then heating to the reaction temperature of 180 ℃, introducing ethylene gas, and keeping the pressure in the kettle stable at the required polymerization pressure (3.0 Mpa); after the temperature and the pressure in the kettle are stable, the ethylene is pressed inA reaction vessel was charged with a solution containing 0.9mg of the transition metal compound obtained in example 1 and 1.5mg of B (C)6F5)3The polymerization was started for 5 min. After the polymerization reaction was completed, ethylene was turned off, the reaction vessel was cooled to 80 ℃ and then unreacted ethylene was discharged, and the reaction solution was discharged into 1L of pure water, washed and filtered, and the polymer was collected and vacuum-dried at a temperature of 50 ℃ to a constant weight, and weighed to obtain 126g of a polymer product, the polymer test results of which are shown in Table 3.
Example 10
The polymerization was carried out as in example 9, with the difference that: 1.5M MAO in toluene was added in an amount of 0.2mL, using 1.5mg of the transition metal compound prepared in example 2, B (C)6F5)3The amount added was 4.6mg, and 114g of a polymer product was obtained, and the polymer test results are shown in Table 3.
Example 11
The polymerization was carried out as in example 9, with the difference that: 1.5M MAO in toluene was added in an amount of 0.4mL, using 1.4mg of the transition metal compound prepared in example 3, B (C)6F5)3The amount added was 7.7mg and the polymerization temperature was 190 ℃ to obtain 168g of a polymer product, the polymer test results of which are shown in Table 3.
Example 12
The polymerization was carried out as in example 9, with the difference that: 250mL of 1-octene was replaced with 100mL of 1-hexene with 1.6mg of the transition metal compound prepared in example 4, B (C)6F5)3The amount added was 6.1mg and the polymerization temperature was 190 ℃ to obtain 360g of a polymer product, the polymer test results of which are shown in Table 3.
Example 13
The polymerization was carried out as in example 9, with the difference that: 1.5mg of the transition metal compound prepared in example 5, B (C)6F5)3The amount added was 6.1mg and the polymerization temperature was 200 ℃ to obtain 330g of a polymer product, the polymer test results of which are shown in Table 3.
Example 14
The polymerization was carried out as in example 13, with the difference that: 1.4mg of the transition metal compound prepared in example 6 was used, and the polymerization temperature was 180 ℃ to obtain 630g of a polymer product, the polymer test results of which are shown in Table 3.
Example 15
The polymerization was carried out as in example 14, with the difference that: A1.5M solution of MAO in toluene was added in an amount of 0.15mL, using 1.4mg of the transition metal compound prepared in example 7, to obtain 66g of a polymer product, the polymer test results of which are shown in Table 3.
Example 16
The polymerization was carried out as in example 14, with the difference that: using 1.3mg of the transition metal compound prepared in example 8, 90g of a polymer product was obtained, and the polymer test results are shown in Table 3.
Comparative example 2: comparative transition metal compounds for polymerization
The polymerization was carried out as in example 16, with the difference that: 1.1mg of the transition metal compound prepared in comparative example 1 was used to obtain 17.1g of a polymer product, and the polymer test results are shown in Table 3.
TABLE 2 polymerization conditions
Note: the "Al/M molar ratio" in Table 2 means the molar ratio of methylaluminoxane to the main catalyst (transition metal compounds prepared in examples 1 to 8 and comparative example 1); "B/M molar ratio" refers to borate or boron species (e.g., B (C)6F5)3) To the main catalyst (transition metal compounds prepared in examples 1 to 8 and comparative example 1).
TABLE 3 polymerization results
Note: the calculation formula of the polymerization activity in Table 3 is: polymerization activity ═ polymer yield ÷ moles of main catalyst ÷ time.
As can be seen from the polymerization results of the above examples and comparative examples, when the transition metal compound of the present invention is used in copolymerization of ethylene/α -olefin together with a co-catalyst, it shows very high polymerization activity at a high temperature of 180 ℃ or more, and is excellent in temperature resistance and copolymerization properties.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Claims (10)
1. A transition metal compound of the formula (I):
Ln1MXn2(I)
wherein, L is one or more of C1-C20 alkyl substituted or unsubstituted N heteroatom-containing aryl or cycloalkyl or C1-C20 alkyl substituted or unsubstituted amine; n is1Is the coordination number of M, and takes an integer ranging from 1 to 3;
m is a group IVB-IIB transition metal atom;
x is halogen or hydrogen atom, or halogen substituted or unsubstituted C1-C20 hydrocarbon group; n is2Is the coordination number of M, and takes an integer ranging from 1 to 3.
2. The transition metal compound according to claim 1, wherein L is one or more of a methyl, ethyl or tert-butyl substituted or unsubstituted indazolyl, indolyl, benzindolyl, carbazolyl, piperidinyl, tetrahydropyrrolyl, cyclohexylamino, cyclopentylamino or anilino group; preferably 7-methyl indazolyl, 7-tert-butyl indazolyl, 5, 7-two methyl indazolyl, 7-ethyl indazolyl, 5, 7-two ethyl indazolyl, 2, 3-two methyl indole, 5-tert-butyl indole, 3-ethyl indole, 5-ethyl indole, 2, 3-two methyl benzene indole, 2-ethyl benzene indole, 5-tert butyl benzene indole, 1,2,3, 4-four hydrogen carbazolyl, piperidine radical, cyclohexyl amino, cyclopentyl amino aniline group, aniline group and four hydrogen pyrrole group in one or more.
3. A transition metal compound according to claim 1 or 2, wherein M is titanium, zirconium or hafnium.
4. A transition metal compound according to any one of claims 1 to 3, selected from the following compounds:
7-methylindazolyl titanium trichloride, 7-tert-butylindazolyl titanium trichloride, 5, 7-dimethylindazolyl titanium trichloride, 7-ethylindazolyl zirconium trichloride, 7-tert-butylindazolyl zirconium trichloride, 5, 7-dimethylindazolyl zirconium trichloride, or 5, 7-diethylindazolyl hafnium trichloride; or
2, 3-dimethylindolytittanium trichloride, 5-tert-butylindolytittanium trichloride, 3-ethylindolyzirconiumtrichloride, 5-ethylindolyzirconiumtrichloride, 2, 3-dimethylindolyhafnium trichloride or 5-tert-butylindolyhafnium trichloride; or
2, 3-dimethylbenzoindolyltitanium trichloride, 2-ethylbenzindolyl zirconium trichloride, or 5-tert-butylbenzoindolyl hafnium trichloride; or
1,2,3, 4-tetrahydrocarbazolyltium trichloride, 1,2,3, 4-tetrahydrocarbazolyzirconium trichloride or 1,2,3, 4-tetrahydrocarbazolyhafnium trichloride; or
Bis (5, 7-dimethylindazolyl) titanium dichloride, bis (7-tert-butylindazolyl) titanium dichloride, bis (7-methylindazolyl) titanium dichloride, 5, 7-dimethylindazolyl (5-tert-butylindolyl) titanium dichloride, 7-methylindazolyl (2, 3-dimethylindolyl) titanium dichloride, bis (5, 7-dimethylindazolyl) zirconium dichloride, bis (7-tert-butylindazolyl) zirconium dichloride, 7-tert-butylindazolyl (5-tert-butylindolyl) zirconium dichloride, 7-methylindolyl (2, 3-dimethylindolyl) hafnium dichloride, or 5, 7-dimethylindazolyl (5-tert-butylindolyl) hafnium dichloride; or
5, 7-dimethylindazolyl (2, 3-dimethylbenzindoliyl) titanium dichloride, 7-tert-butylindazolyl (2, 3-dimethylbenzindoliyl) titanium dichloride, 7-methylindolyl (2, 3-dimethylbenzindoliyl) titanium dichloride, 5, 7-dimethylindazolyl (2, 3-dimethylbenzindoliyl) zirconium dichloride or 5, 7-dimethylindazolyl (2, 3-dimethylbenzindoliyl) hafnium dichloride; or
5, 7-dimethylindazolyl (1,2,3, 4-tetrahydrocarbazolyl) titanium dichloride, 7-tert-butylindazolyl (1,2,3, 4-tetrahydrocarbazolyl) titanium dichloride, 7-methylindazolyl (1,2,3, 4-tetrahydrocarbazolyl) titanium dichloride, 5, 7-dimethylindazolyl (1,2,3, 4-tetrahydrocarbazolyl) zirconium dichloride, 5, 7-dimethylindazolyl (1,2,3, 4-tetrahydrocarbazolyl) hafnium dichloride, or 7-methylindazolyl (1,2,3, 4-tetrahydrocarbazolyl) hafnium dichloride; or
5, 7-dimethylindazolyl (piperidinyl) titanium dichloride, 7-methylindazolyl (cyclopentylamino) titanium dichloride, 5, 7-dimethylindazolyl (anilino) zirconium dichloride, 5, 7-diethylindazolyl (tetrahydropyrrolyl) hafnium dichloride, 7-ethylindazolyl (cyclohexylamino) hafnium dichloride, 7-tert-butylindazolyl (4-tert-butylcyclohexylamino) titanium dichloride, 2, 3-dimethylbenzindolinyl (anilino) zirconium dichloride or 1,2,3, 4-tetrahydrocarbazolyl (tetrahydropyrrolyl) hafnium dichloride.
5. A process for preparing a transition metal compound according to any one of claims 1 to 4, comprising the steps of:
1) one or more C1-C20 alkyl substituted or unsubstituted aromatic ring compounds or aliphatic ring compounds containing N heteroatoms or C1-C20 alkyl substituted or unsubstituted amine compounds are contacted with alkyl lithium to react to obtain a solution component 1 of amino lithium salt;
2) reacting the solution component 1 in the step 1) with IVB-IIB group transition metal halide or a complex thereof and a metal salt reducing agent to obtain a suspension component 2;
3) evaporating the solvent in the suspension component 2 in the step 2) to dryness, then adding an inert solvent for washing treatment, filtering solid residues, adding an alkane solvent for washing treatment again, filtering, and carrying out vacuum drying on the collected solid to obtain a transition metal compound component 3.
6. The method of claim 5, wherein,
in step 1), the alkyl substituted or unsubstituted N-heteroatom-containing aromatic ring compound or aliphatic ring compound of C1-C20 or the alkyl substituted or unsubstituted amine compound of C1-C20 includes the following groups: one or more of an indazolyl, indolyl, benzindolyl, carbazolyl, piperidinyl, tetrahydropyrrolyl, cyclohexylamino, cyclopentylamino or anilino group substituted or unsubstituted with methyl, ethyl or tert-butyl; preferably comprising the following groups: one or more of 7-methylindazolyl, 7-tert-butylindazolyl, 5, 7-dimethylindazolyl, 7-ethylindazolyl, 5, 7-diethylindazolyl, 2, 3-dimethylindolyl, 5-tert-butylindolyl, 3-ethylindolyl, 5-ethylindolyl, 2, 3-dimethylbenzoindolyl, 2-ethylbenzindolyl, 5-tert-butylbenzoindolyl, 1,2,3, 4-tetrahydrocarbazolyl, piperidinyl, cyclohexylamino, cyclopentylamino, anilino and tetrahydropyrrolyl; the alkyl lithium is selected from one or more of methyl lithium, ethyl lithium, isopropyl lithium, n-butyl lithium and tert-butyl lithium;
in step 2), the transition metal halide or complex thereof is selected from: complexes of titanium halides with tetrahydrofuran, preferably [ TiCl3(THF)3]Or [ TiCl4(THF)2](ii) a Complexes of zirconium halides with tetrahydrofuran, preferably [ ZrCl ]3(THF)3]Or [ ZrCl ]4(THF)2](ii) a Or hafnium halides, preferably HfCl4(ii) a The transition metal halide or the complex thereof is more preferably [ TiCl3(THF)3]、[ZrCl3(THF)3]Or HfCl4(ii) a The metal salt reducing agent is selected from lead chloride or silver chloride;
in step 3), the inert solvent is selected from one or more of dichloromethane, chloroform, trichloroethane, chloropropane, benzene, toluene and xylene; the alkane solvent is selected from aliphatic alkanes of C6-C10.
7. The method of claim 5 or 6,
in the step 1), the alkyl substituted or unsubstituted N-containing heterocyclic aromatic ring compound or aliphatic ring compound of C1-C20 or the alkyl substituted or unsubstituted amine compound of C1-C20 is contacted with alkyl lithium under the conditions that: the initial contact reaction temperature is-100 ℃ to 0 ℃, preferably-80 ℃ to-30 ℃, the reaction temperature is 0 ℃ to 60 ℃, and the reaction time is 0.5h to 12 h; preferably in the presence of a solvent, preferably one or more of diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, 2-methylfuran, 2, 5-dimethylfuran and 2, 3-benzofuran, more preferably diethyl ether and/or tetrahydrofuran;
in the step 2), the contact reaction conditions of the solution component 1 and the IVB-IIB transition metal halide or the complex thereof are as follows: the initial contact reaction temperature is-100 ℃ to 0 ℃, preferably-80 ℃ to-30 ℃, the reaction temperature is 0 ℃ to 60 ℃, and the reaction time is 0.5h to 12 h; the conditions of the contact reaction with the metal salt reducing agent are as follows: the reaction temperature is 0-60 ℃, and the reaction time is 0.5-12 h.
8. A process for the polymerization of olefins, wherein the homopolymerization or copolymerization of ethylene is carried out in the presence of a transition metal compound according to any one of claims 1 to 4 or a transition metal compound obtained by the process according to any one of claims 5 to 7 and an activating cocatalyst.
9. The process of claim 8, wherein the cocatalyst is selected from one or more of alkylaluminoxane, alkylaluminum, tris (pentafluorophenyl) boron, or borate; preferably methylaluminoxane and/or tris (pentafluorophenyl) boron, wherein the molar ratio of methylaluminoxane to the transition metal compound is 10 to 1000:1, preferably 50 to 200:1, and the molar ratio of tris (pentafluorophenyl) boron to the transition metal compound is 0 to 15:1, preferably 0 to 5: 1.
10. The process according to claim 9 or 10, wherein the comonomer in the copolymerization is selected from one or more of propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene and styrene, preferably 1-octene and/or 1-hexene.
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| CN1173186A (en) * | 1994-12-19 | 1998-02-11 | 莱昂德尔石油化学公司 | Azametallocene polymerization catalysts |
| WO2003029256A1 (en) * | 2001-10-01 | 2003-04-10 | Dow Global Technologies Inc. | Bulky amido group substituted group 4 metal compounds and polymerization process |
| US20040053776A1 (en) * | 2000-11-21 | 2004-03-18 | Equistar Chemicals, Lp | Single-site catalysts for olefin polymerization |
| CN1503811A (en) * | 2001-02-12 | 2004-06-09 | 伊奎斯塔化学有限公司 | Supported single-site catalysts useful for olefin polymerization |
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| CN1173186A (en) * | 1994-12-19 | 1998-02-11 | 莱昂德尔石油化学公司 | Azametallocene polymerization catalysts |
| US20040053776A1 (en) * | 2000-11-21 | 2004-03-18 | Equistar Chemicals, Lp | Single-site catalysts for olefin polymerization |
| CN1503811A (en) * | 2001-02-12 | 2004-06-09 | 伊奎斯塔化学有限公司 | Supported single-site catalysts useful for olefin polymerization |
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