阅读说明：本技术 限制几何构型茂金属催化剂及其制备方法与应用 (Constrained geometry metallocene catalyst, preparation method and application thereof ) 是由 王文燕 米普科 马丽 许胜� 王立娟 任鹤 王婷兰 孙彬彬 董素琴 牛娜 邵炉 于 2019-09-25 设计创作，主要内容包括：本发明公开了一种限制几何构型茂金属催化剂及其制备方法与应用,该制备方法如下：以2-吡咯甲醛或其复杂衍生物为原料,与茚合成富烯,通过四氢铝锂还原制得配体,再用胺消除法得到高产率的以钛为活性中心催化剂,该类催化剂能够催化烯烃均聚与共聚。以吡咯N杂环替代叔丁胺为给电子体,催化剂分子结构对称,提高了聚合物中α-烯烃的插入率。本发明的催化剂合成路线简单,原料易得,成本低,催化剂收率会大大提高,并具有良好的烯烃聚合催化活性。(The invention discloses a metallocene catalyst with a restricted geometric configuration, a preparation method and an application thereof, wherein the preparation method comprises the following steps: 2-pyrrole formaldehyde or complex derivatives thereof are used as raw materials to synthesize fulvene with indene, ligand is prepared by lithium aluminum hydride reduction, and a high-yield titanium-based active center catalyst is obtained by an amine elimination method and can catalyze olefin homopolymerization and copolymerization. Pyrrole N heterocycle is used as an electron donor to replace tert-butylamine, the molecular structure of the catalyst is symmetrical, and the insertion rate of alpha-olefin in the polymer is improved. The catalyst has the advantages of simple synthetic route, easily obtained raw materials, low cost, greatly improved yield and good catalytic activity for olefin polymerization.)

1. A constrained geometry metallocene catalyst, wherein the constrained geometry metallocene catalyst has the following structure i:

wherein R is¹、R²And R³Each independently selected from H, CH₃-, saturated or containing double bonds, straight-chain or branched C₂-C₁₀One of the hydrocarbon groups; r⁴Is straight-chain or branched C₁-C₅An alkyl group.

2. The constrained geometry metallocene catalyst of claim 1, wherein R is⁴Is CH₃-、CH₃CH₂-、CH₃CH₂CH₂-and CH₃CH₂CH₂CH₂-one of the group consisting.

3. A method for preparing a constrained geometry metallocene catalyst, comprising the steps of:

step 1, reacting 2-pyrrole carboxaldehyde or its derivative with indene to prepare nitrogen-containing fulvene shown in formula III, R¹、R²And R³Each independently selected from H, CH₃-, saturated or containing double bonds, straight-chain or branched C₂-C₁₀One of the hydrocarbon groups;

step 2, reducing nitrogen-containing fulvene in a formula III to generate a pyrrole N heterocyclic-containing ligand in a formula IV; and

step 3, formula IV contains pyrrole NHeterocyclic ligands with Ti [ N (R)⁴)₂]₄A complexation reaction occurs to produce a metallocene catalyst of formula I, R⁴Is straight-chain or branched C₁-C₅An alkyl group;

4. the method of claim 3, wherein R is the metallocene catalyst with a constrained geometry⁴Is CH₃-、CH₃CH₂-、CH₃CH₂CH₂-and CH₃CH₂CH₂CH₂-one of the group consisting.

5. The method of preparing a constrained geometry metallocene catalyst according to claim 3, wherein the step 1 is: dissolving 2-pyrrole formaldehyde shown in the formula II or a derivative thereof and indene in an organic solvent, cooling to-10-5 ℃, dropwise adding pyrrolidine, heating to room temperature, and stirring for reaction for 0.5-20 hours to obtain nitrogen-containing fulvene shown in the formula III;

wherein, the mass ratio of 2-pyrrole formaldehyde or its derivative, indene and tetrahydropyrrole in formula II is 1: 1-5: 1 to 5.

6. The method of preparing a constrained geometry metallocene catalyst according to claim 3, wherein the step 2 is: dissolving the nitrogen-containing fulvene of the formula III obtained in the step 1 in an organic solvent, cooling to-10-5 ℃, dropwise adding lithium aluminum hydride dissolved in the organic solvent, then heating to 40-70 ℃, stirring and reacting for 5-50h to obtain a pyrrole N heterocyclic-containing ligand of the formula IV;

wherein, the molar ratio of the nitrogen-containing fulvene in the formula III to the lithium aluminum hydride is 1: 0.5 to 5.

7. The process for preparing constrained geometry metallocene catalysts according to claim 3, whereinThe step 3 is as follows: dissolving the pyrrole N heterocyclic ring-containing ligand of the formula IV obtained in the step 2 in an organic solvent, cooling to-10-5 ℃, and then dropwise adding Ti [ N (R) dissolved in the organic solvent⁴)₂]₄Heating to 50-100 ℃, and stirring for reaction for 1-30 h to obtain a metallocene catalyst;

wherein, the formula IV contains pyrrole N heterocyclic ligand and Ti [ N (R)⁴)₂]₄In a molar ratio of 1: 0.5 to 5.

8. The method for preparing constrained geometry metallocene catalyst according to claim 3, wherein step 1, step 2 and step 3 are all performed under the protection of inert gas, and the inert gas is one or more selected from the group consisting of nitrogen, helium and argon.

9. A process for the polymerization of olefins carried out under the action of a constrained geometry metallocene catalyst as claimed in claim 1 or 2.

10. The olefin polymerization process of claim 9, wherein the alkene is at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, dicyclopentadiene, 1, 4-butadiene, 1, 5-pentadiene, 1, 6-hexadiene, styrene, alpha-methylstyrene, and divinylbenzene.

11. The olefin polymerization process of claim 9, wherein the constrained geometry metallocene catalyst of claim 1 or 2 is a procatalyst, the alkylaluminum or aluminoxane compound is a cocatalyst, and the molar ratio of the procatalyst to the cocatalyst is 1: 500-2000.

Technical Field

The present invention relates to a metallocene catalyst with a constrained geometry of a pyrrole metallocene, a preparation method thereof, and a method for preparing polyolefin using the same.

Background

When the bridging heteroatom of the ligand forms a semi-sandwich bifunctional compound with the metal atom, they exhibit a high ability to catalyze olefin polymerization under the action of MAO, which is known as Constrained Geometry Catalyst (CGC). The constrained geometry catalyst is characterized in that a constrained geometry substituent group is introduced on a delocalized pi electron bonding group Cp, so that the geometric configuration of a metal atom in a complex is constrained, and an included angle formed by the Cp-a metal central atom-a coordination group connected with a bridging group is smaller than that of a similar complex, so that the constrained geometry catalyst has the characteristic of more open.

In 1990 Dow chemical company synthesized the so-called "constrained configuration catalyst". It is a complex formed by substituting one cyclopentadiene (or indenyl and fluorenyl) in Si1 or C1 bridged metallocene catalyst structure by amino, and a monocyclopentadiene and a transition metal of the IV subgroup by a coordination bond, wherein the bond angle between the monocyclopentadiene, the transition metal and a heteroatom (such as nitrogen) is less than 115 degrees, and a strong Lewis acid system can activate the catalyst into a high-efficiency positive ion. On one hand, the bidentate ligand stabilizes the metal electron cloud, on the other hand, the position of the ligand is deviated due to the existence of the short bridge group, and the active center of the catalyst can be opened only to one direction from the spatial configuration, thereby achieving the purpose of limiting the geometric configuration. Dow chemical company called Constrained-Geometry Catalyst (CGC). The typical structure is shown in formula 1.

Typical structure of CGC of formula 1

The first CGC synthesized by Shapiro and Bercaw et al used t-butyl as the electron donor, and shortly thereafter, the experimenter tried to modify with other groups, such as a more electron-withdrawing benzene ring and adamantane, among others.

Formula 2 first constrained geometry catalyst

Constrained-configuration catalysts substituted with benzene ring and adamantane of formula 3

In addition to alkyl and aryl groups, researchers have also introduced other groups such as sulfonamido, pyrrolyl, hydrazino and imino groups, etc., which are more electron withdrawing than alkyl and aryl groups, so that the Ti-N bond is longer and also facilitates the insertion of alpha-olefins.

Constrained configuration catalysts of other substituent groups of formula 4

Of course, besides N group as electron donor group, there are also groups of heteroatoms such as P, S, O, etc. as electron donor, but compared with the N-containing electron donor, CGC synthesized by using other heteroatoms as electron donor is not ideal in both activity and performance of the obtained polymer, so that currently, research on CGC using other heteroatoms as electron donor is rare, for example, only one example is reported for CGC containing S atom, and there is almost no catalytic activity.

Constrained configuration catalysts with other hetero atoms as electron donating groups of formula 5

Because the unique stereo structure of the CGC catalyst can allow various olefin monomers to be inserted, the CGC catalyst can catalyze olefin homopolymerization and ethylene/alpha-olefin copolymerization. Since the first CGC was synthesized, a series of CGCs were synthesized in nearly 30 years, but most CGCs have little structural difference, the properties of polymers for catalytic polymerization have not been developed, and the development of constrained geometry catalysts with novel structures is very significant in our country where the production of polyolefin products such as low density polyethylene (LLDPE) and POE is subject to many restrictions due to the patent protection of silicon bridge constrained geometry catalysts by Dow company.

Disclosure of Invention

The invention mainly aims to provide a constrained geometry metallocene catalyst, a preparation method and an application thereof, so as to flexibly regulate and control the activity of the constrained geometry metallocene catalyst in the process of catalyzing olefin polymerization and the insertion rate of an alpha-olefin monomer.

In order to achieve the above object, the present invention provides a constrained geometry metallocene catalyst having the following structure of formula i:

wherein R is¹、R²And R³Each independently selected from H, CH₃-, saturated or containing double bonds, straight-chain or branched C₂-C₁₀One of the hydrocarbon groups; r⁴Is straight-chain or branched C₁-C₅An alkyl group.

The constrained geometry metallocene catalyst of the present invention, wherein R is⁴Is CH₃-、CH₃CH₂-、CH₃CH₂CH₂-and CH₃CH₂CH₂CH₂-one of the group consisting.

In order to achieve the above object, the present invention also provides a method for preparing a constrained geometry metallocene catalyst, comprising the steps of:

step 1, reacting 2-pyrrole carboxaldehyde or its derivative with indene to prepare nitrogen-containing fulvene shown in formula III, R¹、R²And R³Each independently selected from H, CH₃-, saturated or containing double bonds, straight-chain or branched C₂-C₁₀One of the hydrocarbon groups;

step 2, reducing nitrogen-containing fulvene in a formula III to generate a pyrrole N heterocyclic-containing ligand in a formula IV; and

step 3, ligand of formula IV containing pyrrole N heterocyclic ring and Ti [ N (R)⁴)₂]₄A complexation reaction occurs to produce a metallocene catalyst of formula I, R⁴Is straight-chain or branched C₁-C₅An alkyl group;

the preparation method of the constrained geometry metallocene catalyst is that R is⁴Is CH₃-、CH₃CH₂-、CH₃CH₂CH₂-and CH₃CH₂CH₂CH₂-one of the group consisting.

The invention relates to a preparation method of a constrained geometry metallocene catalyst, wherein the step 1 is as follows: dissolving 2-pyrrole formaldehyde shown in the formula II or a derivative thereof and indene in an organic solvent, cooling to-10-5 ℃, dropwise adding pyrrolidine, heating to room temperature, and stirring for reaction for 0.5-20 hours to obtain nitrogen-containing fulvene shown in the formula III;

wherein, the mass ratio of 2-pyrrole formaldehyde or its derivative, indene and tetrahydropyrrole in formula II is 1: 1-5: 1 to 5.

The invention relates to a preparation method of a constrained geometry metallocene catalyst, wherein the step 2 is as follows: dissolving the nitrogen-containing fulvene of the formula III obtained in the step 1 in an organic solvent, cooling to-10-5 ℃, dropwise adding lithium aluminum hydride dissolved in the organic solvent, then heating to 40-70 ℃, stirring and reacting for 5-50h to obtain a pyrrole N heterocyclic-containing ligand of the formula IV;

wherein, the molar ratio of the nitrogen-containing fulvene in the formula III to the lithium aluminum hydride is 1: 0.5 to 5.

The invention relates to a preparation method of a constrained geometry metallocene catalyst, wherein the step 3 is as follows: dissolving the pyrrole N heterocyclic ring-containing ligand of the formula IV obtained in the step 2 in an organic solvent, cooling to-10-5 ℃, and then dropwise adding Ti [ N (R) dissolved in the organic solvent⁴)₂]₄Heating to 50-100 ℃, and stirring for reaction for 1-30 h to obtain a metallocene catalyst;

wherein, the formula IV contains pyrrole N heterocyclic ligand and Ti [ N (R)⁴)₂]₄In a molar ratio of 1: 0.5 to 5.

The preparation method of the constrained geometry metallocene catalyst comprises the following steps of 1, 2 and 3, wherein the steps are carried out under the protection of inert gas, and the inert gas is one or more of the group consisting of nitrogen, helium and argon.

In order to achieve the above object, the present invention further provides an olefin polymerization process which is carried out under the action of the constrained geometry metallocene catalyst described above.

The olefin polymerization method of the present invention is characterized in that the olefin is at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, dicyclopentadiene, 1, 4-butadiene, 1, 5-pentadiene, 1, 6-hexadiene, styrene, alpha-methylstyrene and divinylbenzene.

The olefin polymerization reaction method of the invention is characterized in that the constrained geometry metallocene catalyst is a main catalyst, the alkylaluminium or aluminoxane compound is a cocatalyst, and the molar ratio of the main catalyst to the cocatalyst is 1: 500-2000.

The catalyst uses pyrrole heterocyclic ring to replace the traditional tert-butyl group as an electron donor, the catalyst is prepared by an amine elimination method with less steps, the electronic environment and the space environment of a metal center are controlled by the difference of the positions of the substituents on the pyrrole group, and the activity of the prepared polymer and the insertion rate of an alpha-olefin monomer are further regulated and controlled.

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.

The present invention provides a constrained geometry metallocene catalyst having the following structure of formula i:

wherein R is¹、R²、R³、R⁴The structure is respectively as follows:

R¹is H, CH₃-、C₂-C₁₀One of saturated or double bond-containing straight chain hydrocarbon groups or branched chain hydrocarbon groups;

R²is H, CH₃-、C₂-C₁₀One of saturated or double bond-containing straight chain hydrocarbon groups or branched chain hydrocarbon groups;

R³is H, CH₃-、C₂-C₁₀One of saturated or double bond-containing straight chain hydrocarbon groups or branched chain hydrocarbon groups;

R⁴is straight-chain or branched C₁-C₅Alkyl, preferably CH₃-、CH₃CH₂-、CH₃CH₂CH₂-orCH₃CH₂CH₂CH₂-one of, further preferably CH₃-or CH₃CH₂-。

The invention also provides a preparation method of the constrained geometry metallocene catalyst, which comprises the following steps:

step 1, reacting 2-pyrrole carboxaldehyde or its derivative with indene to prepare nitrogen-containing fulvene shown in formula III, R¹、R²And R³Each independently selected from H, CH₃-, saturated or containing double bonds, straight-chain or branched C₂-C₁₀One of the hydrocarbon groups;

step 2, reducing nitrogen-containing fulvene in a formula III to generate a pyrrole N heterocyclic-containing ligand in a formula IV; and

step 3, ligand of formula IV containing pyrrole N heterocyclic ring and Ti [ N (R)⁴)₂]₄A complexation reaction occurs to produce a metallocene catalyst of formula I, R⁴Is straight-chain or branched C₁-C₅An alkyl group;

specifically, step 1 is: dissolving 2-pyrrole-carbaldehyde shown in the formula II or a derivative thereof and indene in an organic solvent in a Schlenk bottle, cooling to-10-5 ℃, for example, placing the Schlenk bottle in an ice-water bath, slowly dropwise adding pyrrolidine, heating to room temperature after dropwise adding, stirring for 0.5-20 hours, preferably stirring for 5-15 hours; and then carrying out liquid separation extraction and washing by using an organic solvent, taking an organic phase, drying the organic phase, and carrying out rotary evaporation to obtain the nitrogen-containing fulvene in the formula III. The mass ratio of 2-pyrrole formaldehyde or its derivative, indene and tetrahydropyrrole is 1: 1-5: 1-5, the preferable ratio of the amount of 2-pyrrole formaldehyde or the derivative thereof, indene and pyrrolidine is 1: 1-3: 1-3. Wherein, the organic solvent is preferably one of methanol, ethanol, formaldehyde, acetaldehyde, diethyl ether, toluene and ethylbenzene.

The step 2 is as follows: dissolving the nitrogen-containing fulvene prepared in the step 1 in an organic solvent such as tetrahydrofuran in a Schlenk bottle, cooling to-10-5 ℃, for example, placing the Schlenk bottle in an ice-water bath, slowly adding a tetrahydrofuran solution dissolved with lithium aluminum hydride into the reaction bottle, withdrawing the ice-water bath, slowly heating to 40-70 ℃, stirring at constant temperature for reaction for 5-50h, adding the organic solvent, separating, extracting, washing, drying an organic phase, and then carrying out rotary evaporation to obtain the ligand. Wherein, the molar ratio of the nitrogen-containing fulvene in the formula III to the lithium aluminum hydride is 1: 0.5 to 5; the organic solvent for extraction and washing is one of ethanol, acetaldehyde, diethyl ether, toluene and ethylbenzene.

And step 3: in a Schlenk flask, Ti (N (R)⁴)₂)₄Dissolving in an organic solvent, cooling to-10-5 ℃, for example, placing in an ice-water bath, dissolving the ligand prepared in the step 2 in the organic solvent, slowly adding into a Schlenk bottle, removing the ice-water bath, heating to 50-100 ℃, stirring at constant temperature for reaction for 1-30 h, draining the solvent after the reaction is finished, and finally, recrystallizing at low temperature in the organic solvent to obtain the product. Wherein the organic solvent is one or more of methane, ethane, propane, ethanol, acetaldehyde, diethyl ether, toluene and ethylbenzene.

The preparation method of the pyrrole metallocene heterocycle constrained geometric configuration metallocene catalyst provided by the invention is carried out under the protection of inert gas in the whole reaction process, wherein the inert gas is one of nitrogen, helium and argon.

The present invention further provides a process for the polymerization of olefins carried out with the constrained geometry metallocene catalyst described above. Preferably, the constrained geometry metallocene catalyst described above is used as a procatalyst and an aluminum alkyl or aluminoxane compound is used as a cocatalyst to catalyze the olefin polymerization reaction. Wherein the alkyl aluminum or the aluminoxane compound is methyl aluminoxane, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum or a mixture thereof, and the mass ratio of the main catalyst to the cocatalyst is 1: 500-2000, preferably 1: 600-1500.

The olefin monomers that the constrained geometry metallocene catalyst of the present invention may be used to catalyze polymerization include at least one of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, dicyclopentadiene, 1, 4-butadiene, 1, 5-pentadiene, 1, 6-hexadiene, styrene, alpha-methylstyrene, and divinylbenzene.

The olefin polymerization reaction can be carried out according to the following method:

ethylene homopolymerization and copolymerization of ethylene and alpha-olefin are carried out in a set of high-pressure reaction device, the capacity of the high-pressure kettle is 250mL, and the temperature and the rotating speed can be monitored and adjusted in real time. Before the reaction, preheating the reaction kettle in vacuum, opening argon gas to wash the reaction kettle for three times after the set temperature is reached, keeping the temperature constant, weighing the main catalyst in a glove box, dissolving the main catalyst in a toluene solvent, sequentially adding a half of the solvent, 1-hexene or 1-octene comonomer, MAO (methyl ammonium oxide) and the main catalyst into a feeding hopper, finally washing the main catalyst with the remaining half of the solvent, flushing the residual catalyst in the feeding hopper into a feeder, closing a valve of the feeder, taking out the glove box, and flushing the solution in the feeder into the reaction kettle by using argon gas. Opening a valve, increasing the pressure of an ethylene steel cylinder to a set value, opening stirring, starting timing, controlling the temperature to be about the set value as far as possible in the reaction process, closing an ethylene inlet valve after the reaction is finished, opening condensed water for cooling, opening a reaction kettle, taking out a lining, pouring a product into a beaker, and adding a hydrochloric acid-ethanol solution (V hydrochloric acid: V ethanol ═ 1:15) to terminate the reaction. The polymer is washed repeatedly by hydrochloric acid-ethanol solution to dissolve aluminum salt remained in the reaction, then washed three times (30mL multiplied by 3) by deionized water, finally placed in a vacuum drying oven, dried at 60 ℃ to constant weight, and the catalytic activity of the catalyst is calculated.

When the catalyst is used for catalyzing ethylene homopolymerization, MAO is used as a cocatalyst, and the catalytic activity is as high as 4.5 multiplied by 10⁶g/(mol. Zr. h); when catalyzing ethylene/1-hexene copolymerization, MAO is used as a cocatalyst, and the catalytic activity reaches 2.3 multiplied by 10⁶g/(mol. Zr. h), 1-hexene insertion rate 9.81%; when catalyzing the copolymerization of ethylene/1-octene, MAO is used as a cocatalyst, and the catalytic activity reaches 1.3 multiplied by 10⁶g/(mol. Zr. h), 1-octene insertion rate 8.84%; compared with the conventional tert-butylamine-based carbon bridge constrained geometry catalyst, such as [ t-BuN(Me)₂C(η⁵-C₅H₄)]ZrCl₂Under the same condition, the insertion rate of the ethylene/1-hexene copolymer obtained by catalysis is only 8.34 percent, the insertion rate of the ethylene/1-octene copolymer is only 5.46 percent, and the catalytic activity is in the same order of magnitude, so the catalyst obtained by the invention has higher industrial application value.

In conclusion, the invention adopts an amine elimination method to synthesize the IV B group constrained geometry catalyst containing pyrrole N heterocycle, simplifies the synthesis steps, the reaction yield reaches more than 90% when synthesizing fulvene and ligand, and the yield is greatly improved at the step of synthesizing the catalyst, so in general, the yield of the catalyst synthesized by the method is improved, researches show that compared with alkyl-N electron donor, the pyrrole group has stronger electron-withdrawing property, so that Zr-N bond is longer, so that the included angle between indenyl, metal central atom and the pyrrole group is smaller than that of the CGC of common alkyl N electron donor, the attack of alpha-olefin is more facilitated, the copolymerization activity of the catalyst of the type is better, and the space structure and electronic environment of an active center are influenced by changing the position of a substituent on the pyrrole group, so that the catalytic behavior of the catalyst is different, effectively improves the catalytic activity and the insertion rate of alpha-olefin in the copolymer.

Moreover, the catalyst provided by the invention has the advantages of simple synthetic route, high catalyst yield, less steps, good activity when being used for catalyzing the copolymerization of ethylene and alpha-olefin, high insertion rate of alpha-olefin monomers and good application value.

The technical solution of the present invention will be further illustrated by the following specific examples.

Example 1

Complex 1[ (. eta.) ]⁵-C₉H₆)CH₂(α-C₄H₃N)]Ti(NMe₂)₂Synthesis of (2)

(1) Fulvene (C)₉H₆)CH(α-C₄H₃NH) preparation

2-Pyrrolecarboxaldehyde (4g, 42mmol) and freshly distilled indene (12.3g, 106mmol) were dissolved in 40mL of methanol in a 200mL Schlenk flask, and pyrrolidine (6g, 84mmol) was slowly added dropwise under an ice-water bath, during which the solution gradually changed from pale yellow to bright yellow, indicating that the reaction had started, and naturally warmed to room temperature after the addition was complete, and stirred for 90 min. Quenching with 50mL of distilled water in ice-water bath, adding glacial acetic acid (5g, 84mmol) to adjust pH to 7, adding 20mL of diethyl ether, separating with separating funnel, collecting upper organic phase, extracting aqueous phase with diethyl ether three times (30 mL. times.3), combining organic phases, washing twice with saturated saline solution, placing the obtained organic phase into an erlenmeyer flask, and adding anhydrous MgSO₄Drying for 6 h. Rotary evaporation gave an earth yellow solid which was separated by column chromatography (eluent: ethyl acetate/petroleum ether: 1/10) to give 6.97g (40mmol) of the pure product in 86% yield.

By passing¹H NMR，¹³C NMR confirmed the chemical structure. (¹H NMR(CDCl₃,25℃):8.32(br s,1H,NH),6.77(s,1H,CH),7.48(m,1H,C₄H₃NH),7.23(m,1H,C₄H₃NH),7.06(m,1H,C₄H₃NH),7.11(m,2H,C₆-H),6.87(m,2H,C₆-H),6.56–6.22(m,2H,Cp-H)；¹³C NMR(100MHz,CDCl₃):δ140.21,136.70,132.61,131.68,129.10,125.47,124.04,123.77,121.21,120.03,117.58,117.12,113.68,110.28.)

(2) Ligand (C)₉H₇)CH₂(α-C₄H₃NH) preparation

7.33g of fulvene (C) in a 200mL Schlenk flask₉H₆)CH(α-C₄H₃NH) (40mmol) was dissolved in 100mL of THF, and 38mL of LiAlH was added under an ice-water bath₄The reaction flask was slowly charged with THF (1M) and a lot of bubbles were observed, indicating that the reaction was proceeding, the dropping rate was controlled to about half an hour, the ice-water bath was removed, the reaction flask was slowly heated to 50 ℃ for 15 hours, and the reaction flask was kept under ice-water bathQuenching with 50mL of water, filtering with Buchner funnel to remove a large amount of aluminum salt, adding 20mL of diethyl ether, separating with separating funnel, collecting the upper organic phase, extracting the aqueous phase with diethyl ether three times (30 mL. times.3), combining the organic phases, washing with saturated saline twice, placing the obtained organic phase into an erlenmeyer flask, and adding anhydrous MgSO₄Drying for 6 h. Rotary evaporation gave a white solid which was separated by column chromatography (eluent: ethyl acetate/petroleum ether: 1/20) to give 5.91g (30mmol) of the pure product in 79% yield.

By passing¹H NMR，¹³C NMR confirmed the chemical structure. (¹H NMR(400MHz,CDCl₃,25℃):δ7.82(br s,NH),6.57(d,1H,C₄H₃NH),6.12(m,1H,C₄H₃NH),6.04(s,1H,C₄H₃NH),3.95(s,2H,-CH₂-),3.32(s,CH₂,C₉H₇),6.20(s,1H,C₉H₇),7.42(d,1H,C₉H₇),7.17-7.26(m,3H,C₉H₇)；¹³C NMR(100MHz,CDCl₃):δ143.72,143.41,140.92,128.96,127.85,125.14,123.74,122.72,118.26,115.62,107.27,105.24,36.63,25.65.)

(3) Complex 1[ (. eta.) ]⁵-C₉H₆)CH₂(α-C₄H₃N)]Ti(NMe₂)₂Synthesis of (2)

A100 mL Schlenk flask was taken, the flask was evacuated and purged with argon three times with a heat gun, and 30mL of freshly distilled toluene and 1.95g of ligand (C) were added₉H₇)CH₂(α-C₄H₃NH) (10.0mmol) and 2.25g Ti (NMe) were added under ice-water bath₂)₄(10mmol), removing the ice water bath, heating to 70 ℃ for reaction for 4h, introducing a small amount of protective gas in the whole reaction process to ensure that the gas by-product is continuously taken away, draining the solvent after the reaction is finished to obtain yellow slightly viscous solid, and recrystallizing at low temperature in a mixed solvent of n-hexane/toluene (1: 1) to obtain 2.15 yellow solid with the yield of 73%.

By passing¹H NMR，¹³C NMR, elemental analysis confirmed its chemical structure. (¹H NMR(400MHz,CDCl₃,25℃):7.45(m,2H,Benzo),6.70(m,2H,Benzo),6.70(m,1H,C₄H₃N),5.99(m,1H,C₄H₃N),5.91(m,1H,C₄H₃N),6.49(m,2H,C₅H₂),4.30-4.26(m,1H,CH₂),3.98-3.94(m,1H,CH₂),3.35(s,6H,(NMe₂)₂,2.24(s,6H,(NMe₂)₂)；¹³C NMR(100MHz,CDCl₃):δ153.22,126.07,124.58,124.09,124.04,123.57,123.29,121.77,121.49,118.07,105.95,101.24,98.56,49.05,45.17,25.98；Anal.Found:C,65.65；H,6.99；N,12.77.)

Example 2

The complex 1 catalyzes ethylene homogeneous polymerization to carry out vacuum preheating on a reaction kettle before reaction, opens argon gas to wash the reaction kettle for three times after the set temperature is 80 ℃, then keeps constant temperature, and feeds in a glove box: the catalyst addition was 10. mu. mol, toluene 100mL, MAO 6.7mL (i.e., Al/Ti ratio of 1000); after the materials are fed from a feeder, the pressure of ethylene is set to be 0.6MPa, after the reaction is carried out for 30min, an ethylene inlet valve is closed, condensed water is opened for cooling, the reaction kettle is opened, the inner lining is taken out, the product is poured into a beaker, and hydrochloric acid-ethanol solution (V hydrochloric acid: V ethanol is 1:15) is added to terminate the reaction. The polymer was washed repeatedly with hydrochloric acid-ethanol solution to dissolve the residual aluminum salt, then washed three times (100 mL. times.3) with deionized water, and finally dried in a vacuum oven at 60 ℃ to constant weight to give 11.5g of a solid with a catalyst activity of 3.6X 10 calculated⁶g/(mol·Ti·h)

Example 3

Complex 1 catalyzed copolymerization of ethylene and 1-hexene

Before the reaction, carrying out vacuum preheating on the reaction kettle, opening argon gas to wash the reaction kettle for three times after the set temperature is 80 ℃, then keeping the constant temperature, and feeding in a glove box: the adding amount of the catalyst is 10 mu mol, the adding amount of the toluene is 100mL, the adding amount of the MAO is 6.7mL (namely the aluminum-titanium ratio is 1000), and the adding amount of the 1-hexene is 20 mL; after feeding from a feeder, setting the ethylene pressure to be 0.6MPa, reacting for 30min,and (3) closing an ethylene inlet valve, opening condensed water for cooling, opening the reaction kettle, taking out the product from the inner liner, pouring the product into a beaker, and adding a hydrochloric acid-ethanol solution (Vhydrochloric acid: Vethanol ═ 1:15) to terminate the reaction. The polymer is washed repeatedly with hydrochloric acid-ethanol solution to dissolve the residual aluminum salt, then washed three times (100mL multiplied by 3) with deionized water, finally put into a vacuum drying oven and dried at 60 ℃ to constant weight to obtain 9.5g of solid, and the calculated catalyst activity is 1.8 multiplied by 10⁶g/(mol. Ti. h), depending on the polymer¹³The C-NMR spectrum showed an insertion of 1-hexene into the copolymer of 8.40%.

Example 4

Complex 1 catalyzed copolymerization of ethylene and 1-octene

Before the reaction, carrying out vacuum preheating on the reaction kettle, opening argon gas to wash the reaction kettle for three times after the set temperature is 80 ℃, then keeping the constant temperature, and feeding in a glove box: the adding amount of the catalyst is 10 mu mol, the adding amount of the toluene is 100mL, the adding amount of the MAO is 6.7mL (namely the aluminum-titanium ratio is 1000), and the adding amount of the 1-octene is 23 mL; after the materials are fed from a feeder, the pressure of ethylene is set to be 0.6MPa, after the reaction is carried out for 30min, an ethylene inlet valve is closed, condensed water is opened for cooling, the reaction kettle is opened, the inner lining is taken out, the product is poured into a beaker, and hydrochloric acid-ethanol solution (V hydrochloric acid: V ethanol is 1:15) is added to terminate the reaction. The polymer is washed repeatedly with hydrochloric acid-ethanol solution to dissolve the residual aluminum salt, then washed three times (100mL multiplied by 3) with deionized water, finally put into a vacuum drying oven and dried at 60 ℃ to constant weight to obtain 6.0g of solid, and the calculated catalyst activity is 1.1 multiplied by 10⁶g/(mol. Ti. h), depending on the polymer¹³The C-NMR spectrum showed that the insertion rate of 1-octene into the copolymer was 7.06%.

Example 5

Complex 2[ (. eta.) ]⁵-C₉H₆)CH₂(α-C₄H₃N)]Ti(NEt₂)₂Synthesis of (2)

A100 mL Schlenk flask was taken, the flask was evacuated and purged with argon three times with a heat gun, and 40mL of freshly distilled toluene and 1.95g of ligand (C) were added₉H₇)CH₂(2-C₄H₃NH) (10.0mmol) was added 3.36g of Ti (NEt) under ice-water bath₂)₄(10mmol), removing the ice water bath, heating to 80 ℃ for reaction for 4h, introducing a small amount of protective gas in the whole reaction process to ensure that the gas by-product is continuously taken away, draining the solvent after the reaction is finished to obtain mauve slightly-viscous solid, and recrystallizing in a mixed solvent of n-hexane/toluene (1: 1) at a low temperature to obtain 2.24g of crimson solid with the yield of 58%.

By passing¹H NMR，¹³C NMR, elemental analysis confirmed its chemical structure. (¹H NMR(400MHz,CDCl₃,25℃):7.34(m,1H,C₄H₃N),6.04(m,1H,C₄H₃N),5.96(m,1H,C₄H₃N),7.15(m,4H,Benzo),6.50(m,1H,C₅H₂),6.13(m,1H,C₅H₂),4.23(s,2H,CH₂),3.52(m,4H,(NEt₂)₂-CH₂),3.38(m,4H,(NEt₂)₂-CH₂),1.09(m,12H,(NEt₂)₂-CH₃)；¹³C NMR(100MHz,CDCl₃):δ143.73,143.42,140.92,128.98,127.85,125.14,123.74,122.73,118.28,115.63,107.27,105.24,42.44,36.64,25.68；Anal.Found:C,61.68；H,7.24；N,9.81.)

Example 6

Complex 2 catalyzed homogeneous ethylene polymerization

Before the reaction, carrying out vacuum preheating on the reaction kettle, opening argon gas to wash the reaction kettle for three times after the set temperature is 80 ℃, then keeping the constant temperature, and feeding in a glove box: the catalyst addition was 10. mu. mol, toluene 100mL, MAO 6.7mL (i.e., aluminum to zirconium ratio of 1000); after the materials are fed from a feeder, the pressure of ethylene is set to be 0.6MPa, after the reaction is carried out for 30min, an ethylene inlet valve is closed, condensed water is opened for cooling, the reaction kettle is opened, the inner lining is taken out, the product is poured into a beaker, and hydrochloric acid-ethanol solution (V hydrochloric acid: V ethanol is 1:15) is added to terminate the reaction. The polymer was washed repeatedly with hydrochloric acid-ethanol solution to dissolve the residual aluminum salt, then washed three times (100 mL. times.3) with deionized water, and finally dried in a vacuum oven at 60 ℃ to constant weight to give 22.5g of a solid with a catalyst activity of 3.6X 10 calculated⁶g/(mol·Ti·h)。

Example 7

Complex 2 catalyzed copolymerization of ethylene and 1-hexene

Before the reaction, carrying out vacuum preheating on the reaction kettle, opening argon gas to wash the reaction kettle for three times after the set temperature is 80 ℃, then keeping the constant temperature, and feeding in a glove box: the adding amount of the catalyst is 10 mu mol, the adding amount of the toluene is 100mL, the adding amount of the MAO is 6.7mL (namely the aluminum-zirconium ratio is 1000), and the adding amount of the 1-hexene is 20 mL; after the materials are fed from a feeder, the pressure of ethylene is set to be 0.6MPa, after the reaction is carried out for 30min, an ethylene inlet valve is closed, condensed water is opened for cooling, the reaction kettle is opened, the inner lining is taken out, the product is poured into a beaker, and hydrochloric acid-ethanol solution (V hydrochloric acid: V ethanol is 1:15) is added to terminate the reaction. The polymer was washed repeatedly with hydrochloric acid-ethanol solution to dissolve the residual aluminum salt, then washed three times (100 mL. times.3) with deionized water, and finally dried in a vacuum oven at 60 ℃ to constant weight to give 11.5g of a solid with a calculated catalyst activity of 1.7X 10⁶g/(mol. Zr. h), depending on the polymer¹³C-NMR spectrum calculated 1-hexene insertion into the copolymer was 9.81%.

Example 8

Complex 2 catalyzed copolymerization of ethylene and 1-octene

Before the reaction, carrying out vacuum preheating on the reaction kettle, opening argon gas to wash the reaction kettle for three times after the set temperature is 80 ℃, then keeping the constant temperature, and feeding in a glove box: the adding amount of the catalyst is 10 mu mol, the adding amount of the toluene is 100mL, the adding amount of the MAO is 6.7mL (namely the aluminum-zirconium ratio is 1000), and the adding amount of the 1-octene is 23 mL; after the materials are fed from a feeder, the pressure of ethylene is set to be 0.6MPa, after the reaction is carried out for 30min, an ethylene inlet valve is closed, condensed water is opened for cooling, the reaction kettle is opened, the inner lining is taken out, the product is poured into a beaker, and hydrochloric acid-ethanol solution (V hydrochloric acid: V ethanol is 1:15) is added to terminate the reaction. The polymer is washed repeatedly with hydrochloric acid-ethanol solution to dissolve the residual aluminum salt, then washed three times (100mL multiplied by 3) with deionized water, finally put into a vacuum drying oven and dried at 60 ℃ to constant weight to obtain 6.5g of solid, and the calculated catalyst activity is 1.2 multiplied by 10⁶g/(mol. Ti. h), depending on the polymer¹³The C-NMR spectrum showed that the insertion rate of 1-octene into the copolymer was 8.84%.

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.