CN112552429B - Supported metallocene catalyst and preparation method and application thereof - Google Patents

Supported metallocene catalyst and preparation method and application thereof Download PDF

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CN112552429B
CN112552429B CN201910910250.1A CN201910910250A CN112552429B CN 112552429 B CN112552429 B CN 112552429B CN 201910910250 A CN201910910250 A CN 201910910250A CN 112552429 B CN112552429 B CN 112552429B
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王文燕
米普科
李冬霞
许胜�
任鹤
李�瑞
董素琴
张瑞
宋磊
马丽
赵瑞达
高宇新
刘敏
邵炉
王�华
牛娜
杨国兴
邹恩广
王立娟
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Abstract

The invention discloses a load type metallocene catalyst and a preparation method and application thereof, wherein the load type metallocene catalyst comprises the following components: a carrier and a pyrrole metallocene heterocyclic compound loaded on the carrier; wherein, the pyrrole metallocene heterocyclic compound has the following structure as shown in the formula I:
Figure DDA0002214316720000011
wherein R is 1 、R 2 And R 3 Each independently selected from H, CH 3 And a saturated or double-bond-containing linear or branched chain C 2 ‑C 10 One of the hydrocarbon groups; r 4 Is straight-chain or branched C 1 ‑C 5 An alkyl group; m is Ti or Zr. The catalyst has high loading rate and good polymerization reaction activity.

Description

Supported metallocene catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of olefin polymerization catalysts, in particular to a supported metallocene catalyst, a preparation method of the supported metallocene catalyst and application of the supported metallocene catalyst in olefin polymerization reaction.
Background
The advent and rise of metallocene catalysts in the 80 s of the 20 th century triggered another revolution in the polyolefin industry beyond Ziegler-Natta catalysts. The catalyst is a kind of single active center metal organic complex composed of transition metal or rare earth metal (especially Ti, Zr or Hf) and at least one cyclopentadienyl or its derivative ligand, and the cocatalyst is mainly Methyl Aluminoxane (MAO) and organic boron compound. The chemical structure of the metallocene catalyst is easy to regulate, so that the properties of the polymer can be customized by designing the structure of the catalyst, such as controlling the size and distribution of molecular weight, the content of comonomer and the like.
The homogeneous metallocene catalyst has the advantages of high catalytic activity, mild reaction conditions and the like, but has the following outstanding defects: the morphology of polymer particles is difficult to control, so that the reactor is seriously stuck, and the bulk density of the obtained polymer is low. In order to solve these problems and to better adapt the existing industrial plants for olefin polymerization (slurry and gas phase polymerization processes), it is necessary to load the metallocene. Metallocene loading is to load a metallocene catalyst on a granular carrier by a physical or chemical method. Usually, the activity of the catalyst is reduced after the catalyst is loaded, and simultaneously, the types of active sites are increased, but polyolefin powder with regular shape and high apparent density can be obtained, and the advantages of a homogeneous catalyst are kept. Other advantages brought by the loading are: the active center is fixed on the carrier, so that the probability of bimolecular inactivation and beta-hydrogen elimination is reduced; the stability of the catalyst is improved; the dosage of the methylaluminoxane is reduced, and the molecular weight of the polymer is improved.
There are many methods for supporting metallocene catalysts, but no report is found on the method for supporting a novel constrained-configuration double-bridged metallocene compound. There are basically two common methods for supporting metallocene compounds, one of which is described in US 5087788, US 554801, US 5719241, etc., wherein after the reaction of an inorganic carrier, alkylaluminoxane and an organometallic metallocene compound in a toluene solvent is completed, a toluene solution of the unreacted organometallic metallocene compound is filtered off, washed several times with hexane, and then dried under reduced pressure to obtain a powder catalyst; secondly, as described in US 4935937, US 4937301 and the like, an alkyl aluminum is reacted with an aqueous inorganic carrier, and then an organometallic metallocene compound is added, and after the reaction is completed, a certain treatment is performed to obtain a powder catalyst.
Chinese patent 201780004061.7 relates to a supported hybrid metallocene catalyst and a method for preparing polyolefin using the same. Wherein the metallocene comprises three species, for a supported hybrid metallocene catalyst capable of producing a polyolefin having excellent processability and exhibiting a multimodal molecular weight distribution.
Chinese patent 201680054968.X provides a method for preparing a supported hybrid metallocene catalyst useful for the preparation of polyolefins, a supported hybrid metallocene catalyst prepared using said method, and a method for preparing polyolefins using said supported hybrid metallocene catalyst.
The catalytic activity and selectivity of the obtained supported catalyst can be greatly changed according to the structural change of the supported compound, so that the research on the supported compound in the field still has great significance.
Disclosure of Invention
The invention mainly aims to provide a supported metallocene catalyst, a preparation method and an application thereof, wherein the supported metallocene catalyst can show higher catalytic activity in olefin polymerization.
In order to achieve the above object, the present invention provides a supported metallocene catalyst comprising:
a carrier and a pyrrole metallocene heterocyclic compound loaded on the carrier;
wherein, the pyrrole metallocene heterocyclic compound has the following structure as shown in the formula I:
Figure BDA0002214316700000021
wherein R is 1 、R 2 And R 3 Each independently selected from H, CH 3 And is saturated or containsHaving double bonds, straight or branched C 2 -C 10 One of the hydrocarbon groups; r 4 Is straight-chain or branched C 1 -C 5 An alkyl group; m is Ti or Zr.
The supported metallocene catalyst provided by the invention comprises 0.5-15% of pyrrole metallocene heterocyclic compound by mass and 85-99.5% of carrier by mass based on the total mass of the supported metallocene catalyst.
The supported metallocene catalyst is characterized in that the carrier is one or more of the group consisting of silica, alumina, magnesium chloride complex, zirconia and zeolite; and/or the carrier is obtained by dehydration, deoxidation and modification.
The supported metallocene catalyst comprises a modifier for modifying a carrier, wherein the modifier is one or more of a group consisting of methylaluminoxane, trimethylaluminum, triethylaluminum and triisobutylaluminum.
The supported metallocene catalyst of the present invention, wherein R is 1 、R 2 And R 3 Each independently selected from H, CH 3 -, saturated or containing double bonds, straight-chain or branched C 2 -C 5 One of the hydrocarbon groups; the R is 4 Is CH 3 -or CH 3 CH 2 -。
The supported metallocene catalyst provided by the invention is characterized in that the pyrrole metallocene heterocyclic compound is:
[(η 5 -C 9 H 6 )CH 2 (2-C 4 H 3 N)]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -C 4 H 2 N))]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -C 4 H 2 N))]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(5-CH 3 -C 4 H 2 N))]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -C 4 HN))]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -5-CH 3 -C 4 HN))]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -5-CH 3 -C 4 HN))]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -5-CH 3 -C 4 N))]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-C 4 H 3 N)]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -C 4 H 2 N))]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -C 4 H 2 N))]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(5-CH 3 -C 4 H 2 N))]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -C 4 HN))]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -5-CH 3 -C 4 HN))]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -5-CH 3 -C 4 HN))]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -5-CH 3 -C 4 N))]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-C 4 H 3 N)]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -C 4 H 2 N))]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -C 4 H 2 N))]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(5-CH 3 -C 4 H 2 N))]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -C 4 HN))]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -5-CH 3 -C 4 HN))]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -5-CH 3 -C 4 HN))]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -5-CH 3 -C 4 N))]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-C 4 H 3 N)]Ti(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -C 4 H 2 N))]Ti(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -C 4 H 2 N))]Ti(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(5-CH 3 -C 4 H 2 N))]Ti(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -C 4 HN))]Ti(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -5-CH 3 -C 4 HN))]Ti(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -5-CH 3 -C 4 HN))]Ti(NEt 2 ) 2 and
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -5-CH 3 -C 4 N))]Ti(NEt 2 ) 2 one or more of the group.
In order to achieve the above object, the present invention also provides a preparation method of the above supported metallocene catalyst, the preparation method comprising the steps of:
step 1, dissolving a carrier modifier in a first solvent, adding a carrier, controlling the temperature of a mixed solution to be 50-100 ℃, and stirring at a constant temperature for 1-40 hours; and
and 2, dissolving the pyrrole metallocene heterocyclic compound in a second solvent, dropwise adding the dissolved pyrrole metallocene heterocyclic compound into the mixed solution prepared in the step 1, controlling the temperature to be between 50 ℃ below zero and 50 ℃, stirring at a constant temperature for 2 to 20 hours, and performing post-treatment to obtain the supported metallocene catalyst.
The preparation method of the supported metallocene catalyst comprises the following steps:
step a, reacting 2-pyrrole-carbaldehyde shown in formula II or a derivative thereof with indene to prepare nitrogen-containing fulvene shown in formula III R 1 、R 2 And R 3 Are respectively and independently selected from H,CH 3 And a saturated or double-bond-containing linear or branched chain C 2 -C 10 One of the hydrocarbon groups;
b, reducing nitrogen-containing fulvene in a formula III to generate a pyrrole N heterocyclic-containing ligand in a formula IV; and
step c, ligand of formula IV containing pyrrole N heterocyclic ring and M [ N (R) 4 ) 2 ] 4 A complexation reaction occurs to produce a metallocene catalyst, R 4 Is straight-chain or branched C 1 -C 5 Alkyl, M is Ti or Zr;
Figure BDA0002214316700000051
the preparation method of the supported metallocene catalyst comprises the following steps: 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 preparation method of the metallocene catalyst comprises the following steps: dissolving the nitrogen-containing fulvene in the formula III obtained in the step a in an organic solvent, cooling to-10-5 ℃, dropwise adding lithium aluminum hydride dissolved in the organic solvent, heating to 40-70 ℃, and stirring for reaction for 5-50h to obtain a pyrrole N heterocyclic ring-containing ligand in 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 preparation method of the metallocene catalyst comprises the following steps: dissolving the pyrrole N heterocyclic ring-containing ligand of the formula IV obtained in the step b in an organic solvent, cooling to-10-5 ℃, and then dropwise adding M [ N (R) dissolved in the organic solvent 4 ) 2 ] 4 Heating to 50-100 ℃, and stirring for reaction for 1-30 h to obtain a metallocene catalyst;
wherein, formula IV contains pyrrole N heterocyclic ligand and M [ N (R) 4 ) 2 ] 4 In a molar ratio of 1: 0.5 to 5.
The preparation method of the supported metallocene catalyst comprises the following step of mixing a first solvent and a second solvent, wherein the first solvent and the second solvent are the same solvent and are one or two of the group consisting of toluene and xylene.
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 supported metallocene catalyst.
The olefin polymerization reaction method is characterized in that the olefin is one or more of a 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, divinylbenzene and 3-chloromethylstyrene.
The olefin polymerization reaction method of the invention is characterized in that the supported 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 invention has the beneficial effects that:
1. the preparation method of the supported catalyst is simple, the production period is short, the supported catalyst can be efficiently prepared under mild reaction conditions, the loss of activity in the supporting process is small, the production cost is low, and the prepared catalyst is high in supporting rate and good in polymerization activity.
2. The pyrrole heterocyclic compound is prepared by replacing a catalyst which adopts tert-butyl as an electron donor in the prior art with pyrrole heterocyclic rings and utilizing an amine elimination method with fewer steps, and the electronic environment and the space environment of a metal center are controlled by adjusting the position difference of substituents on the pyrrole groups, so that the activity of preparing a polymer by catalysis and the insertion rate of an alpha-olefin monomer are regulated and controlled; compared with tert-butylamine, the pyrrole group has stronger electron-withdrawing property, so that the Zr-N bond is longer, the insertion of alpha-olefin is facilitated, higher monomer insertion rate can be obtained, and the polymer with excellent performance is prepared.
Drawings
FIG. 1 is a kinetic curve of a catalyst of the present invention;
FIG. 2 is an electron micrograph of the catalyst of the present invention.
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 invention discloses a supported metallocene catalyst, which comprises a carrier and a pyrrole metallocene heterocyclic compound loaded on the carrier;
wherein, the pyrrole metallocene heterocyclic compound has the following structure as shown in the formula I:
Figure BDA0002214316700000071
wherein R is 1 、R 2 And R 3 Are respectively and independently selected from H, CH 3 And a saturated or double-bond-containing linear or branched chain C 2 -C 10 One of the hydrocarbon groups, preferably H, CH 3 -, saturated or containing double bonds, straight-chain or branched C 2 -C 5 One of the hydrocarbon groups; r 4 Is straight-chain or branched C 1 -C 5 Alkyl, preferably CH 3 -or CH 3 CH 2 -; m is Ti or Zr.
Wherein, the mass content of the pyrrole metallocene heterocyclic compound is 0.5 to 15 percent and the mass content of the carrier is 85 to 99.5 percent based on the total mass of the supported metallocene catalyst.
Wherein, the carrier can be one or more of the group consisting of silicon dioxide, aluminum oxide, magnesium chloride complex, zirconium oxide and zeolite; preferably, the carrier is obtained by dehydration, deoxidation and modification, and the dehydration, deoxidation and the deoxidation of the carrier can be realized by a carrier modifier, and the specific method comprises the steps of dissolving the carrier modifier in a first solvent, adding the carrier, controlling the temperature of a mixed solution to be 50-100 ℃, and stirring at a constant temperature for 1-40 hours. The carrier modifier can be one or more of the group consisting of methylaluminoxane, trimethylaluminum, triethylaluminum and triisobutylaluminum.
The azole metallocene compound of the present invention is further preferably:
[(η 5 -C 9 H 6 )CH 2 (2-C 4 H 3 N)]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -C 4 H 2 N))]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -C 4 H 2 N))]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(5-CH 3 -C 4 H 2 N))]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -C 4 HN))]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -5-CH 3 -C 4 HN))]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -5-CH 3 -C 4 HN))]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -5-CH 3 -C 4 N))]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-C 4 H 3 N)]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -C 4 H 2 N))]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -C 4 H 2 N))]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(5-CH 3 -C 4 H 2 N))]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -C 4 HN))]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -5-CH 3 -C 4 HN))]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -5-CH 3 -C 4 HN))]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -5-CH 3 -C 4 N))]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-C 4 H 3 N)]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -C 4 H 2 N))]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -C 4 H 2 N))]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(5-CH 3 -C 4 H 2 N))]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -C 4 HN))]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -5-CH 3 -C 4 HN))]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -5-CH 3 -C 4 HN))]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -5-CH 3 -C 4 N))]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-C 4 H 3 N)]Ti(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -C 4 H 2 N))]Ti(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -C 4 H 2 N))]Ti(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(5-CH 3 -C 4 H 2 N))]Ti(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -C 4 HN))]Ti(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -5-CH 3 -C 4 HN))]Ti(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -5-CH 3 -C 4 HN))]Ti(NEt 2 ) 2 and
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -5-CH 3 -C 4 N))]Ti(NEt 2 ) 2 one or more of the group.
The preparation method of the supported metallocene catalyst comprises the following steps:
step 1, dissolving a carrier modifier in a first solvent, adding a carrier, controlling the temperature of a mixed solution to be 50-100 ℃, and stirring at a constant temperature for 1-40 hours; and
and 2, dissolving the pyrrole metallocene heterocyclic compound in a second solvent, dropwise adding the dissolved pyrrole metallocene heterocyclic compound into the mixed solution prepared in the step 1, controlling the temperature to be between 50 ℃ below zero and 50 ℃, stirring at a constant temperature for 2 to 20 hours, and performing post-treatment to obtain the supported metallocene catalyst.
The preparation method of the pyrrole metallocene heterocyclic compound comprises the following steps:
step a, reacting 2-pyrrole-carbaldehyde shown in formula II or a derivative thereof with indene to prepare nitrogen-containing fulvene shown in formula III R 1 、R 2 And R 3 Each independently selected from H, CH 3 And a saturated or double-bond-containing linear or branched chain C 2 -C 10 One of the hydrocarbon groups;
b, reducing nitrogen-containing fulvene in a formula III to generate a pyrrole N heterocyclic-containing ligand in a formula IV; and
step c, ligand of formula IV containing pyrrole N heterocyclic ring and M [ N (R) 4 ) 2 ] 4 A complexation reaction occurs to produce a metallocene catalyst, R 4 Is straight-chain or branched C 1 -C 5 Alkyl, M is Ti or Zr;
Figure BDA0002214316700000091
specifically, the preparation method of the pyrrole heterocyclic compound comprises the following steps:
step a, dissolving 2-pyrrole-carbaldehyde or a derivative thereof and indene in a formula II in a Schlenk bottle in an organic solvent, cooling to-10-5 ℃, for example, placing in an ice water bath, and then slowly dropwise adding pyrrolidine, wherein the ratio of the amount of the 2-pyrrole-carbaldehyde or the derivative thereof to the amount of the indene to the amount of the pyrrolidine is 1: 1-5: 1-5; after the dropwise addition, the temperature is raised to the room temperature, and the mixture is stirred for 0.5 to 20 hours to react; and after the reaction is finished, 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. Wherein the organic solvent can be one or more of methanol, ethanol, formaldehyde, acetaldehyde, diethyl ether, toluene and ethylbenzene.
B, dissolving the nitrogen-containing fulvene of the formula III prepared in the step a in an organic solvent such as tetrahydrofuran in a Schlenk bottle, cooling to-10-5 ℃, for example, placing in an ice water bath, then dropwise adding lithium aluminum hydride dissolved in the solvent (such as tetrahydrofuran), withdrawing the ice water bath, slowly heating to 40-70 ℃, reacting for 5-50h, adding the organic solvent, separating, extracting, washing, drying the organic phase, and then performing rotary evaporation to obtain a ligand containing pyrrole N heterocycle 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. Wherein the organic solvent is one or more of ethanol, acetaldehyde, diethyl ether, toluene and ethylbenzene.
Step c, Zr (N (R) in Schlenk bottle 4 ) 2 ) 4 Dissolving in an organic solvent, cooling to-10-5 ℃, for example, placing in an ice-water bath, dissolving the pyrrole N heterocycle-containing ligand of formula IV prepared in the step b in the organic solvent, slowly adding into a Schlenk bottle, removing the ice-water bath, heating to 50-100 ℃, and reacting for 1-30 h.
Or, dissolving the pyrrole N heterocyclic ring-containing ligand of the formula IV obtained in the step b in an organic solvent, cooling to-10-5 ℃, and then dropwise adding Zr [ N (R) dissolved in the organic solvent 4 ) 2 ] 4 After the dripping is finished, the temperature is raised to 50-100 ℃, and the stirring reaction is carried out for 1-30 h.
Wherein, the formula IV contains pyrrole N heterocyclic ligand and Zr [ N (R) 4 ) 2 ] 4 In a molar ratio of 1: 0.5 to 5.
And after the reaction is finished, draining the solvent, and finally recrystallizing in an organic solvent at a low temperature to obtain the pyrrole metallocene heterocyclic compound. Wherein the organic solvent is one or more of methane, ethane, ethanol, acetaldehyde, diethyl ether, toluene and ethylbenzene.
The whole reaction process of the preparation method of the pyrrole metallocene heterocyclic compound is always carried out under the protection of inert gas, and the inert gas can be one of hydrogen, nitrogen, helium and argon.
In the preparation method of the supported metallocene catalyst of the present invention, the first solvent and the second solvent may be the same solvent or different solvents, preferably the same solvent, and more preferably one or two of the group consisting of toluene and xylene.
The amount of the carrier modifier used in the present invention is not particularly limited as long as it functions to remove water oxygen from the carrier.
The kinetic curve of the catalyst prepared by the method is shown in figure 1, and the electron microscope photo of the catalyst is shown in figure 2, so that the activity release of the catalyst is smooth, and the reaction is normally carried out.
The supported metallocene catalyst can catalyze olefin polymerization reaction, and preferably, the supported metallocene catalyst is used as a main catalyst, and an alkylaluminium or aluminoxane compound is used as a cocatalyst to carry out polymerization reaction on olefin; more preferably, the molar ratio of the main catalyst to the cocatalyst is 1: 500-2000.
The kind of olefin is not particularly limited in the present invention, but is preferably one or more 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, α -methylstyrene, divinylbenzene and 3-chloromethylstyrene.
In conclusion, the invention firstly adopts an amine elimination method to synthesize the pyrrole metallocene heterocyclic compound, the reaction yield reaches more than 90 percent when the fulvene and the ligand are synthesized, moreover, the yield is greatly improved in the step of synthesizing the pyrrole heterocyclic compound, so that, in general, the yield of the pyrrole heterocyclic compound synthesized by the method is greatly improved, and researches show that compared with alkyl-N electron donors, the pyrrole base has stronger electron withdrawing property, therefore, the Zr-N bond is longer, so that the included angle between indenyl, metal central atom and pyrrolyl is smaller than that of the common alkyl N electron donor CGC, which is more beneficial to the attack of alpha-olefin, the copolymerization activity of the catalyst is better, and the position of a substituent on the pyrrole group is changed to influence the space structure and the electronic environment of the active center, so that the catalytic behavior of the copolymer is different, and the catalytic activity and the insertion rate of alpha-olefin in the copolymer are effectively improved.
The pyrrole metallocene heterocyclic compound is loaded on the carrier through simple impregnation, so that an active center is fixed on the carrier, the probability of bimolecular inactivation and beta-hydrogen elimination is reduced, and the stability of the catalyst is improved; but also eliminates the disadvantages of homogeneous catalysts: for example, the morphology of polymer particles is difficult to control, the reactor viscosity is severe, the bulk density of the obtained polymer is low, and the like.
The invention mainly evaluates the catalytic performance of the supported metallocene catalyst under normal pressure, and the specific method comprises the following steps: vacuumizing a 250ml three-neck flask, replacing the three times with nitrogen, sequentially adding 100ml of normal hexane and 0.2ml of MAO under the protection of nitrogen, fully stirring, adding 10.0mg of supported catalyst, adding a comonomer under normal pressure, and carrying out copolymerization reaction for 30 minutes at 80 ℃. And (4) drying the obtained polymer in vacuum to constant weight, and measuring the catalytic activity of the catalyst.
The technical solution of the present invention will be further described with specific examples.
Example 1:
reacting 3-CH 3 Cooling the-2-pyrrole-carbaldehyde and indene to 0 ℃, and dropwise adding the pyrrolidine, wherein the mass ratio of the substances of the-2-pyrrole-carbaldehyde to the indene is 1: 1: 5, heating to room temperature, stirring and reacting for 0.5 hour to obtain nitrogen-containing fulvene; then cooling to 2 ℃, and dropwise adding lithium aluminum hydride, wherein the molar ratio of the nitrogen-containing fulvene to the lithium aluminum hydride is 1: 1; heating to 65 ℃, and stirring for reaction for 30h to obtain a pyrrole N heterocyclic ring-containing ligand; cooling to 0 deg.C, and adding Zr (NMe) dissolved in organic solvent 2 ) 4 Heating to 80 deg.C, stirring and reacting for 10h to obtain the invented metallocene catalyst [ eta 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -C 4 H 2 N))]Zr(NMe 2 ) 2 。
The carrier modifier is methylaluminoxane, the inorganic carrier is silicon dioxide, and the preparation method comprises the following steps: dissolving a carrier modifier methylaluminoxane in toluene, adding a carrier, controlling the temperature of a mixed solution to be 80 ℃, and stirring at a constant temperature for 15 hours; and step two, dissolving the pyrrole metallocene heterocyclic compound in a toluene solvent, dripping the pyrrole metallocene heterocyclic compound into the suspension prepared in the step one after the pyrrole metallocene heterocyclic compound is completely dissolved, controlling the temperature at 0 ℃, stirring the mixture at a constant temperature for 20 hours, and removing the solvent, filtering, washing, and carrying out decompression and drying treatment after the reaction is finished to obtain a solid, namely the supported metallocene catalyst.
The evaluation method comprises the following steps: vacuumizing a 250ml three-neck flask, replacing the three times by nitrogen, sequentially adding 100ml of normal hexane and 0.2ml of methylaluminoxane under the protection of the nitrogen, fully stirring, adding 10.0mg of the supported catalyst, adding ethylene under normal pressure, and carrying out copolymerization reaction for 30 minutes at the temperature of 80 ℃. The resulting polymer was vacuum dried to constant weight and the catalytic activity of the catalyst was found to be 15000gPE/g polymer
Example 2:
4-CH is added 3 Cooling the-2-pyrrole-carbaldehyde and indene to 5 ℃, and dropwise adding the pyrrolidine, wherein the mass ratio of the substances of the-2-pyrrole-carbaldehyde to the indene is 1: 2: 4, heating to room temperature, stirring and reacting for 20 hours to obtain nitrogen-containing fulvene; then cooling to-10 ℃, and dropwise adding lithium aluminum hydride, wherein the molar ratio of the nitrogen-containing fulvene to the lithium aluminum hydride is 1: 2, heating to 50 ℃, and stirring for reacting for 50 hours to obtain a pyrrole N heterocyclic ring-containing ligand; cooling to 5 deg.C, dropping Zr (NEt) dissolved in organic solvent 2 ) 4 Heating to 90 deg.C, stirring and reacting for 20h to obtain the invented metallocene catalyst [ (. eta.) ] 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -C 4 H 2 N))]Zr(NEt 2 ) 2 。
The carrier modifier is trimethyl aluminum, the inorganic carrier is silicon dioxide, and the preparation method comprises the following steps: dissolving a carrier modifier in toluene, adding a carrier, controlling the temperature of a mixed solution to be 60 ℃, and stirring at a constant temperature for 10 hours; and step two, dissolving the pyrrole metallocene heterocyclic compound in a toluene solvent, dripping the pyrrole metallocene heterocyclic compound into the suspension prepared in the step one after the pyrrole metallocene heterocyclic compound is completely dissolved, controlling the temperature at minus 30 ℃, stirring for 6 hours at a constant temperature, and removing the solvent, filtering, washing, and carrying out decompression and draining treatment after the reaction is finished to obtain a solid, namely the supported metallocene catalyst. Using the polymerization bench evaluation method of example 1, the cocatalyst trimethylaluminum, the olefin monomer selected from propylene, and the calculated catalyst activity were 12500gPE/g polymer.
Example 3:
4-CH is added 3 Cooling the-2-pyrrole-carbaldehyde and indene to-10 ℃, and dropwise adding the pyrrolidine, wherein the mass ratio of the substances of the-2-pyrrole-carbaldehyde to the indene is 1: 1: 1, heating to room temperature, stirring and reacting for 5 hours to obtain nitrogen-containing fulvene; then cooling to-5 ℃, and dropwise adding lithium aluminum hydride, wherein the molar ratio of the nitrogen-containing fulvene to the lithium aluminum hydride is 1: 3, heating to 60 ℃, and stirring for reaction for 5 hours to obtain a pyrrole N heterocyclic ring-containing ligand; cooling to-5 deg.C, and adding Ti (NMe) dissolved in organic solvent 2 ) 4 Heating to 70 ℃, stirring and reacting for 1-30 h to obtain the metallocene catalyst [ (. eta.) ] 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -C 4 H 2 N))]Ti(NMe 2 ) 2 。
The carrier modifier is triethyl aluminum, the inorganic carrier is silicon dioxide, and the preparation method comprises the following steps: dissolving a carrier modifier in toluene, adding a carrier, controlling the temperature of a mixed solution to be 90 ℃, and stirring at a constant temperature for 20 hours; and step two, dissolving the pyrrole metallocene heterocyclic compound in an aromatic hydrocarbon solvent, dripping the dissolved pyrrole metallocene heterocyclic compound into the suspension prepared in the step one after the pyrrole metallocene heterocyclic compound is completely dissolved, controlling the temperature at 20 ℃, stirring the mixture at a constant temperature for 13 hours, and removing the solvent, filtering, washing, and performing reduced pressure drying treatment after the reaction is finished to obtain a solid, namely the supported metallocene catalyst. Using the polymerization bench evaluation method of example 1, trimethylaluminum as co-catalyst, an olefin monomer selected from 1-butene, and a catalyst activity calculated as 10900gPE/g polymer.
Example 4:
reacting 5-CH 3 Cooling the-2-pyrrole-carbaldehyde and indene to-6 ℃, and dropwise adding the pyrrolidine, wherein the mass ratio of the substances of the-2-pyrrole-carbaldehyde to the indene is 1: 3: 3, heating to room temperature, stirring and reacting for 10 hours to obtain nitrogen-containing fulvene; then cooling to 5 ℃, and dropwise adding lithium aluminum hydride, wherein the molar ratio of the nitrogen-containing fulvene to the lithium aluminum hydride is 1: 4, heating to 40 ℃, and stirring for reacting for 15 hours to obtain a pyrrole N heterocyclic ring-containing ligand; cooling to-10 deg.C, and adding Ti (NEt) dissolved in organic solvent 2 ) 4 Heating to 60 deg.C, stirring and reacting for 5h to obtain the invented metallocene catalyst [ (. eta.) ] 5 -C 9 H 6 )CH 2 (2-(5-CH 3 -C 4 H 2 N))]Ti(NEt 2 ) 2 。
The carrier modifier is triethyl aluminum, the inorganic carrier is silicon dioxide, and the preparation method comprises the following steps: dissolving a carrier modifier in xylene, adding a carrier, controlling the temperature of a mixed solution to be 90 ℃, and stirring at a constant temperature for 5 hours; and step two, dissolving the pyrrole metallocene heterocyclic compound in xylene, dripping the pyrrole metallocene heterocyclic compound into the suspension prepared in the step one after the pyrrole metallocene heterocyclic compound is completely dissolved, controlling the temperature at 30 ℃, stirring for 10 hours at constant temperature, and removing a solvent, filtering, washing, and performing reduced pressure pumping drying treatment after the reaction is finished to obtain a solid, namely the supported metallocene catalyst. Using the polymerization bench evaluation method of example 1, trimethylaluminum as a cocatalyst, an olefin monomer selected from 1-pentene, and a catalyst activity calculated as 8450gPE/g polymer were obtained.
Example 5:
4-CH is added 3 -5-CH 3 Cooling the-2-pyrrole formaldehyde and indene to 2 ℃, and dropwise adding the pyrrolidine, wherein the mass ratio of the substances of the-2-pyrrole formaldehyde to the indene is 1: 4: 2, heating to room temperature, stirring and reacting for 15 hours to obtain nitrogen-containing fulvene; then cooling to 0 ℃, and dropwise adding lithium aluminum hydride, wherein the molar ratio of the nitrogen-containing fulvene to the lithium aluminum hydride is 1: 5, heating to 70 ℃, and stirring for reacting for 25 hours to obtain a pyrrole N heterocyclic ring-containing ligand; cooling to-4 deg.C, and adding Ti (NMe) dissolved in organic solvent 2 ) 4 Heating to 50 deg.C, stirring and reacting for 1h to obtain metallocene catalyst [ (. eta.) ] 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -5-CH 3 -C 4 HN))]Ti(NMe 2 ) 2 。
The carrier modifier is triisobutyl aluminum, the inorganic carrier is silicon dioxide, and the preparation method comprises the following steps: dissolving a carrier modifier in xylene, adding a carrier, controlling the temperature of a mixed solution to be 70 ℃, and stirring at a constant temperature for 1 hour; and step two, dissolving the pyrrole metallocene heterocyclic compound in xylene, dropwise adding the mixture into the suspension prepared in the step one after the pyrrole metallocene heterocyclic compound is completely dissolved, controlling the temperature at 50 ℃, stirring the mixture at a constant temperature for 10 hours, and removing the solvent, filtering, washing, and performing reduced pressure drying treatment after the reaction is finished to obtain a solid, namely the supported metallocene catalyst. Using the polymerization bench evaluation method of example 1, triisobutylaluminum as a cocatalyst, 1-pentene as an olefin monomer, and 7800gPE/g polymer as a catalyst activity were calculated.
Example 6:
reacting 3-CH 3 -5-CH 3 Cooling the-2-pyrrole-carbaldehyde and indene to-3 ℃, and dropwise adding the pyrrolidine, wherein the mass ratio of the substances of the-2-pyrrole-carbaldehyde to the indene is 1: 4: 3, heating to room temperature, stirring and reacting for 12 hours to obtain nitrogen-containing fulvene; then cooling to-6 ℃, and dropwise adding lithium aluminum hydride, wherein the molar ratio of the nitrogen-containing fulvene to the lithium aluminum hydride is 1: 0.5, heating to 55 ℃, stirring and reacting for 45 hours to obtain a ligand containing pyrrole N heterocycle; cooling to 3 deg.C, and adding Ti (NEt) dissolved in organic solvent 2 ) 4 Heating to 100 deg.C, stirring and reacting for 30h to obtain the invented metallocene catalyst [ (. eta.) ] 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -5-CH 3 -C 4 HN))]Ti(NEt 2 ) 2 。
The carrier modifier is methylaluminoxane, the inorganic carrier is silicon dioxide, and the preparation method comprises the following steps: dissolving a carrier modifier in xylene, adding a carrier, controlling the temperature of a mixed solution to be 50 ℃, and stirring at a constant temperature for 40 hours; and step two, dissolving the pyrrole metallocene heterocyclic compound in xylene, dropwise adding the mixture into the suspension prepared in the step one after the pyrrole metallocene heterocyclic compound is completely dissolved, controlling the temperature at 50 ℃, stirring the mixture at a constant temperature for 15 hours, and removing the solvent, filtering, washing, and performing reduced pressure drying treatment after the reaction is finished to obtain a solid, namely the supported metallocene catalyst. Using the polymerization bench evaluation method of example 1, the cocatalyst methylaluminoxane, the olefin monomer selected from 1-pentene, was used, and the catalyst activity was calculated to be 6600gPE/g polymer.
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 (15)

1. A supported metallocene catalyst, wherein the supported metallocene catalyst comprises:
a carrier and a pyrrole metallocene heterocyclic compound loaded on the carrier;
wherein, the pyrrole metallocene heterocyclic compound has the following structure as shown in the formula I:
Figure FDA0002214316690000011
wherein R is 1 、R 2 And R 3 Each independently selected from H, CH 3 And a saturated or double-bond-containing linear or branched chain C 2 -C 10 One of the hydrocarbon groups; r 4 Is straight-chain or branched C 1 -C 5 An alkyl group; m is Ti or Zr.
2. The supported metallocene catalyst according to claim 1, wherein the supported metallocene catalyst comprises 0.5 to 15% by mass of the heterocyclic pyrrole compound and 85 to 99.5% by mass of the carrier, based on the total mass of the supported metallocene catalyst.
3. The supported metallocene catalyst according to claim 2, wherein the carrier is one or more selected from the group consisting of silica, alumina, magnesium chloride complex, zirconia and zeolite; and/or the carrier is obtained by dehydration, deoxidation and modification.
4. The supported metallocene catalyst of claim 3, wherein the modifier for modifying the support is one or more selected from the group consisting of methylaluminoxane, trimethylaluminum, triethylaluminum and triisobutylaluminum.
5. The supported metallocene catalyst of claim 2, wherein R is 1 、R 2 And R 3 Each independently selected from H, CH 3 -, saturated or containing double bonds, straight-chain or branched C 2 -C 5 One of the hydrocarbon groups; said R is 4 Is CH 3 -or CH 3 CH 2 -。
6. The supported metallocene catalyst according to claim 5, wherein the azole metallocene heterocyclic compound is:
[(η 5 -C 9 H 6 )CH 2 (2-C 4 H 3 N)]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -C 4 H 2 N))]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -C 4 H 2 N))]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(5-CH 3 -C 4 H 2 N))]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -C 4 HN))]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -5-CH 3 -C 4 HN))]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -5-CH 3 -C 4 HN))]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -5-CH 3 -C 4 N))]Zr(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-C 4 H 3 N)]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -C 4 H 2 N))]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -C 4 H 2 N))]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(5-CH 3 -C 4 H 2 N))]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -C 4 HN))]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -5-CH 3 -C 4 HN))]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -5-CH 3 -C 4 HN))]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -5-CH 3 -C 4 N))]Zr(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-C 4 H 3 N)]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -C 4 H 2 N))]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -C 4 H 2 N))]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(5-CH 3 -C 4 H 2 N))]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -C 4 HN))]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -5-CH 3 -C 4 HN))]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -5-CH 3 -C 4 HN))]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -5-CH 3 -C 4 N))]Ti(NMe 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-C 4 H 3 N)]Ti(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -C 4 H 2 N))]Ti(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -C 4 H 2 N))]Ti(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(5-CH 3 -C 4 H 2 N))]Ti(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -C 4 HN))]Ti(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -5-CH 3 -C 4 HN))]Ti(NEt 2 ) 2 、
[(η 5 -C 9 H 6 )CH 2 (2-(4-CH 3 -5-CH 3 -C 4 HN))]Ti(NEt 2 ) 2 and
[(η 5 -C 9 H 6 )CH 2 (2-(3-CH 3 -4-CH 3 -5-CH 3 -C 4 N))]Ti(NEt 2 ) 2 one or more of the group.
7. The process for preparing a supported metallocene catalyst according to any of claims 1 to 6, characterized in that it comprises the following steps:
step 1, dissolving a carrier modifier in a first solvent, adding a carrier, controlling the temperature of a mixed solution to be 50-100 ℃, and stirring at a constant temperature for 1-40 hours; and
and 2, dissolving the pyrrole metallocene heterocyclic compound in a second solvent, dropwise adding the dissolved pyrrole metallocene heterocyclic compound into the mixed solution prepared in the step 1, controlling the temperature to be between 50 ℃ below zero and 50 ℃, stirring at a constant temperature for 2 to 20 hours, and performing post-treatment to obtain the supported metallocene catalyst.
8. The method for preparing a supported metallocene catalyst according to claim 7, wherein the method for preparing the heterocyclic pyrrole metallocene compound comprises the steps of:
step a, reacting 2-pyrrole-carbaldehyde shown in formula II or a derivative thereof with indene to prepare nitrogen-containing fulvene shown in formula III R 1 、R 2 And R 3 Each independently selected from H, CH 3 And a saturated or double-bond-containing linear or branched chain C 2 -C 10 One of the hydrocarbon groups;
b, reducing nitrogen-containing fulvene in a formula III to generate a pyrrole N heterocyclic-containing ligand in a formula IV; and
step c, ligand of formula IV containing pyrrole N heterocyclic ring and M [ N (R) 4 ) 2 ] 4 A complexation reaction occurs to produce a metallocene catalyst, R 4 Is straight-chain or branched C 1 -C 5 Alkyl, M is Ti or Zr;
Figure FDA0002214316690000031
9. the method for preparing a supported metallocene catalyst according to claim 8, wherein the step a 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 the 2-pyrrole formaldehyde or the derivatives thereof, indene and tetrahydropyrrole in the formula II is 1: 1-5: 1 to 5.
10. The method for preparing a metallocene catalyst according to claim 8, wherein the step b is: dissolving the nitrogen-containing fulvene in the formula III obtained in the step a in an organic solvent, cooling to-10-5 ℃, dropwise adding lithium aluminum hydride dissolved in the organic solvent, heating to 40-70 ℃, and stirring for reaction for 5-50h to obtain a pyrrole N heterocyclic ring-containing ligand in 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.
11. The method for preparing a metallocene catalyst according to claim 8, wherein the step c is: dissolving the pyrrole N heterocyclic ring-containing ligand of the formula IV obtained in the step b in an organic solvent, cooling to-10-5 ℃, and then dropwise adding M [ N (R) dissolved in the organic solvent 4 ) 2 ] 4 Heating to 50-100 ℃, and stirring for reaction for 1-30 h to obtain a metallocene catalyst;
wherein, formula IV contains pyrrole N heterocyclic ligand and M [ N (R) 4 ) 2 ] 4 In a molar ratio of 1: 0.5 to 5.
12. The method of claim 7, wherein the first solvent and the second solvent are the same solvent and are one or two of the group consisting of toluene and xylene.
13. A process for the polymerization of olefins carried out under the action of a supported metallocene catalyst as claimed in any of claims 1 to 6.
14. The method of claim 13, wherein the olefin is one or more 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, divinylbenzene, and 3-chloromethylstyrene.
15. The olefin polymerization reaction process of claim 13, wherein the supported metallocene catalyst of any one of claims 1 to 6 is a main catalyst, the alkylaluminum or aluminoxane compound is a cocatalyst, and the molar ratio of the main catalyst to the cocatalyst is 1: 500-2000.
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