CN109748987A - Compound, preparation method, including its olefin polymerization catalysis and olefin polymerization catalysis application - Google Patents

Abstract

The present invention provides a kind of compound, preparation method, including its olefin polymerization catalysis and olefin polymerization catalysis application.The structure of the compound is shown in formula I；In Formulas I, R₁The aryl of the naphthenic base of linear or branched alkyl group, C3~C20 selected from C1~C20, C6~C20；R₂And R₃It is respectively and independently selected from the aryl of hydrogen atom, the linear or branched alkyl group of C1~C20, the naphthenic base of C3~C20, C6~C20；X is selected from F, Cl, Br, I or C1~C20 linear or branched alkyl group；Any transition metal atoms of the M in the IIIth B, IV B, VB or VIII race's element.The full heterocyclic compound is as non-metallocene catalyst, ethylene homo conjunction, propylene homo conjunction, ethylene and alpha-olefin copolymer conjunction, propylene and alpha-olefin copolymer conjunction, ethylene and the conjunction of polarity vinyl monomer copolymerization or propylene and the conjunction of polarity vinyl monomer copolymerization, catalyst activity height can be effectively catalyzed.

Description

Compound, preparation method, the olefin polymerization catalysis including it and olefinic polymerization are urged The application of agent

Technical field

The present invention relates to olefin polymerization technology field, in particular to a kind of compound, preparation method including its Olefin polymerization catalysis and olefin polymerization catalysis application.

Background technique

Polyolefin products (such as PE, PP etc.) have many advantages that such as easy processing, thermal stability is good, against weather is good, resistance toization Learn that corrosivity is good and validity period limit for length etc., welcome of the depth by market.But the usual resistance to low temperature of polyolefin is poor, crystallinity is high, Its application range is caused to be restricted.If being inserted into a certain number of higher alkenes (such as 1- octene in molecular polyolefin chain Deng) it is prepared into block copolymer, significant change will occur for the structure and performance of polyolefin, can such as make density polymer than common Polyolefin it is lower, density is in 0.85~0.92g/cm³Between；Glass transition temperature is low, and resistance to low temperature is good；And point It is good to dissipate property, weatherability, flexibility, flexibility and processing performance.Such as: ethylene/1- octene copolymer performance compares ethylene/propene The superior performance of copolymer and Ethylene/1-butene copolymer.

Non-metallocene catalyst comes across nineteen nineties, the coordination atom of this kind of catalyst be nitrogen, phosphorus, oxygen, Sulphur etc..The activated centre of catalyst is single, and the oxytropism of central metal atom is weaker, alkene and polar monomer easy to accomplish Copolymerization, thus the functional polyolefinic material that synthesis performance is excellent.In addition, the design and synthesis of non-metallocene catalyst ligand structure Changeability is big, and activity, the stereoregularity of polymer, molecular weight and the molecular weight distribution of catalyst can be by changing ligand Structure and controlled.It is constantly subjected to people's attention from once there is fast development.

Containing the complex that hetero atom is more in main structure, relative to containing only single heteroatomic complex (such as containing only oxygen, Nitrogen etc.), there are more changeabilities in structure, the space for adjusting polymer architecture and performance is bigger.

Summary of the invention

The main purpose of the present invention is to provide a kind of compound, preparation method, including its olefin polymerization catalysis And the application of olefin polymerization catalysis, with solve in the prior art non-metallocene catalyst because being led in main ring structure containing carbon atom The not high problem of the catalyst activity of cause.

To achieve the goals above, according to an aspect of the invention, there is provided a kind of compound, structure such as Formulas I institute Show:

In Formulas I, R₁The aryl of the naphthenic base of linear or branched alkyl group, C3~C20 selected from C1~C20, C6~C20；R₂With R₃It is respectively and independently selected from the aryl of hydrogen atom, the linear or branched alkyl group of C1~C20, the naphthenic base of C3~C20, C6~C20；X Selected from F, Cl, Br, I or C1~C20 linear or branched alkyl group；M is selected from any one of the IIIth B, IV B, VB or VIII race's element Transition metal atoms.

Further, above-mentioned X is selected from Cl, Br, methyl or ethyl.

Further, above-mentioned M is titanium, zirconium, hafnium, vanadium, rhodium, iron, nickel, cobalt, neodymium, palladium or yttrium.

To achieve the goals above, according to another aspect of the present invention, the preparation method of above compound is provided, is wrapped It includes following steps: ligand compound being reacted with transistion metal compound, obtains the compound of Formulas I, wherein ligand compound Structure is as shown in Formula II:

In Formula II, R₁The aryl of the naphthenic base of linear or branched alkyl group, C3~C20 selected from C1~C20, C6~C20；R₂ And R₃It is respectively and independently selected from the aryl of hydrogen atom, the linear or branched alkyl group of C1~C20, the naphthenic base of C3~C20, C6~C20； Transistion metal compound is MXn, and wherein X is selected from F, Cl, Br, I or C1~C20 linear or branched alkyl group；M is selected from the IIIth B, IV B, any transition metal atoms in VB or VIII race's element, n are the positive integer no more than 4.

Further, in above-mentioned reaction process, the molar ratio of ligand compound and transistion metal compound is 1:1~2；It is excellent Selection of land, in above-mentioned reaction process, the molar ratio of ligand compound and transistion metal compound is 1:1~1.5.

Further, the reaction temperature of above-mentioned reaction process is 0~90 DEG C, preferably 30~70 DEG C；Reaction time be 1~ 10 hours, preferably 2~5 hours.

Further, above-mentioned reaction carries out in the first organic solvent, and preferably the first organic solvent is the saturation of C5~C15 Hydrocarbon, the alicyclic of C5~C10, the aromatic hydrocarbon of C6~C15 and C2~C10 one of saturated heterocyclic hydrocarbon or a variety of.

Further, before the step of being reacted ligand compound with transistion metal compound, above-mentioned preparation side Method further include: by primary amino-compound R₁-NH₂, Grignard Reagent and the second organic solvent mix and reacted, obtain pre-reaction object； By pre-reaction object, the first organic phosphorus compound R₂-PX’₂And the second organic phosphorus compound R₃-PX’₂It mixes and is reacted, obtained Ligand compound；Wherein the first organic phosphorus compound R₂-PX’₂And the second organic phosphorus compound R₃-PX’₂In X ' be that halogen is former Son.

Further, by primary amino-compound R₁-NH₂, Grignard Reagent and the second organic solvent the step of mixing and being reacted In, reaction temperature is 0~70 DEG C, and preferably 10~50 DEG C, the reaction time is 1~10 hour, preferably 2~4 hours；It will be pre- anti- Answer object, the first organic phosphorus compound R₂-PX’₂And the second organic phosphorus compound R₃-PX’₂In the step of mixing and being reacted, instead Answering temperature is 0~70 DEG C, and preferably 10~50 DEG C, the reaction time is 1~5 hour, preferably 2~4 hours.

Further, above-mentioned second organic solvent is selected from the saturated hydrocarbons of C5~C15, the alicyclic of C5~C10, C6~C15 Aromatic hydrocarbon, C2~C10 saturated heterocyclic hydrocarbon or the above solvent composition mixed solvent.

According to another aspect of the present invention, a kind of olefin polymerization catalysis, including major catalyst and co-catalyst are provided, Wherein major catalyst is above-mentioned compound.

Further, above-mentioned co-catalyst is organic metal aluminium compound；It is preferred that organic metal aluminium compound is alkyl aluminum Or alkylaluminoxane；More preferable organic metal aluminium compound is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum And one of methylaluminoxane or a variety of.

Further, the molar ratio of above-mentioned co-catalyst and major catalyst is 100~5000:1, preferably 150~1000: 1。

Further, above-mentioned olefin polymerization catalysis further includes catalyst carrier, and major catalyst is supported on catalyst carrier On；Preferably, catalyst carrier is inorganic oxide or inorganic halides；More preferable inorganic oxide is silica, oxidation Aluminium, inorganic halides are magnesium chloride.

According to another aspect of the present invention, above-mentioned olefin polymerization catalysis is additionally provided in catalysed olefin polymerization Using.

Further, above-mentioned olefin polymerization is following any: the homopolymerization of ethylene, the homopolymerization of propylene, ethylene The combined polymerization of combined polymerization, propylene and alpha-olefin, the combined polymerization of ethylene and polarity vinyl monomer, propylene and polarity alkene with alpha-olefin The combined polymerization of class monomer.

The structure of compound provided by the invention is shown in formula I, main ring not carbon atoms, by three hetero atoms (P, N, P it) is formed with transition metal atoms.This full heterocyclic compound as non-metallocene catalyst, can effectively be catalyzed ethylene homo close, Propylene homo conjunction, ethylene and alpha-olefin copolymer conjunction, propylene and alpha-olefin copolymer conjunction, ethylene and polarity vinyl monomer copolymerization conjunction or third Alkene and polarity vinyl monomer copolymerization are closed, and catalyst activity is high.At the same time, this full heterocyclic compound can also be easy to load On carrier, it is prepared into loaded catalyst, so as to be widely used in different types of olefin polymerization, is efficiently urged Change olefin polymerization.

Specific embodiment

It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.

The application is described in further detail below in conjunction with specific embodiment, these embodiments should not be understood as limitation originally Apply for range claimed.

As background technology part is introduced, containing the complex that hetero atom is more in main structure, relative to containing only list One heteroatomic complex (such as containing only oxygen, nitrogen) has more changeabilities in structure, adjusts the sky of polymer architecture and performance Between it is bigger.But applicant has been surprisingly found that under study for action, all contains in the main ring structure of non-metallocene catalyst in the prior art Carbon atom, the presence of carbon atom adversely affects the catalytic activity of non-metallocene catalyst in main ring structure.

In order to solve this problem, the present invention provides a kind of compound, structure is shown in formula I:

In above-mentioned Formulas I, R₁The virtue of the naphthenic base of linear or branched alkyl group, C3~C20 selected from C1~C20, C6~C20 Base；R₂And R₃It is respectively and independently selected from hydrogen atom, the linear or branched alkyl group of C1~C20, the naphthenic base of C3~C20, C6~C20 Aryl；X is selected from F, Cl, Br, I or C1~C20 linear or branched alkyl group；M is in the IIIth B, IV B, VB or VIII race's element Any transition metal atoms.

Above compound provided by the invention, main ring not carbon atoms, by three hetero atoms (P, N, P) and transition metal Atom forms, and multiple substituent groups are had on ring.This full heterocyclic compound can effectively be catalyzed ethylene as non-metallocene catalyst Homopolymerization, propylene homo are closed, ethylene and alpha-olefin copolymer conjunction, propylene and alpha-olefin copolymer conjunction, ethylene and polarity vinyl monomer are total Polymerization or propylene and polarity vinyl monomer copolymerization are closed, and catalyst activity is high.Meanwhile also simultaneously containing miscellaneous on the main ring of the compound Atom P and N, this has on compound structure and more may be used relative to containing only single heteroatomic complex (such as containing only oxygen, nitrogen) Denaturation, the space for adjusting polymer architecture and performance is bigger, therefore is more conducive to different types of olefinic polymerization, or even make one A little higher alkenes realize homopolymerization and autohemagglutination.In addition, this full heterocyclic compound can also be easy to be supported on carrier, it is prepared into Loaded catalyst, so as to be widely used in different types of olefin polymerization, efficient catalytic olefin polymerization.

The substitution base type that above-mentioned part provides according to the present invention, can obtain different types of full heterocycle Nonmetallocene Object is closed, and each compound is applied and all has higher catalytic activity in olefin polymerization catalysis.In a kind of preferred embodiment party In formula, X is selected from Cl, Br, methyl or ethyl.It is highly preferred that M is selected from titanium, zirconium, hafnium, vanadium, rhodium, iron, nickel, cobalt, neodymium, palladium or yttrium.This The compound formed under a little X, M substituent groups, the olefin polymerization catalysis applicability of formation is more extensive, and there is preferably catalysis to live Property.Meanwhile the active warm area of catalyst is wider, universality is stronger.

According to another aspect of the present invention, a kind of preparation method of above compound is additionally provided comprising following steps: Ligand compound is reacted with transistion metal compound, obtains the compound of Formulas I, wherein the structure of ligand compound such as Formula II It is shown:

In above-mentioned Formula II, R₁The naphthenic base of linear or branched alkyl group, C3~C20 selected from C1~C20, C6~C20 Aryl；R₂And R₃It is respectively and independently selected from hydrogen atom, the linear or branched alkyl group of C1~C20, the naphthenic base of C3~C20, C6~C20 Aryl；Transistion metal compound is MXn, and wherein X is selected from F, Cl, Br, I or C1~C20 linear or branched alkyl group；M is selected from Any transition metal atoms in IIIth B, IV B, VB or VIII race's element, n are the positive integer no more than 4.

It take main chain shown in Formula II as the ligand compound and mistake of full heterocycle using above-mentioned preparation method provided by the invention Metallic compound MXn is crossed to be reacted, P hydrogen atoms directly can occur cooperation and replace with MXn in ligand compound, P for Transition metal atoms M directly occurs complex reaction and forms full heterocycle non-metallocene compound shown in Formulas I.The master of the compound Ring not carbon atoms, are made of three hetero atoms (P, N, P) and transition metal atoms, and multiple substituent groups are had on ring.It is this complete Heterocyclic compound can effectively be catalyzed ethylene homo conjunction, propylene homo conjunction, ethylene and alpha-olefin copolymer as non-metallocene catalyst Conjunction, propylene and alpha-olefin copolymer conjunction, ethylene and the conjunction of polarity vinyl monomer copolymerization or propylene and polarity vinyl monomer copolymerization are closed, catalysis Agent activity is high.Meanwhile also containing hetero atom P and N on the main ring of the compound simultaneously, this heteroatomic matches relative to containing only single It closes object (such as containing only oxygen, nitrogen), there is more changeabilities on compound structure, the space of adjusting polymer architecture and performance is more Greatly, therefore it is more conducive to different types of olefinic polymerization, or even some higher alkenes is made to realize homopolymerization and autohemagglutination.In addition, this The full heterocyclic compound of kind can also be easy to be supported on carrier, loaded catalyst is prepared into, so as to be widely used in In different types of olefin polymerization, efficient catalytic olefin polymerization.

In above-mentioned reaction process, ligand compound can be reacted with the dosage relation of transistion metal compound according to theory It is adjusted.In a preferred embodiment, the molar ratio of ligand compound and transistion metal compound is 1:1~2.It will Within the above range, reaction efficiency is higher for the dosage relation control of the two.It is highly preferred that ligand compound and transition metal compound The molar ratio of object is 1:1~1.5.Reaction rate can be further increased under the ratio, and further increases the conversion ratio of reaction, The excessive waste of raw material is avoided simultaneously.

In a preferred embodiment, the reaction temperature of above-mentioned reaction process be 0~90 DEG C, preferably 30~70 ℃；Reaction time is 1~10 hour, preferably 2~5 hours.Under the process conditions, complex and transistion metal compound Between reaction efficiency it is higher, conversion ratio is higher.

In a preferred embodiment, above-mentioned reaction carries out in the first organic solvent, and the first organic solvent is preferred One from the saturated heterocyclic hydrocarbon of the saturated hydrocarbons of C5~C15, the alicyclic of C5~C10, the aromatic hydrocarbon of C6~C15 and C2~C10 Kind is a variety of.It is reacted in above-mentioned organic solvent, is conducive to improve ligand compound, transistion metal compound and product body The stability of system, while side reaction can also be reduced, carry out reaction more successfully.

As long as just can obtain that purity is higher, the higher compound for meeting Formulas I of yield according to above-mentioned method.On Stating complex shown in Formula II can come from commercial product, can also voluntarily synthesize.In a preferred embodiment, exist It further include preparing ligand compound before the step of above-mentioned ligand compound is reacted with above-mentioned transistion metal compound Step: by primary amino-compound R₁-NH₂, Grignard Reagent and the second organic solvent mix and reacted, obtain pre-reaction object；It will be pre- Reactant, the first organic phosphorus compound R₂-PX’₂And the second organic phosphorus compound R₃-PX’₂It mixes and is reacted, obtain ligand Compound；Wherein the first organic phosphorus compound R₂-PX’₂And the second organic phosphorus compound R₃-PX’₂In X ' be halogen atom.It is logical Above-mentioned simple and easy step is crossed, available purity is higher, the higher compound for meeting Formula II of yield.In addition to this, When meeting the compound of Formulas I using the preparation of above-mentioned preparation method, the abundant raw material of use is easy to get, and specific implementation step is simply easily grasped Make, is suitable for large-scale production.It should be noted that above-mentioned primary amino-compound R₁-NH₂, the first organic phosphorus compound R₂-PX’₂With Two organic phosphorus compound R₃-PX’₂In R₁、R₂、R₃Correspond to the R in above-mentioned ligand compound₁、R₂、R₃。

In a preferred embodiment, by primary amino-compound R₁-NH₂, Grignard Reagent and the second organic solvent mixing simultaneously In the step of being reacted, reaction temperature be 0~70 DEG C, preferably 10~50 DEG C, the reaction time be 1~10 hour, preferably 2 ~4 hours；By pre-reaction object, the first organic phosphorus compound R₂-PX’₂And the second organic phosphorus compound R₃-PX’₂It mixes and carries out In the step of reaction, reaction temperature is 0~70 DEG C, and preferably 10~50 DEG C, the reaction time is 1~5 hour, and preferably 2~4 is small When.Under the process conditions, the reaction efficiency between complex and transistion metal compound is higher, and conversion ratio is higher.

In a preferred embodiment, above-mentioned second organic solvent is selected from the saturated hydrocarbons of C5~C15, C5~C10 The mixed solvent that alicyclic, the aromatic hydrocarbon of C6~C15, the saturated heterocyclic hydrocarbon of C2~C10 or the above solvent form.Above-mentioned organic It is reacted in solvent, is conducive to the steady of the compound for improving primary amino-compound, organic phosphorus compound and meeting formula II obtained It is qualitative, while side reaction can also be reduced, carry out reaction more successfully.

According to another aspect of the invention, a kind of olefin polymerization catalysis is additionally provided comprising major catalyst and helping is urged Agent.Wherein major catalyst is aforesaid compound.As it was noted above, using the Formulas I compound represented as olefinic polymerization catalysis The co-catalyst of agent can significantly improve the catalytic activity of olefin polymerization catalysis because of its full heterocycle Nonmetallocene structure.Together When, because containing P, N hetero atom on its main ring simultaneously, there are more changeabilities on compound structure, adjust polymer architecture and property The space of energy is bigger, therefore is more conducive to different types of olefinic polymerization, or even some higher alkenes is made to realize homopolymerizations and oneself It is poly-.In addition, olefin polymerization catalysis provided by the invention, is also added into co-catalyst other than major catalyst, this can be significant Ground improves the efficiency of major catalyst, and co-catalyst can be by adjusting major catalyst electronic structure, hardness and strength, surface texture Deng activity, selectivity and the stability etc. for improving catalyst entirety.

Above-mentioned co-catalyst can be co-catalyst commonly used in the art.In a preferred embodiment, above-mentioned In olefin polymerization catalysis, co-catalyst is organic metal aluminium compound, and preferably organic metal aluminium compound is alkyl aluminum or alkane Base aikyiaiurnirsoxan beta；It is highly preferred that organic metal aluminium compound be trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum and One of methylaluminoxane is a variety of.

Dosage relation between co-catalyst and major catalyst can be adjusted.In a preferred embodiment, The molar ratio of co-catalyst and major catalyst is 100~5000:1, preferably 150~1000:1.By co-catalyst and main catalytic When the molar ratio of agent is controlled within the above range, it can further improve the catalytic performance of major catalyst, while have catalyst There is the more preferably comprehensive service performance such as mechanical performance, thermal stability.

Major catalyst provided by the invention directly can cooperate catalysis in olefine polymerization with co-catalyst, in a kind of preferred reality It applies in mode, olefin polymerization catalysis further includes catalyst carrier, and major catalyst is supported in the catalyst carrier.It is above-mentioned negative Loadization process belongs to ordinary skill in the art means.For example, can complete to load in the following way: major catalyst is dissolved in In organic solvent, under the conditions of 10~90 DEG C, reacted with carrier 1~8 hour, wherein the molar ratio of carrier and major catalyst is 1: 0.5~20.After reaction, it is washed 4~6 times with inert organic solvents, obtains load type main catalyst.The loading process it is anti- Answer preferably 40~80 DEG C of temperature, the reaction time preferably 2~5 hours, carrier and preferred 1:0.5~10 of major catalyst molar ratio.On The inert organic solvents stated include but is not limited to the saturated hydrocarbons of C5~C15, the alicyclic of C5~C10, C6~C15 aromatic hydrocarbon, The mixed solvent of the saturated heterocyclic hydrocarbon of C2~C10 or above solvent composition.Co-catalyst therein and major catalyst is loaded Carrier exists in a manner of physical mixed.

Preferably, catalyst carrier is inorganic oxide or inorganic halides；More preferable inorganic oxide be silica, Aluminium oxide, inorganic halides are magnesium chloride.

By the way that catalyst is supported, catalyst can be dispersed on the surface of the carrier, to obtain higher specific surface area, mention The catalytic efficiency of high unit mass catalyst；Catalyst carrier can prevent active component from being sintered in use simultaneously, improve The heat resistance of catalyst.The loaded catalyst of preparation can effectively be catalyzed ethylene homo conjunction, propylene homo conjunction, ethylene and α- Alpha-olefinic copolymerization, propylene and alpha-olefin copolymer conjunction, ethylene and the conjunction of polarity vinyl monomer copolymerization and propylene and polarity vinyl monomer are total Polymerization, catalyst activity are high.

In addition, the application the present invention also provides foregoing alkenes polymerization catalyst during catalysed olefin polymerization. As it was noted above, catalyst catalytic activity with higher, and universality is stronger, and it is anti-to be suitable for different types of olefinic polymerization It answers.Such as: alkene homopolymerization reaction, alpha-olefinic copolymerization reaction.

Specific polymeric type is preferably as follows: ethylene homo conjunction, propylene homo conjunction, ethylene and alpha-olefin copolymer conjunction, propylene It is closed with alpha-olefin copolymer conjunction, ethylene and the conjunction of polarity vinyl monomer copolymerization or propylene and polarity vinyl monomer copolymerization, catalyst is urged It is high to change activity.Wherein, alpha-olefin can be the alkene of C3~C20, preferably propylene, 1- butylene, 1- amylene, 1- hexene, 1- octene, 3-methyl-1-butene, 4-methyl-1-pentene, styrene, α-methylstyrene and norbornene；Polarity vinyl monomer can be Containing carbon-carbon double bond, and simultaneous with the compound of polar group, preferably propylene cyanogen, 4- cyano styrene, methyl methacrylate Ester, methyl acrylate or butyl acrylate.Olefinic polymerization is caused using the olefin polymerization catalysis in the present invention, adjusts polymer The space of structure and performance is bigger, be suitable for a greater variety of olefinic monomers, including some higher alkenes realize homopolymerization and from Polymerization；The catalytic activity of the catalyst is high simultaneously, can increase substantially the reaction rate and conversion ratio of olefin polymerization.

When olefin polymerization catalysis catalysis in olefine polymerization provided by the present invention, polymerization temperature is preferably 20~90 DEG C, is gathered Closing the time is preferably 5min~3h, and reaction pressure is preferably 0.1~5MPa, and solvent for use is preferably n-hexane, heptane or toluene Deng.

Beneficial effects of the present invention are further illustrated by the following examples:

The concrete type of the compound of 1 Formulas I of table

Embodiment 1

The embodiment is prepared for ligand compound and procatalyst compound, and poly- using the catalyst alkene It closes, the specific process is as follows:

(1) ligand compound 1 of meeting formula II is prepared

Take 30ml toluene, 12ml (0.1314mol) aniline, the THF of 21.4ml (0.0657mol) methyl-magnesium-chloride (3M) molten Liquid reacts 2h after being heated to 35 DEG C in the schlenk bottle of 300ml, and obtained system is denoted as intermediate system 1；Then, to centre 12ml (0.0657mol) phenyl dichloro phosphorus is added in system 1 to drain, be added into remaining solid after 35 DEG C of reaction 4h 100ml n-hexane, dissolution filter recrystallize filtrate, obtain 11.4g aniiinophenyl phosphorus solid, yield: 62%.

(2) procatalyst compound 1 of meeting formula I is prepared

Under nitrogen protection, the ligand compound 1 of 0.43g meeting formula II is dissolved in 30mL toluene, adds 0.11mL (1mmol) titanium tetrachloride is warming up to 50 DEG C, reacts 4h.Vacuum extracts solvent, and residue is washed 3 times with n-hexane, drains, obtain To the procatalyst compound 1 (Cat.1) of 0.53g meeting formula I.1H NMR(600MHz,CDCl3):δ7.49(4H,m),δ7.42 (2H,t),δ7.09-7.17(5H,m),δ6.68-6.96(4H,m),δ6.67(2H,t),δ6.53(2H,d),δ0.68(6H,s)； Anal.Calcd. (%) for C26H26N2PTiCl2 (580): C, 53.79；H,4.48；N,4.83；found:C,53.77；H, 4.42；N,4.86.

(3) catalyzed ethylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 5mg major catalyst, 100ml toluene, 18mlMAO are sequentially added Solution (10wt%).Three times, temperature rises to 50 DEG C, ethylene pressure 0.7MPa for ventilation, polymerize 120min.With containing 10% hydrochloric acid Ethanol solution terminates reaction, and filtering, obtained polymer with ethanol washing 3 times, then sky is dry for 24 hours at 50 DEG C.

(4) it is catalyzed ethylene copolymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 5mg major catalyst is sequentially added, 80ml toluene, 18mlMAO is molten Liquid (10wt%), 5ml 1- butylene.Three times, temperature rises to 50 DEG C, keeps the ethylene pressure of 0.7MPa, polyase 13 0min for ventilation.With Ethanol solution containing 10% hydrochloric acid terminates reaction, and filtering is then true at 50 DEG C obtained polymer with ethanol washing 3 times Sky is dry for 24 hours.

Embodiment 2

The embodiment is prepared for procatalyst compound, and uses the catalyst olefinic polymerization, prepares liganded The technique of object is closed with embodiment 1, the difference is that:

(1) procatalyst compound 2 of meeting formula I is prepared

According to the method for embodiment 1, ligand compound 2 and 0.23g (1mmol) zirconium chloride of 0.43g meeting formula II is anti- It answers, obtains 0.45g catalyst 2 (Cat.2).1H NMR (600MHz, CDCl3): δ 7.48 (4H, m), δ 7.39 (2H, t), δ 7.03-7.26 (5H, m), δ 6.67-6.92 (4H, m), δ 6.66 (2H, t), δ 6.54 (2H, d), δ 0.68 (6H, s)； Anal.Calcd. (%) for C26H26N2PZrCl2:C:50.08, H:4.17, N:4.49；found:C:50.01,H:4.21, N:4.55。

(2) it is catalyzed propylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 9mg major catalyst, 100ml toluene, tri- second of 3ml are sequentially added Base aluminum solutions (1M).Three times, temperature rises to 40 DEG C, propylene pressure 2.5MPa for ventilation, polymerize 100min.With containing 10% hydrochloric acid Ethanol solution terminates reaction, and filtering obtained polymer with ethanol washing 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

(3) it is catalyzed copolymerization of propylene

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 7mg major catalyst, 80ml toluene, 4ml triethyl group are sequentially added Aluminum solutions (1M), 5ml1- butylene.Three times, temperature rises to 40 DEG C for ventilation, keeps the propylene pressure of 2.5MPa, polymerize 50min.With Ethanol solution containing 10% hydrochloric acid terminates reaction, and filtering is then true at 50 DEG C obtained polymer with ethanol washing 3 times Sky is dry for 24 hours.

Embodiment 3

The embodiment is prepared for procatalyst compound, and uses the catalyst olefinic polymerization, prepares liganded The technique of object is closed with embodiment 1, the difference is that:

(1) procatalyst compound 3 of meeting formula I is prepared

According to the method for embodiment 1, ligand compound 3 and 0.20g (1mmol) yttrium trichloride of 0.43g meeting formula II is anti- It answers, obtains 0.39g catalyst 3 (Cat.3).1H NMR (600MHz, CDCl3): δ 7.49 (4H, m), δ 7.39 (2H, t), δ 7.03-7.21 (5H, m), δ 6.67-6.93 (4H, m), δ 6.66 (2H, t), δ 6.55 (2H, d), δ 0.66 (6H, s)； Anal.Calcd. (%) for C26H26N2PYCl (585): C, 53.33；H,4.44；N,4.79；found:C,53.37；H, 4.41；N,4.75.

(2) catalyzed ethylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 6mg major catalyst is sequentially added, 100ml toluene, 7mlMAO is molten Liquid (10wt%).Three times, temperature rises to 90 DEG C, ethylene pressure 0.8MPa for ventilation, polymerize 90min.With the second for containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering obtained polymer with ethanol washing 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

(3) it is catalyzed ethylene copolymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 6mg major catalyst is sequentially added, 100ml toluene, 7mlMAO is molten Liquid (10wt%), 5ml 1- hexene.Ventilation three times, temperature rises to 20 DEG C, keep 0.8MPa ethylene pressure and 0.6MPa third Alkene pressure, polyase 13 0min.Reaction, filtering, obtained polymer ethanol washing are terminated with the ethanol solution containing 10% hydrochloric acid It 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

Embodiment 4

The embodiment is prepared for procatalyst compound, and uses the catalyst olefinic polymerization, prepares liganded The technique of object is closed with embodiment 1, the difference is that:

(1) procatalyst compound 4 of meeting formula I is prepared

According to the method for embodiment 1, ligand compound 4 and 0.25g (1mmol) neodymium trichloride of 0.43g meeting formula II is anti- It answers, obtains 0.51g catalyst 4 (Cat.4).1H NMR (600MHz, CDCl3): δ 7.50 (4H, m), δ 7.37 (2H, t), δ 7.06-7.24 (5H, m), δ 6.65-6.97 (4H, m), δ 6.68 (2H, t), δ 6.55 (2H, d), δ 0.70 (6H, s)； Anal.Calcd. (%) for C26H26N2PNdCl:C, 48.75；H,4.06；N,4.38；found:C,48.79；H,4.11； N,4.39。

(2) catalyzed ethylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 8mg major catalyst is sequentially added, 100ml toluene, 7mlMAO is molten Liquid (10wt%).Three times, temperature rises to 65 DEG C, ethylene pressure 0.6MPa for ventilation, polymerize 120min.With the second for containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering obtained polymer with ethanol washing 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

(3) it is catalyzed ethylene copolymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 7mg major catalyst is sequentially added, 100ml toluene, 7mlMAO is molten Liquid (10wt%), 5ml 1- octene.Three times, temperature rises to 65 DEG C for ventilation, keeps the ethylene pressure of 0.6MPa, polymerize 10min.With Ethanol solution containing 10% hydrochloric acid terminates reaction, and filtering is then true at 50 DEG C obtained polymer with ethanol washing 3 times Sky is dry for 24 hours.

Embodiment 5

The embodiment is prepared for procatalyst compound, and uses the catalyst olefinic polymerization, prepares liganded The technique of object is closed with embodiment 1, the difference is that:

(1) procatalyst compound 5 of meeting formula I is prepared

According to the method for embodiment 1, ligand compound 5 and 0.21g (1mmol) rhodium chloride of 0.43g meeting formula II is anti- It answers, obtains 0.35g catalyst 5 (Cat.5).1H NMR (600MHz, CDCl3): δ 7.49 (4H, m), δ 7.38 (2H, t), δ 7.06-7.23 (5H, m), δ 6.66-6.94 (4H, m), δ 6.67 (2H, t), δ 6.55 (2H, d), δ 0.69 (6H, s)； Anal.Calcd. (%) for C26H26N2PRhCl (599): C, 52.09；H,4.34；N,4.67；found:C,52.06；H, 4.33；N,4.67.

(2) catalyzed ethylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 5mg major catalyst is sequentially added, 100ml toluene, 3mlMAO is molten Liquid (10wt%).Three times, temperature rises to 50 DEG C, ethylene pressure 0.5MPa for ventilation, polymerize 120min.With the second for containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering obtained polymer with ethanol washing 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

(3) it is catalyzed ethylene copolymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 5mg major catalyst is sequentially added, 100ml toluene, 6mlMAO is molten Liquid (10wt%), 4ml 1- certain herbaceous plants with big flowers alkene.Three times, temperature rises to 70 DEG C for ventilation, keeps the ethylene pressure of 0.5MPa, polymerize 10min.With Ethanol solution containing 10% hydrochloric acid terminates reaction, and filtering is then true at 50 DEG C obtained polymer with ethanol washing 3 times Sky is dry for 24 hours.

Embodiment 6

The embodiment is prepared for procatalyst compound, and uses the catalyst olefinic polymerization, prepares liganded The technique of object is closed with embodiment 1, the difference is that:

(1) procatalyst compound 6 of meeting formula I is prepared

According to the method for embodiment 1, ligand compound 6 and 0.29g (1mmol) vanadous bromide of 0.43g meeting formula II is anti- It answers, obtains 0.37g catalyst 6 (Cat.6).1H NMR (600MHz, CDCl3): δ 7.51 (4H, m), δ 7.38 (2H, t), δ 7.07-7.25 (5H, m), δ 6.67-6.98 (4H, m), δ 6.64 (2H, t), δ 6.57 (2H, d), δ 0.70 (6H, s)； Anal.Calcd. (%) for C26H26N2PVBr (636): C, 49.06；H,4.09；N,4.40；found:C,49.07；H, 4.15；N,4.42.

(2) it is catalyzed propylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 7mg major catalyst, 100ml n-hexane, 5ml tri- are sequentially added Aluminium isobutyl solution (1M).Three times, temperature rises to 35 DEG C, propylene pressure 2.8MPa for ventilation, polymerize 80min.With containing 10% salt The ethanol solution of acid terminates reaction, then filtering is dried in vacuo for 24 hours obtained polymer with ethanol washing 3 times at 50 DEG C.

(3) it is catalyzed copolymerization of propylene

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 6mg major catalyst is sequentially added, 100ml toluene, 4ml tri- is different Butyl aluminum solutions (1M), 6ml styrene.Three times, temperature rises to 35 DEG C for ventilation, keeps the propylene pressure and 2.4MPa of 2.8MPa Ethylene pressure, polyase 13 0min.Reaction is terminated with the ethanol solution containing 10% hydrochloric acid, filtering washes obtained polymer with ethyl alcohol It washs 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

Embodiment 7

The embodiment is prepared for procatalyst compound, and uses the catalyst olefinic polymerization, prepares liganded The technique of object is closed with embodiment 1, the difference is that:

(1) procatalyst compound 7 of meeting formula I is prepared

According to the method for embodiment 1, ligand compound 7 and 0.24g (1mmol) Nickel Chloride of 0.43g meeting formula II is anti- It answers, obtains 0.49g catalyst 7 (Cat.7).1H NMR (600MHz, CDCl3): δ 7.49 (4H, m), δ 7.39 (2H, t), δ 7.00-7.26 (5H, m), δ 6.68-6.96 (4H, m), δ 6.66 (2H, t), δ 6.57 (2H, d), δ 0.69 (6H, s)； Anal.Calcd. (%) for C26H26N2PNiCl (519): C, 60.12；H,5.01；N,5.39；found:C,60.11；H, 5.08；N,5.43.

(2) catalyzed ethylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 6mg major catalyst is sequentially added, 100ml toluene, 4mlMAO is molten Liquid (10wt%).Three times, temperature rises to 55 DEG C, ethylene pressure 0.8MPa for ventilation, polymerize 120min.With the second for containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering obtained polymer with ethanol washing 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

(3) it is catalyzed ethylene copolymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 6mg major catalyst is sequentially added, 100ml toluene, 6mlMAO is molten Liquid (10wt%), 6ml propylene cyanogen.Three times, temperature rises to 55 DEG C for ventilation, keeps the ethylene pressure of 0.8MPa, polymerize 10min.With Ethanol solution containing 10% hydrochloric acid terminates reaction, and filtering is then true at 50 DEG C obtained polymer with ethanol washing 3 times Sky is dry for 24 hours.

Embodiment 8

The embodiment is prepared for procatalyst compound, and uses the catalyst olefinic polymerization, prepares liganded The technique of object is closed with embodiment 1, the difference is that:

(1) procatalyst compound 8 of meeting formula I is prepared

According to the method for embodiment 1, under nitrogen protection, the ligand compound 8 of 0.45g meeting formula II is dissolved in 30mL first Benzene adds 0.19mL (1.7mmol) titanium tetrachloride, is warming up to 50 DEG C, reacts 8h.Vacuum extract solvent, residue use just oneself Alkane washs 3 times, drains, obtains 0.52g catalyst 8 (Cat.8).1H NMR (600MHz, CDCl3): δ 7.46 (4H, m), δ 7.38 (4H, t), δ 7.25 (4H, m), δ 7.03 (1H, t), δ 6.82-6.97 (4H, t), δ 6.55 (1H, m), δ 2.42 (6H, s)；δ0.48 (6H,s)；Anal.Calcd. (%) for C28H30N2PTiCl2:C, 55.35；H,4.94；N,4.61；found:C,55.36； H,4.98；N,4.67.

(2) it is catalyzed propylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 7mg major catalyst is sequentially added, 100ml toluene, 9mlMAO is molten Liquid (10wt%).Three times, temperature rises to 50 DEG C, propylene pressure 3.1MPa for ventilation, polymerize 120min.With the second for containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering obtained polymer with ethanol washing 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

(3) it is catalyzed copolymerization of propylene

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 6mg major catalyst is sequentially added, 100ml toluene, 5mlMAO is molten Liquid (10wt%), 5ml 3-methyl-1-butene.Three times, temperature rises to 50 DEG C for ventilation, keeps the propylene pressure of 3.1MPa, polymerize 10min.Reaction is terminated with the ethanol solution containing 10% hydrochloric acid, filtering obtained polymer with ethanol washing 3 times, then exists It is dried in vacuo for 24 hours at 50 DEG C.

Embodiment 9

The embodiment is prepared for procatalyst compound, and uses the catalyst olefinic polymerization, prepares liganded The technique of object is closed with embodiment 1, the difference is that:

(1) procatalyst compound 9 of meeting formula I is prepared

According to the method for embodiment 1, ligand compound 9 and 0.23g (1mmol) zirconium chloride of 0.45g meeting formula II is anti- It answers, obtains 0.44g catalyst compounds 9 (Cat.9).1H NMR (600MHz, CDCl): δ 7.49 (4H, m), δ 7.37 (4H, t), δ 7.25 (4H, m), δ 7.01 (1H, t), δ 6.81-6.96 (4H, t), δ 6.54 (1H, m), δ 2.43 (6H, s), δ 0.48 (6H, s)； Anal.Calcd. (%) for C28H30N2PZrCl2:C, 51.61；H,4.61；N,4.30；found:C,51.67；H,4.62； N,4.35。

(2) catalyzed ethylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 10mg major catalyst, 100ml toluene, 10mlMAO are sequentially added Solution (10wt%).Three times, temperature rises to 40 DEG C, ethylene pressure 0.8MPa for ventilation, polymerize 100min.With containing 10% hydrochloric acid Ethanol solution terminates reaction, and filtering obtained polymer with ethanol washing 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

(3) it is catalyzed ethylene copolymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 6mg major catalyst is sequentially added, 100ml toluene, 6mlMAO is molten Liquid (10wt%), 6ml 4-methyl-1-pentene.Three times, temperature rises to 40 DEG C for ventilation, keeps the ethylene pressure of 0.8MPa, polymerize 30min.Reaction is terminated with the ethanol solution containing 10% hydrochloric acid, filtering obtained polymer with ethanol washing 3 times, then exists It is dried in vacuo for 24 hours at 50 DEG C.

Embodiment 10

The embodiment is prepared for procatalyst compound, and uses the catalyst olefinic polymerization, prepares liganded The technique of object is closed with embodiment 1, the difference is that:

(1) procatalyst compound 10 of meeting formula I is prepared

According to the method for embodiment 1, ligand compound 10 and 0.20g (1mmol) yttrium trichloride of 0.45g meeting formula II is anti- It answers, obtains 0.46g catalyst compounds 10 (Cat.10).1H NMR (600MHz, CDCl3): δ 7.47 (4H, m), δ 7.38 (4H, T), δ 7.21 (4H, m), δ 7.02 (1H, t), δ 6.85-6.96 (4H, t), δ 6.53 (1H, m), δ 2.47 (6H, s), δ 0.49 (6H, s)；Anal.Calcd. (%) for C28H30N2PYCl:C, 54.81；H,4.89；N,4.57；found:C,54.82；H, 4.87；N,4.54.

(2) catalyzed ethylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 6mg major catalyst, 100ml toluene, tri- second of 8ml are sequentially added Base aluminum solutions (1M).Three times, temperature rises to 40 DEG C, ethylene pressure 0.6MPa for ventilation, polymerize 120min.With containing 10% hydrochloric acid Ethanol solution terminates reaction, and filtering obtained polymer with ethanol washing 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

(3) it is catalyzed ethylene copolymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 6mg major catalyst, 100ml toluene, tri- second of 7ml are sequentially added Base aluminum solutions (1M), 5ml propylene cyanogen.Three times, temperature rises to 40 DEG C for ventilation, keeps the ethylene pressure of 0.6MPa, polymerize 10min. Reaction, filtering, obtained polymer with ethanol washing 3 times, then at 50 DEG C are terminated with the ethanol solution containing 10% hydrochloric acid Vacuum drying is for 24 hours.

Embodiment 11

The embodiment is prepared for procatalyst compound, and uses the catalyst olefinic polymerization, prepares liganded The technique of object is closed with embodiment 1, the difference is that:

(1) procatalyst compound 11 of meeting formula I is prepared

According to the method for embodiment 1, ligand compound 11 and 0.25g (1mmol) neodymium trichloride of 0.45g meeting formula II is anti- It answers, obtains 0.43g catalyst compounds 11 (Cat.11).1H NMR (600MHz, CDCl3): δ 7.48 (4H, m), δ 7.37 (4H, T), δ 7.24 (4H, m), δ 7.02 (1H, t), δ 6.83-6.95 (4H, t), δ 6.56 (1H, m) δ 2.47 (6H, s), δ 0.48 (6H, s)；Anal.Calcd. (%) for C28H30N2PNdCl:C, 50.30；H,4.49；N,4.19；found:C,50.38；H, 4.45；N,4.25.

(2) catalyzed ethylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 6mg major catalyst is sequentially added, 100ml toluene, 7mlMAO is molten Liquid (10wt%).Three times, temperature rises to 80 DEG C, ethylene pressure 0.8MPa for ventilation, polymerize 90min.With the second for containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering obtained polymer with ethanol washing 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

(3) it is catalyzed ethylene copolymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 6mg major catalyst is sequentially added, 100ml toluene, 7mlMAO is molten The 1- octene of liquid (10wt%), 6ml propylene cyanogen and 10ml.Three times, temperature rises to 80 DEG C, keeps the ethylene pressure of 0.8MPa for ventilation Power polymerize 20min.Reaction is terminated with the ethanol solution containing 10% hydrochloric acid, is filtered, obtained polymer with ethanol washing 3 times, Then it is dried in vacuo for 24 hours at 50 DEG C.

Embodiment 12

The embodiment is prepared for procatalyst compound, and uses the catalyst olefinic polymerization, prepares liganded The technique of object is closed with embodiment 1, the difference is that:

(1) procatalyst compound 12 of meeting formula I is prepared

According to the method for embodiment 1, ligand compound 12 and 0.21g (1mmol) rhodium chloride of 0.45g meeting formula II is anti- It answers, obtains 0.37g catalyst 12 (Cat.12).1H NMR (600MHz, CDCl3): δ 7.46 (4H, m), δ 7.37 (4H, t), δ 7.25 (4H, m), δ 7.04 (1H, t), δ 6.85-6.95 (4H, t), δ 6.53 (1H, m), δ 2.42 (6H, s), δ 0.49 (6H, s)； Anal.Calcd. (%) for C28H30N2PRhCl:C, 53.59；H,4.78；N,4.47；found:C,53.55；H,4.72； N,4.46。

(2) it is catalyzed propylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 9mg major catalyst is sequentially added, 100ml toluene, 7mlMAO is molten Liquid (10wt%).Three times, temperature rises to 50 DEG C, propylene pressure 2.7MPa for ventilation, polymerize 120min.With the second for containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering obtained polymer with ethanol washing 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

(3) it is catalyzed copolymerization of propylene

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 6mg major catalyst is sequentially added, 100ml toluene, 6mlMAO is molten The 1- hexene of liquid (10wt%), 5ml propylene cyanogen and 10ml.Three times, temperature rises to 45 DEG C, keeps the propylene pressure of 2.7MPa for ventilation Power polymerize 10min.Reaction is terminated with the ethanol solution containing 10% hydrochloric acid, is filtered, obtained polymer with ethanol washing 3 times, Then it is dried in vacuo for 24 hours at 50 DEG C.

Embodiment 13

The embodiment is prepared for procatalyst compound, and uses the catalyst olefinic polymerization, prepares liganded The technique of object is closed with embodiment 1, the difference is that:

(1) procatalyst compound 13 of meeting formula I is prepared

According to the method for embodiment 1, ligand compound 13 and 0.18g (1mmol) cobaltous dichloride of 0.45g meeting formula II is anti- It answers, obtains 0.35g catalyst 13 (Cat.13).1H NMR(600MHz,CDCl3):δ7.46(4H,m),δ7.37(4H,t),δ 7.22 (4H, m), δ 7.06 (1H, t), δ 6.88-6.97 (4H, t), δ 6.53 (1H, m), δ 2.49 (6H, s), δ 0.48 (6H, s)； Anal.Calcd. (%) for C28H30N2PCoCl:C, 56.47；H,5.04；N,4.71；found:C,56.48；H,5.01； N,4.73。

(2) catalyzed ethylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 7mg major catalyst is sequentially added, 100ml toluene, 7mlMAO is molten Liquid (10wt%).Three times, temperature rises to 50 DEG C, ethylene pressure 0.6MPa for ventilation, polymerize 120min.With the second for containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering obtained polymer with ethanol washing 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

(3) it is catalyzed ethylene copolymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 6mg major catalyst is sequentially added, 100ml toluene, 8mlMAO is molten Liquid (10wt%), 7ml methyl methacrylate.Ventilation three times, temperature rises to 45 DEG C, keep 0.6MPa ethylene pressure and The propylene pressure of 0.7MPa polymerize 10min.Reaction, filtering, obtained polymer are terminated with the ethanol solution containing 10% hydrochloric acid With ethanol washing 3 times, then it is dried in vacuo for 24 hours at 50 DEG C.

Embodiment 14

The embodiment is prepared for procatalyst compound, and uses the catalyst olefinic polymerization, prepares liganded The technique of object is closed with embodiment 1, the difference is that:

(1) procatalyst compound 14 of meeting formula I is prepared

According to the method for embodiment 1, the ligand compound 14 of 0.45g meeting formula II is reacted with 0.24g hafnium tetrachloride, is obtained 0.39g catalyst 14 (Cat.14).1H NMR (600MHz, CDCl3): δ 7.46 (4H, m), δ 7.37 (4H, t), δ 7.23 (4H, M), δ 7.05 (1H, t), δ 6.82-6.96 (4H, t), δ 6.53 (1H, m), δ 2.48 (6H, s), δ 0.49 (6H, s)； Anal.Calcd. (%) for C28H30N2PHfCl2:C, 61.43；H,5.48；N,5.12；found:C,61.45；H,5.51； N,5.16。

(2) catalyzed ethylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 5mg major catalyst is sequentially added, 100ml toluene, 7mlMAO is molten Liquid (10wt%).Three times, temperature rises to 30 DEG C, ethylene pressure 0.7MPa for ventilation, polymerize 130min.With the second for containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering obtained polymer with ethanol washing 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

(3) it is catalyzed ethylene copolymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 5mg major catalyst is sequentially added, 100ml toluene, 7mlMAO is molten Liquid (10wt%), 6ml methyl acrylate.Three times, temperature rises to 30 DEG C for ventilation, keeps the ethylene pressure of 0.7MPa, polymerize 40min.Reaction is terminated with the ethanol solution containing 10% hydrochloric acid, filtering obtained polymer with ethanol washing 3 times, then exists It is dried in vacuo for 24 hours at 50 DEG C.

Embodiment 15

The embodiment is prepared for procatalyst compound, and uses the catalyst olefinic polymerization, prepares liganded The technique of object is closed with embodiment 1, the difference is that:

(1) procatalyst compound 15 of meeting formula I is prepared

According to the method for embodiment 1, under nitrogen protection, the ligand compound 15 of 0.48g meeting formula II is dissolved in 30mL In toluene, 0.22mL (2mmol) titanium tetrachloride is added, is warming up to 50 DEG C, reacts 4h.Vacuum extracts solvent, and residue is with just Hexane washs 3 times, drains, obtains 0.51g catalyst 15 (Cat.15).1H NMR(600MHz,DMSO-d6):δ7.75-7.81 (4H, m), δ 7.23-7.45 (6H, m), δ 7.06 (2H, m), δ 6.78 (1H, d), δ 6.76 (2H, d), δ 6.59 (2H, t), δ 0.15 (6H, s), Anal.Calcd. (%) for C26H23F3N2PTiCl2:C, 49.25；H,3.13；N,4.42；found:C, 49.26；H,3.17；N,4.48.

(2) catalyzed ethylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 5mg major catalyst is sequentially added, 100ml heptane, 7ml tri- is just Hexyl aluminum solutions (1M).Three times, temperature rises to 65 DEG C, ethylene pressure 0.9MPa for ventilation, polymerize 120min.With containing 10% hydrochloric acid Ethanol solution terminate reaction, filtering, obtained polymer with ethanol washing 3 times, be then dried in vacuo for 24 hours at 50 DEG C.

(3) it is catalyzed ethylene copolymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 5mg major catalyst is sequentially added, 100ml toluene, 7ml tri- is just Hexyl aluminum solutions (1M), 5ml ethyl acrylate.Three times, temperature rises to 65 DEG C for ventilation, keeps the ethylene pressure of 0.9MPa, polymerize 10min.Reaction is terminated with the ethanol solution containing 10% hydrochloric acid, filtering obtained polymer with ethanol washing 3 times, then exists It is dried in vacuo for 24 hours at 50 DEG C.

Embodiment 16

The embodiment is prepared for procatalyst compound, and uses the catalyst olefinic polymerization, prepares liganded The technique of object is closed with embodiment 1, the difference is that:

(1) procatalyst compound 16 of meeting formula I is prepared

According to the method for embodiment 1, the ligand compound 16 of 0.48g meeting formula II is reacted with 0.23g zirconium chloride, is obtained 0.53g catalyst 16 (Cat.16).1H NMR(600MHz,DMSO-d6):δ7.74-7.86(4H,m),δ7.25-7.46(6H, m),δ7.04(2H,m),δ6.79(1H,d),δ6.77(2H,d),δ6.61(2H,t),δ0.14(6H,s)；Anal.Calcd. (%) for C26H23F3N2PZrCl2:C, 46.12；H,3.4；N,4.14；found:C,46.17；H,3.9；N,4.13.

(2) it is catalyzed propylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 5mg major catalyst is sequentially added, 100ml toluene, 7mlMAO is molten Liquid (10wt%).Three times, temperature rises to 55 DEG C, propylene pressure 3.2MPa for ventilation, polymerize 120min.With the second for containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering obtained polymer with ethanol washing 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

(3) it is catalyzed copolymerization of propylene

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 9mg major catalyst, 100ml toluene, 11mlMAO are sequentially added Solution (10wt%), 6ml 1- certain herbaceous plants with big flowers alkene.Three times, temperature rises to 55 DEG C, keeps the propylene pressure of 3.2MPa, polyase 13 0min for ventilation. Reaction, filtering, obtained polymer with ethanol washing 3 times, then at 50 DEG C are terminated with the ethanol solution containing 10% hydrochloric acid Vacuum drying is for 24 hours.

Embodiment 17

The embodiment is prepared for procatalyst compound, and uses the catalyst olefinic polymerization, prepares liganded The technique of object is closed with embodiment 1, the difference is that:

(1) procatalyst compound 17 of meeting formula I is prepared

According to the method for embodiment 1, the ligand compound 17 of 0.48g meeting formula II is reacted with 0.20g alchlor, is obtained 0.56g catalyst 17 (Cat.17).1H NMR(600MHz,DMSO-d6):δ7.78-7.92(4H,m),δ7.31-7.52(6H, M), δ 7.07 (2H, m), δ 6.81 (1H, d), δ 6.79 (2H, d), δ 6.58 (2H, t), δ 0.13 (6H, s)；Anal.Calcd. (%) for C26H23F3N2PAlCl:C, 46.26；H,3.41；N,4.15；found:C,46.23；H,3.42；N,4.11.

(2) catalyzed ethylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 8mg major catalyst is sequentially added, 100ml toluene, 5mlMAO is molten Liquid (10wt%).Three times, temperature rises to 50 DEG C, ethylene pressure 0.6MPa for ventilation, polymerize 120min.With the second for containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering obtained polymer with ethanol washing 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

(3) it is catalyzed ethylene copolymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 8mg major catalyst is sequentially added, 100ml toluene, 8mlMAO is molten Liquid (10wt%), 6ml styrene.Three times, temperature rises to 45 DEG C for ventilation, keeps the ethylene pressure of 0.6MPa, polymerize 10min.With Ethanol solution containing 10% hydrochloric acid terminates reaction, and filtering is then true at 50 DEG C obtained polymer with ethanol washing 3 times Sky is dry for 24 hours.

Embodiment 18

The embodiment is prepared for procatalyst compound, and uses the catalyst olefinic polymerization, prepares liganded The technique of object is closed with embodiment 1, the difference is that:

(1) procatalyst compound 18 of meeting formula I is prepared

According to the method for embodiment 1, the ligand compound 18 of 0.48g meeting formula II is reacted with 0.25g samarium trichloride, is obtained 0.49g catalyst compounds 18 (Cat.18).1H NMR(600MHz,DMSO-d6):δ7.75-7.87(4H,m),δ7.25- 7.50 (6H, m), δ 7.04 (2H, m), δ 6.81 (1H, d), δ 6.76 (2H d), δ 6.58 (2H, t), δ 0.14 (6H, s)； Anal.Calcd. (%) for C26H23F3N2PSmCl:C, 42.77；H,3.15；N,3.84；found:C,42.75；H, 3.16；N,3.87.

(2) catalyzed ethylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 5mg major catalyst is sequentially added, 100ml toluene, 5mlMAO is molten Liquid (10wt%).Three times, temperature rises to 45 DEG C, ethylene pressure 0.7MPa for ventilation, polymerize 120min.With the second for containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering obtained polymer with ethanol washing 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

(3) it is catalyzed ethylene copolymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 5mg major catalyst is sequentially added, 100ml toluene, 8mlMAO is molten Liquid (10wt%), 5ml 1- cyclobutenyl-N- acetyl group-l-tyrosine-ethyl ester.Three times, temperature rises to 45 DEG C for ventilation, keeps The ethylene pressure of 0.7MPa polymerize 10min.Reaction, filtering, obtained polymer are terminated with the ethanol solution containing 10% hydrochloric acid With ethanol washing 3 times, then it is dried in vacuo for 24 hours at 50 DEG C.

Embodiment 19

The embodiment is prepared for procatalyst compound, and uses the catalyst olefinic polymerization, prepares liganded The technique of object is closed with embodiment 1, the difference is that:

(1) procatalyst compound 19 of meeting formula I is prepared

According to the method for embodiment 1, the ligand compound 19 of 2.9g meeting formula II is reacted with 1g chloromethyl palladium, is obtained 3.4g catalyst compounds 19 (Cat.19).1H NMR(600MHz,DMSO-d6):δ7.77-7.92(4H,m),δ7.24-7.45 (6H,m),δ7.08(2H,m),δ6.79(1H,d),δ6.75(2H,d),δ6.57(2H,t),δ2.34(3H,s)δ0.15(6H, s)；Anal.Calcd. (%) for C26H23F3N2PPdCH3Cl:C, 50.90；H,3.75；N,4.57；found:C,50.92； H,3.75；N,4.53.

(2) catalyzed ethylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 14mg major catalyst, 100ml toluene, 5mlMAO are sequentially added Solution (10wt%).Three times, temperature rises to 50 DEG C, ethylene pressure 0.5MPa for ventilation, polymerize 120min.With containing 10% hydrochloric acid Ethanol solution terminates reaction, and filtering obtained polymer with ethanol washing 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

(3) it is catalyzed ethylene copolymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 9mg major catalyst is sequentially added, 100ml toluene, 8mlMAO is molten Liquid (10wt%), 6ml 1- hexenyl-N- acetyl group-l-tyrosine-ethyl ester.Three times, temperature rises to 50 DEG C for ventilation, keeps The ethylene pressure of 0.5MPa polymerize 10min.Reaction, filtering, obtained polymer are terminated with the ethanol solution containing 10% hydrochloric acid With ethanol washing 3 times, then it is dried in vacuo for 24 hours at 50 DEG C.

Embodiment 20

The embodiment is prepared for procatalyst compound, and uses the catalyst olefinic polymerization, prepares liganded The technique of object is closed with embodiment 1, the difference is that:

(1) procatalyst compound 20 of meeting formula I is prepared

According to the method for embodiment 1, the ligand compound 20 of 2.9g meeting formula II is reacted with mono- chloroethyl palladium of 1.6g, is obtained 4.8g catalyst 20 (Cat.20).1H NMR (600MHz, DMSO): δ 7.74-7.86 (4H, m), δ 7.25-7.48 (6H, m), δ 7.06(2H,m),δ6.79(1H,d),δ6.77(2H,d),δ6.59(2H,t),δ0.14(6H,s)；Anal.Calcd. (%) for C26H23F3N2PPdEtCl:C,45.09；H,3.32；N,4.05；found:C,45.10；H,3.33；N,4.06.

(2) catalyzed ethylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 14mg major catalyst, 80ml toluene, 10mlMAO are sequentially added Solution (10wt%).Three times, temperature rises to 45 DEG C, ethylene pressure 0.5MPa for ventilation, polymerize 100min.With containing 10% hydrochloric acid Ethanol solution terminates reaction, and filtering obtained polymer with ethanol washing 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

(3) it is catalyzed ethylene copolymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 10mg major catalyst, 100ml toluene, 6mlMAO are sequentially added Solution (10wt%), 6ml 4-methyl-1-pentene.Three times, temperature rises to 45 DEG C for ventilation, keeps the ethylene pressure of 0.5MPa, gathers Close 30min.Reaction is terminated with the ethanol solution containing 10% hydrochloric acid, is filtered, obtained polymer with ethanol washing 3 times, then It is dried in vacuo for 24 hours at 50 DEG C.

Embodiment 21

The embodiment is prepared for procatalyst compound, and uses the catalyst olefinic polymerization, prepares liganded The technique of object is closed with embodiment 1, the difference is that:

(1) procatalyst compound 21 of meeting formula I is prepared

According to the method for embodiment 1, the ligand compound 21 of 3.9g meeting formula II is reacted with 1.9g iron, is obtained 5.1g catalyst compounds 21 (Cat.21).1H NMR(600MHz,DMSO-d6):δ7.76-7.93(4H,m),δ7.28-7.53 (6H, m), δ 7.04 (2H, m), δ 6.78 (1H, d), δ 6.76 (2H, d), δ 6.57 (2H, t), δ 0.15 (6H, s)； Anal.Calcd. (%) for C26H23F3N2PFeCl (645): C, 48.41；H,3.57；N,4.34；found:C,48.44； H,3.58；N,4.38.

(2) it is catalyzed propylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 7mg major catalyst is sequentially added, 80ml toluene, 3mlMAO is molten Liquid (10wt%).Three times, temperature rises to 50 DEG C, propylene pressure 2.3MPa for ventilation, polymerize 120min.With the second for containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering obtained polymer with ethanol washing 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

(3) it is catalyzed copolymerization of propylene

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 9mg major catalyst is sequentially added, 100ml toluene, 2mlMAO is molten Liquid (10wt%), 5ml styrene.Three times, temperature rises to 50 DEG C for ventilation, keeps the propylene pressure of 2.3MPa, polymerize 10min.With Ethanol solution containing 10% hydrochloric acid terminates reaction, and filtering is then true at 50 DEG C obtained polymer with ethanol washing 3 times Sky is dry for 24 hours.

Embodiment 22

The embodiment is prepared for load type main catalyst, and uses the catalyst olefinic polymerization, and concrete technology is such as Under:

(1) preparation of load type main catalyst

Major catalyst in 3g embodiment 8 is dissolved in 45ml toluene, at 65 DEG C, with 0.02g (0.34mmol) titanium dioxide Pasc reaction 5 hours, solvent is removed, is washed four times with toluene, obtains loaded catalyst.ICP method measures titanium in gained catalyst Content is 4.4wt%.

(2) catalyzed ethylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 7mg major catalyst is sequentially added, 100ml toluene, 5mlMAO is molten Liquid (10wt%).Three times, temperature rises to 50 DEG C, ethylene pressure 0.5MPa for ventilation, polymerize 120min.With the second for containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering obtained polymer with ethanol washing 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

(3) it is catalyzed ethylene copolymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 7mg major catalyst is sequentially added, 100ml toluene, 5mlMAO is molten Liquid (10wt%), 6ml 1- hexenyl-N- acetyl group-l-tyrosine-ethyl ester.Three times, temperature rises to 50 DEG C for ventilation, keeps The ethylene pressure of 0.5MPa, polyase 13 0min.Reaction, filtering, obtained polymer are terminated with the ethanol solution containing 10% hydrochloric acid With ethanol washing 3 times, then it is dried in vacuo for 24 hours at 50 DEG C.

Embodiment 23

The embodiment is prepared for load type main catalyst, and uses the catalyst olefinic polymerization, and concrete technology is such as Under:

(1) preparation of load type main catalyst

Major catalyst in 4.2g (6mmol) embodiment 19 is dissolved in 40ml toluene, at 70 DEG C, with 0.03g (0.5mmol) silicon dioxde reaction 6 hours removes solvent, is washed five times with toluene, obtain loaded catalyst.ICP method is measured Gained Palladium Content in Catalyst is 3.3wt%.

(2) catalyzed ethylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 10mg major catalyst is sequentially added, 80ml toluene, 2mlMAO is molten Liquid (10wt%).Three times, temperature rises to 45 DEG C, ethylene pressure 0.5MPa for ventilation, polymerize 100min.With the second for containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering obtained polymer with ethanol washing 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

(3) it is catalyzed ethylene copolymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 10mg major catalyst, 100ml toluene, 2mlMAO are sequentially added Solution (10wt%), 6ml 4-methyl-1-pentene.Three times, temperature rises to 45 DEG C for ventilation, keeps the ethylene pressure of 0.5MPa, gathers Close 30min.Reaction is terminated with the ethanol solution containing 10% hydrochloric acid, is filtered, obtained polymer with ethanol washing 3 times, then It is dried in vacuo for 24 hours at 50 DEG C.

Embodiment 24

The embodiment is prepared for load type main catalyst, and uses the catalyst olefinic polymerization, and concrete technology is such as Under:

(1) preparation of load type main catalyst

Major catalyst in 2.3g (4mmol) embodiment 7 is dissolved in 30ml ethyl alcohol, at 70 DEG C, with 0.38g (4mmol) Magnesium chloride 3 hours, solvent is removed, is washed six times with toluene, obtains loaded catalyst.ICP method measures gained catalyst Middle nickel content is 3.8wt%.

(2) it is catalyzed propylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 7mg major catalyst is sequentially added, 80ml toluene, 2mlMAO is molten Liquid (10wt%).Three times, temperature rises to 50 DEG C, propylene pressure 2.3MPa for ventilation, polymerize 120min.With the second for containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering obtained polymer with ethanol washing 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

(3) it is catalyzed copolymerization of propylene

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 7mg major catalyst is sequentially added, 100ml toluene, 2mlMAO is molten Liquid (10wt%), 5ml styrene.Three times, temperature rises to 50 DEG C, keeps the propylene pressure of 2.3MPa, polyase 13 0min for ventilation.With Ethanol solution containing 10% hydrochloric acid terminates reaction, and filtering is then true at 50 DEG C obtained polymer with ethanol washing 3 times Sky is dry for 24 hours.

Comparative example 1

The comparative example selects catalyst in the prior art, and uses the catalyst olefinic polymerization, concrete technology It is as follows:

(1) major catalyst

Major catalyst structure is as follows:

Wherein X is chlorine atom, and M Ti, R are methyl, have carbon atom on main ring.

(2) catalyzed ethylene polymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 5mg major catalyst is sequentially added, 100ml toluene, 5mlMAO is molten Liquid (10wt%).Three times, temperature rises to 60 DEG C, ethylene pressure 1.2MPa for ventilation, polymerize 120min.With the second for containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering obtained polymer with ethanol washing 4 times, is then dried in vacuo 12h at 40 DEG C.

(3) it is catalyzed ethylene copolymerization

Under the conditions of anhydrous and oxygen-free, in 300ml reaction flask, 5mg major catalyst is sequentially added, 100ml toluene, 5mlMAO is molten Liquid (10wt%), 5ml 1- butylene.Three times, temperature rises to 60 DEG C for ventilation, keeps the propylene pressure of 1.2MPa, polymerize 50min.With Ethanol solution containing 10% hydrochloric acid terminates reaction, and filtering is then true at 40 DEG C obtained polymer with ethanol washing 4 times The dry 12h of sky.

The catalyst olefinic polymerization of embodiment and comparative example the results are shown in Table 2.

Table 2

As shown in table 2, compared with comparative example 1, catalyst made from embodiment 1 to 24 is when being catalyzed ethylene or propylene homo There is higher catalytic activity, it is same when being catalyzed ethylene or propylene with alpha-olefin or polarity vinyl monomer copolymerization to have higher catalysis Activity.The data provided from table 2 can be seen that not only can be high using catalyst made from method provided by the embodiments of the present application The monomer homopolymerization of catalyzed alkene class is imitated, can be copolymerized with efficient catalytic olefin monomer.

It can be seen from the above description that the above embodiments of the present invention realized the following chievements: the present invention mentions The structure of the compound of confession is shown in formula I, main ring not carbon atoms, by three hetero atoms (P, N, P) and transition metal atoms Composition.This full heterocyclic compound can effectively be catalyzed ethylene homo conjunction, propylene homo closes, ethylene as non-metallocene catalyst With alpha-olefin copolymer conjunction, propylene and alpha-olefin copolymer conjunction, ethylene and the conjunction of polarity vinyl monomer copolymerization or propylene and polarity alkenes list Body combined polymerization, catalyst activity are high.At the same time, this full heterocyclic compound can also be easy to be supported on carrier, preparation At loaded catalyst, so as to be widely used in different types of olefin polymerization, efficient catalytic olefinic polymerization is anti- It answers.

The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.

Claims (16)

1. a kind of non-metallocene compound, which is characterized in that the structure of the compound is shown in formula I:

In the Formulas I, the R₁The aryl of the naphthenic base of linear or branched alkyl group, C3~C20 selected from C1~C20, C6~C20； The R₂With the R₃Be respectively and independently selected from hydrogen atom, the linear or branched alkyl group of C1~C20, the naphthenic base of C3~C20, C6~ The aryl of C20；The X is selected from F, Cl, Br, I or C1~C20 linear or branched alkyl group；M is selected from the IIIth B, IV B, VB or VIII race Any transition metal atoms in element.

2. compound according to claim 1, which is characterized in that the X is selected from Cl, Br, methyl or ethyl.

3. compound according to claim 1 or 2, which is characterized in that the M be titanium, zirconium, hafnium, vanadium, rhodium, iron, nickel, cobalt, Neodymium, palladium or yttrium.

4. a kind of preparation method of compound described in any one of claims 1 to 3, which is characterized in that the preparation method The following steps are included: ligand compound is reacted with transistion metal compound, the compound of Formulas I is obtained, wherein described liganded The structure of object is closed as shown in Formula II:

In the Formula II, the R₁The virtue of the naphthenic base of linear or branched alkyl group, C3~C20 selected from C1~C20, C6~C20 Base；The R₂With the R₃It is respectively and independently selected from hydrogen atom, the linear or branched alkyl group of C1~C20, the naphthenic base of C3~C20, C6 The aryl of~C20；

The transistion metal compound is MXn, wherein the X is selected from F, Cl, Br, I or C1~C20 linear or branched alkyl group； Any transition metal atoms of the M in the IIIth B, IV B, VB or VIII race's element, n are the positive integer no more than 4.

5. the preparation method according to claim 4, which is characterized in that in the reaction process, the ligand compound with The molar ratio of the transistion metal compound is 1:1~2, and the preferably described ligand compound rubs with the transistion metal compound You are than being 1:1~1.5.

6. preparation method according to claim 4 or 5, which is characterized in that the reaction temperature of the reaction process is 0~90 DEG C, preferably 30~70 DEG C；Reaction time is 1~10 hour, preferably 2~5 hours.

7. the preparation method according to any one of claim 4 to 6, which is characterized in that the reaction is organic molten first It is carried out in agent, the first preferably described organic solvent is selected from the saturated hydrocarbons of C5~C15, the alicyclic of C5~C10, C6~C15 One of saturated heterocyclic hydrocarbon of aromatic hydrocarbon and C2~C10 is a variety of.

8. the preparation method according to any one of claim 4 to 6, which is characterized in that by the ligand compound with Before the step of transistion metal compound is reacted, the preparation method further include:

By primary amino-compound R₁-NH₂, Grignard Reagent and the second organic solvent mix and reacted, obtain pre-reaction object；

By the pre-reaction object, the first organic phosphorus compound R₂-PX’₂And the second organic phosphorus compound R₃-PX’₂It mixes and carries out anti- It answers, obtains the ligand compound；

Wherein the first organic phosphorus compound R₂-PX’₂And the second organic phosphorus compound R₃-PX’₂In X ' be that halogen is former Son.

9. preparation method according to claim 8, which is characterized in that by the primary amino-compound R₁-NH₂, grignard examination In the step of agent and second organic solvent are mixed and are reacted, reaction temperature be 0~70 DEG C, preferably 10~50 DEG C, Reaction time is 1~10 hour, preferably 2~4 hours；By the pre-reaction object, the first organic phosphorus compound R₂-PX’₂ And the second organic phosphorus compound R₃-PX’₂In the step of mixing and being reacted, reaction temperature be 0~70 DEG C, preferably 10 ~50 DEG C, the reaction time is 1~5 hour, preferably 2~4 hours.

10. preparation method according to claim 8 or claim 9, which is characterized in that second organic solvent is selected from C5~C15 Saturated hydrocarbons, the alicyclic of C5~C10, the aromatic hydrocarbon of C6~C15, the saturated heterocyclic hydrocarbon of C2~C10 or the above solvent composition Mixed solvent.

11. a kind of olefin polymerization catalysis, including major catalyst and co-catalyst, which is characterized in that the major catalyst is power Benefit require any one of 1 to 3 described in compound.

12. olefin polymerization catalysis according to claim 11, which is characterized in that the co-catalyst is organometallic aluminium Compound；It is preferred that the organic metal aluminium compound is alkyl aluminum or alkylaluminoxane；The more preferable organometallic aluminium chemical combination Object is one of trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum and methylaluminoxane or a variety of.

13. olefin polymerization catalysis according to claim 11 or 12, which is characterized in that the co-catalyst and the master The molar ratio of catalyst is 100~5000:1, preferably 150~1000:1.

14. olefin polymerization catalysis according to claim 11 or 12, which is characterized in that the olefin polymerization catalysis is also Including catalyst carrier, the major catalyst is supported in the catalyst carrier；Preferably, the catalyst carrier is inorganic Oxide or inorganic halides；The more preferable inorganic oxide is silica, aluminium oxide, the more preferable inorganic halides For magnesium chloride.

15. olefin polymerization catalysis answering in catalysed olefin polymerization described in a kind of any one of claim 11 to 14 With.

16. application according to claim 15, which is characterized in that the olefin polymerization is following any: ethylene Homopolymerization, the homopolymerization of propylene, the combined polymerization of ethylene and alpha-olefin, propylene and alpha-olefin combined polymerization, ethylene and polarity alkene The combined polymerization of class monomer, the combined polymerization of propylene and polarity vinyl monomer.