CN108264588A

CN108264588A - A kind of major catalyst of olefin polymerization catalysis and preparation method thereof, olefin polymerization catalysis

Info

Publication number: CN108264588A
Application number: CN201611257991.7A
Authority: CN
Inventors: 王科峰; 义建军; 孙天旭; 袁苑; 李荣波; 黄启谷; 王帆; 王静; 李志飞
Original assignee: China Petroleum and Natural Gas Co Ltd
Current assignee: China Petroleum and Natural Gas Co Ltd
Priority date: 2016-12-30
Filing date: 2016-12-30
Publication date: 2018-07-10

Abstract

Olefin polymerization catalysis the present invention relates to a kind of major catalyst of olefin polymerization catalysis and preparation method thereof and comprising the major catalyst.The major catalyst of the olefin polymerization catalysis is full heterocycle non-metallocene compound, shown in the structure such as formula (1) of the compound：In formula, R₁And R₂The one kind being respectively and independently selected from the aryl of the alkyl of C1 C20, the cycloalkyl of C3 C20 and C6 C20；R₃Or R₄One kind that is identical or different, being respectively and independently selected from the aryl of hydrogen atom, the alkyl of C1 C20, the cycloalkyl of C3 C20 and C6 C20；One kind in alkyl of the X selected from halogen and C1 C20；M is transition metal atoms, one kind in III B races, IV B races, VB races and VIII race's element.

Description

A kind of major catalyst of olefin polymerization catalysis and preparation method thereof, olefinic polymerization are urged Agent

Technical field

The invention belongs to olefin polymerization catalysis and olefin coordination polymerization field, and in particular to for ethylene or propylene homo The major catalyst of the olefin polymerization catalysis of conjunction, ethylene/alpha-olefin combined polymerization or propylene/alpha-olefins combined polymerization and its preparation side Method, the olefin polymerization catalysis comprising the major catalyst.

Background technology

Non-metallocene catalyst is because its activated centre is single, the activity of catalyst, the stereoregularity of polymer, molecular weight And molecular weight distribution such as can be controlled to receive significant attention at the characteristics by changing ligand structure；It is and non-metallocene catalyzed The excellent properties of the polymer of agent synthesis have obtained consistent accreditation.

Polyolefin products have many advantages that such as easy processing, thermal stability is good, against weather is good, chemical resistance is good And validity period limit for length etc., it is deep to be welcome by market.But polyolefin (such as PE, PP etc.) resistance to low temperature is poor, crystallinity is high, causes Its application range is restricted.If a certain number of high alpha-olefins (such as 1- octenes) are inserted into molecular polyolefin chain Block copolymer is prepared into, significant change will occur for the structure and performance of polyolefin：It can make density polymer than common polyene Hydrocarbon it is lower, density is in 0.85~0.92g/cm³Between；Glass transition temperature is low, and resistance to low temperature is good, and disperses Property, weatherability, flexibility, flexibility and processing performance are good.The performance ratio ethylene/propene copolymer of ethylene/1- octene copolymers And the superior performance of Ethylene/1-butene copolymer, ethylene/1- octene copolymers replace ethylene/propene copolymer and ethylene/1- fourths The epoch of alkene copolymer are at hand.

Non-metallocene catalyst comes across nineteen nineties, the coordination atom of this kind of catalyst is nitrogen, phosphorus, oxygen, Sulphur etc., the oxytropism of central metal atom is weaker, the copolymerization of alkene and polar monomer easy to implement, so as to which synthesis performance is excellent Functional polyolefinic material.In addition, the design of non-metallocene catalyst ligand structure and synthesis changeability are big.It is from once occurring Fast development, and it is constantly subjected to people's attention.

Containing the complex that hetero atom is more in agent structure, relative to containing only single heteroatomic complex (such as containing only oxygen, Nitrogen etc.), there are more changeabilities in structure, adjust the space bigger of polymer architecture and performance.At present, more non-cyclopentadienyl is studied Ligand has the structures such as [N, N], [N, O], [N, N, O], [P, N, N], [P, N, P], [O, N, N, O], [N, N, O, O].

Ma Lifu [Ma L F, et al.Journal Polymer Science:Part A:Polymer Chemistry, 2008,46:33；Ma L F,et al.Journal Polymer Science:Part A:Polymer Chemistry, 2010,48:417] a series of [N, N] heterocycle non-metallocene compounds are prepared for, it, can be with efficient catalytic ethylene after MAO is activated Polymerization and ethylene/1- hervene copolymers close, and obtain wide/double peak polyethylene.

Keim[George J.P et al.Journal of Molecular Catalysis A:Chemical 110 (1996):77-87] synthesis [N, O], [P, O], [O, O], [S, O] class palladium catalyst, styrene catalyzed and ethylene copolymerization, The relationship between the structure of catalyst ligand and catalytic activity is had studied, [P, O] ligand catalyst activity highest.

Sun Wenhua has synthesized a series of containing [N, N] amino indole class catalyst [Zhang W J, et al.J of Organometallic Chem.2006,691:4759-4767], [N, N, O] pyridyl group salicyl catalyst [Shaofeng Liu,et al.Journal of Polymer Science:Part A:Polymer Chemistry,2008,46:3411- 3423], [P, N, N] and [P, N, P] class catalyst [Hou J X, et al.Organometallics, 2006,25:236- 244], for catalyzed ethylene polymerization, there is certain activity.

Patent 200310108556 reports a kind of complex containing [O, N, N, O] type ligand as olefinic polymerization catalysis Agent, the catalytic activity of catalyst is 10⁵gPE/molTi.h。

Patent CN102030843 discloses a kind of olefinic polymerization non cyclopentadienyl catalyst for containing [N, N, O, O] structure ligand.Catalysis During olefinic polymerization, there is preferable catalytic activity to ethylene homo, ethylene/alpha-olefin, ethylene/polar monomer copolymerization.

It is all former containing carbon atom, hetero atom and transition metal in the main ring structure of non-metallocene catalyst disclosed above Son.

Invention content

The purpose of the present invention is to provide a kind of full heterocycle Nonmetallocenes of major catalyst as olefin polymerization catalysis Compound and preparation method thereof and the olefin polymerization catalysis comprising the major catalyst, above-mentioned olefin polymerization catalysis are used for Catalyzed alkene homopolymerization reaction or alpha-olefinic copolymerization reaction, such as ethylene homo conjunction, propylene homo conjunction, ethylene and alpha-olefin Combined polymerization, propylene and alpha-olefin copolymer conjunction, ethylene and the conjunction of polarity vinyl monomer copolymerization or propylene and polarity vinyl monomer copolymerization are closed.

In order to achieve the above object, one aspect of the present invention provides a kind of major catalyst of olefin polymerization catalysis, should Major catalyst is full heterocycle non-metallocene compound, shown in the structure such as formula (1) of the compound：

In formula, R₁And R₂One be respectively and independently selected from the aryl of the alkyl of C1-C20, the cycloalkyl of C3-C20 and C6-C20 Kind；R₃Or R₄It is identical or different, it is respectively and independently selected from the virtue of hydrogen atom, the alkyl of C1-C20, the cycloalkyl of C3-C20 and C6-C20 One kind in base；One kind in alkyl of the X selected from halogen and C1-C20；M is transition metal atoms, selected from III B races, IV B races, VB One kind in race and VIII race's element.

The major catalyst of olefin polymerization catalysis of the present invention, the X in the formula (1) be preferably Cl, Br, methyl or Ethyl.

The major catalyst of olefin polymerization catalysis of the present invention, the M in the formula (1) be preferably titanium, zirconium, hafnium, vanadium, Rhodium, iron, nickel, cobalt, neodymium, palladium or yttrium.

In the formula (1), M, X, R₁、R₂、R₃And R₄It is respectively provided with following each group and defines (being shown in Table 1)：

Accord with Formula (1) listed by table 1

Table 1

Compound listed by the compound and table 1 that formula (1) is included be full heterocycle non-metallocene compound, main ring structure The full heterocycle being made of Si, N, N and transition metal atoms M carries multiple substituent groups on ring.

Another aspect of the present invention, the present invention provide a kind of preparation method of the major catalyst of olefin polymerization catalysis, It is the preparation method of the major catalyst of above-mentioned olefin polymerization catalysis, is included the following steps：

Ligand compound and transistion metal compound using molar ratio as 1：1-2, preferably 1：1-1.5；It is (excellent in organic solvent Select toluene) in, -50 DEG C -100 DEG C, preferably 0-90 DEG C, more preferable 30-70 DEG C；Reaction 1-10 hours, it is preferably 3-10 hours, more excellent It selects 2-5 hours；After reaction, crystallization obtains the full heterocycle non-metallocene compound；

Wherein, the ligand compound meeting formula (2),

In formula, the R₁、R₂It is respectively and independently selected from the aryl of the alkyl of C1-C20, the cycloalkyl of C3-C20 and C6-C20 One kind；R₃Or R₄It is identical or different, it is respectively and independently selected from hydrogen atom, the alkyl of C1-C20, the cycloalkyl of C3-C20 and C6-C20 Aryl in one kind；

Wherein, the transistion metal compound meeting formula (3)：MX_nFormula (3),

One kind in formula in alkyl of the X selected from halogen and C1-C20；M is transition metal atoms, selected from III B races, IV B races, One kind in VB races and VIII race's element, n are positive integer.

In the formula (2), R₁、R₂、R₃And R₄It is respectively provided with following each group and defines (being shown in Table 2)：

Accord with Formula (2) listed by table 2

Table 2

The preparation method of the major catalyst of olefin polymerization catalysis of the present invention, the X in the formula (3) are preferably selected from Cl, Br, methyl or ethyl.

The preparation method of the major catalyst of olefin polymerization catalysis of the present invention, the M in the formula (3) are preferably Titanium, zirconium, hafnium, vanadium, rhodium, iron, nickel, cobalt, neodymium, palladium or yttrium.

The preparation method of the major catalyst of olefin polymerization catalysis of the present invention, the preparation side of the ligand compound Method preferably includes following steps：

(1) general formula R will be met₂NH₂Or R₃NH₂Primary amino-compound and equimolar amounts Grignard Reagent, 0-70 DEG C reaction It 1-10 hours, is more preferably reacted 2-4 hours at 10-50 DEG C；

(2) organo-silicon compound of the half mole of the primary amino-compound, the organosilicon compound are added Object meets general formula R₁R₂SiX₂, reacted at 0-70 DEG C 1-5 hours, more preferably reacted 2-4 hours at 10-50 DEG C, it is liganded to obtain this Close object.

Another aspect of the present invention, the present invention provide a kind of olefin polymerization catalysis, including major catalyst and co-catalyst, The major catalyst is above-mentioned olefin polymerization main catalyst or is major catalyst obtained by above-mentioned preparation method.

Olefin polymerization catalysis of the present invention, the co-catalyst are preferably organic metal aluminium compound.

Olefin polymerization catalysis of the present invention, the organic metal aluminium compound are preferably alkyl aluminum or alkyl aluminum Hydrolysate alkylaluminoxane；More preferably trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum or methyl alumina Alkane (MAO).

Olefin polymerization catalysis of the present invention, the molar ratio of the co-catalyst and the major catalyst are preferably 100-5000：1；More preferably 150-1000：1.

Major catalyst provided by the invention can directly with co-catalyst coordinate catalysis in olefine polymerization, can also it is supported after It is used cooperatively again with co-catalyst.The method load major catalyst that referenced patent CN200910092169.3 is provided, major catalyst Loading process：The major catalyst for meeting general formula (1) is dissolved in organic solvent, under the conditions of 10-90 DEG C, reacts 1-8 with carrier Hour, the molar ratio of carrier and major catalyst is 1:0.5-20 after reaction, is washed 4-6 times with hexane, obtains support type master Catalyst.Preferred 40-80 DEG C of reaction temperature, the reaction time is 2-5 hours preferred, carrier and major catalyst molar ratio preferably 1:0.5- 10；In major catalyst loading process, the carrier is inorganic oxide and inorganic halides, wherein, inorganic oxide is preferred SiO₂、Al₂O₃；Wherein, the preferred magnesium chloride of inorganic halides.

The present invention also provides aforementioned full heterocycle non-metallocene compound and olefin polymerization catalysis for catalyzed alkene Purposes in homopolymerization reaction or alpha-olefinic copolymerization reaction.

Olefin polymerization catalysis provided by the present invention can effectively be catalyzed ethylene homo closes, propylene homo closes, ethylene and α- Alpha-olefinic copolymerization, propylene and alpha-olefin copolymer conjunction, ethylene and the conjunction of polarity vinyl monomer copolymerization or propylene and polarity vinyl monomer are total to Polymerization, the catalytic activity of catalyst are high.Wherein, alpha-olefin is the alkene of C3-C20, preferably propylene, 1- butylene, 1- amylenes, 1- oneself Alkene, 1- octenes, 3-methyl-1-butene, 4-methyl-1-pentene, styrene, α-methylstyrene and norbornene；Polarity alkenes Monomer is containing carbon-carbon double bond, and simultaneous with the compound of polar group, preferably propylene cyanogen, 4- cyano styrenes, methyl-prop E pioic acid methyl ester, methyl acrylate or butyl acrylate.

For olefin polymerization catalysis provided by the present invention in catalysis in olefine polymerization, polymerization temperature is 20-90 DEG C, during polymerization Between be 5min-3h, the pressure of ethylene or propylene is 0.1-5MPa, and solvent for use is n-hexane, heptane or toluene etc..

The full heterocycle non-metallocene compound of the present invention, main ring not carbon atoms, by three hetero atoms (N, N, Si) and Transition metal atoms form.This catalyst formed by full heterocycle non-metallocene compound 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 is closed with polarity vinyl monomer copolymerization, and catalyst activity is high；The catalyst of this kind of heterocycle Nonmetallocene can be also supported on carrier, Loaded catalyst is prepared, is effectively catalyzed ethylene homo conjunction, propylene homo conjunction, ethylene and alpha-olefin copolymer conjunction, propylene and α-alkene Hydrocarbon combined polymerization, ethylene and the conjunction of polarity vinyl monomer copolymerization and propylene and polarity vinyl monomer copolymerization are closed, and catalyst activity is high.

Olefin polymerization catalysis polymerization activity provided by the present invention is high, and copolymerization performance is superior.It can be used in ethylene homo It closes, propylene homo closes, ethylene and alpha-olefin copolymer conjunction, propylene and alpha-olefin copolymer conjunction, ethylene and polarity vinyl monomer copolymerization close Or propylene is closed with polarity vinyl monomer copolymerization, obtains the polyolefin products with high added value.

Specific embodiment

Following example is method in order to further illustrate the present invention, but be should not be limited thereto.

Embodiment 1

(1) synthesis of ligand compound：

1. take the THF solution (the concentration 3M of methyl-magnesium-chloride) of 30ml toluene, 12ml aniline, 21.4ml containing methyl-magnesium-chloride In the schlenk bottles of 300ml, 2h is reacted after being heated to 35 DEG C, obtained system is denoted as intermediate system 1；Then, to intermediate It is that 12ml diphenyl silicon dichlorides are added in 1, after 35 DEG C are reacted 4h, drains, 100ml n-hexanes is added in into remaining solid, Dissolution filter recrystallizes filtrate, obtains 11.4g anilino- diphenyl silanes, yield：66%.

(2) procatalyst compound 1 is prepared：

Under nitrogen protection, 0.43g ligand compound aniiinophenyl phosphorus is dissolved in 30mL toluene, adds 0.11mL (1mmol) titanium tetrachloride solution is warming up to 50 DEG C, reacts 4h.Vacuum extracts solvent, and residue is washed 3 times with n-hexane, takes out It is dry, obtain 0.53g catalyst 1 (Cat.1).¹H NMR(600MHz,CDCl₃):δ7.49(4H,m),δ7.42(2H,t),δ7.03- 7.10(10H,m),δ6.68-6.96(4H,m),δ6.67(2H,t),δ6.53(2H,d),δ0.68(6H,s)；Anal.Calcd. (%) for C₂₆H₂₆N₂SiTiCl₂(580):C,53.79；H,4.48；N,4.83；found:C,53.77；H,4.42；N,4.86.

(3) ethylene homo closes：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 5mg major catalysts, 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 washs obtained polymer 3 times with ethyl alcohol, and then sky is dry for 24 hours at 50 DEG C.

(4) ethylene copolymerization：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 5mg major catalysts are 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 washs obtained polymer 3 times with ethyl alcohol, then true at 50 DEG C Sky is dry for 24 hours.

Embodiment 2

(1) procatalyst compound 2 is prepared：

According to the method for embodiment 1,1mmol meets the 2 (R of compound of general formula (2)₁=benzyl, R₂=methyl, R₃=benzyl Base, R₄=benzyl) it is reacted with 0.23g (1mmol) zirconium chloride, obtain 0.45g catalyst 2 (Cat.2).¹H NMR(600MHz, CDCl₃)：δ 7.48 (4H, m), δ 7.39 (2H, t), δ 7.03-7.12 (10H, 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 C₂₆H₂₆N₂SiZrCl₂：C:50.08,H:4.17,N: 4.49；found:C:50.01,H:4.21,N:4.55.

(2) propylene homo closes：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 9mg major catalysts, 100ml toluene, 3ml (1M) are sequentially added Triethyl aluminium solution.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 is washed obtained polymer 3 times with ethyl alcohol, is then dried in vacuo for 24 hours at 50 DEG C.

(3) copolymerization of propylene：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 7mg major catalysts, 80ml toluene, 4ml (1M) three are sequentially added Ethyl aluminum solutions, 5ml 1- 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 washs obtained polymer 3 times with ethyl alcohol, then true at 50 DEG C Sky is dry for 24 hours.

Embodiment 3

(1) preparation of procatalyst compound 3：

According to the method for embodiment 1,1mmol meets the 3 (R of compound of general formula (2)₁=cyclohexyl, R₂=methyl, R₃=ring Hexyl, R₄=cyclohexyl) it is reacted with 0.20g (1mmol) yttrium trichloride, obtain 0.39g catalyst 3 (Cat.3).¹H NMR (600MHz,CDCl₃):δ 7.49 (4H, m), δ 7.39 (2H, t), δ 7.03-7.14 (10H, 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 C₂₆H₂₆N₂SiYCl(585):C, 53.33；H,4.44；N,4.79；found:C,53.37；H,4.41；N,4.75.

(2) ethylene homo closes：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 6mg major catalysts are 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 containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering is washed obtained polymer 3 times with ethyl alcohol, is then dried in vacuo for 24 hours at 50 DEG C.

(3) ethylene copolymerization：

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

Embodiment 4

(1) preparation of procatalyst compound 4：

According to the method for embodiment 1,1mmol meets the 4 (R of compound of general formula (2)₁=phenyl, R₂=phenyl, R₃=benzene Base, R₄=cyclopenta) it is reacted with 0.25g (1mmol) neodymium trichloride, obtain 0.51g catalyst 4 (Cat.4).¹H NMR (600MHz,CDCl₃):δ 7.50 (4H, m), δ 7.37 (2H, t), δ 7.02-7.15 (10H, 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 C₂₆H₂₆N₂SiNdCl:C,48.75；H, 4.06；N,4.38；found:C,48.79；H,4.11；N,4.39.

(2) vinyl polymerization：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 8mg major catalysts are 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 containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering is washed obtained polymer 3 times with ethyl alcohol, is then dried in vacuo for 24 hours at 50 DEG C.

(3) ethylene copolymerization：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 7mg major catalysts are sequentially added, 100ml toluene, 7mlMAO is molten Liquid (10wt%), 5ml 1- octenes.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 washs obtained polymer 3 times with ethyl alcohol, then true at 50 DEG C Sky is dry for 24 hours.

Embodiment 5

(1) preparation of procatalyst compound 5：

According to the method for embodiment 1,1mmol meets the 5 (R of compound of general formula (2)₁=cyclopenta, R₂=methyl, R₃=benzene Base, R₄=phenyl) it is reacted with 0.21g (1mmol) rhodium chloride, obtain 0.35g catalyst 5 (Cat.5).¹H NMR(600MHz, CDCl₃):δ 7.49 (4H, m), δ 7.38 (2H, t), δ 7.01-7.12 (10H, 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 C₂₆H₂₆N₂SiRhCl(599):C,52.09；H, 4.34；N,4.67；found:C,52.06；H,4.33；N,4.67.

(2) ethylene homo closes：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 5mg major catalysts are 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 containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering is washed obtained polymer 3 times with ethyl alcohol, is then dried in vacuo for 24 hours at 50 DEG C.

(3) ethylene copolymerization：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 5mg major catalysts are 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 washs obtained polymer 3 times with ethyl alcohol, then true at 50 DEG C Sky is dry for 24 hours.

Embodiment 6

(1) preparation of procatalyst compound 6：

According to the method for embodiment 1,1mmol meets the 6 (R of compound of general formula (2)₁=phenyl, R₂=phenyl, R₃=second Base, R₄=ethyl) it is reacted with 0.29g (1mmol) vanadous bromide, obtain 0.37g catalyst 6 (Cat.6).¹H NMR(600MHz, CDCl₃):δ 7.51 (4H, m), δ 7.38 (2H, t), δ 7.07-7.15 (10H, 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 C₂₆H₂₆N₂SiVBr(636):C,49.06；H, 4.09；N,4.40；found:C,49.07；H,4.15；N,4.42.

(2) propylene homo closes：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 7mg major catalysts, 100ml n-hexanes, 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, and filtering is washed obtained polymer 3 times with ethyl alcohol, is then dried in vacuo for 24 hours at 50 DEG C.

(3) copolymerization of propylene：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 6mg major catalysts are 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

(1) preparation of procatalyst compound 7：

According to the method for embodiment 1,1mmol meets the 7 (R of compound of general formula (2)₁=isopropyl, R₂=isopropyl, R₃= Phenyl, R₄=methyl) it is reacted with 0.24g (1mmol) Nickel Chloride, obtain 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 C₂₆H₂₆N₂SiNiCl(519):C, 60.12；H,5.01；N,5.39；found:C,60.11；H,5.08；N,5.43.

(2) vinyl polymerization：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 6mg major catalysts are 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 containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering is washed obtained polymer 3 times with ethyl alcohol, is then dried in vacuo for 24 hours at 50 DEG C.

(3) ethylene copolymerization：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 6mg major catalysts are 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 washs obtained polymer 3 times with ethyl alcohol, then true at 50 DEG C Sky is dry for 24 hours.

Embodiment 8

(1) preparation of procatalyst compound 8

According to the method for embodiment 1, under nitrogen protection, 1.7mmol is met to the 8 (R of compound of general formula (2)₁=2,6- 3,5-dimethylphenyl, R₂=2,6- 3,5-dimethylphenyl, R₃=phenyl, R₄=phenyl) 30mL toluene is dissolved in, add 0.19mL (1.7mmol) titanium tetrachloride is warming up to 50 DEG C, reacts 8h.Vacuum extracts solvent, and residue is washed 3 times with n-hexane, drained, Obtain 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 C₂₈H₃₀N₂SiTiCl₂:C,55.35；H,4.94；N,4.61；found:C,55.36；H,4.98； N,4.67。

(3) propylene homo closes：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 7mg major catalysts are 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 containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering is washed obtained polymer 3 times with ethyl alcohol, is then dried in vacuo for 24 hours at 50 DEG C.

(4) copolymerization of propylene：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 6mg major catalysts are sequentially added, 100ml toluene, 5mlMAO is molten Liquid (10wt%), 5ml 3-methyl-1-butenes.Three times, temperature rises to 50 DEG C, keeps the propylene pressure of 3.1MPa for ventilation, polymerization 10min.Reaction is terminated with the ethanol solution containing 10% hydrochloric acid, obtained polymer is washed 3 times, Ran Hou by filtering with ethyl alcohol It is dried in vacuo for 24 hours at 50 DEG C.

Embodiment 9

(1) preparation of procatalyst compound 9：

According to the method for embodiment 1,1mmol meets the 9 (R of compound of general formula (2)₁=2,6- 3,5-dimethylphenyl, R₂=first Base, R₃=2,6- 3,5-dimethylphenyl, R₄=2,6- 3,5-dimethylphenyl) it is reacted with 0.23g (1mmol) zirconium chloride, obtain 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 C₂₈H₃₀N₂SiZrCl₂:C,51.61；H,4.61；N,4.30；found:C,51.67；H,4.62；N,4.35.

(2) ethylene homo closes：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 10mg major catalysts, 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 is washed obtained polymer 3 times with ethyl alcohol, is then dried in vacuo for 24 hours at 50 DEG C.

(3) ethylene copolymerization：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 6mg major catalysts are sequentially added, 100ml toluene, 6mlMAO is molten Liquid (10wt%), 6ml 4-methyl-1-pentenes.Three times, temperature rises to 40 DEG C, keeps the ethylene pressure of 0.8MPa for ventilation, polymerization 30min.Reaction is terminated with the ethanol solution containing 10% hydrochloric acid, obtained polymer is washed 3 times, Ran Hou by filtering with ethyl alcohol It is dried in vacuo for 24 hours at 50 DEG C.

Embodiment 10

(1) preparation of procatalyst compound 10：

According to the method for embodiment 1,1mmol meets the 10 (R of compound of general formula (2)₁=2,6- 3,5-dimethylphenyl, R₂=first Base, R₃=2,4,6- trimethylphenyls, R₄=2,4,6- trimethylphenyls) it is reacted with 0.20g (1mmol) yttrium trichloride, it 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 C₂₈H₃₀N₂SiYCl:C,54.81；H,4.89；N,4.57；found:C,54.82；H,4.87；N, 4.54。

(2) ethylene homo closes：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 6mg major catalysts, 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 is washed obtained polymer 3 times with ethyl alcohol, is then dried in vacuo for 24 hours at 50 DEG C.

(3) ethylene copolymerization：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 6mg major catalysts, 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 is terminated with the ethanol solution containing 10% hydrochloric acid, filtering washs obtained polymer 3 times with ethyl alcohol, then at 50 DEG C Vacuum drying is for 24 hours.

Embodiment 11

(1) preparation of procatalyst compound 11：

By the method for looking for embodiment 1,1mmol meets the 11 (R of compound of general formula (2)₁=2,6- 3,5-dimethylphenyl, R₂=first Base, R₃=phenyl, R₄=phenyl) it is reacted with 0.25g (1mmol) neodymium trichloride, obtain 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 C₂₈H₃₀N₂SiNdCl:C,50.30；H,4.49；N,4.19；found:C,50.38；H,4.45；N,4.25.

(2) ethylene homo closes：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 6mg major catalysts are 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 containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering is washed obtained polymer 3 times with ethyl alcohol, is then dried in vacuo for 24 hours at 50 DEG C.

(3) ethylene copolymerization：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 6mg major catalysts are sequentially added, 100ml toluene, 7mlMAO is molten The 1- octenes 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, filtering washs obtained polymer 3 times with ethyl alcohol, Then it is dried in vacuo for 24 hours at 50 DEG C.

Embodiment 12

(1) preparation of procatalyst compound 12：

According to the method for embodiment 1,1mmol meets the 12 (R of compound of general formula (2)₁=2,6- 3,5-dimethylphenyl, R₂=first Base, R₃=cyclopenta, R₄=cyclopenta) it is reacted with 0.21g (1mmol) rhodium chloride, obtain 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 C₂₈H₃₀N₂SiRhCl:C,53.59；H,4.78；N,4.47；found:C,53.55；H,4.72；N,4.46.

(2) propylene homo closes：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 9mg major catalysts are 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 containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering is washed obtained polymer 3 times with ethyl alcohol, is then dried in vacuo for 24 hours at 50 DEG C.

(3) copolymerization of propylene：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 6mg major catalysts are sequentially added, 100ml toluene, 6mlMAO is molten The 1- hexenes 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, filtering washs obtained polymer 3 times with ethyl alcohol, Then it is dried in vacuo for 24 hours at 50 DEG C.

Embodiment 13

(1) preparation of procatalyst compound 13：

According to the method for embodiment 1,1mmol meets the 13 (R of compound of general formula (2)₁=2,6- 3,5-dimethylphenyl, R₂=first Base, R₃=iso-octyl, R₄=iso-octyl) it is reacted with 0.18g (1mmol) cobaltous dichloride, obtain 0.35g catalyst 13 (Cat.13) 。¹H NMR(600MHz,CDCl₃):δ7.46(4H,m),δ7.37(4H,t),δ7.22(4H,m),δ7.06(1H,t),δ6.88- 6.97 (4H, t), δ 6.53 (1H, m), δ 2.49 (6H, s), δ 0.48 (6H, s)；Anal.Calcd. (%) for C₂₈H₃₀N₂SiCoCl:C,56.47；H,5.04；N,4.71；found:C,56.48；H,5.01；N,4.73.

(2) ethylene homo closes：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 7mg major catalysts are 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 containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering is washed obtained polymer 3 times with ethyl alcohol, is then dried in vacuo for 24 hours at 50 DEG C.

(3) ethylene copolymerization：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 6mg major catalysts are sequentially added, 100ml toluene, 8mlMAO is molten Liquid (10wt%), 7ml methyl methacrylates.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 It is washed 3 times with ethyl alcohol, is then dried in vacuo for 24 hours at 50 DEG C.

Embodiment 14

(1) preparation of procatalyst compound 14：

According to the method for embodiment 1,1mmol meets the 14 (R of compound of general formula (2)₁=2,6- 3,5-dimethylphenyl, R₂=first Base, R₃=n-hexyl, R₄=n-hexyl) it is reacted with 0.24g hafnium tetrachlorides, obtain 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),δ6.53(1H,m),δ2.48(6H,s),δ0.49(6H,s)；Anal.Calcd. (%) for C₂₈H₃₀N₂SiHfCl₂:C, 61.43；H,5.48；N,5.12；found:C,61.45；H,5.51；N,5.16.

(2) ethylene homo closes：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 5mg major catalysts are 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 containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering is washed obtained polymer 3 times with ethyl alcohol, is then dried in vacuo for 24 hours at 50 DEG C.

(3) ethylene copolymerization：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 5mg major catalysts are sequentially added, 100ml toluene, 7mlMAO is molten Liquid (10wt%), 6ml methyl acrylates.Three times, temperature rises to 30 DEG C, keeps the ethylene pressure of 0.7MPa for ventilation, polymerization 40min.Reaction is terminated with the ethanol solution containing 10% hydrochloric acid, obtained polymer is washed 3 times, Ran Hou by filtering with ethyl alcohol It is dried in vacuo for 24 hours at 50 DEG C.

Embodiment 15

(1) preparation of procatalyst compound 15

According to the method for embodiment 1, under nitrogen protection, 2mmol is met to the 15 (R of compound of general formula (2)₁=phenyl, R₂=methyl, R₃=2,4,6- trifluorophenyls, R₄=2,4,6- trifluorophenyls) it is dissolved in 30mL toluene, add 0.22mL (2mmol) 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 0.51g catalyst 15 (Cat.15).¹H NMR(600MHz,DMSO-d₆):δ 7.75-7.81 (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 C₂₆H₂₃F₃N₂SiTiCl₂:C,49.25；H,3.13；N,4.42；found:C,49.26；H,3.17；N,4.48.

(2) ethylene homo closes：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 5mg major catalysts are 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 ethyl alcohol is washed 3 times, is then dried in vacuo for 24 hours at 50 DEG C.

(3) ethylene copolymerization：

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

Embodiment 16

(1) preparation of procatalyst compound 16：

According to the method for embodiment 1,1mmol meets the 16 (R of compound of general formula (2)₁=phenyl, R₂=methyl, R₃=2, 6- difluorophenyls, R₄=2,6- difluorophenyl) it is reacted with 0.23g zirconium chlorides, obtain 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 C₂₆H₂₃F₃N₂SiZrCl₂：C, 46.12；H,3.4；N,4.14；found:C,46.17；H,3.9；N,4.13.

(2) propylene homo closes：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 5mg major catalysts are 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 containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering is washed obtained polymer 3 times with ethyl alcohol, is then dried in vacuo for 24 hours at 50 DEG C.

(3) copolymerization of propylene：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 9mg major catalysts, 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 is terminated with the ethanol solution containing 10% hydrochloric acid, filtering washs obtained polymer 3 times with ethyl alcohol, then at 50 DEG C Vacuum drying is for 24 hours.

Embodiment 17

(1) preparation of procatalyst compound 17：

According to the method for embodiment 1,1mmol meets the 17 (R of compound of general formula (2)₁=phenyl, R₂=methyl, R₃=2, 4,6- trifluorophenyls, R₄=2,4,6- trifluorophenyls) it is reacted with 0.20g alchlors, obtain 0.56g catalyst 17 (Cat.17)。¹H NMR(600MHz,DMSO-d₆):δ7.78-7.92(4H,m),δ7.31-7.52(6H,m),δ7.07(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 C₂₆H₂₃F₃N₂SiAlCl:C,46.26；H,3.41；N,4.15；found:C,46.23；H,3.42；N,4.11.

(2) ethylene homo closes：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 8mg major catalysts are 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 containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering is washed obtained polymer 3 times with ethyl alcohol, is then dried in vacuo for 24 hours at 50 DEG C.

(3) ethylene copolymerization：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 8mg major catalysts are 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 washs obtained polymer 3 times with ethyl alcohol, then true at 50 DEG C Sky is dry for 24 hours.

Embodiment 18

(1) preparation of procatalyst compound 18：

According to the method for embodiment 1,1mmol meets the 18 (R of compound of general formula (2)₁=phenyl, R₂=methyl, R₃=2, 4,6- trifluorophenyls, R₄=2,4,6- trifluorophenyls) it is reacted with 0.25g samarium trichlorides, obtain 0.49g catalyst compounds 18 (Cat.18)。¹H NMR(600MHz,DMSO-d₆):δ7.75-7.87(4H,m),δ7.25-7.50(6H,m),δ7.04(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 C₂₆H₂₃F₃N₂SiSmCl:C,42.77；H,3.15；N,3.84；found:C,42.75；H,3.16；N,3.87.

(2) ethylene homo closes：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 5mg major catalysts are 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 containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering is washed obtained polymer 3 times with ethyl alcohol, is then dried in vacuo for 24 hours at 50 DEG C.

(3) ethylene copolymerization：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 5mg major catalysts are sequentially added, 100ml toluene, 8mlMAO is molten Liquid (10wt%), 5ml 1- cyclobutenyls-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 It is washed 3 times with ethyl alcohol, is then dried in vacuo for 24 hours at 50 DEG C.

Embodiment 19

(1) preparation of procatalyst compound 19：

According to the method for embodiment 1,2.9g meets the 19 (R of compound of general formula (2)₁=phenyl, R₂=methyl, R₃=4- fluorine Phenyl, R₄=4- fluorophenyls) it is reacted with 1g chloromethyl palladiums, obtain 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),δ 6.75(2H,d),δ6.57(2H,t),δ2.34(3H,s)δ0.15(6H,s)；Anal.Calcd. (%) for C₂₆H₂₃F₃N₂SiPdCH₃Cl:C,50.90；H,3.75；N,4.57；found:C,50.92；H,3.75；N,4.53.

(2) ethylene homo closes：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 14mg major catalysts, 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 is washed obtained polymer 3 times with ethyl alcohol, is then dried in vacuo for 24 hours at 50 DEG C.

(3) ethylene copolymerization：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 9mg major catalysts are sequentially added, 100ml toluene, 8mlMAO is molten Liquid (10wt%), 6ml 1- hexenyls-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 It is washed 3 times with ethyl alcohol, is then dried in vacuo for 24 hours at 50 DEG C.

Embodiment 20

(1) preparation of procatalyst compound 20：

According to the method for embodiment 1,4.4g meets the 19 (R of compound of general formula (2)₁=phenyl, R₂=methyl, R₃=4- fluorine Phenyl, R₄=4- fluorophenyls) it is reacted with mono- chloroethyl palladiums of 1.6g, obtain 4.8g catalyst 20 (Cat.20).¹H NMR(600MHz, DMSO)：δ7.74-7.86(4H,m),δ7.25-7.48(6H,m),δ7.06(2H,m),δ6.79(1H,d),δ6.77(2H,d),δ 6.59(2H,t),δ0.14(6H,s)；Anal.Calcd. (%) for C₂₆H₂₃F₃N₂SiPdEtCl:C,45.09；H,3.32；N, 4.05；found:C,45.10；H,3.33；N,4.06.

(2) ethylene homo closes：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 14mg major catalysts, 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 is washed obtained polymer 3 times with ethyl alcohol, is then dried in vacuo for 24 hours at 50 DEG C.

(3) ethylene copolymerization：

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

Embodiment 21

(1) preparation of procatalyst compound 21：

According to the method for embodiment 1,3.9g meets the 21 (R of compound of general formula (2)₁=phenyl, R₂=methyl, R₃=2,4, 6- trifluorophenyls, R₄=2,4,6- trifluorophenyls) it is reacted with 1.9g irons, obtain 5.1g catalyst compounds 21 (Cat.21)。¹H NMR(600MHz,DMSO-d₆):δ7.76-7.93(4H,m),δ7.28-7.53(6H,m),δ7.04(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 C₂₆H₂₃F₃N₂SiFeCl(645):C,48.41；H,3.57；N,4.34；found:C,48.44；H,3.58；N,4.38.

(2) propylene homo closes：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 7mg major catalysts are 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 containing 10% hydrochloric acid Alcoholic solution terminates reaction, and filtering is washed obtained polymer 3 times with ethyl alcohol, is then dried in vacuo for 24 hours at 50 DEG C.

(3) copolymerization of propylene：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 9mg major catalysts are 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 washs obtained polymer 3 times with ethyl alcohol, then true at 50 DEG C Sky is dry for 24 hours.

Embodiment 22

(1) preparation of loaded catalyst：

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

(2) ethylene homo closes：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 7mg loaded catalysts are sequentially added, 100ml toluene, 5mlMAO solution (10wt%).Three times, temperature rises to 50 DEG C, ethylene pressure 0.5MPa for ventilation, polymerize 120min.With containing 10% The ethanol solution of hydrochloric acid terminates reaction, and filtering is washed obtained polymer 3 times with ethyl alcohol, is then dried in vacuo at 50 DEG C 24h。

(3) ethylene copolymerization：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 7mg loaded catalysts are sequentially added, 100ml toluene, 5mlMAO solution (10wt%), 6ml 1- hexenyls-N- acetyl group-l-tyrosine-ethyl ester.Three times, temperature rises to 50 DEG C for ventilation, Keep the ethylene pressure of 0.5MPa, polyase 13 0min.Reaction is terminated with the ethanol solution containing 10% hydrochloric acid, filtering is poly- what is obtained It closes object to be washed 3 times with ethyl alcohol, be then dried in vacuo for 24 hours at 50 DEG C.

Embodiment 23

(1) preparation of loaded 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) ethylene homo closes：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 10mg loaded catalysts are sequentially added, 80ml toluene, 2mlMAO solution (10wt%).Three times, temperature rises to 45 DEG C, ethylene pressure 0.5MPa for ventilation, polymerize 100min.With containing 10% The ethanol solution of hydrochloric acid terminates reaction, and filtering is washed obtained polymer 3 times with ethyl alcohol, is then dried in vacuo at 50 DEG C 24h。

(3) ethylene copolymerization：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 10mg loaded catalysts are sequentially added, 100ml toluene, 2mlMAO solution (10wt%), 6ml 4-methyl-1-pentenes.Three times, temperature rises to 45 DEG C, keeps the ethylene pressure of 0.5MPa for ventilation Power, polyase 13 0min.Reaction is terminated with the ethanol solution containing 10% hydrochloric acid, filtering washs obtained polymer 3 times with ethyl alcohol, Then it is dried in vacuo for 24 hours at 50 DEG C.

Embodiment 24

(1) preparation of loaded 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 removes solvent, is washed six times with toluene, obtain loaded catalyst.ICP method measures gained catalyst Middle nickel content is 3.8wt%.

(2) propylene homo closes：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 7mg loaded catalysts are sequentially added, 80ml toluene, 2mlMAO solution (10wt%).Three times, temperature rises to 50 DEG C, propylene pressure 2.3MPa for ventilation, polymerize 120min.With containing 10% The ethanol solution of hydrochloric acid terminates reaction, and filtering is washed obtained polymer 3 times with ethyl alcohol, is then dried in vacuo at 50 DEG C 24h。

(3) copolymerization of propylene：

Under the conditions of anhydrous and oxygen-free, in 300ml reaction bulbs, 7mg loaded catalysts are sequentially added, 100ml toluene, 2mlMAO solution (10wt%), 5ml styrene.Three times, temperature rises to 50 DEG C, keeps the propylene pressure of 2.3MPa for ventilation, polymerization 30min.Reaction is terminated with the ethanol solution containing 10% hydrochloric acid, obtained polymer is washed 3 times, Ran Hou by filtering with ethyl alcohol It is dried in vacuo for 24 hours at 50 DEG C.

The polymerization catalyst of above-described embodiment the results are shown in Table 3.

Table 3

Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art It should all belong to the scope of protection of the present invention.

Claims

1. a kind of major catalyst of olefin polymerization catalysis, which is characterized in that the major catalyst is full heterocycle Nonmetallocene chemical combination Object, shown in the structure such as formula (1) of the compound：

In formula, R₁And R₂The one kind being respectively and independently selected from the aryl of the alkyl of C1-C20, the cycloalkyl of C3-C20 and C6-C20； R₃Or R₄It is identical or different, it is respectively and independently selected from the aryl of hydrogen atom, the alkyl of C1-C20, the cycloalkyl of C3-C20 and C6-C20 In one kind；One kind in alkyl of the X selected from halogen and C1-C20；M is transition metal atoms, selected from III B races, IV B races, VB races With one kind in VIII race's element.

2. the major catalyst of olefin polymerization catalysis according to claim 1, which is characterized in that the X in the formula (1) is Cl, Br, methyl or ethyl.

3. the major catalyst of olefin polymerization catalysis according to claim 1 or 2, which is characterized in that in the formula (1) M is titanium, zirconium, hafnium, vanadium, rhodium, iron, nickel, cobalt, neodymium, palladium or yttrium.

4. a kind of preparation method of the major catalyst of olefin polymerization catalysis is claim 1-3 any one of them alkene The preparation method of the major catalyst of polymerization catalyst, which is characterized in that include the following steps：

Ligand compound and transistion metal compound using molar ratio as 1：1-2, in organic solvent, -50 DEG C -100 DEG C, reaction 3-10 hours, after reaction, crystallization obtained the full heterocycle non-metallocene compound；

Wherein, the ligand compound meeting formula (2),

In formula, the R₁、R₂One be respectively and independently selected from the aryl of the alkyl of C1-C20, the cycloalkyl of C3-C20 and C6-C20 Kind；R₃Or R₄It is identical or different, it is respectively and independently selected from the virtue of hydrogen atom, the alkyl of C1-C20, the cycloalkyl of C3-C20 and C6-C20 One kind in base；

Wherein, the transistion metal compound meeting formula (3)：MX_nFormula (3),

One kind in formula in alkyl of the X selected from halogen and C1-C20；M is transition metal atoms, selected from III B races, IV B races, VB races With one kind in VIII race's element, n is positive integer.

5. the preparation method of the major catalyst of olefin polymerization catalysis according to claim 4, which is characterized in that the formula (3) X in is selected from Cl, Br, methyl or ethyl.

6. the preparation method of the major catalyst of olefin polymerization catalysis according to claim 4, which is characterized in that the formula (3) M in is titanium, zirconium, hafnium, vanadium, rhodium, iron, nickel, cobalt, neodymium, palladium or yttrium.

7. the preparation method of the major catalyst of olefin polymerization catalysis according to claim 4, which is characterized in that described to match The preparation method of body compound includes the following steps：

(1) general formula R will be met₂NH₂Or R₃NH₂Primary amino-compound and equimolar amounts Grignard Reagent reaction, 0-70 DEG C reaction 1-10 hours；

(2) organo-silicon compound of the half mole of the primary amino-compound, the organo-silicon compound symbol are added Close general formula R₁R₂SiX₂, reacted 1-5 hours at 0-70 DEG C, obtain the ligand compound.

8. a kind of olefin polymerization catalysis, which is characterized in that including major catalyst and co-catalyst, the major catalyst is right It is required that 1-3 any one of them olefin polymerization main catalyst or made for claim 4-7 any one of them preparation methods The major catalyst obtained.

9. olefin polymerization catalysis according to claim 8, which is characterized in that the co-catalyst is organic metal calorize Close object.

10. olefin polymerization catalysis according to claim 9, which is characterized in that the organic metal aluminium compound is alkane The hydrolysate alkylaluminoxane of base aluminium or alkyl aluminum.

11. according to claim 8-10 any one of them olefin polymerization catalysis, which is characterized in that the co-catalyst and institute The molar ratio for stating major catalyst is 100-5000：1.