CN108395449A - Bis-phenol oxygroup imine ligand zirconium compounds and its preparation method and application - Google Patents
Bis-phenol oxygroup imine ligand zirconium compounds and its preparation method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
Abstract
The present invention relates to bis-phenol oxygroup imine ligand zirconium compounds and its preparation method and application, are 1 in molar ratio with halogenation zirconium compounds after bis-phenol imines ligand compound is reacted with lithium alkylide:1.0~1.5 react in organic media, and controlling reaction temperature is 78~110 DEG C, is reacted 2~96 hours, and using filter, concentration, recrystallization processing obtains bis-phenol oxygroup imine ligand zirconium compounds, and alkene homopolymerization and copolymerization are applied in the presence of alkylaluminoxane.Compared with prior art, raw material of the present invention is easy to get, synthetic route is simple, product yield is high, Nature comparison is stablized, there is higher catalytic activity simultaneously, the polyethylene, polypropylene and ethylene and propylene, the copolymer of ethylene and 1 hexene, ethylene and 1 octene of high molecular weight and narrow molecular weight distribution can be obtained, disclosure satisfy that the needs of industrial department.
Description
Technical field
The present invention relates to field of olefin polymerisation, more particularly, to a kind of bis-phenol oxygroup imine ligand zirconium compounds and its preparation
Application in method and olefinic polymerization.
Background technology
The polyolefine materials such as polyethylene (PE) and polypropylene (PP) have that intensity is high, density is low, resistance to chemical corrosion is strong and
The advantages such as manufacturing cost is low can be used to a certain extent with common materials such as replacing paper, timber, glass, metal and concrete
It is very extensive on the way, it has also become the polymer material that the world today is most widely used.Wherein, polyethylene is in general synthetic resin
The maximum kind of yield, the thermoplastic most wide as purposes are mainly used to manufacture film, container, pipeline, monofilament, electric wire
Cable, daily necessities etc. can also be used as the high frequencies insulating materials such as manufacture TV, radar.LLDPE is ethylene and a small amount of advanced
The copolymer of alpha-olefin, there are short-chain branch in molecule, there's almost no long-chain branch, have the high and low temperature resistant energy of good toughness, intensity
The advantages that power, also has better environmental stress crack resistance.(Macromol.Chem.Phys.,2017,218,490-499；
Macromolecules,2016,49,1229-1241；Angew.Chem.Int.Ed.,2003,42,5010-5030；
Chem.Eur.J.,2006,12,7546-7556；Can.J.Chem.Eng.,2012,90,646-671).
The research of new catalyst is most important for pushing the development of polyolefine material.The progress of catalyst technology is not only
The performance that cost can be reduced, production capacity is improved, improve polyolefin, can also develop the novel green wood with property
Material, makes it be applied in more wide field.Therefore, the research and development of polyolefin catalyst is always International Academic
Boundary and industrial circle focus of attention and hot spot.The fifties in last century, the discovery of Ziegler-Natta catalyst resulted in high density
The birth of polyethylene (HDPE) and high isotactic polypropylene (iPP), is greatly promoted the development of polymer chemistry, has established alkene
The basis of polymer industry has pushed the industrialization revolution of olefinic polymerization.The beginning of the eighties, Kaminsky et al. have found by trimethyl aluminium
The metallocene catalyst efficiency that forms of hydrolysate methylaluminoxane (MAO) and Cp2ZrCl2 it is very high, opened since then efficiently
The new page of single centre metallocene catalyst.The appearance of the mid-90 in last century, non-metallocene catalyst are catalyzed polyolefin
Another frontier has been opened up in the research and development of agent.Fujita of Japanese Mitsui companies et al. utilizes salicylaldiminato class titanium family metal network
Close the catalytic polymerization research that object has carried out ethylene, propylene and-alkene.Such catalyst ligand structure is easy to modify, and passes through design
Catalyst backbone structure can regulate and control the performance of catalyst, can obtain different molecular weight northylen, stereoregular polypropylene, also
Ethylene and alpha-olefin copolymer can be catalyzed, so as to develop new type polyolefin material numerous in variety (J.Am.Chem.Soc.,
2001,123,6847-6856).Americanized scholar Brookhart reports-diimine class nickel catalyst can high activity urge
Change vinyl polymerization and obtain High molecular weight polyethylene, and the degree of branching of polymer can be controlled by changing reaction condition, obtains
The unformed various polymer (Macromolecules, 2006,39,6341-6354) to high-crystallinity.Grubbs research teams
Ethylene, propylene polymerization can be catalyzed by having synthesized the neutral nickel catalyst one pack system of salicylide ligand, and such catalyst is to hetero atom
Have good tolerance, ethylene and polar monomer copolymerization can be catalyzed, receive industrial quarters favor (Science, 2000,287,
460-462)。
In conclusion although the research of olefin polymerization catalysis has been achieved for larger breakthrough, there are many difficult points
It needs to capture, as polymer higher molecular weight and relatively narrow molecular weight distribution can't be realized simultaneously, it is difficult to regulate and control comonomer
Distribution in polymer chain, catalyst synthesis step is more, it is expensive the problems such as, limit its industrially apply model
It encloses.
Invention content
One of the object of the invention is the zirconium compounds of open a kind of bis-phenol oxygroup imine ligand.
The second purpose of the present invention is the preparation methods of open bis-phenol oxygroup imine ligand zirconium compounds.
When the three of the object of the invention are open bis-phenol oxygroup imine ligand zirconium compounds as catalyst, catalysis ethylene,
Or propylene polymerization obtains polyethylene, polypropylene.
When the four of the object of the invention are open bis-phenol oxygroup imine ligand zirconium compounds as catalyst, be catalyzed ethylene and
Propylene, ethylene and 1- hexenes, ethylene and 1- Octene Polymerizations obtain copolymer.
The purpose of the present invention can be achieved through the following technical solutions：
Bis-phenol oxygroup imine ligand zirconium compounds provided by the invention has following general formula：
R1~R4Respectively represent hydrogen, C1~C10The alkyl of straight chain, branch or cyclic structure, cumyl, alkoxy, silylation, C7
~C20The alkyl of single or multiple aryl substitution, halogen；R5Represent C1~C10The alkyl of straight chain, branch or cyclic structure, C6~C10It is single
Or the substituted or unsubstituted benzyl of more alkyl, halogen；R6Represent halogen；N represents 3~8 positive integer.
R1~R4Preferably hydrogen, C1~C6The alkyl of straight chain, branch or cyclic structure, cumyl, methoxyl group, isopropoxy are different
Butoxy, trimethyl silicon substrate, triisopropylsilyl or chlorine, bromine, iodine；R5Preferably C1~C6Straight chain, branch or cricoid alkyl,
C6~C10The substituted or unsubstituted benzyl of single or multiple alkyl, fluorine, chlorine；R6Preferably fluorine or chlorine；N is preferably 3~6 positive integer.
Typical bis-phenol oxygroup imine ligand zirconium compounds structural formula is as follows：
The complex compound with electron donating group can be high living on the bis-phenol oxygroup imine ligand zirconium compounds being prepared
Property cause ethylene or alpha-olefine polymerizing, show that the charge density for increasing metal center is conducive to improve the electrophilicity of metal center.
In addition, there is imine moiety the complex compound of big steric hindrance substituent group can obtain the higher polymer of molecular weight.The fragrant oxygen of non-bridging
Imines (FI) Zr catalyst causes olefinic polymerization, and resulting polymers molecular weight is relatively low, and molecular weight distribution is wider, this is because：1)
There are a variety of isomers under complex solution state, various configuration isomers can cause polymerization in polymerization process, cause to polymerize
Object molecular weight distribution is wider；2) imine moiety skeleton steric hindrance is smaller, causes chain growth and chain termination rate all very fast, therefore
The molecular weight of polymer is relatively low.Therefore, the present invention considers to overcome the two unfavorable factors by adjusting space and electronic effect,
The bisphenols imine ligand containing different alkylidene bridgings is designed, the substituent group with different spaces steric hindrance and electronic effect is introduced,
The stability and the steric hindrance around central metal for improving corresponding zirconium compounds structure, to realize that highly active catalytic alkene is poly-
It closes, obtains the polymer of high molecular weight and narrow molecular weight distribution.
The bis-phenol oxygroup imine ligand zirconium compounds preparation method of the present invention includes the following steps：Shown in formula (II)
Bis-phenol imines ligand compound is reacted with lithium alkylide, and the ligand lithium salts and halogenation zirconium compounds of generation are anti-in organic media
It answers, bis-phenol oxygroup imine ligand zirconium compounds (I) is obtained through filtering, concentration, recrystallization processing.
Reaction equation is as follows：
Bis-phenol imines ligand compound in above-mentioned preparation method represented by formula (II), substituent group such as R1~R5With it is full
The requirement of each corresponding group of foot bis-phenol oxygroup imine ligand zirconium compounds of the present invention is consistent.
Described zirconium halide is Zr (R6)4Or Zr (R6)42THF, wherein R6For halogen group.
The molar ratio of bis-phenol imines ligand compound shown in formula and halogenation zirconium compounds is preferably 1:1.0~1.5.
Reaction temperature be -78~110 DEG C, preferably -20~80 DEG C, the reaction time be 2~96 hours, preferably 2~48
Hour.
Described organic media is selected from tetrahydrofuran, ether, toluene, benzene, chloroform, dichloromethane, petroleum ether and n-hexane
One or both of.
Catalyst described in the present invention is that a kind of efficient olefin polymerization catalysis can under alkylaluminoxane co-catalysis
For ethylene, the homopolymerization and ethylene and propylene of propylene, ethylene and 1- hexenes, ethylene and the reaction of 1- octene copolymers.
Using bis-phenol oxygroup imine ligand zirconium compounds of the present invention as major catalyst, alkylaluminoxane is co-catalyst, makes second
The homopolymerization at 0~150 DEG C of alkene or propylene, the molar ratio of major catalyst and co-catalyst is 1 when homopolymerization:1~100000, preferably 1:
50~10000；The pressure of ethylene or propylene is 0.1~10.0MPa, preferably 0.1~5.0MPa.
Using bis-phenol oxygroup imine ligand zirconium compounds of the present invention as major catalyst, alkylaluminoxane is co-catalyst, makes second
Alkene and propylene are copolymerized at 0~150 DEG C, and the molar ratio of major catalyst and co-catalyst is 1 when copolymerization:1~100000, preferably 1:
50~10000；The gross pressure of ethylene and propylene is 0.1~10.0MPa, preferably 0.1~5.0MPa；The pressure ratio of ethylene and propylene
It is 1:9~9:1, preferably 3:7~7:3.
Using bis-phenol oxygroup imine ligand zirconium compounds of the present invention as major catalyst, alkylaluminoxane is co-catalyst, makes second
Alkene and 1- hexenes are copolymerized at 0~150 DEG C, and the molar ratio of major catalyst and co-catalyst is 1 when copolymerization:1~100000, preferably
1:50~10000；Ethylene pressure is 0.1~10.0MPa, preferably 0.1~5.0MPa；The molar ratio of catalyst and 1- hexenes is 1:
1000-100000, preferably 1:2000-50000.
Using bis-phenol oxygroup imine ligand zirconium compounds of the present invention as major catalyst, alkylaluminoxane is co-catalyst, makes second
Alkene and 1- octenes are copolymerized at 0~150 DEG C, and the molar ratio of major catalyst and co-catalyst is 1 when copolymerization:1~100000, preferably
1:50~10000；Ethylene pressure is 0.1~10.0MPa, preferably 0.1~5.0MPa；The molar ratio of catalyst and 1- octenes is 1:
1000-100000, preferably 1:2000-50000.
Compared with prior art, catalyst preparation convenience provided by the invention, property are stablized, while having higher catalysis
Activity by introducing big steric group on fragrant oxygen ring, while designing the alkylidene bridging of different chain length, effectively regulates and controls skeleton
The space of structure and electronic factor build specific spatial coordination environment and charge density around complex metal center, hair
Potential of the complex compound in terms of regulation and control polymerisation and resin microstructure is waved, overcomes polymer molecular weight relatively low and molecular weight
It is distributed wide unfavorable factor, and then obtains the polyolefin of high molecular weight and narrow molecular weight distribution, disclosure satisfy that wanting for industrial department
It asks.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Embodiment 1
The synthesis of ligand L 1
3,5- di-tert-butyl salicylaldehydes (4.68g, 20mmol), absolute ethyl alcohol are sequentially added into 100mL reaction bulbs
(50mL) and 1.0g molecular sievesIt is stirred at room temperature 5 minutes, 1,3- propane diamine (0.74g, 10mmol), return stirring is added
Reaction 16 hours.Reaction solution filters, and filtrate decompression removes solvent, and product (4.11g, yield are recrystallized to give through petroleum ether：
81.1%).
1H NMR(CDCl3,400MHz):δ 10.93 (s, 2H, OH), 8.56 (s, 2H, CH=N), 7.20 (d, 2H,4J=
2.2Hz,ArH),6.80(d,2H,4J=2.2Hz, ArH), 3.71 (t, 4H,3J=7.5Hz, NCH2),2.01(m,2H,
CH2CH2CH2),1.43(s,18H,C(CH3)3),1.28(s,18H,C(CH3)3).13C NMR(CDCl3,100MHz):δ161.4,
154.3,140.4,135.4,123.2,122.7,121.5,59.4,34.5,32.2,31.6,25.0.Anal.Calcd.for
C33H50N2O2:C,78.21；H,9.95；N,5.53.Found:C,78.47；H,10.02；N, 5.77%.
Embodiment 2
The synthesis of ligand L 2
3- tertiary butyl -5- cresotinic acids aldehyde (3.84g, 20mmol), absolute ethyl alcohol are sequentially added into 100mL reaction bulbs
(50mL) and 1.0g molecular sievesIt is stirred at room temperature 5 minutes, 1,3- propane diamine (0.74g, 10mmol), return stirring is added
Reaction 16 hours.Reaction solution filters, and filtrate decompression removes solvent, and product (2.87g, yield are recrystallized to give through petroleum ether：
70.2%).
1H NMR(CDCl3,400MHz):δ 10.79 (s, 2H, OH), 8.44 (s, 2H, CH=N), 7.37 (d, 2H,4J=
2.4Hz,ArH),7.08(d,2H,4J=2.4Hz, ArH), 3.95 (t, 4H,3J=7.2Hz, NCH2),2.36(s,6H,
ArCH3),1.40(s,18H,C(CH3)3).13C NMR(CDCl3,100MHz):δ161.4,157.3,140.4,135.4,
123.2,122.7,121.5,61.9,34.5,31.6,21.6.Anal.Calcd.for C26H36N2O2:C,76.43；H,8.88；
N,6.86.Found:C,76.47；H,9.02；N, 6.77%.
Embodiment 3
The synthesis of ligand L 3
2- hydroxyl -3- cumyl -5- methoxy benzophenones (5.69g, 20mmol), nothing are sequentially added into 100mL reaction bulbs
Water-ethanol (50mL), 1 drop formic acid and 1.0g molecular sievesIt is stirred at room temperature 5 minutes, 1,3- of addition propane diamine (0.74g,
10mmol), return stirring reacts 16 hours.Reaction solution filters, and filtrate decompression removes solvent, and product is recrystallized to give through petroleum ether
(3.25g, yield：53.6%).
1H NMR(CDCl3,400MHz):δ10.12(s,2H,OH),7.35-7.13(m,12H,ArH),6.85(d,2H,4J
=2.4Hz, ArH), 3.81 (s, 6H, OCH3),3.67(t,3J=7.2Hz, 4H, NCH2),2.11(m,2H,CH2CH2CH2),
1.81(s,6H,NCCH3),1.69(s,12H,CPh(CH3)2).13CNMR(CDCl3,100MHz):δ164.6,154.3,152.9,
150.6,132.7,129.2,128.2,126.2,113.4,112.2,55.8,52.9,36.5,32.8,31.2,
17.7.Anal.Calcd.for C39H46N2O4:C,77.20；H,7.64；N,4.62.Found:C,77.41；H,7.75；N,
4.56%.
Embodiment 4
The synthesis of ligand L 4
Sequentially add 3,5- Dibromosalicylaldehydes (5.60g, 20mmol) into 100mL reaction bulbs, absolute ethyl alcohol (50mL) and
1.0g molecular sieveIt is stirred at room temperature 5 minutes, 1,5- pentanediamines (1.02g, 10mmol) is added, return stirring reaction 16 is small
When.Reaction solution filters, and filtrate decompression removes solvent, and product (3.55g, yield are recrystallized to give through petroleum ether：56.7%).
1H NMR(CDCl3,400MHz):δ 13.17 (s, 2H, OH), 8.66 (s, 2H, CH=N), 7.84 (d, 2H,4J=
2.4Hz,ArH),7.70(d,2H,4J=2.4Hz, ArH), 3.74 (t, 4H,3J=7.2Hz, NCH2),1.63(m,4H,
NCH2CH2),1.29(m,2H,CH2CH2CH2).13C NMR(CDCl3,100MHz):δ160.2,157.5,131.0,129.0,
116.1,113.5,61.8,31.3,24.8.Anal.Calcd.for C19H18Br4N2O2:C,36.46；H,6.74；N,
5.45.Found:C,36.29；H,6.87；N, 5.35%.
Embodiment 5
The synthesis of ligand L 5
Sequentially added into 100mL reaction bulbs 3- (dimethylisopropyl silicon substrate) -5- cresotinic acids aldehyde (4.72g,
20mmol), absolute ethyl alcohol (50mL) and 1.0g molecular sievesIt is stirred at room temperature 5 minutes, 1,3- of addition pentanediamines (0.74g,
10mmol), return stirring reacts 16 hours.Reaction solution filters, and filtrate decompression removes solvent, and product is recrystallized to give through petroleum ether
(2.39g, yield：46.8%).
1H NMR(CDCl3,400MHz):δ 10.96 (s, 2H, OH), 8.37 (s, 2H, CH=N), 7.55 (d, 2H,4J=
2.2Hz,ArH),7.22(d,2H,4J=2.2Hz, ArH), 3.66 (t, 4H,3J=7.5Hz, NCH2),2.36(s,3H,
ArCH3),1.98(m,2H,CH2CH2CH2),1.45(sept,2H,3J=6.8Hz, CH (CH3)2),0.97(d,12H,CH
(CH3)2),0.25(s,12H,SiCH3).13C NMR(CDCl3,100MHz):δ164.2,157.5,137.8,131.2,130.4,
127.3,123.8,59.7,34.2,32.0,21.3,18.6,1.2.Anal.Calcd.for C29H46N2O2Si2:C,68.18；
H,9.08；N,5.48.Found:C,68.38；H,9.14；N, 5.51%.
Embodiment 6
The synthesis of zirconium complex Z1
Under argon atmosphere, to ligand 2,2 '-(propylidene -1,6- di-imidogen)-two is added in Schlenk bottles of 100mL
(4,6- DI-tert-butylphenol compounds) (0.76g, 1.5mmol) and 20mL tetrahydrofurans, are stirred at room temperature dissolving, cold with liquid nitrogen/ethanol bath
But to -78 DEG C, n-BuLi hexane solution (1.6mol/L, 1.88mL, 3.0mmol) is then slowly added dropwise, room is added dropwise
Temperature is stirred to react 2 hours.Reaction solution is cooled to 0 DEG C with ice-water bath, zirconium chloride tetrahydrofuran complex is then added
(0.566g, 1.5mmol), -10 DEG C are stirred to react 24 hours.Solvent and volatile materials are removed under vacuum, and dichloromethane is added
(20mL) extraction dissolving reaction product, stirs 30 minutes, is filtered after standing 8 hours, and concentrated solvent to solution muddiness is added appropriate
N-hexane adjust polarity, crystallizing at room temperature, be precipitated greenish yellow solid, filtering, washed with n-hexane, obtain zirconium complex Z1 (0.76g,
Yield：76.1%).
Three isomers C2:Cs:C1=0.62:0.18:0.20.1H NMR of C2-isomer(CDCl3,
400MHz):δ8.16(s,2H,CHN),7.52(d,2H,4J=2.2Hz, ArH), 7.04 (d, 2H,4J=2.2Hz, ArH), 3.53
(t,4H,3J=5.4Hz, CH2CH2CH2),1.86(p,2H,3J=5.4Hz, CH2CH2CH2),1.49(s,18H,C(CH3)3),
1.28(s,18H,C(CH3)3).13C NMR(CDCl3,100MHz):δ168.9,151.4,138.5,137.7,128.3,123.7,
37.7,34.5,31.6,30.0,24.5.Anal.Calcd.for C33H48Cl2N2O4Zr:C,59.44；H,7.26；N,
4.20.Found:C,59.83；H,7.08；N, 3.96%.
Embodiment 7
The synthesis of titanium complex Z2
Under argon atmosphere, to (1, the 9- dimethyl-pentylidene -1,8- bis- of ligand 2,2 '-is added in Schlenk bottles of 100mL
Imido grpup)-two (4- methoxyl group -6- cumyl phenols) (0.95g, 1.5mmol) and 20mL tetrahydrofurans, dissolving is stirred at room temperature, uses
Liquid nitrogen/ethanol bath is cooled to -78 DEG C, be then slowly added dropwise n-BuLi hexane solution (1.6mol/L, 1.88mL,
3.0mmol), it is added dropwise and reaction 2 hours is stirred at room temperature.Reaction solution is cooled to 0 DEG C with ice-water bath, zirconium chloride is then added
Reaction 24 hours is stirred at room temperature in tetrahydrofuran complex (0.566g, 1.5mmol).Solvent and volatile materials are removed under vacuum,
Dichloromethane (20mL) is added and extracts dissolving reaction product, stirs 30 minutes, is filtered after standing 8 hours, concentrated solvent to solution
Muddiness is added appropriate n-hexane and adjusts polarity, and greenish yellow solid is precipitated in crystallizing at room temperature, and filtering is washed with n-hexane, obtains zirconium network
Close object Z2 (0.61g, yield：51.3%).
Three isomers C2:Cs:C1=0.65:0.15:0.20.1H NMR of C2-isomer(CDCl3,
400MHz):δ7.29-7.13(m,12H,ArH),6.85(d,2H,4J=2.5Hz, ArH), 3.81 (s, 6H, OCH3),3.53(t,
4H,3J=6.0Hz, NCH2),1.89(s,6H,CH3), C=N 1.69 (s, 12H, PhC (CH3)2),1.61(m,4H,
CH2CH2CH2),1.32(m,2H,CH2CH2CH2).13C NMR(CDCl3,100MHz):δ157.7,128.8,127.6,127.4,
121.8,120.9,80.0,65.7,61.0,50.5,25.8,25.4,24.0.Anal.Calcd.for C41H48Cl2N2O4Zr:
C,61.95；H,6.09；N,3.52.Found:C,62.15；H,6.10；N, 3.65%.
Embodiment 8
The synthesis of titanium complex Z3
Under argon atmosphere, to ligand 2,2 '-(ethylidene -1,5- di-imidogen)-two is added in Schlenk bottles of 100mL
(4,6- dibromophenol) (0.88g, 1.5mmol) and 20mL tetrahydrofurans, are stirred at room temperature dissolving, be cooled to liquid nitrogen/ethanol bath-
78 DEG C, n-BuLi hexane solution (1.6mol/L, 1.88mL, 3.0mmol) is then slowly added dropwise, is added dropwise and is stirred at room temperature
Reaction 2 hours.Reaction solution is cooled to 0 DEG C with ice-water bath, be then added zirconium chloride tetrahydrofuran complex (0.566g,
1.5mmol), it is stirred to react 24 hours for 50 DEG C.Solvent and volatile materials are removed under vacuum, and dichloromethane (20mL) is added and extracts
Reaction product is dissolved, is stirred 30 minutes, is filtered after standing 8 hours, concentrated solvent to solution muddiness is added appropriate n-hexane and adjusts
Greenish yellow solid is precipitated in polarity, crystallizing at room temperature, and filtering is washed with n-hexane, obtains zirconium complex Z3 (0.55g, yield：
49.3%).
Three isomers C2:Cs:C1=0.70:0.12:0.18.1H NMR of C2-isomer(CDCl3,
400MHz):δ8.16(s,2H,CHN),7.55(d,2H,4J=2.4Hz, ArH), 7.02 (d, 2H,4J=2.4Hz, ArH), 3.91
(t,4H,3J=6.2Hz, NCH2).13C NMR(CDCl3,100MHz):δ163.7,160.2,138.3,131.9,129.0,
116.3,35.8.Anal.Calcd.for C16H10Br4Cl2N2O2Zr:C,25.83；H,1.35；N,3.77.Found:C,
26.12；H,1.40；N, 3.52%.
Embodiment 9
The synthesis of titanium complex Z4
Under argon atmosphere, to ligand 2,2 '-(propylidene -1,6- di-imidogen)-two is added in Schlenk bottles of 100mL
[4- methyl -6- (dimethylisopropyl silicon substrate) phenol] (0.77g, 1.5mmol) and 20mL tetrahydrofurans, is stirred at room temperature dissolving,
Be cooled to -78 DEG C with liquid nitrogen/ethanol bath, be then slowly added dropwise n-BuLi hexane solution (1.6mol/L, 1.88mL,
3.0mmol), it is added dropwise and reaction 2 hours is stirred at room temperature.Reaction solution is cooled to 0 DEG C with ice-water bath, zirconium chloride is then added
Reaction 24 hours is stirred at room temperature in tetrahydrofuran complex (0.566g, 1.5mmol).Solvent and volatile materials are removed under vacuum,
Dichloromethane (20mL) is added and extracts dissolving reaction product, stirs 30 minutes, is filtered after standing 8 hours, concentrated solvent to solution
Muddiness is added appropriate n-hexane and adjusts polarity, and greenish yellow solid is precipitated in crystallizing at room temperature, and filtering is washed with n-hexane, obtains zirconium network
Close object Z4 (0.39g, yield：38.7%).
Three isomers C2:Cs:C1=0.71:0.09:0.20.1H NMR of C2-isomer(400MHz,
CDCl3):δ8.03(s,2H,CHN),7.16(d,2H,4J=2.4Hz, ArH), 6.73 (d, 2H,4J=2.4Hz, ArH), 3.75
(t,4H,3J=6.0Hz, NCH2),2.38(s,6H,ArCH3),2.01(m,2H,NCH2CH2),1.49(m,2H,CH(CH3)2),
1.06(d,12H,3J=6.0Hz, CH (CH3)2),0.25(s,12H,SiCH3).13C NMR(CDCl3,100MHz):δ164.4,
159.5,138.2,135.3,127.3,123.2,122.1,35.1,34.1,31.8,21.4,18.6,
1.2.Anal.Calcd.for C29H44Cl2N2O2Si2Zr:C,51.91；H,6.61；N,4.18.Found:C,52.14；H,
6.34；N, 3.81%.
Embodiment 10
The synthesis of titanium complex Z5
Under argon atmosphere, to ligand 2,2 '-(propylidene -1,6- di-imidogen)-two is added in Schlenk bottles of 100mL
(4- methyl -6- cumyl phenols) (0.82g, 1.5mmol) and 20mL tetrahydrofurans, is stirred at room temperature dissolving, cold with liquid nitrogen/ethanol bath
But to -78 DEG C, n-BuLi hexane solution (1.6mol/L, 1.88mL, 3.0mmol) is then slowly added dropwise, room is added dropwise
Temperature is stirred to react 2 hours.Reaction solution is cooled to 0 DEG C with ice-water bath, zirconium chloride tetrahydrofuran complex is then added
Reaction 24 hours is stirred at room temperature in (0.566g, 1.5mmol).Solvent and volatile materials are removed under vacuum, and dichloromethane is added
(20mL) extraction dissolving reaction product, stirs 30 minutes, is filtered after standing 8 hours, and concentrated solvent to solution muddiness is added appropriate
N-hexane adjust polarity, crystallizing at room temperature, be precipitated greenish yellow solid, filtering, washed with n-hexane, obtain zirconium complex Z5 (0.46g,
Yield：43.4%).
Three isomers C2:Cs:C1=0.75:0.05:0.20.1H NMR of C2-isomer(400MHz,
CDCl3):δ8.08(s,2H,CHN),7.45-6.95(m,14H,ArH),3.53(t,4H,3J=6.8Hz, NCH2),2.35(s,
6H,ArCH3),2.13-1.80(br,2H,CH2CH2CH2),1.69(s,12H,CPh(CH3)2),1.52(s,12H,CPh
(CH3)2).13C NMR(CDCl3,100MHz):δ162.4,151.2,150.5,138.9,131.6,129.2,128.0,127.7,
126.5,126.1,125.0,124.1,36.5,34.1,31.8,30.6,25.6,21.9.Anal.Calcd.for
C37H40Cl2N2O2Zr:C,62.87；H,5.70；N,3.96.Found:C,62.72；H,5.61；N, 4.07%.
Embodiment 11
The synthesis of titanium complex Z6
Under argon atmosphere, to ligand 2,2 '-(propylidene -1,6- di-imidogen)-two is added in Schlenk bottles of 100mL
(6- adamantyls phenol) (0.83g, 1.5mmol) and 20mL tetrahydrofurans, is stirred at room temperature dissolving, is cooled down with liquid nitrogen/ethanol bath
To -78 DEG C, n-BuLi hexane solution (1.6mol/L, 1.88mL, 3.0mmol) is then slowly added dropwise, room temperature is added dropwise
It is stirred to react 2 hours.Reaction solution is cooled to 0 DEG C with ice-water bath, zirconium chloride tetrahydrofuran complex is then added
(0.566g, 1.5mmol), 70 DEG C are stirred to react 28 hours.Solvent and volatile materials are removed under vacuum, and dichloromethane is added
(20mL) extraction dissolving reaction product, stirs 30 minutes, is filtered after standing 8 hours, and concentrated solvent to solution muddiness is added appropriate
N-hexane adjust polarity, crystallizing at room temperature, be precipitated greenish yellow solid, filtering, washed with n-hexane, obtain zirconium complex Z6 (0.33g,
Yield：33.6%).
Three isomers C2:Cs:C1=0.77:0.03:0.20.1H NMR of C2-isomer(400MHz,
CDCl3):δ7.92(s,2H,CHN),7.52-6.95(m,6H,ArH),3.53(t,4H,3J=6.8Hz, NCH2),2.06-1.61
(m,32H,NCH2CH2and Adamantyl).13C NMR(CDCl3,100MHz):δ163.9,156.7,135.2,132.6,
129.2,124.1,121.1,43.5,43.2,36.8,36.3,34.1,31.8,30.6,28.4,24.3.Anal.Calcd.for
C37H44Cl2N2O2Zr:C,62.51；H,6.24；N,3.94.Found:C,62.89；H,6.25；N, 4.35%.
Embodiment 12
Under nitrogen protection, the toluene solution of 150mL toluene and 3.33mL methylaluminoxane is added in stainless steel polymeric kettle
(1.5mol/L) adjusts kettle liquid temperature and to 50 DEG C and keeps stable, weighs 0.50 μm of ol catalyst Z 1 and is dissolved in toluene and is added
Into reaction kettle.The rapid ethylene pressure that adjusts to 1.0MPa and starts timing, and keeps constant ethylene pressure in the course of the polymerization process.
After reaction 30 minutes, stopping is passed through ethylene gas, and 5% hydrochloric acid-ethanol solution is added in the ethylene gas in slow release polymeric kettle
Polymerization is terminated, filtering obtains white solid polyethylene.Vacuum drying is until constant weight.Yield：5.6g, Mη=4.5 × 106G/mol, point
Son amount distribution PDI=2.5.
Embodiment 13
Under nitrogen protection, the toluene solution of 150mL toluene and 3.33mL methylaluminoxane is added in stainless steel polymeric kettle
(1.5mol/L) adjusts kettle liquid temperature and to 20 DEG C and keeps stable, weighs 0.50 μm of ol catalyst Z 1 and is dissolved in toluene and is added
Into reaction kettle.The rapid ethylene pressure that adjusts to 1.0MPa and starts timing, and keeps constant ethylene pressure in the course of the polymerization process.
After reaction 30 minutes, stopping is passed through ethylene gas, and 5% hydrochloric acid-ethanol solution is added in the ethylene gas in slow release polymeric kettle
Polymerization is terminated, filtering obtains white solid polyethylene.Vacuum drying is until constant weight.Yield：3.3g, Mη=6.1 × 106G/mol, point
Son amount distribution PDI=2.4.
Embodiment 14
Under nitrogen protection, the toluene solution of 150mL toluene and 1.67mL ethylaluminoxanes is added in stainless steel polymeric kettle
(1.5mol/L) adjusts kettle liquid temperature and to 70 DEG C and keeps stable, weighs 0.50 μm of ol catalyst Z 2 and is dissolved in toluene and is added
Into reaction kettle.The rapid ethylene pressure that adjusts to 2.0MPa and starts timing, and keeps constant ethylene pressure in the course of the polymerization process.
After reaction 30 minutes, stopping is passed through ethylene gas, and 5% hydrochloric acid-ethanol solution is added in the ethylene gas in slow release polymeric kettle
Polymerization is terminated, filtering obtains white solid polyethylene.Vacuum drying is until constant weight.Yield：2.7g, Mη=7.6 × 104G/mol, point
Son amount distribution PDI=3.8.
Embodiment 15
Under nitrogen protection, the toluene solution of 150mL toluene and 3.33mL methylaluminoxane is added in stainless steel polymeric kettle
(1.5mol/L) adjusts kettle liquid temperature and to 50 DEG C and keeps stable, weighs 0.50 μm of ol catalyst Z 3 and is dissolved in toluene and is added
Into reaction kettle.The rapid ethylene pressure that adjusts to 0.5MPa and starts timing, and keeps constant ethylene pressure in the course of the polymerization process.
After sixty minutes, stopping is passed through ethylene gas, and 5% hydrochloric acid-ethanol solution is added in the ethylene gas in slow release polymeric kettle for reaction
Polymerization is terminated, filtering obtains white solid polyethylene.Vacuum drying is until constant weight.Yield：8.4g, Mη=3.9 × 105G/mol, point
Son amount distribution PDI=4.3.
Embodiment 16
Under nitrogen protection, the toluene of 150mL toluene and 6.66mL modified methylaluminoxanes is added in stainless steel polymeric kettle
Solution (1.5mol/L) adjusts kettle liquid temperature and to 90 DEG C and keeps stable, weighs 0.50 μm of ol catalyst Z 4 and be dissolved in toluene
It is added in reaction kettle.The rapid ethylene pressure that adjusts to 3.0MPa and starts timing, and keeps ethylene pressure in the course of the polymerization process
It is constant.After reaction 30 minutes, stopping is passed through ethylene gas, and 5% hydrochloric acid-second is added in the ethylene gas in slow release polymeric kettle
Alcoholic solution terminates polymerization, and filtering obtains white solid polyethylene.Vacuum drying is until constant weight.Yield：10.6g Mη=8.3 ×
104G/mol, molecular weight distribution PDI=5.6.
Embodiment 17
Under nitrogen protection, 150mL n-hexanes are added in stainless steel polymeric kettle and the toluene of 3.33mL methylaluminoxane is molten
Liquid (1.5mol/L) adjusts kettle liquid temperature and to 20 DEG C and keeps stable, weighs 0.50 μm of ol catalyst Z 5 and be dissolved in n-hexane
It is added in reaction kettle.The rapid ethylene pressure that adjusts to 1.0MPa and starts timing, and keeps ethylene pressure in the course of the polymerization process
It is constant.After reaction 30 minutes, stopping is passed through ethylene gas, and 5% hydrochloric acid-second is added in the ethylene gas in slow release polymeric kettle
Alcoholic solution terminates polymerization, and filtering obtains white solid polyethylene.Vacuum drying is until constant weight.Yield：3.6g, Mη=1.3 × 105g/
Mol, molecular weight distribution PDI=2.9.
Embodiment 18
Under nitrogen protection, the toluene of 150mL dichloromethane and 3.33mL methylaluminoxane is added in stainless steel polymeric kettle
Solution (1.5mol/L) adjusts kettle liquid temperature and to 30 DEG C and keeps stable, weighs 0.50 μm of ol catalyst Z 6 and be dissolved in dichloromethane
It is added in reaction kettle in alkane.The rapid ethylene pressure that adjusts to 1.0MPa and starts timing, and keeps ethylene in the course of the polymerization process
Pressure is constant.After reaction 30 minutes, stopping is passed through ethylene gas, and 5% salt is added in the ethylene gas in slow release polymeric kettle
Acid-ethanol solution terminates polymerization, and filtering obtains white solid polyethylene.Vacuum drying is until constant weight.Yield：2.7g, Mη=1.1
×105G/mol, molecular weight distribution PDI=3.0.
Embodiment 19
Under nitrogen protection, the toluene solution of 150mL toluene and 3.33mL ethylaluminoxanes is added in stainless steel polymeric kettle
(1.5mol/L) adjusts kettle liquid temperature and to 50 DEG C and keeps stable, weighs 0.50 μm of ol catalyst Z 1 and is dissolved in toluene and is added
Into reaction kettle.The rapid propylene pressure that adjusts to 1.0MPa and starts timing, and keeps propylene pressure constant in the course of the polymerization process.
After reaction 30 minutes, stopping is passed through propylene gas, and 5% hydrochloric acid-ethanol solution is added in the propylene gas in slow release polymeric kettle
Polymerization is terminated, filtering obtains white solid polypropylene.Vacuum drying is until constant weight.Yield：4.4g, Mη=1.6 × 106G/mol, point
Son amount distribution PDI=3.6.
Embodiment 20
Under nitrogen protection, the toluene solution of 150mL toluene and 3.33mL methylaluminoxane is added in stainless steel polymeric kettle
(1.5mol/L) adjusts kettle liquid temperature and to 30 DEG C and keeps stable, weighs 1.50 μm of ol catalyst Zs 2 and is dissolved in toluene and is added
Into reaction kettle.The rapid propylene pressure that adjusts to 3.0MPa and starts timing, and keeps propylene pressure constant in the course of the polymerization process.
After reaction 30 minutes, stopping is passed through propylene gas, and 5% hydrochloric acid-ethanol solution is added in the propylene gas in slow release polymeric kettle
Polymerization is terminated, filtering obtains white solid polypropylene.Vacuum drying is until constant weight.Yield：6.5g, Mη=7.2 × 105G/mol, point
Son amount distribution PDI=3.8.
Embodiment 21
Under nitrogen protection, 150mL n-hexanes are added in stainless steel polymeric kettle and the toluene of 3.33mL ethylaluminoxanes is molten
Liquid (1.5mol/L) adjusts kettle liquid temperature and to 50 DEG C and keeps stable, weighs 0.50 μm of ol catalyst Z 2 and be dissolved in n-hexane
It is added in reaction kettle.The rapid propylene pressure that adjusts to 1.0MPa and starts timing, and keeps propylene pressure in the course of the polymerization process
It is constant.After reaction 30 minutes, stopping is passed through propylene gas, and 5% hydrochloric acid-second is added in the propylene gas in slow release polymeric kettle
Alcoholic solution terminates polymerization, and filtering obtains white solid polypropylene.Vacuum drying is until constant weight.Yield：3.5g, Mη=2.3 × 106g/
Mol, molecular weight distribution PDI=4.0.
Embodiment 22
Under nitrogen protection, the toluene of 150mL dichloromethane and 3.33mL methylaluminoxane is added in stainless steel polymeric kettle
Solution (1.5mol/L) adjusts kettle liquid temperature and to 30 DEG C and keeps stable, weighs 0.50 μm of ol catalyst Z 2 and be dissolved in dichloromethane
It is added in reaction kettle in alkane.The rapid propylene pressure that adjusts to 1.0MPa and starts timing, and keeps propylene in the course of the polymerization process
Pressure is constant.After reaction 30 minutes, stopping is passed through propylene gas, and 5% salt is added in the propylene gas in slow release polymeric kettle
Acid-ethanol solution terminates polymerization, and filtering obtains white solid polypropylene.Vacuum drying is until constant weight.Yield：3.6g, Mη=1.3
×106G/mol, molecular weight distribution PDI=4.1.
Embodiment 23
Under nitrogen protection, the toluene solution of 200mL toluene and 3.33mL methylaluminoxane is added in stainless steel polymeric kettle
(1.5mol/L) adjusts kettle liquid temperature and to 50 DEG C and keeps stable, weighs 0.50 μm of ol catalyst Z 1 and is dissolved in toluene and is added
Into reaction kettle.The rapid ethylene pressure that adjusts is to 1.0MPa, then pours propylene gas, and it is 2.0MPa to make gross pressure.Start timing, and
Keep gas pressure constant in the course of the polymerization process.After reaction 30 minutes, stopping is passed through gas, the pressure in slow release polymeric kettle
Power, the hydrochloric acid-ethanol solution for being added 5% terminate polymerization, and filtering obtains white solid copolymer from ethylene and propylene.Vacuum drying is straight
To constant weight.Yield：2.4g, Mη=5.8 × 105G/mol, molecular weight distribution PDI=5.2.
Embodiment 24
Under nitrogen protection, the toluene solution of 200mL toluene and 3.33mL methylaluminoxane is added in stainless steel polymeric kettle
(1.5mol/L) adjusts kettle liquid temperature and to 50 DEG C and keeps stable, weighs 0.50 μm of ol catalyst Z 1 and is dissolved in toluene and is added
Into reaction kettle.The rapid ethylene pressure that adjusts is to 1.0MPa, then pours propylene gas, and it is 2.0MPa to make gross pressure in kettle.Start to count
When, and keep gas pressure constant in the course of the polymerization process.After reaction 30 minutes, stopping is passed through gas, in slow release polymeric kettle
Pressure, be added 5% hydrochloric acid-ethanol solution terminate polymerization, filtering, obtain white solid copolymer from ethylene and propylene.Vacuum is dry
It is dry until constant weight.Yield：2.4g, Mη=5.8 × 105G/mol, molecular weight distribution PDI=5.2.
Embodiment 25
Under nitrogen protection, the toluene solution of 200mL toluene and 3.33mL methylaluminoxane is added in stainless steel polymeric kettle
(1.5mol/L) adjusts kettle liquid temperature and to 50 DEG C and keeps stable, weighs 0.50 μm of ol catalyst Z 2 and is dissolved in toluene and is added
Into reaction kettle.The rapid ethylene pressure that adjusts is to 1.0MPa, then pours propylene gas, and it is 1.5MPa to make gross pressure in kettle.Start to count
When, and keep gas pressure constant in the course of the polymerization process.After reaction 30 minutes, stopping is passed through gas, in slow release polymeric kettle
Pressure, be added 5% hydrochloric acid-ethanol solution terminate polymerization, filtering, obtain white solid copolymer from ethylene and propylene.Vacuum is dry
It is dry until constant weight.Yield：3.6g, Mη=3.4 × 105G/mol, molecular weight distribution PDI=2.7.
Embodiment 26
Under nitrogen protection, the toluene of 200mL toluene and 3.33mL modified methylaluminoxanes is added in stainless steel polymeric kettle
Solution (1.5mol/L) adjusts kettle liquid temperature and to 50 DEG C and keeps stable, weighs 0.50 μm of ol catalyst Z 2 and be dissolved in toluene
It is added in reaction kettle.The rapid ethylene pressure that adjusts is to 0.5MPa, then pours propylene gas, and it is 2.0MPa to make gross pressure in kettle.It opens
Beginning timing, and keep gas pressure constant in the course of the polymerization process.After reaction 30 minutes, stopping is passed through gas, slow release polymerization
Pressure in kettle, the hydrochloric acid-ethanol solution for being added 5% terminate polymerization, and filtering obtains white solid copolymer from ethylene and propylene.Very
Sky is dry until constant weight.Yield：4.5g, Mη=3.7 × 105G/mol, molecular weight distribution PDI=3.0.
Embodiment 27
Under nitrogen protection, the toluene solution of 200mL toluene and 3.33mL methylaluminoxane is added in stainless steel polymeric kettle
(1.5mol/L) adjusts kettle liquid temperature and to 50 DEG C and keeps stable, weighs 0.50 μm of ol catalyst Z 4 and is dissolved in toluene and is added
Into reaction kettle.The rapid ethylene pressure that adjusts is to 1.0MPa, then pours propylene gas, and it is 2.0MPa to make gross pressure in kettle.Start to count
When, and keep gas pressure constant in the course of the polymerization process.After reaction 30 minutes, stopping is passed through gas, in slow release polymeric kettle
Pressure, be added 5% hydrochloric acid-ethanol solution terminate polymerization, filtering, obtain white solid copolymer from ethylene and propylene.Vacuum is dry
It is dry until constant weight.Yield：5.9g, Mη=5.9 × 105G/mol, molecular weight distribution PDI=2.9.
Embodiment 28
Under nitrogen protection, the toluene solution of 200mL toluene and 6.66mL methylaluminoxane is added in stainless steel polymeric kettle
(1.5mol/L) adjusts kettle liquid temperature and to 20 DEG C and keeps stable, weighs 1.50 μm of ol catalyst Zs 4 and is dissolved in toluene and is added
Into reaction kettle.The rapid ethylene pressure that adjusts is to 2.0MPa, then pours propylene gas, and it is 2.5MPa to make gross pressure in kettle.Start to count
When, and keep gas pressure constant in the course of the polymerization process.After reaction 30 minutes, stopping is passed through gas, in slow release polymeric kettle
Pressure, be added 5% hydrochloric acid-ethanol solution terminate polymerization, filtering, obtain white solid copolymer from ethylene and propylene.Vacuum is dry
It is dry until constant weight.Yield：9.6g, Mη=6.1 × 105G/mol, molecular weight distribution PDI=3.7.
Embodiment 29
Under nitrogen protection, 200mL n-hexanes are added in stainless steel polymeric kettle and the toluene of 3.33mL methylaluminoxane is molten
Liquid (1.5mol/L) adjusts kettle liquid temperature and to 60 DEG C and keeps stable, weighs 0.50 μm of ol catalyst Z 4 and be dissolved in n-hexane
It is added in reaction kettle.The rapid ethylene pressure that adjusts is to 1.0MPa, then pours propylene gas, and it is 2.0MPa to make gross pressure in kettle.It opens
Beginning timing, and keep gas pressure constant in the course of the polymerization process.After reaction 30 minutes, stopping is passed through gas, slow release polymerization
Pressure in kettle, the hydrochloric acid-ethanol solution for being added 5% terminate polymerization, and filtering obtains white solid copolymer from ethylene and propylene.Very
Sky is dry until constant weight.Yield：4.2g, Mη=6.3 × 105G/mol, molecular weight distribution PDI=3.8.
Embodiment 30
Under nitrogen protection, the toluene solution of 200mL toluene and 3.33mL methylaluminoxane is added in stainless steel polymeric kettle
(1.5mol/L) adjusts kettle liquid temperature and to 50 DEG C and keeps stable, weighs 0.50 μm of ol catalyst Z 4 and is dissolved in toluene and is added
Into reaction kettle.The rapid ethylene pressure that adjusts is to 1.0MPa, then pours propylene gas, and it is 2.0MPa to make gross pressure in kettle.Start to count
When, and keep gas pressure constant in the course of the polymerization process.After reaction 120 minutes, stopping is passed through gas, in slow release polymeric kettle
Pressure, be added 5% hydrochloric acid-ethanol solution terminate polymerization, filtering, obtain white solid copolymer from ethylene and propylene.Vacuum is dry
It is dry until constant weight.Yield：12.8g Mη=6.9 × 105G/mol, molecular weight distribution PDI=4.5.
Embodiment 31
Under nitrogen protection, 200mL toluene, the toluene solution of 3.33mL methylaluminoxane are added in stainless steel polymeric kettle
(1.5mol/L) and 10mmol 1- hexenes adjust kettle liquid temperature and to 50 DEG C and keep stable, it is molten to weigh 0.50 μm of ol catalyst Z 1
Solution is added in toluene in reaction kettle.The rapid ethylene pressure that adjusts to 1.0MPa and starts timing, and protects in the course of the polymerization process
Hold constant ethylene pressure.After reaction 30 minutes, stopping is passed through ethylene, and 5% salt is added in the ethylene in slow release polymeric kettle
Acid-ethanol solution terminates polymerization, and filtering obtains white solid ethylene and 1- hexene copolymers.Vacuum drying is until constant weight.Yield：
3.2g, Mη=1.1 × 106G/mol, molecular weight distribution PDI=2.4.
Embodiment 32
Under nitrogen protection, 200mL toluene, the toluene solution of 3.33mL methylaluminoxane are added in stainless steel polymeric kettle
(1.5mol/L) and 100mmol 1- hexenes adjust kettle liquid temperature and to 50 DEG C and keep stable, weigh 0.50 μm of ol catalyst Z 2
It is dissolved in toluene and is added in reaction kettle.The rapid ethylene pressure that adjusts to 1.0MPa and starts timing, and in the course of the polymerization process
Keep constant ethylene pressure.After reaction 30 minutes, stopping is passed through ethylene, and 5% salt is added in the ethylene in slow release polymeric kettle
Acid-ethanol solution terminates polymerization, and filtering obtains white solid ethylene and 1- hexene copolymers.Vacuum drying is until constant weight.Yield：
6.2g, Mη=5.0 × 105G/mol, molecular weight distribution PDI=3.7.
Embodiment 33
Under nitrogen protection, 200mL n-hexanes, the toluene solution of 3.33mL methylaluminoxane are added in stainless steel polymeric kettle
(1.5mol/L) and 100mmol 1- hexenes adjust kettle liquid temperature and to 50 DEG C and keep stable, weigh 0.50 μm of ol catalyst Z 2
N-hexane is dissolved in be added in reaction kettle.The rapid ethylene pressure that adjusts to 1.0MPa and starts timing, and in the course of the polymerization process
Keep constant ethylene pressure.After sixty minutes, stopping is passed through ethylene, and 5% salt is added in the ethylene in slow release polymeric kettle for reaction
Acid-ethanol solution terminates polymerization, and filtering obtains white solid ethylene and 1- hexene copolymers.Vacuum drying is until constant weight.Yield：
4.9g, Mη=1.1 × 106G/mol, molecular weight distribution PDI=4.3.
Embodiment 34
Under nitrogen protection, 200mL n-hexanes, the toluene solution of 3.33mL methylaluminoxane are added in stainless steel polymeric kettle
(1.5mol/L) and 100mmol 1- hexenes adjust kettle liquid temperature and to 50 DEG C and keep stable, weigh 0.50 μm of ol catalyst Z 2
N-hexane is dissolved in be added in reaction kettle.The rapid ethylene pressure that adjusts to 1.0MPa and starts timing, and in the course of the polymerization process
Keep constant ethylene pressure.After sixty minutes, stopping is passed through ethylene, and 5% salt is added in the ethylene in slow release polymeric kettle for reaction
Acid-ethanol solution terminates polymerization, and filtering obtains white solid ethylene and 1- hexene copolymers.Vacuum drying is until constant weight.Yield：
3.5g, Mη=1.9 × 106G/mol, molecular weight distribution PDI=4.5.
Embodiment 35
Under nitrogen protection, 200mL n-hexanes, the toluene solution of 3.33mL methylaluminoxane are added in stainless steel polymeric kettle
(1.5mol/L) and 100mmol 1- hexenes adjust kettle liquid temperature and to 100 DEG C and keep stable, weigh 0.50 μm of ol catalyst Z 4
N-hexane is dissolved in be added in reaction kettle.The rapid ethylene pressure that adjusts to 1.0MPa and starts timing, and in the course of the polymerization process
Keep constant ethylene pressure.After sixty minutes, stopping is passed through ethylene, and 5% salt is added in the ethylene in slow release polymeric kettle for reaction
Acid-ethanol solution terminates polymerization, and filtering obtains white solid ethylene and 1- hexene copolymers.Vacuum drying is until constant weight.Yield：
7.2g, Mη=4.9 × 105G/mol, molecular weight distribution PDI=2.6.
Embodiment 36
Under nitrogen protection, 200mL toluene, the toluene solution of 3.33mL methylaluminoxane are added in stainless steel polymeric kettle
(1.5mol/L) and 20mmol 1- octenes adjust kettle liquid temperature and to 50 DEG C and keep stable, it is molten to weigh 0.50 μm of ol catalyst Z 3
Solution is added in toluene in reaction kettle.The rapid ethylene pressure that adjusts to 1.0MPa and starts timing, and protects in the course of the polymerization process
Hold constant ethylene pressure.After reaction 30 minutes, stopping is passed through ethylene, and 5% salt is added in the ethylene in slow release polymeric kettle
Acid-ethanol solution terminates polymerization, and filtering obtains white solid ethylene and 1- octene copolymers.Vacuum drying is until constant weight.Yield：
2.8g, Mη=4.7 × 105G/mol, molecular weight distribution PDI=2.6.
Embodiment 37
Under nitrogen protection, 200mL toluene, the toluene solution of 3.33mL methylaluminoxane are added in stainless steel polymeric kettle
(1.5mol/L) and 50mmol 1- octenes adjust kettle liquid temperature and to 70 DEG C and keep stable, it is molten to weigh 0.50 μm of ol catalyst Z 4
Solution is added in toluene in reaction kettle.The rapid ethylene pressure that adjusts to 2.5MPa and starts timing, and protects in the course of the polymerization process
Hold constant ethylene pressure.After reaction 30 minutes, stopping is passed through ethylene, and 5% salt is added in the ethylene in slow release polymeric kettle
Acid-ethanol solution terminates polymerization, and filtering obtains white solid ethylene and 1- octene copolymers.Vacuum drying is until constant weight.Yield：
5.0g, Mη=7.3 × 105G/mol, molecular weight distribution PDI=2.9.
Embodiment 38
Under nitrogen protection, 200mL toluene, the toluene solution of 3.33mL methylaluminoxane are added in stainless steel polymeric kettle
(1.5mol/L) and 50mmol 1- octenes adjust kettle liquid temperature and to 50 DEG C and keep stable, it is molten to weigh 0.50 μm of ol catalyst Z 5
Solution is added in toluene in reaction kettle.The rapid ethylene pressure that adjusts to 4.0MPa and starts timing, and protects in the course of the polymerization process
Hold constant ethylene pressure.After reaction 30 minutes, stopping is passed through ethylene, and 5% salt is added in the ethylene in slow release polymeric kettle
Acid-ethanol solution terminates polymerization, and filtering obtains white solid ethylene and 1- octene copolymers.Vacuum drying is until constant weight.Yield：
4.6g, Mη=8.3 × 105G/mol, molecular weight distribution PDI=3.3.
Embodiment 39
Under nitrogen protection, 200mL dichloromethane is added in stainless steel polymeric kettle, the toluene of 3.33mL methylaluminoxane is molten
Liquid (1.5mol/L) and 50mmol 1- octenes adjust kettle liquid temperature and to 50 DEG C and keep stable, weigh 0.50 μm of ol catalyst Z 5
Dichloromethane is dissolved in be added in reaction kettle.The rapid ethylene pressure that adjusts to 2.0MPa and starts timing, and in polymerization process
Middle holding constant ethylene pressure.After sixty minutes, stopping is passed through ethylene, and the ethylene in slow release polymeric kettle is added 5% for reaction
Hydrochloric acid-ethanol solution terminates polymerization, and filtering obtains white solid ethylene and 1- octene copolymers.Vacuum drying is until constant weight.Production
Amount：6.5g, Mη=1.3 × 106G/mol, molecular weight distribution PDI=3.3.
Embodiment 40
Under nitrogen protection, 200mL toluene, the toluene solution of 3.33mL methylaluminoxane are added in stainless steel polymeric kettle
(1.5mol/L) and 50mmol 1- octenes adjust kettle liquid temperature and to 50 DEG C and keep stable, it is molten to weigh 0.50 μm of ol catalyst Z 6
Solution is added in toluene in reaction kettle.The rapid ethylene pressure that adjusts to 1.0MPa and starts timing, and protects in the course of the polymerization process
Hold constant ethylene pressure.After reaction 30 minutes, stopping is passed through ethylene, and 5% salt is added in the ethylene in slow release polymeric kettle
Acid-ethanol solution terminates polymerization, and filtering obtains white solid ethylene and 1- octene copolymers.Vacuum drying is until constant weight.Yield：
3.0g, Mη=2.2 × 105G/mol, molecular weight distribution PDI=2.8.
Embodiment 41
Bis-phenol oxygroup imine ligand zirconium compounds, general structure are as follows：
In formula (I)：
R1~R4Respectively represent hydrogen, cumyl, methoxyl group, isopropoxy；R5For C2The alkyl of straight chain；R6For fluorine；N is 3.
The preparation method of this kind of bis-phenol oxygroup imine ligand zirconium compounds, using following steps：
After bis-phenol imines ligand compound is reacted with butyl lithium, with halogenation zirconium compounds Zr (R6)4It is 1 in molar ratio:
1.0 react in tetrahydrofuran, and controlling reaction temperature is -78 DEG C, reacts 96h, and using filter, concentration, recrystallization processing obtains
Bis-phenol oxygroup imine ligand zirconium compounds.
The general structure of bis-phenol imines ligand compound is as follows：
The bis-phenol oxygroup imine ligand zirconium compounds being prepared in the presence of methylaluminoxane be applied to alkene homopolymerization and
Copolymerization.
Using bis-phenol oxygroup imine ligand zirconium compounds as major catalyst, using methylaluminoxane as co-catalyst, make ethylene 0
The molar ratio of homopolymerization at DEG C, major catalyst and co-catalyst is 1:1；The pressure of ethylene is 0.1MPa.
Using bis-phenol oxygroup imine ligand zirconium compounds as major catalyst, using methylaluminoxane as co-catalyst, make ethylene and
Propylene is copolymerized at 150 DEG C, and the molar ratio of major catalyst and co-catalyst is 1 when copolymerization:50；The gross pressure of ethylene and propylene is
5.0MPa；The pressure ratio of ethylene and propylene is 1:9.
Using bis-phenol oxygroup imine ligand zirconium compounds as major catalyst, using methylaluminoxane as co-catalyst, make ethylene and
1- hexenes are copolymerized at 0~150 DEG C, and the molar ratio of major catalyst and co-catalyst is 1:10000；Ethylene pressure is 5.0MPa；
The molar ratio of catalyst and 1- hexenes is 1:2000.
Using bis-phenol oxygroup imine ligand zirconium compounds as major catalyst, using methylaluminoxane as co-catalyst, make ethylene and
1- octenes are copolymerized at 80 DEG C, and the molar ratio of major catalyst and co-catalyst is 1:100000, ethylene pressure 10.0MPa；It urges
Agent and the molar ratio of 1- octenes are 1:50000.
Embodiment 42
Bis-phenol oxygroup imine ligand zirconium compounds, general structure are as follows：
In formula (I)：
R1~R4Cumyl respectively, methoxyl group, trimethyl silicon substrate, triisopropylsilyl；R5For C6Or more alkyl；R6For chlorine；N is
6。
The preparation method of bis-phenol oxygroup imine ligand zirconium compounds, using following steps：
After bis-phenol imines ligand compound is reacted with tert-butyl lithium, with halogenation zirconium compounds Zr (R6)42THF,
Middle R6It is in molar ratio 1 for halogen group:1.5 react in organic media, and controlling reaction temperature is 110 DEG C, react 2h, then
Through filtering, concentration, recrystallization processing obtains bis-phenol oxygroup imine ligand zirconium compounds.
The general structure of bis-phenol imines ligand compound is as follows：
Bis-phenol oxygroup imine ligand zirconium compounds is applied to alkene homopolymerization and copolymerization in the presence of isopropylaluminoxane.
Using bis-phenol oxygroup imine ligand zirconium compounds as major catalyst, using isopropylaluminoxane as co-catalyst, make propylene
The molar ratio of the homopolymerization at 150 DEG C, major catalyst and co-catalyst is 1:100000, the pressure of propylene is~10.0MPa.
Using bis-phenol oxygroup imine ligand zirconium compounds as major catalyst, using isopropylaluminoxane as co-catalyst, make ethylene
It is copolymerized at 100 DEG C with propylene, the molar ratio of major catalyst and co-catalyst is 1 when copolymerization:100000, ethylene and propylene it is total
Pressure is 10.0MPa, and the pressure ratio of ethylene and propylene is 7:3.
Using bis-phenol oxygroup imine ligand zirconium compounds as major catalyst, using isopropylaluminoxane as co-catalyst, make ethylene
It is copolymerized at 150 DEG C with 1- hexenes, the molar ratio of major catalyst and co-catalyst is 1:100000, ethylene pressure is
The molar ratio of 10.0MPa, catalyst and 1- hexenes is 1:100000.
Using bis-phenol oxygroup imine ligand zirconium compounds as major catalyst, using isopropylaluminoxane as co-catalyst, make ethylene
It is copolymerized at 150 DEG C with 1- octenes, the molar ratio of major catalyst and co-catalyst is 1:100000, ethylene pressure 10.0MPa,
The molar ratio of catalyst and 1- octenes is 1:100000.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (10)
1. bis-phenol oxygroup imine ligand zirconium compounds, which is characterized in that the compound structure general formula is as follows：
In formula (I)：
R1~R4Respectively represent hydrogen, C1~C10The alkyl of straight chain, branch or cyclic structure, cumyl, alkoxy, silylation, C7~C20
The alkyl or halogen of single or multiple aryl substitution；R5Represent C1~C10The alkyl of straight chain, branch or cyclic structure, C6~C10Dan Huo
The substituted or unsubstituted benzyl of more alkyl, halogen；R6Represent halogen；N represents 3~8 positive integer.
2. bis-phenol oxygroup imine ligand zirconium compounds according to claim 1, which is characterized in that R1~R4Preferably hydrogen, C1
~C6The alkyl of straight chain, branch or cyclic structure, cumyl, methoxyl group, isopropoxy, isobutoxy, trimethyl silicon substrate, three isopropyls
Base silicon substrate, chlorine, bromine or iodine；R5Preferably C1~C6Straight chain, branch or cricoid alkyl, C6~C10Single or multiple alkyl, fluorine, chlorine take
Generation or unsubstituted benzyl；R6Preferably fluorine or chlorine；N is preferably 3~6 positive integer.
3. the preparation method of bis-phenol oxygroup imine ligand zirconium compounds as described in claim 1, which is characterized in that this method is adopted
Use following steps：
It is 1 in molar ratio with halogenation zirconium compounds after bis-phenol imines ligand compound is reacted with lithium alkylide:1.0~1.5
It is reacted in organic media, controlling reaction temperature is -78~110 DEG C, reacts 2~96h, and using filter, concentration, recrystallization processing obtains
Obtain bis-phenol oxygroup imine ligand zirconium compounds.
4. the preparation method of bis-phenol oxygroup imine ligand zirconium compounds according to claim 3, which is characterized in that described
The general structure of bis-phenol imines ligand compound is as follows：
The lithium alkylide is one kind in lithium methide, butyl lithium or tert-butyl lithium,
The halogenation zirconium compounds is Zr (R6)4Or Zr (R6)42THF, wherein R6For halogen group,
The organic media is in tetrahydrofuran, ether, toluene, benzene, chloroform, dichloromethane, petroleum ether or n-hexane
One or two,
Reaction temperature is preferably -20~80 DEG C, and the reaction time is preferably 2~48h.
5. it is equal that bis-phenol oxygroup imine ligand zirconium compounds as described in claim 1 is applied to alkene in the presence of alkylaluminoxane
Poly- and copolymerization.
6. the application of bis-phenol oxygroup imine ligand zirconium compounds according to claim 5, which is characterized in that the alkyl
Aikyiaiurnirsoxan beta is selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane or isopropylaluminoxane；Alkene be selected from ethylene, third
Alkene, 1- hexenes or 1- octenes.
7. the application of bis-phenol oxygroup imine ligand zirconium compounds according to claim 5, which is characterized in that with bis-phenol oxygroup
Imine ligand zirconium compounds is major catalyst, using alkylaluminoxane as co-catalyst, keeps ethylene or propylene equal at 0~150 DEG C
Poly-, the molar ratio of major catalyst and co-catalyst is 1:1~100000, preferably 1:50~10000；The pressure of ethylene or propylene is
0.1~10.0MPa, preferably 0.1~5.0MPa.
8. the application of bis-phenol oxygroup imine ligand zirconium compounds according to claim 5, which is characterized in that with bis-phenol oxygroup
Imine ligand zirconium compounds is major catalyst, using alkylaluminoxane as co-catalyst, keeps ethylene and propylene total at 0~150 DEG C
Poly-, the molar ratio of major catalyst and co-catalyst is 1 when copolymerization:1~100000, preferably 1:50~10000；Ethylene and propylene
Gross pressure is 0.1~10.0MPa, preferably 0.1~5.0MPa；The pressure ratio of ethylene and propylene is 1:9~9:1, preferably 3:7~7:
3。
9. the application of bis-phenol oxygroup imine ligand zirconium compounds according to claim 5, which is characterized in that with bis-phenol oxygroup
Imine ligand zirconium compounds is major catalyst makes ethylene and 1- hexenes at 0~150 DEG C using alkylaluminoxane as co-catalyst
The molar ratio of copolymerization, major catalyst and co-catalyst is 1:1~100000, preferably 1:50~10000；Ethylene pressure be 0.1~
10.0MPa, preferably 0.1~5.0MPa；The molar ratio of catalyst and 1- hexenes is 1:1000-100000, preferably 1:2000-
50000。
10. the application of bis-phenol oxygroup imine ligand zirconium compounds according to claim 5, which is characterized in that with bis-phenol oxygen
Base imine ligand zirconium compounds is major catalyst makes ethylene and 1- octenes at 0~150 DEG C using alkylaluminoxane as co-catalyst
The molar ratio of lower copolymerization, major catalyst and co-catalyst is 1:1~100000, preferably 1:50~10000；Ethylene pressure is 0.1
~10.0MPa, preferably 0.1~5.0MPa；The molar ratio of catalyst and 1- octenes is 1:1000-100000, preferably 1:2000-
50000。
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| CN111592561A (en) * | 2020-05-29 | 2020-08-28 | 上海化工研究院有限公司 | Asymmetric diimine titanium group metal complex and preparation method and application thereof |
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