CN105985478B - A kind of method for preparing ethylene copolymer - Google Patents
A kind of method for preparing ethylene copolymer Download PDFInfo
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- CN105985478B CN105985478B CN201510096551.7A CN201510096551A CN105985478B CN 105985478 B CN105985478 B CN 105985478B CN 201510096551 A CN201510096551 A CN 201510096551A CN 105985478 B CN105985478 B CN 105985478B
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Abstract
The present invention relates to olefin coordination polymerization field, disclose a kind of method for preparing ethylene copolymer, this method is included under olefin polymerization conditions, in the presence of an inert solvent, ethene, comonomer are contacted with catalyst and polymerize, which contains catalyst precarsor and alkylaluminoxane, wherein, the catalyst precarsor has the structure shown in Formulas I, R1、R2And R4It is each independently the alkyl of hydrogen atom or C1 C20；R3For phenyl, halogenophenyl or alkoxyl phenyl；M is titanium, zirconium or hafnium.With higher catalytic efficiency when preparing ethylene copolymer using this method, and the molecular weight distribution of ethylene copolymer is relatively narrow.
Description
Technical field
The present invention relates to olefin coordination polymerization field, and in particular, to a kind of method for preparing ethylene copolymer.
Background technology
Since the 21th century, with national economy level raising and national defense industry needs, high molecular material, especially
It is that polyolefine material plays more and more important effect：Since polyolefinic raw materials enrich cheap, shaping is easily worked, is existed every year
The polyolefin products of production have exceeded 100,000,000 tons in world wide, become one of industry of maximum-norm；Polyolefine material has
The features such as relatively small density, good chemical proofing, water resistance and good mechanical strength, electrical insulating property, can
It is not only daily miscellaneous in agricultural, packaging, automobile, electric appliance etc. for film, tubing, plate, various moulded products, electric wire etc.
Have been widely used in terms of product, provide convenience for the clothing, food, lodging and transportion -- basic necessities of life of the mankind, it is also strategic in national defence, the energy, aerospace etc.
Great function is played in project.
Wherein, ethylene copolymer product has superior performance, and comonomer type is various, including 1- octenes, 1- hexenes,
1- butylene, propylene and polar monomer etc..By adjusting comonomer type and dosage, linear low density polyethylene can be both obtained
Alkene, can also obtain thermoplastic elastomer (TPE), moreover it is possible to obtain rubber, application is quite varied.Particularly the special construction of elastomer is assigned
Its excellent mechanical property, rheological property and ageing-resistant performance is given, low-temperature flexibility is good, dosage is few during as plastics impact resilience agent,
It is cost-effective, it can be widely applied for modifying plastics.
The booming of polyolefin industry has benefited from Ziegler-Natta catalyst and metallocene catalyst matching somebody with somebody for representative
The fast development of position polymerization.Be developed so far, for Ziegler-Natta catalyst and metallocene catalyst research increasingly into
It is ripe, but in such catalyst, it can effectively be catalyzed the catalyst type of ethylene copolymerization and few.Therefore, Nonmetallocene is urged
Agent is increasingly becoming the emphasis studied at present.Salicylaldimine ligand transition-metal catalyst belongs to one kind therein.Utilize water
What poplar aldimine closed that titanium catalyst is capable of high activity catalyzes and synthesizes the homopolymers such as polyethylene, polypropylene (Tian J, Hustad P
D,Coates G W,J.Am.Chem.Soc.2001,123,5134；Mitanti M,Mohri J,Yoshida Y,et al.,
J.Am.Chem.Soc.2002,124,3327), and can realize the alternating copolymerization of ethene and propylene, obtain a kind of functional
Thermoplastic elastomer.In addition, using such catalyst can realize ethene and 1- hexenes or alkene with polar functional group without
Rule copolymerization (Rick F, Makot M, Terunori F, Macromolecules2005,38,1546；Terao H,Ishii S,
Mitanti M, et al., J.Am.Chem.Soc.2008,130,17636), expanded the application range of titanium metal catalyst.
Patent application CN101864010B discloses a kind of catalysis in olefine polymerization or the bimetallic catalyst precursor of combined polymerization.
The catalyst precarsor is based on salicylaldimine ligand and group iv transition metals.The catalyst precarsor mainly using pentafluoroaniline with
Bridging salicylide is condensed to yield ligand, then ligand and Ti are complexed to obtain catalyst, but the catalyst synthetic route is cumbersome, cost
It is high, and the molecular weight distribution of copolymer that alpha-olefin is obtained with ethylene copolymer is wider.
Patent application CN101200404A discloses a kind of method of synthesizing short-chain olefin by ethylene oligomerization, and this method is by bearing
Generation ethylene oligomerization reaction synthesizes under the action of being loaded in the catalyst in ionic liquid, wherein, catalyst is sub- by double salicylaldehyde
Amine nickel complex is formed with alkyl aluminum, and this method products therefrom is ethylene low polymer.But double bigcatkin willows of the patent application publication
The yield of aldimine nickel complex is relatively low, in addition, ethylene polymerization activity is relatively low.
Therefore, research and development are a kind of has the non-metallocene catalyst system that high catalytic efficiency, molecular weight distribution are relatively narrow and use
The preparation method of the simple ethylene copolymer of standby technique, has important practical significance.
The content of the invention
The defects of the purpose of the invention is to overcome the prior art, there is provided a kind of new method for preparing ethylene copolymer,
The molecular weight distribution with higher catalytic efficiency and ethylene copolymer is relatively narrow when preparing ethylene copolymer using this method, uses
Non-metallocene catalyst preparation process it is simple.
Therefore, to achieve these goals, the present invention provides a kind of method for preparing ethylene copolymer, this method to include
Under olefin polymerization conditions, in the presence of an inert solvent, ethene, comonomer are contacted with catalyst and polymerize, it is described to urge
Agent contains catalyst precarsor and alkylaluminoxane, wherein, which has the structure shown in Formulas I,
Wherein, R1、R2And R4It is each independently hydrogen atom or the alkyl of C1-C20；R3For phenyl, halogenophenyl or
Alkoxyl phenyl；M is titanium, zirconium or hafnium.
The catalyst precarsor prepared used in the method for ethylene copolymer of the present invention, preparation method is simple, and cost is low,
It is reproducible, it is easy to industrialize.
The catalyst prepared used in the method for ethylene copolymer of the present invention, is by above-mentioned catalyst precarsor and alkyl
Aikyiaiurnirsoxan beta forms, and due to the bimetallic synergistic effect in structure, and has organic substituent on phenyl ring, therefore the catalyst
With high catalytic efficiency.Specifically, the catalyst used in the method for preparing ethylene copolymer of the invention is for being catalyzed
During ethylene copolymer, catalytic efficiency (polymerization activity) may be up to 5 × 106g·mol-1(Ti)·h-1More than, the ethylene copolymer of gained
Weight average molecular weight be 200,000 or so, molecular weight distribution be 2 or so, the molar content that comonomer can introduce is 1.8-12.4%
Between.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Fig. 1 is the reaction equation for preparing the catalyst precarsor of the present invention.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of method for preparing ethylene copolymer, this method is included under olefin polymerization conditions, lazy
In the presence of property solvent, ethene, comonomer are contacted with catalyst and polymerize, which contains catalyst precarsor and alkyl
Aikyiaiurnirsoxan beta, wherein, which has the structure shown in Formulas I,
Wherein, R1、R2And R4It is each independently hydrogen atom or the alkyl of C1-C20；R3For phenyl, halogenophenyl or
Alkoxyl phenyl；M is titanium, zirconium or hafnium.
In the catalyst precarsor of the method for the present invention, in Formulas I, R1、R2And R4It may be the same or different.The alkane of C1-C20
Base can be straight chain or side chain.Preferably, the alkyl of C1-C20 is the alkyl of C1-C6.Wherein, C1-C20
Straight or branched alkyl can include but is not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group,
The tert-butyl group, n-pentyl, 2- methyl butyls, 3- methyl butyls, 2,2- dimethyl propyls, n-hexyl, 2- methyl amyls, 3- methylpents
It is base, 4- methyl amyls, n-heptyl, 2- methylhexyls, 3- methylhexyls, 4- methylhexyls, 5- methylhexyls, n-heptyl, just pungent
Base, n-nonyl, positive decyl, 3,7- dimethyl octyl group, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base,
N-hexadecyl, n-octadecane base, NSC 77136 base and n-eicosane base.
In the catalyst precarsor of the method for the present invention, in Formulas I, under preferable case, halogenophenyl is pentafluorophenyl group, 2- fluorobenzene
The fluoro- 3- chlorphenyls of base, 2,4 difluorobenzene base, 4- or the chloro- 2,3,5,6- tetrafluoros phenyl of 4-；Alkoxyl phenyl is to methoxybenzene
Base.
The present inventor has found under study for action, by specific R1-R4The formed catalyst precarsor of combination is as catalysis
Fabulous catalytic effect can be obtained during the catalytic component of ethylene copolymer, it is preferable that R1For the tert-butyl group, R2For the tert-butyl group, R3For five
Fluorophenyl, R4For hydrogen, M is titanium, and the catalyst precarsor is the catalyst precarsor with Open architecture shown in formula II；Alternatively, R1
For methyl, R2For the tert-butyl group, R3For phenyl, R4For methyl, M is titanium, and the bimetallic catalyst precursor is with being opened shown in formula III
The catalyst precarsor of formula structure is put,
In the catalyst precarsor of the method for the present invention, under preferable case, the preparation method of the catalyst precarsor includes：It is being complexed
Under reaction condition, the compound with structure shown in formula IV and the compound with structure shown in Formula V are connect in organic solvent
Touch, obtain having the catalyst precarsor of structure shown in Formulas I,
Wherein, R1、R2And R4It is each independently hydrogen atom or the alkyl of C1-C20；R3For phenyl, halogenophenyl or
Alkoxyl phenyl；M is titanium, zirconium or hafnium.
It is as shown in Figure 1 to prepare the above-mentioned reaction equation with the catalyst precarsor of structure shown in formula I.
In the preparation method of the catalyst precarsor of the method for the present invention, on R1、R2、R3And R4Restriction can be by above
Description is reasonably selected, and is not being repeated herein.
In the preparation method of the catalyst precarsor of the method for the present invention, the compound with structure shown in formula IV can be according to such as
It is prepared by lower method：By 6,6'- (1Z, 1'Z)-(4,4'- alkyl substituent methyl double (4,1- penylenes) it is double (imines -1- substitutions -
1- subunits)) double (methyl isophthalic acid-substitution-1- subunits) double (2- alkyl substituted phenols) (according to Eur.Polym.J.2012,48,191-
The preparation method that 199 documents are recorded is made) (1eq) is dissolved in dichloromethane solvent, it will be added at -78 DEG C in the solution to containing
In the dichloromethane solution for having (double tetrahydrofuran) titanium tetrachloride (1.8-2.2eq), when reaction 1 is small under low temperature, recover to room temperature
And 40 DEG C are heated to, when the reaction was continued 8-16 is small.After reaction, solvent is removed with vacuum line, residue dichloromethane
Wash and filtered by diatomite, filtrate is drained, crude product is recrystallized with dichloromethane/n-hexane, obtains red brown solid.
In the preparation method of the catalyst precarsor of the method for the present invention, the compound with structure shown in Formula V can be according to such as
It is prepared by lower method：- 6- ((aryl substituted imine base) methyl) phenol (1eq) is substituted to be dissolved in ether solvent in (E) -2- alkyl
In, the hexane solution containing n-BuLi (0.95-1.05eq) is added (in hexane solution into the solution at -78 DEG C
The concentration of n-BuLi is 1.67M) afterwards reaction 1 it is small when, recover to 25 DEG C of room temperature, the reaction was continued 10-20 minutes, to obtain the final product.
In the preparation method of the catalyst precarsor of the method for the present invention, compound with structure shown in formula IV with Formula V
The molar ratio of the compound of shown structure can change in a wider scope, be not particularly limited, and under preferable case, have
The compound of structure shown in formula IV is 1 with the molar ratio with the compound of structure shown in Formula V：1.8-2.2.
In the preparation method of the catalyst precarsor of the method for the present invention, the condition of contact can change in a wider scope,
As long as ensure that the compound with structure shown in formula IV is with the compound reaction generation target product with structure shown in Formula V
Can, under preferable case, the condition of contact includes：Temperature is 0-40 DEG C, more preferably 20-30 DEG C；When time is 8-24 small,
When more preferably 10-15 is small.
In the preparation method of the catalyst precarsor of the method for the present invention, for organic solvent, there is no particular limitation, Ke Yiwei
The various atent solvents not reacted with reactant and product well known to field of olefin polymerisation technical staff, under preferable case,
Organic solvent is the one or more in tetrahydrofuran, ether, 1,4- dioxane and dichloromethane.These solvents can be independent
Use, can also be used in mixed way.The dosage of organic solvent can according to formula IV the compound of structure with Formula V institute
Show that the dosage of the compound of structure is reasonably selected, this is known to those skilled in the art, and details are not described herein.
In the preparation method of the catalyst precarsor of the method for the present invention, this method is additionally may included in after reaction completion, will
Organic solvent removes.Wherein, for the method that removes organic solvent, there is no particular limitation, can use well known in the art each
Kind method, for example, vacuum line removes organic solvent etc. except organic solvent, revolving, it is known to those skilled in the art, herein will
Repeat no more.
In the preparation method of the catalyst precarsor of the method for the present invention, sterling, this method can also include inciting somebody to action in order to obtain
To product purified the step of.For the method for purifying, there is no particular limitation, can use well known in the art various
Purification process carries out, and such as recrystallizes.For recrystallizing solvent used, there is no particular limitation, can be known in the art
Various solvents, such as can be dichloromethane and/or n-hexane.
In the method for preparing ethylene copolymer of the present invention, the molar ratio of catalyst precarsor and alkylaluminoxane can compared with
Change, be not particularly limited in big scope, but in order to enable catalysis in olefine polymerization is played the role of in the collaboration of both materials,
Under preferable case, the molar ratio of catalyst precarsor and alkylaluminoxane is 1：200-2000, more preferably 1：200-1000.
In the method for preparing ethylene copolymer of the present invention, for alkylaluminoxane, there is no particular limitation, can be to urge
The common various alkylaluminoxanes as co-catalyst in agent field, can have straight chain, side chain or cyclic structure.It is preferred that
In the case of, alkyl is the straight or branched alkyl of C1-C5 in alkylaluminoxane.The example of the straight or branched alkyl of C1-C5 can
To include but not limited to：It is methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, different
Amyl group, tertiary pentyl and neopentyl.It is further preferred that alkyl is methyl or isobutyl group, more preferably methyl in alkylaluminoxane.
In the method for preparing ethylene copolymer of the present invention, under preferable case, alkylaluminoxane is methylaluminoxane (MAO)
And/or modified methylaluminoxane (MMAO).
In the method for preparing ethylene copolymer of the present invention, for comonomer, there is no particular limitation, can be ability
The common various comonomers in domain, under preferable case, comonomer is propylene, the two of the α substituted olefines of C4-C10 and C4-C10
One or more in alkene.The α substituted olefines of C4-C10 are more preferably one kind in 1- hexenes, 1- octenes and 1- decene
Or it is a variety of, the alkadienes of C4-C10 is more preferably 1,5- hexadienes and/or Isosorbide-5-Nitrae-pentadiene.
The method of the ethylene copolymer of the present invention, which is to use, employs aforementioned catalytic agent precursor and alkyl containing the present invention
The above-mentioned catalyst of aikyiaiurnirsoxan beta.
In the method for preparing ethylene copolymer of the present invention, olefinic polyreaction condition can be the conventional choosing of this area
Select, under preferable case, olefinic polyreaction carries out in an inert atmosphere.Inert atmosphere refers to does not occur chemistry with reactant and product
Any one gas or admixture of gas of reaction, such as the one or more in nitrogen and periodic table of elements zero group gas.Keep
The method of inert atmosphere can be passed through into reaction system it is above-mentioned do not chemically reacted with reactant and product it is any one
Kind gas or admixture of gas.
In the method for preparing ethylene copolymer of the present invention, for atent solvent, there is no particular limitation, can be ability
The common various atent solvents not reacted with reactant and product in domain, under preferable case, atent solvent is aromatic hydrocarbons and/or alkane
Hydrocarbon, it is further preferred that aromatic hydrocarbons is benzene and/or toluene, alkane is n-hexane and/or normal heptane.
In the method for preparing ethylene copolymer of the present invention, for the condition of olefinic polyreaction, there is no particular limitation,
Olefin polymerization conditions that can be well known in the art, under preferable case, the condition of olefinic polyreaction includes：Polymerization temperature is
0-80 DEG C, vinyl polymerization pressure is 0.1-3MPa, and polymerization time is 5-30 minutes.
In the method for preparing ethylene copolymer of the present invention, ethylene copolymer reaction further includes to be added after completion of the polymerization reaction
Terminator, so that polymerisation terminates, i.e. inactivate activated centre.For terminator, there is no particular limitation, can be alkene
The various terminators that living polymer chains can be terminated in polymerization field.Such as can be water, methanol, ethanol, positive third
One or more in alcohol and isopropanol.
Embodiment
The present invention is further illustrated for following embodiment, but is not intended to limit the present invention.
In following preparation example, embodiment and comparative example, unless stated otherwise, the compound used and reagent etc. are commercially available
Product.
The method that the performance test of polyethylene is related to is as follows：
Fusing point is measured by differential scanning calorimeter, and differential scanning calorimeter is purchased from PE companies of the U.S., model PE
DSC-7, determination condition include：Nitrogen, heating rate are 10 DEG C/min.
The weight average molecular weight (Mw) and number-average molecular weight (Mn) of polyethylene are measured by gel permeation chrommatograph, gel chromatography
Instrument is purchased from Shimadzu Corporation, model LC-10AT, and determination condition includes：Mobile phase is THF, and standard sample is Narrow distribution polystyrene,
Test temperature is 25 DEG C.
The content of comonomer is measured by nuclear magnetic resonance chemical analyser in ethylene copolymer, nuclear magnetic resonance chemical analyser purchase
From Bruke companies, model Bruke-300, determination condition includes：Measuring temperature is 110 DEG C.
The preparation method of compound with structure shown in formula IV is：By 6,6'- (1E, 1'E)-(4,4' methylene bis
(4,1- penylenes) is double (imines -1- substitution -1- subunits)) double (methyl isophthalic acid-substitution -1- subunits) double (2- t-butyl phenols) (according to
The preparation method that Eur.Polym.J.2012,48,191-199 documents are recorded is made) (3.41mmol) be dissolved in dichloromethane solvent
In (dosage of dichloromethane is 30mL), it will be added at -78 DEG C in the solution to containing tetrachloro double (tetrahydrofurans) and close titanium
In the dichloromethane solution (dosage of dichloromethane is 30mL) of (6.82mmol), when reaction 1 is small at -78 DEG C, recover to room temperature
25 DEG C and be heated to 40 DEG C, the reaction was continued 16 it is small when.After reaction, solvent is removed with vacuum line, residue dichloromethane
Alkane washs simultaneously to be filtered by diatomite, and filtrate is drained, crude product with dichloromethane/n-hexane (dichloromethane and n-hexane
Volume ratio is 1：5) recrystallize, obtain the red brown solid W of 2.97g.
The hydrogen modal data of W is：1H NMR(CDCl3,400MHz):δ 8.25 (br s, 2H, CH=N), 7.74 (d, 2H, J=
7.6Hz, ArH), 7.49 (d, 2H, J=7.6Hz, ArH), 7.35 (d, 4H, J=8.4Hz, ArH), 7.31 (d, 4H, J=
8.4Hz, ArH), 7.23 (t, 2H, J=7.6Hz, ArH), 5.36 (br s, 2H, CH2),4.22(br s,8H,O(CH2)2),
1.75(br s,8H,CH2),1.60(s,18H,C(CH3)3)。
The carbon modal data of W is：13C NMR(CD2Cl2,400MHz):δ167.0,162.5,150.2,141.1,138.6,
134.8,134.2,129.7,128.2,125.2,124.7,77.3,41.4,35.8,30.0,25.9。
The elemental analysis of W is the results show that Anal.Calc.for C43H52Cl6F10N2O4Ti2(%):C,53.28；H,
5.41；N, 2.89.Found (%):C,53.32；H,5.40；N,2.89.
From upper result, the structural formula of W is shown below.
Preparation example 1
This preparation example is used to illustrate the preparation with the catalyst precarsor of structure shown in Formula II.
(E) -2- tert-butyl groups -6- ((pentafluorophenyl group imido grpup) methyl) phenol (2.24mmol) is dissolved in ether solvent (second
The dosage of ether is 30mL) in, the hexane solution (hexane solution containing n-BuLi is added into the solution at -78 DEG C
The concentration of middle n-BuLi is 1.67M, and the amount of n-BuLi is 2.35mmol) when reaction 1 is small afterwards, recovers to 25 DEG C, continue anti-
Answer 15 minutes, obtain having the structural formula of the compound Y1, Y1 of structure shown in Formula V to be shown below (referring to bibliography：
J.Am.Chem.Soc.2002,124,3327-3336)。
Foregoing obtained solution (solution i.e. containing compound Y1) is transferred to containing above-mentioned by double angular pins at -78 DEG C
In the dichloromethane solution (dosage of dichloromethane is 30mL) of compound W (1.12mmol) with structure shown in formula IV, and
At such a temperature reaction 4 it is small when, system is then gradually brought to 25 DEG C, then react 12 it is small when.After reaction, vacuum line is used
Solvent is removed, residue is washed with dichloromethane and filtered by diatomite, and filtrate is drained, crude product with dichloromethane/
(volume ratio of dichloromethane and n-hexane is 1 to n-hexane：5) recrystallize, obtain 0.69g bronzing product A1 (yield 43%).
The elemental analysis of A1 is the results show that Anal.Calc.for C69H62Cl4F10N4O4Ti2(%):C,57.60；H,
4.34；N, 3.89.Found (%):C,57.64；H,4.36；N,3.90.
FD-MS:m/z 1438.1(calcd 1438.2)。
Structure and above-mentioned data from Y1 and W, A1 have structure shown in Formula II.
Preparation example 2
This preparation example is used to illustrate the preparation with the catalyst precarsor of structure shown in formula III.
(E) -2- methyl -6- ((phenyl imine base) methyl) phenol (3.00mmol) is dissolved in the ether solvent (use of ether
Measure as 30mL) in, hexane solution (the positive fourth in hexane solution containing n-BuLi is added into the solution at -78 DEG C
The concentration of base lithium is 1.67M, and the amount of n-BuLi is 3.05mmol) afterwards reaction 1 it is small when, recover to 25 DEG C, the reaction was continued 15 points
Clock, obtains having the structural formula of the compound Y2, Y2 of structure shown in Formula V to be shown below (referring to bibliography：
J.Am.Chem.Soc.2001,123,6847-6856)。
Foregoing obtained solution (solution i.e. containing compound Y2) is transferred to containing above-mentioned by double angular pins at -78 DEG C
In the dichloromethane solution (dosage of dichloromethane is 30mL) of compound W (1.50mmol) with structure shown in formula IV, and
At such a temperature reaction 4 it is small when, system is then gradually brought to 25 DEG C, then react 12 it is small when.After reaction, vacuum line is used
Solvent is removed, residue is washed with dichloromethane and filtered by diatomite, and filtrate is drained, crude product with dichloromethane/
(volume ratio of dichloromethane and n-hexane is 1 to n-hexane：5) recrystallize, obtain 0.96g bronzing product A2 (yield 53%).
The elemental analysis of A2 is the results show that Anal.Calc.for C65H64Cl4N4O4Ti2(%):C,64.91；H,5.36；
N, 4.66.Found (%):C,65.02；H,5.52；N,4.39.
FD-MS:m/z 1202.3(calcd 1202.0)。
Structure and above-mentioned data from Y2 and W, A2 have structure shown in formula III.
Preparation example 3
This preparation example is used to illustrate the preparation with the catalyst precarsor of structure shown in Formula II.
(E) -2- tert-butyl groups -6- ((pentafluorophenyl group imido grpup) methyl) phenol (2.24mmol) is dissolved in ether solvent (second
The dosage of ether is 30mL) in, the hexane solution (hexane solution containing n-BuLi is added into the solution at -78 DEG C
The concentration of middle n-BuLi is 1.67M, and the amount of n-BuLi is 2.35mmol) when reaction 1 is small afterwards, recovers to 25 DEG C, continue anti-
Answer 15 minutes.Afterwards, the solution is transferred to containing the above-mentioned compound with structure shown in formula IV by double angular pins at -78 DEG C
In the dichloromethane solution (dosage of dichloromethane is 30mL) of W (1.24mmol), and at such a temperature reaction 4 it is small when, then
System is gradually brought to 0 DEG C, then react 24 it is small when.After reaction, solvent is removed with vacuum line, residue dichloromethane
Alkane washs simultaneously to be filtered by diatomite, and filtrate is drained, crude product with dichloromethane/n-hexane (dichloromethane and n-hexane
Volume ratio is 1：5) recrystallize, obtain 0.98g bronzing product A3 (yield 61%).
As known by the foregoing results, A3 has structure shown in Formula II.
Preparation example 4
This preparation example is used to illustrate the preparation with the catalyst precarsor of structure shown in formula III.
(E) -2- methyl -6- ((phenyl imine base) methyl) phenol (3.00mmol) is dissolved in the ether solvent (use of ether
Measure as 30mL) in, hexane solution (the positive fourth in hexane solution containing n-BuLi is added into the solution at -78 DEG C
The concentration of base lithium is 1.67M, and the amount of n-BuLi is 3.05mmol) afterwards reaction 1 it is small when, recover to 25 DEG C, the reaction was continued 15 points
Clock.Afterwards, the solution is transferred to containing the above-mentioned compound W with structure shown in formula IV by double angular pins at -78 DEG C
In the dichloromethane solution (dosage of dichloromethane is 30mL) of (1.36mmol), and at such a temperature reaction 4 it is small when, then will
System is gradually brought to 40 DEG C, then react 8 it is small when.After reaction, solvent is removed with vacuum line, residue dichloromethane
Wash and filtered by diatomite, filtrate is drained, crude product dichloromethane/n-hexane (body of dichloromethane and n-hexane
Product is than being 1：5) recrystallize, obtain 0.39g bronzing product A4 (yield 24%).
As known by the foregoing results, A4 has structure shown in formula III.
Embodiment 1
The present embodiment is used for the method that explanation prepares ethylene copolymer.
500mL polymeric kettles after heat drying are vacuumized into logical nitrogen twice, then ethylene gas is passed through after vacuumizing, so
The toluene solution 6.8mL (concentration 12mg/mL) of methylaluminoxane, 1- hexene 15mL, at anhydrous and oxygen-free are sequentially added afterwards
The n-hexane 150mL of reason, and the toluene solution 4mL (2.5 μm of ol/mL) containing catalyst precarsor A1.Lead under mechanical stirring
Enter the ethene that pressure is 0.3MPa, and react 20min in 25 DEG C at this pressure, add ethanol afterwards and terminate reaction, gathered
Compound 5.21g, is computed determining, polymerization activity is 1.56 × 106g·mol-1(Ti)·h-1。
Fusing point is measured as 103 DEG C；Measure the M of polyethylenewFor 1.9 × 105, molecular weight distribution Mw/MnFor 1.92；Measure 1-
Ahexene content is 5.3%.
Embodiment 2
The present embodiment is used for the method that explanation prepares ethylene copolymer.
500mL polymeric kettles after heat drying are vacuumized into logical nitrogen twice, then ethylene gas is passed through after vacuumizing, so
The toluene solution 6.8mL (concentration 12mg/mL) of methylaluminoxane, 1- octene 15mL, at anhydrous and oxygen-free are sequentially added afterwards
The n-hexane 150mL of reason, and the toluene solution 4mL (2.5 μm of ol/mL) containing catalyst precarsor A2.Lead under mechanical stirring
Enter the ethene that pressure is 0.3MPa, and react 20min in 25 DEG C at this pressure, add ethanol afterwards and terminate reaction, gathered
Compound 5.84g, is computed determining, polymerization activity 1.75 × 106g·mol-1(Ti)·h-1。
Fusing point is measured as 95 DEG C；Measure the M of polyethylenewFor 1.9 × 105, molecular weight distribution Mw/MnFor 2.07；It is pungent to measure 1-
Alkene content is 6.7%.
Embodiment 3
The present embodiment is used for the method that explanation prepares ethylene copolymer.
500mL polymeric kettles after heat drying are vacuumized into logical nitrogen twice, then ethylene gas is passed through after vacuumizing, so
The toluene solution 13.6mL (concentration 12mg/mL) of methylaluminoxane, 1- decene 15mL, at anhydrous and oxygen-free are sequentially added afterwards
The n-hexane 150mL of reason, and the toluene solution 8mL (2.5 μm of ol/mL) containing catalyst precarsor A3.Lead under mechanical stirring
Enter the ethene that pressure is 0.1MPa, and react 10min in 50 DEG C at this pressure, add ethanol and terminate reaction, obtain polymer
2.44g, is computed determining, polymerization activity 7.32 × 105g·mol-1(Ti)·h-1。
Fusing point is measured as 107 DEG C；Measure the M of polyethylenewFor 2.2 × 105, molecular weight distribution Mw/MnFor 2.01；Measure 1-
Decene content is 4.1%.
Embodiment 4
The present embodiment is used for the method that explanation prepares ethylene copolymer.
500mL polymeric kettles after heat drying are vacuumized into logical nitrogen twice, then ethylene gas is passed through after vacuumizing, so
The toluene solution 6.8mL (concentration 12mg/mL) of methylaluminoxane, 1,5- hexadiene 15mL, by anhydrous nothing are sequentially added afterwards
The normal heptane 300mL of oxygen processing, and the toluene solution 4mL (2.5 μm of ol/mL) containing catalyst precarsor A4.In mechanical agitation
Under be passed through pressure be 1.5MPa ethene, and at this pressure in 0 DEG C react 30min, add ethanol terminate reaction, polymerize
Thing 7.25g, is computed determining, polymerization activity 1.45 × 106g·mol-1(Ti)·h-1。
Fusing point is measured as 118 DEG C；Measure the M of polyethylenewFor 2.0 × 105, molecular weight distribution Mw/MnFor 2.19；Measure 1,
5- hexadienes content is 3.3%.
Embodiment 5
The present embodiment is used for the method that explanation prepares ethylene copolymer.
500mL polymeric kettles after heat drying are vacuumized into logical nitrogen twice, then ethylene gas is passed through after vacuumizing, so
The toluene solution 6.8mL (concentration 12mg/mL) of methylaluminoxane, 1- hexene 100mL, at anhydrous and oxygen-free are sequentially added afterwards
The n-hexane 250mL of reason, and the toluene solution 4mL (2.5 μm of ol/mL) containing catalyst precarsor A1.Lead under mechanical stirring
Enter the ethene that pressure is 3MPa, and react 20min in 25 DEG C at this pressure, add ethanol afterwards and terminate reaction, polymerize
Thing 17.47g, is computed determining, polymerization activity is 5.29 × 106g·mol-1(Ti)·h-1。
Fusing point is measured as 127 DEG C；Measure the M of polyethylenewFor 2.5 × 105, molecular weight distribution Mw/MnFor 2.18；Measure 1-
Ahexene content is 1.8%.
Embodiment 6
According to the method for embodiment 1, the difference is that, the amount of the 1- hexenes of addition is 5mL.Polymer 11.43g is obtained, is passed through
Calculate and determine, polymerization activity is 3.43 × 106g·mol-1(Ti)·h-1。
Fusing point is measured as 123 DEG C；Measure the M of polyethylenewFor 1.8 × 105, molecular weight distribution Mw/MnFor 1.86；Measure 1-
Ahexene content is 2.7%.
Embodiment 7
According to the method for embodiment 1, the difference is that, the amount of the 1- hexenes of addition is 10mL.
Polymer 8.87g is obtained, is computed determining, polymerization activity is 2.66 × 106g·mol-1(Ti)·h-1；Measure molten
Point is 116 DEG C；Measure the M of polyethylenewFor 2.5 × 105, molecular weight distribution Mw/MnFor 2.20；Measuring 1- ahexene contents is
3.4%.
Embodiment 8
According to the method for embodiment 1, the difference is that, the amount of the 1- hexenes of addition is 50mL.
Polymer 2.77g is obtained, is computed determining, polymerization activity is 8.31 × 105g·mol-1(Ti)·h-1；Measure molten
Point is 70 DEG C；Measure the M of polyethylenewFor 1.8 × 105, molecular weight distribution Mw/MnFor 2.30；Measuring 1- ahexene contents is
12.4%.
Embodiment 9
According to the method for embodiment 1, the difference is that, the amount of the n-hexane handled by anhydrous and oxygen-free of addition is 300mL.
Polymer 13.6g is obtained, is computed determining, polymerization activity is 4.08 × 106g·mol-1(Ti)·h-1；Measure molten
Point is 119 DEG C；Measure the M of polyethylenewFor 2.1 × 105, molecular weight distribution Mw/MnFor 2.04；Measuring 1- ahexene contents is
3.3%.
Comparative example 1
According to the method for embodiment 1, the difference is that, replace catalyst precarsor with the compound W with structure shown in formula IV
A1。
Polymer 0.104g is obtained, is computed determining, polymerization activity is 3.1 × 104g·mol-1(Ti)·h-1；Measure molten
Point is 111 DEG C；Measure the M of polyethylenewFor 3.2 × 105, molecular weight distribution Mw/MnFor 12.7；Measuring 1- ahexene contents is
6.8%.
Embodiment 1 is understood compared with comparative example 1, in ethylene copolymer, before containing catalyst provided by the invention
The catalyst of body, can obtain considerably higher polymerization activity and substantially narrower molecular weight distribution.
Find out, the method for preparing ethylene copolymer of the invention that there is high catalytic efficiency from the data of embodiment 1-9,
Catalytic efficiency (polymerization activity) may be up to 5 × 106g·mol-1(Ti)·h-1More than, the Weight-average molecular of the ethylene copolymer of gained
Measure as 200,000 or so, molecular weight distribution is 2 or so, and the molar content that comonomer can introduce is between 1.8-12.4%.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (13)
- A kind of 1. method for preparing ethylene copolymer, it is characterised in that this method is included under olefin polymerization conditions, molten in inertia In the presence of agent, ethene, comonomer are contacted with catalyst and polymerize, the catalyst contains catalyst precarsor and alkyl aluminum Oxygen alkane, wherein, which has the structure shown in Formulas I,Wherein, R1、R2And R4It is each independently hydrogen atom or the alkyl of C1-C20；R3For phenyl or halogenophenyl；M is Titanium, zirconium or hafnium.
- 2. according to the method described in claim 1, wherein, the alkyl of the C1-C20 is the alkyl of C1-C6；The halogenophenyl For pentafluorophenyl group, 2- fluorophenyls, 2,4 difluorobenzene base, the fluoro- 3- chlorphenyls of 4- or the chloro- 2,3,5,6- tetrafluoros phenyl of 4-.
- 3. according to the method described in claim 1, wherein, R1And R2For the tert-butyl group, R3For pentafluorophenyl group, R4For hydrogen, M is titanium.
- 4. according to the method described in claim 1, wherein, R1And R4For methyl, R2For the tert-butyl group, R3For phenyl, M is titanium.
- 5. according to the method described in claim 1, wherein, the preparation method of the catalyst precarsor includes：In complex reaction bar Under part, the compound with structure shown in formula IV is contacted in organic solvent with the compound with structure shown in Formula V, is obtained Catalyst precarsor with structure shown in Formulas I,Wherein, R1、R2And R4It is each independently hydrogen atom or the alkyl of C1-C20；R3For phenyl or halogenophenyl；M is Titanium, zirconium or hafnium.
- 6. according to the method described in claim 1, wherein, the molar ratio of the catalyst precarsor and alkylaluminoxane is 1：200- 2000。
- 7. according to the method described in claim 6, wherein, the molar ratio of the catalyst precarsor and alkylaluminoxane is 1：200- 1000。
- 8. according to the method described in any one in claim 1,6 or 7, wherein, alkyl is C1-C5 in the alkylaluminoxane Straight or branched alkyl.
- 9. according to the method described in claim 8, wherein, alkyl is methyl or isobutyl group in the alkylaluminoxane.
- 10. according to the method described in claim 1, wherein, the comonomer is propylene, the α substituted olefines and C4- of C4-C10 One or more in the alkadienes of C10.
- 11. according to the method described in claim 1, wherein, the atent solvent is aromatic hydrocarbons and/or alkane.
- 12. according to the method for claim 11, wherein, the aromatic hydrocarbons is benzene and/or toluene；The alkane is n-hexane And/or normal heptane.
- 13. according to the method described in claim 1, wherein, the condition of the olefinic polymerization includes：Polymerization temperature is 0-80 DEG C, Vinyl polymerization pressure is 0.1-3MPa, and polymerization time is 5-30 minutes.
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| US5912311A (en) * | 1995-09-29 | 1999-06-15 | Univation Technologies, Llc | Olefin polymerization method comprising allyl-cycloalkadienyl dianions as catalyst precursors |
| CN102268032A (en) * | 2011-06-16 | 2011-12-07 | 北京大学 | Bimetallic heteroligand catalyst precursor and synthetic method and application thereof |
| CN103804551A (en) * | 2012-11-09 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method of ethylene copolymer |
| CN103804550A (en) * | 2012-11-09 | 2014-05-21 | 中国石油化工股份有限公司 | Catalyst precursor and its preparation method, catalyst and its application, and ethylene polymerization method |
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| US5912311A (en) * | 1995-09-29 | 1999-06-15 | Univation Technologies, Llc | Olefin polymerization method comprising allyl-cycloalkadienyl dianions as catalyst precursors |
| CN102268032A (en) * | 2011-06-16 | 2011-12-07 | 北京大学 | Bimetallic heteroligand catalyst precursor and synthetic method and application thereof |
| CN103804551A (en) * | 2012-11-09 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method of ethylene copolymer |
| CN103804550A (en) * | 2012-11-09 | 2014-05-21 | 中国石油化工股份有限公司 | Catalyst precursor and its preparation method, catalyst and its application, and ethylene polymerization method |
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