CN107266638B - A kind of block copolymer and preparation method thereof - Google Patents
A kind of block copolymer and preparation method thereof Download PDFInfo
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- CN107266638B CN107266638B CN201610212948.2A CN201610212948A CN107266638B CN 107266638 B CN107266638 B CN 107266638B CN 201610212948 A CN201610212948 A CN 201610212948A CN 107266638 B CN107266638 B CN 107266638B
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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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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- 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
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
- C08F4/6428—Component covered by group C08F4/64 with an organo-aluminium compound with an aluminoxane, i.e. a compound containing an Al-O-Al- group
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- C08F2400/00—Characteristics for processes of polymerization
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- C—CHEMISTRY; METALLURGY
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- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
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Abstract
The present invention relates to high molecular material and synthesis of polymer material technical field, a kind of block copolymer and preparation method thereof is disclosed.This method is included under olefin polymerization conditions, in the presence of an inert solvent, ethylene, comonomer is contacted with catalyst and carry out polymerization reaction, and catalyst contains catalyst precarsor and alkylaluminoxane, which has structure shown in Formulas I, 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 includes: first to contact comonomer with catalyst to carry out the first polymerization reaction that ethylene, comonomer are contacted to the method for carrying out polymerization reaction with catalyst, then contacts ethylene with the first polymerization reaction system in the presence of comonomer and carries out the second polymerization reaction.Diblock, three block and more block ethylene block copolymers can be prepared in this method, and the narrow molecular weight distribution of block copolymer, fusing point are high.
Description
Technical field
The present invention relates to high molecular material and synthesis of polymer material technical fields, and in particular, to a kind of block copolymerization
Object and preparation method thereof.
Background technique
Since the 21th century, with the needs of raising and the national defense industry of national economy level, high molecular material, especially
It is that polyolefine material plays increasingly important role: since polyolefinic raw materials enrich cheap, is easily worked molding, exists every year
The polyolefin products produced in world wide have been more than 100,000,000 tons, become one of industry of maximum-norm；Polyolefine material has
It the features such as relatively small density, good chemical resistance, 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, wire and cable etc.
Have been widely used in terms of product, provides convenience for the clothing, food, lodging and transportion -- basic necessities of life of the mankind, also in national defence, the energy, aerospace etc. is strategic
Great function is played in project.
It is catalysis that polyolefin elastomer (Polyolefin elastomer, POE), which is DOW chemical company, the U.S. with metallocene,
The thermoplastic elastomer (TPE) of agent being distributed with narrow molecular weight distribution and uniform short-chain branch.The main property of this elastomer
It can protrude very much, be more than conventional elastomers in very various performance indicators.The heat resisting temperature of material is enhanced, permanent deformation
Reduce, the main mechanical properties such as tensile strength, tearing strength all have significant improvement.Multiduty POE elastomer can
More than PVC, EVA, SBR, EMA and EPDM, POE may replace traditional EPDM from now on.Since the excellent properties of POE make it in vapour
Garage's industry, electric wire and cable jacket, plastics toughening agent etc. are all applied widely.But the use temperature of such material is most
At 70 DEG C hereinafter, being unfavorable for applied at elevated temperature.Therefore the processable temperature for improving polyolefin elastomer class product has greater significance.
Summary of the invention
The purpose of the invention is to overcome drawbacks described above in the prior art, a kind of block copolymer and its preparation are provided
Method, this method can prepare diblock copolymer, and the narrow molecular weight distribution of block copolymer, and fusing point is high.
To achieve the goals above, in a first aspect, the present invention provides a kind of preparation method of block copolymer, this method
It is included under olefin polymerization conditions, in the presence of an inert solvent, ethylene, comonomer is contacted with catalyst and polymerize instead
It answers, the catalyst contains catalyst precarsor and alkylaluminoxane, wherein the catalyst precarsor has 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；
Wherein, ethylene, comonomer are contacted with catalyst the method for carrying out polymerization reaction include: first by comonomer with
Catalyst contact carries out the first polymerization reaction, then ethylene is contacted with the first polymerization reaction system in the presence of comonomer into
The second polymerization reaction of row.
Second aspect, the present invention provides the block copolymers that preceding method is prepared.
The ethylene block copolymer of diblock can be prepared (according to excellent in the preparation method of block copolymer of the invention
The embodiment of choosing carries out the ethylene block copolymer of the available three block of the above polymerization reaction of three steps and more blocks), gather
Activity is closed 104-105g·mol-1(M)·h-1Between (wherein, M be titanium, zirconium or hafnium), resulting block copolymer is divided equally again
Son amount is between 100,000-22 ten thousand, and molecular weight distribution is less than 2.0, and fusing point may be up to 120 DEG C, and comonomer (hard section) can introduce
Molar content is 20-50%, and the molar content of the copolymerization units (soft segment) of comonomer and ethylene is 50-80%, and the present invention
The method for preparing block copolymer used in catalyst precarsor, preparation method is simple, at low cost, reproducible, is easy to
Industrialization.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is the reaction equation for preparing catalyst precarsor of the invention.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
In a first aspect, this method is included in olefinic polymerization item the present invention provides a kind of preparation method of block copolymer
Under part, in the presence of an inert solvent, ethylene, comonomer is contacted with catalyst and carry out polymerization reaction, the catalyst contains
Catalyst precarsor and alkylaluminoxane, wherein the catalyst precarsor has 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；
Wherein, ethylene, comonomer are contacted with catalyst the method for carrying out polymerization reaction include: first by comonomer with
Catalyst contact carries out the first polymerization reaction, then ethylene is contacted with the first polymerization reaction system in the presence of comonomer into
The second polymerization reaction of row.
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, be also possible to branch.Preferably, the alkyl of C1-C20 is the alkyl of C1-C6.Wherein, C1-C20
Linear or branched alkyl group can include but is not limited to: methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group,
Tert-butyl, n-pentyl, 2- methyl butyl, 3- methyl butyl, 2,2- dimethyl propyl, n-hexyl, 2- methyl amyl, 3- methylpent
It is base, 4- methyl amyl, n-heptyl, 2- methylhexyl, 3- methylhexyl, 4- methylhexyl, 5- methylhexyl, n-heptyl, just pungent
Base, n-nonyl, positive decyl, 3,7- dimethyl octyl, 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- chlorphenyl of base, 2,4 difluorobenzene base, 4- or the chloro- 2,3,5,6- tetrafluoro phenyl of 4-；The carbon of alkoxy is former in alkoxyl phenyl
Subnumber is 1-6, it is further preferred that alkoxyl phenyl is p-methoxyphenyl.
The present inventor has found under study for action, by specific R1-R4Catalyst precarsor composed by combining is as catalysis
Fabulous catalytic effect can be obtained when ethylene and/or the catalytic component of comonomer polymerization, it is preferable that R1For tert-butyl, R2For
Tert-butyl, R3For pentafluorophenyl group, R4For hydrogen, M is titanium, and the catalyst precarsor is the catalysis with Open architecture shown in formula II
Agent precursor；Alternatively, R1For methyl, R2For tert-butyl, R3For phenyl, R4For methyl, M is titanium, and the catalyst precarsor is with formula
The catalyst precarsor of Open architecture shown in III,
In the method for the present invention, under preferable case, this method further includes being prepared by the following method catalyst precarsor: being complexed
Under reaction condition, the compound with structure shown in formula IV is connect in organic solvent with the compound with structure shown in Formula V
Touching, obtains the 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, halogenophenyl or
Alkoxyl phenyl；M is titanium, zirconium or hafnium.
The reaction equation for preparing the above-mentioned catalyst precarsor with structure shown in formula I is as shown in Figure 1.
In the preparation method of the catalyst precarsor of the method for the present invention, about 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
Prepared by lower method: by 6,6'- (1Z, the 1'Z)-(bis- (imines -1- substitutions-of 4,4'- alkyl substituent methyl bis- (4,1- penylenes)
1- subunit)) bis- (methyl-1-substitution-1- subunit) bis- (2- alkyl substituted phenols) (according to Eur.Polym.J.2012,48,191-
The preparation method that 199 documents are recorded is made) (1eq) be dissolved in dichloromethane solvent, it will be added in the solution at -78 DEG C to containing
It in the dichloromethane solution for having (double tetrahydrofuran) titanium tetrachloride (1.8-2.2eq), reacts 1 hour, restores to room temperature under low temperature
And 40 DEG C are heated to, the reaction was continued 8-16 hours.After reaction, solvent is removed with vacuum line, residue methylene chloride
It washs and is filtered by diatomite, filtrate is drained, crude product is recrystallized with methylene chloride/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
Prepared by lower method: replacing -6- ((aryl substituted imine base) methyl) phenol (1eq) to be dissolved in ether solvent in (E) -2- alkyl
In, the hexane solution containing n-BuLi (0.95-1.05eq) is added into the solution at -78 DEG C (in hexane solution
The concentration of n-BuLi be 1.67M) afterwards react 1 hour, restore to 25 DEG C of room temperature, the reaction was continued 10-20 minutes to get.
In the preparation method of the catalyst precarsor of the method for the present invention, compound with structure shown in formula IV with there is 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 molar ratio of the compound of structure shown in formula IV and the compound with structure shown in Formula V is 1:1.8-2.2.
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 guaranteeing that the compound with structure shown in formula IV is reacted with the compound with structure shown in Formula V generates target product i.e.
Can, under preferable case, the condition of contact includes: that temperature is 0-40 DEG C, further preferably 20-30 DEG C；Time is 8-24 hours,
Further preferably 10-15 hours.
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 one of tetrahydrofuran, ether, 1,4- dioxane and methylene chloride or a variety of.These solvents can be independent
It uses, can also be used in mixed way.The dosage of organic solvent can be according to the compound with structure shown in formula IV and 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 can also include after the reaction was completed, inciting somebody to action
Organic solvent removal.Wherein, for the method for removal organic solvent, there is no particular limitation, can be using 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
It repeats no more.
In the preparation method of the catalyst precarsor of the method for the present invention, sterling, this method can also include that will obtain 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, such as recrystallization.For recrystallizing solvent used, there is no particular limitation, can be well known in the art
Various solvents, such as can be methylene chloride and/or n-hexane.
In the method for preparing block copolymer of the invention, the molar ratio of catalyst precarsor and alkylaluminoxane can compared with
It changes, is not particularly limited in big range, but in order to enable catalysis in olefine polymerization is played the role of in the collaboration of both substances,
Under preferable case, the molar ratio of catalyst precarsor and alkylaluminoxane is 1:200-2000, further preferably 1:200-1000.
In the method for preparing block copolymer of the invention, for alkylaluminoxane, there is no particular limitation, can be to urge
Agent field is commonly used as the various alkylaluminoxanes of co-catalyst, can have straight chain, branch or cyclic structure.It is preferred that
In the case of, alkyl is the linear or branched alkyl group of C1-C5 in alkylaluminoxane.The example of the linear or branched alkyl group of C1-C5 can
To include but is not limited to: methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, different
Amyl, 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 block copolymer of the invention, under preferable case, alkylaluminoxane is methylaluminoxane (MAO)
And/or modified methylaluminoxane (MMAO).
In the method for preparing block copolymer of the invention, for comonomer, there is no particular limitation, can be ability
The common various comonomers in domain, under preferable case, comonomer is the alkadienes of propylene, the alhpa olefin of C4-C10 and C4-C10
One of or it is a variety of.The alhpa olefin of C4-C10 is more preferably one of 1- butylene, 1- hexene, 1- octene and 1- decene
Or it is a variety of, the alkadienes of C4-C10 is more preferably 1,5- hexadiene and/or Isosorbide-5-Nitrae-pentadiene.
The preparation method of block copolymer of the invention is using using containing aforementioned catalytic agent precursor of the invention
With the above-mentioned catalyst of alkylaluminoxane.
In the method for preparing block copolymer of the invention, olefin polymerization condition can be the conventional choosing of this field
It selects, under preferable case, olefin polymerization carries out in an inert atmosphere.Inert atmosphere, which refers to, does not occur chemistry with reactants and products
Any one gas or admixture of gas of reaction, such as one or more of nitrogen and periodic table of elements zero group gas.It keeps
The method of inert atmosphere can for be passed through into reaction system it is above-mentioned do not chemically reacted with reactants and products it is any one
Kind gas or admixture of gas.
In the method for preparing block copolymer of the invention, for atent solvent, there is no particular limitation, can be ability
The common various atent solvents not react 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 at least one of n-hexane, hexamethylene and normal heptane.
In the method for preparing block copolymer of the invention, according to the needs of actual production, diblock, three embedding can be prepared
Section and more block ethylene elastomers, it is therefore preferable that in the case of, ethylene, comonomer are contacted with catalyst and polymerize instead
The method answered further include: after the ethylene in the second polymerization reaction reacts completely, third polymerization is carried out in the presence of comonomer
Reaction；Or
After the ethylene in the second polymerization reaction reacts completely, the third polymerization successively in the presence of progress comonomer is anti-
It answers, the 4th polymerization reaction in the presence of comonomer and ethylene；Or
After the ethylene in the second polymerization reaction reacts completely, the third polymerization successively in the presence of progress comonomer is anti-
It answers, the 4th polymerization reaction in the presence of comonomer and ethylene, and after the ethylene in the 4th polymerization reaction reacts completely, altogether
The 5th polymerization reaction is carried out in the presence of polycondensation monomer.
It will be understood by those skilled in the art that the present invention is polymerize using above-mentioned catalyst system catalysis ethylene block
When, diblock, three embedding can be prepared in the aforementioned method for carrying out polymerization reaction that contacts ethylene, comonomer with catalyst
Section, four blocks, five block ethylene elastomers, in addition, according to actual needs, in conjunction with the method for the present invention, those skilled in the art
The ethylene elastomer of more blocks can be prepared, details are not described herein.
In the method for preparing block copolymer of the invention, for the condition of olefin polymerization, there is no particular limitation,
Olefin polymerization conditions that can be well known in the art, under preferable case, the condition of the first polymerization reaction includes: that polymerization temperature is
0-25 DEG C, polymerization pressure 0.1-1MPa, polymerization time 2-10h；And/or second polymerization reaction condition include: polymerization temperature
Degree is 0-25 DEG C, polymerization pressure 0.1-1MPa, polymerization time 0.25-1h.
Under preferable case, the condition of third polymerization reaction includes: that polymerization temperature is 0-25 DEG C, polymerization pressure 0.1-
1MPa, polymerization time 2-10h；And/or the 4th the condition of polymerization reaction include: polymerization temperature be 0-25 DEG C, polymerization pressure is
0.1-1MPa, polymerization time 0.25-1h；And/or the 5th polymerization reaction condition include: polymerization temperature be 0-25 DEG C, polymerization
Pressure is 0.1-1MPa, polymerization time 2-10h.If not specified, the pressure in the present invention is gauge pressure.
In the method for preparing block copolymer of the invention, further include terminator is added after completion of the polymerization reaction so that
Polymerization reaction terminates, that is, inactivates activated centre.For terminator, there is no particular limitation, can be in field of olefin polymerisation
It is various can be to the terminator that living polymer chains are terminated.It such as can be water, methanol, ethyl alcohol, normal propyl alcohol and isopropanol
One of or it is a variety of.
Second aspect, the present invention also provides the block copolymers that preceding method is prepared.Block copolymerization of the invention
The weight average molecular weight of object is between 10-22 ten thousand, and molecular weight distribution is less than 2.0, and fusing point may be up to 120 DEG C, comonomer (hard section)
The molar content that can be introduced is 20-35%, and the molar content of the copolymerization units (soft segment) of comonomer and ethylene is 65-80%.
Embodiment
The present invention is further illustrated for embodiment below, but is not intended to limit the present invention.
In following preparation example, embodiment and comparative example, unless stated otherwise, compound and reagent for using etc. are commercially available
Product.
The method that the performance test of block copolymer is related to is as follows:
Fusing point passes through differential scanning calorimeter DSC (DSC 822e, METTLER TOLEDO) and it measures, heating rate 10
DEG C/min, data are read on second of scanning curve.
Comonomer in the weight average molecular weight (Mw) of block copolymer, number-average molecular weight (Mn) and block copolymer, altogether
Polycondensation monomer and the molar content of ethylene copolymer unit are measured by gel permeation chrommatograph, with 1,2,4- trichloro-benzenes as eluant, eluent
It is completed on Waters GPC2000CV instrument, detector is that Waters RI detector and Waters Viscometer are detected
Device, chromatographic column are 5 μm of PL gel columns (Polymer Laboratories), and test temperature is 150 DEG C, flow velocity 1.0mL/
min.Data are mark with polystyrene by Waters Empower software (2002 version) processing, weight average molecular weight and dispersion degree
Standard obtains.
Compound with structure shown in formula IV the preparation method comprises the following steps: by 6,6'- (1E, 1'E)-(4,4' methylene bis
(4,1- penylene) is bis- (imines-1- substitution-1- subunit)) bis- (methyl-1-substitution-1- subunit) bis- (2- t-butyl phenols) (according to
The preparation method that Eur.Polym.J.2012,48,191-199 document is recorded is made) (3.41mmol) be dissolved in dichloromethane solvent
In (dosage of methylene chloride is 30mL), it will be added in the solution to containing tetrachloro bis- (tetrahydrofurans) at -78 DEG C and close titanium
In the dichloromethane solution (dosage of methylene chloride is 30mL) of (6.82mmol), reacts 1 hour, restore to room temperature at -78 DEG C
25 DEG C and it is heated to 40 DEG C, the reaction was continued 16 hours.After reaction, solvent is removed with vacuum line, residue dichloromethane
Alkane is washed and is filtered by diatomite, and filtrate is drained, crude product with methylene chloride/n-hexane (methylene chloride and n-hexane
Volume ratio is 1:5) recrystallization, obtain the red brown solid W of 2.97g.
The hydrogen modal data of W are as follows: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 are as follows: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.
By upper result it is found that the structural formula of W is shown below.
Preparation example 1
This preparation example is used to illustrate the preparation of the catalyst precarsor with structure shown in Formula II.
(E) -2- tert-butyl -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) it reacts 1 hour afterwards, restore to 25 DEG C, continues anti-
Answer 15 minutes, the structural formula for obtaining the compound Y1, Y1 with structure shown in Formula V be shown below (referring to bibliography:
J.Am.Chem.Soc.2002,124,3327-3336)。
Aforementioned obtained solution (solution i.e. containing compound Y1) is transferred to by double angular pins containing above-mentioned at -78 DEG C
In the dichloromethane solution (dosage of methylene chloride is 30mL) of compound W (1.12mmol) with structure shown in formula IV, and
It reacts 4 hours at such a temperature, system is then gradually brought to 25 DEG C, then react 12 hours.After reaction, vacuum line is used
Solvent is removed, residue washed with methylene chloride and by diatomite filter, filtrate is drained, crude product with methylene chloride/
N-hexane (volume ratio of methylene chloride and n-hexane is 1:5) recrystallization, obtains 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)。
As structure and the above-mentioned data of Y1 and W it is found that A1 has structure shown in Formula II.
Preparation example 2
This preparation example is used to illustrate the preparation of the catalyst precarsor with 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
Amount is 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) react 1 hour afterwards, restore to 25 DEG C, the reaction was continued 15 points
Clock, the structural formula for obtaining the compound Y2, Y2 with structure shown in Formula V be shown below (referring to bibliography:
J.Am.Chem.Soc.2001,123,6847-6856)。
Aforementioned obtained solution (solution i.e. containing compound Y2) is transferred to by double angular pins containing above-mentioned at -78 DEG C
In the dichloromethane solution (dosage of methylene chloride is 30mL) of compound W (1.50mmol) with structure shown in formula IV, and
It reacts 4 hours at such a temperature, system is then gradually brought to 25 DEG C, then react 12 hours.After reaction, vacuum line is used
Solvent is removed, residue washed with methylene chloride and by diatomite filter, filtrate is drained, crude product with methylene chloride/
N-hexane (volume ratio of methylene chloride and n-hexane is 1:5) recrystallization, obtains 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)。
As structure and the above-mentioned data of Y2 and W it is found that A2 has structure shown in formula III.
Preparation example 3
This preparation example is used to illustrate the preparation of the catalyst precarsor with structure shown in Formula II.
(E) -2- tert-butyl -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) it reacts 1 hour afterwards, restore to 25 DEG C, continues anti-
It answers 15 minutes.Later, the solution is transferred to by double angular pins containing the above-mentioned compound with structure shown in formula IV at -78 DEG C
In the dichloromethane solution (dosage of methylene chloride is 30mL) of W (1.24mmol), and reaction 4 hours at such a temperature, then
System is gradually brought to 0 DEG C, then is reacted 24 hours.After reaction, solvent is removed with vacuum line, residue dichloromethane
Alkane is washed and is filtered by diatomite, and filtrate is drained, crude product with methylene chloride/n-hexane (methylene chloride and n-hexane
Volume ratio is 1:5) recrystallization, 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 of the catalyst precarsor with 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
Amount is 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) react 1 hour afterwards, restore to 25 DEG C, the reaction was continued 15 points
Clock.Later, the solution is transferred to by double angular pins containing the above-mentioned compound W with structure shown in formula IV at -78 DEG C
It in the dichloromethane solution (dosage of methylene chloride is 30mL) of (1.36mmol), and reacts 4 hours, then will at such a temperature
System is gradually brought to 40 DEG C, then reacts 8 hours.After reaction, solvent is removed with vacuum line, residue methylene chloride
It washs and is filtered by diatomite, filtrate is drained, crude product methylene chloride/n-hexane (body of methylene chloride and n-hexane
Product is than being 1:5) recrystallization, 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 for illustrating block copolymer and preparation method thereof of the invention.
500mL polymeric kettle after heating and drying is vacuumized into logical nitrogen twice, then is passed through 0.1MPa third after vacuumizing
Then alkene sequentially adds the toluene solution 13.3mL (concentration 1.5mmol/mL) of methylaluminoxane, handles by anhydrous and oxygen-free
Toluene 150mL, and the toluene solution 5mL (10 μm of ol/mL) containing catalyst precarsor A1.It is passed through pressure under mechanical stirring
For the propylene of 0.3MPa, and at this pressure in 0 DEG C of reaction 2h, then pass to ethylene the reaction was continued the 1h of 0.32Mpa, then plus
Enter ethyl alcohol and terminate reaction, obtain polymer 12.2g, be computed determination, polymerization activity is 4.07 × 104g·mol-1(Ti)·h-1。
It determines that the polymer that the present embodiment obtains is propylene-propylene-ethylene block copolymerization object through gpc analysis, measures polypropylene block
Content be 21mol%, the content of the third ethylene block is 79mol%.
Measuring fusing point is 131.3 DEG C；Measure the M of block copolymerwIt is 1.85 × 105, molecular weight distribution Mw/MnIt is 1.69.
Embodiment 2
The present embodiment is for illustrating block copolymer and preparation method thereof of the invention.
500mL polymeric kettle after heating and drying is vacuumized into logical nitrogen twice, then is passed through 0.1Mpa third after vacuumizing
Then alkene sequentially adds the toluene solution 13.3mL (concentration 1.5mmol/mL) of isobutyl aluminium alkoxide, at anhydrous and oxygen-free
The toluene 150mL of reason, and the toluene solution 5mL (10 μm of ol/mL) containing catalyst precarsor A2.It is passed through pressure under mechanical stirring
Power is the propylene of 0.3MPa, and at this pressure in 5 DEG C of reaction 5h, then passes to ethylene the reaction was continued the 0.3h of 0.15Mpa, so
Ethyl alcohol is added afterwards and terminates reaction, obtains polymer 7.7g, is computed determination, polymerization activity is 1.45 × 104g·mol-1(Ti)·
h-1。
It determines that the polymer that the present embodiment obtains is propylene-propylene-ethylene block copolymerization object through gpc analysis, measures polypropylene block
Content be 46mol%, the content of the third ethylene block is 54mol%.
Measuring fusing point is 129.1 DEG C；Measure the M of block copolymerwIt is 1.37 × 105, molecular weight distribution Mw/MnIt is 1.36.
Embodiment 3
The present embodiment is for illustrating block copolymer and preparation method thereof of the invention.
500mL polymeric kettle after heating and drying is vacuumized into logical nitrogen twice, then is passed through 0.1Mpa third after vacuumizing
Then alkene sequentially adds the toluene solution 13.3mL (concentration 1.5mmol/mL) of methylaluminoxane, handles by anhydrous and oxygen-free
Toluene 150mL, and the toluene solution 5mL (10 μm of ol/mL) containing catalyst precarsor A3.It is passed through pressure under mechanical stirring
For the propylene of 0.8MPa, and at this pressure in 25 DEG C of reaction 8h, ethylene the reaction was continued the 0.5h of 0.9Mpa is then passed to, then
Ethyl alcohol is added and terminates reaction, obtains polymer 26.3g, is computed determination, polymerization activity is 3.1 × 104g·mol-1(Ti)·h-1。
It determines that the polymer that the present embodiment obtains is propylene-propylene-ethylene block copolymerization object through gpc analysis, measures polypropylene block
Content be 28mol%, the content of the third ethylene block is 72mol%.
Measuring fusing point is 134.1 DEG C；Measure the M of block copolymerwIt is 2.13 × 105, molecular weight distribution Mw/MnIt is 1.55.
Embodiment 4
The present embodiment is for illustrating block copolymer and preparation method thereof of the invention.
500mL polymeric kettle after heating and drying is vacuumized into logical nitrogen twice, then is passed through 0.1MPa 1- after vacuumizing
Then butylene sequentially adds the toluene solution 13.3mL (concentration 1.5mmol/mL) of methylaluminoxane, at anhydrous and oxygen-free
The toluene 150mL of reason, and the toluene solution 5mL (10 μm of ol/mL) containing catalyst precarsor A1.It is passed through pressure under mechanical stirring
Power is the 1- butylene of 0.3MPa, and at this pressure in 0 DEG C of reaction 2h, then passes to ethylene the reaction was continued the 1h of 0.32Mpa, so
Ethyl alcohol is added afterwards and terminates reaction, obtains polymer 11.2g, is computed determination, polymerization activity is 3.4 × 104g·mol-1(Ti)·
h-1。
It determines that the polymer that the present embodiment obtains is 1- butylene-fourth ethylene block copolymer through gpc analysis, measures 1- butylene
The content of block is 26mol%, and the content of fourth ethylene block is 74mol%.
Measuring fusing point is 119.4 DEG C；Measure the M of block copolymerwIt is 2.2 × 105, molecular weight distribution Mw/MnIt is 1.75.
Embodiment 5
The present embodiment is for illustrating block copolymer and preparation method thereof of the invention.
500mL polymeric kettle after heating and drying is vacuumized into logical nitrogen twice, then is passed through 0.1MPa third after vacuumizing
Then alkene sequentially adds the toluene solution 13.3mL (concentration 1.5mmol/mL) of methylaluminoxane, handles by anhydrous and oxygen-free
Toluene 150mL, and the toluene solution 5mL (10 μm of ol/mL) containing catalyst precarsor A1.It is passed through pressure under mechanical stirring
For the propylene of 0.3MPa, and at this pressure in 0 DEG C of reaction 2h, ethylene the reaction was continued the 1h of 0.32Mpa is then passed to, is then taken out
Ethylene is removed in vacuum, then is passed through propylene the reaction was continued the 2h of 0.3Mpa, ethyl alcohol is then added and terminates reaction, obtains polymer
14.6g。
It determines that polymer that the present embodiment obtains is the-the third Ethylene-Propylene Block Copolymer of propylene through gpc analysis, measures the
The content of one section of polypropylene block is 17mol%, and the content of the third ethylene block is 67mol%, and the content of second segment polypropylene block is
16mol%.
Measuring fusing point is 130.7 DEG C；Measure the M of block copolymerwIt is 1.94 × 105, molecular weight distribution Mw/MnIt is 1.46.
Embodiment 6
The present embodiment is for illustrating block copolymer and preparation method thereof of the invention.
500mL polymeric kettle after heating and drying is vacuumized into logical nitrogen twice, then is passed through 0.1Mpa third after vacuumizing
Then alkene sequentially adds the toluene solution 13.3mL (concentration 1.5mmol/mL) of methylaluminoxane, handles by anhydrous and oxygen-free
Toluene 150mL, and the toluene solution 5mL (10 μm of ol/mL) containing catalyst precarsor A1.It is passed through pressure under mechanical stirring
For the propylene of 0.3MPa, and at this pressure in 0 DEG C of reaction 1h, ethylene the reaction was continued the 0.5h of 0.32Mpa is then passed to, then
Removing ethylene is vacuumized, then is passed through propylene the reaction was continued the 1h of 0.3Mpa, then is passed through ethylene the reaction was continued the 0.5h of 0.32Mpa,
Then ethyl alcohol is added and terminates reaction, obtains polymer 15.3g.
Determine that the polymer that the present embodiment obtains is the-the third ethylene-propylene of propylene-propylene-ethylene block copolymerization object through gpc analysis,
The content for measuring first segment polypropylene block is 11mol%, and the content of the third ethylene block of first segment is 42mol%, second segment propylene
The content of block is 10mol%, and the content of the third ethylene block of second segment is 37mol%.
Measuring fusing point is 128.0 DEG C；Measure the M of block copolymerwIt is 1.71 × 105, molecular weight distribution Mw/MnIt is 1.51.
Embodiment 7
The present embodiment is for illustrating block copolymer and preparation method thereof of the invention.
500mL polymeric kettle after heating and drying is vacuumized into logical nitrogen twice, then is passed through 0.1Mpa third after vacuumizing
Then alkene sequentially adds the toluene solution 13.3mL (concentration 1.5mmol/mL) of methylaluminoxane, handles by anhydrous and oxygen-free
Toluene 150mL, and the toluene solution 5mL (10 μm of ol/mL) containing catalyst precarsor A1.It is passed through pressure under mechanical stirring
For the propylene of 0.3MPa, and at this pressure in 0 DEG C of reaction 1h, ethylene the reaction was continued the 0.5h of 0.32Mpa is then passed to, is taken out true
Sky removes ethylene, then passes to propylene the reaction was continued the 1h of 0.3Mpa, then is passed through ethylene the reaction was continued the 0.5h of 0.32Mpa, takes out
Vacuum removes ethylene again, then passes to propylene the reaction was continued the 1h of 0.3Mpa, and ethyl alcohol is then added and terminates reaction, obtains polymer
13.6g。
Determine that the polymer that the present embodiment obtains is total for the-the third ethylene-propylene blocks of the-the third ethylene-propylene of propylene through gpc analysis
Polymers, the content for measuring first segment polypropylene block is 10mol%, and the content of the third ethylene block of first segment is 38mol%, second segment
The content of polypropylene block is 9mol%, and the content of the third ethylene block of second segment is 34mol%, and the content of third section polypropylene block is
9mol%.
Measuring fusing point is 137.9 DEG C；Measure the M of block copolymerwIt is 1.84 × 105, molecular weight distribution Mw/MnIt is 1.39.
Comparative example 1
According to the method for embodiment 1, unlike, catalyst precarsor is replaced with the compound W with structure shown in formula IV
A1。
Polymer 1.67g is obtained, determination is computed, polymerization activity is 5.5 × 103g·mol-1(Ti)·h-1.As a result table
It is bright, trace amount polymer is obtained when being passed through propylene, can not be characterized, and just obtains random copolymerization when being only passed through ethylene again
Object.
Measuring fusing point is 74.4 DEG C；Measure the M of copolymerwIt is 3.2 × 105, molecular weight distribution Mw/MnIt is 4.72.
By embodiment 1 compared with comparative example 1 it is found that when preparing block copolymer, urged using containing provided by the invention
The catalyst of agent precursor can obtain considerably higher polymerization activity, obvious narrower molecular weight distribution, considerably higher molten
Point.
The ethylene of diblock, three block and more blocks can be prepared in the preparation method of block copolymer of the invention
Block copolymer, polymerization activity is 104-105g·mol-1(M)·h-1Between (wherein, M be titanium, zirconium or hafnium), resulting block
The weight average molecular weight of copolymer is between 100,000-22 ten thousand, and molecular weight distribution is less than 2.0, and fusing point may be up to 120 DEG C, comonomer
The molar content that (hard section) can introduce is 20-50%, and the molar content of the copolymerization units (soft segment) of comonomer and ethylene is 50-
80%, and catalyst precarsor used in the method for preparing block copolymer of the invention, preparation method is simple, and it is at low cost,
It is reproducible, it is easy to industrialize.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
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 also be regarded as the disclosure of the present invention.
Claims (21)
1. a kind of preparation method of block copolymer, which is characterized in that this method is included under olefin polymerization conditions, molten in inertia
In the presence of agent, ethylene, comonomer are contacted with catalyst and carry out polymerization reaction, the catalyst contains catalyst precarsor and alkane
Base aikyiaiurnirsoxan beta, wherein the catalyst precarsor has structure shown in Formulas I,
Wherein, R1、R2And R4It is each independently hydrogen atom or the alkyl of C1-C20；R3For phenyl, halogenophenyl or alcoxyl
Base phenyl；M is titanium, zirconium or hafnium；
Wherein, it includes: first by comonomer and catalysis that ethylene, comonomer are contacted to the method for carrying out polymerization reaction with catalyst
Agent contact carries out the first polymerization reaction, then contacts with the first polymerization reaction system ethylene in the presence of comonomer and carries out the
Dimerization reaction.
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- fluorophenyl, 2,4 difluorobenzene base, the fluoro- 3- chlorphenyl of 4- or the chloro- 2,3,5,6- tetrafluoro phenyl of 4-；The alkane
The carbon atom number of alkoxy is 1-6 in phenyl.
3. according to the method described in claim 2, wherein, the alkoxyl phenyl is p-methoxyphenyl.
4. according to the method described in claim 1, wherein, R1And R2For tert-butyl, R3For pentafluorophenyl group, R4For hydrogen, M is titanium.
5. according to the method described in claim 1, wherein, R1And R4For methyl, R2For tert-butyl, R3For phenyl, M is titanium.
6. according to the method described in claim 1, wherein, this method further includes before being prepared by the following method the catalyst
Body: under the conditions of complex reaction, by the compound with structure shown in formula IV with the compound with structure shown in Formula V organic
It is contacted in solvent, obtains the 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, halogenophenyl or alcoxyl
Base phenyl；M is titanium, zirconium or hafnium.
7. according to the method described in claim 6, wherein, the compound with structure shown in formula IV has Formula V with described
The molar ratio of the compound of shown structure is 1:1.8-2..
8. according to the method described in claim 6, wherein, the condition of the contact includes: that temperature is 0-40 DEG C, time 8-24
Hour.
9. according to the method described in claim 6, wherein, the organic solvent be tetrahydrofuran, ether, Isosorbide-5-Nitrae-dioxane and
One of methylene chloride is a variety of.
10. according to the method described in claim 1, wherein, the molar ratio of the catalyst precarsor and alkylaluminoxane is 1:
200-2000。
11. according to the method described in claim 10, wherein, the molar ratio of the catalyst precarsor and alkylaluminoxane is 1:
200-1000。
12. according to the method described in claim 1, wherein, alkyl is the linear chain or branched chain alkane of C1-C5 in the alkylaluminoxane
Base.
13. according to the method for claim 12, wherein alkyl is methyl or isobutyl group in the alkylaluminoxane.
14. according to the method for claim 13, wherein alkyl is methyl in the alkylaluminoxane.
15. according to the method described in claim 10, wherein, alkyl is the linear chain or branched chain of C1-C5 in the alkylaluminoxane
Alkyl.
16. according to the method for claim 15, wherein alkyl is methyl or isobutyl group in the alkylaluminoxane.
17. according to the method for claim 16, wherein alkyl is methyl in the alkylaluminoxane.
18. according to the method described in claim 1, wherein, the comonomer is the alhpa olefin and C4-C10 of propylene, C4-C10
One of alkadienes or a variety of.
19. method described in any one of -18 according to claim 1, wherein contact ethylene, comonomer with catalyst
Carry out polymerization reaction method further include: after the ethylene in the second polymerization reaction reacts completely, in the presence of comonomer into
The reaction of row third polymerization；Or
After the ethylene in the second polymerization reaction reacts completely, successively the third polymerization in the presence of progress comonomer is reacted, altogether
The 4th polymerization reaction in the presence of polycondensation monomer and ethylene；Or
After the ethylene in the second polymerization reaction reacts completely, successively the third polymerization in the presence of progress comonomer is reacted, altogether
The 4th polymerization reaction in the presence of polycondensation monomer and ethylene, and after the ethylene in the 4th polymerization reaction reacts completely, it is single in copolymerization
The 5th polymerization reaction is carried out in the presence of body.
20. method described in any one of -18 according to claim 1, wherein the condition of the first polymerization reaction includes: polymerization
Temperature is 0-25 DEG C, polymerization pressure 0.1-1MPa, polymerization time 2-10h；And/or
The condition of second polymerization reaction includes: that polymerization temperature is 0-25 DEG C, polymerization pressure 0.1-1MPa, and polymerization time is
0.25-1h。
21. according to the method for claim 19, wherein the condition of third polymerization reaction includes: that polymerization temperature is 0-25 DEG C,
Polymerization pressure is 0.1-1MPa, polymerization time 2-10h；And/or
The condition of 4th polymerization reaction includes: that polymerization temperature is 0-25 DEG C, polymerization pressure 0.1-1MPa, and polymerization time is
0.25-1h；And/or
The condition of 5th polymerization reaction includes: that polymerization temperature is 0-25 DEG C, polymerization pressure 0.1-1MPa, polymerization time 2-
10h。
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|---|---|---|---|---|
| CN1362972A (en) * | 2000-01-26 | 2002-08-07 | 三井化学株式会社 | Olefin polymers and production process thereof |
| CN1671756A (en) * | 2002-07-30 | 2005-09-21 | 伊奎斯塔化学有限公司 | Polyolefin block copolymers |
| 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 |
| CN104725540A (en) * | 2013-12-18 | 2015-06-24 | 中国石油化工股份有限公司 | Ethylene copolymer preparation method |
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| EP2550308A4 (en) * | 2010-03-25 | 2014-07-30 | Agency Science Tech & Res | SELF-ASSEMBLED MULTINUCLEAR CATALYST FOR OLEFIN POLYMERIZATION |
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| CN1362972A (en) * | 2000-01-26 | 2002-08-07 | 三井化学株式会社 | Olefin polymers and production process thereof |
| CN1671756A (en) * | 2002-07-30 | 2005-09-21 | 伊奎斯塔化学有限公司 | Polyolefin block copolymers |
| 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 |
| CN104725540A (en) * | 2013-12-18 | 2015-06-24 | 中国石油化工股份有限公司 | Ethylene copolymer preparation method |
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