CN105985478A - Method for preparing vinyl copolymer - Google Patents
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Abstract
The invention relates to the field of olefin coordination polymerization, and discloses a method for preparing a vinyl copolymer. The method includes the steps that under the olefin polymerization and inert solvent conditions, ethylene, comonomer and catalysts are in contact for polymerization, wherein the catalysts contain catalyst precursors and alkylaluminoxane, the catalyst precursors are of the structure shown in the formula I (please see the specification), R1, R2 and R4 are independently hydrogen atoms or alkyl of C1 to C20, R3 is phenyl or chlorophenyl or alkoxyphenyl, and M is titanium or zirconium or hafnium. When the vinyl copolymer is prepared is prepared with the method, high catalytic efficiency is achieved, and the molecular weight distribution of the vinyl copolymer is narrow.
Description
Technical field
The present invention relates to olefin coordination polymerization field, in particular it relates toA kind of method preparing ethylene copolymer。
Background technology
Since entering 21 century, along withNationalThe raising of economic level and the needs of national defense industry, macromolecular material, particularly polyolefine material plays the most important effect: owing to polyolefinic raw materials enriches cheap, it is easily worked molding, the annual polyolefin products worldwide produced has exceeded 100,000,000 tons, one of industry becoming maximum-norm；Polyolefine material has relatively small density, the features such as good chemical proofing, resistance to water and good mechanical strength, electrical insulating property, can be used for thin film, tubing, sheet material, various moulded products, electric wire etc., not only have been widely used in terms of the daily use Sundry goods such as agricultural, packaging, automobile, electrical equipment, clothing, food, lodging and transportion--basic necessities of life for the mankind are provided convenience, and also play great function in the Strategic projects such as national defence, the energy, Aero-Space.
Wherein, ethylene copolymer product has superior performance, and comonomer type is various, including 1-octene, 1-hexene, 1-butylene, propylene and polar monomer etc..By regulation comonomer type and consumption, both can obtain linear low density polyethylene, it is also possible to obtain thermoplastic elastomer (TPE), moreover it is possible to obtain rubber, apply quite varied.The particularly special construction of elastomer gives the mechanical property of its excellence, rheological property and ageing-resistant performance, and during as plastics impact resilience agent, low-temperature flexibility is good, consumption is few, cost performance is high, it is possible to be widely used in modifying plastics.
Polyolefin industry flourish has benefited from the fast development of Ziegler-Natta catalyst and coordination polymerization that metallocene catalyst is representative.Being developed so far, the research for Ziegler-Natta catalyst and metallocene catalyst is the most ripe, but in such catalyst, it is possible to the effectively catalyst type of catalyzed ethylene combined polymerization is the most few.Therefore, non-metallocene catalyst is increasingly becoming the emphasis of research at present.Salicylaldimine ligand transition-metal catalyst belongs to one therein.Utilize salicylic alidehyde imine to close titanium catalyst and highly active can catalyze and synthesize the homopolymer 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 it is capable of the alternating copolymerization of ethylene and propylene, obtains a kind of thermoplastic elastomer of good performance.It addition, utilize such catalyst to be capable of ethylene and 1-hexene or olefin random copolymerization (Rick F, Makot M, the Terunori F, Macromolecules 2005,38,1546 with polar functional group；Terao H, Ishii S, Mitanti M, et al., J.Am.Chem.Soc.2008,130,17636), expanded the range of application of titanium catalyst.
Patent application CN101864010B discloses the bimetallic catalyst precursor of a kind of catalysis in olefine polymerization or combined polymerization.This catalyst precarsor is based on salicylaldimine ligand and group iv transition metals.This catalyst precarsor mainly utilizes pentafluoroaniline and bridging salicylide to be condensed to yield part, then part and Ti complexation are obtained catalyst, but this catalyst synthetic route is loaded down with trivial details, with high costs, and the molecular weight distribution of copolymer that alpha-olefin obtains with ethylene copolymer is wider.
Patent application CN101200404A discloses a kind of method of synthesizing short-chain olefin by ethylene oligomerization, the method is that ethylene oligomerization reaction synthesis occurs under the effect by the catalyst being supported in ionic liquid, wherein, catalyst is made up of with alkyl aluminum double salicylaldehyde imine nickel complex, and the method products therefrom is ethylene low polymer.But, the productivity of the double salicylaldehyde imine nickel complex of this patent application publication is relatively low, it addition, ethylene polymerization activity is relatively low.
Therefore, research and develop and a kind of there is the preparation method of the simple ethylene copolymer of non-metallocene catalyst preparation technology that high catalytic efficiency, molecular weight distribution are narrower and use, have important practical significance.
Summary of the invention
The invention aims to overcome the defect of prior art, a kind of new method preparing ethylene copolymer is provided, utilizing the method to have the molecular weight distribution of higher catalytic efficiency and ethylene copolymer when preparing ethylene copolymer narrower, the non-metallocene catalyst preparation technology of use is simple.
Therefore, to achieve these goals, the invention providesA kind of method preparing ethylene copolymer, the method is included under olefin polymerization conditions, in the presence of an inert solvent, ethylene, comonomer is contacted with catalyst and is polymerized, and described catalyst contains catalyst precarsor and alkylaluminoxane, and wherein, this catalyst precarsor has the structure shown in Formulas I,
Wherein, R1、R2And R4EachIndependentGround is the alkyl of hydrogen atom or 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 low cost is reproducible, it is easy to industrialization.
The catalyst prepared used in the method for ethylene copolymer of the present invention, it is made up of above-mentioned catalyst precarsor and alkylaluminoxane, due to the bimetallic synergism in structure, and having organic substituent on phenyl ring, therefore this catalyst has high catalytic efficiency.Specifically, the catalyst used in the method preparing ethylene copolymer of the present invention is when for catalyzed ethylene copolymerization, and catalytic efficiency (polymerization activity) may be up to 5 × 106g·mol-1(Ti)·h-1Above, the weight average molecular weight of the ethylene copolymer of gained is about 200,000, and molecular weight distribution is about 2, and the molar content that comonomer can introduce is between 1.8-12.4%.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Figure 1It it is the reaction equation of the catalyst precarsor preparing the present invention.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
The invention providesA kind of method preparing ethylene copolymer, the method is included under olefin polymerization conditions, in the presence of an inert solvent, ethylene, comonomer is contacted with catalyst and is polymerized, and this catalyst contains catalyst precarsor and alkylaluminoxane, and wherein, this catalyst precarsor has the structure shown in Formulas I,
Wherein, R1、R2And R4EachIndependentGround is the alkyl of hydrogen atom or C1-C20；R3For phenyl, halogenophenyl or alkoxyl phenyl；M is titanium, zirconium or hafnium.
In the catalyst precarsor of the inventive method, in Formulas I, R1、R2And R4Can be identical, it is also possible to different.The alkyl of C1-C20 can be straight chain, it is also possible to be side chain.Preferably, the alkyl of C1-C20 is the alkyl of C1-C6.Wherein, the straight or branched alkyl of C1-C20 can include but not limited to: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, 2-methyl butyl, 3-methyl butyl, 2, 2-dimethyl propyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, 3, 7-dimethyl octyl group, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-octadecane base, AI3-36122 base and AI3-28404 base.
In the catalyst precarsor of the inventive method, in Formulas I, under preferable case, halogenophenyl is chloro-2,3,5, the 6-tetrafluoro phenyl of pentafluorophenyl group, 2-fluorophenyl, 2,4 difluorobenzene base, 4-fluoro-3-chlorphenyl or 4-；Alkoxyl phenyl is p-methoxyphenyl.
The present inventor finds under study for action, by specific R1-R4Fabulous catalytic effect can be obtained, it is preferable that R when the catalyst precarsor formed is as the catalytic component of catalyzed ethylene copolymerization1For the tert-butyl group, R2For the tert-butyl group, R3For pentafluorophenyl group, R4For hydrogen, M is titanium, and described catalyst precarsor is the catalyst precarsor with Open architecture shown in formula II；Or, R1For methyl, R2For the tert-butyl group, R3For phenyl, R4For methyl, M is titanium, and described bimetallic catalyst precursor is the catalyst precarsor with Open architecture shown in formula III,
In the catalyst precarsor of the inventive method, under preferable case, the preparation method of this catalyst precarsor includes: under the conditions of complex reaction, the compound with structure shown in formula IV is contacted in organic solvent with the compound with structure shown in Formula V, obtain the catalyst precarsor with structure shown in Formulas I
Wherein, R1、R2And R4EachIndependentGround is the alkyl of hydrogen atom or C1-C20；R3For phenyl, halogenophenyl or alkoxyl phenyl；M is titanium, zirconium or hafnium.
Prepare the reaction equation of the above-mentioned catalyst precarsor with structure shown in formula ISuch as figure 1Shown in.
In the preparation method of the catalyst precarsor of the inventive method, about R1、R2、R3And R4Restriction reasonably can be selected by described above, do not repeating.
nullIn the preparation method of the catalyst precarsor of the inventive method，The compound with structure shown in formula IV can be prepared according to following method: by 6,6'-(1Z,1'Z)-(4,4'-alkyl substituent methyl double (4,1-penylene) double (imines-1-replaces-1-subunit)) double (methyl isophthalic acid-replacement-1-subunit) double (2-alkyl substituted phenols) (according to Eur.Polym.J.2012,48,The preparation method that 191 199 documents are recorded prepares) (1eq) be dissolved in dichloromethane solvent，This solution will be added to the dichloromethane solution containing (double tetrahydrofuran) titanium tetrachloride (1.8-2.2eq) at 78 DEG C，React 1 hour under low temperature，Recover to room temperature and be heated to 40 DEG C，Continue reaction 8-16 hour.After reaction terminates, being removed by solvent with vacuum line, residue from dichloromethane is washed and is filtered by kieselguhr, filtrate drained, thick product dichloromethane/normal hexane recrystallization, obtains red brown solid.
In the preparation method of the catalyst precarsor of the inventive method, the compound with structure shown in Formula V can be prepared according to following method: is dissolved in ether solvent by (E)-2-alkyl replacement-6-((aryl substituted imine base) methyl) phenol (1eq), at 78 DEG C, in this solution, add the hexane solution (in hexane solution, the concentration of n-BuLi is 1.67M) containing n-BuLi (0.95-1.05eq) react 1 hour afterwards, recover to room temperature 25 DEG C, continue reaction 10-20 minute, to obtain final product.
In the preparation method of the catalyst precarsor of the inventive method, the compound with structure shown in formula IV can change with the mol ratio of the compound with structure shown in Formula V in wider scope, it is not particularly limited, under preferable case, the compound with structure shown in formula IV is 1:1.8-2.2 with the mol ratio of the compound with structure shown in Formula V.
In the preparation method of the catalyst precarsor of the inventive method, the condition of contact can change in wider scope, as long as ensureing that the compound with structure shown in formula IV and the compound with structure shown in Formula V react generation target product, under preferable case, the condition of contact includes: temperature is 0-40 DEG C, more preferably 20-30 DEG C；Time is 8-24 hour, more preferably 10-15 hour.
In the preparation method of the catalyst precarsor of the inventive method, for organic solvent, there is no particular limitation, can 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 or more in oxolane, ether, Isosorbide-5-Nitrae-dioxane and dichloromethane.These solvents can be used alone, it is also possible to is used in mixed way.The consumption of organic solvent reasonably can select according to the consumption of the compound with the compound with structure shown in Formula V with structure shown in formula IV, and this is known to those skilled in the art, does not repeats them here.
In the preparation method of the catalyst precarsor of the inventive method, the method is additionally may included in after reaction completes, and is removed by organic solvent.Wherein, for removing the method for organic solvent, there is no particular limitation, can use various method well known in the art, and such as, vacuum line is evaporated off organic solvent etc. except organic solvent, rotation, the most known to those skilled in the art, will not be described in great detail at this.
In the preparation method of the catalyst precarsor of the inventive method, in order to obtain sterling, the method can also include the step being purified by the product obtained.For the method for purification, there is no particular limitation, and various purification process well known in the art can be used to carry out, such as recrystallization etc..For the solvent used by recrystallization, there is no particular limitation, the various solvents that can be known in the art, such as, can be dichloromethane and/or normal hexane.
In the method preparing ethylene copolymer of the present invention, the mol ratio of catalyst precarsor and alkylaluminoxane can change in the larger context, it is not particularly limited, but so that both materials work in coordination with the effect playing catalysis in olefine polymerization, under preferable case, the mol ratio of catalyst precarsor and alkylaluminoxane is 1:200-2000, more preferably 1:200-1000.
In the method preparing ethylene copolymer of the present invention, for alkylaluminoxane, there is no particular limitation, can be the conventional various alkylaluminoxanes as promoter of catalyst field, can have straight chain, side chain or circulus.Under preferable case, in alkylaluminoxane, alkyl is the straight or branched alkyl of C1-C5.The example of the straight or branched alkyl of C1-C5 can include but not limited to: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl and neopentyl.It is further preferred that alkyl is methyl or isobutyl group, more preferably methyl in alkylaluminoxane.
In the method preparing ethylene copolymer of the present invention, under preferable case, alkylaluminoxane is MAO (MAO) and/or modified methylaluminoxane (MMAO).
In the method preparing ethylene copolymer of the present invention, for comonomer, there is no particular limitation, can be various comonomers commonly used in the art, under preferable case, comonomer be one or more in the alkadienes of propylene, the α substituted olefine of C4-C10 and C4-C10.One or more in the α substituted olefine of C4-C10 more preferably 1-hexene, 1-octene and 1-decene, the alkadienes of C4-C10 more preferably 1,5-hexadiene and/or Isosorbide-5-Nitrae-pentadiene.
The method of the ethylene copolymer of the present invention is to use the Above-mentioned catalytic agent precursor that have employed containing the present invention and the above-mentioned catalyst of alkylaluminoxane.
In the method preparing ethylene copolymer of the present invention, olefinic polyreaction condition can be the conventional selection of this area, and under preferable case, olefinic polyreaction is carried out in an inert atmosphere.Inert atmosphere refer to not with reactant and any one gas of product generation chemical reaction or admixture of gas, such as one or more in nitrogen and periodic table of elements zero group gas.Keep the method for inert atmosphere can be passed through in reaction system above-mentioned not with reactant and any one gas of product generation chemical reaction or admixture of gas.
In the method preparing ethylene copolymer of the present invention, for atent solvent, there is no particular limitation, can be the various atent solvents not reacted with reactant and product commonly used in the art, under preferable case, atent solvent is aromatic hydrocarbons and/or alkane, it is further preferred that aromatic hydrocarbons is benzene and/or toluene, alkane is normal hexane and/or normal heptane.
In the method 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 minute.
In the method preparing ethylene copolymer of the present invention, ethylene copolymer reaction is additionally included in addition terminator after polyreaction completes, so that polyreaction terminates, i.e. make active center inactivate.For terminator, there is no particular limitation, can be the various terminators that can terminate living polymer chains in field of olefin polymerisation.Can be such as one or more in water, methanol, ethanol, normal propyl alcohol and isopropanol.
Embodiment
The present invention is further illustrated for below example, but and is not so limited 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 relates to is as follows:
Fusing point is measured by differential scanning calorimeter, and differential scanning calorimeter is purchased from PE company of the U.S., and model is PE DSC-7, and condition determination includes: nitrogen, and heating rate is 10 DEG C/min.
Weight average molecular weight (Mw) and the number-average molecular weight (Mn) of polyethylene are measured by gel permeation chrommatograph, gel permeation chrommatograph is purchased from Shimadzu Corporation, and model is LC-10AT, and condition determination includes: flowing is mutually for THF, standard sample is Narrow distribution polystyrene, and test temperature is 25 DEG C.
In ethylene copolymer, the content of comonomer is measured by nuclear magnetic resonance chemical analyser, and nuclear magnetic resonance chemical analyser is purchased from Bruke company, and model is Bruke-300, and condition determination includes: measuring temperature is 110 DEG C.
nullThe preparation method of the compound with structure shown in formula IV is: by 6,6'-(1E,1'E)-(4,4'-di-2-ethylhexylphosphine oxide (4,1-penylene) double (imines-1-replaces-1-subunit)) double (methyl isophthalic acid-replacement-1-subunit) double (2-t-butyl phenols) (according to Eur.Polym.J.2012,48,The preparation method that 191 199 documents are recorded prepares) (3.41mmol) be dissolved in dichloromethane solvent (consumption of dichloromethane is 30mL)，This solution will be added to the dichloromethane solution (consumption of dichloromethane is 30mL) closing titanium (6.82mmol) containing tetrachloro double (oxolane) at 78 DEG C，React 1 hour at-78 DEG C，Recover to room temperature 25 DEG C and be heated to 40 DEG C，Continue reaction 16 hours.After reaction terminates, being removed by solvent with vacuum line, residue from dichloromethane is washed and is filtered by kieselguhr, filtrate drained, thick product dichloromethane/normal hexane (dichloromethane is 1:5 with the volume ratio of normal hexane) recrystallization, obtains 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 elementary analysis result of W shows, 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 has the preparation of the catalyst precarsor of structure shown in Formula II for explanation.
(the E)-2-tert-butyl group-6-((pentafluorophenyl group imido grpup) methyl) phenol (2.24mmol) is dissolved in ether solvent (consumption of ether is 30mL), (in hexane solution, the concentration of n-BuLi is 1.67M to add the hexane solution containing n-BuLi at 78 DEG C in this solution, the amount of n-BuLi is 2.35mmol) react 1 hour afterwards, recover to 25 DEG C, continue reaction 15 minutes, obtain the compound Y1 with structure shown in Formula V, the structural formula of Y1 is shown below and (sees list of references: J.Am.Chem.Soc.2002, 124, 3327-3336).
In 78 DEG C of dichloromethane solutions (consumption of dichloromethane is 30mL) that the aforementioned solution (i.e. containing the solution of compound Y1) obtained is transferred to containing the above-mentioned compound W (1.12mmol) with structure shown in formula IV by double angular pins, and react 4 hours at such a temperature, then system is gradually brought to 25 DEG C, then reacts 12 hours.After reaction terminates, with vacuum line, solvent is removed, residue from dichloromethane is washed and is filtered by kieselguhr, filtrate is drained, thick product dichloromethane/normal hexane (dichloromethane is 1:5 with the volume ratio of normal hexane) recrystallization, obtains 0.69g bronzing product A 1 (productivity 43%).
The elementary analysis result of A1 shows, 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)。
From structure and the above-mentioned data of Y1 and W, A1 has structure shown in Formula II.
Preparation example 2
This preparation example has the preparation of the catalyst precarsor of structure shown in formula III for explanation.
(E)-2-methyl-6-((phenyl imine base) methyl) phenol (3.00mmol) is dissolved in ether solvent (consumption of ether is 30mL), (in hexane solution, the concentration of n-BuLi is 1.67M to add the hexane solution containing n-BuLi at 78 DEG C in this solution, the amount of n-BuLi is 3.05mmol) react 1 hour afterwards, recover to 25 DEG C, continue reaction 15 minutes, obtain the compound Y2 with structure shown in Formula V, the structural formula of Y2 is shown below and (sees list of references: J.Am.Chem.Soc.2001, 123, 6847-6856).
In 78 DEG C of dichloromethane solutions (consumption of dichloromethane is 30mL) that the aforementioned solution (i.e. containing the solution of compound Y2) obtained is transferred to containing the above-mentioned compound W (1.50mmol) with structure shown in formula IV by double angular pins, and react 4 hours at such a temperature, then system is gradually brought to 25 DEG C, then reacts 12 hours.After reaction terminates, with vacuum line, solvent is removed, residue from dichloromethane is washed and is filtered by kieselguhr, filtrate is drained, thick product dichloromethane/normal hexane (dichloromethane is 1:5 with the volume ratio of normal hexane) recrystallization, obtains 0.96g bronzing product A 2 (productivity 53%).
The elementary analysis result of A2 shows, 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)。
From structure and the above-mentioned data of Y2 and W, A2 has structure shown in formula III.
Preparation example 3
This preparation example has the preparation of the catalyst precarsor of structure shown in Formula II for explanation.
(the E)-2-tert-butyl group-6-((pentafluorophenyl group imido grpup) methyl) phenol (2.24mmol) is dissolved in ether solvent (consumption of ether is 30mL), (in hexane solution, the concentration of n-BuLi is 1.67M to add the hexane solution containing n-BuLi at 78 DEG C in this solution, the amount of n-BuLi is 2.35mmol) react 1 hour afterwards, recover to 25 DEG C, continue reaction 15 minutes.Afterwards, in 78 DEG C of dichloromethane solutions (consumption of dichloromethane is 30mL) that this solution is transferred to containing the above-mentioned compound W (1.24mmol) with structure shown in formula IV by double angular pins, and react 4 hours at such a temperature, then system is gradually brought to 0 DEG C, then reacts 24 hours.After reaction terminates, with vacuum line, solvent is removed, residue from dichloromethane is washed and is filtered by kieselguhr, filtrate is drained, thick product dichloromethane/normal hexane (dichloromethane is 1:5 with the volume ratio of normal hexane) recrystallization, obtains 0.98g bronzing product A 3 (productivity 61%).
As known by the foregoing results, A3 has structure shown in Formula II.
Preparation example 4
This preparation example has the preparation of the catalyst precarsor of structure shown in formula III for explanation.
(E)-2-methyl-6-((phenyl imine base) methyl) phenol (3.00mmol) is dissolved in ether solvent (consumption of ether is 30mL), (in hexane solution, the concentration of n-BuLi is 1.67M to add the hexane solution containing n-BuLi at 78 DEG C in this solution, the amount of n-BuLi is 3.05mmol) react 1 hour afterwards, recover to 25 DEG C, continue reaction 15 minutes.Afterwards, in 78 DEG C of dichloromethane solutions (consumption of dichloromethane is 30mL) that this solution is transferred to containing the above-mentioned compound W (1.36mmol) with structure shown in formula IV by double angular pins, and react 4 hours at such a temperature, then system is gradually brought to 40 DEG C, then reacts 8 hours.After reaction terminates, with vacuum line, solvent is removed, residue from dichloromethane is washed and is filtered by kieselguhr, filtrate is drained, thick product dichloromethane/normal hexane (dichloromethane is 1:5 with the volume ratio of normal hexane) recrystallization, obtains 0.39g bronzing product A 4 (productivity 24%).
As known by the foregoing results, A4 has structure shown in formula III.
Embodiment 1
The method that the present embodiment prepares ethylene copolymer for explanation.
500mL polymeric kettle evacuation after heat drying is led to nitrogen twice, it is passed through ethylene gas again after evacuation, then the toluene solution 6.8mL (concentration is 12mg/mL) of MAO it is sequentially added into, 1-hexene 15mL, through the normal hexane 150mL that anhydrous and oxygen-free processes, and the toluene solution 4mL (2.5 μm ol/mL) containing catalyst precarsor A1.Being passed through the ethylene that pressure is 0.3MPa under mechanical stirring, and react 20min in 25 DEG C at this pressure, add ethanol afterwards and terminate reaction, obtain polymer 5.21g, be computed determining, polymerization activity is 1.56 × 106g·mol-1(Ti)·h-1。
Recording fusing point is 103 DEG C；Record the M of polyethylenewIt is 1.9 × 105, molecular weight distribution Mw/MnIt is 1.92；Recording 1-ahexene content is 5.3%.
Embodiment 2
The method that the present embodiment prepares ethylene copolymer for explanation.
500mL polymeric kettle evacuation after heat drying is led to nitrogen twice, it is passed through ethylene gas again after evacuation, then the toluene solution 6.8mL (concentration is 12mg/mL) of MAO it is sequentially added into, 1-octene 15mL, through the normal hexane 150mL that anhydrous and oxygen-free processes, and the toluene solution 4mL (2.5 μm ol/mL) containing catalyst precarsor A2.It is passed through the ethylene that pressure is 0.3MPa under mechanical stirring, and reacts 20min in 25 DEG C at this pressure, add ethanol afterwards and terminate reaction, obtain polymer 5.84g, be computed determining, polymerization activity 1.75 × 106g·mol-1(Ti)·h-1。
Recording fusing point is 95 DEG C；Record the M of polyethylenewIt is 1.9 × 105, molecular weight distribution Mw/MnIt is 2.07；Recording 1-octene content is 6.7%.
Embodiment 3
The method that the present embodiment prepares ethylene copolymer for explanation.
500mL polymeric kettle evacuation after heat drying is led to nitrogen twice, it is passed through ethylene gas again after evacuation, then the toluene solution 13.6mL (concentration is 12mg/mL) of MAO it is sequentially added into, 1-decene 15mL, through the normal hexane 150mL that anhydrous and oxygen-free processes, and the toluene solution 8mL (2.5 μm ol/mL) containing catalyst precarsor A3.It is passed through the ethylene that pressure is 0.1MPa under mechanical stirring, and reacts 10min in 50 DEG C at this pressure, add ethanol and terminate reaction, obtain polymer 2.44g, be computed determining, polymerization activity 7.32 × 105g·mol-1(Ti)·h-1。
Recording fusing point is 107 DEG C；Record the M of polyethylenewIt is 2.2 × 105, molecular weight distribution Mw/MnIt is 2.01；Recording 1-decene content is 4.1%.
Embodiment 4
The method that the present embodiment prepares ethylene copolymer for explanation.
500mL polymeric kettle evacuation after heat drying is led to nitrogen twice, it is passed through ethylene gas again after evacuation, then the toluene solution 6.8mL (concentration is 12mg/mL) of MAO it is sequentially added into, 1,5-hexadiene 15mL, through the normal heptane 300mL that anhydrous and oxygen-free processes, and the toluene solution 4mL (2.5 μm ol/mL) containing catalyst precarsor A4.It is passed through the ethylene that pressure is 1.5MPa under mechanical stirring, and reacts 30min in 0 DEG C at this pressure, add ethanol and terminate reaction, obtain polymer 7.25g, be computed determining, polymerization activity 1.45 × 106g·mol-1(Ti)·h-1。
Recording fusing point is 118 DEG C；Record the M of polyethylenewIt is 2.0 × 105, molecular weight distribution Mw/MnIt is 2.19；Recording 1,5-hexadiene content is 3.3%.
Embodiment 5
The method that the present embodiment prepares ethylene copolymer for explanation.
500mL polymeric kettle evacuation after heat drying is led to nitrogen twice, it is passed through ethylene gas again after evacuation, then the toluene solution 6.8mL (concentration is 12mg/mL) of MAO it is sequentially added into, 1-hexene 100mL, through the normal hexane 250mL that anhydrous and oxygen-free processes, and the toluene solution 4mL (2.5 μm ol/mL) containing catalyst precarsor A1.Being passed through the ethylene that pressure is 3MPa under mechanical stirring, and react 20min in 25 DEG C at this pressure, add ethanol afterwards and terminate reaction, obtain polymer 17.47g, be computed determining, polymerization activity is 5.29 × 106g·mol-1(Ti)·h-1。
Recording fusing point is 127 DEG C；Record the M of polyethylenewIt is 2.5 × 105, molecular weight distribution Mw/MnIt is 2.18；Recording 1-ahexene content is 1.8%.
Embodiment 6
According to the method for embodiment 1, except for the difference that, the amount of the 1-hexene of addition is 5mL.Obtaining polymer 11.43g, be computed determining, polymerization activity is 3.43 × 106g·mol-1(Ti)·h-1。
Recording fusing point is 123 DEG C；Record the M of polyethylenewIt is 1.8 × 105, molecular weight distribution Mw/MnIt is 1.86；Recording 1-ahexene content is 2.7%.
Embodiment 7
According to the method for embodiment 1, except for the difference that, the amount of the 1-hexene of addition is 10mL.
Obtaining polymer 8.87g, be computed determining, polymerization activity is 2.66 × 106g·mol-1(Ti)·h-1；Recording fusing point is 116 DEG C；Record the M of polyethylenewIt is 2.5 × 105, molecular weight distribution Mw/MnIt is 2.20；Recording 1-ahexene content is 3.4%.
Embodiment 8
According to the method for embodiment 1, except for the difference that, the amount of the 1-hexene of addition is 50mL.
Obtaining polymer 2.77g, be computed determining, polymerization activity is 8.31 × 105g·mol-1(Ti)·h-1；Recording fusing point is 70 DEG C；Record the M of polyethylenewIt is 1.8 × 105, molecular weight distribution Mw/MnIt is 2.30；Recording 1-ahexene content is 12.4%.
Embodiment 9
According to the method for embodiment 1, except for the difference that, the amount through the normal hexane of anhydrous and oxygen-free process of addition is 300mL.
Obtaining polymer 13.6g, be computed determining, polymerization activity is 4.08 × 106g·mol-1(Ti)·h-1；Recording fusing point is 119 DEG C；Record the M of polyethylenewIt is 2.1 × 105, molecular weight distribution Mw/MnIt is 2.04；Recording 1-ahexene content is 3.3%.
Comparative example 1
According to the method for embodiment 1, except for the difference that, catalyst precarsor A1 is replaced with the compound W with structure shown in formula IV.
Obtaining polymer 0.104g, be computed determining, polymerization activity is 3.1 × 104g·mol-1(Ti)·h-1；Recording fusing point is 111 DEG C；Record the M of polyethylenewIt is 3.2 × 105, molecular weight distribution Mw/MnIt is 12.7；Recording 1-ahexene content is 6.8%.
Embodiment 1 is compared with comparative example 1 and understands, when ethylene copolymer, use the catalyst of the catalyst precarsor provided containing the present invention, it is possible to obtain considerably higher polymerization activity and substantially narrower molecular weight distribution.
Find out, the method preparing ethylene copolymer of the present invention have high catalytic efficiency from the data of embodiment 1-9, catalytic efficiency (polymerization activity) may be up to 5 × 106g·mol-1(Ti)·h-1Above, the weight average molecular weight of the ethylene copolymer of gained is about 200,000, and molecular weight distribution is about 2, 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; but, the present invention is not limited to the detail in above-mentioned embodiment, in the technology concept of the present invention; technical scheme can be carried out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that, each concrete technical characteristic described in above-mentioned detailed description of the invention, in the case of reconcilable, can be combined by any suitable means, in order to avoid unnecessary repetition, various possible compound modes are illustrated by the present invention the most separately.
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. the method preparing ethylene copolymer, it is characterised in that the method is included in olefinic polymerization
Under the conditions of, in the presence of an inert solvent, ethylene, comonomer are contacted with catalyst and is polymerized, institute
Stating catalyst and contain catalyst precarsor and alkylaluminoxane, wherein, this catalyst precarsor has shown in Formulas I
Structure,
Wherein, R1、R2And R4It is each independently the alkyl of hydrogen atom or C1-C20；R3For benzene
Base, halogenophenyl or alkoxyl phenyl；M is titanium, zirconium or hafnium.
Method the most according to claim 1, wherein, the alkyl of described C1-C20 is C1-C6
Alkyl；Described halogenophenyl is pentafluorophenyl group, 2-fluorophenyl, 2,4 difluorobenzene base, 4-fluoro-3-chlorobenzene
Base or 4-chloro-2,3,5,6-tetrafluoro phenyl；Described alkoxyl phenyl is p-methoxyphenyl.
Method the most according to claim 1, wherein, R1And R2For the tert-butyl group, R3For phenyl-pentafluoride
Base, R4For hydrogen, M is titanium.
Method the most according to claim 1, wherein, R1And R4For methyl, R2For the tert-butyl group,
R3For phenyl, M is titanium.
Method the most according to claim 1, wherein, the preparation method bag of described catalyst precarsor
Include: under the conditions of complex reaction, the compound with structure shown in formula IV is tied with having shown in Formula V
The compound of structure contacts in organic solvent, obtains the catalyst precarsor with structure shown in Formulas I,
Wherein, R1、R2And R4It is each independently the alkyl of hydrogen atom or C1-C20；R3For benzene
Base, halogenophenyl or alkoxyl phenyl；M is titanium, zirconium or hafnium.
Method the most according to claim 1, wherein, described catalyst precarsor and alkylaluminoxane
Mol ratio be 1:200-2000, preferably 1:200-1000.
7. according to the method described in claim 1 or 6, wherein, in described alkylaluminoxane, alkyl is
The straight or branched alkyl of C1-C5, preferably methyl or isobutyl group, more preferably methyl.
Method the most according to claim 1, wherein, described comonomer is propylene, C4-C10
α substituted olefine and C4-C10 alkadienes in one or more.
Method the most according to claim 1, wherein, described atent solvent is aromatic hydrocarbons and/or alkane,
Described aromatic hydrocarbons is preferably benzene and/or toluene；Described alkane is preferably normal hexane and/or normal heptane.
Method the most according to claim 1, wherein, the condition of described olefinic polymerization includes: poly-
Closing temperature and be 0-80 DEG C, vinyl polymerization pressure is 0.1-3MPa, and polymerization time is 5-30 minute.
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| CN110563771A (en) * | 2018-06-05 | 2019-12-13 | 中国科学院上海有机化学研究所 | Metal complex, intermediate, preparation method and application thereof |
| CN114316109A (en) * | 2021-12-03 | 2022-04-12 | 国家能源集团宁夏煤业有限责任公司 | Propylene, alpha-olefin copolymer and preparation method thereof |
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