CN104725540A - Ethylene copolymer preparation method - Google Patents

Ethylene copolymer preparation method Download PDF

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CN104725540A
CN104725540A CN201310699081.4A CN201310699081A CN104725540A CN 104725540 A CN104725540 A CN 104725540A CN 201310699081 A CN201310699081 A CN 201310699081A CN 104725540 A CN104725540 A CN 104725540A
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preparation
formula
alkyl
hydrogen
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CN104725540B (en
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韩书亮
李传清
徐林
于国柱
贺小进
毕海鹏
吴宁
郝建国
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The present invention provides an ethylene copolymer preparation method, which comprises that: in the presence of an olefin polymerization catalyst, ethylene and alpha-olefin are subjected to a polymerization reaction in a solvent, wherein the olefin polymerization catalyst contains a bimetallic catalyst precursor having a structure represented by a formula (I) and alkyl aluminoxane, R1, R2, R3, R4, R1<'>, R2<'>, R3<'> and R4<'> are the same or different and are respectively and independently hydrogen, phenyl or C1-C20 alkyl, R5 and R5<'> are the same or different and are respectively and independently hydrogen or C1-C20 alkyl, and M1 and M2 are the same or different and are respectively and independently one selected from titanium, zirconium and hafnium. According to the present invention, when the olefin polymerization catalyst is used for catalysis of ethylene and alpha-olefin copolymerization, the high polymerization activity is provided. The formula I is defined in the instruction.

Description

A kind of preparation method of ethylene copolymer
Technical field
The present invention relates to a kind of preparation method of ethylene copolymer.
Background technology
Because polyolefinic raw materials enriches cheap, easy machine-shaping, the polyolefin products of worldwide producing every year has exceeded 100,000,000 tons, one of industry becoming maximum-norm.Polyolefine material has the features such as relatively little density, good chemical proofing, water tolerance and good physical strength, electrical insulating property, can be used for film, tubing, sheet material, various moulded products, electric wire etc., not only have been widely used in the daily use Sundry goods such as agricultural, packaging, automobile, electrical equipment, for the clothing, food, lodging and transportion--basic necessities of life of the mankind are provided convenience, but also play great function in the Strategic projects such as national defence, the energy, aerospace.
Wherein, ethylene copolymer product has superior performance, and alpha-olefin is of a great variety, comprises 1-octene, 1-hexene, 1-butylene, propylene and polar monomer etc.By regulating comonomer type and consumption, both can obtain linear low density polyethylene, also can obtain thermoplastic elastomer, can also rubber be obtained, applying very extensive.Particularly elastomeric special construction gives the mechanical property of its excellence, rheological property and ageing-resistant performance, good as low-temperature flexibility during the agent of plastics impact-resistance, consumption is few, cost performance is high, is widely used in modifying plastics.
Polyolefin industry flourish has benefited from the fast development that Ziegler-Natta catalyst and metallocene catalyst are the polycoordination of representative.Be developed so far, the research for Ziegler-Natta catalyst and metallocene catalyst is day by day ripe, but in such catalyzer, can the effective catalyst type of catalyzed ethylene copolymerization few.Therefore, non-metallocene catalyst becomes the emphasis of research at present gradually.Salicylaldimine ligand transition-metal catalyst belongs to one wherein.
CN101864010A discloses the bimetallic catalyst precursor of a kind of catalysis in olefine polymerization or copolymerization.This catalyst precursor is based on salicylaldimine ligand and IV group 4 transition metal, and it mainly utilizes penta fluoro benzene amine and the condensation of bridging salicylic aldehyde to obtain part, then part and Ti complexing are obtained catalyzer.But the synthetic route of this catalyst precursor is loaded down with trivial details, with high costs, and ratio is lower when alpha-olefin and ethylene copolymer, and molecular weight distribution is wider.
CN101200404A discloses a kind of method of synthesizing short-chain olefin by ethylene oligomerization, the method carries out ethylene oligomerization reaction under being included in the existence of the catalyzer of load in ionic liquid, wherein, catalyzer is made up of double salicylaldehyde imine nickel complex and aluminum alkyls, and the method products therefrom is ethylene low polymer.But the productive rate of double salicylaldehyde imine nickel complex is lower disclosed in CN101200404A, in addition, ethylene polymerization activity is also lower.
Therefore, how to obtain and there is high catalytic activity and the simple ethylene copolymer of preparation technology remains a technical problem urgently to be resolved hurrily.
Summary of the invention
The object of the invention is to the defect overcoming prior art, and a kind of preparation method of new ethylene copolymer is provided.
The invention provides a kind of preparation method of ethylene copolymer, under the method is included in the existence of olefin polymerization catalysis, ethene and alpha-olefin are carried out polyreaction in a solvent, wherein, described olefin polymerization catalysis contains the bimetallic catalyst precursor and alkylaluminoxane with structure shown in formula I
formula I,
Wherein, R 1, R 2, R 3, R 4, R 1', R 2', R 3' and R 4' identical or different, and be hydrogen, phenyl or C independently of one another 1-C 20alkyl; R 5and R 5' identical or different, and be hydrogen or C independently of one another 1-C 20alkyl; M 1and M 2identical or different, and be the one in titanium, zirconium and hafnium independently of one another.
Olefin polymerization catalysis provided by the invention contains the above-mentioned bimetallic catalyst precursor based on salicylaldimine ligand structure and alkylaluminoxane, because the bimetal in bimetallic catalyst precursor structure has synergy, and phenyl ring has organic substituent, and therefore olefin polymerization catalysis provided by the invention has higher catalytic efficiency.Particularly, olefin polymerization catalysis provided by the invention, when for catalyzed ethylene and alpha-olefin copolymer, compared with the single-metal reforming catalyst close with structure in prior art, has higher catalytic efficiency, and catalytic efficiency (polymerization activity) can reach 10 5g/ (molcath).In addition, adopt olefin polymerization catalysis provided by the invention that the introducing ratio of alpha-olefin can be made to reach about 12mol%, and the preparation method of described bimetallic catalyst precursor is simple, cost is low, reproducible, is easy to industrialization.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of ethylene copolymer, under the method is included in the existence of olefin polymerization catalysis, ethene and alpha-olefin are carried out polyreaction in a solvent, wherein, described olefin polymerization catalysis contains the bimetallic catalyst precursor and alkylaluminoxane with structure shown in formula I
formula I,
Wherein, R 1, R 2, R 3, R 4, R 1', R 2', R 3' and R 4' identical or different, and be hydrogen, phenyl or C independently of one another 1-C 20alkyl; R 5and R 5' identical or different, and be hydrogen or C independently of one another 1-C 20alkyl; M 1and M 2identical or different, and be the one in titanium, zirconium and hafnium independently of one another.
According to the present invention, the M in different bimetallic catalyst precursors 1and M 2can be identical, also can be different, and be the one in titanium, zirconium and hafnium independently of one another.Preferably, M 1and M 2be titanium.
According to the present invention, R 1, R 2, R 3, R 4, R 5, R 1', R 2', R 3' and R 4' and R 5' can be identical, be all hydrogen atom; Or, R 1, R 2, R 3, R 4, R 1', R 2', R 3' and R 4' be hydrogen, phenyl or C independently of one another 1-C 20alkyl, R 5and R 5' be hydrogen or C independently of one another 1-C 20alkyl, and R 1, R 2, R 3and R 4in at least one be C 1-C 20alkyl or phenyl, R 1', R 2', R 3' and R 4' at least one be C 1-C 20alkyl or phenyl.
In the present invention, described alkyl can be straight chain, also can be side chain.Described C 1-C 20straight or branched alkyl can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, 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, Octadecane base, NSC 77136 base and NSC 62789 base.
Particularly, the structure meeting above-mentioned requirements can include but not limited to: R 1, R 2, R 3, R 4, R 5, R 1', R 2', R 3', R 4' and R 5' can be hydrogen; Or, R 1and R 1' can be C 1-C 20alkyl or phenyl, R 2, R 3, R 4, R 2', R 3' and R 4' can be hydrogen, R 5and R 5' can be hydrogen or C 1-C 20alkyl; Or, R 2and R 2' can be C 1-C 20alkyl or phenyl, R 1, R 3, R 4, R 1', R 3' and R 4' can be hydrogen, R 5and R 5' can be hydrogen or C 1-C 20alkyl; Or, R 3and R 3' can be C 1-C 20alkyl or phenyl, R 1, R 2, R 4, R 1', R 2' and R 4' can be hydrogen, R 5and R 5' can be hydrogen or C 1-C 20alkyl; Or, R 4and R 4' can be C 1-C 20alkyl or phenyl, R 1, R 2, R 3, R 1', R 2' and R 3' can be hydrogen, R 5and R 5' can be hydrogen or C 1-C 20alkyl; Or, R 1, R 2, R 1' and R 2' can be C 1-C 20alkyl or phenyl, R 3, R 4, R 3' and R 4' can be hydrogen, R 5and R 5' can be hydrogen or C 1-C 20alkyl; Or, R 1, R 3, R 1' and R 3' can be C 1-C 20alkyl or phenyl, R 2, R 4, R 2' and R 4' can be hydrogen, R 5and R 5' can be hydrogen or C 1-C 20alkyl; Or, R 1, R 4, R 1' and R 4' be C 1-C 20alkyl or phenyl, R 2, R 3, R 2' and R 3' can be hydrogen, R 5and R 5' can be hydrogen or C 1-C 20alkyl; Or, R 2, R 3, R 2' and R 3' can be C 1-C 20alkyl or phenyl, R 1, R 4, R 1' and R 4' can be hydrogen, R 5and R 5' can be hydrogen or C1-C 20alkyl; Or, R 2, R 4, R 2' and R 4' can be C 1-C 20alkyl or phenyl, R 1, R 3, R 1' and R 3' be hydrogen, R 5and R 5' can be hydrogen or C 1-C 20alkyl; Or, R 3, R 4, R 3' and R 4' can be C 1-C 20alkyl or phenyl, R 1, R 2, R 1' and R 2' can be hydrogen, R 5and R 5' can be hydrogen or C 1-C 20alkyl; Or, R 1, R 2, R 3, R 1', R 2' and R 3' can be C 1-C 20alkyl or phenyl, R 4and R 4' be hydrogen, R 5and R 5' can be hydrogen or C 1-C 20alkyl; Or, R 1, R 3, R 4, R 1', R 3' and R 4' can be C 1-C 20alkyl or phenyl, R 2and R 2' can be hydrogen, R 5and R 5' can be hydrogen or C1-C 20alkyl; Or, R 1, R 2, R 4, R 1', R 2' and R 4' can be C 1-C 20alkyl or phenyl, R 3and R 3' can be hydrogen, R 5and R 5' can be hydrogen or C 1-C 20alkyl; Or, R 2, R 3, R 4, R 2', R 3' and R 4' can be C 1-C 20alkyl or phenyl, R 1and R 1' can be hydrogen, R 5and R 5' can be hydrogen or C 1-C 20alkyl; Or, R 1, R 2, R 3, R 4, R 1', R 2', R 3' and R 4' can be C 1-C 20alkyl or phenyl, R 5and R 5' can be hydrogen or C 1-C 20alkyl.
The present inventor finds under study for action, preferably, and R 1and R 1' identical or different, and be C independently of one another 1-C 20alkyl or phenyl; R 2, R 3, R 4, R 5, R 2', R 3', R 4' and R 5' be hydrogen, by above specific R 1-R 5and R 1'-R 5' coordinate the mixture of bimetallic catalyst precursor and the alkylaluminoxane formed can obtain fabulous catalytic effect as when olefin polymerization catalysis catalyzed ethylene and alpha-olefin copolymer.
Further preferably, R 1and R 1' identical or different, and be tertiary butyl or phenyl independently of one another; R 2, R 3, R 4, R 5, R 2', R 3', R 4' and R 5' be hydrogen, M 1and M 2for titanium.More preferably, R 1and R 1' be tertiary butyl, R 2, R 3, R 4, R 5, R 2', R 3', R 4' and R 5' be hydrogen, M 1and M 2be titanium, now, corresponding described bimetallic catalyst precursor has the structure shown in formula II; Or, R 1and R 1' be phenyl independently of one another, R 2, R 3, R 4, R 5, R 2', R 3', R 4' and R 5' be hydrogen, M 1and M 2be titanium, now, corresponding described bimetallic catalyst precursor has the structure shown in formula III,
formula II,
formula III.
According to the present invention, described bimetallic catalyst precursor can prepare according to existing various method, preferably, prepares in accordance with the following methods: under complex reaction condition, is MCl by compound and the general formula with structure shown in formula IV 4(THF) 2compound contact in organic solvent,
formula IV,
Wherein, R 1, R 2, R 3, R 4, R 1', R 2', R 3' and R 4' identical or different, and be hydrogen, phenyl or C independently of one another 1-C 20alkyl; R 5and R 5' identical or different, and be hydrogen or C independently of one another 1-C 20alkyl; M is the one in titanium, zirconium and hafnium.
Particularly, the preparation process of described bimetallic catalyst precursor can be carried out with reference to following reaction formula.
About R 1, R 2, R 3, R 4, R 5, R 1', R 2', R 3', R 4' and R 5' concrete restriction can by above describe reasonably select, therefore not to repeat here.
According to the present invention, described general formula is MCl 4(THF) 2compound can close titanium for tetrachloro two (tetrahydrofuran (THF)), tetrachloro two (tetrahydrofuran (THF)) closes zirconium and tetrachloro two (tetrahydrofuran (THF)) closes one in hafnium, preferably, described general formula is MCl 4(THF) 2compound be that tetrachloro two (tetrahydrofuran (THF)) closes titanium.
The compound that the present invention has a structure shown in formula IV to described and general formula are MCl 4(THF) 2the consumption of compound be not particularly limited, such as, described in there is the compound of structure shown in formula IV and general formula is MCl 4(THF) 2the mol ratio of compound can be 1:1.8-2.5, be preferably 1:2-2.2.
According to the present invention, solvent used in the preparation process of described ethylene copolymer can be identical with organic solvent used in described bimetallic catalyst precursor preparation process, also can be different, and can be the existing various inert substance do not reacted with generation product with reactant independently of one another, such as, can be one or more in tetrahydrofuran (THF), ether, Isosorbide-5-Nitrae-dioxane, methylene dichloride, benzene, toluene, normal hexane and hexanaphthene independently of one another.These solvents can be used alone, also can be used in combination.The consumption of described solvent can be selected according to the consumption of ethene and alpha-olefin, and the consumption of described organic solvent can according to having the compound of structure shown in formula IV and general formula is MCl 4(THF) 2the consumption of compound reasonably select, therefore not to repeat here.
The present invention is to having the compound of structure shown in formula IV and general formula is MCl 4(THF) 2the condition that contacts in organic solvent of compound be not particularly limited, as long as can ensure to have the compound of structure shown in formula IV and general formula is MCl 4(THF) 2compound generation complex reaction generate target product.Preferably, the condition of described contact comprises elder generation and contact 0.5-3 hour at-85 DEG C to-70 DEG C, then contacts 8-24 hour at 0-60 DEG C; More preferably, the condition of described contact comprises elder generation and contact 1-2 hour at-80 DEG C to-75 DEG C, then contacts 12-20 hour at 20-40 DEG C.
According to the present invention, after the preparation of described bimetallic catalyst precursor completes, also need described organic solvent to remove.Wherein, the method removing described organic solvent can adopt various method well known in the art to carry out, and such as, vacuum line removes organic solvent, revolves and steam except organic solvent etc., all can know, will repeat no more at this these those skilled in the art.
In addition, in order to obtain the higher bimetallic catalyst precursor of purity, the preparation method of described bimetallic catalyst precursor can also comprise the step of the product obtained being carried out purifying.The method of described purifying can adopt various purification process well known in the art to carry out, as recrystallization etc.Recrystallization solvent used can be such as methylene dichloride and/or normal hexane.
The present invention is not particularly limited the bimetallic catalyst precursor contained in described olefin polymerization catalysis and alkylaluminoxane, but in order to make, these two kinds of materials are collaborative plays catalyzed ethylene and alpha-olefin carries out copolymerization, the mol ratio of described bimetallic catalyst precursor and alkylaluminoxane is preferably 1:200-2000, is more preferably 1:200-1000.
According to the present invention, the various alkylaluminoxanes being used as promotor that described alkylaluminoxane can be commonly used for catalyst field such as, can be C 1-C 5the alkylaluminoxane of straight or branched, be preferably methylaluminoxane (MAO) and/or modified methylaluminoxane (MMAO).
Main improvements of the present invention are to have employed a kind of olefin polymerization catalysis comprising bimetallic catalyst precursor newly, and the consumption of the kind of alpha-olefin, ethene and alpha-olefin and concrete polymeric reaction condition all can be same as the prior art.
Particularly, the condition of described polyreaction can be the routine selection of this area, and such as, generally including temperature of reaction can be-30 DEG C to 80 DEG C, is preferably 20-60 DEG C; Reaction pressure can be 0.5-10atm, is preferably 1-5atm; Reaction times can be 1-60min, is preferably 20-40min.In addition, in order to overcome oxygen inhibition, obtain having the ethylene copolymer of larger molecular weight, described polyreaction is preferably carried out in an inert atmosphere.Described inert atmosphere refer to not with any one gas or the gaseous mixture of reactant and product generation chemical reaction, as one or more in nitrogen and periodic table of elements zero group gas.Keep the method for inert atmosphere can for pass in polymerization reaction system above-mentioned not with any one gas or the gaseous mixture of reactant and product generation chemical reaction.
In addition, the preparation method of described ethylene copolymer also comprises and adds terminator after completion of the polymerization reaction, to make active centre inactivation.Described terminator can be the various terminator that can stop living polymer chains in field of olefin polymerisation, such as, can be one or more in water, methyl alcohol, ethanol, n-propyl alcohol and Virahol.
Below will be described the present invention by embodiment, but embodiments of the invention have more than and are limited to following examples.
In following examples, the method that the performance test of polymkeric substance relates to is as follows:
Fusing point is measured by dsc (DSC), and PE company of concrete employing U.S. model is that the differential scanning calorimeter of PE DSC-7 measures, and wherein, temperature rise rate is 10 DEG C/min.Weight-average molecular weight (Mw) and number-average molecular weight (Mn) are measured by gel chromatography (GPC), and the model adopting Shimadzu Corporation is the gel chromatograph of LC-10AT, and moving phase is THF, and standard is Narrow distribution polystyrene, and probe temperature is 25 DEG C.
Unless stated otherwise, the compound used in following preparation example, embodiment and comparative example and reagent etc. are commercially available product.
Preparation example 1
This preparation example is for illustration of the preparation of bimetallic catalyst precursor with structure shown in formula (II).
By 6, 6'-(1E, 1'E)-(4, 4'-methylene-bis (4, 1-penylene) two (imines-1-replace-1-subunit)) two (methyl isophthalic acid-replacement-1-subunit) two (2-t-butyl phenol) (according to Eur.Polym.J.2012, 48, the preparation method that 191-199 document is recorded obtains, lower same) (1.77g, 3.41mmol) be dissolved in dichloromethane solvent (consumption of methylene dichloride is 30mL), at-78 DEG C, this solution is added to and closes titanium (2.28g containing tetrachloro two (tetrahydrofuran (THF)), in dichloromethane solution (consumption of methylene dichloride is 30mL) 6.82mmol), react 1 hour under low temperature, return to room temperature 25 DEG C, continue reaction 16 hours.After reaction terminates, removed by solvent with vacuum line, residue from dichloromethane washs and passes through diatomite filtration, filtrate drained, thick product methylene dichloride/normal hexane recrystallization, obtains the red brown solid of 2.97g, be denoted as bimetallic catalyst precursor A1, determine as calculated, productive rate is 90%.
Results of elemental analyses shows, Anal.Calc.for C 57h 52cl 6f 10n 2o 5ti 2(%): C, 54.99; H, 3.45; N, 3.09.Found (%): C, 54.73; H, 3.79; N, 2.89.FD-MS:m/z966.5(calcd966.1)。
Preparation example 2
This preparation example is for illustration of the preparation of bimetallic catalyst precursor with structure shown in formula (II).
By 6, 6'-(1E, 1'E)-(4, 4'-methylene-bis (4, 1-penylene) two (imines-1-replaces-1-subunit)) two (methyl isophthalic acid-replacement-1-subunit) two (2-t-butyl phenol) (0.24g, 0.46mmol) be dissolved in dichloromethane solvent (consumption of methylene dichloride is 30mL), at-78 DEG C, this solution is added to and closes titanium (0.32g containing tetrachloro two (tetrahydrofuran (THF)), in dichloromethane solution (consumption of methylene dichloride is 30mL) 0.96mmol), react 1 hour under low temperature, return to room temperature and be heated to 40 DEG C, continue reaction 12 hours.After reaction terminates, removed by solvent with vacuum line, residue from dichloromethane washs and passes through diatomite filtration, filtrate drained, thick product methylene dichloride/normal hexane recrystallization, obtains the red brown solid of 0.41g, be denoted as bimetallic catalyst precursor A2, productive rate is 93%.
Characterization result is identical with preparation example 1.
Preparation example 3
This preparation example is for illustration of the preparation of bimetallic catalyst precursor with structure shown in formula (II).
By 6, 6'-(1E, 1'E)-(4, 4'-methylene-bis (4, 1-penylene) two (imines-1-replaces-1-subunit)) two (methyl isophthalic acid-replacement-1-subunit) two (2-t-butyl phenol) (0.57g, 1.10mmol) be dissolved in dichloromethane solvent (consumption of methylene dichloride is 30mL), at-78 DEG C, this solution is added to and closes titanium (0.81g containing tetrachloro two (tetrahydrofuran (THF)), in dichloromethane solution (consumption of methylene dichloride is 30mL) 2.42mmol), react 1 hour under low temperature, return to room temperature 20 DEG C, continue reaction 20 hours.After reaction terminates, removed by solvent with vacuum line, residue from dichloromethane washs and passes through diatomite filtration, filtrate drained, thick product methylene dichloride/normal hexane recrystallization, obtains the red brown solid of 0.88g, be denoted as bimetallic catalyst precursor A3, productive rate is 83%.
Characterization result is identical with preparation example 1.
Preparation example 4
This preparation example is for illustration of the preparation of bimetallic catalyst precursor with structure shown in formula (II).
By 6, 6'-(1E, 1'E)-(4, 4'-methylene-bis (4, 1-penylene) two (imines-1-replaces-1-subunit)) two (methyl isophthalic acid-replacement-1-subunit) two (2-t-butyl phenol) (0.22g, 0.42mmol) be dissolved in dichloromethane solvent (consumption of methylene dichloride is 30mL), at-78 DEG C, this solution is added to and closes titanium (0.28g containing tetrachloro two (tetrahydrofuran (THF)), in dichloromethane solution (consumption of methylene dichloride is 30mL) 0.84mmol), react 1 hour under low temperature, return to room temperature and be heated to 40 DEG C, continue reaction 12 hours.After reaction terminates, removed by solvent with vacuum line, residue from dichloromethane washs and passes through diatomite filtration, filtrate drained, thick product methylene dichloride/normal hexane recrystallization, obtains the red brown solid of 0.33g, be denoted as bimetallic catalyst precursor A4, productive rate is 80%.
Characterization result is identical with preparation example 1.
Preparation example 5
This preparation example is for illustration of the preparation of bimetallic catalyst precursor with structure shown in formula III.
By 6, 6'-(1E, 1'E)-(4, 4'-methylene-bis (4, 1-penylene) two (imines-1-replaces-1-subunit)) two (methyl isophthalic acid-replacement-1-subunit) two (2-phenylphenol) material (0.51g, 0.91mmol, purchased from Alfa company) be dissolved in dichloromethane solvent (consumption of methylene dichloride is 30mL), at-78 DEG C, this solution is added to and closes titanium (0.60g containing tetrachloro two (tetrahydrofuran (THF)), in dichloromethane solution (consumption of methylene dichloride is 30mL) 1.82mmol), react 1 hour under low temperature, return to room temperature and be heated to 40 DEG C, continue reaction 12 hours.After reaction terminates, removed by solvent with vacuum line, residue from dichloromethane washs and passes through diatomite filtration, filtrate drained, thick product methylene dichloride/normal hexane recrystallization, obtains the red brown solid of 0.95g, be denoted as bimetallic catalyst precursor A5, productive rate is 87%.
Results of elemental analyses shows, Anal.Calc.for C 60h 83cl 6n 2o 4ti 2(%): C, 59.82; H, 6.94; N, 2.33.Found (%): C, 59.80; H, 6.92; N, 2.34.FD-MS:m/z1203.40(calcd1203.34)。
Embodiment 1
This embodiment is for illustration of the preparation method of ethylene copolymer provided by the invention.
Ethene and 1-hervene copolymer: the 500mL polymeric kettle after heat drying is vacuumized logical nitrogen twice, pass into ethylene gas after vacuumizing again, then add the toluene solution 6mL(12mg/mL of methylaluminoxane (MAO) successively), 1-hexene 15mL, through the normal hexane 100mL of anhydrous and oxygen-free process and containing the toluene solution 4mL(2.5 μm ol/mL of bimetal metal catalysts precursors A1 with structure shown in formula (II)).Pass into the ethene that pressure is 3atm under mechanical stirring, and at this pressure in 25 DEG C of reaction 20min, add ethanol termination reaction afterwards, obtain polymkeric substance 0.103g, determine as calculated, polymerization activity is 3.1 × 10 4gmol -1(Ti) h -1.
It is 81 DEG C that DSC records fusing point; GPC records poly M wbe 1.6 × 10 5, molecular weight distribution M w/ M nbe 2.92; The content that high temperature nuclear-magnetism carbon spectrum records 1-hexene structural unit is 8.9mol%.
Embodiment 2
This embodiment is for illustration of the preparation method of ethylene copolymer provided by the invention.
Ethene and 1-hervene copolymer: the 500mL polymeric kettle after heat drying is vacuumized logical nitrogen twice, pass into ethylene gas after vacuumizing again, then add the toluene solution 3.4mL(12mg/mL of methylaluminoxane (MAO) successively), 1-hexene 15mL, through the normal hexane 150mL of anhydrous and oxygen-free process and containing the toluene solution 4mL(2.5 μm ol/mL of bimetal metal catalysts precursors A2 with structure shown in formula (II)).Pass into the ethene that pressure is 3atm under mechanical stirring, and at this pressure in 25 DEG C of reaction 20min, add ethanol termination reaction afterwards, obtain polymkeric substance 0.116g, determine as calculated, polymerization activity is 3.5 × 10 4gmol -1(Ti) h -1.
It is 86 DEG C that DSC records fusing point; GPC records poly M wbe 2.4 × 10 5, molecular weight distribution M w/ M nbe 2.77; The content that high temperature nuclear-magnetism carbon spectrum records 1-hexene structural unit is 8.0mol%.
Embodiment 3
This embodiment is for illustration of the preparation method of ethylene copolymer provided by the invention.
Ethene and 1-hervene copolymer: the 500mL polymeric kettle after heat drying is vacuumized logical nitrogen twice, pass into ethylene gas after vacuumizing again, then add the toluene solution 6.8mL(12mg/mL of methylaluminoxane (MAO) successively), 1-hexene 15mL, through the normal hexane 150mL of anhydrous and oxygen-free process and containing the toluene solution 4mL(2.5 μm ol/mL of bimetal metal catalysts precursors A3 with structure shown in formula (II)).Pass into the ethene that pressure is 3atm under mechanical stirring, and at this pressure in 25 DEG C of reaction 20min, add ethanol termination reaction afterwards, obtain polymkeric substance 0.267g, determine as calculated, polymerization activity is 8.0 × 10 4gmol -1(Ti) h -1.
It is 120 DEG C that DSC records fusing point; GPC records poly M wbe 2.9 × 10 5, molecular weight distribution M w/ M nbe 3.03; The content that high temperature nuclear-magnetism carbon spectrum records 1-hexene structural unit is 2.9mol%.
Embodiment 4
This embodiment is for illustration of the preparation method of ethylene copolymer provided by the invention.
Ethene and 1-hervene copolymer: the 500mL polymeric kettle after heat drying is vacuumized logical nitrogen twice, pass into ethylene gas after vacuumizing again, then add the toluene solution 6.8mL(12mg/mL of methylaluminoxane (MAO) successively), 1-hexene 10mL, through the normal hexane 150mL of anhydrous and oxygen-free process and containing the toluene solution 4mL(2.5 μm ol/mL of bimetal metal catalysts precursors A4 with structure shown in formula (II)).Pass into the ethene that pressure is 3atm under mechanical stirring, and at this pressure in 25 DEG C of reaction 20min, add ethanol termination reaction afterwards, obtain polymkeric substance 0.202g, determine as calculated, polymerization activity is 6.1 × 10 4gmol -1(Ti) h -1.
It is 108 DEG C that DSC records fusing point; GPC records poly M wbe 2.0 × 10 5, molecular weight distribution M w/ M nbe 2.69; The content that high temperature nuclear-magnetism carbon spectrum records 1-hexene structural unit is 5.5mol%.
Embodiment 5
This embodiment is for illustration of the preparation method of ethylene copolymer provided by the invention.
Ethene and 1-hervene copolymer: the 500mL polymeric kettle after heat drying is vacuumized logical nitrogen twice, pass into ethylene gas after vacuumizing again, then add the toluene solution 6.8mL(12mg/mL of methylaluminoxane (MAO) successively), 1-hexene 15mL, through the normal hexane 300mL of anhydrous and oxygen-free process and containing the toluene solution 4mL(2.5 μm ol/mL of bimetal metal catalysts precursors A1 with structure shown in formula (II)).Pass into the ethene that pressure is 3atm under mechanical stirring, and at this pressure in 25 DEG C of reaction 20min, add ethanol termination reaction afterwards, obtain polymkeric substance 0.131g, determine as calculated, polymerization activity is 3.9 × 10 4gmol -1(Ti) h -1.
It is 115 DEG C that DSC records fusing point; GPC records poly M wbe 2.3 × 10 5, molecular weight distribution M w/ M nbe 2.82; The content that high temperature nuclear-magnetism carbon spectrum records 1-hexene structural unit is 4.9mol%.
Embodiment 6
This embodiment is for illustration of the preparation method of ethylene copolymer provided by the invention.
Ethene and 1-hervene copolymer: the 500mL polymeric kettle after heat drying is vacuumized logical nitrogen twice, pass into ethylene gas after vacuumizing again, then add the toluene solution 6.8mL(12mg/mL of methylaluminoxane (MAO) successively), 1-hexene 10mL, through the normal hexane 150mL of anhydrous and oxygen-free process and containing the toluene solution 2mL(2.5 μm ol/mL of bimetal metal catalysts precursors A2 with structure shown in formula (II)).Pass into the ethene that pressure is 3atm under mechanical stirring, and at this pressure in 25 DEG C of reaction 20min, add ethanol termination reaction afterwards, obtain polymkeric substance 0.176g, determine as calculated, polymerization activity is 1.1 × 10 5gmol -1(Ti) h -1.
It is 93 DEG C that DSC records fusing point; GPC records poly M wbe 1.8 × 10 5, molecular weight distribution M w/ M nbe 2.52; The content that high temperature nuclear-magnetism carbon spectrum records 1-hexene structural unit is 7.2mol%.
Embodiment 7
This embodiment is for illustration of the preparation method of ethylene copolymer provided by the invention.
Ethene and 1-hervene copolymer: the 500mL polymeric kettle after heat drying is vacuumized logical nitrogen twice, pass into ethylene gas after vacuumizing again, then add the toluene solution 6.8mL(12mg/mL of methylaluminoxane (MAO) successively), 1-hexene 10mL, through the normal hexane 150mL of anhydrous and oxygen-free process and containing the toluene solution 2mL(2.5 μm ol/mL of bimetal metal catalysts precursors A3 with structure shown in formula (II)).Pass into the ethene that pressure is 3atm under mechanical stirring, and at this pressure in 25 DEG C of reaction 20min, add ethanol termination reaction afterwards, obtain polymkeric substance 0.176g, determine as calculated, polymerization activity is 1.1 × 10 5gmol -1(Ti) h -1.
It is 93 DEG C that DSC records fusing point; GPC records poly M wbe 2.5 × 10 5, molecular weight distribution M w/ M nbe 2.81; The content that high temperature nuclear-magnetism carbon spectrum records 1-hexene structural unit is 7.2mol%.
Embodiment 8
This embodiment is for illustration of the preparation method of ethylene copolymer provided by the invention.
Ethene and 1-hervene copolymer: the 500mL polymeric kettle after heat drying is vacuumized logical nitrogen twice, pass into ethylene gas after vacuumizing again, then add the toluene solution 6.8mL(12mg/mL of methylaluminoxane (MAO) successively), 1-hexene 10mL, through the normal hexane 150mL of anhydrous and oxygen-free process and containing the toluene solution 4mL(2.5 μm ol/mL of bimetal metal catalysts precursors A1 with structure shown in formula (II)).Pass into the ethene that pressure is 5atm under mechanical stirring, and at this pressure in 25 DEG C of reaction 20min, add ethanol termination reaction afterwards, obtain polymkeric substance 0.296g, determine as calculated, polymerization activity is 8.9 × 10 5gmol -1(Ti) h -1.
It is 118 DEG C that DSC records fusing point; GPC records poly M wbe 2.9 × 10 5, molecular weight distribution M w/ M nbe 2.99; The content that high temperature nuclear-magnetism carbon spectrum records 1-hexene structural unit is 2.9mol%.
Embodiment 9
This embodiment is for illustration of the preparation method of ethylene copolymer provided by the invention.
Ethene and 1-hervene copolymer: the 500mL polymeric kettle after heat drying is vacuumized logical nitrogen twice, pass into ethylene gas after vacuumizing again, then add the toluene solution 6.8mL(12mg/mL of methylaluminoxane (MAO) successively), 1-hexene 10mL, through the normal hexane 150mL of anhydrous and oxygen-free process and containing the toluene solution 4mL(2.5 μm ol/mL of bimetal metal catalysts precursors A1 with structure shown in formula (II)).Pass into the ethene that pressure is 1atm under mechanical stirring, and at this pressure in 25 DEG C of reaction 20min, add ethanol termination reaction afterwards, obtain polymkeric substance 0.081g, determine as calculated, polymerization activity is 2.4 × 10 5gmol -1(Ti) h -1.
It is 53 DEG C that DSC records fusing point; GPC records poly M wbe 3.1 × 10 5, molecular weight distribution M w/ M nbe 3.03; The content that high temperature nuclear-magnetism carbon spectrum records 1-hexene structural unit is 12.1mol%.
Embodiment 10
This embodiment is for illustration of the preparation method of ethylene copolymer provided by the invention.
Ethene and 1-hervene copolymer: the 500mL polymeric kettle after heat drying is vacuumized logical nitrogen twice, pass into ethylene gas after vacuumizing again, then add the toluene solution 6.8mL(12mg/mL of methylaluminoxane (MAO) successively), 1-hexene 10mL, through the normal hexane 150mL of anhydrous and oxygen-free process and containing the toluene solution 4mL(2.5 μm ol/mL of bimetal metal catalysts precursors A1 with structure shown in formula (II)).Pass into the ethene that pressure is 3atm under mechanical stirring, and at this pressure in 40 DEG C of reaction 20min, add ethanol termination reaction afterwards, obtain polymkeric substance 0.162g, determine as calculated, polymerization activity is 4.9 × 10 5gmol -1(Ti) h -1.
It is 68 DEG C that DSC records fusing point; GPC records poly M wbe 1.9 × 10 5, molecular weight distribution M w/ M nbe 2.42; The content that high temperature nuclear-magnetism carbon spectrum records 1-hexene structural unit is 10.4mol%.
Embodiment 11
This embodiment is for illustration of the preparation method of ethylene copolymer provided by the invention.
Ethene and 1-octene copolymer: the 500mL polymeric kettle after heat drying is vacuumized logical nitrogen twice, pass into ethylene gas after vacuumizing again, then add the toluene solution 6.8mL(12mg/mL of methylaluminoxane (MAO) successively), 1-octene 10mL, through the normal hexane 150mL of anhydrous and oxygen-free process and containing the toluene solution 4mL(2.5 μm ol/mL of bimetal metal catalysts precursors A1 with structure shown in formula (II)).Pass into the ethene that pressure is 3atm under mechanical stirring, and at this pressure in 40 DEG C of reaction 20min, add ethanol termination reaction afterwards, obtain polymkeric substance 0.185g, determine as calculated, polymerization activity is 5.6 × 10 5gmol -1(Ti) h -1.
It is 62 DEG C that DSC records fusing point; GPC records poly M wbe 2.3 × 10 5, molecular weight distribution M w/ M nbe 2.72; The content that high temperature nuclear-magnetism carbon spectrum records 1-octene structural unit is 11.1mol%.
Embodiment 12
This embodiment is for illustration of the preparation method of ethylene copolymer provided by the invention.
Ethene and 1-decene copolymerization: the 500mL polymeric kettle after heat drying is vacuumized logical nitrogen twice, pass into ethylene gas after vacuumizing again, then add the toluene solution 6.8mL(12mg/mL of methylaluminoxane (MAO) successively), 1-decene 10mL, through the normal hexane 150mL of anhydrous and oxygen-free process and containing the toluene solution 4mL(2.5 μm ol/mL of bimetal metal catalysts precursors A1 with structure shown in formula (II)).Pass into the ethene that pressure is 3atm under mechanical stirring, and at this pressure in 40 DEG C of reaction 20min, add ethanol termination reaction afterwards, obtain polymkeric substance 0.137g, determine as calculated, polymerization activity is 4.1 × 10 5gmol -1(Ti) h -1.
It is 72 DEG C that DSC records fusing point; GPC records poly M wbe 2.5 × 10 5, molecular weight distribution M w/ M nbe 2.63; The content that high temperature nuclear-magnetism carbon spectrum records 1-decene structural unit is 9.3mol%.
Embodiment 13
This embodiment is for illustration of the preparation method of ethylene copolymer provided by the invention.
Ethylene copolymer is prepared according to the method for embodiment 12, unlike, the bimetal metal catalysts precursors A5 with structure shown in formula III with the identical mole number of bimetal metal catalysts precursors A1 of structure shown in formula (II) substitutes, obtain polymkeric substance 0.158g, determine as calculated, polymerization activity is 4.7 × 10 5gmol -1(Ti) h -1.
It is 85 DEG C that DSC records fusing point; GPC records poly M wbe 3.1 × 10 5, molecular weight distribution M w/ M nbe 2.55; The content that high temperature nuclear-magnetism carbon spectrum records 1-decene structural unit is 8.4mol%.
As can be seen from the above results, when described olefin polymerization catalysis provided by the invention is used for catalyzed ethylene and alpha-olefin copolymer, there is higher polymerization activity.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.

Claims (10)

1. the preparation method of an ethylene copolymer, under the method is included in the existence of olefin polymerization catalysis, ethene and alpha-olefin are carried out polyreaction in a solvent, it is characterized in that, described olefin polymerization catalysis contains the bimetallic catalyst precursor and alkylaluminoxane with structure shown in formula I
formula I,
Wherein, R 1, R 2, R 3, R 4, R 1', R 2', R 3' and R 4' identical or different, and be hydrogen, phenyl or C independently of one another 1-C 20alkyl; R 5and R 5' identical or different, and be hydrogen or C independently of one another 1-C 20alkyl; M 1and M 2identical or different, and be the one in titanium, zirconium and hafnium independently of one another.
2. preparation method according to claim 1, wherein, M 1and M 2for titanium.
3. preparation method according to claim 1 and 2, wherein, R 1and R 1' identical or different, and be C independently of one another 1-C 20alkyl or phenyl; R 2, R 3, R 4, R 5, R 2', R 3', R 4' and R 5' be hydrogen.
4. preparation method according to claim 3, wherein, R 1and R 1' identical or different, and be tertiary butyl or phenyl independently of one another; R 2, R 3, R 4, R 5, R 2', R 3', R 4' and R 5' be hydrogen.
5. preparation method according to claim 4, wherein, described bimetallic catalyst precursor has the structure shown in formula II or formula III,
formula II
formula III.
6. the preparation method according to claim 1,2,4 or 5, wherein, described bimetallic catalyst precursor prepares in accordance with the following methods: under complex reaction condition, is MCl by compound and the general formula with structure shown in formula IV 4(THF) 2compound contact in organic solvent,
formula IV,
Wherein, R 1, R 2, R 3, R 4, R 1', R 2', R 3' and R 4' identical or different, and be hydrogen, phenyl or C independently of one another 1-C 20alkyl; R 5and R 5' identical or different, and be hydrogen or C independently of one another 1-C 20alkyl; M is the one in titanium, zirconium and hafnium.
7. preparation method according to claim 6, wherein, described general formula is MCl 4(THF) 2compound be that tetrachloro two (tetrahydrofuran (THF)) closes titanium, tetrachloro two (tetrahydrofuran (THF)) closes zirconium and tetrachloro two (tetrahydrofuran (THF)) closes one in hafnium.
8. preparation method according to claim 7, wherein, described in there is the compound of structure shown in formula IV and general formula is MCl 4(THF) 2the mol ratio of compound be 1:1.8-2.5, be preferably 1:2-2.2.
9. preparation method according to claim 6, wherein, the condition of described contact comprises elder generation and contact 0.5-3 hour at-85 DEG C to-70 DEG C, then contacts 8-24 hour at 0-60 DEG C; Preferably, the condition of described contact comprises elder generation and contact 1-2 hour at-80 DEG C to-75 DEG C, then contacts 12-20 hour at 20-40 DEG C.
10. preparation method according to claim 1, wherein, the mol ratio of described bimetallic catalyst precursor and alkylaluminoxane is 1:200-2000; Preferably, described alkylaluminoxane is C 1-C 5the alkylaluminoxane of straight or branched; More preferably, described alkylaluminoxane is methylaluminoxane.
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CN107652320A (en) * 2017-09-30 2018-02-02 南京晓庄学院 One kind limitation configuration bimetallic compound and preparation method and application
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CN102268032A (en) * 2011-06-16 2011-12-07 北京大学 Bimetallic heteroligand catalyst precursor and synthetic method and application thereof
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CN101864010A (en) * 2010-06-21 2010-10-20 北京大学 Bimetallic catalyst precursor and application thereof to olefin polymerization or copolymerization
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