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CN103804551A - Preparation method of ethylene copolymer - Google Patents

Preparation method of ethylene copolymer Download PDF

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CN103804551A
CN103804551A CN201210445946.XA CN201210445946A CN103804551A CN 103804551 A CN103804551 A CN 103804551A CN 201210445946 A CN201210445946 A CN 201210445946A CN 103804551 A CN103804551 A CN 103804551A
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catalyst precursor
contact
alkyl
structure shown
pressure
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CN103804551B (en
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于国柱
韩书亮
贺小进
邵明波
李传清
徐林
解希铭
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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 invention discloses a preparation method of an ethylene copolymer, and the method is as follows: in the presence of an organic solvent and a cocatalyst, performing first contact of ethylene and a first catalyst precursor, and then performing second contact of a mixture obtained by the first contact and a second catalyst precursor, wherein the first catalyst precursor is a compound with the structure shown in formula I, the second catalyst precursor is a compound with the structure shown in formula II; the first contact conditions include the contact temperature of-30 DEG C to 120 DEG C, the contact pressure of 0.1-1MPa, and the contact time of 2-15min; the second contact conditions include the contact temperature of-30 DEG C to 150 DEG C, the contact pressure of 0.1-1MPa, and the contact time is 1-60min. The ethylene copolymer with excellent performances can be obtained by the preparation method of the ethylene copolymer.

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
Polyolefine material is owing to having relatively little density, and good chemical proofing, water tolerance and the good feature such as physical strength, electrical insulating property, be widely used in national economy every field.
The functionalization research of alkene is the focus of research always, and the synthetic of functional polyolefin is mainly to obtain by conventional alkene (as ethene, propylene etc.) and functionalization olefin-copolymerization.Such polyolefine has various types of organo-functional group, on the one hand polyolefinic chemically modified is become and is more prone to; Aspect the polyolefinic crystallinity of adjustment, intensity, fastness to rubbing, dyeability and surface properties, all playing very important active effect (Padwa A R, Prog.Polym.Sci.1989,14,811) on the other hand.Therefore, the polyolefine of functionalization has an application prospect very widely industrial.
Wherein, ethylene copolymer product has superior performance, and comonomer is of a great variety, comprises 1-octene, 1-hexene, 1-butylene, propylene and polar monomer etc.By regulating comonomer kind and consumption, both can obtain linear low density polyethylene, also can obtain thermoplastic elastomer, can also obtain rubber, apply very extensive.Particularly elastomeric special construction is given its excellent mechanical property, rheological property and ageing-resistant performance, and during as the agent of plastics impact-resistance, low-temperature flexibility is good, consumption is few, cost performance is high, is widely used in modifying plastics.
Polyolefin industry flourish has benefited from the fast development of the polycoordination that Ziegler-Natta catalyst and metallocene catalyst are representative.Nowadays, non-metallocene catalyst becomes the focus of polycoordination area research, and salicylaldimine ligand transition-metal catalyst belongs to one wherein.Such catalyzer has good olefin catalytic activity, for example: salicylic alidehyde imine closes nickel catalyzator both can realize the oligomerisation of ethene, obtains oligopolymer (the Song L P of four and six carbon atom, Zhao W, Huang J L, et al., Chin.J.Chem.2005,23,669), can realize again the homopolymerization of ethene, obtain having polyethylene (Younkin T R, the Connor E F of side chain, Henderson J I, et al., Science 2000,287,460); And closing titanium catalyst, salicylic alidehyde imine can highly actively 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 can realize the alternating copolymerization of ethene and propylene, obtain a kind of well behaved thermoplastic elastomer.In addition, utilize such catalyzer can realize ethene and 1-hexene or alkene random copolymerization (Rick F, Makot M, 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), expand the range of application of titanium metal catalyzer.
CN101168581A discloses a kind of environment-friendly preparation method thereof of molecular weight controllable polyethylene.Vinyl monomer obtains by emulsion catalyzed polymerization in aqueous phase system, and catalyzer is salicylic alidehyde imine nickel complex.Poly molecular weight, polymerization temperature, catalyst concn, catalyst system and aqueous polymerization system solid content are realized regulation and control.The method has mainly utilized the olefinic polymerization of salicylic alidehyde imine nickel complex as catalyst to realize the control to molecular weight of polyethylene and distribution thereof.
CN101864010B 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.This catalyst precursor has mainly utilized bimetallic synergy to come catalyzed alkene homopolymerization or copolymerization.Also only have 4.1 × 10 but the polymerization activity of the open vinyl polymerization of CN101864010B is the highest 4g/ (molh), in addition, this catalyst precursor is mainly used in ethylene homo or ethene and substituted olefine copolymerization.
Tradition ethylene copolymer is under Ziegler-Natta catalyst existence condition, makes ethene and alpha-olefin as comonomer, as propylene, butylene etc. carry out copolymerization and produce at certain pressure and temperature.When high pressure, be difficult for adding comonomer, and comonomer price is often than ethene costliness, therefore, the development of ethylene copolymer has been subject to the restriction of comonomer, catalytic efficiency and polymerizing condition.
Therefore, how further reduce the requirement of comonomer and polymerizing condition is remained in field of olefin polymerisation to a problem of needing solution badly.
Summary of the invention
Object of the present invention provides the preparation method of the higher and ethylene copolymer that polymerizing condition is gentle of a kind of catalytic efficiency.
The invention provides a kind of preparation method of ethylene copolymer, wherein, the method is included under organic solvent and promotor existence, ethene and the first catalyst precursor are carried out to first to be contacted, then the first contact gained mixture is carried out to second with the second catalyst precursor and contact, wherein, described the first catalyst precursor is the compound with structure shown in formula I, described the second catalyst precursor is the compound with structure shown in formula II
Wherein, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 5', R 6', R 7' and R 8' be the alkyl of hydrogen or C1-C20 independently of one another;
The condition of described the first contact comprises that Contact Temperature is-30 ℃ to 120 ℃, and contact pressure is 0.1-1MPa, and be 2-15min duration of contact; The condition of described the second contact comprises that Contact Temperature is-30 ℃ to 150 ℃, and contact pressure is 0.1-1MPa, and be 1-60min duration of contact.
In the present invention, use continuously two kinds of salicylic alidehyde imine metalloid catalyst precursor co-catalysis ethylene polymerizations that catalytic performance is different, in the situation that using single ethylene monomer, can obtain ethylene copolymer, its advantage is the step of removing additional comonomer from, directly synthesizing ethylene multipolymer, so not only greatly improve catalytic efficiency and reduced the requirement to polymeric reaction condition, also reduced production cost simultaneously, and acquisition has been better than the polymerization effect of catalyst system in the past.
Other features and advantages of the present invention are described in detail the embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of ethylene copolymer, the method is included under organic solvent and promotor existence, ethene and the first catalyst precursor are carried out to first to be contacted, then the first contact gained mixture being carried out to second with the second catalyst precursor contacts, wherein, described the first catalyst precursor is the compound with structure shown in formula I, and described the second catalyst precursor is the compound with structure shown in formula II
Figure BDA00002377042600041
Wherein, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 5', R 6', R 7' and R 8' be the alkyl of hydrogen or C1-C20 independently of one another;
The condition of described the first contact comprises that Contact Temperature is-30 ℃ to 120 ℃, and contact pressure is 0.1-1MPa, and be 2-15min duration of contact; The condition of described the second contact comprises that Contact Temperature is-30 ℃ to 150 ℃, and contact pressure is 0.1-1MPa, and be 1-60min duration of contact.
In the present invention, described alkyl can be straight chain, can be also side chain.The example of the alkyl of described C1-C20 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-methyl hexyl, 3-methyl hexyl, 4-methyl hexyl, 5-methyl hexyl, 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.
In the present invention, the first catalyst precursor of structure shown in formula I, is the nickel-metal catalyst based on salicylaldimine ligand, also uses with promotor the effect of playing catalyst for oligomerization.According to the present invention, shown in formula I in structure, R 1, R 2, R 3and R 4can be identical, be all hydrogen atom; Or, R 1, R 2, R 3and R 4be the alkyl of hydrogen or C1-C20 independently of one another, and R 1, R 2, R 3and R 4in at least one alkyl that is C1-C20.
Particularly, the first catalyst precursor structure example that meets above-mentioned requirements can include but not limited to: R 1, R 2, R 3and R 4be hydrogen; R 1can be the alkyl of C1-C20, R 2, R 3and R 4be hydrogen independently of one another; Or, R 2can be the alkyl of C1-C20, R 1, R 3and R 4be hydrogen independently of one another; Or, R 3can be the alkyl of C1-C20, R 1, R 2and R 4be hydrogen independently of one another; Or, R 4can be the alkyl of C1-C20, R 1, R 2and R 3be hydrogen independently of one another; Or, R 1and R 2can be the alkyl of C1-C20, R 3and R 4for hydrogen; Or, R 3and R 4can be the alkyl of C1-C20, R 1and R 2for hydrogen; Or, R 1and R 3can be the alkyl of C1-C20, R 2and R 4for hydrogen; Or, R 1and R 4can be the alkyl of C1-C20, R 2and R 3for hydrogen; Or, R 2and R 4can be the alkyl of C1-C20, R 1and R 3for hydrogen; Or, R 2and R 3can be the alkyl of C1-C20, R 1and R 4for hydrogen; Or, R 1, R 2and R 3can be the alkyl of C1-C20, R 4for hydrogen; Or, R 2, R 3and R 4can be the alkyl of C1-C20, R 1for hydrogen; Or, R 1, R 3and R 4can be the alkyl of C1-C20, R 2for hydrogen; Or, R 1, R 2and R 4can be the alkyl of C1-C20, R 3for hydrogen; Or, R 1, R 2, R 3and R 4it can be the alkyl of C1-C20.
The present inventor finds under study for action, by specific R 1-R 4the catalyst precursor forming can be obtained fabulous catalytic effect during for the catalyzer of catalyzed ethylene polymerization, therefore, preferably, R 1can be the alkyl of C1-C4, R 2, R 3and R 4be hydrogen independently of one another; Or, R 2can be the alkyl of C1-C4, R 1, R 3and R 4be hydrogen independently of one another; Or, R 3can be the alkyl of C1-C4, R 1, R 2and R 4be hydrogen independently of one another; Or, R 4can be the alkyl of C1-C4, R 1, R 2and R 3be hydrogen independently of one another.
More preferably, R 1can be the alkyl of C1-C4, R 2, R 3and R 4be hydrogen independently of one another, most preferably, R 1for tertiary butyl, R 2, R 3and R 4be hydrogen independently of one another, described the first catalyst precursor is the compound with structure shown in formula III,
Figure BDA00002377042600061
In the present invention, the second catalyst precursor of structure shown in formula II, is the titanium metal catalyzer based on salicylaldimine ligand, also uses with promotor the effect of playing catalyst for copolymerization.According to the present invention, R 5, R 6, R 7, R 8, R 5', R 6', R 7' and R 8' can be identical, be all hydrogen atom; Or, R 5, R 6, R 7, R 8, R 5', R 6', R 7' and R 8' be the alkyl of hydrogen or C1-C20 independently of one another, and R 5, R 6, R 7and R 8in at least one alkyl that is C1-C20, R 5', R 6', R 7' and R 8' at least one alkyl that is C1-C20.
Particularly, the second catalyst precursor structure example that meets above-mentioned requirements can include but not limited to: R 5, R 6, R 7, R 8, R 5', R 6', R 7' and R 8' be hydrogen atom; Or, R 5and R 5' can be the alkyl of C1-C20, R 6, R 7, R 8, R 6', R 7' and R 8' be hydrogen independently of one another; Or, R 6and R 6' can be the alkyl of C1-C20, R 5, R 7, R 8, R 5', R 7' and R 8' be hydrogen independently of one another; Or, R 7and R 7' can be the alkyl of C1-C20, R 5, R 6, R 8, R 5', R 6' and R 8' be hydrogen independently of one another; Or, R 8and R 8' can be the alkyl of C1-C20, R 5, R 6, R 7, R 5', R 6' and R 7' be hydrogen independently of one another; Or, R 5, R 6, R 5' and R 6' can be the alkyl of C1-C20, R 7, R 8, R 7' and R 8' be hydrogen independently of one another; Or, R 5, R 7, R 5' and R 7' can be the alkyl of C1-C20, R 6, R 8, R 6' and R 8' be hydrogen independently of one another; Or, R 5, R 8, R 5' and R 8' can be the alkyl of C1-C20, R 6, R 7, R 6' and R 7' be hydrogen independently of one another; Or, R 6, R 7, R 6' and R 7' can be the alkyl of C1-C20, R 5, R 8, R 5' and R 8' be hydrogen independently of one another; Or, R 6, R 8, R 6' and R 8' can be the alkyl of C1-C20, R 5, R 7, R 5' and R 7' be hydrogen independently of one another; Or, R 7, R 8, R 7' and R 8' can be the alkyl of C1-C20, R 5, R 6, R 5' and R 6' be hydrogen independently of one another; Or, R 5, R 6, R 7, R 5', R 6' and R 7' can be the alkyl of C1-C20, R 8and R 8' be hydrogen independently of one another; R 6, R 7, R 8, R 6', R 7' and R 8' can be the alkyl of C1-C20, R 5and R 5' be hydrogen independently of one another; Or, R 5, R 7, R 8, R 5', R 7' and R 8' can be the alkyl of C1-C20, R 6and R 6' be hydrogen independently of one another; R 5, R 6, R 8, R 5', R 6' and R 8' can be the alkyl of C1-C20, R 7and R 7' be hydrogen independently of one another; Or, R 5, R 5', R 6, R 7, R 8, R 6', R 7' and R 8' be the alkyl of C1-C20.
The present inventor finds under study for action, by specific R 5-R 8and R 5'-R 8' catalyst precursor that forms can obtain fabulous catalytic effect during for the catalyzer of catalyzed ethylene polymerization, therefore, preferably, R 5and R 5' can be the alkyl of C1-C4, R 6, R 7, R 8, R 6', R 7' and R 8' be hydrogen independently of one another; Or, R 6and R 6' can be the alkyl of C1-C4, R 5, R 7, R 8, R 5', R 7' and R 8' be hydrogen independently of one another; Or, R 7and R 7' can be the alkyl of C1-C4, R 5, R 6, R 8, R 5', R 6' and R 8' be hydrogen independently of one another; Or, R 8and R 8' can be C 1-C 4alkyl, R 5, R 6, R 7, R 5', R 6' and R 7' be hydrogen independently of one another.
More preferably, R 5and R 5' can be the alkyl of C1-C4, R 6, R 7, R 8, R 6', R 7' and R 8' be hydrogen independently of one another, most preferably, R 5and R 5' can be methyl, R 6, R 7, R 8, R 6', R 7' and R 8' be hydrogen independently of one another, described the second catalyst precursor has the compound of structure shown in formula IV,
Figure BDA00002377042600081
According to the present invention, ethene and the first catalyst precursor first condition contacting of carrying out is not particularly limited, as long as make vinyl monomer generation oligomerisation reaction, for example, ethene comprises that with the first catalyst precursor first condition contacting of carrying out Contact Temperature can be-30 ℃ to 120 ℃, contact pressure can be 0.1-1MPa, can be 2-15min duration of contact, and preferably, Contact Temperature can be 20 ℃ to 80 ℃, contact pressure can be 0.1-0.5MPa, and can be 5-10min duration of contact.
According to the present invention, the first contact gained mixture and the second catalyst precursor second condition contacting of carrying out is not particularly limited, can changes in the larger context, as long as make the first contact gained mixture generation copolyreaction, for example, the condition of described the second contact comprises that Contact Temperature is-30 ℃ to 150 ℃, and contact pressure is 0.1-1MPa, and be 1-60min duration of contact, preferably, Contact Temperature is 20 ℃ to 80 ℃, and contact pressure is 0.1-0.5MPa, and be 5-20min duration of contact.
According to the present invention, mol ratio to described the first catalyst precursor and the second catalyst precursor is not particularly limited, can change in the larger context, as long as make described the first catalyst precursor and the second catalyst precursor play respectively the effect of catalyst for oligomerization and catalyst for copolymerization under the effect of promotor, under preferable case, the mol ratio of described the first catalyst precursor and the second catalyst precursor can be 1:0.9-10, more preferably 1:2-5.
According to the present invention, wherein, the mol ratio of described the first catalyst precursor and promotor can change in the larger context, be not particularly limited, as long as make described catalyst precursor play respectively the effect of catalyst for oligomerization and catalyst for copolymerization under the effect of promotor, under preferable case, the mol ratio of described the first catalyst precursor and promotor can be 1:200-2000, more preferably 1:200-1000, most preferably is 1:200-420.
The inventor finds through research, be that the second catalyst precursor that salicylic alidehyde imine closes nickel catalyzator precursor and has a structure shown in formula IV is that salicylic alidehyde imine closes titanium catalyst precursor continuously for ethylene polymerization by first catalyst precursor with structure shown in formula III, can obtain beyond thought catalytic effect.This may be due to activity and the selectivity of utilizing salicylic alidehyde imine to close nickel precursor, and salicylic alidehyde imine closes activity and the copolymerized ability of titanium, and the kinetics matching of these two kinds of catalyst precursors has improved the catalytic efficiency of ethylene polymerization greatly.
According to the present invention, the consumption of described the first catalyst precursor can change in wider scope, under preferable case, and organic solvent described in 1L relatively, the consumption of the first catalyst precursor is 0.01-0.05g, more preferably 0.012-0.025g.It should be noted that, the consumption of described organic solvent refers to the summation of the consumption of the organic solvent existing in whole reaction system.
According to the present invention, described organic solvent can be the known various inert solvents that do not react with resultant with reactant of field of olefin polymerisation technician, under preferable case, described organic solvent can be selected from one or more in benzene, toluene, normal hexane and normal heptane.
According to the present invention, described promotor can be the known various promotors of field of olefin polymerisation technician, and usually, described promotor can be alkylaluminoxane, and the alkyl in described alkylaluminoxane can be the alkyl of C1-C5.Preferably, described alkylaluminoxane can be methylaluminoxane.
Below will describe the present invention by embodiment, but embodiments of the invention have more than and are limited to following examples.
In following examples, the mensuration of ethylene copolymer fusing point is measured by dsc (DSC), and adopting PE company of U.S. model is the differential scanning calorimeter of PE DSC-7, and test condition comprises that temperature rise rate is 10 ℃/min; Weight-average molecular weight (Mw) and the number-average molecular weight (Mn) of ethylene copolymer are measured by gel chromatography (GPC), the gel chromatograph that the model that adopts Shimadzu company is LC-10AT, moving phase is THF, and standard is Narrow distribution polystyrene, and probe temperature is 25 ℃.
The mensuration of a rate of ethylene copolymer is by nmr determination, and concrete condition determination is with reference to prior art.
Unless stated otherwise, compound and the reagent etc. in following examples and comparative example, used are commercially available product.
Embodiment 1
The present embodiment is for illustrating the synthetic of ethylene copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then add successively the toluene solution 5mL(12mg/mL of methylaluminoxane (MAO)), through the normal hexane 150mL of anhydrous and oxygen-free processing, and contain first catalyst precursor with structure shown in formula III (according to document Science 2000,287,460 record methods make, below identical) toluene solution 2mL(1.98mg/mL).Under mechanical stirring, pass into the ethene that pressure is 0.1MPa, and under this pressure in 20 ℃ reaction 5min, add afterwards and contain second catalyst precursor with structure shown in formula IV (according to document Macromolecules 2005,38,1546 record methods make, identical below) toluene solution 4mL(1.80mg/mL), pressure and temperature remains unchanged, continue reaction 20 minutes, add ethanol termination reaction, obtain ethene polymers 2.03g, determine as calculated, polymerization activity is 6.1 × 10 5gPE/ (molTih).
It is 120.1 ℃ that DSC records fusing point; GPC records the M of ethylene copolymer wbe 3.8 × 10 5, M w/ M nbe 2.65; It is 3.0% that nuclear-magnetism carbon spectrum records a rate.
Comparative example 1
Adopt the method identical with embodiment 1 to carry out the polymerization of ethene, different is, only adopt the catalyst precursor of structure shown in formula IV, the 500mL polymeric kettle being about to after heat drying vacuumizes twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then add successively the toluene solution 5mL(12mg/mL of methylaluminoxane (MAO)), through the normal hexane 150mL of anhydrous and oxygen-free processing, and the toluene solution 4mL(1.80mg/mL that contains the catalyst precursor with structure shown in formula IV).Under mechanical stirring, pass into the ethene that pressure is 0.1MPa, and under this pressure in 20 ℃ reaction 5min, add ethanol termination reaction, obtain ethene polymers 2.68g.Determine as calculated, polymerization activity is 4.0 × 10 6gPE/ (molTih).
It is 139.2 ℃ that DSC records fusing point; GPC records polyvinyl M wbe 2.3 × 10 5, M w/ M nbe 1.67, nuclear-magnetism carbon spectrum records without a rate, and this polymkeric substance is non-multipolymer.
Embodiment 2
The present embodiment is for illustrating the synthetic of ethylene copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then add successively the toluene solution 5mL(12mg/mL of methylaluminoxane (MAO)), through the normal hexane 150mL of anhydrous and oxygen-free processing, and the toluene solution 2mL(1.98mg/mL that contains first catalyst precursor with structure shown in formula III).Under mechanical stirring, pass into the ethene that pressure is 0.1MPa, and react 5 minutes in 20 ℃ under this pressure, add afterwards the toluene solution 6mL(1.80mg/mL that contains second catalyst precursor with structure shown in formula IV), pressure and temperature remains unchanged, continue reaction 20 minutes, add ethanol termination reaction, obtain ethene polymers 3.53g, determine as calculated, polymerization activity is 7.1 × 10 5gPE/ (molTih).
It is 123.6 ℃ that DSC records fusing point; GPC records the M of ethylene copolymer wbe 6.2 × 10 5, M w/ M nbe 2.72, it is 2.6% that nuclear-magnetism carbon spectrum records a rate.
Embodiment 3
The present embodiment is for illustrating the synthetic of ethylene copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then add successively the toluene solution 5mL(12mg/mL of methylaluminoxane (MAO)), through the normal hexane 150mL of anhydrous and oxygen-free processing, and the toluene solution 2mL(1.98mg/mL that contains first catalyst precursor with structure shown in formula III).Under mechanical stirring, pass into the ethene that pressure is 0.1MPa, and react 5min in 20 ℃ under this pressure, add afterwards the toluene solution 4mL(1.80mg/mL that contains second catalyst precursor with structure shown in formula IV), pressure and temperature remains unchanged, continue reaction 20 minutes, add ethanol termination reaction, obtain ethene polymers 1.87g, determine as calculated, polymerization activity is 5.6 × 10 5gPE/ (molTih).
It is 120.3 ℃ that DSC records fusing point; GPC records the M of ethylene copolymer wbe 4.5 × 10 5, M w/ M nbe 2.73; It is 2.4% that nuclear-magnetism carbon spectrum records a rate.
Embodiment 4
The present embodiment is for illustrating the synthetic of ethylene copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then add successively the toluene solution 10mL(12mg/mL of methylaluminoxane (MAO)), through the normal hexane 150mL of anhydrous and oxygen-free processing, and the toluene solution 2mL(1.98mg/mL that contains first catalyst precursor with structure shown in formula III).Under mechanical stirring, pass into the ethene that pressure is 0.1MPa, and react 5min in 20 ℃ under this pressure, add afterwards the toluene solution 4mL(1.80mg/mL that contains second catalyst precursor with structure shown in formula IV), pressure and temperature remains unchanged, continue reaction 20 minutes, add ethanol termination reaction, obtain ethene polymers 2.34g, determine as calculated, polymerization activity is 7.0 × 10 5gPE/ (molTih).
It is 121.5 ℃ that DSC records fusing point; GPC records the M of ethylene copolymer wbe 5.4 × 10 5, M w/ M nbe 2.35; It is 2.8% that nuclear-magnetism carbon spectrum records a rate.
Embodiment 5
The present embodiment is for illustrating the synthetic of ethylene copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then add successively the toluene solution 5mL(12mg/mL of methylaluminoxane (MAO)), through the normal hexane 150mL of anhydrous and oxygen-free processing, and the toluene solution 1mL(1.98mg/mL that contains first catalyst precursor with structure shown in formula III).Under mechanical stirring, pass into the ethene that pressure is 0.1MPa, and react 5min in 20 ℃ under this pressure, add afterwards the toluene solution 4mL(1.80mg/mL that contains second catalyst precursor with structure shown in formula IV), pressure and temperature remains unchanged, continue reaction 20 minutes, add ethanol termination reaction, obtain ethene polymers 3.23g, determine as calculated, polymerization activity is 9.7 × 10 5gPE/ (molTih).
It is 127.3 ℃ that DSC records fusing point; GPC records the M of ethylene copolymer wbe 4.9 × 10 5, M w/ M nbe 1.92; It is 1.9% that nuclear-magnetism carbon spectrum records a rate.
Embodiment 6
The present embodiment is for illustrating the synthetic of ethylene copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then add successively the toluene solution 10mL(12mg/mL of methylaluminoxane (MAO)), through the normal hexane 150mL of anhydrous and oxygen-free processing, and the toluene solution 4mL(1.98mg/mL that contains first catalyst precursor with structure shown in formula III).Under mechanical stirring, pass into the ethene that pressure is 0.1MPa, and react 5min in 20 ℃ under this pressure, add afterwards the toluene solution 4mL(1.80mg/mL that contains second catalyst precursor with structure shown in formula IV), pressure and temperature remains unchanged, continue reaction 20 minutes, add ethanol termination reaction, obtain ethene polymers 1.65g, determine as calculated, polymerization activity is 5.0 × 10 5gPE/ (molTih).
It is 119.7 ℃ that DSC records fusing point; GPC records the M of ethylene copolymer wbe 1.9 × 10 5, M w/ M nbe 2.02, it is 3.1% that nuclear-magnetism carbon spectrum records a rate.
Embodiment 7
The present embodiment is for illustrating the synthetic of ethylene copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then add successively the toluene solution 5mL(12mg/mL of methylaluminoxane (MAO)), through the normal hexane 150mL of anhydrous and oxygen-free processing, and the toluene solution 2mL(1.98mg/mL that contains first catalyst precursor with structure shown in formula III).Under mechanical stirring, pass into the ethene that pressure is 0.1MPa, and react 5min in 20 ℃ under this pressure, add afterwards the toluene solution 2mL(1.80mg/mL that contains second catalyst precursor with structure shown in formula IV), pressure and temperature remains unchanged, continue reaction 20 minutes, add ethanol termination reaction, obtain ethene polymers 1.28g, determine as calculated, polymerization activity is 7.7 × 10 5gPE/ (molTih).
It is 120.0 ℃ that DSC records fusing point; GPC records the M of ethylene copolymer wbe 2.2 × 10 5, M w/ M nbe 2.54, it is 3.0% that nuclear-magnetism carbon spectrum records a rate.
Embodiment 8
The present embodiment is for illustrating the synthetic of ethylene copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then add successively the toluene solution 5mL(12mg/mL of methylaluminoxane (MAO)), through the normal hexane 150mL of anhydrous and oxygen-free processing, and the toluene solution 2mL(1.98mg/mL that contains first catalyst precursor with structure shown in formula III).Under mechanical stirring, pass into the ethene that pressure is 0.1MPa, and react 2 minutes in 20 ℃ under this pressure, add afterwards the toluene solution 4mL(1.80mg/mL that contains second catalyst precursor with structure shown in formula IV), pressure and temperature remains unchanged, continue reaction 20 minutes, add ethanol termination reaction, obtain ethene polymers 2.43g, determine that as calculated polymerization activity is 7.3 × 10 5gPE/ (molTih).
It is 123.5 ℃ that DSC records fusing point; GPC records the M of ethylene copolymer wbe 3.8 × 10 5, M w/ M nbe 1.91, it is 2.7% that nuclear-magnetism carbon spectrum records a rate.
Embodiment 9
The present embodiment is for illustrating the synthetic of ethylene copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then add successively the toluene solution 5mL(12mg/mL of methylaluminoxane (MAO)), through the normal hexane 150mL of anhydrous and oxygen-free processing, and the toluene solution 2mL(1.98mg/mL that contains first catalyst precursor with structure shown in formula III).Under mechanical stirring, pass into the ethene that pressure is 0.1MPa, and react 10 minutes in 20 ℃ under this pressure, add afterwards the toluene solution 4mL(1.80mg/mL that contains second catalyst precursor with structure shown in formula IV), pressure and temperature remains unchanged, continue reaction 20 minutes, add ethanol termination reaction, obtain ethene polymers 1.03g, determine as calculated, polymerization activity is 3.1 × 10 5gPE/ (molTih).
It is 118.5 ℃ that DSC records fusing point; GPC records the M of ethylene copolymer wbe 1.8 × 10 5, M w/ M nbe 2.44, it is 3.4% that nuclear-magnetism carbon spectrum records a rate.
Embodiment 10
The present embodiment is for illustrating the synthetic of ethylene copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then add successively the toluene solution 5mL(12mg/mL of methylaluminoxane (MAO)), through the normal hexane 150mL of anhydrous and oxygen-free processing, and the toluene solution 2mL(1.98mg/mL that contains first catalyst precursor with structure shown in formula III).Under mechanical stirring, pass into the ethene that pressure is 0.1MPa, and react 5 minutes in 20 ℃ under this pressure, add afterwards the toluene solution 4mL(1.80mg/mL that contains second catalyst precursor with structure shown in formula IV), pressure and temperature remains unchanged, continue reaction 10 minutes, add ethanol termination reaction, obtain ethene polymers 1.43g, determine as calculated, polymerization activity is 8.6 × 10 5gPE/ (molTih).
It is 121.3 ℃ that DSC records fusing point; GPC records the M of ethylene copolymer wbe 3.6 × 10 5, M w/ M nbe 2.12, it is 2.9% that nuclear-magnetism carbon spectrum records a rate.
Embodiment 11
The present embodiment is for illustrating the synthetic of ethylene copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then add successively the toluene solution 5mL(12mg/mL of methylaluminoxane (MAO)), through the normal hexane 150mL of anhydrous and oxygen-free processing, and the toluene solution 2mL(1.98mg/mL that contains first catalyst precursor with structure shown in formula III).Under mechanical stirring, pass into the ethene that pressure is 0.1MPa, and react 5 minutes in 20 ℃ under this pressure, add afterwards the toluene solution 4mL(1.80mg/mL that contains second catalyst precursor with structure shown in formula IV), pressure and temperature remains unchanged, continue reaction 30 minutes, add ethanol termination reaction, obtain ethene polymers 2.81g, determine as calculated, polymerization activity is 5.6 × 10 5gPE/ (molTih).
It is 123.9 ℃ that DSC records fusing point; GPC records the M of ethylene copolymer wbe 4.1 × 10 5, M w/ M nbe 2.58, it is 2.7% that nuclear-magnetism carbon spectrum records a rate.
Embodiment 12
The present embodiment is for illustrating the synthetic of ethylene copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then add successively the toluene solution 5mL(12mg/mL of modified methylaluminoxane (MMAO)), through the toluene 150mL of anhydrous and oxygen-free processing, and the toluene solution 2mL(1.98mg/mL that contains first catalyst precursor with structure shown in formula III).Under mechanical stirring, pass into the ethene that pressure is 0.1MPa, and react 5 minutes in 20 ℃ under this pressure, add afterwards the toluene solution 4mL(1.80mg/mL that contains second catalyst precursor with structure shown in formula IV), pressure and temperature remains unchanged, continue reaction 20 minutes, add ethanol termination reaction, obtain ethene polymers 2.49g, determine as calculated, polymerization activity is 7.7 × 10 5gPE/ (molTih).
It is 119.6 ℃ that DSC records fusing point; GPC records the M of ethylene copolymer wbe 1.5 × 10 5, M w/ M nbe 2.23, it is 3.0% that nuclear-magnetism carbon spectrum records a rate.
Embodiment 13
The present embodiment is for illustrating the synthetic of ethylene copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then add successively the toluene solution 5mL(12mg/mL of methylaluminoxane (MAO)), through the normal hexane 150mL of anhydrous and oxygen-free processing, and the toluene solution 2mL(1.98mg/mL that contains first catalyst precursor with structure shown in formula III).Under mechanical stirring, pass into the ethene that pressure is 0.1MPa, and react 5 minutes in 80 ℃ under this pressure, add afterwards the toluene solution 4mL(1.80mg/mL that contains second catalyst precursor with structure shown in formula IV), pressure and temperature remains unchanged, continue reaction 20 minutes, add ethanol termination reaction, obtain ethene polymers 1.13g, determine as calculated, polymerization activity is 3.4 × 10 5gPE/ (molTih).
It is 117.9 ℃ that DSC records fusing point; GPC records the M of ethylene copolymer wbe 2.2 × 10 5, M w/ M nbe 1.93, it is 3.6% that nuclear-magnetism carbon spectrum records a rate.
Embodiment 14
The present embodiment is for illustrating the synthetic of ethylene copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then add successively the toluene solution 5mL(12mg/mL of methylaluminoxane (MAO)), through the normal hexane 150mL of anhydrous and oxygen-free processing, and the toluene solution 2mL(1.98mg/mL that contains first catalyst precursor with structure shown in formula III).Under mechanical stirring, pass into the ethene that pressure is 0.5MPa, and react 5 minutes in 20 ℃ under this pressure, add afterwards the toluene solution 4mL(1.80mg/mL that contains second catalyst precursor with structure shown in formula IV), pressure and temperature remains unchanged, continue reaction 20 minutes, add ethanol termination reaction, obtain ethene polymers 4.16g, determine as calculated, polymerization activity is 1.3 × 10 6gPE/ (molTih).
It is 126.3 ℃ that DSC records fusing point; GPC records the M of ethylene copolymer wbe 5.6 × 10 5, M w/ M nbe 2.84, it is 2.1% that nuclear-magnetism carbon spectrum records a rate.
Can find out from the data of embodiment 1 and comparative example 1, preparation method provided by the invention can directly utilize vinyl monomer to prepare ethylene copolymer.

Claims (10)

1. the preparation method of an ethylene copolymer, the method is included under organic solvent and promotor existence, ethene and the first catalyst precursor are carried out to first to be contacted, then the first contact gained mixture being carried out to second with the second catalyst precursor contacts, it is characterized in that, described the first catalyst precursor is the compound with structure shown in formula I, and described the second catalyst precursor is the compound with structure shown in formula II
Figure FDA00002377042500011
Wherein, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 5', R 6', R 7' and R 8' be the alkyl of hydrogen or C1-C20 independently of one another;
The condition of described the first contact comprises that Contact Temperature is-30 ℃ to 120 ℃, and contact pressure is 0.1-1MPa, and be 2-15min duration of contact; The condition of described the second contact comprises that Contact Temperature is-30 ℃ to 150 ℃, and contact pressure is 0.1-1MPa, and be 1-60min duration of contact.
2. method according to claim 1, wherein, the condition of described the first contact comprises that Contact Temperature is 20 ℃ to 80 ℃, and contact pressure is 0.1-0.5MPa, and be 5-10min duration of contact; The condition of described the second contact comprises that Contact Temperature is 20 ℃ to 80 ℃, and contact pressure is 0.1-0.5MPa, and be 5-20min duration of contact.
3. method according to claim 1, wherein, the mol ratio of described the first catalyst precursor and the second catalyst precursor is 1:0.9-10, is preferably 1:2-5.
4. method according to claim 1, wherein, the mol ratio of described the first catalyst precursor and promotor is 1:200-2000, is preferably 1:200-1000.
5. method according to claim 1, wherein, described the first catalyst precursor is the compound with structure shown in formula III,
Figure FDA00002377042500021
6. method according to claim 1, wherein, described the second catalyst precursor is the compound with structure shown in formula IV,
Figure FDA00002377042500022
7. method according to claim 4, wherein, described promotor is alkylaluminoxane.
8. method according to claim 7, wherein, the alkyl that in described alkylaluminoxane, alkyl is C1-C5, preferably, described alkylaluminoxane is methylaluminoxane.
9. method according to claim 1, wherein, organic solvent described in 1L relatively, the consumption of the first catalyst precursor is 0.01-0.05g.
10. according to the method described in any one in claim 1-9, wherein, described organic solvent is one or more in benzene, toluene, normal hexane and normal heptane.
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