CN106810629A - A kind of spherical graphite alkene/magnesium-supported polyethylene catalysts of halogenation - Google Patents
A kind of spherical graphite alkene/magnesium-supported polyethylene catalysts of halogenation Download PDFInfo
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- CN106810629A CN106810629A CN201510873154.6A CN201510873154A CN106810629A CN 106810629 A CN106810629 A CN 106810629A CN 201510873154 A CN201510873154 A CN 201510873154A CN 106810629 A CN106810629 A CN 106810629A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
Abstract
The present invention proposes a kind of spherical graphite alkene/magnesium-supported polyethylene catalysts of halogenation, catalyst composition includes ball-type graphene oxide, 10~25wt% magnesium, 35~55wt% halogens and 5~20wt% titanium compounds of 5~20wt%, and catalyst is prepared as follows：1) homogeneous solution is dispersed into by graphene oxide is ultrasonically treated in water；2) homogeneous solution and liquid nitrogen mixing quick break and solidify, solidfied material is vacuum dried, obtains spherical alumina Graphene；3) spherical alumina Graphene is mixed with alkyl halide magnesium in organic solvent, 12~48hr is mixed at 50~80 DEG C, obtain the mol ratio 0.5~1.2 of complex carrier predecessor, the spherical alumina Graphene and alkyl halide magnesium；4) carrier predecessor obtains graphene oxide/magnesium halide carrier through washing, 0.5~2hr of vacuum drying；5) graphene oxide/magnesium halide carrier mixes with titanium compound at 100~120 DEG C, and catalyst is obtained through filtering, vacuum drying.The catalyst can prepare high performance Graphene/superhigh molecular weight polyethylene material for home position polymerization reaction.
Description
Technical field
The present invention relates to a kind of support type polyethylene catalysts, and in particular to a kind of spherical graphite alkene/halogenation
Magnesium-supported polyethylene catalysts, catalyst prepares Graphene/supra polymer suitable for home position polymerization reaction
Weight northylen.
Background technology
Graphene (Graphene) is a kind of sp being made up of carbon atom2Hybridized orbit composition hexangle type is in honeybee
The individual layer laminated structure new material of nest lattice, its only one of which carbon atom thickness is most thin in existing known materials
One kind, it is and very rigid.The chemical property of Graphene is structurally similar similar to CNT
Lamellar clay, this design feature makes it have in polymer performance is improved and possesses huge potentiality.But,
Due to there is stronger Van der Waals force between the lamella of Graphene, easily produce to pile up and reunite, in common solvent
Dispersiveness is also poor, therefore, improve the dispersiveness of Graphene, improve Graphene compatible with polymeric matrix
Property, seem extremely important in theoretical research and practical application area, it is the focus of current concern.
Graphene oxide is the oxide of Graphene, compared with Graphene, containing certain on its surface and side
The functional group such as carboxyl, hydroxyl, epoxy radicals, readily soluble hydrophilic and between polymer interaction is stronger,
Therefore more applications are gradually obtained in polymer modification.The Graphene or graphene oxide having been reported that/poly-
The preparation method of compound composite material mainly has four kinds：Melt-blending process, solution mixing method, emulsion mixing method
And situ aggregation method.Situ aggregation method is that graphene/graphene oxide is directly mixed to prepare with polymerized monomer
Polymer composites.Compared to other three kinds of methods, situ aggregation method has two important advantages, and one is
, by supported active center, can obtain replicating the polymer of catalyst granules form；Two is if can be by stone
Black alkene is dispersed in polymeric matrix, and the property of composite can more be stablized, component is homogeneous, feature
Unanimously, this 2 points it is particularly important in special material is prepared.
Ultra-high molecular weight polyethylene (abbreviation UHMWPE), is the polyethylene of molecular weight more than 1,500,000.With
Common engineering plastics are compared, and UHMWPE has not available for general material because of the molecular weight of its superelevation
Performance advantage.
At present, the catalyst of UHMWPE is produced in industrial market with metallocene catalyst or Ziegler-receive
Based on tower catalyst, ziegler-natta catalyzed system is occupied with the polymerization activity and relatively low cost of its stabilization
Staple market.In heterogeneous carrier high-efficiency ziegler-natta catalyzed polymerization-filling, catalyst form and its
Certain relation is there is between the form and particle of the prepared polymer of polymerization.But only suitable
Under catalyst preparation conditions and specific polymerizing condition, catalyst and morphology reproduction can be just obtained
Result.Therefore, appropriate molecular weight and its distribution, the good polymer beads of form are for supra polymer
Processing, production and the extensive use of weight northylen have prior meaning.In consideration of it, how will catalysis
The structure and three-dimensional effect of agent carrier are preferably combined with the performance of catalyst active center, are being catalyzed it
Controllability is produced always to be problem demanding prompt solution polymer architecture and form in journey.
CN201310014709.2 prepares ultra-high molecular weight polyethylene/graphite alkene using liquid phase situ aggregation method
Composite, comprises the following steps：Graphene is as catalyst carrier and transistion metal compound in certain bar
Reaction is made solid catalyst under part, preparation is then reacted under the liquid-phase condition that inert hydrocarbon diluent is present super
High molecular weight polyethylene graphene composite material.Air specifically by Graphene filler at 110~300 DEG C
Or heat 1.0~10.0h in inert gas；Treated graphene dispersion in unreactive hydrocarbons solvent, so
After add transistion metal compound, controlling reaction temperature is 10~200 DEG C, is filtered after 0.5~6.0h of reaction
And collect solid product, N of the solid product that will be obtained at 60 DEG C21h is dried under environment, solid is obtained and is urged
Agent.Graphene exists simultaneously as catalyst carrier and reinforcer in inert hydrocarbon diluent in the invention
Liquid-phase condition under react, can both be loaded by catalyst and improve polymerization activity, and resulting compound
Graphene reaches dispersed in material, and composite property is excellent.
Similarly, CN201310014708.8 discloses gas phase situ aggregation method and prepares superhigh molecular weight polyethylene
Alkene/graphene composite material, comprises the following steps：Graphene is used as catalyst carrier and transition metal compound
Thing reacts be made solid catalyst under certain condition, then anti-under the gas phase condition existed without diluent
Ultra-high molecular weight polyethylene graphene composite material should be prepared.First by Graphene filler at 110~300 DEG C
Air or inert gas in heat 1.0~10.0h；Again by treated graphene dispersion in unreactive hydrocarbons
In solvent, transistion metal compound is subsequently adding, controlling reaction temperature is 10~200 DEG C, reaction 0.5~
Solid product is filtered and collected after 6.0h, N of the solid product that will be obtained at 60 DEG C21h is dried under environment,
Solid catalyst is obtained, vinyl polymerization is subsequently used for and is obtained ultra-high molecular weight polyethylene-graphene composite material.
Although reporting Graphene in Patents as catalyst carrier and obtaining preferable result,
It is.Inventor pass through further study showed that, individually the catalyst with Graphene as carrier substantially have it is several
The shortcoming of aspect：One is directly to make carrier using flake graphite alkene, thus to the form of prepared catalyst
Can not control, cannot get the olefin polymerization catalysis of particulate form, thus duplication catalyst can not be acquired
The particulate polymer granules of particle shape, polymer can only be the form of powdery；And Graphene and catalysis
Titanium activated centre binding ability is poor in agent, causes catalyst activity relatively low, and easily generates oligomer,
It is unfavorable for industrializing continuous production.Two is that Graphene is a kind of surface inactive carbon material, described by patent
Inert hydrocarbon solvent such as C5-C10Alkane, gasoline, kerosene or petroleum ether in it is dispersed very difficult；
Three be Graphene be monoatomic layer thickness two-dimension nano materials, in incompatible dicyandiamide solution easily occur phase
Separate and unstable, itself reunion and overlapping can be quite serious, thus catalyst active center is difficult uniformly
Graphenic surface is loaded and is distributed in, catalyst Graphene in follow-up polymerization also would become hard to dispersed and divide
It is distributed in polymeric matrix, composite knot performance can be caused unsatisfactory.
In a word, the document reported at present is directly loaded using graphene film with activated centre, then is led to
Cross in-situ polymerization and prepare Graphene/composite polyolefine material, although such material to a certain extent can be with
The performance of polyolefine material is improved, but it is more random due to being distributed between graphene sheet layer and lamella, hold very much
Reunion is easily caused, and the macromolecular chain grown between different lamellas and lamella in polymerization is due to growing direction
It is different, it is impossible to prevent the phenomenon of a large amount of molecular entanglements, cause the physical crosslinking between polyethylene molecule, this
Processing for ultra-high molecular weight polyethylene is very unfavorable, while also causing molecules align and the crystallization of polymer
Degree changes, and influences the performance of material.
CN102120573A discloses a kind of preparation method of graphene nanospheres, is by graphite and oxidation stone
Black alkene carries out reacting the graphite for obtaining graphene nanospheres attachment under microwave；The Graphene is received again
The graphite of rice ball attachment is disperseed, is centrifuged and collected supernatant liquor, obtains final product the graphene nanospheres.
A kind of method that CVD prepares globular graphite alkene flower is also disclosed that in WO2010/128650A2.It is above-mentioned
The three-dimensional material of Graphene is all formed in method by chemical reaction using self assembly mode, in practical application
In, even if can be good at dispersion is also to be disperseed in spherical mode, Graphene ball or Graphene flower are difficult dispersion
It is monomer Graphene, thus weakens the advantageous property of graphene film, limits its range of application.
The method for preparing globular graphite alkene that CN201110439517.7 is proposed, is to disperse graphene in water or wine
In essence, by ultrasonically treated or ball milling, granulating and drying is then carried out, obtain globular graphite alkene；Or by graphite
Then alkene powder, dispersed with stirring carries out granulating and drying in water, obtains globular graphite alkene.Making described in it
The equipment that grain drying is used is pyrolysis granulating and drying equipment, freezing granulating and drying equipment, it is also possible to sprayed with fluidisation
Mist Granulation Equipments.The globular graphite alkene for obtaining can be applied to catalyst carrier, medicament transport, lithium ion battery
And ultracapacitor.It is further noted that this globular graphite alkene point can be made by ultrasonically treated in invention
Dissipate the graphite alkene monomer for less than 10 layers, the fabulous advantageous property for remaining original monomer Graphene, just
In various fields are applied to, security performance is high, can continuously prepare production, and treating capacity is controllable, suitably
Large-scale production.
The content of the invention
It is an object of the invention to provide a kind of spherical graphite alkene/magnesium-supported polyethylene catalysts of halogenation, it is applicable
Graphene/ultra-high molecular weight polyethylene is prepared in home position polymerization reaction.
Inventor is by experiment and furthers investigate discovery, traditional polyethylene catalysts carrier, such as silica,
Aluminum oxide, magnesium chloride etc. only have lifting to catalysis activity, and cannot by conventional polymeric control rate of polymerization and
Two aspects of crystalline rate come improve polymerization in tangling phenomenon.Directly can not be from as carrier with Graphene
Fundamentally solve the problems, such as that high performance catalyst is prepared and material high degree of dispersion.And use Graphene/magnesium halide
Complex carrier, by effective control grapheme material surface oxygen functional group, between the remaining functional group of solution
Adjacent excessively near problem so that have larger space between loading magnesium halide by oxygen-containing functional group, so as to load
Activated centre and activated centre between have substantially interval, greatly reduce the entanglement of polymerization initial stage strand,
It is very beneficial for improving crystalline rate.
Based on this, the present invention proposes spherical graphite alkene/magnesium-supported polyethylene catalysts of halogenation, can be by original
Position polymerization prepares Graphene/ultra-high molecular weight polyethylene.
The purpose of the present invention is achieved by the following technical programs：
A kind of spherical graphite alkene/magnesium-supported polyethylene catalysts of halogenation, it is characterised in that with mass percent
Meter, catalyst composition include 5~20% ball-type graphene oxide, 10~25% magnesium, 35~55% halogens and
5~20% titanium compounds, and catalyst is prepared as follows：
1) homogeneous solution is dispersed into by graphene oxide is ultrasonically treated in water；
2) homogeneous solution and liquid nitrogen mixing quick break and solidify, solidfied material is vacuum dried, obtains spherical
Graphene oxide；
3) spherical alumina Graphene is mixed with alkyl halide magnesium in organic solvent, is mixed at 50~80 DEG C
12~48hr, obtains the mol ratio of complex carrier predecessor, the spherical alumina Graphene and alkyl halide magnesium
0.5~1.2；
4) carrier predecessor obtains graphene oxide/magnesium halide carrier through washing, 0.5~2hr of vacuum drying；
5) graphene oxide/magnesium halide carrier mixes with titanium compound at 100~120 DEG C, through filtering, very
Sky is dried to obtain catalyst.
Wherein, the organic solvent is selected from the one kind in tetrahydrofuran, n-hexane, hexamethylene, normal heptane.
Alkyl is selected from C in described alkyl halide magnesium1-C4Alkyl.
Described titanium compound meets formula TiXn(OR)4-n, R is carbon atom numerical digit 1-20 in formula
Alkyl；X is halogen；N is 0~4 integer, is chosen in particular from titanium tetrachloride, titanium tetrabromide, the tetraiodo
Change titanium, four titanium butoxides, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl epoxide titanium or trichlorine one
Ethanolato-titanium, preferably titanium tetrachloride.
Described catalyst preparation step 2) in, graphene oxide homogeneous solution and liquid nitrogen mixing quick break
And solidify, solidfied material is vacuum dried, and it is 10 to dry vacuum-5~10-7MPa, drying time is 6~10hr；
It is further preferred that vacuum drying vacuum is 10-6MPa, drying time is 8 hours.
Graphene oxide of the present invention is graphite to be aoxidized under strong acid effect and obtains, and can use prior art
The various methods of report, such as Brodie methods, Staudenmaier methods and Hummers methods.It is likely to directly
It is commercially available.
The present invention is proposed, mixed in preparation process (3) spherical alumina Graphene and the alkyl halide magnesium of catalyst
Before conjunction, it is preferable that first pre-processed spherical alumina Graphene, described pretreatment is by spherical oxygen
Graphite alkene is heat-treated 2~4 hours at 50~100 DEG C.
Present invention further propose that, in the preparation process (5) of catalyst, it is preferable that titanium compound is molten
Liquid is added in graphene oxide/magnesium halide carrier, and stirring reaction 2~4 hours, leach titanium at 100~120 DEG C
The titanium compound of compound solution and secondary addition equivalent, stirring reaction 2~4 hours at 100~120 DEG C,
Filter and washed with solvent, be vacuum dried to obtain catalyst.
The method present invention that catalyst is used for vinyl polymerization is not limited further, only enumerates the polymerization of one
Process, specifically includes：By 0.01~0.1g of polyethylene catalysts of the present invention be distributed to 2~20ml just oneself
In alkane solution, it is added in reactor, is stirred after addition 3~30ml triethyl aluminums and be passed through ethylene gas,
It is 500~1000Kpa to control air pressure in kettle, and reaction temperature is stopping after 40~80 DEG C of 0.5~2 hours of reaction
Reaction, obtains Graphene/ultra-high molecular weight polyethylene.
The present invention prepares efficient polyethylene catalysts with specific catalyst composition and its preparation technology, special
Not Shi Yongyu ultra-high molecular weight polyethylene synthesis, but it is anti-to be also suitable for the synthesis of various polyolefine materials
Should.Its beneficial technique effect is embodied in：1) graphene sheet layer pattern is solidified using spray chilling, system
For the spherical graphene particles of micron for going out three-dimensional ball shape structure, macromolecular chain is set to increase with ball in the course of the polymerization process
Centered on shape carrier material, divergence expression growth can effectively reduce what a large amount of molecular entanglements were reunited
Phenomenon；2) activated centre is adjusted by catalyst support structures modification to be distributed in carrier surface and duct,
Duplication of the conjugated polymer to carrier and catalyst is acted on, and expands the oxygen-containing official on graphene oxide layer surface
Interval between rolling into a ball, solves the reunion of Graphene, and the consistency problem with polymer.The present invention
The catalyst is showed by in-situ polymerization, the caking and superfine powder that large area is not resulted in polymerization process
As, being conducive to continuous production, industrial prospect is good, and can obtain the graphite with good antistatic property
Alkene/ultra-high molecular weight polyethylene.
Brief description of the drawings
Fig. 1 is the TEM figures of the graphene oxide of preparation in embodiment 1.
Fig. 2 is the SEM figures of the spherical alumina Graphene of preparation in embodiment 1.
Fig. 3 is the SEM figures of the graphene oxide/butylmagnesium chloride ball type carrier of preparation in embodiment 1.
Fig. 4 is the SEM of the graphene oxide/butylmagnesium chloride base polyethylene catalysts of preparation in embodiment 1
Figure.
Specific embodiment
Below by specific embodiment, the present invention will be described in more detail, so that technical solution of the present invention is more
Should be readily appreciated that, grasp, but should not be understood as limitation of the invention.Experiment side described in following embodiments
Method, unless otherwise specified, is conventional method；The reagent and material, unless otherwise specified, can be from
Commercial sources are obtained.
Embodiment 1
First, the preparation (self-control) of graphene oxide
Add the concentration of 23mL for the concentrated sulfuric acid of 98wt% in dry beaker, ice bath is cooled to 0 DEG C of left side
The right side, adds the solid mixture of 1g graphite powders and 0.5g sodium nitrate, and stirring is slowly added to 3g permanganic acid
Potassium, the stirring reaction 2h at a temperature of no more than 20 DEG C obtains the first mixed liquor, and solution is in thick ink
Green；
First mixed liquor is warmed up to 35 DEG C or so, continues stirring reaction 30min, obtain the second mixed liquor,
Mixed liquor is changed into brown from blackish green；
46mL deionized waters are slowly added dropwise to continuous in the second mixed liquor, temperature is controlled at 100 DEG C or so,
After continuing to stir 20min, stop stirring, the concentration for adding 3mL is the H of 30wt%2O2Reduction residual
Oxidant, obtain suspension, solution is changed into glassy yellow；
Suspension is filtered while hot, much filtrate is washed until nothing in filtrate with the HCl solution that concentration is 5wt%
Untill sulfate radical is detected, it is subsequently placed in 60 DEG C of drying box and fully dries, its color is by golden yellow
Become black, then pulverized and sieved with pulverizer, that is, obtain graphene oxide.As shown in Figure 1, it is seen that prepare
Graphene oxide be two-dimensional slice layer structure.
2nd, the preparation of ball-type Graphene
Graphene oxide in deionized water ultrasound 30min and be made into concentration be 10mg/mL uniform oxygen
Graphite alkene dispersion liquid；
Gun spraying method is used, spray gun air inflow is adjusted, by moment after dispersion liquid and the quick mixed aerosol of liquid nitrogen
Solidification, volatilization removal liquid nitrogen, just volatilization is complete to treat liquid nitrogen, and cured product inserted into vacuum cavity, and with dividing
Sub- pumping is to 10-6MPa, persistently takes out 8 hours, removes moisture removal, obtains good fluidity, particle size
Uniform ball-type Graphene, determines its specific surface area for 120m2/g。
Place a sample into 60 DEG C of baking oven, heat 3 hours, carry out heating response, obtain particle diameter for 60 μm
Spherical alumina Graphene, as shown in Fig. 2 it is spherical porous graphene oxide that electromicroscopic photograph is visible.
3rd, the preparation of graphene oxide/butylmagnesium chloride complex carrier
In tetrahydrofuran solution, it is by the spherical alumina Graphene of 0.8g functionalization and 50mL concentration
The butylmagnesium chloride mixing of 0.02mol/mL, continuous uniform stirs 24 hours at 60 DEG C, obtains reaction and produces
Thing；
Product is cleaned 3 times with tetrahydrofuran and n-hexane respectively, excessive butylmagnesium chloride is removed,
It is 10 in vacuum-6Vacuum drying obtains the ball type carrier of Graphene/butylmagnesium chloride for 8 hours under MPa.
As shown in Figure 3, it is seen that complex carrier continues to keep the spherical network loose structure of graphene oxide.
4th, the load of catalyst
Complex carrier is added in 50mL titanium tetrachloride solutions, stirring reaction 2 hours, leach at 115 DEG C
Titanium tetrachloride solution and secondary addition 50mL titanium tetrachloride solutions, stirring reaction 2 hours at 115 DEG C,
Cleaned with n-hexane 6 times, wash excessive titanium tetrachloride off, vacuum drying obtains spherical graphite alkenyl catalyst,
Starvation and water are stored.As shown in figure 4, being also from the visible prepared catalyst of stereoscan photograph
Spherical porous structure, preferably maintains carrier condensed state structure form.
5th, polymerisation
Gained 0.068g spherical graphite alkenyl catalyst is distributed in 13.6mL hexane solutions, 7mL is taken
It is added in the reactor of 3.5kg hexanes, adds 10mL triethyl aluminums, stirs and be passed through ethylene gas afterwards
Body, gas pressure is 800Kpa, heat 70 DEG C reaction 1.5 hours after, stop reaction, obtain Graphene/
Ultra-high molecular weight polyethylene.
Embodiment 2-4
Using preparation process same as Example 1.Difference is to be walked in the preparation of spherical graphite alkene
Suddenly, the uniform graphene oxide dispersion liquid that concentration is 8mg/mL, 6mg/mL and 4mg/mL is made into respectively,
130m is respectively obtained after spraying2/g、150m2/ g and 170m2The spherical graphite alkene of/g.
Embodiment 5
First, the preparation of graphene oxide
With embodiment 1.
2nd, the preparation of ball-type Graphene
Graphene oxide ultrasound 30min in deionized water is made into the uniform oxidation that concentration is 10mg/mL
Graphene aqueous solution, the graphene oxide dispersion for obtaining；
Gun spraying method is used, spray gun air inflow is adjusted, by moment after dispersion liquid and the quick mixed aerosol of liquid nitrogen
Solidification, volatilization removal liquid nitrogen, just volatilization is complete to treat liquid nitrogen, and cured product inserted into vacuum cavity, and with dividing
Sub- pumping is to 10-6MPa, persistently takes out 8 hours, removes moisture removal, obtains good fluidity, particle size
Uniform sample.Its specific surface area is determined for 120m2/g。
3rd, the preparation of graphene oxide/magnesium chloride complex carrier, catalyst load and polymerisation
With embodiment 1.
Comparative example 1
Spherical graphite alkene carrier is changed and does common sheet graphene oxide (Mo Xi Science and Technology Ltd.s, specific surface
Product 120-140m2/ g), preparation, catalyst load and the polymerization of graphene oxide/magnesium chloride complex carrier are anti-
Should be with embodiment 1, what is obtained the results are shown in Table 1.
Comparative example 2
In addition to saving the preparation process of graphene oxide/butylmagnesium chloride complex carrier, other preparation process
It is same as Example 1, with ball-type Graphene directly as catalyst carrier, the results are shown in Table 1.
Polymerization result is evaluated, test result such as table 1：
Table 1：The performance characterization of catalyst and graphene oxide/ultra-high molecular weight polyethylene
From the result of table 1, the ultra-high molecular weight polyethylene prepared by catalyst in-situ polymerization of the present invention
With conductance higher, illustrate that Graphene can be homogeneously dispersed in base polyethylene, form good
Conductive nano network.Compared with comparative example, the polyethylene molecular chain degree of order is high, chain entanglement low degree.This
Process highly beneficial for ultra-high molecular weight polyethylene.For ultra-high molecular weight polyethylene because molecular weight is high,
The melt viscosity that entanglement degree is caused greatly is improved and the shortcoming of unworkability improves significantly.Meanwhile, from table
Middle result understands.The supra polymer of different molecular weight can be also obtained by the catalyst using different specific surface areas
Weight northylen, realizes molecular weight Modulatory character within the specific limits.
Claims (9)
1. a kind of spherical graphite alkene/magnesium-supported polyethylene catalysts of halogenation, it is characterised in that with quality percentage
Than meter, catalyst composition includes 5~20% ball-type graphene oxide, 10~25% magnesium, 35~55% halogens
And 5~20% titanium compounds, and catalyst is prepared as follows：
1) homogeneous solution is dispersed into by graphene oxide is ultrasonically treated in water；
2) homogeneous solution and liquid nitrogen mixing quick break and solidify, solidfied material is vacuum dried, obtains spherical
Graphene oxide；
3) spherical alumina Graphene is mixed with alkyl halide magnesium in organic solvent, is mixed at 50~80 DEG C
12~48hr, obtains the mol ratio of complex carrier predecessor, the spherical alumina Graphene and alkyl halide magnesium
0.5~1.2；
4) carrier predecessor obtains graphene oxide/magnesium halide carrier through washing, 0.5~2hr of vacuum drying；
5) graphene oxide/magnesium halide carrier mixes with titanium compound at 100~120 DEG C, through filtering, very
Sky is dried to obtain catalyst,
Wherein, described titanium compound meets formula TiXn(OR)4-n, R is carbon number in formula
It is the alkyl of 1-20；X is halogen；N is 0~4 integer.
2. polyethylene catalysts according to claim 1, it is characterised in that described catalyst preparation
Step 2) solidfied material is vacuum dried, and it is 10 to dry vacuum-5~10-7MPa, drying time is 6~10hr.
3. polyethylene catalysts according to claim 2, it is characterised in that described catalyst preparation
Step 2) solidfied material is vacuum dried, and vacuum drying vacuum is 10-6MPa, drying time is 8 small
When.
4. polyethylene catalysts according to claim 1, it is characterised in that the organic solvent is selected from
One kind in tetrahydrofuran, n-hexane, hexamethylene, normal heptane.
5. polyethylene catalysts according to claim 1, it is characterised in that described alkyl halide magnesium
Middle alkyl is selected from C1-C4Alkyl.
6. polyethylene catalysts according to claim 1, it is characterised in that described titanium compound choosing
From titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide, a chlorine triethoxy
Titanium, dichlorodiethyl epoxide titanium or the ethanolato-titanium of trichlorine one.
7. polyethylene catalysts according to claim 6, it is characterised in that described titanium compound is
Titanium tetrachloride.
8. polyethylene catalysts one of according to claim 1 to 7, it is characterised in that in spherical oxygen
Before graphite alkene mixes with alkyl halide magnesium, first spherical alumina Graphene is heat-treated at 50~100 DEG C
2~4 hours.
9. polyethylene catalysts one of according to according to claim 1 to 7, it is characterised in that catalysis
Agent preparation process 5), it is that compound titanium solution is added in graphene oxide/magnesium halide carrier, 100~120
Stirring reaction 2~4 hours at DEG C, leach the titanium compound of compound titanium solution and secondary addition equivalent,
Stirring reaction 2~4 hours at 100~120 DEG C, filter and are washed with solvent, are vacuum dried to obtain catalyst.
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| CN108373151A (en) * | 2018-05-25 | 2018-08-07 | 清华-伯克利深圳学院筹备办公室 | A kind of preparation method of more fold hollow graphene microballoons |
| CN108373151B (en) * | 2018-05-25 | 2019-12-31 | 清华-伯克利深圳学院筹备办公室 | Preparation method of multi-fold hollow graphene oxide microspheres |
| CN111100346A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Preparation method of polyethylene/graphene nanocomposite |
| CN110342516A (en) * | 2019-07-09 | 2019-10-18 | 哈尔滨工程大学 | A kind of MXene material of three-dimensional crosslinking structure and preparation method thereof |
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