CN104592430A - Polyethylene catalyst carrier material with ultrahigh molecular weight and preparation method thereof - Google Patents
Polyethylene catalyst carrier material with ultrahigh molecular weight and preparation method thereof Download PDFInfo
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Abstract
The invention provides a polyethylene catalyst carrier material with an ultrahigh molecular weight and a preparation method thereof. The preparation method comprises the following steps: mixing a graphene oxide aqueous solution with a silica sol to obtain a mixed dispersion solution; spraying the mixed dispersion solution into liquid nitrogen, performing atomization, then curing instantly, volatizing to remove the liquid nitrogen, and performing vacuum drying to remove water so as to obtain a sample; heating the sample to perform activation reaction, thereby obtaining a graphene oxide/silicon dioxide spherical catalyst carrier material; mixing the graphene oxide/silicon dioxide spherical catalyst carrier material with butyl magnesium chloride in a tetrahydrofuran solution, and stirring for reaction to obtain a reaction product; and cleaning the reaction product, and heating at 600 DEG C for 2 hours to obtain the polyethylene catalyst carrier material with the ultrahigh molecular weight. The catalyst carrier provided by the invention can effectively reduce entanglement of polymer molecular chains, so that a graphene/ultrahigh-molecular-weight polyethylene composite material can be prepared.
Description
Technical field
The present invention relates to a kind of extra high-molecular polythene catalyst solid support material and preparation method thereof, belong to catalyst technical field.
Background technology
Ultrahigh molecular weight polyethylene(UHMWPE) (English name ultra-high molecular weight polyethylene is called for short UHMWPE) is the polyethylene of molecular weight more than 1,500,000.Compared with common engineering plastics, UHMWPE has advantage (the Kwideok Park not available for general material because of the molecular weight of its superelevation, Gladius Lewis, JoonB.Park, et al.UHMWPE [J] .Encyclopedia of Biomaterials and Biomedical Engineering.2012 (4): 2925-2934).But, the mechanical property of polymkeric substance is strongly depend on its characterization of molecules, while increase polymericular weight, also adverse influence can be caused to its workability, this entanglement quantity mainly causing each chain to be adjacent between chain due to the minimizing of chain termination quantity increases (Lippits, D.R.Controlling themeltingkinetics of polymers; A route to a new melt state.PhD.Thesis, Eindhoven University ofTechnology, 2007.).Therefore, how to find the balance of chainpropagation in the course of the polymerization process and chain entanglement, important factor (the Yohan Champouret solving its processing characteristics, Sanjay Rastogi, eterogeneity in theDistribution of Entanglement Density during Polymerization in Disentangled UltrahighMolecular Weight Polyethylene.Macromolecules 2011,44,4952 – 4960).Current industrial regulatory molecule quantifier elimination mainly concentrates on adjustment and " hydrogen tune " two kinds of modes of polymerization technique, but the control measures of these two kinds of modes exchange the defect that whole molecule scale reveals randomness, unstable and uncontrollability, regulating effect is bad, repeatable poor.
At present, in domestic industrial market, UHMWPE catalyzer is based on metallocene catalyst and Qi Ge-Natta catalyst, and Qi Ge-Natta-catalyzed system occupies domestic principal market with its stable polymerization activity and lower cost.In heterogeneous carrier high-efficiency Qi Ge-Natta-catalyzed polymerization-filling, catalyzer form be polymerized with it prepared by the form of polymkeric substance and particle between there is certain relation.But only under suitable catalyst preparation conditions and specific polymerizing condition, just can obtain the result of catalyzer and the reproduction of polymer beads state.Because suitable molecular weight and distribution thereof, the good polymer beads of form is for the processing of ultrahigh molecular weight polyethylene(UHMWPE) and widespread use important in inhibiting.Given this, how the structure of support of the catalyst and steric effect are better combined with the performance of catalyst active center, make it in catalytic process, produce controllability to polymer architecture and form and always be problem demanding prompt solution.
Graphene (Graphene) is a kind of novel material of the individual layer sheet structure be made up of carbon atom, is a kind ofly to form with sp2 hybridized orbital the flat film that hexangle type is honeycomb lattice by carbon atom, only has the two-dimensional material of a carbon atom thickness.Graphene is not only one the thinnest in known materials, also unusual rigid; As simple substance, the speed that it at room temperature transmits electronics is all faster than known conductor, and Graphene is very similar to carbon nanotube in the chemically, and at the similar laminated clay of configuration aspects, this constructional feature makes it have huge potentiality improving in polymer performance to have, not only improve mechanical property, and the functional attributes such as electricity and calorifics of polymkeric substance can be changed.
The preparation method of current Graphene/polymer composites mainly contains four kinds: melt-blending process, solution mixing method, emulsion hybrid system and situ aggregation method.Situ aggregation method is mixed with monomer by Graphene, adds initiator initiation reaction, finally obtained polymer composites.Compare other three kinds of methods, situ aggregation method has two important advantages, and one is by supported active center, can obtain the product of catalyzer and the reproduction of polymer beads state; Two is can be dispersed in polymeric matrix by graphene uniform, allows the character of matrix material is more stable, component is homogeneous, feature is consistent.These 2 prepare in special material particularly important.But the viscosity that the shortcoming that the current situ aggregation method used prepares Graphene/polymer composites is the polymkeric substance adding Graphene (or graphene oxide) increases, polyreaction is made to become complicated.
Because the surface properties of Graphene is stablized, so be difficult to by chemical method supported active center, compare Graphene, graphene oxide lamella then has abundant oxygen-containing functional group on the surface, and what these functional groups made Graphene and other material compounds become is very easy to.And due to Graphene be a kind ofly form with sp2 hybridized orbital the flat film that hexangle type is honeycomb lattice by carbon atom, only have the two-dimensional material of a carbon atom thickness, so have 2630m again
2super large theoretical specific surface area (Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV, the et al.Electric Field Effect in Atomically Thin Carbon Films.Science.2004 of/g; 306 (5696): 666-669.), and functional group's distribution aligns mutually, but, due to the concrete too vicinity of the oxygen-containing functional group that graphene oxide lamella enriches on the surface, be easy to the entanglement causing polymerization primary growth process Middle molecule chain.
The document reported at present all uses the graphene film that do not have specific morphology and active centre to carry out load, Graphene/composite polyolefine material is prepared again by polymerization, although such material can improve the performance of polyolefine material, but it is comparatively random owing to distributing between graphene sheet layer and lamella, be easy to cause reunion, and when being polymerized, different lamella is from the macromolecular chain grown between lamella because growing direction is different, cannot stop the phenomenon of a large amount of molecular entanglement.
In addition, because grapheme material bulk density is lower, and spheroidal particle undercapacity after making support of the catalyst, in load-reaction process, spheroid is very easily broken, carries out ultrasonic self-assembly by surface of graphene oxide oxygen-containing functional group and nanometer silicon dioxide particle, can obtain higher-strength graphene/silicon dioxide matrix material, also the excellent improved action of Graphene to polymkeric substance can not be changed, and can reduce costs greatly, increase catalyst bulk density, improve support strength.
Summary of the invention
In view of the defect that above-mentioned prior art exists, the object of the invention is to propose a kind of extra high-molecular polythene catalyst solid support material and preparation method thereof, this material contains spherical graphite thiazolinyl, this preparation method effectively can avoid the generation of propagation process Middle molecule chain entanglement, the Graphene/ultrahigh molecular weight polyethylene(UHMWPE) composite carrier prepare favorable dispersity, mixing.
Object of the present invention is achieved by the following technical programs:
A preparation method for extra high-molecular polythene catalyst solid support material, comprises the steps:
Graphene oxide water solution mixed with silicon sol, stir, ultrasonic disperse is even, obtains mixed dispersion liquid;
Mixed dispersion liquid be sprayed in liquid nitrogen, instantaneous solidification after atomization, liquid nitrogen is removed in volatilization, and cured product is inserted vacuum cavity, and moisture is removed in vacuum-drying, obtains sample;
Sample is carried out reacting by heating, obtains the spherical catalyst support material of graphene oxide/silicon-dioxide;
In tetrahydrofuran solution, mixed by spherical for graphene oxide/silicon-dioxide catalyst support material with butyl magnesium chloride solution, at 50 ~ 80 DEG C, Keep agitation reaction 12 ~ 48 hours, obtains reaction product;
Reaction product carried out cleaning the excessive butylmagnesium chloride of removing, then under ar gas environment, 400 ~ 800 DEG C of heat 30 ~ 120 minutes, obtain extra high-molecular polythene catalyst solid support material.
According to specific embodiments, the preparation method of above-mentioned extra high-molecular polythene catalyst solid support material, comprises the steps:
Graphene oxide water solution is mixed with silicon sol, stirs 30 minutes, within ultrasonic 1 hour, be uniformly dispersed, the mixed dispersion liquid obtained;
Adjustment spray gun air input is to 30mL/s, and mixed dispersion liquid be sprayed in liquid nitrogen, instantaneous solidification after atomization, liquid nitrogen is removed in volatilization, cured product is inserted vacuum cavity and (is evacuated to 10 with molecular pump
-6mPa, continues to take out 8 hours), moisture is removed in vacuum-drying, obtains good fluidity, the sample of particle size uniformity;
Sample is inserted in the baking oven of certain temperature, heating for some time, carry out reacting by heating, remove excessive oxygen-containing functional group on the one hand, moisture micro-in removing sample on the other hand, sample is played simultaneously and necessarily solidify reinforcement effect, obtain the spherical catalyst support material of graphene oxide/silicon-dioxide.
In tetrahydrofuran solution, mixed with butylmagnesium chloride by spherical for graphene oxide/silicon-dioxide catalyst support material, at 80 DEG C, Keep agitation reacts 48 hours, obtains reaction product;
Reaction product tetrahydrofuran (THF) and normal hexane are cleaned 3 times, removes excessive butylmagnesium chloride, then under ar gas environment, 600 DEG C of heat 2 hours, obtain extra high-molecular polythene catalyst solid support material.
In above-mentioned preparation method, reacting by heating is carried out to sample, namely preliminary thermal treatment is carried out to graphene oxide, can the oxygen-containing functional group on effective Quality control surface, make remaining functional group while not affecting supported catalyst active centre, reduce the problem that adjacent functionality is excessively near, thus make oxygen-containing functional group have comparatively large-spacing each other after load butylmagnesium chloride, make between the active centre of its load and active centre, there is obvious interval, thus in the process of polymeric chain growth, effectively avoid the generation of chain and chain entanglement, this feature is very beneficial for the processing characteristics improving ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE).And the composite carrier prepared, in the course of processing of polymer materials, experience the thermal treatment of comparatively high temps, make its further natural reduction become Graphene, thus present the excellent comprehensive performance of Graphene in the composite.
In above-mentioned preparation method; graphene sheet layer pattern is fixed by (in liquid nitrogen) spray chilling (under vacuum conditions) method of drying; prepare size evenly, the Graphene spheroidal particle of size tunable; macromolecular chain is made to increase centered by spherical support materials in the course of the polymerization process; divergence expression grows; the phenomenon that a large amount of molecular entanglement of very effective minimizing is reunited, solves the bottleneck problem of ultrahigh molecular weight polyethylene(UHMWPE) large-scale production.
In above-mentioned preparation method, employ silicon sol, silicon-dioxide has as traditional catalyst support material that cost is low, intensity advantages of higher, sample reacting by heating in preparation method, generates the mixture of nano silicon and Graphene, does not only affect the specific surface area of composite carrier, also the excellent modifying function of Graphene to polymkeric substance can not be changed, and reduce costs greatly, increase catalyst bulk density, improve solid support material intensity.
In above-mentioned preparation method, preferably, in the quality of solid matter, graphene oxide water solution: silicon sol=1: 10 ~ 1:5; Preferred, graphene oxide water solution: silicon sol=1: 10.
In above-mentioned preparation method, preferably, the concentration of described graphene oxide water solution is 0.05 ~ 0.5g graphene oxide/50 ~ 500mL deionized water.
In above-mentioned preparation method, preferably, vacuum drying vacuum tightness is 10
-5~ 10
-7mPa, time of drying is 6 ~ 10 hours; Preferred, vacuum drying vacuum tightness is 10
-6mPa, time of drying is 8 hours.
In above-mentioned preparation method, preferably, the temperature of reacting by heating is 30 ~ 60 DEG C, and the time is 6 ~ 12 hours.
In above-mentioned preparation method, preferably, the spherical catalyst support material of graphene oxide/silicon-dioxide and the mass volume ratio example of butyl magnesium chloride solution be 0.5 ~ 1g: 30 ~ 50mL, wherein, the concentration of described butyl magnesium chloride solution is 0.01 ~ 0.1mol/mL.
In above-mentioned preparation method, preferably, this preparation method also comprises the step preparing graphene oxide:
Be the solid mixture adding Graphite Powder 99 and SODIUMNITRATE in the vitriol oil of 98wt% to concentration, then add potassium permanganate, at the temperature of 5 ~ 20 DEG C, stirring reaction 1 ~ 2 hour, obtains the first mixed solution;
First mixed solution is warming up to 30 ~ 40 DEG C, continues stirring reaction 20 ~ 40min, obtain the second mixed solution;
In the second mixed solution, add deionized water, after continuing stirring 20 ~ 40min at 95 ~ 100 DEG C, add the H that concentration is 30wt%
2o
2, obtain suspension;
Filtered by suspension, much filtrate washing, to sulfate radical-free is detected, dry, pulverize and powderedly namely obtains graphene oxide;
Wherein, the vitriol oil, Graphite Powder 99, SODIUMNITRATE, potassium permanganate, deionized water, H
2o
2amount ratio be 20 ~ 30mL:0.5 ~ 2g:0.5 ~ 1g:3 ~ 5g:40 ~ 60mL:3 ~ 5mL.
According to embodiment, the preparation of graphene oxide comprises:
In 98% vitriol oil, adding the solid mixture of Graphite Powder 99 and SODIUMNITRATE, then add potassium permanganate, being no more than stirring reaction 2h at the temperature of 20 DEG C, obtaining the first mixed solution;
First mixed solution is warming up to 35 DEG C, continues stirring reaction 30min, obtain the second mixed solution;
In the second mixed solution, add deionized water, after continuing to stir 20min at 100 DEG C, add the H that concentration is 30wt%
2o
2, obtain suspension;
Filtered by suspension, much filtrate washing is to sulfate radical-free is detected, dry, shatter, sieve, and namely obtains graphene oxide;
Wherein, the consumption of the vitriol oil: the consumption of Graphite Powder 99: the consumption of SODIUMNITRATE: the consumption of potassium permanganate: the consumption of deionized water: H
2o
2consumption=23mL: 1g: 0.5g: 3g: 46mL: 3mL.
In above-mentioned preparation method, graphene oxide solution prepares like this: get 0.05 ~ 0.5g graphene oxide powder, joins in 50 ~ 500mL deionized water, after stirring, ultrasonic 0.5 ~ 2 hour, obtains graphene oxide solution.
According to specific embodiments, the preparation of above-mentioned graphene oxide adopts traditional Hummers method, comprising:
In the beaker of drying, add the vitriol oil of 23mL, ice bath is cooled to about 0 DEG C, adds the solid mixture of 1g Graphite Powder 99 and 0.5g SODIUMNITRATE, stir, slowly add 3g potassium permanganate, be no more than stirring reaction 2h at the temperature of 20 DEG C, obtain the first mixed solution, solution is thick blackish green;
First mixed solution is warmed up to about 35 DEG C, and continue stirring reaction 30min, obtain the second mixed solution, mixed solution becomes brown from blackish green;
In the second mixed solution, slowly drip 46mL deionized water continuously, control temperature, at about 100 DEG C, after continuing to stir 20min, stops stirring, then adds the 30%H of 3mL
2o
2the oxygenant that reduction is residual, obtain suspension, solution becomes glassy yellow;
By suspension filtered while hot, much filtrate 5%HCl solution washing until in filtrate sulfate radical-free be detected, the loft drier being then placed in 60 DEG C is fully dry, and its color becomes black by golden yellow, pulverize and sieve with pulverizer again, namely obtain graphene oxide.By graphene oxide ultrasonic disperse in deionized water, namely graphene oxide water solution is obtained.
In above-mentioned preparation method, preferably, this preparation method also comprises the step preparing silicon sol: ethanol, ammoniacal liquor, deionized water are stirred 5 ~ 10 minutes at 30 ~ 50 DEG C, then add tetraethoxy, continue stirring reaction 8 ~ 12 hours, namely obtain silicon sol; Wherein, the amount ratio of ethanol, ammoniacal liquor, deionized water, tetraethoxy is 80 ~ 100mL:3 ~ 5mL:3 ~ 6mL:1 ~ 3mL.
According to specific embodiments, above-mentioned silicon sol adopts stober legal system standby, comprising:
In 90mL ethanol, add 3.8mL ammoniacal liquor, 4.6mL deionized water, put into 50 DEG C of thermostatic baths and stir, after 5 minutes, add 2mL tetraethoxy, react and form silicon sol after 12 hours.According to the temperature of isothermal reaction, the particle diameter of silicon sol can be adjusted.As 50 DEG C of reactions, obtain the silicon sol of particle diameter 30nm, 60 DEG C of reactions, obtain the silicon sol of particle diameter 60nm.
In above-mentioned preparation method, preferably, this preparation method also comprises the step of preparation butylmagnesium chloride: be that the n-propylcarbinyl chloride of 1:1 ~ 1:5 and the mixing solutions of tetrahydrofuran (THF) instill with the speed constant pressure funnel of 0.5 ~ 1mL/min and magnesium powder is housed, dewaters in the reaction vessel of tetrahydrofuran (THF) and iodine by volume ratio, 50 ~ 80 DEG C of continuously stirring reactions 2 ~ 4 hours, obtain butyl magnesium chloride solution; Wherein the amount ratio of the mixing solutions of n-propylcarbinyl chloride and tetrahydrofuran (THF), magnesium powder, the tetrahydrofuran (THF) that dewaters, iodine is 20 ~ 28mL:1 ~ 1.5g:15 ~ 20mL:0.05 ~ 0.1g.Preferred, the preparation of butylmagnesium chloride comprises: in flask, first add 1 ~ 1.5g magnesium powder, the tetrahydrofuran (THF) after 15 ~ 20mL dewaters, 0.05 ~ 0.1g iodine grain.And then in beaker, add 5 ~ 8mL n-propylcarbinyl chloride and 15 ~ 20mL tetrahydrofuran (THF), be moved in constant pressure funnel after mixing.Last again in solution slowly instill in the flask that magnesium powder is housed, after instillation about 5 ~ 8mL, be warming up to 50 ~ 80 DEG C and continuously stirring 2 ~ 4 hours, filter out residual solids, obtain butyl magnesium chloride solution, by solution sealed storage.
According to embodiment, this preparation method also comprises the step of preparation butylmagnesium chloride: in flask, first add 1.2g magnesium powder, the tetrahydrofuran (THF) after 15mL dewaters, 0.08g iodine grain.Then in beaker, add 5mL n-propylcarbinyl chloride and 15mL tetrahydrofuran solution, be moved into after mixing in constant pressure funnel, this solution is slowly instilled with the speed of 0.8mL/min in the flask of magnesium powder, start after instilling about 5mL to stir 4 hours at 80 DEG C, filter out residual solids, obtain butyl magnesium chloride solution, by solution sealed storage.
The extra high-molecular polythene catalyst solid support material that the present invention also provides above-mentioned preparation method to obtain, this solid support material is the spherical complex carrier material of the graphene/silicon dioxide/butylmagnesium chloride of molecular weight 200 ~ 4,000,000.
The present invention consists of catalyzer and structure design carrys out the extra high-molecular polythene catalyst of synthesizing efficient, carrys out synthetic molecular weight and molecular weight distribution is controlled and polymer morphology and the good ultrahigh molecular weight polyethylene(UHMWPE) of processing characteristics by the optimization of the composite of catalyst component and polymerization technique; The viscosity of the polymkeric substance after adding Graphene can be reduced in situ aggregation method, reduce polyreaction complexity, the interval between the oxygen-containing functional group on graphene oxide lamella surface can be expanded, and fixing graphene sheet layer pattern, avoid the generation of polymeric chain propagation process medium chain and chain entanglement, and stop the phenomenon that a large amount of molecular entanglement is reunited, in addition, catalyst support material granule strength can also be improved.
Outstanding effect of the present invention is:
1) preparation method of the present invention can obtain the solid support material of polymer beads " reproduction " granules of catalyst form.After being prepared into porous spherical carrier, relatively directly use on the graphene film active centre hole wall that can be dispersed in ball type carrier surface or hole.
Compared with conventional ultra high molecular weight polyethylene catalyzer, traditional catalyst is as silicon-dioxide, aluminum oxide, magnesium chloride etc., only there is lifting to catalytic activity, and cannot to the molecular weight of ultrahigh molecular weight polyethylene(UHMWPE) polymkeric substance, the critical natures such as molecular weight distribution are improved, conventional polymeric is made to need to improve the tangling phenomenon in polymerization by control rate of polymerization and crystallization rate two aspects, catalyzer of the present invention controls surfaces of carrier materials oxygen-containing functional group by effective, adjacent excessively near problem between remaining functional group can be solved, make by having comparatively large-spacing between oxygen-containing functional group load butylmagnesium chloride, thus make between the active centre of its load and active centre, there is obvious interval, greatly reduce the entanglement of polymerization initial stage molecular chain, be very beneficial for improving crystallization rate.
2) method of atomizing freeze drying is adopted to be fixed by graphene sheet layer pattern; macromolecular chain is made to increase centered by spherical support materials in the course of the polymerization process; divergence expression grows; effectively can reduce the phenomenon that a large amount of molecular entanglement is reunited, solve the bottleneck problem of ultrahigh molecular weight polyethylene(UHMWPE) large-scale production.
3) prepare the spherical Graphene particle of micron of three-dimensional ball shape structure, and rely on Graphene to advise positive reticulated structure, active centre is uniformly distributed, effectively reduces molecular entanglement.
4) catalyst support material of the present invention not only can carry out synthetic molecular weight by the optimization of the composite of catalyst component and polymerization technique and molecular weight distribution is controlled and polymer morphology and the good ultrahigh molecular weight polyethylene(UHMWPE) of processing characteristics, and due to the existence of Graphene, can use the way of in-situ polymerization that Graphene and ultrahigh molecular weight polyethylene(UHMWPE) are carried out compound uniformly and effectively, Graphene/ultrahigh molecular weight polyethylene(UHMWPE) high performance composite can be prepared.
Accompanying drawing explanation
Fig. 1 a is the TEM figure of the graphene oxide of embodiment 1;
Fig. 1 b is the XRD figure of the graphene oxide of embodiment 1;
Fig. 1 c is the TEM figure of the silicon sol of embodiment 2;
Fig. 1 d is the graphene oxide of embodiment 3 and the TEM figure of silicon sol composite solution;
Fig. 2 a is the spherical catalyst support material (SGO-SiO of graphene oxide/silicon-dioxide of embodiment 3
2) SEM figure;
Fig. 2 b is SEM figure under the spherical catalyst support material high power of graphene oxide/silicon-dioxide of embodiment 3;
Fig. 2 c is that the spherical complex carrier material SEM of the graphene/silicon dioxide/butylmagnesium chloride of embodiment 3 schemes;
Fig. 2 d is the spherical catalyst EDX element phenogram of the graphene/silicon dioxide/butylmagnesium chloride/titanium tetrachloride of embodiment 4;
Fig. 2 e is the SEM figure of the spherical catalyst of the graphene/silicon dioxide/butylmagnesium chloride/titanium tetrachloride of embodiment 4.
Embodiment
Below by specific embodiment, method of the present invention is described, be easier to make technical solution of the present invention understand, grasp, but the present invention is not limited thereto.Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment 1
The graphene oxide that the present embodiment provides a kind of extra high-molecular polythene catalyst solid support material used, this graphene oxide is prepared by following method:
The concentration adding 23mL in the beaker of drying is the vitriol oil of 98wt%, ice bath is cooled to about 0 DEG C, add the solid mixture of 1g Graphite Powder 99 and 0.5g SODIUMNITRATE, stir, slowly add 3g potassium permanganate, being no more than stirring reaction 2h at the temperature of 20 DEG C, obtain the first mixed solution, solution is thick blackish green;
First mixed solution is warmed up to about 35 DEG C, and continue stirring reaction 30min, obtain the second mixed solution, mixed solution becomes brown from blackish green;
In the second mixed solution, slowly drip 46mL deionized water continuously, control temperature, at about 100 DEG C, after continuing to stir 20min, stop stirring, then the concentration adding 3mL is the H of 30wt%
2o
2the oxygenant that reduction is residual, obtain suspension, solution becomes glassy yellow;
By suspension filtered while hot, much filtrate concentration be 5wt% HCl solution washing until in filtrate sulfate radical-free be detected, then the loft drier being placed in 60 DEG C is fully dry, its color becomes black by golden yellow, pulverize and sieve with pulverizer again, namely obtain graphene oxide (as shown in Fig. 1 a, 1b).The lamella of the graphene oxide of gained is of a size of 5 ~ 50 μm.
Embodiment 2
The silicon sol that the present embodiment provides a kind of extra high-molecular polythene catalyst solid support material used, this silicon sol is prepared by following method:
In 90mL ethanol, add 3.8mL ammoniacal liquor, 4.6mL deionized water, put into 50 DEG C of thermostatic baths and stir, after 5 minutes, add 2mL tetraethoxy, react after 12 hours and form silicon sol (30nm particle diameter), as illustrated in figure 1 c.
Embodiment 3
The present embodiment provides a kind of extra high-molecular polythene catalyst solid support material, and this solid support material is the spherical complex carrier material of graphene/silicon dioxide/butylmagnesium chloride, and this solid support material is prepared by following method:
The graphene oxide of embodiment 1 gained is made in deionized water for ultrasonic 30min the uniform graphene oxide water solution that concentration is 10mg/mL, graphene oxide water solution is mixed with the solid content mass ratio of 1:7.5 with the silicon sol of embodiment 2 gained, stir 30 minutes, within ultrasonic 1 hour, be uniformly dispersed, the mixed dispersion liquid (as shown in Figure 1 d) obtained;
Adjustment spray gun air input, mixed dispersion liquid be sprayed in liquid nitrogen, make solution first be atomized rear instantaneous solidification, liquid nitrogen is removed in volatilization, treats that liquid nitrogen has just volatilized completely, cured product is inserted vacuum cavity, and is evacuated to 10 with molecular pump
-6mPa, continues to take out 8 hours, removes moisture, obtains good fluidity, the sample of particle size uniformity;
Sample is inserted in the baking oven of 200 DEG C, heating 2h, carry out reacting by heating, remove excessive oxygen-containing functional group on the one hand, moisture micro-in removing sample on the other hand, plays sample simultaneously and necessarily solidifies reinforcement effect, obtain the spherical catalyst support material of graphene oxide/silicon-dioxide (as shown in Fig. 2 a, Fig. 2 b), tested by BET, specific surface area is 459.28m
2/ g.
In tetrahydrofuran solution, the butylmagnesium chloride being 0.02mol/mL by the spherical catalyst support material of 0.8g graphene oxide/silicon-dioxide and 50mL concentration mixes, and at 60 DEG C, continuous uniform stirs 24 hours, obtains reaction product;
Reaction product is cleaned 3 times with tetrahydrofuran (THF) and normal hexane respectively, remove excessive butylmagnesium chloride, under ar gas environment, 600 DEG C of heat 2 hours, obtain the spherical complex carrier material (as shown in Figure 2 c) of graphene/silicon dioxide/butylmagnesium chloride.
Embodiment 4
The present embodiment, using the support of the catalyst of the composite carrier of embodiment 3 as preparation UHMWPE, carries out catalytically active assessment.
The Primary Catalysts titanium tetrachloride of the present embodiment, internal electron donor diisobutyl phthalate, composite carrier supported catalyst, wherein Ti content is 9%, obtain UHMWPE catalyzer (spherical catalyst of graphene/silicon dioxide/butylmagnesium chloride/titanium tetrachloride, as shown in Fig. 2 d, 2e).
UHMWPE catalyzer is used for UHMWPE polymerization, conventionally, controlling still internal gas pressure is 0.8MPa, and temperature is adjusted to 70 DEG C, and reaction 2h, obtains UHMWPE.
Evaluate catalytic result, test result is: catalytic activity 2.45 × 10
4g/ (mmolTih), polymerization kinetics is comparatively steady, and Young's modulus is 826 ± 34MPa, and tensile strength 87 ± 9MPa records resulting polymers molecular weight 2.3 × 10 by conventional viscosity method
6g/mol, recording electric conductivity by conventional four probe method is 0.2S/m.
Therefore, the larger graphene/silicon dioxide spherical carrier of catalyst material of specific surface area is prepared by graphene oxide and the ultrasonic self-assembly of silicon-dioxide and atomizing freeze drying method, and by supported on carriers catalyzer, prepare mixed uniformly Graphene/ultra-high molecular weight polyethylene composite material.
Claims (10)
1. a preparation method for extra high-molecular polythene catalyst solid support material, comprises the steps:
Graphene oxide water solution mixed with silicon sol, stir, ultrasonic disperse is even, obtains mixed dispersion liquid;
Mixed dispersion liquid be sprayed in liquid nitrogen, instantaneous solidification after atomization, liquid nitrogen is removed in volatilization, and cured product is inserted vacuum cavity, and moisture is removed in vacuum-drying, obtains sample;
Sample is carried out reacting by heating, obtains the spherical catalyst support material of graphene oxide/silicon-dioxide;
In tetrahydrofuran solution, mixed by spherical for graphene oxide/silicon-dioxide catalyst support material with butyl magnesium chloride solution, at 50 ~ 80 DEG C, Keep agitation reaction 12 ~ 48 hours, obtains reaction product;
Reaction product carried out cleaning the excessive butylmagnesium chloride of removing, then under ar gas environment, 400 ~ 800 DEG C of heat 30 ~ 120 minutes, obtain extra high-molecular polythene catalyst solid support material.
2. preparation method according to claim 1, is characterized in that: in the quality of solid matter, graphene oxide water solution: silicon sol=1: 10 ~ 1:5.
3. preparation method according to claim 2, is characterized in that: the concentration of described graphene oxide water solution is 0.05 ~ 0.5g graphene oxide/50 ~ 500mL deionized water.
4. preparation method according to claim 1, is characterized in that: vacuum drying vacuum tightness is 10
-5~ 10
-7mPa, time of drying is 6 ~ 10 hours.
5. preparation method according to claim 1, is characterized in that: the temperature of reacting by heating is 30 ~ 60 DEG C, and the time is 6 ~ 12 hours.
6. preparation method according to claim 1, it is characterized in that: the ratio of the spherical catalyst support material of graphene oxide/silicon-dioxide and butyl magnesium chloride solution is 0.5 ~ 1g: 30 ~ 50mL, wherein, the concentration of described butyl magnesium chloride solution is 0.01 ~ 0.1mol/mL.
7. preparation method according to claim 1, is characterized in that: this preparation method also comprises the step preparing graphene oxide:
Be the solid mixture adding Graphite Powder 99 and SODIUMNITRATE in the vitriol oil of 98wt% to concentration, then add potassium permanganate, at the temperature of 5 ~ 20 DEG C, stirring reaction 1 ~ 2 hour, obtains the first mixed solution;
First mixed solution is warming up to 30 ~ 40 DEG C, continues stirring reaction 20 ~ 40min, obtain the second mixed solution;
In the second mixed solution, add deionized water, after continuing stirring 20 ~ 40min at 95 ~ 100 DEG C, add the H that concentration is 30wt%
2o
2, obtain suspension;
Filtered by suspension, much filtrate washing, to sulfate radical-free is detected, dry, pulverize and powderedly namely obtains graphene oxide;
Wherein, the vitriol oil, Graphite Powder 99, SODIUMNITRATE, potassium permanganate, deionized water, H
2o
2amount ratio be 20 ~ 30mL:0.5 ~ 2g:0.5 ~ 1g:3 ~ 5g:40 ~ 60mL:3 ~ 5mL.
8. preparation method according to claim 1, is characterized in that: this preparation method also comprises the step preparing silicon sol:
By ethanol, ammoniacal liquor, deionized water 30 ~ 50 DEG C of mix and blends 5 ~ 10 minutes, then add tetraethoxy, continue stirring reaction 8 ~ 12 hours, namely obtain silicon sol;
Wherein, the amount ratio of ethanol, ammoniacal liquor, deionized water, tetraethoxy is 80 ~ 100mL:3 ~ 5mL:3 ~ 6mL:1 ~ 3mL.
9. preparation method according to claim 1, is characterized in that: this preparation method also comprises the step of preparation butylmagnesium chloride:
Be that the n-propylcarbinyl chloride of 1:1 ~ 1:5 and the mixing solutions of tetrahydrofuran (THF) instill with the speed of 0.5 ~ 1ml/min and magnesium powder is housed, dewaters in the reaction vessel of tetrahydrofuran (THF) and iodine by volume ratio, 50 ~ 80 DEG C of continuously stirring reactions 2 ~ 4 hours, obtain butyl magnesium chloride solution;
Wherein, the amount ratio of the mixing solutions of n-propylcarbinyl chloride and tetrahydrofuran (THF), magnesium powder, the tetrahydrofuran (THF) that dewaters, iodine is 20 ~ 28mL:1 ~ 1.5g:15 ~ 20mL:0.05 ~ 0.1g.
10. the extra high-molecular polythene catalyst solid support material of the molecular weight that the preparation method described in any one of claim 1 ~ 9 obtains, is characterized in that: this solid support material is the spherical complex carrier material of the graphene/silicon dioxide/butylmagnesium chloride of molecular weight 200 ~ 4,000,000.
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