CN104926968A - Novel carbon material/polyisoprene nano-grade composite material preparation method - Google Patents
Novel carbon material/polyisoprene nano-grade composite material preparation method Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 50
- 229920001195 polyisoprene Polymers 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 30
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 22
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 6
- -1 graphene oxide/hydroxylated carbon nanotube Chemical class 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 238000006555 catalytic reaction Methods 0.000 claims description 19
- 150000001336 alkenes Chemical class 0.000 claims description 18
- 239000002041 carbon nanotube Substances 0.000 claims description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 16
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 150000001805 chlorine compounds Chemical class 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 230000033444 hydroxylation Effects 0.000 claims description 11
- 238000005805 hydroxylation reaction Methods 0.000 claims description 11
- 238000002203 pretreatment Methods 0.000 claims description 11
- 229940073589 magnesium chloride anhydrous Drugs 0.000 claims description 9
- 239000002114 nanocomposite Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 229940091250 magnesium supplement Drugs 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 4
- 229960002337 magnesium chloride Drugs 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims 1
- 238000003801 milling Methods 0.000 claims 1
- 239000011943 nanocatalyst Substances 0.000 claims 1
- 238000004445 quantitative analysis Methods 0.000 claims 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 claims 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000002071 nanotube Substances 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002508 compound effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
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- 231100000614 poison Toxicity 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 238000007493 shaping process Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a novel carbon material/polyisoprene nano-grade composite material preparation method. The novel carbon material/polyisoprene nano-grade composite material mainly comprises three components of graphene oxide/hydroxylated nanotube/polyisoprene. According to the invention, a graphene oxide/hydroxylated carbon nanotube/anhydrous magnesium chloride loaded Ziegler-Natta catalyst is prepared with a high-energy ball milling in-situ reaction process. Under the existence of an alkyl metal compound cocatalyst, the prepared loaded catalyst can initiate isoprene polymerization, such that the carbon material/polyisoprene nano-grade composite material is obtained. With the method, carbon material dispersion in the composition is more uniform. The composition has better mechanical performances than those of polyisoprene obtained with other Ziegler-Natta catalysts.
Description
Technical field
The present invention relates to the preparation method of a kind of new carbon/polyisoprene nano composite material, be specifically related to a kind of employing and prepare graphene oxide/magnesium-supported Ziegler-Natta catalyst of hydroxylation carbon nanotube/anhydrous chlorides of rase through high-energy ball milling reaction in－situ technique, the supported catalyst of preparation can cause isoprene polymerization under alkyl metal cpd promotor exists, and prepares the method for a kind of carbon material/polyisoprene nano composite material.
Background technology
Along with the high speed exhibition of science and technology, the requirement of people to polymer materials application performance improves constantly.Be devoted to existing excellent in toughness polymer materials, have again higher hardness concurrently; Both required that polymkeric substance possessed excellent mechanical performance, required again that it was easy to machine-shaping.And these are to the requirement of material over-all properties, single polymkeric substance is often difficult to meet.Therefore polymkeric substance carries out composite modified research and more and more comes into one's own, and become the main direction of studying of development of new high-performance polymer material, and the preparation method of carbon nanotube and Graphene and composite polyolefine material mainly contains two kinds: physical blending process and situ aggregation method.Situ aggregation method refers to and is dispersed in polymer monomer by carbon material, adds initiator, and trigger monomer in-situ polymerization generates polymer, obtains polymkeric substance/carbon material matrix material.This method is considered to improve carbon material dispersion and strengthen itself and polymeric matrix the most effective interactional method.
Graphene, as a kind of novel functional material, has high intensity, excellent conductivity, but also has good thermal conductivity.Current, Graphene/polymer composites has obtained applying comparatively widely, Graphene is as nano reinforcement component, and a small amount of interpolation can make the electric property of polymkeric substance, heat conductivility, mechanical property, thermal characteristics and gas barrier property be largely increased.In addition, Graphene only has molecular level thickness, and two basal plane other material all adsorbable, therefore has the incomparable advantage of other nano materials using it as support of the catalyst.
Carbon nanotube (Carbon nanotubes, CNTs) be monodimension nanometer material, high length-diameter ratio (tensile strength of single wall CNTs can reach 100 times of steel), density low (density is only 1/7th of steel), good toughness, intensity are high, and (its Young's modulus is up to 1.2TPa, tensile break strength reaches 50-200GPa) etc. feature.Nanoparticle has special surface effects, quantum size effect, small-size effect and macro quanta tunnel effect etc. simultaneously, and the matrix material be composited by it shows unique performance in mechanics, optics, calorifics and electromagnetism etc.
This invention have employed graphite oxide and the hydroxylation carbon nanotube carrier as alkene catalyst, adopts the mode of first grinding altogether with Magnesium Chloride Anhydrous after pretreatment to prepare carbon material alkene catalyst.Effect of Pretreatment is mainly reflected in following two aspects: play for graphite oxide and hydroxylation carbon nanotube the effect that removing wherein may poison active ingredient impurity, and therefore pretreated carbon nanotube is high for the preparation of Ziegler-Natta catalyst catalytic efficiency when catalysis isoprene polymerization; 2, pretreating reagent can directly and graphite oxide and hydroxylation carbon nano tube surface various hydroxyl generation chemical reaction, polymerization is prepared in the process of carbon material/polyisoprene matrix material in position, this catalyzer is formed the activated species of isoprene polymerization under aluminum compound effect, useful load amount is easy to control, the lower height of catalytic efficiency.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of new carbon/polyisoprene nano composite material.
The present invention successfully prepares the carrier loaded Ziegler-Natta catalyst of carbon material/Magnesium Chloride Anhydrous by high-energy ball milling method.By regulating the ratio of carbon material/Magnesium Chloride Anhydrous, the pretreatment mode of carbon material and Ball-milling Time, thus control effective distribution in anhydrous chlorides of rase magnesium carrier of carbon material in mixed system and internal microstructure.Carbon material is through pre-treatment and high-energy ball milling reaches the effective dispersion of carbon material in supported catalyst, thus it is dispersed and prepare high-performance polymer in the polymkeric substance of this catalyst preparing to realize carbon material.
For achieving the above object, the present invention is achieved by the following technical solutions:
A kind of olefin polymerization catalysis that is carrier with carbon material/Magnesium Chloride Anhydrous, it is characterized in that described olefin polymerization catalysis with carbon material/Magnesium Chloride Anhydrous for carrier, load Ziegler-Natta catalyst, described Ziegler-Natta catalyst is titanium metal compound, the mass percent that carbon material carrier accounts for catalyzer total mass is 0.1 ~ 50%, the mass percentage that described Ziegler-Natta catalyst accounts for catalyzer total mass is 0.1 ~ 3.8%, and surplus is anhydrous chlorides of rase magnesium carrier; Described titanium metal compound general formula as catalyst active center is TiX
n, X is halogen, n=0,1,2 or 3.
Present invention also offers the preparation method of described olefin polymerization catalysis, it comprises the steps:
1) by the vacuum-drying of described carbon material carrier, one of following two kinds of modes are adopted to carry out pre-treatment:
A. by the vacuum-treat of carbon material carrier, introduce organic solvent and pre-treatment medium, at 40-60 DEG C, anhydrous and oxygen-free soaks and leaves standstill 10 ~ 50 hours, has reacted rear decompression and has steamed solvent and vacuum-drying;
B. by the vacuum-treat of carbon material carrier, introduce organic solvent and pre-treatment medium, at 40-60 DEG C, anhydrous and oxygen-free stirs 2 ~ 10 hours, has reacted rear decompression and has steamed solvent and vacuum-drying.
Under two kinds of modes, the mass ratio of described pre-treatment medium and carbon material is 0.5 ~ 5:1; Pre-treatment medium adopts titanium tetrahalide or aluminum contained compound Al (OR ')
nr
3-n, 0≤n≤3, R and R ' carbonatoms is the alkyl of 2 ~ 10.
2) by described step 1) carbon material carrier, anhydrous chlorides of rase magnesium carrier and the Ziegler-Natta catalyst prepared add in ball grinder, adopts the load of high-energy ball milling method original position to obtain described olefin polymerization catalysis.
Invention further provides described olefin polymerization catalysis and preparing the application in polyisoprene matrix material, described olefin polymerization catalysis and aluminum contained compound is composite is polymerized for catalysis isoprene monomer.
Embodiment
The carbon material supported Catalysts and its preparation method that following specific embodiment is just invented makes detailed explanation.But these embodiments do not limit the scope of the invention, also should not be construed as and only have condition provided by the invention, parameter or numerical value to implement the present invention.
Embodiment 1
The present embodiment comprises the following steps with the preparation method of the polyolefin catalyst of anhydrous chlorides of rase magnesium carrier:
1, add 50.0 grams of Magnesium Chloride Anhydrouss under nitrogen environment to dry and replace in the ball grinder of sealing after three times through high pure nitrogen, then inject 2.5ml analytical pure titanium tetrachloride;
2, reinforced complete, ball grinder is put into planetary ball mill, grinding 5h.Derive the catalyzer prepared.
The magnesium-supported Ziegler-Natta catalyst of anhydrous chlorides of rase that the present embodiment is obtained, titanium elements mass percentage is 1.98wt%, and magnesium elements mass percentage is 23.48wt%.Described Magnesium Chloride Anhydrous carried catalyst mode of appearance is Powdered.
This catalyzer can be used to prepare polyisoprene, specifically can be prepared in the steps below:
Under vacuum state, 750ml isoprene monomer is added in reactor, add 1.2ml triisobutyl aluminium and 0.4 gram of magnesium-supported Ziegler-Natta catalyst of anhydrous chlorides of rase successively, through 0 DEG C of pre-polymerization 20min, polymeric reaction temperature is 25 DEG C, polyreaction 6h, adds acidic ethanol and stop polyreaction after being polymerized, vacuum-drying at 30 DEG C, obtains about 90 grams of carbon material/polyisoprene matrix materials.
In this reaction, product catalyst efficiency is 1875g/g.Ti.h, and after the mixture sample obtained 135 DEG C of melting compressing tablets, the tensile strength of II type dumbbell shaped mixture batten is 27.0MPa, and ash content is 0.52%
Embodiment 2
The present embodiment comprises the following steps with the preparation method of the olefin polymerization catalysis that carbon material/Magnesium Chloride Anhydrous is carrier:
1, join in 100ml polymerization flask by 5.0 grams of dried graphene oxides and hydroxylation carbon nanotube mass than the carbon material being 1 under nitrogen environment, normal temperature high vacuum 24 hours, 40 DEG C of waters bath with thermostatic control put into by reaction flask after high pure nitrogen replaces three times.After add 20ml anhydrous hexane, stir after 5 minutes, add 5ml titanium tetrachloride, at 40 DEG C, constant temperature stirs 24 hours, after having reacted, solvent steams at reduced pressure conditions, further under a high vacuum 100 DEG C keep stirring drying in 30 minutes after obtain the pre-treatment thing of carbon material support of the catalyst;
2, add 45.0 grams of Magnesium Chloride Anhydrouss and above-mentioned pretreated carbon material under nitrogen environment to dry and replace in the ball grinder of sealing after three times through high pure nitrogen, then inject 2.5ml analytical pure titanium tetrachloride.Reinforced complete, ball grinder is put into planetary ball mill, grinding 5h.Derive the catalyzer prepared.
The magnesium-supported Ziegler-Natta catalyst of this carbon material/anhydrous chlorides of rase, titanium elements mass percentage is 2.36wt%, and magnesium elements mass percentage is 20.88wt%, and carbon mass percentage is 9.88%.
This catalyzer can be used to prepare polyisoprene, specifically can be prepared in the steps below:
Under vacuum state, 750ml isoprene monomer is added in reactor, add 1.2ml triisobutyl aluminium and 0.4 gram of magnesium-supported Ziegler-Natta catalyst of carbon material/anhydrous chlorides of rase successively, through 0 DEG C of pre-polymerization 20min, polymeric reaction temperature is 25 DEG C, polyreaction 6h, adds acidic ethanol and stop polyreaction after being polymerized, vacuum-drying at 30 DEG C, obtains about 125 grams of carbon material content about 0.04% Dark grey polyisoprene nano composite materials provided by the invention.
In this reaction, product catalyst efficiency is 2604g/g.Ti.h, and after the mixture sample obtained 135 DEG C of melting compressing tablets, the tensile strength of II type dumbbell shaped mixture batten is 39.8MPa, and ash content is 0.25%.
Embodiment 3
The present embodiment comprises the following steps with the preparation method of the olefin polymerization catalysis that carbon material/Magnesium Chloride Anhydrous is carrier:
1, under nitrogen environment by 5.0 grams of carbon materials and hydroxylation carbon nanotube mass than be 1 carbon material and hydroxylation carbon nanotube mass fully drier than the carbon material being 1.
2, add 45.0 grams of Magnesium Chloride Anhydrouss under nitrogen environment and above-mentionedly replace in the ball grinder of three time after sealing to dry through high pure nitrogen than the carbon material being 1 without pre-treatment carbon material and hydroxylation carbon nanotube mass, then injecting 2.5ml analytical pure titanium tetrachloride.
3, reinforced complete, grinding 5h.Derive the catalyzer prepared.
This carbon material and hydroxylation carbon nanotube mass Ziegler-Natta catalyst more magnesium-supported than the carbon material/anhydrous chlorides of rase being 1, titanium elements mass percentage is 2.32wt%, magnesium elements mass percentage is 20.80wt%, and carbon mass percentage is 9.60%.
This catalyzer can be used to prepare polyisoprene, specifically can be prepared in the steps below:
Under vacuum state, 750ml isoprene monomer is added in reactor, add 1.2ml triisobutyl aluminium and 0.4 gram of magnesium-supported Ziegler-Natta catalyst of carbon material/anhydrous chlorides of rase successively, through 0 DEG C of pre-polymerization 20min, polymeric reaction temperature is 25 DEG C, polyreaction 6h, adds acidic ethanol and stop polyreaction after being polymerized, vacuum-drying at 30 DEG C, obtains about 118 grams of Dark grey polyisoprene nano composite materials provided by the invention;
In this reaction, product catalyst efficiency is 2458g/g.Ti.h, and after the mixture sample obtained 135 DEG C of melting compressing tablets, the tensile strength of II type dumbbell shaped mixture batten is 38.6MPa, and ash content is 0.32%.
Above embodiment only in order to technical scheme of the present invention to be described, but not is limited; Although with reference to previous embodiment to invention has been detailed description, for the person of ordinary skill of the art, still can modify to the technical scheme described in previous embodiment, or equivalent replacement is carried out to wherein portion of techniques feature; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of the present invention's technical scheme required for protection.
Claims (8)
1. the preparation method of new carbon/polyisoprene nano composite material, it is characterized in that described olefin polymerization catalysis with carbon material/Magnesium Chloride Anhydrous for composite carrier load titanium system Ziegler-Natta catalyst, upper catalyzer and aluminum contained compound is composite is polymerized for catalysis isoprene monomer.
2. olefin polymerization catalysis according to claim 1, it is characterized in that: the mass percent that carbon material carrier accounts for catalyzer total mass is 0.1 ~ 50%, the mass percentage that described Ziegler-Natta catalyst accounts for catalyzer total mass is 0.1 ~ 3.8%, and surplus is anhydrous chlorides of rase magnesium carrier; Described titanium system Ziegler-Natta catalyst active ingredient is the one in titanium tetrachloride, titanous chloride, titanium tetrabromide and/or titanium tetra iodide.
3. olefin polymerization catalysis according to claim 1, is characterized in that: described carbon material carrier is graphene oxide and hydroxylation carbon nanotube mixture, and the two mass ratio is 1 ~ 2.
4. prepare a method for the arbitrary described olefin polymerization catalysis of claim 1-4, it is characterized in that comprising the steps:
1) in a nitrogen environment the mixture of the graphene oxide after vacuum-drying and hydroxylation carbon nanotube is added polymerization flask, under normal temperature, vacuum-treat 0.5 ~ 4 hour, carries out water bath with thermostatic control after high pure nitrogen replaces 3 times under 40-60 DEG C of condition; Add organic solvent, stir after 30-60 minute, add pre-treatment solvents, the mass ratio of described pre-treatment medium and carbon material is 0.5 ~ 5:1, and under 40-60 DEG C of condition, constant temperature stirs 2 ~ 10 hours, reacts complete, steam solvent at reduced pressure conditions, obtain carbon material Vehicle element thing;
2) in a nitrogen environment quantitative magnesium chloride and pretreated carbon material are added the ball grinder of replacing sealing after three times through high pure nitrogen, inject the pure titanium tetrachloride of quantitative analysis, ball grinder is put into high energy ball mill grind, obtained Ziegler-Natta olefinic polymerization nanocatalyst.
5. the preparation method of olefin polymerization catalysis according to claim 4, described pre-treatment medium is titanium tetrahalide or aluminum contained compound Al (OR ')
nr
3-n, 0≤n≤3, R and R ' carbonatoms is the alkyl of 2 ~ 10, preferred trimethyl aluminium, triethyl aluminum, triisobutyl aluminium or methylaluminoxane.
6. the preparation method of olefin polymerization catalysis according to claim 4, is characterized in that described organic solvent to be the total number of carbon atoms is the alkane of 5 ~ 10, ether and/or tetrahydrofuran (THF) that naphthenic hydrocarbon that the total number of carbon atoms is 5 ~ 10, the total number of carbon atoms are 2 ~ 12.
7. the preparation method of olefin polymerization catalysis according to claim 4, it is characterized in that described high-energy ball milling adopts planetary ball mill, drum's speed of rotation is 300 ~ 500r/min, and milling time is 4 ~ 24h, and ratio of grinding media to material is 2:1 ~ 5:1.
8. the preparation method of a kind of new carbon/polyisoprene nano composite material according to claim 1, it is characterized in that, preparation method is as follows: the process of poly-unit anhydrous and oxygen-free, add olefin polymerization catalysis described in quantitative isoprene, aluminum contained compound, right 4 successively, wherein, the mol ratio of isoprene and active ingredient is 1:1*10
5, the mol ratio of aluminum compound and active ingredient is 5 ~ 100:1,0 ~ 5 DEG C of pre-polymerization 20 ~ 30min, and 15 ~ 60 DEG C of constant temperature polymerization 8 ~ 48h, acidic ethanol stops polyreaction, and drying is prepared and obtains a kind of new carbon/polyisoprene nano composite material.
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| CN101225128A (en) * | 2007-01-19 | 2008-07-23 | 中国石油化工股份有限公司 | Spherical complex carrier for olefin polymerization catalyst and preparation method thereof |
| CN103058172A (en) * | 2013-01-15 | 2013-04-24 | 清华大学 | Preparation method of carbon nanometer tube-graphene composite material |
| KR20140136256A (en) * | 2013-05-20 | 2014-11-28 | 부산대학교 산학협력단 | Method and process of metal catalyst for fuel cell using a complex compound, and fuel cell electrode adopting the catalyst and fuel cell comprising the electrode |
| CN104387507A (en) * | 2014-11-17 | 2015-03-04 | 青岛科技大学 | Diolefin polymerization catalyst with carbon nano-tube/anhydrous magnesium chloride as carrier as well as preparation method and application of diolefin polymerization catalyst |
| CN104926960A (en) * | 2015-03-12 | 2015-09-23 | 青岛科技大学 | Diolefin polymerization catalyst with graphene/magnesium chloride as carrier, and preparation method and application thereof |
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