CN106543301B - A kind of preparation method and application for the Ziegler-Natta catalyst efficiently preparing low entanglement polyethylene - Google Patents
A kind of preparation method and application for the Ziegler-Natta catalyst efficiently preparing low entanglement polyethylene Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method and applications for the Ziegler Natta catalyst efficiently preparing low entanglement polyethylene, include the following steps：It is stirred in tetrahydrofuran using the porous carrier and Polyhedral oligomeric silsesquioxanes molecule/Mg mixtures for the alcohol absorption being prepared, filters, solid powder is dried to free-flowing, the carrier for preparing low entanglement polyethylene catalysts is obtained；Alkyl aluminum is recycled, the carrier of the catalyst of alkyl aluminum modification is prepared；Finally, TiCl4Tetrahydrofuran solution the carrier of the catalyst being modified to alkyl aluminum is added, after stirring, solid powder is washed with tetrahydrofuran solution, it is dry to flowing freely, obtain the Ziegler Natta catalyst for efficiently preparing low entanglement polyethylene.POSS can be assembled into the microballoon of 20 100nm of grain size in porous carrier duct, effectively it is separated by active point, increase activated centre spacing, it is suppressed that the overlapping generation of chain in polymerization process can efficiently prepare low entanglement polyethylene under >=60 DEG C of polymerization temperature.
Description
Technical field
The present invention relates to olefin polymerization catalyst technical field, refer specifically to a kind of efficiently preparing low entanglement polyethylene
The preparation method of the preparation method of Ziegler-Natta catalyst and low entanglement polyethylene.
Background technology
Polyethylene Chain tangled structure is its highly important condensed state structure, is largely determined high molecular molten
The performances such as body viscoplasticity, segment dynamics, processing also determine microscopic appearance and performance after PE Processing.1mg points
Son amount is point content of in 1,000,000 commercial UHMPWE primary particles, tangling up to 1014It is a.A large amount of chain entanglement so that material is molten
Body viscosity is big, and processing is abnormal difficult.After UHMWPE is at fibre, a large amount of chain entanglement can also make fiber thickness uneven, generate crystal knot
Structure defect causes tensile strength of fiber and modulus there was only the 1/3 of theoretical value, and this severely limits UHMWPE products in the military and people
With the extensive use in equal fields.Therefore, the polyethylene particle for preparing low entanglement degree has important theoretical significance and reality
Border application value.
Rastogi et al. (Macromolecules 2011,44,4952-4960) by Ti-base catalyst at low temperature into
Row homogeneous polymerization (- 10~30 DEG C) has synthesized the UHMWPE of low entanglement.In the environment of homogeneous polymerization, catalyst active center that
This is apart from each other, reduces chain and overlaps probability, the rate of polymerization of low temperature polymerization is less than crystalline rate, the Polyethylene Chain of growth in addition
Section crystallizes immediately in nascent, forms the unimolecule lattice structure of " single chain monocrystal ", low entanglement has been prepared in situ out
UHMWPE.However, reactor wall sticking phenomenon is serious in homogeneous polymerization, it is not easy to carry out continuous production；And polymerization process needs to consume
A large amount of co-catalyst, product particle pattern is poor, high energy consumption, process economics are poor.Mecking et al. (Journal of the
American Chemical Society, 2013,135,11645-11650) low entanglement polyethylene is prepared for by aqueous polymerization
It is nanocrystalline.It transition Ni catalyst and contact ethylene and takes the lead in becoming lipophilic nanoparticle after being activated after water-soluble, enclose
The surfactant being wound on around nanoparticle is incompatible with polyethylene thermodynamics, and surfactant is made to be divided into polymerisation
Several micro- reaction members；Under low temperature, the strand of growth is limited at preferential crystallization in micro- reaction member, it is suppressed that strand
Overlapping probability of happening, to which the polyethylene for obtaining low entanglement is nanocrystalline.The crystallinity of its product is more than 90%, still, water
The preparation process of dissolubility Ni base catalyst is sufficiently complex, and catalyst yield is low, and polymerization activity is not high, and only 6 × 103gPE/mol
Nihbar, and product isolates and purifies complexity, process economics are poor.Patent CN201210005685 discloses a kind of support type
The method of the low entanglement polyethylene of catalyst preparation selects surface to only have the POSS molecules load polyolefin catalyst of 1 load byte,
Using the geometric dimension of single POSS molecules itself, the distance in activated centre is increased, it is poly- to be prepared for low entanglement super high molecular weight
Ethylene.However, since the geometric dimension of POSS molecules is small (0.01-10nm), POSS molecules disperse on porous support in addition
Randomness causes the increased limited extent of spacing between activated centre, limits its ability of regulation and control tangled in Polyethylene Chain.Specially
Polystyrene film is wrapped in porous carrier surface by profit 201510114917, the strong ethylene resistance to mass tranfer built using polystyrene
Environment inhibits the rate of chain growth of polymerization initial stage, can prepare low entanglement polyethylene in polymerization initial stage.
In conclusion the prior art is in regulation and control polyethylene primary particle chain winding degree, there is also problems, it would be highly desirable to high
Effect, cheap and easy to get, chain entanglement regulating effect is high, and the non-equal of low entanglement polyethylene can be prepared under >=60 DEG C of polymerization temperature
Phase catalyst.
Invention content
The technical problem to be solved by the invention for the present situation of prior art is to provide one kind efficiently prepare it is low tangle it is poly-
The preparation method of the preparation method of the Ziegler-Natta catalyst of ethylene and low entanglement polyethylene.
Technical solution is used by the present invention solves above-mentioned technical problem：
A kind of preparation method for the Ziegler-Natta catalyst efficiently preparing low entanglement polyethylene, feature include with
Lower step：
(1) after the porous carrier in 20nm-10 μm of aperture being mixed 4-6h with alcohol in tetrahydrofuran solution, alcohol modification is obtained
Porous carrier, porous carrier 1-5 time of alcohol modification, the porous carrier that acquisition is adsorbed by alcohol are washed with tetrahydrofuran；
(2) by organic substituent methyl, ethyl, propyl, isopropyl, the isobutyl of Polyhedral oligomeric silsesquioxanes molecule
One or more substitutions in base, tertiary butyl and hydroxyl, wherein being modified containing hydroxyl number 1-3 on 1 POSS molecule
Polyhedral oligomeric silsesquioxanes molecule；
(3) by the Polyhedral oligomeric silsesquioxanes molecule of the modification in step (2) and Mg compounds in tetrahydrofuran solution
In be mixed with Polyhedral oligomeric silsesquioxanes molecule/Mg mixtures, wherein on Polyhedral oligomeric silsesquioxanes molecule hydroxyl with
The molar ratio of Mg atoms is 0.01%-10%, preferably 0.05%-4%；
(4) mixture of the Polyhedral oligomeric silsesquioxanes molecule/Mg prepared in step (3) is added into step (1)
The porous carrier of the alcohol absorption of preparation, after stirring 4-8h in tetrahydrofuran, filtering dries solid powder to free-flowing,
Obtain preparing the carrier of low entanglement polyethylene catalysts；
(5) excessive alkyl aluminum is added to the carrier for preparing low entanglement polyethylene catalysts of the gained into step (4), is stirred
4-8h is mixed, is washed 3-8 times with tetrahydrofuran solution, extra alkyl aluminum is removed, solid powder is dried to free-flowing and is obtained
The carrier for the catalyst that alkyl aluminum is modified；
(6) by TiCl4Or TiCl3Tetrahydrofuran solution the catalyst being modified to the alkyl aluminum of gained in step (5) is added
Carrier, the wherein weight ratio of Ti atoms and the carrier is that 0.1wt%-10wt% is washed after stirring 4-8h with tetrahydrofuran solution
Wash solid powder 3-10 times, it is dry to flowing freely, obtain the Ziegler-Natta catalysis for efficiently preparing low entanglement polyethylene
The ethylene polymerization activity of agent, catalyst is 5*105-2*107g PE/mol Ti·h·bar。
The further preferred embodiment of the present invention is：The porous carrier is selected from silica, aluminium oxide, zirconium oxide, two
Titanium oxide, silica-alumina, illiteracy open up soil.
The further preferred embodiment of the present invention is：The alcohol include ethyl alcohol, propyl alcohol, n-butyl alcohol, ethylene glycol, propylene glycol,
In 1,4 butanediols.
The further preferred embodiment of the present invention is：The Mg compounds are magnesium chloride, magnesium bromide, magnesium ethylate, hydrogen-oxygen
Change magnesium one kind or two kinds of mixtures.
The further preferred embodiment of the present invention is：The molar ratio of the alcohol and Mg atoms is 1-10.
The further preferred embodiment of the present invention is：The molecular diameter 0.1-20nm of the Polyhedral oligomeric silsesquioxanes；
It is preferred that 1-10nm.
The further preferred embodiment of the present invention is：The alkyl aluminum includes trimethyl aluminium, trimethyl aikyiaiurnirsoxan beta, triethyl group
The mixture of aluminium and the two.
A kind of preparation method of low entanglement polyethylene, it is characterised in that in slurry polymerization reactor, addition co-catalyst,
Ethylene and the Ziegler-Natta catalyst for efficiently preparing low entanglement polyethylene, are warming up to 60~90 DEG C, adjust polymerization pressure to
1~30bar, 0.1~5h of polymerisation are to get to the low entanglement polyethylene.
The further preferred embodiment of the present invention is：The co-catalyst is alkyl aluminum compound, Al atoms and catalyst
Ti atomic molar ratios be 10-200.
The further preferred embodiment of the present invention is：The weight average molecular weight range 10000- of the low entanglement polyethylene prepared
10000000g/mol。
Compared with the prior art, the advantages of the present invention are as follows：By the POSS molecules of a small amount of hydroxyl modification and a large amount of Mgization
Object is closed to be complexed in advance (the molar ratio 0.01%-10% of hydroxyl and Mg atoms, preferably 0.05%-4% on POSS molecules).On the one hand,
After the complexing of POSS molecules and Mg compounds, the geometry of POSS molecules can be used as the heterogeneous nucleation agent of Mg compounds crystallization,
So that POSS forms the crystallite of size 30-100nm with Mg compounds.The crystallite crystalline structure is stablized, and cannot load in Ti activity
The heart.Therefore, which becomes the large scale grid between porous carrier surface Ti active sites, eliminates the double of catalyst active center
Metal deactivation phenomenom improves catalyst ethylene polymerization activity, and the formation for substantially inhibiting Polyethylene Chain overlapping.Can >=
Low entanglement polyethylene is efficiently prepared under 60 DEG C of polymerization temperature.The initial entanglement degree of gained polyethylene can be in 5%-50%
(being equivalent to saturation entanglement degree) regulation and control.
Description of the drawings
Fig. 1 be prepared in embodiment 1 storage modulus of polyethylene at any time establish curve graph.
Specific implementation mode
Present invention is further described in detail with reference to embodiments.
The embodiment of the present invention meets the following conditions when the processing performance and mechanical property to product are tested：
The operation of all air-sensitive substances is all made of the double line anhydrous and oxygen-free operating method of standard vacuum；Agents useful for same is equal
It is used after needing refinement treatment.
The molecular weight of polymer and its distribution are characterized with gel permeation chromatograph (PL-GPC-220), 1,2,4- trichloro-benzenes
As solvent, sample preparation is filtered at 160 DEG C, using the polystyrene of narrower molecular weight distribution as standard specimen, is measured at 160 DEG C.It is poly-
The tensile strength for closing object is measured according to national standard GB/T1040.The low entanglement characteristic of polymer is tested by rheology.Utilize rheology
Segment melt dynamics is analyzed, the low entanglement characteristic of Study Polymer Melts is tested by rheology.In the analysis of rheology, segment twines
Average molecular weight (Me) between node is inversely proportional with chain winding density, and the elasticity modulus (G ') of Me and rubbery plateau region is available as follows
Relational expression quantitative description：
G'=gNρRT/Me
Wherein, gNFor Quantitative factor；ρ is density；R is gas constant；T is absolute temperature.
The increase of the certain melt Elastic Modulus of temperature represents the increase of chain winding density.Therefore, pass through rotating flow
The formation mechenism that chain is wound in polymerization process can quantitatively be described by becoming analysis.Rheology test is surveyed by an axial strain rheometer
Fixed (HAAKE III instrument).120 DEG C, under the conditions of 20tons by polyethylene powder tabletting 30min, diameter 8mm is made
Sample is used for Research on The Rheology.Chassis between rheometer parallel-plate is heated to 160 DEG C in a nitrogen environment.Stablize 5min to start
Rheological experiment.Dynamic frequency scanning is tested with fixed frequency 1Hz.Dynamic time scanning is to fix 1rad/s tests.According to rotation
The storage modulus that rheology measures at 160 DEG C establishing in curve at any time, starting storage modulus and maximum storage modulus (energy storage
Modulus is not changing over time, and system reaches thermodynamic stability) GN 0Than the entanglement under sample initial state can be characterized
Degree.The UHMWPE bought in the market, molecular weight 2300000g/mol, GN 0=0.95, show that there is sample high chain to twine
Knot degree.
Embodiment 1：
(1) is by the porous carrier SiO of the apertures 1.0g 20nm21,4- butanediols with 6mmol are in 20mL tetrahydrofurans
(THF) after mixing 4h in solution, the porous carrier of alcohol modification is obtained, wash the porous carrier 5 times that alcohol is modified with 20mLTHF, obtains
Obtain the porous carrier adsorbed by 1,4- butanediols；(2) uses the organic substituent of Polyhedral oligomeric silsesquioxanes (POSS) molecule
Methyl and hydroxyl substitution obtain modified Polyhedral oligomeric silsesquioxanes wherein containing hydroxyl number 2 on 1 POSS molecule
Molecule, POSS molecular diameters are 1nm；(3) is by the Polyhedral oligomeric silsesquioxanes molecule and 6mmol of the modification in step (2)
MgCl2(1,4-butanediol and the molar ratio of magnesium atom be 1) is 4% by the molar ratio of hydroxyl moles in POSS and Mg atoms,
It is mixed in 20mLTHF, prepares Polyhedral oligomeric silsesquioxanes molecule/Mg mixtures；(4) multi-panel that will be prepared in step (3)
The porous carrier of the 1,4-butanediol absorption prepared into step (1) is added in oligomeric silsesquioxanes molecule/Mg mixtures,
After stirring 8h in THF, solid powder is dried to free-flowing, obtains the carrier for preparing low entanglement polyethylene catalysts by filtering；
(5) carrier for preparing low entanglement polyethylene catalysts of the gained into step (4) is added in 10mmol triethyl aluminums by, stirs 8h,
It is washed 8 times with THF, removes extra triethyl aluminum, solid powder is dried to free-flowing and obtains the catalysis of alkyl aluminum modification
The carrier of agent；(6) is by TiCl4The carrier of the catalyst of the alkyl aluminum modification of the gained into step (5) is added in THF solution, wherein
The weight ratio of Ti atoms and the carrier is that 10wt% washs solid powder 10 times after stirring 4h with THF, dry extremely to flow freely,
Obtain the Ziegler-Natta catalyst for efficiently preparing low entanglement polyethylene.
Slurry polymerization reactor is heated to 60 DEG C, adjusting polymerization pressure is 1bar, sequentially adds 200mL toluene, 5mL tri-
Ziegler-Natta catalyst prepared by aluminium ethide (molar ratio of Al atoms and Ti atoms is 100), ethylene and 0.03g is to anti-
It answers in device, starts polymerisation.Stop after polymerization 1h, products therefrom molecular weight is 500,000 g/mol, and the vinyl polymerization of catalyst is lived
Property 8.2*106g PE/mol Ti·h·bar。GN 0=0.45 (such as Fig. 1), catalyst can efficiently prepare low poly- second of tangling
Alkene.
Embodiment 2：
(1) by the porous carrier aluminium oxide of the apertures 1.0g 100nm and the n-butyl alcohol of 6mmol at 20mL tetrahydrofurans (THF)
After mixing 4h in solution, the porous carrier of alcohol modification is obtained, washs to obtain the porous carrier 1 time of alcohol modification with 20mL THF, obtains
Obtain the porous carrier adsorbed by n-butyl alcohol；(2) is by the special fourth of the organic substituent of Polyhedral oligomeric silsesquioxanes (POSS) molecule
Base and hydroxyl substitution obtain modified Polyhedral oligomeric silsesquioxanes point wherein containing hydroxyl number 3 on 1 POSS molecule
Son, POSS molecular diameters are 10nm；(3) is by the Polyhedral oligomeric silsesquioxanes molecule and 0.6mmol of the modification in step (2)
Magnesium ethylate (n-butyl alcohol and magnesium molar ratio are 10) is 0.05% by the molar ratio of hydroxyl moles in POSS and Mg atoms,
It is mixed in 20mLTHF, prepares Polyhedral oligomeric silsesquioxanes/Mg mixtures；(4) Polyhedral Oligomeric times that will be prepared in step (3)
The porous carrier of the n-butyl alcohol absorption prepared into step (1) is added in the mixture of half siloxanes/Mg, after stirring 4h in THF,
Filtering, solid powder is dried to free-flowing, the carrier for preparing low entanglement polyethylene catalysts is obtained；(5) is by 10mmol tri-
The carrier for preparing low entanglement polyethylene catalysts of the gained into step (4) is added in aluminium ethide, stirs 4h, is washed 3 times with THF,
Extra triethyl aluminum is removed, solid powder is dried to the carrier for flowing freely the catalyst for obtaining alkyl aluminum modification；(6).
By TiCl3THF solution be added the carrier of the catalyst being modified to the alkyl aluminum of gained in step (5), wherein Ti atoms with should
The weight ratio of carrier is that 1wt% washs solid powder 3 times after stirring 8h with THF, dry to flowing freely, and obtains and efficiently prepares
The Ziegler-Natta catalyst of low entanglement polyethylene.
Slurry polymerization reactor is heated to 80 DEG C, pressure 10bar, sequentially adds 200mL toluene, 0.5mL triethyl aluminums
In Ziegler-Natta catalyst to reactor prepared by (molar ratio of Al atoms and Ti atoms is 10), ethylene and 0.03g,
Start polymerisation.Stop after polymerization 5h, products therefrom molecular weight is 5,000,000 g/mol, the ethylene polymerization activity 2* of catalyst
107g PE/mol Ti·h·bar。GN 0=0.25, catalyst can efficiently prepare low entanglement polyethylene, and molecular weight of product
Reach ultra-high molecular weight polyethylene rank.
Embodiment 3：
(1) is molten in 20mL tetrahydrofurans (THF) by the ethyl alcohol of the porous carrier titanium dioxide in 1 μm of apertures 1.0g and 6mmol
After mixing 6h in liquid, the porous carrier of alcohol modification is obtained, washs to obtain the porous carrier 5 times of alcohol modification with 20mL THF, obtains
By the porous carrier of Ethanol Adsorption；(2) by the organic substituent isopropyl of Polyhedral oligomeric silsesquioxanes (POSS) molecule and
Hydroxyl replaces, wherein containing hydroxyl number 1 on 1 POSS molecule, obtains modified Polyhedral oligomeric silsesquioxanes molecule,
POSS molecular diameters are 20nm；(3) is by the Polyhedral oligomeric silsesquioxanes molecule of the modification in step (2) and 3mmol hydroxides
Magnesium (ethyl alcohol and magnesium molar ratio are 2) is 10% by the molar ratio of hydroxyl moles in POSS and Mg atoms, is mixed in 20mLTHF
It closes, prepares Polyhedral oligomeric silsesquioxanes/Mg mixtures；(4) Polyhedral oligomeric silsesquioxanes/Mg that will be prepared in step (3)
Mixture be added to the porous carrier of the Ethanol Adsorption prepared in step (1), after stirring 6h in THF, filtering, by solid powder
End is dry to flowing freely, and obtains the carrier for preparing low entanglement polyethylene catalysts；(5) by 10mmol triethyl aluminums be added to
The carrier for preparing low entanglement polyethylene catalysts of gained in step (4), stirs 4h, is washed 1 time with THF, remove extra three
Aluminium ethide dries solid powder to the carrier for flowing freely the catalyst for obtaining alkyl aluminum modification；(6) is by TiCl3THF
The carrier of the catalyst of the alkyl aluminum modification of the gained into step (5), the wherein weight ratio of Ti atoms and the carrier is added in solution
Solid powder is washed with THF 5 times, dry to flowing freely, acquisition efficiently prepares low entanglement polyethylene for 5wt% after stirring 6h
Ziegler-Natta catalyst.
Slurry polymerization reactor is heated to 90 DEG C, pressure 30bar, sequentially adds 200mL toluene, 10mL trimethyl aluminas
Ziegler-Natta catalyst prepared by alkane (molar ratio of Al atoms and Ti atoms is 200), ethylene and 0.03g is to reactor
In, start polymerisation.Stop after polymerase 10 .1h, products therefrom molecular weight is 10,000,000 g/mol, and the vinyl polymerization of catalyst is lived
Property 7.2*106g PE/mol Ti·h·bar。GN 0=0.15, catalyst can efficiently prepare low entanglement polyethylene, and product
Molecular weight reaches ultra-high molecular weight polyethylene rank.
Embodiment 4：
(1) by the ethylene glycol of the porous carrier zirconium oxide in 10 μm of apertures 1.0g and 6mmol at 20mL tetrahydrofurans (THF)
After mixing 4h in solution, the porous carrier of alcohol modification is obtained, washs to obtain the porous carrier 3 times of alcohol modification with 20mL THF, obtains
Obtain the porous carrier adsorbed by ethylene glycol；(2) is by the organic substituent ethyl of Polyhedral oligomeric silsesquioxanes (POSS) molecule
Replace with hydroxyl, POSS molecular diameters are 0.5nm, wherein containing hydroxyl number 1 on 1 POSS molecule, obtain the more of modification
Face oligomeric silsesquioxanes molecule；(3) is by the Polyhedral oligomeric silsesquioxanes molecule of the modification in step (2) and 1mmol brominations
Magnesium (ethylene glycol and magnesium molar ratio are 6) is 0.01% by the molar ratio of hydroxyl moles in POSS and Mg atoms, in 20mL THF
Middle mixing prepares Polyhedral oligomeric silsesquioxanes molecule/Mg mixtures；(4) the Polyhedral Oligomeric sesquialter that will be prepared in step (3)
The porous carrier of the ethylene glycol absorption prepared into step (1) is added in the mixture of siloxane molecule/Mg, and 5h is stirred in THF
Afterwards, it filters, solid powder is dried to free-flowing, the carrier for preparing low entanglement polyethylene catalysts is obtained；(5) will
The carrier for preparing low entanglement polyethylene catalysts of the gained into step (4) is added in 10mmol triethyl aluminums, stirs 4h, uses THF
Washing 5 times, removes extra triethyl aluminum, and solid powder is dried to the load for flowing freely the catalyst for obtaining alkyl aluminum modification
Body；(6) is by TiCl3THF solution the carrier of the catalyst being modified to the alkyl aluminum of gained in step (5) is added, wherein Ti is former
The weight ratio of son and the carrier is that 0.1wt% washs solid powder 5 times after stirring 6h with THF, dry to flowing freely, and is obtained
Efficiently prepare the Ziegler-Natta catalyst of low entanglement polyethylene.
Slurry polymerization reactor is heated to 70 DEG C, pressure 30bar, sequentially adds 200mL toluene, 2mL trimethyl aluminiums (Al
60) molar ratio of atom and Ti atoms is, in the Ziegler-Natta catalyst to reactor for preparing of ethylene and 0.05g, starts
Polymerisation.Stop after polymerase 10 .5h, products therefrom molecular weight is 10000g/mol, the ethylene polymerization activity 8.2* of catalyst
106g PE/mol Ti·h·bar。GN 0=0.35, catalyst can efficiently prepare low entanglement polyethylene.
Embodiment 5：
(1) by the propyl alcohol of the porous carrier silica-alumina in 10 μm of apertures 1.0g and 6mmol in 20mL tetrahydrofurans
(THF) after mixing 4h in solution, the porous carrier of alcohol modification is obtained, is washed to obtain the porous carrier 3 of alcohol modification with 20mL THF
It is secondary, obtain the porous carrier adsorbed by propyl alcohol；(2) uses the organic substituent of Polyhedral oligomeric silsesquioxanes (POSS) molecule
Propyl and hydroxyl substitution, POSS molecular diameters are 2nm, wherein containing hydroxyl number 1 on 1 POSS molecule, obtain modification
Polyhedral oligomeric silsesquioxanes molecule；(3) is by the Polyhedral oligomeric silsesquioxanes molecule of the modification in step (2) and 1mmol bromines
It is 0.01% to change magnesium (propyl alcohol and magnesium molar ratio are 6) by the molar ratio of hydroxyl moles in POSS and Mg atoms, in 20mL THF
Middle mixing prepares Polyhedral oligomeric silsesquioxanes molecule/Mg mixtures；(4) the Polyhedral Oligomeric sesquialter that will be prepared in step (3)
The porous carrier of the propyl alcohol absorption prepared into step (1) is added in the mixture of siloxane molecule/Mg, after stirring 5h in THF,
Filtering, solid powder is dried to free-flowing, the carrier for preparing low entanglement polyethylene catalysts is obtained；(5) is by 10mmol tri-
The carrier for preparing low entanglement polyethylene catalysts of the gained into step (4) is added in aluminium methyl, stirs 4h, is washed 5 times with THF,
Extra trimethyl aluminium is removed, solid powder is dried to the carrier for flowing freely the catalyst for obtaining alkyl aluminum modification；(6).
By TiCl4THF solution be added the carrier of the catalyst being modified to the alkyl aluminum of gained in step (5), wherein Ti atoms with should
The weight ratio of carrier is that 0.5wt% washs solid powder 5 times after stirring 6h with THF, dry to flowing freely, and obtains efficiently system
The Ziegler-Natta catalyst of standby low entanglement polyethylene.
Slurry polymerization reactor is heated to 70 DEG C, pressure 30bar, sequentially adds 200mL toluene, 2mL trimethyl aluminiums (Al
60) molar ratio of atom and Ti atoms is, in the Ziegler-Natta catalyst to reactor for preparing of ethylene and 0.05g, starts
Polymerisation.Stop after polymerase 10 .5h, products therefrom molecular weight is 500000g/mol, the ethylene polymerization activity 2* of catalyst
106g PE/mol Ti·h·bar。GN 0=0.45, catalyst can efficiently prepare low entanglement polyethylene.
Embodiment 6：
(1) it is molten in 20mL tetrahydrofurans (THF) with the propylene glycol of 6mmol to be opened up soil by for the porous carrier illiteracy in 1 μm of apertures 1.0g
After mixing 6h in liquid, the porous carrier of alcohol modification is obtained, washs to obtain the porous carrier 5 times of alcohol modification with 20mL THF, obtains
The porous carrier adsorbed by propylene glycol；(2) is by the organic substituent isobutyl group of Polyhedral oligomeric silsesquioxanes (POSS) molecule
Replace with hydroxyl, wherein containing hydroxyl number 1 on 1 POSS molecule, obtain modified Polyhedral oligomeric silsesquioxanes molecule,
POSS molecular diameters are 10nm；(3) is by the Polyhedral oligomeric silsesquioxanes molecule of the modification in step (2) and 3mmol hydroxides
Magnesium (propylene glycol and magnesium molar ratio are 2) is 10% by the molar ratio of hydroxyl moles in POSS and Mg atoms, is mixed in 20mLTHF
It closes, prepares Polyhedral oligomeric silsesquioxanes/Mg mixtures；(4) Polyhedral oligomeric silsesquioxanes/Mg that will be prepared in step (3)
Mixture be added to the porous carrier of the propylene glycol absorption prepared in step (1), after stirring 6h in THF, filtering, by solid
Powder is dried to free-flowing, and the carrier for preparing low entanglement polyethylene catalysts is obtained；(5) is by 10mmol trimethyl aikyiaiurnirsoxan betas
The carrier for preparing low entanglement polyethylene catalysts of the gained into step (4) is added, stirs 4h, is washed 1 time with THF, removes more
Remaining trimethyl aikyiaiurnirsoxan beta dries solid powder to the carrier for flowing freely the catalyst for obtaining alkyl aluminum modification；(6) will
TiCl4THF solution the carrier of the catalyst being modified to the alkyl aluminum of gained in step (5), wherein Ti atoms and the load is added
The weight ratio of body is that 5wt% washs solid powder 5 times after stirring 6h with THF, and dry to flowing freely, acquisition efficiently prepares low
The Ziegler-Natta catalyst of entanglement polyethylene.
Slurry polymerization reactor is heated to 90 DEG C, pressure 30bar, sequentially adds 200mL toluene, 10mL trimethyl aluminas
Ziegler-Natta catalyst prepared by alkane (molar ratio of Al atoms and Ti atoms is 100), ethylene and 0.01g is to reactor
In, start polymerisation.Stop after polymerase 10 .1h, products therefrom molecular weight is 5,000,000 g/mol, and the vinyl polymerization of catalyst is lived
Property 5*106g PE/mol Ti·h·bar。GN 0=0.15, catalyst can efficiently prepare low entanglement polyethylene, and product point
Son amount reaches ultra-high molecular weight polyethylene rank.
Claims (1)
1. a kind of preparation method for the Ziegler-Natta catalyst efficiently preparing low entanglement polyethylene, feature includes following
Step：
(1) after the porous carrier in 20nm-10 μm of aperture being mixed 4-6h with alcohol in tetrahydrofuran solution, the more of alcohol modification are obtained
Hole carrier washs porous carrier 1-5 time of alcohol modification, the porous carrier that acquisition is adsorbed by alcohol with tetrahydrofuran；
(2) by the organic substituent methyl of Polyhedral oligomeric silsesquioxanes molecule, ethyl, propyl, isopropyl, isobutyl group, spy
One or more substitutions in butyl and hydroxyl, wherein obtaining the more of modification containing hydroxyl number 1-3 on 1 POSS molecule
Face oligomeric silsesquioxanes molecule；
(3) the Polyhedral oligomeric silsesquioxanes molecule of the modification in step (2) and Mg compounds are mixed in tetrahydrofuran solution
Conjunction prepares Polyhedral oligomeric silsesquioxanes molecule/Mg mixtures, and hydroxyl and Mg are former wherein on Polyhedral oligomeric silsesquioxanes molecule
The molar ratio of son is 0.01%-10%；
(4) mixture of the Polyhedral oligomeric silsesquioxanes molecule/Mg prepared in step (3) is added and is prepared into step (1)
Alcohol absorption porous carrier, in tetrahydrofuran stir 4-8h after, filtering, solid powder is dried to free-flowing, is obtained
Prepare the carrier of low entanglement polyethylene catalysts；
(5) excessive alkyl aluminum is added to the carrier for preparing low entanglement polyethylene catalysts of the gained into step (4), stirs 4-
8h is washed 3-8 times with tetrahydrofuran solution, removes extra alkyl aluminum, solid powder is dried to free-flowing and obtains alkyl
The carrier for the catalyst that aluminium is modified；
(6) by TiCl4Or TiCl3Tetrahydrofuran solution the load of the catalyst being modified to the alkyl aluminum of gained in step (5) is added
The weight ratio of body, wherein Ti atoms and the carrier is 0.1wt%-10wt%, after stirring 4-8h, is washed with tetrahydrofuran solution solid
Body powder 3-10 times, it is dry to flowing freely, the Ziegler-Natta catalyst for efficiently preparing low entanglement polyethylene is obtained, is urged
The ethylene polymerization activity of agent is 5*105-2*107g PE/mol Ti·h·bar；
The porous carrier is in silica, aluminium oxide, zirconium oxide, titanium dioxide, silica-alumina, montmorillonite
One or more；
The alcohol includes one or more of ethyl alcohol, propyl alcohol, n-butyl alcohol, ethylene glycol, propylene glycol, 1,4- butanediols；
The Mg compounds are magnesium chloride, magnesium bromide, magnesium ethylate, magnesium hydroxide one kind or two kinds of mixtures；
The molar ratio of the alcohol and Mg atoms is 1-10；
The molecular diameter 0.1-20nm of the Polyhedral oligomeric silsesquioxanes；
The alkyl aluminum include trimethyl aluminium, trimethyl aikyiaiurnirsoxan beta, triethyl aluminum and the two mixture.
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| CN103113500A (en) * | 2013-01-29 | 2013-05-22 | 北京化工大学 | Alkene coordination polymerization catalyst as well as preparation method and application thereof |
| CN103193908A (en) * | 2012-01-09 | 2013-07-10 | 宁波大学 | Method for preparing superstrong UHMWPE fiber and related catalyst |
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| CN1050389A (en) * | 1989-09-18 | 1991-04-03 | 中国科学院长春应用化学研究所 | High copolymerization, high-random ethylene/alpha-olefin polymerizing catalyst |
| CN103193908A (en) * | 2012-01-09 | 2013-07-10 | 宁波大学 | Method for preparing superstrong UHMWPE fiber and related catalyst |
| CN103113500A (en) * | 2013-01-29 | 2013-05-22 | 北京化工大学 | Alkene coordination polymerization catalyst as well as preparation method and application thereof |
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