CN106543301A - A kind of preparation method and application of the Ziegler Natta catalyst for efficiently preparing low entanglement polyethylene - Google Patents
A kind of preparation method and application of the Ziegler Natta catalyst for efficiently preparing low entanglement polyethylene Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method and application of the Ziegler Natta catalyst for efficiently preparing low entanglement polyethylene, comprises the following steps：Stirred in tetrahydrofuran using the porous carrier and Polyhedral oligomeric silsesquioxanes molecule/Mg mixture of the alcohol absorption for preparing, filter, pressed powder is dried to free-flowing, obtains preparing the carrier of low entanglement polyethylene catalysts；Alkyl aluminum is recycled, the carrier of the modified catalyst of alkyl aluminum is prepared；Finally, TiCl4Tetrahydrofuran solution add to alkyl aluminum the carrier of the catalyst being modified, after stirring, wash pressed powder with tetrahydrofuran solution, is dried to free-flowing, is efficiently prepared the Ziegler Natta catalyst of low entanglement polyethylene.POSS can be assembled into the microsphere of 20 100nm of particle diameter in porous carrier duct, active site position is separated by effectively, increase active center spacing, it is suppressed that the overlapping generation of chain in polymerization process, low entanglement polyethylene can be efficiently prepared 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 prepare 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 determined to a great extent high molecular molten
The performances such as body viscoelasticity, segment kinetics, processing, also determine microscopic appearance and performance after PE Processing.1mg point
During son amount is for 1,000,000 commercial UHMPWE primary particles, the content of tangling is up to 1014It is individual.Substantial amounts of chain entanglement causes material to melt
Body viscosity is big, and processing is abnormal difficult.Into after fibre, substantial amounts of chain entanglement can also make fiber thickness uneven to UHMWPE, produce crystal knot
Structure defect, causes tensile strength of fiber and modulus there was only the 1/3 of theoretical value, this severely limits UHMWPE products in the military and people
With etc. field extensive application.Therefore, the polyethylene particle for preparing low entanglement degree has important theoretical significance and reality
Border using value.
Rastogi et al. (Macromolecules 2011,44,4952-4960) is entered at low temperature by Ti-base catalyst
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 the overlapping probability of chain, and the rate of polymerization of low temperature polymerization is less than crystalline rate, the Polyethylene Chain of growth in addition
There is crystallization in nascent in section, form the unimolecule lattice structure of " single chain monocrystal " immediately, and low entanglement has been prepared in original position
UHMWPE.However, reactor wall sticking phenomenon is serious in homogeneous polymerization, it is difficult continuously to be produced；And polymerization process needs to consume
Substantial amounts of promoter, 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.Water miscible rear transition Ni catalyst takes the lead in being changed into oil loving nanoparticle with contact ethylene and after being activated, and encloses
The surfactant being wound on around nanoparticle is incompatible with polyethylene thermodynamics, makes surfactant be divided into polyreaction
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, so as to the polyethylene for obtaining low entanglement is nanocrystalline.The degree of crystallinity of its product be more than 90%, but, 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, only has the POSS molecules load polyolefin catalyst of 1 load byte from surface,
Using the physical dimension of single POSS molecules itself, the distance in active center is increased, be prepared for low entanglement super high molecular weight and gather
Ethylene.However, due to the physical dimension of POSS molecules little (0.01-10nm), POSS molecules are scattered on porous support in addition
Randomness, causes the limited extent that spacing increases between active center, 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, suppresses the rate of chain growth of polymerization initial stage, can prepare low entanglement polyethylene in polymerization initial stage.
In sum, also there are problems in regulation and control polyethylene primary particle chain winding degree in prior art, it would be highly desirable to high
Effect, cheap and easy to get, chain entanglement regulating effect are high, and the non-equal of low entanglement polyethylene can be prepared under >=60 DEG C of polymerization temperature
Phase catalyst.
The content of the invention
The technical problem to be solved is the present situation for prior art, there is provided one kind efficiently prepares low entanglement and gathers
The preparation method of the preparation method of the Ziegler-Natta catalyst of ethylene and low entanglement polyethylene.
The present invention solve the technical scheme that adopted of above-mentioned technical problem for：
A kind of preparation method of the Ziegler-Natta catalyst for efficiently preparing low entanglement polyethylene, its feature include with
Lower step：
(1), after the porous carrier in 20nm-10 μm of aperture being mixed 4-6h in tetrahydrofuran solution with alcohol, obtain alcohol and be modified
Porous carrier, alcohol modified porous carrier 1-5 time is washed with tetrahydrofuran, is obtained by the porous carrier of alcohol absorption；
(2) by the organic substituent methyl of Polyhedral oligomeric silsesquioxanes molecule, ethyl, propyl group, isopropyl, isobutyl
One or more replacement 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 modified Polyhedral oligomeric silsesquioxanes molecule in step (2) and Mg compounds in tetrahydrofuran solution
In be mixed with Polyhedral oligomeric silsesquioxanes molecule/Mg mixture, wherein on Polyhedral oligomeric silsesquioxanes molecule hydroxyl with
The mol ratio of Mg atoms is 0.01%-10%, preferred 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, filters, pressed powder is dried to free-flowing in tetrahydrofuran,
Obtain preparing the carrier of low entanglement polyethylene catalysts；
(5) excessive alkyl aluminum is added the carrier for preparing low entanglement polyethylene catalysts of the gained into step (4), is stirred
4-8h is mixed, is washed 3-8 time with tetrahydrofuran solution, removed unnecessary alkyl aluminum, pressed powder is dried to free-flowing and is obtained
The carrier of the modified catalyst of alkyl aluminum；
(6) by TiCl4Or TiCl3Tetrahydrofuran solution add to the modified catalyst of the alkyl aluminum of gained in step (5)
Carrier, the wherein weight ratio of Ti atoms and the carrier is 0.1wt%-10wt%, after stirring 4-8h, is washed with tetrahydrofuran solution
Pressed powder 3-10 time is washed, is dried to flowing freely, the Ziegler-Natta for efficiently being prepared low entanglement polyethylene is catalyzed
Agent, the ethylene polymerization activity of catalyst is 5*105-2*107g PE/mol Ti·h·bar。
Further preferred version is the present invention：Described porous carrier selected from silicon dioxide, aluminium oxide, zirconium oxide, two
Titanium oxide, silica-alumina, illiteracy open up soil.
Further preferred version is the present invention：Described alcohol include ethanol, propanol, n-butyl alcohol, ethylene glycol, Propylene Glycol,
In 1,4 butanediols.
Further preferred version is the present invention：Described Mg compounds are magnesium chloride, magnesium bromide, magnesium ethylate, hydrogen-oxygen
Change magnesium one kind or two kinds of mixture.
Further preferred version is the present invention：Described alcohol is 1-10 with the mol ratio of Mg atoms.
Further preferred version is the present invention：The molecular diameter 0.1-20nm of described Polyhedral oligomeric silsesquioxanes；
It is preferred that 1-10nm.
Further preferred version is the present invention：Described alkyl aluminum includes trimethyl aluminium, trimethyl aikyiaiurnirsoxan beta, triethyl group
Aluminum and its mixture of the two.
A kind of preparation method of low entanglement polyethylene, it is characterised in that in slurry polymerization reactor, addition promoter,
Ethylene and efficiently prepare the Ziegler-Natta catalyst of low entanglement polyethylene, be warming up to 60～90 DEG C, adjust polymerization pressure to
1～30bar, 0.1～5h of polyreaction, that is, obtain described low entanglement polyethylene.
Further preferred version is the present invention：Described promoter is alkyl aluminum compound, Al atoms and catalyst
Ti atomic molars ratio be 10-200.
Further preferred version is the present invention：Weight average molecular weight range 10000- of the low entanglement polyethylene for preparing
10000000g/mol。
Compared with prior art, it is an advantage of the current invention that：By the POSS molecules of a small amount of hydroxyl modification and substantial amounts of Mgization
The pre- complexation of compound (mol ratio 0.01%-10% of hydroxyl and Mg atoms, preferred 0.05%-4% on POSS molecules).On the one hand,
After POSS molecules and Mg compound complexations, the geometry of POSS molecules can as the heterogeneous nucleation agent of Mg compound crystals,
So that POSS forms the crystallite of size 30-100nm with Mg compounds.The crystallite crystalline structure is stable, it is impossible to load Ti it is active in
The heart.Therefore, the crystallite becomes the large scale grid between porous carrier surface Ti active site, eliminates the double of catalyst active center
Metal deactivation phenomenom, improves catalyst ethylene polymerization activity, and the formation for significantly inhibiting Polyethylene Chain overlapping.Can >=
Low entanglement polyethylene is prepared under 60 DEG C of polymerization temperature efficiently.The initial entanglement degree of gained polyethylene can be in 5%-50%
(equivalent to saturation entanglement degree) regulation and control.
Description of the drawings
Fig. 1 is that the storage moduluss of polyethylene are prepared in embodiment 1 to set up curve chart with the time.
Specific embodiment
With reference to embodiments the present invention is described in further detail.
The embodiment of the present invention meets following condition when the processing characteristics and mechanical property to product is tested：
The operation of all air-sensitive materials adopts the double line anhydrous and oxygen-free operational approach of standard vacuum；Agents useful for same is equal
Use after needing refinement treatment.
The molecular weight of polymer and its distribution are characterized with chromatograph of gel permeation (PL-GPC-220), 1,2,4- trichloro-benzenes
As solvent, at 160 DEG C, sample preparation is filtered, using the polystyrene of narrower molecular weight distribution as standard specimen, determined at 160 DEG C.It is poly-
The tensile strength of compound is measured according to GB GB/T1040.The low entanglement characteristic of polymer is tested by rheology.Using rheology
Analysis segment melt kinetics, the low entanglement characteristic of Study Polymer Melts are tested by rheology.In rheol analysis, segment is twined
Mean molecule quantity (Me) between node is inversely proportional to chain winding density, and Me is available with the elastic modelling quantity (G ') of rubbery plateau region 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 that chain winds density.Therefore, by rotating flow
Become the formation mechenism that analysis can quantitatively describe chain winding in polymerization process.Rheology test is surveyed by an axial strain flow graph
Fixed (HAAKE III instrument).120 DEG C, under the conditions of 20tons by polyethylene powder tabletting 30min, diameter 8mm is obtained
Sample, for Research on The Rheology.Chassis between flow graph parallel-plate is heated to 160 DEG C in a nitrogen environment.Stable 5min starts
Rheological experiment.Dynamic frequency scanning is tested with fixed frequency 1Hz.Dynamic time scanning is tested with fixing 1rad/s.According to rotation
The storage moduluss that rheology is determined at 160 DEG C are set up in curve with the time, initial storage moduluss and maximum storage moduluss (energy storage
Modulus is not being changed over, and system reaches Thermodynamically stable state) GN 0Than the entanglement under sample initial state can be characterized
Degree.The UHMWPE bought on market, molecular weight are 2300000g/mol, GN 0=0.95, show that there is sample high chain to twine
Knot degree.
Embodiment 1：
(1). by the porous carrier SiO of 1.0g apertures 20nm2With the 1,4- butanediols of 6mmol in 20mL tetrahydrofurans
(THF) after mixing 4h in solution, the modified porous carrier of alcohol is obtained, wash the porous carrier 5 times that alcohol is modified with 20mLTHF, obtain
Obtain the porous carrier adsorbed by 1,4- butanediols；(2). the organic substituent of Polyhedral oligomeric silsesquioxanes (POSS) molecule is used
Methyl and hydroxyl replace, wherein containing hydroxyl number 2 on 1 POSS molecule, obtain modified Polyhedral oligomeric silsesquioxanes
Molecule, POSS molecular diameters are 1nm；(3). by modified Polyhedral oligomeric silsesquioxanes molecule and 6mmol in step (2)
MgCl2(BDO is 1 with the mol ratio of magnesium atom) is 4% by the mol ratio of hydroxyl moles in POSS and Mg atoms,
Mix in 20mLTHF, prepare Polyhedral oligomeric silsesquioxanes molecule/Mg mixture；(4). the multiaspect that will be prepared in step (3)
Oligomeric silsesquioxanes molecule/Mg mixture adds the porous carrier of the BDO absorption prepared into step (1),
After 8h is stirred in THF, filter, pressed powder is dried to free-flowing, obtains preparing the carrier of low entanglement polyethylene catalysts；
(5). 10mmol triethyl aluminums are added into the carrier for preparing low entanglement polyethylene catalysts of the gained into step (4), 8h is stirred,
Washed with THF 8 times, remove unnecessary triethyl aluminum, pressed powder is dried to free-flowing and obtains the modified catalysis of alkyl aluminum
The carrier of agent；(6). by TiCl4THF solution adds the carrier of the modified catalyst of the alkyl aluminum of the gained into step (5), wherein
The weight ratio of Ti atoms and the carrier is 10wt%, after stirring 4h, wash pressed powder 10 times with THF, is dried to free-flowing,
The Ziegler-Natta catalyst of low entanglement polyethylene is prepared efficiently.
Slurry polymerization reactor is heated to into 60 DEG C, regulation polymerization pressure is 1bar, sequentially adds 200mL toluene, 5mL tri-
Ziegler-Natta catalyst prepared by aluminium ethide (Al atoms with the mol ratio of Ti atoms be 100), ethylene and 0.03g is to anti-
In answering device, start polyreaction.Stop after polymerization 1h, products therefrom molecular weight is 500,000 g/mol, 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 n-butyl alcohol of the porous carrier aluminium oxide of 1.0g apertures 100nm and 6mmol at 20mL tetrahydrofurans (THF)
After mixing 4h in solution, the modified porous carrier of alcohol is obtained, wash the porous carrier 1 time for obtaining that alcohol is modified with 20mL THF, obtain
Obtain the porous carrier adsorbed by n-butyl alcohol；(2). by the organic substituent of Polyhedral oligomeric silsesquioxanes (POSS) molecule spy's fourth
Base and hydroxyl replace, wherein containing hydroxyl number 3 on 1 POSS molecule, obtain modified Polyhedral oligomeric silsesquioxanes point
Son, POSS molecular diameters are 10nm；(3). by modified Polyhedral oligomeric silsesquioxanes molecule and 0.6mmol in step (2)
Magnesium ethylate (n-butyl alcohol is 10 with magnesium mol ratio) is 0.05% by the mol ratio of hydroxyl moles in POSS and Mg atoms,
Mix in 20mLTHF, prepare Polyhedral oligomeric silsesquioxanes/Mg mixture；(4). by the Polyhedral Oligomeric times prepared in step (3)
The mixture of half siloxanes/Mg adds the porous carrier of the n-butyl alcohol absorption prepared into step (1), after stirring 4h in THF,
Filter, pressed powder is dried to free-flowing, obtains preparing the carrier of low entanglement polyethylene catalysts；(5). by 10mmol tri-
Aluminium ethide adds the carrier for preparing low entanglement polyethylene catalysts of the gained into step (4), stirs 4h, is washed with THF 3 times,
Unnecessary triethyl aluminum is removed, pressed powder is dried to free-flowing the carrier for obtaining the modified catalyst of alkyl aluminum；(6).
By TiCl3THF solution add to the carrier of the modified catalyst of the alkyl aluminum of gained in step (5), wherein Ti atoms with should
The weight ratio of carrier is 1wt%, after stirring 8h, wash pressed powder 3 times with THF, is dried to flowing freely, and obtains efficiently preparation
The Ziegler-Natta catalyst of low entanglement polyethylene.
Slurry polymerization reactor is heated to into 80 DEG C, pressure 10bar sequentially adds 200mL toluene, 0.5mL triethyl aluminums
Ziegler-Natta catalyst prepared by (mol ratio of Al atoms and Ti atoms is 10), ethylene and 0.03g into reactor,
Start polyreaction.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). will be 1 μm of the porous carrier titanium dioxide in 1.0g apertures molten in 20mL tetrahydrofurans (THF) with the ethanol of 6mmol
After mixing 6h in liquid, the modified porous carrier of alcohol is obtained, wash with 20mL THF and obtain the modified porous carrier of alcohol 5 times, acquisition
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). by the modified Polyhedral oligomeric silsesquioxanes molecule in step (2) and 3mmol hydroxides
Magnesium (ethanol is 2 with magnesium mol ratio) is 10% by the mol ratio of hydroxyl moles in POSS and Mg atoms, is mixed in 20mLTHF
Close, prepare Polyhedral oligomeric silsesquioxanes/Mg mixture；(4). the Polyhedral oligomeric silsesquioxanes/Mg that will be prepared in step (3)
Mixture add to the porous carrier of the Ethanol Adsorption prepared in step (1), after stirring 6h in THF, filter, by solid powder
End is dried to flowing freely, and obtains preparing the carrier of low entanglement polyethylene catalysts；(5). by 10mmol triethyl aluminums add to
The carrier for preparing low entanglement polyethylene catalysts of gained in step (4), stirs 4h, is washed with THF 1 time, removes unnecessary three
Aluminium ethide, pressed powder is dried to free-flowing the carrier for obtaining the modified catalyst of alkyl aluminum；(6). by TiCl3THF
Solution is added to the carrier of the modified catalyst of the alkyl aluminum of gained in step (5), wherein the weight ratio of Ti atoms and the carrier
For 5wt%, after stirring 6h, wash pressed powder 5 times with THF, be dried to free-flowing, efficiently prepared low entanglement polyethylene
Ziegler-Natta catalyst.
Slurry polymerization reactor is heated to into 90 DEG C, pressure 30bar sequentially adds 200mL toluene, 10mL trimethyl aluminas
Ziegler-Natta catalyst prepared by alkane (Al atoms are 200 with the mol ratio of Ti atoms), ethylene and 0.03g is to reactor
In, start polyreaction.Stop after polymerase 10 .1h, products therefrom molecular weight is 10,000,000 g/mol, 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 1.0g apertures and 6mmol at 20mL tetrahydrofurans (THF)
After mixing 4h in solution, the modified porous carrier of alcohol is obtained, wash the porous carrier 3 times for obtaining that alcohol is modified with 20mL THF, obtain
Obtain the porous carrier adsorbed by ethylene glycol；(2). 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 modified many
Face oligomeric silsesquioxanes molecule；(3). by the modified Polyhedral oligomeric silsesquioxanes molecule in step (2) and 1mmol brominations
Magnesium (ethylene glycol is 6 with magnesium mol ratio) is 0.01% by the mol ratio of hydroxyl moles in POSS and Mg atoms, in 20mL THF
Middle mixing, prepares Polyhedral oligomeric silsesquioxanes molecule/Mg mixture；(4). the Polyhedral Oligomeric sesquialter that will be prepared in step (3)
The mixture of siloxane molecule/Mg adds the porous carrier of the ethylene glycol absorption prepared into step (1), and 5h is stirred in THF
Afterwards, filter, pressed powder is dried to free-flowing, obtains preparing the carrier of low entanglement polyethylene catalysts；(5). will
10mmol triethyl aluminums add the carrier for preparing low entanglement polyethylene catalysts of the gained into step (4), stir 4h, use THF
Washing 5 times, removes unnecessary triethyl aluminum, and pressed powder is dried to free-flowing the load for obtaining the modified catalyst of alkyl aluminum
Body；(6). by TiCl3THF solution add to the carrier of the modified catalyst of the alkyl aluminum of gained in step (5), wherein Ti is former
Son is 0.1wt% with the weight ratio of the carrier, after stirring 6h, wash pressed powder 5 times with THF, is dried to flowing freely, acquisition
The Ziegler-Natta catalyst of low entanglement polyethylene is prepared efficiently.
Slurry polymerization reactor is heated to into 70 DEG C, pressure 30bar sequentially adds 200mL toluene, 2mL trimethyl aluminium (Al
The mol ratio of atom and Ti atoms for 60), the Ziegler-Natta catalyst for preparing of ethylene and 0.05g into reactor, start
Polyreaction.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 propanol of the porous carrier silica-alumina in 10 μm of 1.0g apertures and 6mmol in 20mL tetrahydrofurans
(THF) after mixing 4h in solution, the modified porous carrier of alcohol is obtained, is washed with 20mL THF and obtain the modified porous carrier 3 of alcohol
It is secondary, obtain the porous carrier adsorbed by propanol；(2). the organic substituent of Polyhedral oligomeric silsesquioxanes (POSS) molecule is used
Propyl group and hydroxyl replace, and POSS molecular diameters are 2nm, wherein containing hydroxyl number 1 on 1 POSS molecule, obtain modified
Polyhedral oligomeric silsesquioxanes molecule；(3). by the modified Polyhedral oligomeric silsesquioxanes molecule in step (2) and 1mmol bromines
It is 0.01% by the mol ratio of hydroxyl moles in POSS and Mg atoms to change magnesium (propanol is 6 with magnesium mol ratio), in 20mL THF
Middle mixing, prepares Polyhedral oligomeric silsesquioxanes molecule/Mg mixture；(4). the Polyhedral Oligomeric sesquialter that will be prepared in step (3)
The mixture of siloxane molecule/Mg adds the porous carrier of the propanol absorption prepared into step (1), after stirring 5h in THF,
Filter, pressed powder is dried to free-flowing, obtains preparing the carrier of low entanglement polyethylene catalysts；(5). by 10mmol tri-
Aluminium methyl adds the carrier for preparing low entanglement polyethylene catalysts of the gained into step (4), stirs 4h, is washed with THF 5 times,
Unnecessary trimethyl aluminium is removed, pressed powder is dried to free-flowing the carrier for obtaining the modified catalyst of alkyl aluminum；(6).
By TiCl4THF solution add to the carrier of the modified catalyst of the alkyl aluminum of gained in step (5), wherein Ti atoms with should
The weight ratio of carrier is 0.5wt%, after stirring 6h, wash pressed powder 5 times with THF, is dried to flowing freely, and obtains efficiently system
The Ziegler-Natta catalyst of standby low entanglement polyethylene.
Slurry polymerization reactor is heated to into 70 DEG C, pressure 30bar sequentially adds 200mL toluene, 2mL trimethyl aluminium (Al
The mol ratio of atom and Ti atoms for 60), the Ziegler-Natta catalyst for preparing of ethylene and 0.05g into reactor, start
Polyreaction.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). 1 μm of the porous carrier in 1.0g apertures is covered and opens up native molten in 20mL tetrahydrofurans (THF) with the Propylene Glycol of 6mmol
After mixing 6h in liquid, the modified porous carrier of alcohol is obtained, wash with 20mL THF and obtain the modified porous carrier of alcohol 5 times, acquisition
The porous carrier adsorbed by Propylene Glycol；(2). 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). by the modified Polyhedral oligomeric silsesquioxanes molecule in step (2) and 3mmol hydroxides
Magnesium (Propylene Glycol is 2 with magnesium mol ratio) is 10% by the mol ratio of hydroxyl moles in POSS and Mg atoms, is mixed in 20mLTHF
Close, prepare Polyhedral oligomeric silsesquioxanes/Mg mixture；(4). the Polyhedral oligomeric silsesquioxanes/Mg that will be prepared in step (3)
Mixture add to the porous carrier of the Propylene Glycol absorption prepared in step (1), after stirring 6h in THF, filter, by solid
Powder is dried to free-flowing, obtains preparing the carrier of low entanglement polyethylene catalysts；(5). by 10mmol trimethyl aikyiaiurnirsoxan beta
The carrier for preparing low entanglement polyethylene catalysts of the gained into step (4) is added, 4h is stirred, is washed with THF 1 time, removed many
Remaining trimethyl aikyiaiurnirsoxan beta, pressed powder is dried to free-flowing the carrier for obtaining the modified catalyst of alkyl aluminum；(6). will
TiCl4THF solution add to the carrier of the modified catalyst of the alkyl aluminum of gained in step (5), wherein Ti atoms and the load
The weight ratio of body is 5wt%, after stirring 6h, wash pressed powder 5 times with THF, is dried to free-flowing, is efficiently prepared low
The Ziegler-Natta catalyst of entanglement polyethylene.
Slurry polymerization reactor is heated to into 90 DEG C, pressure 30bar sequentially adds 200mL toluene, 10mL trimethyl aluminas
Ziegler-Natta catalyst prepared by alkane (Al atoms are 100 with the mol ratio of Ti atoms), ethylene and 0.01g is to reactor
In, start polyreaction.Stop after polymerase 10 .1h, products therefrom molecular weight is 5,000,000 g/mol, 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 (10)
1. a kind of preparation method of the Ziegler-Natta catalyst for efficiently preparing low entanglement polyethylene, its feature includes following
Step：
(1), after the porous carrier in 20nm-10 μm of aperture being mixed 4-6h in tetrahydrofuran solution with alcohol, modified many of alcohol are obtained
Hole carrier, washs alcohol modified porous carrier 1-5 time, obtains by the porous carrier of alcohol absorption with tetrahydrofuran；
(2) by the organic substituent methyl of Polyhedral oligomeric silsesquioxanes molecule, ethyl, propyl group, isopropyl, isobutyl group, spy
One or more replacement in butyl and hydroxyl, wherein containing hydroxyl number 1-3 on 1 POSS molecule, obtains modified many
Face oligomeric silsesquioxanes molecule；
(3) the modified Polyhedral oligomeric silsesquioxanes molecule in step (2) is mixed in tetrahydrofuran solution with Mg compounds
Conjunction prepares Polyhedral oligomeric silsesquioxanes molecule/Mg mixture, and wherein on Polyhedral oligomeric silsesquioxanes molecule, hydroxyl is former with Mg
The mol ratio of son is 0.01%-10%, preferred 0.05%-4%；
(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, filter, pressed powder is dried to free-flowing, is obtained
Prepare the carrier of low entanglement polyethylene catalysts；
(5) excessive alkyl aluminum is added the carrier for preparing low entanglement polyethylene catalysts of the gained into step (4), 4- is stirred
8h, is washed 3-8 time with tetrahydrofuran solution, is removed unnecessary alkyl aluminum, pressed powder is dried to free-flowing and obtains alkyl
The carrier of the modified catalyst of aluminum；
(6) by TiCl4Or TiCl3Tetrahydrofuran solution add to the load of the modified catalyst of the alkyl aluminum of gained in step (5)
Body, wherein Ti atoms are 0.1wt%-10wt% with the weight ratio of the carrier, after stirring 4-8h, wash solid with tetrahydrofuran solution
Body powder 3-10 time, is dried to flowing freely, is efficiently prepared the Ziegler-Natta catalyst of low entanglement polyethylene, urged
The ethylene polymerization activity of agent is 5*105-2*107g PE/mol Ti·h·bar。
2. the preparation of a kind of Ziegler-Natta catalyst for efficiently preparing low entanglement polyethylene according to claim 1
Method, it is characterised in that：Described porous carrier is selected from silicon dioxide, aluminium oxide, zirconium oxide, titanium dioxide, silicon oxide-oxidation
Aluminum, illiteracy open up one or more in soil.
3. the preparation of a kind of Ziegler-Natta catalyst for efficiently preparing low entanglement polyethylene according to claim 1
Method, it is characterised in that：Described alcohol includes the one kind in ethanol, propanol, n-butyl alcohol, ethylene glycol, Propylene Glycol, 1,4 butanediols
Or it is several.
4. the preparation of a kind of Ziegler-Natta catalyst for efficiently preparing low entanglement polyethylene according to claim 1
Method, it is characterised in that：Described Mg compounds are magnesium chloride, magnesium bromide, magnesium ethylate, magnesium hydroxide one kind or two kinds of mixing
Thing.
5. the preparation of a kind of Ziegler-Natta catalyst for efficiently preparing low entanglement polyethylene according to claim 1
Method, it is characterised in that：Described alcohol is 1-10 with the mol ratio of Mg atoms.
6. the preparation of a kind of Ziegler-Natta catalyst for efficiently preparing low entanglement polyethylene according to claim 1
Method, it is characterised in that：The molecular diameter 0.1-20nm of described Polyhedral oligomeric silsesquioxanes；It is preferred that 1-10nm.
7. according to a kind of preparation side of the Ziegler-Natta catalyst for efficiently preparing low entanglement polyethylene described in claim 1
Method, it is characterised in that：Described alkyl aluminum includes trimethyl aluminium, trimethyl aikyiaiurnirsoxan beta, triethyl aluminum and its mixture of the two.
8. a kind of preparation method of low entanglement polyethylene, it is characterised in that in slurry polymerization reactor, adds promoter, second
Alkene and the Ziegler-Natta catalyst of low entanglement polyethylene is efficiently prepared, be warming up to 60～90 DEG C, polymerization pressure adjusted to 1
～30bar, 0.1～5h of polyreaction, that is, obtain described low entanglement polyethylene.
9. the preparation method of a kind of low entanglement polyethylene according to claim 8, it is characterised in that：Described promoter
For alkyl aluminum compound, Al atoms are 10-200 with the Ti atomic molars ratio of catalyst.
10. the preparation method of a kind of low entanglement polyethylene according to claim 8, it is characterised in that：The low entanglement for preparing
Weight average molecular weight range 10000-10000000g/mol of polyethylene.
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| CN112724688B (en) * | 2020-12-28 | 2022-08-05 | 浙江万马专用线缆科技有限公司 | High-strength cable sheath material, preparation method thereof and cable sheath |
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