CN115490794B - Ultra-high molecular weight polyethylene powder and preparation method thereof - Google Patents
Ultra-high molecular weight polyethylene powder and preparation method thereof Download PDFInfo
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- CN115490794B CN115490794B CN202110682972.3A CN202110682972A CN115490794B CN 115490794 B CN115490794 B CN 115490794B CN 202110682972 A CN202110682972 A CN 202110682972A CN 115490794 B CN115490794 B CN 115490794B
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- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 title claims abstract description 59
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 title claims abstract description 59
- 239000000843 powder Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 239000002245 particle Substances 0.000 claims abstract description 44
- 239000011777 magnesium Substances 0.000 claims abstract description 34
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 34
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 30
- 239000010936 titanium Substances 0.000 claims abstract description 30
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 28
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005977 Ethylene Substances 0.000 claims abstract description 11
- 239000012442 inert solvent Substances 0.000 claims abstract description 8
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims abstract description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- -1 titanium halides Chemical class 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000002681 magnesium compounds Chemical class 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
- SXSVTGQIXJXKJR-UHFFFAOYSA-N [Mg].[Ti] Chemical compound [Mg].[Ti] SXSVTGQIXJXKJR-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 claims description 2
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Chemical group 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims description 2
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 2
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 238000000975 co-precipitation Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 10
- 239000000047 product Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000725 suspension Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000003701 inert diluent Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/06—Catalyst characterized by its size
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention belongs to the technical field of polymer preparation, and discloses a preparation method of ultra-high molecular weight polyethylene powder, which comprises the following steps: in the presence of Ziegler-Natta catalyst system and inert solvent, ethylene is polymerized at 30-120 deg.c and 0.05-10MPa; the Ziegler-Natta type catalyst system comprises a magnesium-containing titanium catalyst component A and a cocatalyst B, wherein the average particle size of the magnesium-containing titanium catalyst component A is less than 2 microns. The average grain diameter of the product prepared by the preparation method is lower than 100 microns, the bulk density is higher, and the molecular weight is high.
Description
Technical Field
The invention belongs to the technical field of polymer preparation, and in particular relates to ultra-high molecular weight polyethylene powder and a preparation method thereof.
Background
Ultra high molecular weight polyethylene (Ultra-High Molecular Weight Polyethylene, abbreviated as UHMWPE) is a thermoplastic material with special properties, typically having a molecular weight of over 150 ten thousand. Because of its high molecular weight, the melt is highly viscous and essentially non-flowing, and difficult to granulate, the product is typically a powder granulate.
The main processing method of UHMWPE products is still a traditional compression molding mode, and is used for mass production of plates, sheets and the like with different thicknesses. The forming mode has certain requirements on powder products, the size, the particle uniformity and the bulk density of the powder can influence the energy consumption and the product performance, and generally, the smaller and more uniform powder particles are, the higher the bulk density is, the more the processing energy consumption is reduced and the product performance is improved; meanwhile, UHMWPE is also used as a functional additive for improving the wear resistance, lubrication and other performances of plastics, rubber, paint, oil and the like, and when the UHMWPE is used for the purpose, the powder particle size is expected to be smaller, so that stable dispersion is facilitated. Therefore, there is a real need for UHMWPE powder particles of smaller particle size.
At present, the particle size of UHMWPE powder is generally about 200 microns, and the particle size of UHMWPE powder for gel spinning is slightly smaller, but the average particle size of UHMWPE products is generally more than 100 microns. The method for obtaining UHMWPE powder with the small particle size below 100 microns mainly comprises product classification, generally lower yield and higher cost; there are reports of reducing the particle size by grinding, but grinding is generally required at a lower temperature, and the uniformity of the product is poor and the cost is higher than that of the classification method.
Therefore, there is an urgent need to develop a technology for preparing UHMWPE products having an average particle size of 100 microns or less, which meets the demands of people in production and living.
In the prior art, few methods for preparing UHMWPE powder particle products below 100 microns are reported. There are two ways in which this can be achieved in theory. Firstly, the activity of the catalyst is reduced, because the average particle size of UHMWPE powder has a definite relation with the activity of the catalyst, but the catalyst has low activity, which causes the defects of more catalyst residues in the product, product color change and the like, and is also unfavorable for production control; and secondly, a catalyst with smaller particle size is adopted, but the catalyst particle size is limited by the preparation process of the catalyst, and when the catalyst particle size is smaller than 5 microns, sedimentation, separation and drying in the catalyst preparation process are difficult to smoothly carry out. In summary, the prior art has not solved the problem of producing small particle size UHMWPE particles.
Disclosure of Invention
In view of the above, an object of the present invention is to provide an ultra-high molecular weight polyethylene powder and a method for producing the same, which obtain UHMWPE particles having an average particle diameter of 100 μm or less in a polymerizer by controlling polymerization conditions using a catalyst having a smaller particle diameter.
The first aspect of the present invention provides a process for preparing an ultra-high molecular weight polyethylene powder, the process comprising: in the presence of Ziegler-Natta catalyst system and inert solvent, ethylene is polymerized at 30-120 deg.c and 0.05-10MPa;
the Ziegler-Natta type catalyst system comprises a magnesium-containing titanium catalyst component A and a cocatalyst B, wherein the average particle size of the magnesium-containing titanium catalyst component A is less than 2 microns.
The second aspect of the invention provides ultra-high molecular weight polyethylene powder prepared by the preparation method.
In the preparation method, ethylene is subjected to polymerization reaction in the presence of a Ziegler-Natta catalyst system and an inert solvent, the polymerization reaction temperature and the polymerization pressure are controlled, and the ultra-high molecular weight polyethylene is prepared, so that the average particle size of the obtained ultra-high molecular weight polyethylene powder is lower than 100 microns, and the bulk density and the molecular weight are higher.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
According to a first aspect of the present invention, there is provided a process for preparing ultra-high molecular weight polyethylene powder, the process comprising: in the presence of Ziegler-Natta catalyst system and inert solvent, ethylene is polymerized at 30-120 deg.c and 0.05-10MPa;
the Ziegler-Natta type catalyst system comprises a magnesium-containing titanium catalyst component A and a cocatalyst B, wherein the average particle size of the magnesium-containing titanium catalyst component A is less than 2 microns.
According to the present invention, the magnesium-containing titanium catalyst component a refers to a general magnesium-containing titanium element solid catalyst component for olefin polymerization, which can employ a large amount of magnesium/titanium-containing solids well known to those skilled in the art. Preferably, the magnesium-containing titanium catalyst component A is prepared by the following method: dissolving a magnesium compound to form a uniform solution; and then re-precipitating the solid precipitate containing magnesium/titanium in the presence of the halide of titanium and the derivative thereof and an optional precipitation aid to obtain the magnesium-titanium-containing catalyst component A. The magnesium compound is preferably a magnesium halide, magnesium alkoxide or magnesium haloalkoxide.
The preparation method of the magnesium-containing titanium catalyst component A can be carried out by referring to the prior art. For example, the following method may be employed: dissolving magnesium halide in inert diluent containing organic epoxy compound, organic phosphorus compound and alcohol compound under stirring to form uniform solution, adding titanium compound into the uniform solution of magnesium halide at-30-60 deg.C, preferably-30-5 deg.C in the presence of optional precipitation aid, heating reaction mixture to 60-110 deg.C, stirring suspension at this temperature for 0.5-8 hr, filtering mother liquor, washing with inert diluent to obtain magnesium-titanium catalyst component A.
In the present invention, the magnesium-containing titanium catalyst component A may be in the form of a dry powder or a slurry dispersed in a solvent, preferably in the form of a slurry (suspension) when it is added to the reaction system. The use of a slurry form reduces the risk of agglomeration of the particles.
The average grain diameter of the magnesium-containing titanium catalyst component A is below 2 microns, and in the preparation process, if a stainless steel filter screen is adopted, the obtained magnesium-containing titanium catalyst component A is less or not obtained. The filtering material of the filter is formed by sintering UHMWPE powder particles at high temperature.
Preferably, the UHMWPE powder has particle size less than 325 μm and viscosity average molecular weight of 200-600 ten thousand, and is sintered at 100-250deg.C for 0.5-4 hr after filling mould.
In the invention, the auxiliary agentThe catalyst B is an organic aluminum compound with a general formula of AlR n X 3-n Wherein R is hydrogen, hydrocarbon group with 1-20 carbon atoms, preferably alkyl, aralkyl and aryl with 1-20 carbon atoms; x is halogen, preferably chlorine and bromine; n is a number of 0 < n.ltoreq.3.
Specific examples of the organoaluminum compounds include, but are not limited to: trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydride, diisobutylaluminum monohydride, diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride, ethylaluminum dichloride.
The organoaluminum compound is preferably triethylaluminum or triisobutylaluminum.
In the present invention, the molar ratio of aluminum in the organoaluminum compound to titanium in the magnesium-containing titanium catalyst component A is 5 to 5000:1, preferably 20 to 500:1.
According to the invention, the inert solvent may be a linear or branched alkane, preferably hexane, heptane, octane, decane or derivatives thereof.
Preferably, the temperature of the polymerization reaction is 40-90 ℃, when the temperature is too high, ethylene molecules are easy to undergo free radical polymerization, and the molecular weight of the prepared polyethylene is not high; too low a temperature, the catalyst activity is low or does not polymerize.
The pressure of the polymerization reaction is preferably 0.1-5MPa, the concentration of ethylene monomer is increased when the pressure is too high, the activity of the catalyst is high, and the bulk density of the prepared polyethylene powder is low; too low a pressure, low catalyst activity or no polymerization.
Parameters not defined in the present invention are all conventional in the art.
According to a second aspect of the present invention, there is provided an ultra-high molecular weight polyethylene powder prepared by the above-described preparation method.
In the present invention, the average particle size of the ultra-high molecular weight polyethylene powder is less than 100 microns, preferably less than 80 microns; bulk density greater than 0.3g/L; the viscosity average molecular weight is more than 300 ten thousand.
The invention will be further illustrated with reference to the following examples. But are not limited by these examples.
In the following examples and comparative examples:
polymer apparent density (BD): reference ASTM D1895-96;
polymer molecular weight (Mw): a viscosity method;
average particle diameter of polymer: CAMSIZER particle analyzer.
Examples 1-3 illustrate the process for preparing the ultra high molecular weight polyethylene powder of the invention.
Example 1
Preparation of magnesium-containing titanium catalyst component A: adding 9.6 g of magnesium chloride, 100 ml of toluene, 6.0 ml of epichlorohydrin, 7.2 ml of tributyl phosphate and 15.2 ml of ethanol into a reaction kettle, reacting for 1 hour at the stirring rotation speed of 450rpm and the temperature of 55 ℃, adding 1.6 g of phthalic anhydride, continuously reacting for 1 hour, cooling to-30 ℃, slowly dropwise adding 80 ml of titanium tetrachloride within 4 hours, heating to 80 ℃ within 4 hours, keeping the temperature for 5.0 hours, filtering a mother solution by a filter (the filtering material of the filter is UHMWPE powder particles with the granularity less than 325 microns, the viscosity average molecular weight is 500 ten thousand, the UHMWPE powder particles are sintered for 2 hours at 200 ℃ after filling a mould), washing twice with 120 ml of toluene at 60 ℃, washing for 4 times by using organic solvent hexane, and finally adding 1000 ml of hexane to prepare a catalyst suspension, wherein the average particle size of solid particles is 1.4 microns.
Preparation of ultra-high molecular weight polyethylene powder: the 2-liter polymerization reactor was alternately purged with nitrogen and evacuated three times, 1 liter of n-hexane, 2mmol of triethylaluminum and 0.2 ml of the catalyst suspension were added, the temperature was raised to 60℃and ethylene was added to maintain the reactor pressure at 0.5MPa, and the reaction was carried out at 60℃for 1 hour. And after the reaction is finished, cooling, separating and collecting the polymer.
Example 2
Preparation of magnesium-containing titanium catalyst component A: as in example 1.
Preparation of ultra-high molecular weight polyethylene powder: the 2 liter polymerization reactor was alternately purged with nitrogen and evacuated three times, 1 liter of n-hexane, 2mmol of triethylaluminum and 0.5 ml of the catalyst suspension were added, the temperature was raised to 80℃and ethylene was added to maintain the reactor pressure at 0.2MPa, and the reaction was carried out at 80℃for 2 hours. And after the reaction is finished, cooling, separating and collecting the polymer.
Example 3
Preparation of magnesium-containing titanium catalyst component A: as in example 1.
Preparation of ultra-high molecular weight polyethylene powder: the 2-liter polymerization reactor was alternately purged with nitrogen and evacuated three times, 1 liter of n-hexane, 2mmol of triethylaluminum and 1.0 ml of the catalyst suspension were added, the temperature was raised to 50℃and ethylene was added to maintain the reactor pressure at 0.7MPa, and the reaction was carried out at 50℃for 5 hours. And after the reaction is finished, cooling, separating and collecting the polymer.
Comparative example 1
Preparation of magnesium-containing titanium catalyst component A: adding 4.8 g of magnesium chloride, 55 ml of toluene, 3.0 ml of epichlorohydrin, 3.6 ml of tributyl phosphate and 7.6 ml of ethanol into a reaction kettle, reacting for 1 hour at the stirring rotation speed of 450rpm and the temperature of 55 ℃, adding 0.8 g of phthalic anhydride, continuing to react for 1 hour, cooling to-30 ℃, slowly dropwise adding 40 ml of titanium tetrachloride within 4 hours, heating to 80 ℃ within 4 hours, keeping the temperature for 2.0 hours, filtering by a filter screen, washing twice with 120 ml of toluene at 60 ℃, washing for 4 times by using organic solvent hexane, and finally drying the suspension to obtain 6.5 g of catalyst component. The average particle size of the solid particles was measured to be 5.8 microns.
Preparation of ultra-high molecular weight polyethylene powder: a2-liter polymerization reactor was alternately purged with nitrogen and evacuated three times, 1 liter of n-hexane, 2mmol of triethylaluminum and 5 mg of catalyst were added, the temperature was raised to 70℃and ethylene was added to maintain the reactor pressure at 0.7MPa, and the reaction was carried out at 70℃for 2 hours. And after the reaction is finished, cooling, separating and collecting the polymer.
The polymer powders prepared in each of the examples and comparative examples were tested and the data are shown in Table 1.
TABLE 1
| Numbering device | Average particle size (micron) | BD(g/L) | Viscosity average molecular weight (Wan) |
| Example 1 | 73 | 0.35 | 420 |
| Example 2 | 35 | 0.41 | 332 |
| Example 3 | 58 | 0.33 | 640 |
| Comparative example 1 | 150 | 0.32 | 380 |
From the data in Table 1, it can be seen that UHMWPE is produced using the process of the present invention, the average particle size of the product is less than 100 microns, the bulk density is high, and the molecular weight is high.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
Claims (16)
1. The preparation method of the ultra-high molecular weight polyethylene powder is characterized by comprising the following steps: in the presence of Ziegler-Natta catalyst system and inert solvent, ethylene is polymerized at 30-120 deg.c and 0.05-10MPa;
the Ziegler-Natta catalyst system comprises a magnesium-containing titanium catalyst component A and a cocatalyst B, wherein the average particle size of the magnesium-containing titanium catalyst component A is less than 2 microns;
the magnesium-containing titanium catalyst component A is prepared by the following method: dissolving a magnesium compound to form a uniform solution; re-precipitating a solid precipitate containing magnesium/titanium in the presence of titanium halides and derivatives thereof and optionally a co-precipitation agent; the filtration of the solid precipitate containing magnesium/titanium is carried out by adopting a filter, and the filtering material of the filter is formed by sintering UHMWPE powder particles at high temperature.
2. The process for producing an ultra-high molecular weight polyethylene powder according to claim 1, wherein,
the magnesium compound is selected from magnesium halide, magnesium alkoxide or magnesium haloalkoxide.
3. The process for producing an ultra-high molecular weight polyethylene powder according to claim 1, wherein,
the particle size of UHMWPE powder is less than 325 μm, the viscosity average molecular weight is 200-600 ten thousand, and the UHMWPE powder is sintered at 100-250deg.C for 0.5-4 hr after filling mould.
4. The process for preparing ultra-high molecular weight polyethylene powder according to claim 1, wherein the cocatalyst B is an organoaluminum compound having the general formula AlR n X 3-n Wherein R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms; x is halogen; n is 0<n is less than or equal to 3.
5. The process for producing ultra-high molecular weight polyethylene powder according to claim 4, wherein R is an alkyl group having 1 to 20 carbon atoms, an aralkyl group or an aryl group.
6. The process for preparing an ultra-high molecular weight polyethylene powder according to claim 4, wherein X is chlorine or bromine.
7. The process for producing ultra-high molecular weight polyethylene powder according to claim 4, wherein said organoaluminum compound is at least one selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydride, diisobutylaluminum monohydride, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichloride.
8. The method for producing an ultra-high molecular weight polyethylene powder according to claim 7, wherein said organoaluminum compound is triethylaluminum or triisobutylaluminum.
9. The method for producing an ultra high molecular weight polyethylene powder according to any one of claims 4 to 8, wherein the molar ratio of aluminum in the organoaluminum compound to titanium in the magnesium-containing titanium catalyst component a is 5 to 5000:1.
10. The method for producing ultra-high molecular weight polyethylene powder according to claim 9, wherein the molar ratio of aluminum in the organoaluminum compound to titanium in the magnesium-titanium-containing catalyst component a is 20 to 500:1.
11. The method for producing ultra-high molecular weight polyethylene powder according to claim 1, wherein the inert solvent is a linear or branched alkane.
12. The method for producing ultra-high molecular weight polyethylene powder according to claim 11, wherein the inert solvent is hexane, heptane, octane or decane.
13. The process for preparing ultra-high molecular weight polyethylene powder according to claim 1, wherein the polymerization reaction is carried out at a temperature of 40 to 90℃and a pressure of 0.1 to 5MPa.
14. An ultra-high molecular weight polyethylene powder prepared by the preparation method of any one of claims 1 to 13.
15. The ultra-high molecular weight polyethylene powder according to claim 14, wherein the ultra-high molecular weight polyethylene powder has an average particle size of less than 100 microns; bulk density greater than 0.3g/L; the viscosity average molecular weight is more than 300 ten thousand.
16. The ultra-high molecular weight polyethylene powder according to claim 15, wherein the ultra-high molecular weight polyethylene powder has an average particle size of less than 80 microns.
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| EP3310820A1 (en) * | 2015-06-22 | 2018-04-25 | Council of Scientific and Industrial Research | Catalysts for preparation of ultra high molecular weight polyethylene (uhmwpe) and process for preparation thereof |
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| CN1746197A (en) * | 2004-09-08 | 2006-03-15 | 上海化工研究院 | Ultrahigh-molecular weight polyethylene catalyst, its preparation and use thereof |
| CN103772537A (en) * | 2012-10-19 | 2014-05-07 | 中国石油化工股份有限公司 | Ultrahigh molecular weight polyethylene preparation method |
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