CN105985465A - Ultrahigh molecular weight polyethylene catalyst and preparation method of ultrahigh molecular weight polyethylene - Google Patents
Ultrahigh molecular weight polyethylene catalyst and preparation method of ultrahigh molecular weight polyethylene Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 title claims abstract description 19
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 title claims abstract description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000005977 Ethylene Substances 0.000 claims abstract description 32
- 238000013329 compounding Methods 0.000 claims abstract description 19
- 229920000573 polyethylene Polymers 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 15
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 6
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 229910052749 magnesium Inorganic materials 0.000 claims description 24
- 239000011777 magnesium Substances 0.000 claims description 24
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 20
- 150000002148 esters Chemical class 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 13
- 239000012188 paraffin wax Substances 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 238000005660 chlorination reaction Methods 0.000 claims description 10
- 239000004705 High-molecular-weight polyethylene Substances 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- BRRYKAGZJJHJMG-UHFFFAOYSA-J [Mg][Ti](Cl)(Cl)(Cl)Cl Chemical compound [Mg][Ti](Cl)(Cl)(Cl)Cl BRRYKAGZJJHJMG-UHFFFAOYSA-J 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- 150000002736 metal compounds Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- -1 polyethylene Polymers 0.000 abstract description 21
- 238000006116 polymerization reaction Methods 0.000 abstract description 19
- 239000004698 Polyethylene Substances 0.000 abstract description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- RVDLHGSZWAELAU-UHFFFAOYSA-N 5-tert-butylthiophene-2-carbonyl chloride Chemical compound CC(C)(C)C1=CC=C(C(Cl)=O)S1 RVDLHGSZWAELAU-UHFFFAOYSA-N 0.000 abstract 1
- 230000003213 activating effect Effects 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000013019 agitation Methods 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 229910001507 metal halide Inorganic materials 0.000 description 6
- 150000005309 metal halides Chemical class 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 1
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 description 1
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 1
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 1
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention belongs to the technical field of polyethylene preparation, and relates to an ultrahigh molecular weight polyethylene catalyst and a preparation method of ultrahigh molecular weight polyethylene6-C16Adding transition metal compound titanium tetrachloride into the straight-chain alkane, compounding the magnesium ethoxide and the titanium tetrachloride, adding tetraethoxysilane, and filtering, washing and pre-activating to prepare the ultra-high molecular weight polyethylene catalyst. The preparation method of polyethylene is that alkyl aluminum is added into a single stirring kettle type slurry reactor as a cocatalyst; adding a catalyst into a single stirred tank slurry reactor; introducing ethylene; at a certain temperature and pressure, the ultrahigh molecular weight polyethylene is obtained through polymerization reaction. The invention has the advantages that: the method can prepare the ultra-high molecular weight polyethylene catalyst, and the ultra-high molecular weight polyethylene with different molecular weights can be prepared by adjusting the preparation process and the polymerization process of the catalyst, wherein the molecular weight of the product is 300-.
Description
Technical field
The invention belongs to field of chemical technology, relate to a kind of extra high-molecular polythene catalyst and surpass
The preparation method of High molecular weight polyethylene.
Background technology
Chinese patent CN 94105011 refers to a kind of dialkyl magnesium and reacts formation halogenation with halogenating agent
Reactive magnesium thing, then react with titanium compound, narrow particle size distribution can be prepared, the superelevation that granularity is little is divided
Sub-weight northylen, course of reaction is complicated.The present invention directly uses magnesium dichloride to be that carrier prepares catalyst,
And then carry out polyreaction, obtain ultra-high molecular weight polyethylene product.
The preparation of the ultra-high molecular weight polyethylene that Chinese patent CN93103156.7 relates to uses double load
Body catalyst, and the present invention is supported catalyst, prepared ultra-high molecular weight polyethylene molecular weight is
300-500 ten thousand.
Chinese invention patent CN103554310A, discloses a kind of spherical carrier loaded type olefinic polymerization and urges
The preparation method of agent, it is by joining in solvent by alkoxyl magnesium ball type carrier, forms alkoxyl
Magnesium ball type carrier slurry, the chemical treatments being subsequently adding Group IVB metal halide processes, filter,
Wash and be dried and obtain.Additionally, embodiment 1 discloses specifically embodiment, i.e. alkoxyl magnesium
Ball type carrier uses diethoxy magnesium ball type carrier, and (sphericity is 1.25, and bulk density is 0.35g/cm3, and
And mean diameter is 25 microns), solvent uses decane, the chemical treatments of Group IVB metal halide
Use titanium tetrachloride.Weigh 2g diethoxy magnesium ball, after addition decane solvent under 200rpm rotating speed
Stir 1 hour, and be heated to 85 DEG C and make slurry system full and uniform dispersion, 0.5 hour the most wherein
The most at the uniform velocity drip titanium tetrachloride, then proceed to stir 2 hours, filter, hexane washing 3 times, every time
Hexane consumption 30ml, at 60 DEG C, vacuum drying obtains spherical carrier loaded type olefin polymerization catalysis.Its
Middle proportioning is, alkoxyl magnesium ball type carrier and solvent burden ratio are 1g:30ml, with Group IVB metal halide
The chemical treatments quality proportioning of thing is 1:35.Spherical carrier loaded type olefin polymerization catalysis is designated as
CAT-1.This catalyst is particularly suitable under slurry polymerization conditions preparing the polyethylene of super high molecular weight.
This patent adds at the chemistry of substantial amounts of Group IVB metal halide in preparing catalyst process
Reason agent, catalyst cost is high.
Chinese patent CN102775528A, discloses the preparation side of a kind of Ziegler-Natta catalyst
Method, including: magnesium halide alcohol adduct, alkyl aluminum compound and transition metal halide are mixed, after reaction
Obtain Ziegler-Natta catalyst.This invention additionally provides the preparation method of a kind of polyethylene, urges helping
Under the effect of Ziegler-Natta catalyst prepared by agent and the present invention, by ethylene at the second organic solvent
In carry out polyreaction, obtain polyethylene.This invention is made with magnesium halide alcohol adduct by alkyl aluminum compound
With, obtain magnesium-alumina supporter, reacted with magnesium-alumina supporter by transition metal subsequently, make transition metal load
On magnesium-alumina supporter, due to the introducing of aluminium element, improve the load factor of transition metal, so that urging
Agent has higher catalysis activity.Test result indicate that, the load of titanium in Ziegler-Natta catalyst
Rate is 10～15wt%, and catalyst activity is 40000～65000g-PE/g-cat h.
The preparation process of catalyst disclosed in this patent is complicated.
Summary of the invention
The technical scheme is that to overcome present in prior art that catalyst cost is high, preparing
Journey is complicated, and proposes a kind of extra high-molecular polythene catalyst and the preparation side of ultra-high molecular weight polyethylene
Method.The method can prepare a kind of extra high-molecular polythene catalyst, prepares work by this catalyst
Skill and the adjustment of polymerization technique, can prepare the ultra-high molecular weight polyethylene of different molecular weight, molecular weight product
It is 3,000,000～5,000,000.
Technical scheme:
The preparation method of a kind of extra high-molecular polythene catalyst, comprises the steps:
Carrier magnesium ethylate is scattered in organic solvent C6-C16Linear paraffin in, 80 DEG C～90 DEG C of temperature
Under degree, with revolution as 50rpm～1000rpm is stirred, add transistion metal compound four chlorination
Titanium, compounds with titanium tetrachloride magnesium ethylate；
Described magnesium ethylate is compounding by weight accounting for weight for magnesium ethylate with titanium tetrachloride
10.0%～99.0%；
Add morphology modifier tetraethyl orthosilicate, wherein, the mol ratio of magnesium and ester be 2:1～10:1 it
Between；
After having reacted, filter, wash, pre-activate, complete goods.
Described magnesium ethylate is compounding by weight accounting for weight for magnesium ethylate with titanium tetrachloride
10.0%～99.0%.
Described magnesium ethylate is 46% with the compounding of titanium tetrachloride by weight.
Described magnesium and the preferred mol ratio of ester are 3:1.
A kind of method of described catalyst synthesizing super high molecular weight polyethylene, comprises the steps:
Adding alkyl aluminum in single stirring autoclave slurry phase reactor is promoter；
Described extra high-molecular polythene catalyst is added single stirring autoclave slurry phase reactor；
When single stirring autoclave slurry phase reactor temperature rises to 50 DEG C, open ethylene feed valve, be passed through second
Alkene；
Reaction temperature controls at 60 DEG C～70 DEG C, and reaction pressure controls at 0.5Mpa～0.7Mpa；
Being passed through ethylene, be polymerized 2 hours, reaction obtains ultra-high molecular weight polyethylene.
The formula of described promoter alkyl aluminum is AlRnX3-nIn formula, R is the alkane of carbon number 1～10
Base, X is halogen, X particularly chlorine and bromine, and n is the number of 0 < n≤3.
Described reaction temperature controls at 64 DEG C.
Described reaction pressure controls at 0.55Mpa.
Described super high molecular weight is 3,000,000～5,000,000.
Beneficial effects of the present invention:
The catalyst preparation cost of the present invention is low, preparation process simple, and catalyst form is good.
In prior art, as patent CN103554310A adds substantial amounts of in preparing catalyst process
The chemical treatments of Group IVB metal halide, catalyst cost is high.And the present invention is to prepare catalyst
During, the addition of Group IVB metal halide is quantitative, and current enforcement ratio is 10% to the maximum.
The effect of the electron donor tetraethyl orthosilicate added in the prior art is to improve catalyst active center
Rate of chain growth.And the present invention adds morphology modifier tetraethyl orthosilicate in preparation process, improve
The particle shape of catalyst, the catalyst of preparation demonstrates good polymer beads in the course of the polymerization process
Morphing effects.
Accompanying drawing explanation
This specification has 3 width accompanying drawings.
Fig. 1. the process flow diagram of catalyst is prepared for the present invention；
Fig. 2. for the method flow schematic diagram of synthesizing super high molecular weight polyethylene of the present invention；
Fig. 3. for the stereoscan photograph comparison diagram of synthesizing super high molecular weight polyethylene particle of the present invention；
Fig. 3 a. adds morphology modifier picture；Fig. 3 b. does not adds morphology modifier picture.
Detailed description of the invention
Below in conjunction with the accompanying drawings embodiments of the invention are further described.
As it is shown in figure 1, the present invention prepares the preparation method of a kind of extra high-molecular polythene catalyst,
Comprise the steps:
Carrier magnesium ethylate is scattered in the linear paraffin of organic solvent C6-C16, at 80 DEG C～90 DEG C
At a temperature of, with revolution as 50rpm～1000rpm is stirred, add transistion metal compound four chlorination
Titanium, compounds with titanium tetrachloride magnesium ethylate；
Described magnesium ethylate is compounding by weight accounting for weight for magnesium ethylate with titanium tetrachloride
10.0%～99.0% compounds；
Add morphology modifier tetraethyl orthosilicate, wherein, the mol ratio of magnesium and ester be 2:1～10:1 it
Between；
After having reacted, filter, wash, pre-activate, complete goods.
Described magnesium ethylate is compounding by weight accounting for weight for magnesium ethylate with titanium tetrachloride
10.0%～99.0%.
Described magnesium ethylate is 46% with the compounding of titanium tetrachloride by weight.
Described magnesium and the preferred mol ratio of ester are 3:1.
As in figure 2 it is shown, the preparation method of a kind of ultra-high molecular weight polyethylene of the present invention, including walking as follows
Rapid:
(1) carrier magnesium ethylate is scattered in the linear paraffin of organic solvent C6-C16, at 80-
At a temperature of 90 DEG C, agitation revolution 50-1000rpm, add transistion metal compound titanium tetrachloride, ethyoxyl
Magnesium is compounding by weight accounting for the 10.0%～99.0% of weight for magnesium ethylate with titanium tetrachloride；
Adding morphology modifier tetraethyl orthosilicate, the mol ratio of magnesium and ester is between 2:1 10:1；React
Cheng Hou, filters, washs, pre-activate；
(2) adding alkyl aluminum in stirring autoclave slurry phase reactor is promoter, and its formula is
In AlRnX3-n formula, R is the alkyl of carbon number 1～10, and X is halogen, X particularly chlorine and bromine, n
It it is the number of 0 < n≤3；
(3) catalyst in (1) is added polymerization reaction kettle；
(4), when polymeric kettle temperature rises to 50 DEG C, open ethylene feed valve, be passed through ethylene；
(5) reaction temperature controls at 60 DEG C-70 DEG C, and reaction pressure controls at 0.5Mpa-0.7Mpa；
(6) being passed through ethylene, be polymerized 2 hours, reaction obtains polymerizate.
Prepare a kind of extra high-molecular polythene catalyst, by this catalyst preparation process and polymerization work
The adjustment of skill, can prepare the ultra-high molecular weight polyethylene of different molecular weight, and molecular weight product is 300-500
Ten thousand.
Embodiment 1
Carrier magnesium ethylate is scattered in the linear paraffin of organic solvent C6-C16,80 DEG C of temperature
Under, agitation revolution 200rpm, add transistion metal compound titanium tetrachloride, magnesium ethylate and titanium tetrachloride
Compounding add tetraethyl orthosilicate by weight accounting for the 10% of weight for magnesium ethylate, magnesium rubs with ester
That ratio is 2:1；After having reacted, filter, wash, pre-activate, it is added with promoter triethyl aluminum
Enter polymerization reaction kettle；When still temperature rises to 50 DEG C, open ethylene feed valve, be passed through ethylene；Reaction temperature
Controlling at 60 DEG C, reaction pressure controls at 0.50Mpa；It is passed through ethylene, reacts 2 hours, be polymerized
Product.Its molecular weight is 3,200,000.
Embodiment 2
Carrier magnesium ethylate is scattered in the linear paraffin of organic solvent C6-C16,80 DEG C of temperature
Under, agitation revolution 280rpm, add transistion metal compound titanium tetrachloride, magnesium ethylate and four chlorinations
The compounding of titanium accounts for the 12% of weight for magnesium ethylate by weight, adds tetraethyl orthosilicate, magnesium and ester
Mol ratio be 4:1；After having reacted, filter, wash, pre-activate, by itself and promoter three second
Base aluminum adds polymerization reaction kettle；When still temperature rises to 50 DEG C, open ethylene feed valve, be passed through ethylene；
Reaction temperature controls at 62 DEG C, and reaction pressure controls at 0.50Mpa；Being passed through ethylene, reaction 2 is little
Time, obtain polymerizate.Its molecular weight is 3,500,000.
Embodiment 3
Carrier magnesium ethylate is scattered in the linear paraffin of organic solvent C6-C16,80 DEG C of temperature
Under, agitation revolution 280rpm, add transistion metal compound titanium tetrachloride, magnesium ethylate and four chlorinations
The compounding of titanium accounts for the 16% of weight for magnesium ethylate by weight, adds tetraethyl orthosilicate, magnesium and ester
Mol ratio be 5:1；After having reacted, filter, wash, pre-activate, by itself and promoter three second
Base aluminum adds polymerization reaction kettle；When still temperature rises to 50 DEG C, open ethylene feed valve, be passed through ethylene；
Reaction temperature controls at 64 DEG C, and reaction pressure controls at 0.50Mpa；Being passed through ethylene, reaction 2 is little
Time, obtain polymerizate.Its molecular weight is 3,800,000.
Embodiment 4
Carrier magnesium ethylate is scattered in the linear paraffin of organic solvent C6-C16,85 DEG C of temperature
Under, agitation revolution 300rpm, add transistion metal compound titanium tetrachloride, magnesium ethylate and four chlorinations
The compounding of titanium accounts for the 21% of weight for magnesium ethylate by weight, adds tetraethyl orthosilicate, magnesium and ester
Mol ratio be 6:1；After having reacted, filter, wash, pre-activate, by itself and promoter three second
Base aluminum adds polymerization reaction kettle；When still temperature rises to 50 DEG C, open ethylene feed valve, be passed through ethylene；
Reaction temperature controls at 64 DEG C, and reaction pressure controls at 0.55Mpa；Being passed through ethylene, reaction 2 is little
Time, obtain polymerizate.Its molecular weight is 4,000,000.
Embodiment 5
Carrier magnesium ethylate is scattered in the linear paraffin of organic solvent C6-C16,90 DEG C of temperature
Under, agitation revolution 400rpm, add transistion metal compound titanium tetrachloride, magnesium ethylate and four chlorinations
The compounding of titanium accounts for the 46% of weight for magnesium ethylate by weight, adds tetraethyl orthosilicate, magnesium and ester
Mol ratio be 3:1；After having reacted, filter, wash, pre-activate, by itself and promoter three second
Base aluminum adds polymerization reaction kettle；When still temperature rises to 50 DEG C, open ethylene feed valve, be passed through ethylene；
Reaction temperature controls at 64 DEG C, and reaction pressure controls at 0.55Mpa；Being passed through ethylene, reaction 2 is little
Time, obtain polymerizate.Its molecular weight is 4,800,000.
Embodiment 6
Carrier magnesium ethylate is scattered in the linear paraffin of organic solvent C6-C16,90 DEG C of temperature
Under, agitation revolution 300rpm, add transistion metal compound titanium tetrachloride, magnesium ethylate and four chlorinations
The compounding of titanium accounts for the 52% of weight for magnesium ethylate by weight, adds tetraethyl orthosilicate, magnesium and ester
Mol ratio be 4:1；After having reacted, filter, wash, pre-activate, by itself and promoter three second
Base aluminum adds polymerization reaction kettle；When still temperature rises to 50 DEG C, open ethylene feed valve, be passed through ethylene；
Reaction temperature controls at 66 DEG C, and reaction pressure controls at 0.60Mpa；Being passed through ethylene, reaction 2 is little
Time, obtain polymerizate.Its molecular weight is 4,300,000.
Embodiment 7
Carrier magnesium ethylate is scattered in the linear paraffin of organic solvent C6-C16,80 DEG C of temperature
Under, agitation revolution 300rpm, add transistion metal compound titanium tetrachloride, magnesium ethylate and four chlorinations
The compounding of titanium accounts for the 99% of weight for magnesium ethylate by weight, adds tetraethyl orthosilicate, magnesium and ester
Mol ratio be 3:1；After having reacted, filter, wash, pre-activate, by itself and promoter dichloro
Aluminium ethide adds polymerization reaction kettle；When still temperature rises to 50 DEG C, open ethylene feed valve, be passed through second
Alkene；Reaction temperature controls at 60 DEG C, and reaction pressure controls at 0.60Mpa；It is passed through ethylene, reacts 2
Hour, obtain polymerizate.Its molecular weight is 3,500,000.
Embodiment 8
Carrier magnesium ethylate is scattered in the linear paraffin of organic solvent C6-C16,80 DEG C of temperature
Under, agitation revolution 200rpm, add transistion metal compound titanium tetrachloride, magnesium ethylate and four chlorinations
The compounding of titanium accounts for the 71% of weight for magnesium ethylate by weight, adds tetraethyl orthosilicate, magnesium and ester
Mol ratio be 2:1；After having reacted, filter, wash, pre-activate, by itself and promoter one chlorine
Diethyl base aluminum adds polymerization reaction kettle；When still temperature rises to 50 DEG C, open ethylene feed valve, be passed through
Ethylene；Reaction temperature controls at 60 DEG C, and reaction pressure controls at 0.55Mpa；It is passed through ethylene, reaction
2 hours, obtain polymerizate.Its molecular weight is 3,300,000.
By the concrete data of above example as shown in Table 1:
The preparation of table one catalyst and polymerization experiment tables of data
Claims (10)
1. the preparation method of an extra high-molecular polythene catalyst, it is characterised in that: include walking as follows
Rapid:
Carrier magnesium ethylate is scattered in organic solvent C6-C16Linear paraffin in, 80 DEG C～90 DEG C of temperature
Under degree, with revolution as 50rpm～1000rpm is stirred, add transistion metal compound four chlorination
Titanium, compounds with titanium tetrachloride magnesium ethylate；
Described magnesium ethylate and titanium tetrachloride compounding is 10.0%～99.0% to compound by weight；
Add morphology modifier tetraethyl orthosilicate, wherein, the mol ratio of magnesium and ester be 2:1～10:1 it
Between；
After having reacted, filter, wash, pre-activate, complete goods.
The preparation method of a kind of extra high-molecular polythene catalyst the most according to claim 1, its
It is characterised by: described magnesium ethylate is compounding by weight accounting for weight for magnesium ethylate with titanium tetrachloride
10.0%～99.0%.
The preparation method of a kind of extra high-molecular polythene catalyst the most according to claim 2, its
It is characterised by: described magnesium ethylate is compounding by weight accounting for weight for magnesium ethylate with titanium tetrachloride
46%.
The preparation method of a kind of extra high-molecular polythene catalyst the most according to claim 1, its
It is characterised by: described magnesium and the preferred mol ratio of ester are 3:1.
5. one kind utilizes the ultra-high molecular weight polyethylene that in claim 1 to 4 prepared by any one method to urge
Agent.
6. utilizing a method for catalyst synthesizing super high molecular weight polyethylene described in claim 5, it is special
Levy and be, comprise the steps:
Adding alkyl aluminum in single stirring autoclave slurry phase reactor is promoter；
Described extra high-molecular polythene catalyst is added single stirring autoclave slurry phase reactor；
When single stirring autoclave slurry phase reactor temperature rises to 50 DEG C, open ethylene feed valve, be passed through second
Alkene；
Reaction temperature controls at 60 DEG C～70 DEG C, and reaction pressure controls at 0.5Mpa～0.7Mpa；
Being passed through ethylene continuously, be polymerized 2 hours, reaction obtains ultra-high molecular weight polyethylene.
The method of synthesizing super high molecular weight polyethylene the most according to claim 6, it is characterised in that:
The formula of described promoter alkyl aluminum is AlRnX3-nIn formula, R is the alkyl of carbon number 1～10, and X is
Halogen, X particularly chlorine and bromine, n is the number of 0 < n≤3.
The method of synthesizing super high molecular weight polyethylene the most according to claim 7, it is characterised in that:
Described reaction temperature controls at 64 DEG C.
The technique of synthesizing super high molecular weight polyethylene the most according to claim 7, it is characterised in that:
Described reaction pressure controls at 0.55Mpa.
The technique of synthesizing super high molecular weight polyethylene the most according to claim 7, it is characterised in that:
Described super high molecular weight is 300～5,000,000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510078777.4A CN105985465A (en) | 2015-02-13 | 2015-02-13 | Ultrahigh molecular weight polyethylene catalyst and preparation method of ultrahigh molecular weight polyethylene |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108276508A (en) * | 2018-01-31 | 2018-07-13 | 公安县瑞凯高分子材料股份有限公司 | A kind of ultra-high molecular weight polyethylene and preparation method thereof and high temperature resistant sand streak wax |
| CN108359033A (en) * | 2018-01-31 | 2018-08-03 | 公安县瑞凯高分子材料股份有限公司 | A kind of High molecular weight polyethylene and preparation method thereof and corrosion-resistant sand streak wax |
| CN110724255A (en) * | 2019-11-14 | 2020-01-24 | 中国科学院过程工程研究所 | Compound catalyst and application thereof in preparation of bio-based polycarbonate |
| CN112638958A (en) * | 2018-07-19 | 2021-04-09 | 博里利斯股份公司 | Process for preparing UHMWPE homopolymer |
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| CN101659715A (en) * | 2008-08-29 | 2010-03-03 | 中国石油天然气股份有限公司 | Preparation method of high-activity high-efficiency polyethylene catalyst |
| CN102453172A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Method for homopolymerizing or copolymerizing ethylene |
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| CN101659715A (en) * | 2008-08-29 | 2010-03-03 | 中国石油天然气股份有限公司 | Preparation method of high-activity high-efficiency polyethylene catalyst |
| CN102453172A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Method for homopolymerizing or copolymerizing ethylene |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108276508A (en) * | 2018-01-31 | 2018-07-13 | 公安县瑞凯高分子材料股份有限公司 | A kind of ultra-high molecular weight polyethylene and preparation method thereof and high temperature resistant sand streak wax |
| CN108359033A (en) * | 2018-01-31 | 2018-08-03 | 公安县瑞凯高分子材料股份有限公司 | A kind of High molecular weight polyethylene and preparation method thereof and corrosion-resistant sand streak wax |
| CN112638958A (en) * | 2018-07-19 | 2021-04-09 | 博里利斯股份公司 | Process for preparing UHMWPE homopolymer |
| CN112638958B (en) * | 2018-07-19 | 2023-06-02 | 博里利斯股份公司 | Process for preparing UHMWPE homopolymers |
| US11680114B2 (en) | 2018-07-19 | 2023-06-20 | Borealis Ag | Process for the preparation of an UHMWPE homopolymer |
| US11965052B2 (en) | 2018-07-19 | 2024-04-23 | Borealis Ag | Process for the preparation of an UHMWPE homopolymer |
| CN110724255A (en) * | 2019-11-14 | 2020-01-24 | 中国科学院过程工程研究所 | Compound catalyst and application thereof in preparation of bio-based polycarbonate |
| CN110724255B (en) * | 2019-11-14 | 2021-05-04 | 中国科学院过程工程研究所 | Compound catalyst and application thereof in preparation of bio-based polycarbonate |
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