CN106866849B - Ethylene polymerization main catalyst, preparation method thereof and ethylene polymerization catalyst containing main catalyst - Google Patents
Ethylene polymerization main catalyst, preparation method thereof and ethylene polymerization catalyst containing main catalyst Download PDFInfo
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- CN106866849B CN106866849B CN201510917781.5A CN201510917781A CN106866849B CN 106866849 B CN106866849 B CN 106866849B CN 201510917781 A CN201510917781 A CN 201510917781A CN 106866849 B CN106866849 B CN 106866849B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 120
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 49
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000005977 Ethylene Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002685 polymerization catalyst Substances 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000000725 suspension Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 150000002681 magnesium compounds Chemical class 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract 3
- 239000002245 particle Substances 0.000 claims description 37
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 28
- 229920002554 vinyl polymer Polymers 0.000 claims description 28
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 24
- -1 hydroxyl ethyl Chemical group 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 8
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000001282 iso-butane Substances 0.000 claims description 2
- 235000013847 iso-butane Nutrition 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 230000002459 sustained effect Effects 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 2
- 150000003609 titanium compounds Chemical class 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 1
- 238000009826 distribution Methods 0.000 description 18
- 230000000694 effects Effects 0.000 description 15
- 239000004698 Polyethylene Substances 0.000 description 12
- 229920000573 polyethylene Polymers 0.000 description 12
- 238000012512 characterization method Methods 0.000 description 10
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 7
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003426 co-catalyst Substances 0.000 description 6
- 235000011147 magnesium chloride Nutrition 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000002952 polymeric resin Substances 0.000 description 6
- 229920003002 synthetic resin Polymers 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- 230000008901 benefit Effects 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
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 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
- 229910000831 Steel Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001507 sample dispersion Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- 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)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a main catalyst for ethylene polymerization and a catalyst containing the same, wherein the main catalyst comprises a magnesium compound, a composite solvent, a carboxylic acid monoester compound and a titanium compound, and the preparation method comprises the following steps of mixing the magnesium compound and the composite solvent to form a transparent solution, mixing the transparent solution with the monoester compound and the titanium compound respectively until complete precipitation is achieved to obtain a main catalyst suspension, carrying out curing reaction on the main catalyst suspension, washing and drying the cured main catalyst suspension to obtain the main catalyst.
Description
Technical field
The present invention relates to olefin polymerization catalysis field more particularly to a kind of vinyl polymerization major catalyst and its preparation sides
Method, and the ethylene rolymerization catalyst containing the major catalyst.
Background technique
From the seventies after efficient Zigler-Natta ethylene rolymerization catalyst is succeeded in developing, world's polyethylene industry is had occurred
Great change.Over nearly more than 20 years, with the development of ethene polymerization process, the catalyst to match with polymerization technique also achieves considerable
Progress, wherein Ziegler-Natta catalyst is catalyzed by its excellent polymerization and mature application technology in polyethylene
Agent still occupies an important position in field, still has a large amount of patent application to occur in recent years.In these patent applications, announce
The ethylene rolymerization catalysts of many different performances, such as the active lifetime of some catalyst are long, some catalyst can be prepared
The polyethylene of broad peak or bimodal molecular weight distribution.It is analyzed from technical standpoint, the Ziegler-Natta announced in these patents is urged
Agent is mainly used for the preparation of a certain quasi-polyethylene PP Pipe Compound, and the performance of catalyst is to meet such polyethylene special-purpose material
It is required that and design.
At present in ethylene slurry polymerization processes industrially, the average grain of the Ziegler-Natta catalyst used
Size is substantially at 10.0 microns or less.Such as in Chinese patent CN1229092 and CN102875708, the catalyst of preparation
Average particle size particle size is between 5.0-10.0 microns.Form when according to Ziegler-Natta catalyst catalyzed ethylene polymerization is multiple
Effect processed, polyethylene particle will grow formation on the basis of catalyst granules, necessarily cause small catalyst particles particle shape in this way
At small polyethylene resin particles, final result is exactly in the ethene polymerization process caused industrially, polyvinyl resin
Fine powder content is higher, brings difficulty to the steady operating of technique, more seriously, such catalyst would be unavailable for production pair
Polyvinyl resin powder has some PP Pipe Compounds of strict demand, such as haloflex PP Pipe Compound.Due to the poly- second for chlorination
Alkene powder will complete the chlorination reaction of polyethylene in water phase using chlorine, after excessive fine powder content will cause water phase and chlorination
The separation of polyethylene powder is difficult.Therefore, special dedicated for haloflex it is necessary to prepare a kind of catalyst of bulky grain
The production of materials.
Chinese patent CN1229092 discloses the preparation method of a kind of vinyl polymerization or copolymerization catalyst, in patent
Catalyst is to be dissolved in organic epoxy compound object, organic phosphorus compound and alcohol compound by magnesium halide to form homogeneous solution,
The halide effect with a kind of benzene compound anhydride as precipitation additive effect and transition metals Ti obtains again.It is precipitated helping
Under the effect of agent benzene compound anhydride, obtained catalyst average particle size lower than 10.0 microns, and particle shape compared with
Difference.In Chinese patent CN102875708, using organosilicon compound instead of benzene compound anhydride, the particle of catalyst
Form is improved, but the average particle size particle size of catalyst still is below 10.0 microns.
Summary of the invention
The purpose of the present invention is to provide a kind of vinyl polymerization major catalyst and preparation method thereof, which has catalysis
The big advantage of active height, uniform particle sizes, average particle size particle size, copolymerization performance is excellent, is suitable for producing haloflex PP Pipe Compound
Equal products.
Another object of the present invention is to provide a kind of ethylene rolymerization catalysts containing above-mentioned vinyl polymerization major catalyst.
In order to achieve the above objectives, the present invention provides a kind of vinyl polymerization major catalyst, by magnesium chloride, double solvents, carboxylic acid
Monoester compound and TiCl4 are made, the molar ratio of the magnesium chloride, double solvents, dicarboxylic acid monoester compound and TiCl4 are as follows: 1:
1.1-10:0.05-2:0.5-50;The average particle size particle size D50 of the vinyl polymerization major catalyst is 5-50 microns;
The double solvents includes tributyl phosphate, epoxychloropropane and ethyl alcohol, and the dosage of the double solvents is often to rub
That magnesium compound meter, tributyl phosphate are 0.3-3.5 moles, and epoxychloropropane is 0.3-3.5 moles, and ethyl alcohol rubs for 0.5-3.0
You;
The dicarboxylic acid monoester compound is methyl acrylate, ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, first
Base hydroxy-ethyl acrylate, ethyl methacrylate, butyl methacrylate, methyl methacrylate or ethyl acetate.
Vinyl polymerization major catalyst of the present invention, wherein the double solvents preferably further includes inertia dispersing agent, institute
Stating inertia dispersing agent is preferably hydro carbons and/or halogenated hydrocarbon.
Vinyl polymerization major catalyst of the present invention, wherein the inertia dispersing agent be preferably selected from by hexane, heptane,
At least one of octane, toluene, dimethylbenzene, 1,2- dichloroethanes, chlorocyclohexane and the formed group of chlorobenzene.
Vinyl polymerization major catalyst of the present invention, wherein the average particle size particle size D50 of the vinyl polymerization major catalyst
Preferably 10-30 microns.
In order to achieve the above objectives, the present invention also provides a kind of preparation methods of above-mentioned vinyl polymerization major catalyst, including with
Lower step:
S1: at 25-100 DEG C, magnesium chloride and double solvents being mixed, and formed within sustained response 10 minutes to 20 hours transparent molten
Liquid;
S2: at -10 DEG C to 50 DEG C, clear solution obtained in step S1 being mixed with dicarboxylic acid monoester compound and TiCl4,
TiCl4 is added drop-wise in clear solution in 30 minutes to 5 hours, and then reaction obtains major catalyst suspension;
S3: at 25 DEG C to 150 DEG C, it is small that major catalyst suspension obtained in step S2 is subjected to slaking reaction 0.5 to 15
When;
S4: the major catalyst suspension after curing in step S3 is washed with atent solvent, is dried, main catalytic is obtained
Agent.
The preparation method of vinyl polymerization major catalyst of the present invention, wherein in step S3, preferred slaking reaction 1 to 5
Hour.
The preparation method of vinyl polymerization major catalyst of the present invention, wherein in step S4, the atent solvent is best
Selected from by least one of iso-butane, pentane, hexane, heptane and the formed group of hexamethylene.
In the preparation method of vinyl polymerization major catalyst of the present invention, TiCl4Charge temperature and charging rate pair
Critically important to the form control of solid particle, higher charge temperature and faster charging rate will be unfavorable for regular solid particle
Formation, therefore define TiCl in step S24Addition temperature and time;There is the grain shape of catalyst in the slaking reaction
Favorable influence, slaking reaction time and temperature defined by the present invention can make the size distribution narrow of catalyst, while
The intensity of catalyst particle can be improved, to reduce particle fragmentation phenomenon of catalyst during catalyzed ethylene polymerization.
In order to achieve the above objectives, the present invention also provides a kind of ethylene rolymerization catalysts, including following components:
Above-mentioned vinyl polymerization major catalyst or the vinyl polymerization major catalyst as made from above-mentioned method;
Organo-aluminum compound is general formula AlRgX3-gAt least one of shown compound, in formula, R C1-C20Hydrocarbon
Base, X are halogen, and g is integer and 1 < g 3.
Ethylene rolymerization catalyst of the present invention, wherein the organo-aluminum compound is preferably by AlEt3, Al (iso-
Bu) 3, at least one of Al (n-C6H13) 3, Al (n-C8H17) 3 and the formed group of AlEt2Cl.
The invention has the benefit that ethylene rolymerization catalyst average particle size particle size is larger, and there is good particle
Form and very narrow size distribution, in the copolymerization of ethylene and other alpha-olefins, the insertion rate of comonomer obviously compared with
It is high.Catalyst of the invention is suitable for the slurry polymerization processes of ethylene, is suitable for preparing the production of haloflex PP Pipe Compound.
Detailed description of the invention:
Fig. 1 is the stereoscan photograph of catalyst prepared by embodiment 1.
Specific embodiment
The present invention is further illustrated by the following examples, and however, the present invention is not limited to these examples.
The test of the average grain diameter and its size distribution of catalyst
In hexane by catalyst sample dispersion, using Malvern Instruments Ltd. company, Britain
The size distribution curve of Mastersizer laser particle size analyzer test sample, wherein
The average grain diameter of catalyst is provided with D (50);
Size distribution Span=(D (90)-D (10))/D (50) of catalyst;
D (50) is whole particles in the size distribution curve of Mastersizer laser particle size analyzer test in formula
50% diameter is lower than the diameter value of the value;D (10) is that 10% diameter of whole particles is lower than the diameter value of the value;D(90)
It is that 90% diameter of whole particles is lower than the diameter value of the value.
Ethylene homo closes
The major catalyst of 1L hexane, 1mmol triethyl aluminum (co-catalyst) and 10mg is added to 2L stainless steel stirred tank
In, temperature is then risen to 80 DEG C, is added at one time the hydrogen of 0.2MPa, is then maintained the gross pressure of system with ethylene
1.0MPa carries out polymerization reaction, after reaction 2 hours, stops that ethylene, cooling, pressure release, polyethylene powder weighing is added.With polyethylene
The weight of powder calculates the activity of catalyst divided by the dosage of major catalyst.
Ethylene and butene-1 combined polymerization
The major catalyst of 1L hexane, 1mmol triethyl aluminum (co-catalyst), 20ml butene-1 and 10mg are added to 2L not
It becomes rusty in steel stirred tank, temperature is then risen to 80 DEG C, is added at one time the hydrogen of 0.2MPa, then with ethylene by the stagnation pressure of system
Power maintains 1.0MPa and carries out polymerization reaction, after reaction 2 hours, stops that ethylene, cooling, pressure release, polyethylene powder weighing is added.
The activity of catalyst is calculated divided by the dosage of major catalyst with the weight of polyethylene powder.
Embodiment 1
In the reactor being sufficiently displaced from by nitrogen, magnesium dichloride 4.0g, toluene 60ml, ethyl alcohol are sequentially added
6.0ml, tributyl phosphate 3.0ml, epoxychloropropane 2.0ml, are warming up to 65 DEG C, are stirred continuously until that solid is completely dissolved to be formed
Uniform solution.- 15 DEG C are then cooled to, 0.5ml hydroxyethyl methacrylate is added, 30ml was slowly added dropwise within the used time 1 hour
TiCl4, after being added dropwise to complete, it is warming up to 85 DEG C and is stirred to react 2h.After the reaction was completed, stop stirring, staticly settle, filter, then use
After hexane washs 4 times, it is dried to obtain solid main catalyst particle.
Major catalyst and co-catalyst triethyl aluminum collectively constitute catalyst, size distribution, activity and the polymerization of catalyst
The characterization result of resin is as shown in table 1.
Embodiment 2
0.5ml hydroxyethyl methacrylate in the preparation of 1 major catalyst of embodiment is adjusted to 0.4ml ethyl acrylate,
The suspension of last catalyst is stirred to react at 85 DEG C, 0.5h, and other conditions are same as Example 1.
The characterization result of the size distribution of catalyst, activity and polymer resin is as shown in table 1.
Embodiment 3
0.5ml hydroxyethyl methacrylate in the preparation of 1 major catalyst of embodiment is adjusted to 0.5ml methacrylic acid second
The suspension of ester, last catalyst is stirred to react 15h at 85 DEG C, and other conditions are same as Example 1.
The characterization result of the size distribution of catalyst, activity and polymer resin is as shown in table 1.
Embodiment 4
0.5ml hydroxyethyl methacrylate in the preparation of 1 major catalyst of embodiment is adjusted to 0.5ml methacrylic acid fourth
The suspension of ester, last catalyst is stirred to react 1h at 85 DEG C, and other conditions are same as Example 1.
The characterization result of the size distribution of catalyst, activity and polymer resin is as shown in table 1.
Embodiment 5
0.5ml hydroxyethyl methacrylate in the preparation of 1 major catalyst of embodiment is adjusted to 0.4ml ethyl acetate, most
The suspension of rear catalyst is stirred to react 5h at 85 DEG C, and other conditions are same as Example 1.
The characterization result of the size distribution of catalyst, activity and polymer resin is as shown in table 1.
Embodiment 6
0.5ml hydroxyethyl methacrylate in the preparation of 1 major catalyst of embodiment is adjusted to 1.0ml, last catalyst
Suspension be stirred to react 2h at 85 DEG C, other conditions are same as Example 1.
The characterization result of the size distribution of catalyst, activity and polymer resin is as shown in table 1.
Embodiment 7
The charging sequence of 0.5ml hydroxyethyl methacrylate in the preparation of 1 major catalyst of embodiment is changed to drip at -15 DEG C
Add 30ml TiCl4After completing and stirring 0.5h, the suspension of last catalyst is stirred to react 5h, other conditions and reality at 85 DEG C
It is identical to apply example 1.
The characterization result of the size distribution of catalyst, activity and polymer resin is as shown in table 1.
Comparative example 1
In the reactor being sufficiently displaced from by nitrogen, magnesium dichloride 4.0g, toluene 60ml, ethyl alcohol are sequentially added
6.0ml, tributyl phosphate 3.0ml, epoxychloropropane 2.0ml, are warming up to 65 DEG C, are stirred continuously until that solid is completely dissolved to be formed
Uniform solution.It is then warming up to 85 DEG C and is stirred to react 2h.After the reaction was completed, stop stirring, staticly settle, filter, then use oneself
After alkane washs 4 times, it is dried to obtain solid main catalyst particle.
Major catalyst and co-catalyst triethyl aluminum collectively constitute catalyst, size distribution, activity and the polymerization of catalyst
The characterization result of resin is as shown in table 1.
Comparative example 2
In the reactor being sufficiently displaced from by nitrogen, magnesium dichloride 4.0g, toluene 60ml, ethyl alcohol are sequentially added
6.0ml, tributyl phosphate 3.0ml, epoxychloropropane 2.0ml, are warming up to 65 DEG C, are stirred continuously until that solid is completely dissolved to be formed
Uniform solution.The phthalic anhydride of 1.1g is then added, is warming up to 85 DEG C and is stirred to react 2h.After the reaction was completed, stop stirring
It mixes, staticly settles, filter, then after washing 4 times with hexane, be dried to obtain solid main catalyst particle.
Major catalyst and co-catalyst triethyl aluminum collectively constitute catalyst, size distribution, activity and the polymerization of catalyst
The characterization result of resin is as shown in table 1.
Comparative example 3
The phthalic anhydride of 1.1g in the preparation of 2 major catalyst of comparative example is adjusted to tetraethoxysilane 3.4ml,
His condition is identical as comparative example 2.
Major catalyst and co-catalyst triethyl aluminum collectively constitute catalyst, size distribution, activity and the polymerization of catalyst
The characterization result of resin is as shown in table 1.
Table 1
From the data of table 1 it is found that the catalyst average particle size in embodiment is all larger than 10.0 microns, and granularity point
Cloth is relatively narrow, and Span value is respectively less than 1.3.Catalyst of the invention closes and when combined polymerization being catalyzed ethylene homo, obtained polymerization
The molecular weight distribution of product is significantly greater than comparative example, and when being catalyzed ethylene and butene-1 combined polymerization, the insertion rate of butene-1 is obvious
Higher than comparative example.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to protection scope of the present invention.
Claims (8)
1. a kind of vinyl polymerization major catalyst, which is characterized in that by magnesium chloride, double solvents, dicarboxylic acid monoester compound and TiCl4
It is made, the double solvents includes tributyl phosphate, epoxychloropropane and ethyl alcohol, and dosage of each component is with every mole of magnesium compound
Meter, tributyl phosphate are 0.3-3.5 moles, and epoxychloropropane is 0.3-3.5 moles, and ethyl alcohol is 0.5-3.0 moles;The chlorination
Magnesium, double solvents include the sum of tributyl phosphate, epoxychloropropane and ethyl alcohol total amount, dicarboxylic acid monoester compound and TiCl4Rub
That ratio are as follows: 1:1.1-10:0.05-2:0.5-50;The average particle size particle size D50 of the vinyl polymerization major catalyst is 5-50 microns;
The dicarboxylic acid monoester compound is methyl acrylate, ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, methyl-prop
Olefin(e) acid hydroxyl ethyl ester, ethyl methacrylate, butyl methacrylate, methyl methacrylate or ethyl acetate;
The preparation method of the vinyl polymerization major catalyst the following steps are included:
S1: at 25-100 DEG C, magnesium chloride and double solvents are mixed, 10 minutes to 20 hours formation clear solutions of sustained response;
S2: at -15 DEG C, by clear solution obtained in step S1 and dicarboxylic acid monoester compound and TiCl4Mixing, TiCl4Several times
Clear solution is added in 30 minutes to 5 hours, obtains major catalyst suspension;
S3: at 25 DEG C to 150 DEG C, major catalyst suspension obtained in step S2 is carried out slaking reaction 0.5 to 15 hour;
S4: the major catalyst suspension after curing in step S3 is washed with atent solvent, is dried, major catalyst is obtained.
2. vinyl polymerization major catalyst according to claim 1, which is characterized in that the double solvents further includes inertia point
Powder, the inertia dispersing agent are hydro carbons and/or halogenated hydrocarbon.
3. vinyl polymerization major catalyst according to claim 2, which is characterized in that the inertia dispersing agent is selected from by oneself
At least one of alkane, heptane, octane, toluene, dimethylbenzene, 1,2- dichloroethanes, chlorocyclohexane and the formed group of chlorobenzene.
4. vinyl polymerization major catalyst according to claim 1, which is characterized in that the vinyl polymerization major catalyst is averaged
Particle size D50 is 10-30 microns.
5. vinyl polymerization major catalyst according to claim 1, which is characterized in that in step S3, slaking reaction 1 to 5 is small
When.
6. vinyl polymerization major catalyst according to claim 1, which is characterized in that in step S4, the atent solvent choosing
At least one of free iso-butane, pentane, hexane, heptane and the formed group of hexamethylene.
7. a kind of ethylene rolymerization catalyst, which is characterized in that including following components:
Vinyl polymerization major catalyst described in any one of claims 1-6;
Organo-aluminum compound is general formula AlRgX3-gAt least one of shown compound, in formula, R C1-C20Alkyl, X is
Halogen, g are integer and 1 < g £ 3.
8. ethylene rolymerization catalyst according to claim 7, which is characterized in that the organo-aluminum compound is by AlEt3、
Al(iso-Bu)3、Al(n-C6H13)3、Al(n-C8H17)3And AlEt2At least one of formed group of Cl.
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