CN1050136C - Preparation of high performance supported catalyst for propylene polymerization - Google Patents
Preparation of high performance supported catalyst for propylene polymerization Download PDFInfo
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- CN1050136C CN1050136C CN94115522A CN94115522A CN1050136C CN 1050136 C CN1050136 C CN 1050136C CN 94115522 A CN94115522 A CN 94115522A CN 94115522 A CN94115522 A CN 94115522A CN 1050136 C CN1050136 C CN 1050136C
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- titanium
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- catalyst
- magnesium chloride
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- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 title description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 28
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 20
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 14
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 150000003608 titanium Chemical class 0.000 claims abstract description 8
- 239000012456 homogeneous solution Substances 0.000 claims abstract description 7
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 239000011949 solid catalyst Substances 0.000 claims abstract description 6
- 150000001336 alkenes Chemical class 0.000 claims abstract description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 22
- 239000010936 titanium Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 6
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 150000003609 titanium compounds Chemical class 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002574 poison Substances 0.000 abstract description 2
- 231100000614 poison Toxicity 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 238000011282 treatment Methods 0.000 abstract description 2
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 229930195734 saturated hydrocarbon Natural products 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- -1 polypropylene Polymers 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 235000010210 aluminium Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- DGLFSNZWRYADFC-UHFFFAOYSA-N chembl2334586 Chemical compound C1CCC2=CN=C(N)N=C2C2=C1NC1=CC=C(C#CC(C)(O)C)C=C12 DGLFSNZWRYADFC-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to a taniferous catalyst of a magnesium chloride carrier for the homopolymerization of olefin, and the preparation thereof. Magnesium chloride, benzoic anhydride, 2-ethylhexanol and an analyzing agent in the class of titanium are mixed and react for forming a homogeneous solution in the class of hydrocarbon; the solution is orderly treated by a mixed solution comprising titanium tetrachloride or itanium alkoxychloride and low-carbon saturated hydrocarbon and by dibutyl phthalate; a titaniferous solid catalyst obtained by the treatment of the titanium tetrachloride is used as a component A; AlEt3 is used as a component B; dibenzodimethoxysilane is used as a component C; and the component A, the component B and the component C form the catalyst system. The catalyst has the advantages of good poison resisting performance, high and stable activity, strong capacity of orientation, good obtained resinousness, no fine powder, etc.
Description
The invention relates to the preparation method of carried catalyst for polymerization of olefin.The preparation method of carried catalyst for polymerization of olefin and relevant technologies have many patent documentations.One of characteristics of these technology are magnesium chloride and alcohol (＞C
6) the uniform MgCl of effect generation
2-ester compound solution is used TiCl again
4Handle the crystallization MgCl that obtains containing titanium chloride with dibutyl phthalate
2The catalyst A component, as EP282,341 (or JP87/56,726), GB2111066.Such catalyzer has higher activity and very high directional property.These class methods are owing to adopt dissolving crystallized method to obtain catalyzer, and fine powder content is higher, reaches 1～5%; Catalyst tolerates toxicity can be relatively poor, need use the higher propylene feedstocks of purity and the activator of higher concentration during polymerization, and the later stage activity has bigger decay when being used for polymerization, causes propylene conversion to decrease.In addition, because the MgCl of such catalyzer
2-ester compound needs at comparatively high temps (100～130 ℃) synthetic, generally can only adopt the inert solvent of boiling point more than 120 ℃, this inert solvent and TiCl
4Boiling point approaching, when useless raw material reclaims, separate difficulty, yield is low, so Catalyst Production cost height, environmental pollution is also bigger.Characteristics of the present invention are to adopt industrial raw material higher alcohols, lower carbon number hydrocarbons, phthalic anhydride cheap and easy to get and add an amount of titanium class and help and analyse agent and pressing synthetic MgCl under the heat condition
2The homogeneous solution of-ester complex compound, then under the refrigerated condition with such solution and specific TiCl
4Or inhomogeneous reaction is carried out in alkoxyl group titanium chloride-lower carbon number hydrocarbons mixing solutions contact, reach the purpose of control catalyst particle shape and surface tissue, after the processing of titanium tetrachloride or alkoxyl group titanium chloride and carboxylicesters, titanium tetrachloride is handled, obtain solids containing titanium catalyst component (A), constitute catalyst system of the present invention jointly with component (B), component (C).This catalyst activity is high and stable, and resistance to poison is good, applies on full scale plant at present.
The supported catalyst system of the present invention's preparation contains ingredient of solid catalyst (A), comprises magnesium chloride, carboxylicesters, titanium chloride etc.; Component (B) is a triethyl aluminum; Component (C) is a dimethoxydiphenylsilane.
Feature of the present invention is magnesium chloride to be helped with phthalic anhydride, 2-Ethylhexyl Alcohol and titanium class analyse the agent hybrid reaction and make MgCl in varsol
2The homogeneous solution of-ester complex compound, hydro carbons.This homogeneous solution successively through the mixed solvent of titanium tetrachloride or alkoxyl group titanium chloride and hydrocarbon composition and dibutyl phthalate handle, titanium tetrachloride handles to make and contains magnesium chloride and carboxylicesters and titaniferous ingredient of solid catalyst (A).Concrete steps are: magnesium chloride, 2-Ethylhexyl Alcohol, varsol etc. are added reactor, be warming up to 90～130 ℃ after the sealing, pressure rises to 0.1～0.7MPa, reacts 1.0～3.0 hours, adds phthalic anhydride, titanium class again and helps and analyse agent and continue to react under this temperature and pressure 1.5～2.0 hours.The mole of magnesium chloride and phthalic anhydride 1: 0.1～1: 0.2; Magnesium chloride is 1: 2.5～1: 4 with the mol ratio of alcohol, and varsol and magnesium chloride ratio are 6ml/g, and it is 0.2g/g that the titanium class helps the ratio of analysing agent and magnesium chloride.The mixing solutions that 1: 1.7 volume ratio of this homogeneous solution and titanium tetrachloride or alkoxyl group titanium chloride and hydro carbons is formed generates magnesium chloride-ester-titanium chloride cenotype at-35 ℃～0 ℃ after contacting, and is warming up in 2～6 hours in 100～130 ℃ of this section intervals then.At 65 ℃ of recovery part varsols in the scope of the temperature spot that is risen to.Add dibutyl phthalate and handled 1～3 hour, dibutyl phthalate and magnesium chloride mol ratio are 0.010～0.015.Filtered while hot is removed TiCl
4Or the alkoxyl group titanium chloride gets solid chemical compound, continues to use TiCl
4New liquid is handled once, removes by filter TiCl
4Waste liquid is used hexane wash 4～6 times again, and obtaining with the magnesium chloride is the titaniferous of carrier and the solid catalyst of carboxylicesters (A).The general formula of titanium compound is Ti (OR)
nCl
4-n, wherein R is an alkyl, 0≤n≤3.
The varsol that the present invention uses is C
5～C
8Straight or branched or ring-type saturated alkane or its hydrocarbon mixture, preferably hexane, pentane or heptane.The general formula of alkoxyl group titanium chloride is Ti (OR)
xCl
4-xWherein R is an alkyl, 1≤x≤4.Ti (OC preferably
8H
17)
2Cl
2
It is Ti (OC that the titanium class helps the general formula of analysing agent
8H
17)
mCl
4-m, 0≤m≤3.Ti (OC preferably
8H
17)
2Cl
2
When catalyst system of the present invention was used for polymerization, the mol ratio of the titanium in the triethyl aluminum in aluminium and the component (A) was 30～500, preferably 50～200.The mol ratio of the aluminium in the dimethoxydiphenylsilane in silicon and the component (B) is 0.02～1.0, preferably 0.05～0.3.
The catalyst system that adopts the present invention to make is applicable to the body batchwise polymerization.Its catalyst system salient features with at present similar preferably outside catalyst system is equal to or slightly better, also has following advantage as catalytic activity, directional property, apparent density etc.:
1, catalyst tolerates toxicity can be good, and initial reaction stage is steadily active, and is active high and stable lasting, is applicable to general refinery gas to be the polypropylene production technique of raw material.
2, the polypropylene product that obtains with the polymerization catalyst of the present invention preparation, mechanical property is good, and melting index is regulated easily, helps many trades mark Products Development.
3, Preparation of Catalyst adopts the lower carbon number hydrocarbons solvent, and main raw material recovery technology is simple and easy and yield is high, has alleviated environmental pollution greatly, and has reduced the Catalyst Production cost.
Example 1:
Anhydrous MgCl
2(5.0g 52.5 mmole), anhydrous 2-Ethylhexyl Alcohol 24ml (157.5 mmole) and dry hexane 30ml, reaction is 1.5 hours under 100 ℃ of 0.25MPa pressure, add 1.5g phthalic anhydride (10.1 mmole) then, two different octyloxy titanium dichloride 1.0g, continue reaction 1.5 hours, form homogeneous solution.This solution was added in 30 minutes in the mixed solvent of being made up of 90 milliliters of titanium tetrachlorides and 150 milliliters of hexanes that is refrigerated to-16 ℃, in 3 hours, be warming up to 100 ℃ then, after 80 ℃, begin distillation and reclaim hexane solvent.Add dibutyl phthalate 1.8ml (0.7 mmole) and handled 2.0 hours, remove by filter reaction solution, once with 90 milliliters of titanium tetrachloride re-treatments.Filter, collect solid product,, wash altogether five times with 50 milliliters of dry hexane wash.With suspension vacuum-drying, obtain titaniferous ingredient of solid catalyst (A), mainly consist of: Ti 2.6% Mg 18.8% Cl 61.4%.Example 2:
At the clean volume of displacement is in 35 liters of autoclaves, add 24 liters of liquid refinery gas propylene (the propylene quality index sees Table 1), solids containing titanium catalyst component (A) 0.12 mmole (calculating) that adds 13.7 mmole triethyl aluminums, 2.0 mmole dimethoxydiphenylsilanes and example 1 preparation more successively with titanium, add hydrogen 40PPm, be warming up to 78 ℃ of polyase 13 .0 hours, and obtained 8.3 kilograms of polypropylene.Polymerizing condition and result are respectively referring to the example in table 2 and the table 32.Example 3:
With 150 milliliters of hexanes in 150 milliliters of heptane replacement examples 1, other condition is constant.Polymerization process is with example 2, and polymerizing condition and result are respectively referring to the example in table 2 and the table 33.Example 4:
With 90 milliliters of (i-C
8H
17O)
2TiCl
2Replace 90 milliliters of TiCl in the example 1
4, other condition is with example 1, and polymerization process is with example 2, and polymerizing condition and result are respectively referring to the example in table 2 and the table 34.Example 5:
Do not add titanium and help and analyse agent, other condition is with example 1, and polymerization process is with example 2, and polymerizing condition and result are respectively referring to the example in table 2 and the table 35.Example 6:
Utilize the catalyzer (A) in the example 1, Al/Ti changes 70 into during with polymerization, and other condition is with example 2, and the result is respectively referring to the example in table 2 and the table 36.Example 7:
Utilize the catalyst component (A) in the example 1, [H during with polymerization
2] changing 190PPm into, other condition is with example 6, and the result is respectively referring to the example in table 2 and the table 37.Comparative example:
According to EP282, the preparation of 341 methods, catalyzer titaniferous 2.3%, Al/Ti in the polymerization process (mol ratio) changes 240 into, and other is with example 2, and the result is referring to the comparative example in table 2 and the table 3.
Table 1 raw material propylene (refinery gas) is formed
| Form | C ＝ 3?％ | C° 3％ | C ≡ 2PPm | C 3 ≡C 3 ＝＝PPm | H 2O PPm | O 2PPm | Total S PPm | CO PPm | CO 2PPm |
| Content | 99.8 | ＜0.2 | 1 | 15 | 15-28 | 8-9 | 2.0 | 1 | 1.5 |
Table 2 polymerizing condition and polymerization activity
| Example | The Al/Ti mol ratio | The Al/Si mol ratio | [H 2]/[C ＝ 3] PPm |
| 3 | 110 | 6.7 | 40 |
| 3 | 110 | 6.7 | 40 |
| 4 | 110 | 6.7 | 40 |
| 5 | 110 | 6.7 | 40 |
| 6 | 70 | 6.7 | 40 |
| 7 | 70 | 6.7 | 190 |
| Comparative example | 240 | 6.6 | 40 |
Continuous table
Annotate: activity stability K=(the 3rd hour activity/first hour activity)
| Example | Active | Activity stability K | |
| ×10 3PP/gCat | ×10 6PP/gTi | ||
| 3 | 36 | 1.38 | 0.8 |
| 3 | 30 | 1.10 | 0.8 |
| 4 | 27 | 1.05 | 0.7 |
| 5 | 25 | 0.85 | 0.8 |
| 6 | 35 | 1.35 | 0.8 |
| 7 | 37 | 1.40 | 0.8 |
| Comparative example | 16 | 0.70 | 0.4 |
Table 3 acrylic resin performance index
| Example | Degree of isotacticity % | Chlorine root PPm | Ash PPm | Apparent density g/ml | Melting index g/10min |
| 2 | 97.2 | 10.8 | 120 | 0.41 | 3.8 |
| 3 | 97.5 | 15 | 127 | 0.41 | 3.0 |
| 4 | 97.2 | 20 | 150 | 0.41 | 1.9 |
| 5 | 95.0 | 33 | 160 | 0.39 | 2.1 |
| 6 | 97.7 | 11.2 | 90 | 0.42 | 3.3 |
| 7 | 97.4 | 10.4 | 95 | 0.42 | 25 |
| Comparative example | 98.0 | 47 | 205 | 0.41 | 2.1 |
Continuous table
| Example | Granularity | Tensile strength MPa | Elongation % | |||
| ＞40 orders | The 40-80 order | The 80-100 order | ＜100 orders | |||
| 2 | 90.6 | 8.1 | 0.2 | 0 | 37.5 | 240 |
| 3 | 80.5 | 19.0 | 0.2 | 0.1 | 37.2 | 300 |
| 4 | 84.0 | 14.7 | 1.0 | 0.3 | 36.8 | 320 |
| 5 | 21 | 64.5 | 2.3 | 12 | 35.7 | 140 |
| 6 | 92 | 7.7 | 0.3 | 0 | 37.7 | 220 |
| 7 | 90.4 | 9.3 | 0.2 | 0 | 37.2 | 460 |
| Comparative example | 18 | 78.1 | 2.4 | 1.8 | 33.4 | 270 |
Claims (5)
1, a kind of preparation method who is used for the carried catalyst of alkene homopolymerization, described catalyst system contains (A), (B), (C) three kinds of components:
(A) being is the titaniferous of carrier and the ingredient of solid catalyst of carboxylicesters with the magnesium chloride, titanium compound general formula Ti (OR)
nCl
4-n, wherein R is an alkyl, 0≤n≤3;
(B) be AlEt
3
(C) be (C
6H
5)
2Si (OCH
3)
2
Its invention is characterised in that uses MgCl
2, 2-Ethylhexyl Alcohol, phthalic anhydride, titanium class help analyses agent Ti (OC
8H
17)
mCl
4-m, 0≤m≤3 wherein are at C
5～C
8Confined reaction in stable hydrocarbon or its hydrocarbon mixture, reaction pressure are 0.1～0.7MPa, and 90～130 ℃ of temperature generate magnesium chloride-ester compound homogeneous solution, more successively with titanium tetrachloride or alkoxyl group titanium chloride Ti (OR)
xCl
4-x, 1≤x≤4 wherein, R is an alkyl, handles with mixed solvent, the dibutyl phthalate of hydrocarbon composition, titanium tetrachloride handles and make (A) component.
2, Preparation of catalysts method as claimed in claim 1 is characterized in that described varsol is pentane, hexane or heptane.
3, Preparation of catalysts method as claimed in claim 1, adding titanium class helps and analyses agent Ti (OC when it is characterized in that preparing
8H
17)
2Cl
2
4, Preparation of catalysts method as claimed in claim 1 is characterized in that in 65～130 ℃ of this section intervals, and the part lower carbon number hydrocarbons solvent in the reaction solvent is reclaimed in distillation simultaneously.
5, Preparation of catalysts method as claimed in claim 1 is characterized in that the alkoxyl group titanium chloride is Ti (OC
8H
17)
2Cl
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94115522A CN1050136C (en) | 1994-09-10 | 1994-09-10 | Preparation of high performance supported catalyst for propylene polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94115522A CN1050136C (en) | 1994-09-10 | 1994-09-10 | Preparation of high performance supported catalyst for propylene polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1118354A CN1118354A (en) | 1996-03-13 |
| CN1050136C true CN1050136C (en) | 2000-03-08 |
Family
ID=5037555
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94115522A Expired - Fee Related CN1050136C (en) | 1994-09-10 | 1994-09-10 | Preparation of high performance supported catalyst for propylene polymerization |
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| Country | Link |
|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100484970C (en) * | 2007-04-30 | 2009-05-06 | 中国石油化工股份有限公司 | Method for preparing solid catalyst in olefin polymerization catalyst |
| CN101906177B (en) * | 2009-06-04 | 2012-06-27 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58138707A (en) * | 1982-02-12 | 1983-08-17 | Mitsui Petrochem Ind Ltd | Preparation of polyolefin |
| EP0115833A1 (en) * | 1983-01-28 | 1984-08-15 | Phillips Petroleum Company | Polyolefin polymerization process and catalyst |
| US4585749A (en) * | 1983-09-28 | 1986-04-29 | Phillips Petroleum Company | Process for the preparation of an olefin polymerization catalyst |
-
1994
- 1994-09-10 CN CN94115522A patent/CN1050136C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58138707A (en) * | 1982-02-12 | 1983-08-17 | Mitsui Petrochem Ind Ltd | Preparation of polyolefin |
| EP0115833A1 (en) * | 1983-01-28 | 1984-08-15 | Phillips Petroleum Company | Polyolefin polymerization process and catalyst |
| US4585749A (en) * | 1983-09-28 | 1986-04-29 | Phillips Petroleum Company | Process for the preparation of an olefin polymerization catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1118354A (en) | 1996-03-13 |
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