CN1513885A - Catalyst composition for olefine polymerization or copolymerization - Google Patents
Catalyst composition for olefine polymerization or copolymerization Download PDFInfo
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- CN1513885A CN1513885A CNA031461867A CN03146186A CN1513885A CN 1513885 A CN1513885 A CN 1513885A CN A031461867 A CNA031461867 A CN A031461867A CN 03146186 A CN03146186 A CN 03146186A CN 1513885 A CN1513885 A CN 1513885A
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Abstract
A catalyst for polymerizing or copolymerizing olefin is prepared through preparing Mg-contained solution from alkyl magnesium, alkoxy magnesium and carboxylic acid anhydride, treating it by halide of transition metal, organic silane and an electron doner, and depositing the catalyst. Its advantages are high activity, high stereo-orientation, high sensitivity to hydrogen regulation, and insoluble to hydrocarbon.
Description
Technical field
The present invention relates to a kind of olefinic polymerization or copolymerization catalyst component.
Background technology
Z-N (Ziegler-Natta) catalyst system that is used for olefinic polymerization all has report at various countries' patent documentation, especially in U.S. Pat 4,298,718, US 4,495,388 disclose with behind the carrier of active magnesium chloride as the ziegler-natta catalyzed component, the high efficiency load type polyolefin catalyst has obtained significant progress, just can find out the further developing of Ziegler-Natta catalyst of magnesium halide load in following patent documentation: US 4,460,701, US 4,562,173 and US 4,784,983 and Chinese patent: 85100997,98111780,94115522,98801094,97112768,97110324,98800687,99125567,00801711 etc.
Summary of the invention
Can learn from above-mentioned prior art, the used precursor magnesium compound of active magnesium chloride support of preparation supported polyolefin catalyst all adopts single magnesium compound, the inventor greatly improves as its activity of preparation activated carbon precursor carrier by discovering in a large number with the mixture that comprises the alkoxyl magnesium compound that alkyl magnesium compound and alkoxyl magnesium compound or conversion form, and catalytic performance greatly improves.
This catalyst component provided by the invention comprises the activated carbon carrier, is carried on transistion metal compound and electron donor on this activated carbon carrier, this activated carbon carrier comprises the alkoxyl magnesium compound that alkyl magnesium compound and alkoxyl magnesium compound or conversion form, wherein:
Alkyl magnesium compound has following general formula (1):
RMgR’
R and R ' are identical or different C in the formula (1)
2-C
12Alkyl, for example magnesium ethide, dipropyl magnesium, dibutylmagnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, diphenyl magnesium, methylethyl magnesium, ethyl-butyl magnesium or octyl group dibutyl magnesium, these alkyl magnesium can be used separately also can mix use.Preferred C
4-C
8Alkyl magnesium, more preferably dibutylmagnesium;
The alkoxyl magnesium compound has following general formula (2):
Mg(OR)
2
R is C in the formula (2)
6-C
12Alkyl, for example two hexyloxy magnesium, two octyloxy magnesium, didecyl oxygen base magnesium,
Preferred two octyloxy magnesium; The mol ratio of alkyl magnesium and alkoxyl magnesium is 0.5-2: 10, be preferably 1-2: 10.
According to said alkoxyl magnesium in the preferred catalyst components of the present invention is that the alcohol adduct of magnesium halide and transition metal halide reaction make or alkyl magnesium is reacted with alcohol and made.
Electron donor(ED) in the preferred catalyst components provided by the invention is from diethyl phthalate, n-butyl phthalate, diisobutyl phthalate, optional a kind of or its mixture of dimixo-octyl phthalate.
The present invention also provides a kind of and has prepared the method for activated carbon carrier by alkyl magnesium and alkoxyl magnesium, and this activated carbon carrier is handled the method that obtains a kind of catalyst component for olefin.
Reaction obtains said alkoxyl magnesium under the condition of magnesium halide alcohol adduct in transition metal halide, or alkyl magnesium and pure direct reaction are obtained said alkoxyl magnesium; Earlier with magnesium chloride, magnesium bromide, magnesium iodide or magnesium fluoride, preferred magnesium chloride one class magnesium halide is as aromatic hydrocarbons such as toluene, ethylbenzene, dimethylbenzene, trimethylbenzene or methyl-ethyl benzenes; As naphthenic hydrocarbon such as hexanaphthene with as pentane, hexane, heptane, octane, nonane, decane or 200# solvent wet goods alkane, in preferred decane and the 200# solvent oil one class hydro carbons non-polar solvent with such as C such as hexanol, 2-ethyl-1-hexanol, octanol or decyl alcohol
6-C
12Alcohol in any alcohol or its mixture reaction can generate alcohol adduct, more preferably C
6-C
8Alcohol, 2-ethyl-1-hexanol most preferably, the mol ratio of magnesium halide and alcohol is 1: 6-1: 2, temperature of reaction is 60 ℃-170 ℃, preferable reaction temperature is 120 ℃-140 ℃; Add then such as aromatic series or aliphatic anhydride, for example, diacetyl oxide, propionic anhydride, butyryl oxide, Succinic anhydried, benzoyl oxide or Tetra hydro Phthalic anhydride etc., preferred Tetra hydro Phthalic anhydride one class carboxylic acid anhydride reaction forms homogeneous solution; This solution is used such as a kind of silicoorganic compound that are selected from tri-methyl-chlorosilane, trimethylethoxysilane, dimethyldichlorosilane(DMCS), tetraethoxysilane, dimethylformamide dimethyl oxygen base alkane silicon, diethyl dimethoxy silane, the phenylbenzene diethoxy silane, preferred tetraethoxysilane, uses such as TiCl
4, TiBr
4, Ti (OCH
3) Cl
3, Ti (OCH
3)
3Cl or Ti (OC
2H
5)
2Cl
2,, preferred TiCl
4One class titanium tetrahalide or alkoxyl group halogenated titanium and use such as n-butyl phthalate, diisobutyl phthalate, di-iso-amyl phthalate, dimixo-octyl phthalate, ethyl benzoate, p-methylphenyl ethyl benzoate, methyl p-methoxybenzoate, paraethoxybenxoic acid acetic ester, diethyl succinate, dibutyl succinate or Polycizer W 260 etc. are preferably common processing of diisobutyl phthalate one class aromatic series or aliphatics multi-carboxylate and obtain titaniferous ingredient of solid catalyst.
Or in the melt that contains the activated carbon component that above-mentioned excessive alkyl magnesium and pure direct reaction obtain, form homogeneous solution after adding above-mentioned carboxylic acid anhydride and solvent, the above-mentioned silicoorganic compound of this solution, halogenated titanium and using such as n-butyl phthalate, diisobutyl phthalate, di-iso-amyl phthalate, dimixo-octyl phthalate, ethyl benzoate, the p-methylphenyl ethyl benzoate, methyl p-methoxybenzoate, paraethoxybenxoic acid acetate, diethyl succinate, dibutyl succinate or Polycizer W 260 etc. are preferably common processing of diisobutyl phthalate one class aromatic series or aliphatics multi-carboxylate and obtain titaniferous ingredient of solid catalyst.
The solid catalyst that propylene polymerization prepared according to the methods of the invention or copolymerization are used mainly contains magnesium, titanium, halogen and internal electron donor component.In the gained solid catalyst: titanium content is 0.3-10%wt, more preferably 0.8-6%wt, most preferably 1-4%wt; Mg content is 5-35%wt, preferred 10-27%wt, most preferably 15-22%wt; Content of halogen is 30-75%wt, preferred 38-70%wt, most preferably 50-60%wt; Internal electron donor content is 3-15%wt, preferred 5-14%wt, most preferably 8-11%wt.
The grain diameter of this catalyst component of solid that above-mentioned two kinds of methods make is 10-60um, preferred 10-25um.The specific surface of this catalyst component is 70-400m2/g, and pore volume is not less than the 0.25cm3/ gram, and wherein the pore radius of the hole of 40-60% is made up of the hole greater than 0.1um.The catalyzer of preparation has high polymerization activity, and high hydrogen response can obtain the alfon and the multipolymer of high degree of isotacticity, wide molecular weight distribution.
The inventor adopts different methods to prepare the activated carbon carrier, when after deliberation, contrast finds that new olefin polymerization catalysis provided by the invention is used for propylene polymerization with the solid catalyst of activated carbon preparing carriers, reactive behavior height, hydrogen response are good, can obtain the alfon and the multipolymer of high degree of isotacticity, wide molecular weight distribution.
The catalyst component of the present invention's preparation both can be used for propylene homopolymerization or copolymerization, also can be used for vinyl polymerization or copolymerization.
With solid titanium catalyst component and alkenyl aluminium, aluminum dialkyl monohalide, sesquialter alkyl aluminum halide, dihalide aluminum alkyls or the alkyl aluminum hydride of the present invention's preparation, preferred triethyl aluminum one class organo-aluminium compound and general formula are the R of (3)
nSi (OR ')
4-nSilicoorganic compound use together and carry out propylene polymerization, can carry out prepolymerization before the polymerization, polymerization can be a slurry polymerization, it also can be mass polymerization, when slurry polymerization, can use non-polar solvents such as hydrogenated gasoline, hexane, heptane, hexanaphthene as reaction medium, polymerization can be continuously, intermittently or semi-continuous.
(3) R is an alkyl identical or inequality with R ' in the formula, 0＜N＜4;
For example: ethyl triethoxysilane, the n-propyl triethoxyl silane, tertiary butyl triethoxyl silane, vinyltriethoxysilane, phenyl triethoxysilane, vinyl three butoxy silanes, dimethoxydiphenylsilane, phenyl methyl dimethoxy silane, di-p-tolyl dimethoxy silane, the p-methylphenyl methyl dimethoxysilane, dicyclohexyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, 2-norbornylene triethoxyl silane, second, isobutyl dimethoxy silane, diisopropyl dimethoxy silane, 2-norbornylene methyl dimethoxysilane, dicyclopentyl dimethoxyl silane, the hexenyl Trimethoxy silane, the cyclopentyl triethoxyl silane, three cyclopentyl methoxy silane, di-t-butyl dimethyl oxygen base silane and cyclopentyl dimethyl methyl TMOS.Preferred cyclohexyl methyl dimethoxy silane.
The pre-polymerization of catalyst component provided by the invention.Prepolymerization reaction is under polymerizing condition, and catalyst component is contacted with organo-aluminium compound and a kind of alkene, and preferred prepolymerization is in the presence of such as organosilane, carries out in as inertia alkane such as hexanes, and the pre-polymerization multiple is 1-20.
In propylene polymerization, the polymeric reaction temperature scope is 50 ℃-120 ℃, more excellent 65 ℃-80 ℃.The polymerization pressure scope is normal pressure-100 kilogram/cm
3, more excellent 10-50 kilogram/cm
3
During with catalyzer provided by the invention and polymerization process polypropylene, can obtain high normal polypropylene, polyacrylic degree of isotacticity reaches as high as 99%, and adjustable in the scope of 91-99%.
Can obtain the polypropylene of wide molecular weight distribution with above-mentioned catalyzer provided by the invention and polymerization process.Because the polypropylene that the present invention obtains has high degree of isotacticity and wide molecular weight distribution, so be particularly suitable as the extrusion of flat film special material.
The polypropylene, the polyethylene that obtain with above-mentioned catalyzer provided by the invention and polymerization process can mix with various additives.As: static inhibitor, thermo-stabilizer, anti, protective agent, nucleator, oxidation inhibitor, pigment, dye well is inorganic or organic filler.Can produce the polymkeric substance of various anti-impacts, film, fiber, the various trades mark of injection moulding, carry out various forming process.
Specific embodiments
The invention will be further described below by embodiment.
Embodiment 1:
Preparation activated carbon solution: reflux exchanger is being housed, mechanical stirrer, heating unit and thermometer, add the 4.8g Magnesium Chloride Anhydrous successively in the 250ml glass reactor after nitrogen is fully replaced, 25 milliliters of 200# solvent oils, 39ml 2-ethyl-1-hexanol, be heated to 130 ℃, react after 2 hours and to add the 2.1g Tetra hydro Phthalic anhydride and kept 1 hour, be cooled to the homogeneous solution that slowly adds 50ml titanium tetrachloride and 0.4ml tetraethoxy after the room temperature, slowly add the 0.006mmol dibutylmagnesium when at the uniform velocity being warming up to certain temperature after adding, it is standby to room temperature to react 0.5 hour postcooling.
Preparation ingredient of solid catalyst: after the 400ml glass reactor is fully replaced with nitrogen, add the 200ml titanium tetrachloride, be cooled to-20 ℃, the solution that slowly adds above-mentioned preparation, add and add the 3ml diisobutyl phthalate when back is warming up to 110 ℃ at a slow speed by certain heat-up rate, after reacting two hours under this temperature, filtered while hot.In the solids that obtains, add 200ml TiCl
4, be warming up to 110 ℃ rapidly, handle filtered while hot after 2 hours, the solids that obtains repeats repeatedly to wash with hexane, and vacuum-drying gets ingredient of solid catalyst.
Embodiment 2:
Preparation activated carbon solution: reflux exchanger is being housed, mechanical stirrer, heating unit and thermometer, add the 4.8g Magnesium Chloride Anhydrous successively in the 250ml glass reactor after nitrogen is fully replaced, 25 milliliters of 200# solvent oils, 20ml 2-ethyl-1-hexanol, be heated to 130 ℃, react after 2 hours and to add the 1.0g Tetra hydro Phthalic anhydride and kept 1 hour, be cooled to the homogeneous solution that slowly adds 50ml titanium tetrachloride and 0.2ml tetraethoxy after the room temperature, slowly add the 0.006mmol dibutylmagnesium when at the uniform velocity being warming up to certain temperature after adding, it is standby to room temperature to react 0.5 hour postcooling.
Preparation ingredient of solid catalyst: with embodiment 1
Embodiment 3:
Preparation activated carbon solution:
Be equipped with in 250ml glass reactor reflux exchanger, mechanical stirrer and thermometer, after nitrogen is fully replaced, add the 25ml200# solvent oil, 0.05 mmole dibutylmagnesium, control and add 0.09 mmole 2-ethyl-1-hexanol under certain temperature slowly, slowly heat up, react at a certain temperature and add the 1.1g Tetra hydro Phthalic anhydride after 2 hours to continue reaction standby after 2 hours.
The preparation ingredient of solid catalyst:
In the 400ml glass reactor after nitrogen is fully replaced, add the 200ml titanium tetrachloride, 0.3ml tetraethoxy, be cooled to-20 ℃, slowly add above-mentioned activated carbon solution, add the 3ml diisobutyl phthalate when the certain heat-up rate of control rises to 110 ℃ after finishing, react after two hours filtered while hot.In the solids that obtains, add 200ml TiCl
4, 110 ℃ down handle 2 hours after filtered while hot, the solids that obtains is with hexane repeated washing repeatedly, vacuum-drying gets ingredient of solid catalyst.
Embodiment 4:
The preparation of activated carbon solution is with embodiment 3
The preparation ingredient of solid catalyst:
In the 400ml glass reactor after fully replacing with nitrogen, add the 200ml titanium tetrachloride, 0.3ml tetraethoxy, be cooled to-20 ℃, slowly drip the above-mentioned active magnesium chloride solution of preparation, add the 2ml diisobutyl phthalate when in 2-3 hour, being warming up to 40 ℃ after dripping, continue to be warming up to 110 ℃, react after two hours filtered while hot.In the solids that obtains, add 200ml TiCl
4, filtered while hot after handling 2 hours under 110 ℃, the solids that obtains repeats repeatedly to wash with hexane, and vacuum-drying makes ingredient of solid catalyst.
Comparative Examples 1:
Preparation activated carbon solution: add 4.8g Magnesium Chloride Anhydrous, 25 milliliters of 200# solvent oils, 39ml 2-ethyl-1-hexanol in 250ml glass reactor reflux exchanger, mechanical stirrer, heating unit and thermometer, after nitrogen is fully replaced successively being equipped with, be heated to 130 ℃, react after 2 hours and to add the 2.1g Tetra hydro Phthalic anhydride and kept 1 hour, be cooled to the homogeneous solution that slowly adds 50ml titanium tetrachloride and 0.4ml tetraethoxy after the room temperature, standby.
The preparation ingredient of solid catalyst is with embodiment 1.
Bulk propylene polymerization:
To the ingredient of solid catalyst 10-15mg that adds embodiment 1,2 and 3, Comparative Examples 1 with the propylene gas pump drainage in good four the 5 liter polymeric kettles respectively, 2.5 mmole triethyl aluminum, 0.1 mmole cyclohexyl methyl dimethoxy silane, 0.04 mol of hydrogen, 2.3L liquid propylene, be warming up to 70 ℃ under stirring, reacted 2 hours down at 70 ℃, termination reaction obtains polypropylene.
The ethene slurry polymerization:
In the 2 liter polymeric kettles of replacing, add and purify good hexane through High Purity Hydrogen, stir and add 5 mmole triethyl aluminums down, the ingredient of solid catalyst 10-15mg of embodiment 4, add 1.8kg/cm2 hydrogen after being warmed up to 80 ℃, add a certain amount of ethylene gas after a period of stabilisation, keep polymerization system pressure at 7kg/cm2, constantly make-up ethylene gas maintenance system pressure is 7kg/cm2, react cooling discharge after 2 hours, obtain polyethylene.
The physical property measurement of table 1 catalyst component and proximate analysis result
* the amount of Ti, Mg, Cl and ester is represented with WT%.
The polymerization evaluation result of table 2 catalyst component
Annotate: embodiment 1, embodiment 2, embodiment 3, Comparative Examples 1 are the bulk propylene polymerization evaluation result
Embodiment 4 is an ethene slurry polymerization evaluation result.
Above-mentioned comparative illustration, catalyst component provided by the invention can make the homopolymer and the multipolymer of high reactivity, high degree of isotacticity, wide molecular weight distribution.
Those skilled in the art can carry out all changes and modification after reading the technical scheme that the present invention discloses, but these changes and revising all within the claim protection domain that application is awaited the reply.
Claims (9)
1. olefinic polymerization or copolymerization catalyst component, it is characterized in that this catalyst component comprises the activated carbon carrier, is carried on transistion metal compound and electron donor on this activated carbon carrier, this activated carbon carrier comprises alkyl magnesium compound and alkoxyl magnesium compound, and the mol ratio of alkyl magnesium and alkoxyl magnesium is 0.5-2: 10; Described alkyl magnesium compound has following general formula (1):
RMgR’
R and R ' are identical or different C in the formula (1)
2-C
12Alkyl, for example magnesium ethide, dipropyl magnesium, dibutylmagnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, diphenyl magnesium, methylethyl magnesium, ethyl-butyl magnesium or octyl group dibutyl magnesium, or its mixture;
Described alkoxyl magnesium compound has following general formula (2):
Mg(OR)
2
R is C in the formula (2)
6-C
12Alkyl, for example two hexyloxy magnesium, two octyloxy magnesium, didecyl oxygen base magnesium,
2. according to the catalyst component of claim 1, it is characterized in that described alkyl magnesium is C
4-C
8Alkyl magnesium, described alkoxyl magnesium is two octyloxy magnesium.
3. according to the catalyst component of claim 1, it is characterized in that said alkoxyl magnesium is the alcohol adduct of magnesium halide and the transition metal halide reaction makes or alkyl magnesium is reacted with alcohol and made.
4. according to the catalyst component of claim 3, it is characterized in that said alkoxyl magnesium is monobasic saturated alcohol or its mixture of alcohol for selecting in the alcohol adduct of magnesium halide from hexanol, 2-ethyl-1-hexanol, octanol or decyl alcohol.
5. according to the catalyst component of claim 3 or 4, it is characterized in that said magnesium halide is a Magnesium Chloride Anhydrous.
6. according to the catalyst component of claim 1, it is characterized in that said electron donor(ED) a kind of or its mixture for choosing wantonly from diethyl phthalate, n-butyl phthalate, diisobutyl phthalate, dimixo-octyl phthalate.
7. according to the catalyst component of claim 1, it is characterized in that the mol ratio of alkyl magnesium and alkoxyl magnesium is 1-2 in the said activated carbon component: 10.
8. according to the catalyst component of above-mentioned each claim, the grain diameter that it is characterized in that said catalyst component is 10-60um, specific surface is 70-400m2/g, and pore volume is not less than the 0.25cm3/ gram, and wherein the pore radius of the hole of 40-60% is made up of the hole greater than 0.1um.
9. according to the catalyst component of above-mentioned each claim, its spy is in this solid catalyst: titanium content is that 0.3-10%wt, Mg content are that 5-35%wt, content of halogen are that 30-75%wt, internal electron donor content are 3-15%wt.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03146186 CN1241955C (en) | 2003-07-28 | 2003-07-28 | Catalyst composition for olefine polymerization or copolymerization |
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|---|---|---|---|
| CN 03146186 CN1241955C (en) | 2003-07-28 | 2003-07-28 | Catalyst composition for olefine polymerization or copolymerization |
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| CN1241955C CN1241955C (en) | 2006-02-15 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103608363A (en) * | 2011-07-04 | 2014-02-26 | 东邦钛株式会社 | Solid catalyst component for olefin polymerization, and catalyst |
| CN109206547A (en) * | 2017-07-03 | 2019-01-15 | 中国石化扬子石油化工有限公司 | A kind of external electron donor of the catalyst for polymerization of propylene of Ziegler-Natta type and catalyst comprising it |
-
2003
- 2003-07-28 CN CN 03146186 patent/CN1241955C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103608363A (en) * | 2011-07-04 | 2014-02-26 | 东邦钛株式会社 | Solid catalyst component for olefin polymerization, and catalyst |
| CN103608363B (en) * | 2011-07-04 | 2016-03-02 | 东邦钛株式会社 | Solid catalyst component for olefin polymerization and catalyzer |
| CN109206547A (en) * | 2017-07-03 | 2019-01-15 | 中国石化扬子石油化工有限公司 | A kind of external electron donor of the catalyst for polymerization of propylene of Ziegler-Natta type and catalyst comprising it |
| CN109206547B (en) * | 2017-07-03 | 2021-02-05 | 中国石化扬子石油化工有限公司 | External electron donor of Ziegler-Natta type propylene polymerization catalyst and catalyst containing same |
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| CN1241955C (en) | 2006-02-15 |
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