CN103102434B - Preparation method for olefin polymerization catalyst - Google Patents
Preparation method for olefin polymerization catalyst Download PDFInfo
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- CN103102434B CN103102434B CN201310034066.8A CN201310034066A CN103102434B CN 103102434 B CN103102434 B CN 103102434B CN 201310034066 A CN201310034066 A CN 201310034066A CN 103102434 B CN103102434 B CN 103102434B
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Abstract
The invention relates to a preparation method for an olefin polymerization catalyst. The preparation method comprises the following steps of: heating magnesium chloride, an organic liquid emulsifier and alcohol compounds to be molten at 100-150 DEG C; adding molten liquid into an inert solvent and obtaining magnesium halide alcohol compound spherical particles after carrying out cooling, precipitation, filtering and drying; adding the magnesium halide alcohol compound spherical particles into titanium tetrachloride liquid and carrying out reaction; gradually raising the temperature to 40-100 DEG C, adding sulfonyl compounds or composites of sulfonyl compounds and the other internal electron donors as the internal electron donors; adding titanium tetrachloride and carrying out reaction at 80-140 DEG C, filtering, and repeating the steps for 1-3 times; and washing solid particles for 3-6 times by using a polar solvent or a composite solvent of the polar solvent and a non-polar solvent, and obtaining a spherical solid catalyst after drying. According to the preparation method for the olefin polymerization catalyst, the preparation process is simple, the prepared catalyst is high in efficiency and good in stereo positioning performance, and a polymer is high in isotacticity and performance density.
Description
Technical field
The present invention relates to a kind of preparation method for olefin polymerization catalysis.
Background technology
High-performance Ziegler-Natta (Z-N) type polyolefin catalyst adopts magnesium halide in active as the carrier of catalyzer usually, take titanium compound as Primary Catalysts, by adding three components as internal electron donor to improve stereoselective, the performance such as hydrogen response and particle form of catalyzer.The selection of internal electron donor structure and the control of catalyst preparation process are considerable.
In Chinese patent ZL200710118854.X, we have selected a kind of novel component containing sulfonyl compound structure as internal electron donor; catalyzer containing this novel internal electron donor shows higher catalytic activity, hydrogen response, and polymkeric substance has higher degree of isotacticity, apparent density.
In Chinese patent ZL200810226206.0, we have selected a kind of novel component containing sulfonyl compound structure and a kind of ester class or ether compound compound as internal electron donor; catalyzer containing this compound internal electron donor shows higher catalytic activity, hydrogen response, and polymkeric substance has higher degree of isotacticity, apparent density.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of olefin polymerization catalysis, on the basis of above-mentioned patent, improve containing the solid catalyst preparation technology of sulfonyl compound structure as the olefinic polymerization of internal electron donor further.It adopts magnesium halide in active as the carrier of catalyzer; take halogenated titanium as Primary Catalysts; using containing one or more sulfonyl compounds or sulfonyl compound with give the mixture of electronics as internal electron donor in other, adopt polar organic solvent to carry out carrying out washing treatment to catalyzer, eventually through filtering, the method Kaolinite Preparation of Catalyst such as drying.
The preparation method of a kind of olefin polymerization catalysis of the present invention is:
(1) magnesium halide, organic liquid emulsifying agent, alcohol compound are heated in autoclave 100-150 DEG C fully to stir and make it disperse;
(2) obtaining general formula after joining cooling in inert solvent, precipitation, filtration, drying is MgCl
2the magnesium halide alcohol adduct spheroidal particle of nROH;
(3) be MgCl by general formula
2the magnesium halide alcohol adduct spheroidal particle of nROH adds in halogenated titanium liquid, and temperature of reaction is-40-0 DEG C, and the reaction times is 0.1-3 hour;
(4) be warming up to 40-100 DEG C, add one or more sulfonyl compound sulfonyl compounds and other in the mixture of electronics as internal electron donor, reaction 0.5-3 hour;
(5) add titanium tetrachloride at 80-140 DEG C, reaction 0.5-3 hour, filters, repeats this step 1-3 time;
(6) wash solid particulate 3-6 time with the double solvents of one or more organic polar solvents or polar organic solvent and non-polar organic solvent, after drying, obtain spherical solid catalyzer.
For in such scheme:
Described organic liquid emulsifying agent is selected from white oil or silicone oil or both mixtures;
Described inert solvent is selected from naphthenic hydrocarbon, C7-C20 aromatic hydrocarbons, the C1-C20 substituted arene of C1-C20 straight-chain paraffin, C1-C20 branched paraffin, C3-C20 naphthenic hydrocarbon, C4-C20 replacement, and the hydrogen in described alkane, naphthenic hydrocarbon and aromatic hydrocarbons can be optionally substituted by halogen;
Described general formula is MgCl
2in the magnesium halide alcohol adduct spheroidal particle formula of nROH, R is selected from the alkyl of C2-C20.
Described magnesium halide alcohol adduct and titanium tetrachloride consumption with Ti/Mg mol ratio for 1-100;
The compound of described alkylsulfonyl is disulfonyl base alkane, disulfonyl base alkene, disulfonyl cycloalkane, disulfonyl base silane, disulfonyl basic ring silane, disulfonyl base dialkyl tin, disulfonyl base dialkyl are plumbous or contain heteroatomic derivative, disulfonyl base imines class, the sub-phosphine class of disulfonyl base, disulfonyl base arsenous class or contain heteroatomic derivative, (replacement) sulphonic acid anhydride, sulfo-or seleno derivative.
In the preparation method of described olefin polymerization catalysis, other internal electron donor compound is selected from ester class and ether compound.
Described organic polar solvent is selected from: halogenated alkane, halogenated aryl hydrocarbon, second cyanogen, ethyl acetate, ether, toluene;
Organic non-polar solvent of described mixing is selected from: hexane, pentane, heptane, hexanaphthene, sherwood oil.
Olefin polymerization catalysis prepared by the preparation method of described olefin polymerization catalysis is for CH
2the catalyzer of=CHR olefinic polyreaction, wherein R is the alkyl or aryl of hydrogen or C1-C6.
The existence in the non-taxis titanium active centre in catalyzer can strengthen the consumption of other promotors in polymerization process, affect the performance of polymkeric substance, the present invention adopts the non-taxis titanium active centre in polar solvent process catalyst preparation process, catalyst Ti content be can effectively reduce, catalyzer and polymer performance improved.
Specific implementation method
Embodiment 1
The preparation of magnesium halide alcohol adduct spheroidal particle: room temperature adds Magnesium Chloride Anhydrous 84g to A still (1L), nitrogen replacement atmosphere adds dehydrated alcohol 177ml.Be warming up to 125 DEG C, react 4 hours, obtain the alcohol adduct clarified.Add organic liquid emulsifying agent (100ml silicone oil (40cs)+400ml white oil), continue stirring 1 hour.
Add organic liquid emulsifying agent (100ml silicone oil (40cs)+200ml white oil) in B still (2.5L), be warming up to 125 DEG C.Add 3L normal hexane in C still (5L), be cooled to-30 DEG C.
By the reactant transfer in A still in B still, high-speed stirring, time 8min.While keeping high-speed stirring, material in B still is transferred to C still, opens C still simultaneously and stir.Shift complete, C still is warming up to room temperature, with hexanes wash product five times, obtains solid chlorine magnesium alcoholate carrier after drying.
The preparation of catalyst component: add 500mlTiCl in 1L reaction flask
4, be cooled to-20 ° of C, to TiCl
4in add 15 grams of solid chlorine magnesium alcoholate carriers, be warmed up to 0 ° of C, continue to be warmed up to 40 ° of C, add N-p-methoxy-phenyl-two (trifluoromethanesulfonic acid acyl group) amine 2 grams, continue to be warmed up to 120 ° of C and react 0.5-3 hour, filter, then add equivalent TiCl
4reaction, above process repeats 2 times; Wash solid particulate 6 times with polar organic solvent 1,2-ethylene dichloride and non-polar organic solvent hexane (volume ratio is 1:1), after drying, obtain spherical solid catalyzer.
Aggregation test: in the 250ml fully replaced through high pure nitrogen tri-mouthfuls of reaction flasks, with propylene gas displacement twice, make to keep propylene atmosphere in reaction flask, normal heptane 70ml is added in bottle, holding temperature is 50 DEG C, add triethyl aluminum 10mmol again, dimethoxydiphenylsilane (DDS) 0.4mmol.Add catalyzer 38-42mg afterwards, and rinse with 30ml normal heptane, all catalyzer are all added in normal heptane solvent.Keep normal pressure propylene supply 1h, with 100ml10% hydrochloric acid-ethanolic soln cancellation reaction, then use filtered on buchner funnel reaction solution, after gained polypropylene solid washing with alcohol at baking oven to constant weight, weigh calculated activity.
Embodiment 2
Method is with embodiment 1, and difference adopts chlorobenzene and hexane (volume ratio is 1:1) in the washing stage, and washing solid particulate 5 times, obtains spherical solid catalyzer after drying.
Embodiment 3
Method is with embodiment 1, and difference adopts methylene dichloride and hexane (volume ratio is 1:1) in the washing stage, and washing solid particulate 6 times, obtains spherical solid catalyzer after drying.
Comparing embodiment 1
Method is with embodiment 1, and difference adopts hexane in the washing stage, and washing solid particulate 6 times, obtains spherical solid catalyzer after drying.
The analysis of catalyzer and performance test: the mensuration of titanium content: catalyzer through peracid treatment, Ti
4+with H
2o
2form yellow complex, select the light of 420nm wavelength to carry out the spectrophotometry of titanium.Activity rating: adopt normal pressure what slurry propylene polymerization mode: in the 250ml fully replaced through high pure nitrogen tri-mouthfuls of reaction flasks, with propylene gas displacement twice, make to keep propylene atmosphere in reaction flask, normal heptane 70ml is added in bottle, holding temperature is 50 DEG C, add triethyl aluminum again, dimethoxydiphenylsilane (DDS).Add catalyzer afterwards, and rinse with 30ml normal heptane, all catalyzer are all added in normal heptane solvent, keep Ti:Al:Si(mol ratio)=1:450:45.Continuous supply propylene keeps synthesis under normal pressure 1h, with 100ml10% hydrochloric acid-ethanolic soln cancellation reaction, then uses filtered on buchner funnel reaction solution, after gained polypropylene solid washing with alcohol at baking oven to constant weight, weigh calculated activity.
The mensuration of apparent density: adopt funnel to be placed in funnel and add, sample holder ware is placed on funnel support base, adjustment funnel spout and the distance of containing between sample are 10cm, pour sample into funnel until sample holder ware fills with, bulk density of weighing of materialsing.
The mensuration of degree of isotacticity: by the normal heptane of a certain amount of polymkeric substance boiling at apparatus,Soxhlet's extracting 6h, measure the percentage composition that the weight (Winsol) of not dissolving part accounts for gross weight (Wp), be its degree of isotacticity: II=Winsol/Wp × 100%.
Catalyst test result, sees the following form:
Claims (8)
1. a preparation method for olefin polymerization catalysis, is characterized in that:
(1) magnesium chloride, organic liquid emulsifying agent, alcohol compound are heated to 100 ~ 150 DEG C of meltings in autoclave, and fully stirring makes it disperse; The mol ratio of alcohol and magnesium chloride is 2-4, and it is 4-15 that organic liquid emulsifying agent volume rises with the ratio of the magnesia amount gram of magnesium chloride;
(2) magnesium halide alcohol adduct spheroidal particle is obtained after joining cooling in inert solvent, precipitation, filtration, drying;
(3) join in titanium tetrachloride liquid by magnesium halide alcohol adduct spheroidal particle, temperature of reaction is-40 ~ 0 DEG C, and the reaction times is 0.1 ~ 3 hour; Magnesium halide alcohol adduct particle and titanium tetrachloride consumption with Ti/Mg mol ratio for 1-100;
(4) progressively 40-100 DEG C is warming up to, add the mixture of one or more sulfonyl compounds or sulfonyl compound and other internal electron donor as internal electron donor, the mol ratio of electron donor total amount and magnesium halide alcohol adduct is 0.01-1, reaction 0.5-3 hour;
(5) add titanium tetrachloride at 80-140 DEG C, reaction 0.5-3 hour, filters, repeats this step 1-3 time;
(6) wash solid particulate 3-6 time with the double solvents of one or more polar solvents or polar solvent and non-polar solvent, after drying, obtain spherical solid catalyzer.
2. the preparation method of a kind of olefin polymerization catalysis according to claim 1, is characterized in that: described sulfonyl compound is disulfonyl base alkane, disulfonyl base alkene, disulfonyl cycloalkane, disulfonyl base silane, disulfonyl basic ring silane, disulfonyl base dialkyl tin, disulfonyl base dialkyl are plumbous or contain heteroatomic derivative, disulfonyl base imines class, the sub-phosphine class of disulfonyl base, disulfonyl base arsenous class or contain heteroatomic derivative.
3. the preparation method of a kind of olefin polymerization catalysis according to claim 1, is characterized in that: described organic liquid emulsifying agent is selected from white oil or silicone oil or both mixtures.
4. the preparation method of a kind of olefin polymerization catalysis according to claim 1, is characterized in that: described alcohol compound is selected from the combination of one or more in compound shown in general formula R OH, and in formula, R is selected from the alkyl of C2-C20.
5. the preparation method of a kind of olefin polymerization catalysis according to claim 1, is characterized in that: described inert solvent is selected from naphthenic hydrocarbon, the C7-C20 aromatic hydrocarbons of C1-C20 straight-chain paraffin, C1-C20 branched paraffin, C3-C20 naphthenic hydrocarbon, C4-C20 replacement;
6. the preparation method of a kind of olefin polymerization catalysis according to claim 1, is characterized in that: polar solvent is selected from: halogenated alkane, halogenated aryl hydrocarbon, second cyanogen, ethyl acetate, ether, toluene; The non-polar solvent of mixing is selected from: hexane, pentane, heptane, hexanaphthene, sherwood oil.
7. the preparation method of olefin polymerization catalysis according to claim 1, is characterized in that: other internal electron donor compound described is selected from ester class and ether compound.
8. the application of olefin polymerization catalysis prepared of the preparation method of olefin polymerization catalysis according to claim 1, is characterized in that: for CH
2the catalyzer of=CHR olefinic polyreaction, wherein R is the alkyl or aryl of hydrogen or C1-C6.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323650A (en) * | 2007-06-13 | 2008-12-17 | 中国石油天然气股份有限公司 | Olefin polymerizing catalyst, preparation and use thereof |
| CN101735346A (en) * | 2008-11-07 | 2010-06-16 | 中国石油天然气股份有限公司 | Propylene homopolymerized or copolymerized catalyst and preparation method and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323650A (en) * | 2007-06-13 | 2008-12-17 | 中国石油天然气股份有限公司 | Olefin polymerizing catalyst, preparation and use thereof |
| CN101735346A (en) * | 2008-11-07 | 2010-06-16 | 中国石油天然气股份有限公司 | Propylene homopolymerized or copolymerized catalyst and preparation method and application thereof |
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