CN100362024C - Highly active supporting method of non-metallocene catalyst - Google Patents
Highly active supporting method of non-metallocene catalyst Download PDFInfo
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- CN100362024C CN100362024C CNB2004100660686A CN200410066068A CN100362024C CN 100362024 C CN100362024 C CN 100362024C CN B2004100660686 A CNB2004100660686 A CN B2004100660686A CN 200410066068 A CN200410066068 A CN 200410066068A CN 100362024 C CN100362024 C CN 100362024C
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Abstract
The present invention relates to a high activity loading method of a non-metallocene catalyst. A carrier acts with a chemical activating agent to obtain a modifying carrier; a magnesium compound is dissolved in a tetrahydrofuran-alcohol mixing system to form a solution, the modifying carrier is added into the solution to react, and a composite carrier is prepared by filtering washing, drying and extracting; the non-metallocene catalyst for olefin polymerization is dissolved in a solvent, then reacts with the composite carrier, and is scoured, filtered, dried and extracted to preprare the loading non-metallocene catalyst. The method can also comprises that before the carrier acts with the chemical activating agent, thermal activation processing is carried out; before the composite carrier reacts with the catalyst, the composite carrier firstly acts with a chemical processing agent to prepare the modifying composite carrier which reacts with the catalyst to prepare the loading non-metallocene catalyst. The present invention can obtain the loading catalyst with high activity, and obtain the loading catalyst with high performance by less methylaluminoxane. Polyolefine prepared by the catalyst prepared by the present invention has favorable particle shape.
Description
Technical field
The invention belongs to the load technical field of catalyzer, relate to a kind of load method of non-metallocene catalyst, be a kind of on complex carrier load non-metallocene metal olefin polymerization catalysis, by load, obtain highly active load type non-metallocene catalyst.This composite carrier load type non-metallocene catalyst can be used for catalysis in olefine polymerization and copolymerization, especially for the homopolymerization of catalyzed ethylene or the copolymerization of ethene and other alpha-olefin.
Background technology
Known homogeneous transition-metal catalyst has very high catalytic activity in olefinic polymerization, as unsupported Ziegler-Natta catalyst, metallocene calalyst for polymerization of olefine, constrained geometry olefin polymerization catalysis or non-metallocene olefin polymerization catalyst.The non-metallocene olefin polymerization catalyst ligating atom is an oxygen, nitrogen, sulphur and carbon etc., do not contain cyclopentadienyl group, be to find phase earlier 1990s and obtain launching to study, its catalytic activity can meet or exceed metallocene calalyst for polymerization of olefine, and kept the polymkeric substance of metallocene catalysis system controlled simultaneously, narrow molecular weight distribution, can carry out molecule to polymkeric substance cuts out, the polymericular weight and the degree of branching such as can regulate and control at advantage, and because a little less than this type of catalyzer oxytropism, can realize the copolymerization of polar monomer and alkene, thereby produce the functional polyolefin material of excellent performance.
During polymerization in homogeneous phase, the phenomenon that the polymkeric substance of formation can produce sticking still and twine stirring rake, this heat exchange to material in the normal operation of reactor and the reactor has bigger influence, is unfavorable for industrialized continuous production.In addition, need a large amount of promotor methylaluminoxane in the homogeneous catalysis system, polyolefinic production cost is increased, and because the introducing of a large amount of promotors, product performance have also been produced adverse influence, some in addition need in postorder processing, remove the aluminium of introducing in the polymerization process, further increased the cost of process.A kind of olefinic polymerization that patent WO03/010207 is prepared and copolymerization catalyst or catalyst system, have olefinic polymerization widely and copolymerization performance, be applicable to the polymerization technique of various ways, but when olefinic polymerization, need higher promotor consumption could obtain suitable olefin polymerizating activity, and polymerization process exist sticking still phenomenon.
Experience (Chem Rev, 2000,100:1347 according to the metallocene calalyst for polymerization of olefine industrial applications; Chem Rev, 2000,100:1377), the loadization of homogeneous phase non-metallocene olefin polymerization catalyst is very necessary.
The main purpose of catalyst cupportization is the granulating form for polymerization that improves catalyzer and polymkeric substance.It shows as the initial activity that has suitably reduced catalyzer to a certain extent, thereby reduces even avoided caking or the poly-cruelly phenomenon in the polymerization process; Catalyzer can improve the form of polymkeric substance after loadization, improve the apparent density of polymkeric substance, can make it satisfy more polymerization technique process, as vapour phase polymerization or slurry polymerization etc., the process of load simultaneously can reduce Preparation of catalysts and olefinic polymerization cost significantly, improve polymerization, prolong polymerization catalyst active lifetime etc.EP0206794 use MAO is oxide support modified and use metallocenes subsequently, has objectively limited the controllability of the performance of solid support material to the polymer particles granularity.EP685494 acts on hydrophilic oxide with methylaluminoxane, with polyfunctionality organic crosslinking agent and the MAO/ of use activation subsequently metallocene complex, might reduce the tap density of polymerisate, is unfavorable for the industry use.
Patent CN1352654 selects for use organoaluminum, organosilicon, organic-magnesium and organoboron compound to handle carrier, single site olefin polymerization catalysts of load heteroatom ligand then, and resulting loaded catalyst has high reactivity and long storage life.EP295312 has described under the situation that the organic or inorganic bead-type substrate exists, and aluminoxanes solution is contacted with a kind of solvent that can not dissolve aikyiaiurnirsoxan beta, causes aikyiaiurnirsoxan beta to be deposited on the carrier.WO97/26285 describes the method for preparing carried metallocene catalyst under the high pressure, and the production cycle is long, and load efficiency is not high.And CN1307065 handles carrier back loading metallocene catalyst with alkylaluminoxane under the ultra-sonic oscillation effect, and the load process is also uneconomical.
In order to improve the bonding strength between carrier and the catalyzer, CN1162601 adopts the difunctionality linking agent to continue to handle the carrier of process aikyiaiurnirsoxan beta or alkylaluminium cpd processing.Patent CN1174849 handles the silicon-dioxide of dehydroxylation in the toluene medium with MAO after, load metallocene catalyst does not more provide the polymerization activity data of loaded catalyst in the literary composition.Patent CN1120550 proposes a kind of method of catalyst cupportization, it is mainly with hydrophilic, macropore, inorganic carrier in small, broken bits, react with aikyiaiurnirsoxan beta after elder generation's thermal activation, then with multifunctional organic crosslinking agent reaction, mix with the reaction product of metallocenes and activator at last, thereby make carried type metallocene catalyst, but the consumption of aikyiaiurnirsoxan beta is higher in loading process.CN1053673 adopts microwave action that catalyzer and the promotor that loads on the solid support material are contacted with each other in suspension, and then makes a kind of loaded catalyst of rock steady structure, but this method needs microwave device, and it is also remarkable to operate.CN1323319 adopts catalystic material to flood the porous particle carrier of mechanical flow state, the catalyst solution that is about to be equivalent to pore volume is sprayed onto on the carrier, and then drying makes loaded catalyst, this load method objectively requires the solubleness of catalyzer enough big, otherwise can not guarantee the homogeneity and the charge capacity of catalyst cupport.Patent WO96/00243 has described a kind of preparation method of supported catalyst compositions, be included in the two indenyl metallocenes and the aikyiaiurnirsoxan beta of mixing bridging in the solvent and form solution, described solution is combined with porous support, and the cumulative volume of wherein said solution is lower than the liquor capacity when forming slurries.
The catalyzer that with the Magnesium Chloride Anhydrous is carrier demonstrates advantages of high catalytic activity in olefin polymerization process, but this type of catalyzer is highly brittle, and is broken easily in polymerization reactor, thereby causes polymer morphology bad.Silicon dioxide carried catalyzer has good flowability, can be used for gas fluidised bed polymerisation, but silicon dioxide carried metallocene and non cyclopentadienyl catalyst then show lower catalytic activity.Therefore, just may prepare and have high catalytic activity, the catalyzer of the controlled and good abrasion strength resistance of globule size if magnesium chloride and silicon-dioxide are well organically combined.
EP0878484 has reported the MgCl with low content of magnesium chloride (less than 3%)
2/ SiO
2The catalyzer of two carrier loaded zirconium metallocene-prepared can be used for the homopolymerization or the copolymerization of ethene, has catalytic activity preferably.
Patent CN1364817 discloses magnesium chloride/silicon dioxide carried beta-diketon half metallocene-titanium metal Preparation of catalysts method and aggregated application, and its ethylene polymerization activity reaches 7.42 * 10
6Gram polyethylene/mole titanium hour, but in the patent less than concrete data about polymkeric substance granulating aspect of performance.
Patent EP260130 proposes loaded metallocene or non-luxuriant transition-metal catalyst are carried on the silica-gel carrier of methylaluminoxane processing, and the non-luxuriant transition metal here only is meant ZrCl
4, TiCl
4Perhaps VOCl
3, what patent was thought optimum is the mixture of carrier surface through organic-magnesium or magnesium compound and aluminum alkyls, but this process more complicated needs through many preparation processes.
Patent WO03/047752A1 and WO03/047751A1 provide the load method of composite catalyst (Z-N and metallocene catalyst or non-metallocene catalyst and metallocene catalyst) on silica gel, patent is thought, the muriate of titanium or vanadium or chlorine oxonium compound are the non-metallocene catalyst components, and the catalyzer that obtains thus is a bimetallic catalyst.
The activity of olefin polymerization catalysis is the most important condition of its application.But non-metallocene catalyst is through after the inert support load, and the catalysis in olefine polymerization activity all can have minimizing more or less, some in addition actively reduce by one more than the order of magnitude, thereby cause loaded catalyst uneconomical on using.Person more very, behind active the reduction, the resulting polymers ash content increases, and needs additional deliming technology aborning, more causes cost to increase and the complexity of production equipment, has limited its further application in catalyzed polyolefin production.
Summary of the invention
For this reason, the objective of the invention is to provide on the basis of existing technology a kind of high activity loading method of non-metallocene catalyst.By different polymerizing conditions, can obtain polyethylene product or ethene and other alpha-olefin copolymer product of different polymerization activities and different performance.New catalyst provided by the invention can also improve the form of polymkeric substance; Increase the tap density of polymkeric substance and improve polymerization activity.
The present invention relates to the load metallization processes of a class non-metallocene olefin polymerization catalyst on complex carrier.It can be used for catalysis in olefine polymerization and copolymerization process, homopolymerization and ethene and other alpha-olefin as catalyzed ethylene, comprise the copolymerization of the alpha-olefin of 3 or more carbon atoms, as with propylene, iso-butylene, butylene, amylene, hexene, octene and decene, diolefin such as divinyl, 1, the 7-octadiene, 1, the binary of 4-hexadiene or cycloolefin such as norbornylene etc., ternary or more polybasic copolymerization.
The high activity loading method of non-metallocene catalyst of the present invention may further comprise the steps:
With carrier and chemical activating agent effect, obtain modifying carrier;
Magnesium compound is dissolved in tetrahydrofuran (THF)-pure mixed system forms solution, will modify carrier again and join in this solution and react, washing after filtration, dry and drain after make complex carrier;
Non-metallocene olefin polymerization catalyst is dissolved in the solvent, drains with the filtration of complex carrier reaction after scouring, drying then, make load type non-metallocene catalyst.
The prioritization scheme of above method is one or two in the increase following steps:
Porosu solid as carrier carries out thermal activation treatment;
Complex carrier and chemical processing agent effect make the modification complex carrier.
The meaning of two steps that prioritization scheme is increased is described as follows:
Metal oxide surface generally all is the tart surface hydroxyl is arranged, can to make it inactivation with catalyst reaction.Before using, carrier will experience the dehydroxylation process, and it can be under vacuum or inert atmosphere, calcination activation.Carrier roasting 1～24h under 100-1000 ℃, inert atmosphere or reduced pressure finishes.Here said inert atmosphere be meant only contain in the gas and trace or do not contain can with the component of carrier reaction.Roasting condition is preferably at 500～800 ℃, N
2Or continuing 2～12h under the Ar atmosphere, optimum is 4～8h.Carrier through thermal activation need be preserved under inert atmosphere.
The purpose of the thermal activation of silica-gel carrier is to make carrier surface have highly active group, report (JAm Chem Soc is arranged, 1996,118:401) point out, when drying temperature is 200 ℃～500 ℃, the oh group that is easy to remove is reversibly removed, produce the siloxane groups of low reaction activity, but surpass under 600 ℃ the situation at drying temperature, oh group forcibly is removed, change into water, produce and to have the high ring stress and the siloxane groups of high reaction activity very.Also can adopt chemical activating agent that the functional group of carrier surface is changed into other nonreactive siloxane groups.
Complex carrier can directly contact with non-metallocene olefin polymerization catalyst solution, thereby load obtains carry type non-metallocene calalyst for polymerization of olefine.But originally discover if obtain active more excellent carry type non-metallocene calalyst for polymerization of olefine, further handle making that to modify complex carrier be very crucial.Compare with the extra activity that loaded catalyst is obtained, the cost of this treatment step is inappreciable.
This process is that complex carrier is contacted with chemical processing agent, adopts solution dipping method, carrier impregnation is stirred 0.5～72h in the chemical treatment agent solution, preferred 2～24h, most preferably 2～6h.Chemical processing agent is selected from chemical activating agent and is selected from one or more polynary treatment agents of forming in halogenide, alkylate, alkoxy compound or the halogenated alkyl compounds of aikyiaiurnirsoxan beta, aluminum alkyls, borine, IVA, IVB or VB family metal.
Increase after the step of prioritization scheme, each step of present method can be stated as:
Porosu solid as carrier carries out thermal activation treatment;
With carrier after the thermal activation and chemical activating agent effect, obtain modifying carrier;
Magnesium compound is dissolved in tetrahydrofuran (THF)-pure mixed system forms solution, will modify carrier again and join in this solution and react, washing after filtration, dry and drain after make complex carrier;
Complex carrier and chemical processing agent effect make the modification complex carrier; Non-metallocene olefin polymerization catalyst is dissolved in the solvent, then with complex carrier or modification complex carrier
The reaction after scouring filters, drying is drained, and makes load type non-metallocene catalyst.The used porosu solid of the present invention can be arbitrarily, the surface has the porosu solid of functional group.It can be: contain the organic materials of organo-functional group such as polyethylene, polypropylene, polybutene, polyvinyl alcohol, cyclodextrin and above-mentioned polymkeric substance based on monomeric multipolymer, polyester, polymeric amide, polyvinyl chloride, polyacrylic ester, polymethacrylate, polystyrene or partial cross-linked polymkeric substance, organo-functional group are selected from hydroxyl, primary amino, secondary amino group, sulfonic group, carboxyl, amide group, the mono-substituted amide group of N-, sulfonic acid amido, the mono-substituted sulfonic acid amido of N-, sulfydryl, acylimino and hydrazide group.Preferred partial cross-linked styrene polymer with surface hydroxyl functional group; IIA, IIIA, IVA family and IVB family metal oxide are at interior solid inorganic oxide or halogenide, as silicon oxide (silica gel), aluminum oxide, magnesium oxide, titanium oxide, zirconium white, Thorotrast, magnesium chloride, and inorganic oxide mixture and the mixed oxide formed, functional group is selected from surface hydroxyl or carboxyl.Or the oxidation material for preparing by the pyrohydrolysis process by gaseous metal oxide compound or silicon compound; Clay or molecular sieve are as mica, polynite, wilkinite, diatomite, ZSM-5, MCM-41.Relatively more suitable is that the surface has oh group as carrier of the present invention, comprise silicon oxide and with one or more IIA, IIIA family mixed oxide, as silicon oxide-magnesia mixed oxide, the silica-alumina mixed oxide, preferred silicon oxide, aluminum oxide and silicon oxide and one or more IIA, the mixed oxide of the metal oxide of IIIA family is as solid support material, (suitable silica-gel carrier is arbitrarily can be by the commerical prod of buying to preferred silica gel as carrier, as, Grace 955, Grace 948, Grace SP9-351, Grace SP9-485, Grace SP9-10046, Davsion Syloid 245, ES70, ES70X, ES70Y, ES757, Aerosi1812, or CS-2133 and MS-3040), silica gel is before being used for carrier, preferably at 100-1000 ℃, under inert atmosphere or the reduced pressure, drying or roasting 1～24h carried out thermal activation;
The surface-area (BET method mensuration) that is fit to the carrier of wanting required for the present invention is preferably from 10～1000m
2/ g is more preferably from 100～600m
2/ g.Preferred 0.1～the 4cm of pore volume (determination of nitrogen adsorption)
3Between/the g, more preferably at 0.2～2cm
3/ g.The median size of carrier (laser particle analyzer mensuration) is preferably from 1～500 μ m, more preferably from 1～100 μ m.In above-mentioned solid support material, preferred IIA, IIIA, IVA family and IVB family metal oxide are at interior solid inorganic oxide or halide carrier with surface hydroxyl, most preferably silica gel.It can be any form, as granular, spherical, aggregate or other form.The content of hydroxyl can be measured with known technology, as infrared spectroscopy, nuclear magnetic resonance method, titanium tetrachloride method, metal alkylide or metal hydride titration technique.
The chemical activating agent that is used for chemical activation for can with the compound of carrier surface hydroxyl reaction, as metal halide, metal alkyls, metal alkoxide thing, silicoorganic compound or their mixture.
Magnesium compound is selected from magnesium halide, alkoxyl group magnesium halide, alkoxyl magnesium in the load method, or their mixture.In the process with the silica gel of thermal activation and magnesium compound effect, described tetrahydrofuran (THF)-pure mixed solvent is selected from tetrahydrofuran (THF)-Fatty Alcohol(C12-C14 and C12-C18), tetrahydrofuran (THF)-cyclic alcohol or tetrahydrofuran (THF)-aromatic alcohol, tetrahydrofuran-ethyl alcohol.The preferred magnesium halide of magnesium compound, magnesium chloride most preferably, magnesium chloride and silica gel mass ratio are 1: 0.1～40, the best is 1: 1～10.
Non-metallocene olefin polymerization catalyst is dissolved in the solvent, contact with above-mentioned carrier, carry out solution method dipping or incipient impregnation process, perhaps first solution impregnation, carry out the incipient impregnation process behind the filtration drying again, thereby finish the load process of non-metallocene catalyst on carrier.
Used solvent can be mineral oil or different liquid hydrocarbons in the load process, typical solvent is the varsol of from 5 to 12 carbon atoms, or the varsol that is replaced by the chlorine atom, or the aliphatic solvent of 6 to 10 carbon atoms, the cycloaliphatic solvent of 6 to 12 carbon atoms, preferred tetrahydrofuran (THF), toluene or hexane.
Non-metallocene olefin polymerization catalyst involved in the present invention is the title complex with following structure:
Wherein:
M:1,2 or 3;
Q:0 or 1;
D:0 or 1;
N:1,2,3 or 4;
M: transition metal atoms;
X: be to comprise halogen atom, hydrogen atom, C
1-C
30Alkyl and C
1-C
30Replacement alkyl, oxy radical, nitrogen-containing group, sulfur-containing group, boron-containing group, contain aluminium base group, phosphorus-containing groups, silicon-containing group, germanic group or contain tin group at interior group, several X can be identical, also can be different, can also be each other in key Cheng Huan;
In the structural formula all parts electronegative sum absolute value should with metal M in the structural formula positively charged absolute value identical, all parts comprise X and polydentate ligand;
A: Sauerstoffatom, sulphur atom, selenium atom, R
21N or R
21P;
B: refer to nitrogen-containing group, phosphorus-containing groups or C
1-C
30Hydro carbons;
D: refer to Sauerstoffatom, sulphur atom, selenium atom, contain C
1-C
30The nitrogen-containing group of alkyl, contain C
1-C
30The nitrogenous or C of alkyl
1-C
30Alkyl phosphorus-containing groups, wherein N, O, S, Se, P are ligating atom;
E: refer to nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group, phosphorus-containing groups, wherein N, O, S, Se, P are ligating atom;
G: be inertia group, comprise the alkyl of C1-C30, substituted hydrocarbon radical or the safing function group of C1-C30;
→: refer to singly-bound or two key;
...: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
R
1, R
2, R
3, R
21Be hydrogen, C
1-C
30Alkyl, halogen atom, C
1-C
30Substituted hydrocarbon radical or safing function group, R
1, R
2, R
3, R
21Group can be the same or different to each other, wherein adjacent group such as R
1, R
2, R
3Part can be each other in key Cheng Huan;
Alkyl refers to contain C
1-C
30Alkyl, C
1-C
30Cyclic hydrocarbon group, C
2-C
30Group, the C of carbon-carbon double bonds
2-C
30Carbon containing carbon triple-linked group, C
6-C
30Aryl radical, C
8-C
30Condensed ring alkyl or C
4-C
30Heterogeneous ring compound.
The non-metallocene catalyst that preferably has following array structure.
Non-metallocene catalyst with composite carrier load of the present invention is a Primary Catalysts, with one of aikyiaiurnirsoxan beta, aluminum alkyls, Lewis acid or boron fluorine cpd is promotor, the alkene that can be used for catalysis C2～C10, especially ethene, or contain the functional groups organic monomer and carry out slurry polymerization, vapour phase polymerization, letex polymerization, solution polymerization or copolymerization, optimum is used for slurry polymerization.
In the present invention, element and metal be under the jurisdiction of certain gang all be meant by the family of this periodic table of elements and group corresponding to the family of IUPAC system marshalling or group as foundation.
Beneficial effect: adopt load method disclosed by the invention, can on loaded catalyst, obtain high non-metallocene catalyst charge capacity.
Adopt load method of the present invention, can obtain the highly active loaded catalyst of catalysis in olefine polymerization;
The present invention finds, adopts load method provided by the present invention, only needs the fewer methylaluminoxane just can the high loaded catalyst of obtained performance;
The present invention finds, adopts the prepared prepared polyolefine of carry type non-metallocene calalyst for polymerization of olefine of the present invention to have good particle form.
New catalyst provided by the invention has also improved the form of polymkeric substance; Increased the tap density of polymkeric substance.
Embodiment
Embodiment 1, and the high activity loading method of non-metallocene catalyst mainly may further comprise the steps:
Carrier porous solid adopts silica gel G race 955, with silica gel at 500～800 ℃, N
2Or continue drying or roasting 4～8h under the Ar atmosphere.Dehydroxylation silica gel through thermal activation need be preserved under inert atmosphere.
Chemical activating agent adopts titanium tetrachloride; With carrier and the titanium tetrachloride effect after the activation, filtration washing dry with drain after obtain modifying carrier.The mass ratio of titanium tetrachloride and silica gel is 1: 40;
Magnesium chloride is dissolved in the tetrahydrofuran-ethyl alcohol mixed system forms solution, will modify carrier again and join in this solution, fully reaction forms transparent system under 0～60 ℃ of agitation condition.Time is 1～48 hour, preferred 4～24 hours.Washing after filtration, dry and drain after make complex carrier.The magnesium chloride water content should be less than 1% of quality, and median size is 1～100 μ m, preferred 20～40 μ m; Specific surface area is 5～100m
2/ g, preferred 5～30m
2/ g.
Magnesium Chloride Anhydrous joined in tetrahydrofuran (THF)-pure mixed system to stir form solution, improve whipping temp and help to shorten dissolution process, temperature range is from 0～60 ℃, preferred 40～50 ℃.
Adopt methylaluminoxane that complex carrier is carried out chemically modified, obtain modifying complex carrier;
The non-metallocene olefin polymerization catalyst that will have following structure is dissolved in the solvent:
Then with complex carrier or modify that complex carrier contact the after scouring filtration, drying is drained into load type non-metallocene catalyst.
Resulting thus complex carrier, modification complex carrier and load type non-metallocene catalyst replicating vector form all are pressed powders that do, flowable.
" non-metallocene olefin polymerization catalyst " involved in the present invention is that the same domain technician is known, so the non-metallocene olefin polymerization catalyst in the present embodiment can be replaced with any one similar catalyst, its reactions steps is basic identical.
Embodiment 1-1, substantially the same manner as Example 1, but following change is arranged:
Magnesium fluoride is dissolved in tetrahydrofuran (THF)-methanol mixed system forms solution.
Embodiment 1-2, substantially the same manner as Example 1, but following change is arranged:
Magnesium iodide is dissolved in tetrahydrofuran (THF)-propyl alcohol mixed system forms solution.
Embodiment 1-3, substantially the same manner as Example 1, but following change is arranged:
Magnesium bromide is dissolved in tetrahydrofuran (THF)-butanols mixed system forms solution.
Embodiment 1-4, substantially the same manner as Example 1, but following change is arranged:
Chemical activating agent adopts the metal halide zirconium tetrachloride; With carrier and the zirconium tetrachloride effect after the activation, filtration washing dry with drain after obtain modifying carrier.The mass ratio of zirconium chloride and silica gel is 1: 40;
Magnesium chloride is dissolved in tetrahydrofuran (THF)-amylalcohol mixed system forms solution.
Embodiment 1-5, substantially the same manner as Example 1, but following change is arranged:
Magnesium chloride is dissolved in tetrahydrofuran (THF)-hexanol mixed system forms solution.
Embodiment 1-6, substantially the same manner as Example 1, but following change is arranged:
Chemical activating agent adopts the metal halide zirconium bromide; With carrier and the zirconium bromide effect after the activation, filtration washing dry with drain after obtain modifying carrier.The mass ratio of zirconium bromide and silica gel is 1: 40;
Magnesium chloride is dissolved in tetrahydrofuran (THF)-hexanol mixed system forms solution.
Embodiment 1-7, substantially the same manner as Example 1, but following change is arranged:
Chemical activating agent adopts the metal halide aluminum fluoride; With carrier and the aluminum fluoride effect after the activation, filtration washing dry with drain after obtain modifying carrier.The mass ratio of aluminum fluoride and silica gel is 1: 40;
Magnesium chloride is dissolved in tetrahydrofuran (THF)-enanthol mixed system forms solution.
Embodiment 2, and is substantially the same manner as Example 1, but following change is arranged:
Non-metallocene olefin polymerization catalyst changes the compound with following structural formula into:
The thermal activation condition of carrier silica gel is: under 100-1000 ℃, reduced pressure, and drying or roasting 2～12h;
The mass ratio of magnesium chloride and silica gel is 1: 0.1;
Chemical activating agent adopts titanium tetrachloride;
Behind the silica gel and titanium tetrachloride solution reaction certain hour through thermal activation, the filtration washing drying obtains modifying carrier.The length in silica gel and titanium tetrachloride solution reaction times is to having influence on the content of titanium tetrachloride on the silica gel surface, and long-time reaction can obtain the silica-gel carrier of high titanium tetrachloride content, and the short period of time is then opposite.Find that through the present invention 0.5～24h can obtain more excellent result, optimum is to adopt reaction 1～6h.Temperature is unqualified here, but clearly, under lower temperature condition, the waste that titanium tetrachloride leaves reaction system because of vaporization is very little, and this helps the load efficiency of titanium tetrachloride on silica-gel carrier, improves the content of titanium tetrachloride.For the catalysis in olefine polymerization catalyzer, high titanium tetrachloride content will help to improve the catalysis in olefine polymerization activity of catalyzer, but in the operating process of reality, the content of raising titanium tetrachloride also is not easy, generally need under the long at low temperatures condition, adopt pure titanium tetrachloride to soak carrier, perhaps adopt and repeatedly soak carrier.One of characteristic of the present invention can provide a kind of carrier of high titanium tetrachloride content exactly under the condition of gentleness.Titanium tetrachloride solution can be the titanium tetrachloride and the solvent mixture that can form stable performance, character homogeneous arbitrarily with titanium tetrachloride, the hexane solution of preferred titanium tetrachloride.Filtration washing solvent optimal selection hexane solvent;
Dried modified silica-gel carrier is the flowable powder of doing.
Tetrahydrofuran (THF)-pure mixed system changes tetrahydrofuran (THF)-cyclic alcohol into, and present embodiment is tetrahydrofuran (THF)-hexalin;
Wherein the dissolved magnesium compound changes the alkoxyl group magnesium halide into, and present embodiment is MgClOCH
3
The modifier that complex carrier is carried out chemically modified changes aluminum alkyls into, for example: trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, etc.
Embodiment 2-1, substantially the same manner as Example 2, but following change is arranged:
Tetrahydrofuran (THF)-pure mixed system changes tetrahydrofuran (THF)-cyclopentanol into;
Magnesium compound changes MgClOCH into
2CH
3
The modifier that complex carrier is carried out chemically modified changes triethyl aluminum into.
Embodiment 2-2, substantially the same manner as Example 2, but following change is arranged:
Tetrahydrofuran (THF)-pure mixed system changes tetrahydrofuran (THF)-ring octanol into;
Magnesium compound changes MgClOC into
4H
9
The modifier that complex carrier is carried out chemically modified changes triisobutyl aluminium into;
Embodiment 2-3, substantially the same manner as Example 2, but following change is arranged:
Magnesium compound changes MgBrOCH into
3
Embodiment 2-4, substantially the same manner as Example 2, but following change is arranged:
Magnesium compound changes MgBrOCH into
2CH
3
Embodiment 2-5, substantially the same manner as Example 2, but following change is arranged:
Magnesium compound changes MgBrOC into
4H
9
Embodiment 3, and is substantially the same manner as Example 1, but following change is arranged:
The thermal activation condition of carrier silica gel is: drying or roasting 1～24h carry out under the Ar atmosphere;
The mass ratio of magnesium chloride and silica gel is 1: 10;
Embodiment 4, and is basic identical with embodiment 1～3, but following change is arranged:
Silica gel does not carry out thermal activation, and direct and magnesium chloride effect obtains complex carrier; The mass ratio of magnesium chloride and silica gel is 1: 1.
Embodiment 5, and is basic identical with embodiment 1～3, but following change is arranged:
Direct and the non-metallocene olefin polymerization catalyst reaction of complex carrier with the chemical processing agent effect, need not made the modification complex carrier.
Embodiment 6, and is basic identical with embodiment 1～3, but following two changes are arranged simultaneously:
Silica gel does not carry out thermal activation, and direct and magnesium chloride effect obtains complex carrier; The mass ratio of magnesium chloride and silica gel is 1: 1;
Direct and the non-metallocene olefin polymerization catalyst reaction of complex carrier with the chemical processing agent effect, need not made the modification complex carrier.
Embodiment 7, and is basic identical with embodiment 1～3 or 4～6, but following change is arranged:
Porosu solid as carrier changes into: IIA, IIIA, IVA family and IVB family metal oxide be at interior solid inorganic oxide or halogenide, as: aluminum oxide, magnesium oxide, titanium oxide, zirconium white, Thorotrast, magnesium chloride.
Embodiment 8, and is basic identical with embodiment 1～3 or 4～6, but following change is arranged:
Being used to prepare the chemical processing agent of modifying complex carrier changes into: the mixture of methylaluminoxane and titanium tetrachloride;
Tetrahydrofuran (THF)-pure mixed system changes tetrahydrofuran (THF)-aromatic alcohol into, for example: tetrahydrofuran (THF)-phenyl methanol, tetrahydrofuran (THF)-phenylethyl alcohol, tetrahydrofuran (THF)-phenyl butanols, tetrahydrofuran (THF)-naphthyl carbinol, tetrahydrofuran (THF)-naphthyl ethanol, tetrahydrofuran (THF)-naphthyl butanols, etc.;
Wherein the dissolved magnesium compound changes into: alkoxyl magnesium, for example: Mg (OCH
3)
2, Mg (OCH
2CH
3) 2, Mg (OC
4H
9) 2 etc.;
Factors such as various chemical activating agents involved in the present invention, magnesium compound, tetrahydrofuran (THF)-pure mixed solvent, solvent, in those skilled in the art's professional range, available multiple known equivalent is replaced, and does not influence the enforcement of the inventive method.
Claims (8)
1. the high activity loading method of a non-metallocene catalyst may further comprise the steps:
With carrier and chemical activating agent effect, obtain modifying carrier;
Magnesium compound is dissolved in tetrahydrofuran (THF)-pure mixed system forms solution, will modify carrier again and join in this solution and react, washing after filtration, dry and drain after make complex carrier;
Non-metallocene olefin polymerization catalyst is dissolved in the solvent, drains with the filtration of complex carrier reaction after scouring, drying then, make load type non-metallocene catalyst;
Described chemical activating agent be can with the compound of carrier surface hydroxyl reaction, be selected from metal halide, metal alkyls, metal alkoxide thing, silicoorganic compound or their mixture.
2. according to the high activity loading method of the described non-metallocene catalyst of claim 1, it is characterized in that, also be provided with in the following steps one or two:
As the porosu solid of carrier with the chemical activating agent effect before, carry out thermal activation treatment earlier;
Complex carrier with the chemical processing agent effect, made the modification complex carrier earlier before reacting with non-metallocene olefin polymerization catalyst, modify the reaction of complex carrier and non-metallocene olefin polymerization catalyst and make load type non-metallocene catalyst;
Described chemical processing agent is selected from chemical activating agent and is selected from one or more polynary treatment agents of forming in halogenide, alkylate, alkoxy compound or the halogenated alkyl compounds of aikyiaiurnirsoxan beta, aluminum alkyls, borine, IVA, IVB or VB family metal.
3. according to the high activity loading method of claim 1 or 2 described non-metallocene catalysts, it is characterized in that:
Porosu solid as carrier is a porous organic material, this porous organic material is selected from: IIA, IIIA, IVA family and IVB family metal oxide are at interior inorganic oxide, or oxidation mixture and mixed oxide, or the oxidation material for preparing by the pyrohydrolysis process by gaseous metal oxide compound or silicon compound;
Described magnesium compound is selected from magnesium halide, alkoxyl group magnesium halide, alkoxyl magnesium, or their mixture;
In the process with carrier and magnesium compound effect, described tetrahydrofuran (THF)-pure mixed solvent is selected from tetrahydrofuran (THF)-Fatty Alcohol(C12-C14 and C12-C18), tetrahydrofuran (THF)-cyclic alcohol or tetrahydrofuran (THF)-aromatic alcohol;
Used solvent is mineral oil or different liquid hydrocarbons in the load process, be selected from the varsol of from 5 to 12 carbon atoms, or the varsol that is replaced by the chlorine atom, or the aliphatic solvent of 6 to 10 carbon atoms, or the cycloaliphatic solvent of 6 to 12 carbon atoms.
4. according to the high activity loading method of the described non-metallocene catalyst of claim 3, it is characterized in that:
Described non-metallocene olefin polymerization catalyst is the title complex with following structure:
Wherein:
M:1,2 or 3;
Q:0 or 1;
D:0 or 1;
N:1,2,3 or 4;
M: transition metal atoms;
X: be to comprise halogen atom, hydrogen atom, C
1-C
30Alkyl and C
1-C
30Replacement alkyl, oxy radical, nitrogen-containing group, sulfur-containing group, boron-containing group, contain aluminium base group, phosphorus-containing groups, silicon-containing group, germanic group or contain tin group at interior group, several X can be identical, also can be different, can also be each other in key Cheng Huan;
In the structural formula all parts electronegative sum absolute value should with metal M in the structural formula positively charged absolute value identical, all parts comprise X and polydentate ligand;
A: Sauerstoffatom, sulphur atom, selenium atom, R
21N or R
21P;
B: refer to nitrogen-containing group, phosphorus-containing groups or C
1-C
30Hydro carbons;
D: refer to Sauerstoffatom, sulphur atom, selenium atom, contain C
1-C
30The nitrogen-containing group of alkyl, contain C
1-C
30Alkyl nitrogenous or contain C
1-C
30Alkyl phosphorus-containing groups, wherein N, O, S, Se, P are ligating atom;
E: refer to nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group, phosphorus-containing groups, wherein N, O, S, Se, P are ligating atom;
G: be inertia group, comprise the alkyl of C1-C30, substituted hydrocarbon radical or the safing function group of C1-C30;
→: refer to singly-bound or two key;
...: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
Above-described R
1, R
2, R
3, R
21Be hydrogen, C
1-C
30Alkyl, halogen atom, C
1-C
30Substituted hydrocarbon radical or safing function group, wherein, R
1, R
2, R
3, R
21Group can be the same or different to each other, wherein adjacent group R
1, R
2, R
3Part can be each other in key Cheng Huan;
Alkyl refers to contain C
1-C
30Alkyl, C
1-C
30Cyclic hydrocarbon group, C
2-C
30Group, the C of carbon-carbon double bonds
2-C
30Carbon containing carbon triple-linked group, C
6-C
30Aryl radical, C
8-C
30Condensed ring alkyl or C
4-C
30Heterogeneous ring compound.
5. according to the high activity loading method of the described non-metallocene catalyst of claim 4, it is characterized in that:
Described non-metallocene olefin polymerization catalyst is selected from the non-metallocene catalyst with following array structure:
Porosu solid as carrier adopts silica gel;
Described magnesium compound adopts magnesium chloride, and the mass ratio of magnesium chloride and silica gel is 1: 0.1～40;
Described tetrahydrofuran (THF)-pure mixed solvent adopts tetrahydrofuran-ethyl alcohol;
Described solvent mineral oil or different liquid hydrocarbons adopt tetrahydrofuran (THF), toluene or hexane.
6. according to the high activity loading method of claim 4 or 5 described non-metallocene catalysts, it is characterized in that:
Silica gel as carrier carried out thermal activation before being used for carrier, condition is: under 100～1000 ℃, inert atmosphere or reduced pressure, and drying or roasting 1～24h;
The mass ratio of described magnesium chloride and silica gel is 1: 1;
The mass ratio of described magnesium chloride and tetrahydrofuran (THF) is 1: 5～25, and magnesium chloride and alcoholic acid mass ratio are 1: 1～8.
7. according to the high activity loading method of the described non-metallocene catalyst of claim 6, it is characterized in that:
As the overheated activatory condition of the silica gel of carrier be: at 500～800 ℃, N
2Or lasting 2～12h under the Ar atmosphere; The mass ratio of described magnesium chloride and tetrahydrofuran (THF) is 1: 10～20, and magnesium chloride and alcoholic acid mass ratio are 1: 2～6.
8. according to the high activity loading method of the described non-metallocene catalyst of claim 7, it is characterized in that:
As the silica gel of carrier be: 4～8h through time of thermal activation.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100660686A CN100362024C (en) | 2004-12-17 | 2004-12-17 | Highly active supporting method of non-metallocene catalyst |
| KR1020077016440A KR101075404B1 (en) | 2004-12-17 | 2005-10-21 | Supported non-metallocene olefin polymerization catalyst, preparation and use thereof |
| JP2007545817A JP5346469B2 (en) | 2004-12-17 | 2005-10-21 | Supported nonmetallocene olefin polymerization catalyst, preparation method and use method thereof |
| US11/793,046 US7875568B2 (en) | 2004-12-17 | 2005-10-21 | Supported nonmetallocene olefin polymerization catalyst, preparation method and use thereof |
| PCT/CN2005/001737 WO2006063501A1 (en) | 2004-12-17 | 2005-10-21 | Supported non-metallocene olefin polymerization catalyst, and preparation and use thereof |
| EP05801846.6A EP1829897B1 (en) | 2004-12-17 | 2005-10-21 | Supported non-metallocene olefin polymerization catalyst, and preparation and use thereof |
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| CNB2004100660686A CN100362024C (en) | 2004-12-17 | 2004-12-17 | Highly active supporting method of non-metallocene catalyst |
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| CN100362024C true CN100362024C (en) | 2008-01-16 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9399690B2 (en) | 2013-06-18 | 2016-07-26 | Lg Chem, Ltd. | Silica support, preparation method thereof and metallocene catalyst using the same |
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| CN101412765B (en) * | 2007-10-16 | 2012-04-04 | 中国石化扬子石油化工有限公司 | Load type catalyst, load type non-metallocene catalyst and preparations thereof |
| JP5480147B2 (en) | 2007-10-16 | 2014-04-23 | 中国石化揚子石油化工有限公司 | Supported nonmetallocene catalyst and method for producing the same |
| JP5480148B2 (en) | 2007-10-16 | 2014-04-23 | 中国石化揚子石油化工有限公司 | Magnesium compound-supported nonmetallocene catalyst and production thereof |
| CN101412766B (en) * | 2007-10-16 | 2011-10-19 | 中国石化扬子石油化工有限公司 | Magnesium compound load type non-metallocene catalyst and preparation thereof |
| CN101412769B (en) * | 2007-10-16 | 2014-05-07 | 中国石化扬子石油化工有限公司 | Load type non-metallocene catalyst and preparation thereof |
| JP5670460B2 (en) | 2009-10-26 | 2015-02-18 | 中国石油化工股▲ふん▼有限公司 | Supported nonmetallocene catalyst, process for its production and use thereof |
| JP5523572B2 (en) | 2009-10-26 | 2014-06-18 | 中国石油化工股▲ふん▼有限公司 | Supported nonmetallocene catalyst, process for its production and use thereof |
| EP2500364B1 (en) | 2009-11-13 | 2020-03-04 | China Petroleum & Chemical Corporation | Supported non-metallocene catalyst preparation method and application thereof |
| WO2011057469A1 (en) | 2009-11-13 | 2011-05-19 | 中国石油化工股份有限公司 | Supported non-metallocene catalyst and preparation method and uses thereof |
| CN102399321B (en) * | 2010-09-16 | 2014-03-19 | 中国石油化工股份有限公司 | Supported non-metallocene catalyst, and its preparation method and application |
| CN102964483B (en) * | 2011-08-31 | 2015-04-08 | 中国石油化工股份有限公司 | Supported non-metallocene catalyst, preparation method and application |
| CN102964482B (en) * | 2011-08-31 | 2015-04-01 | 中国石油化工股份有限公司 | Supported non-metallocene catalyst, preparation method and application |
| CN115888845A (en) * | 2022-11-18 | 2023-04-04 | 萍乡市路盟环保新材料研发中心有限公司 | Spherical catalyst pressed by mould |
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