CN101412766A - Magnesium compound load type non-metallocene catalyst and preparation thereof - Google Patents

Magnesium compound load type non-metallocene catalyst and preparation thereof Download PDF

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CN101412766A
CN101412766A CN 200710162667 CN200710162667A CN101412766A CN 101412766 A CN101412766 A CN 101412766A CN 200710162667 CN200710162667 CN 200710162667 CN 200710162667 A CN200710162667 A CN 200710162667A CN 101412766 A CN101412766 A CN 101412766A
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magnesium compound
metallocene catalyst
type non
load type
preparation
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CN101412766B (en
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顾越峰
姚小利
李传峰
马忠林
王亚明
陈韶辉
李晓强
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Sinopec Yangzi Petrochemical Co Ltd
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Sinopec Yangzi Petrochemical Co Ltd
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Priority to PCT/CN2008/001739 priority patent/WO2009052701A1/en
Priority to EP08841802.5A priority patent/EP2202246B1/en
Priority to KR1020107003494A priority patent/KR101206940B1/en
Priority to JP2010529215A priority patent/JP5480148B2/en
Priority to US12/671,654 priority patent/US8716416B2/en
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Abstract

The invention relates to a magnesium compound supported non-metallocene catalyst, which is obtained by directly contacting a compound of catalytic active metal and a magnesium compound containing a non-metallocene ligand through an in-situ supporting method. The preparation method for the magnesium compound supported non-metallocene catalyst has simple, feasible and flexible process, and has more adjustable parameters to the polymerization activity of the catalyst. When the supported non-metallocene catalyst and a catalyst promoter are adopted to form a catalytic system for the homopolymerization/copolymerization of olefins, the obtained polymer has high bulk density and low ash, and the molecular weight distribution of the polymer has wide adjustable range.

Description

A kind of magnesium compound load type non-metallocene catalyst and preparation method thereof
Technical field
The present invention relates to a kind of for olefines polymerization load type non-metallocene catalyst.Particularly, the present invention relates to a kind of magnesium compound load type non-metallocene catalyst, it is by original position load method the catalytically-active metals compound directly to be contacted with the magnesium compound that contains the Nonmetallocene part to obtain.By with the combination of promotors such as magnesium compound load type non-metallocene catalyst of the present invention and aikyiaiurnirsoxan beta and aluminum alkyls, can be used for the homopolymerization/copolymerization of catalyzed alkene.
Background technology
The non-metallocene catalyst that the middle and later periods nineties 20th century occurs, be called luxuriant rear catalyst again, the central atom of Primary Catalysts has comprised nearly all transition metal, be after Ziegler, Ziegler-Natta and metallocene catalyst the 4th generation olefin polymerization catalysis, such catalyzer has reached on some performance or even has surpassed metallocene catalyst.Non-metallocene catalyst does not contain cyclopentadienyl group, ligating atom is oxygen, nitrogen, sulphur and phosphorus, it is characterized in that central ion has stronger Electron Affinities, and have cis alkyl or halogen metal division center, carrying out alkene insertion and σ-key easily shifts, the easy alkylation of central metal helps the generation at cation activity center; The title complex that forms has the geometric configuration of qualification, stereoselectivity, electronegativity and chirality controllability. in addition, the metal-carbon key that forms polarizes easily, is beneficial to the polymerization of alkene. therefore, even under higher polymeric reaction temperature, also can obtain the olefin polymer of higher molecular weight.
But homogenous olefin polymerization catalyst has been proved it in olefinic polyreaction has active duration short, sticking still, high methylaluminoxane consumption easily, and obtains the too low or too high weak point of polymericular weight, has seriously limited its industrial application.
A kind of alkene homopolymerization/catalyst for copolymerization or catalyst system that patent ZL01126323.7, ZL02151294.9, ZL02110844.7 and WO03/010207 are prepared, has alkene homopolymerization/copolymerization performance widely, be applicable to the polymerization technique of various ways, but need higher promotor consumption during in olefinic polymerization at the disclosed catalyzer of this patent or catalyst system, could obtain suitable olefin polymerizating activity, and exist sticking still phenomenon in the polymerization process.
Common way be with non-metallocene catalyst by certain load technology, make loaded catalyst, thereby improve the polymerization of alkene and the particle form of resulting polymers.It shows as the initial activity that has suitably reduced catalyzer to a certain extent, prolong the polymerization activity life-span of catalyzer, reduce even avoided caking or the poly-cruelly phenomenon in the polymerization process, improve the form of polymkeric substance, improve the apparent density of polymkeric substance, can make it satisfy more polymerization technique process, as vapour phase polymerization or slurry polymerization etc.
At patent ZL01126323.7, ZL02151294.9, the disclosed non-metallocene catalyst of ZL02110844.7 and WO03/010207, patent CN1539855A, CN1539856A, CN1789291A, CN1789292A, CN1789290A, WO/2006/063501,200510119401.x carry out load Deng having adopted variety of way, obtain load type non-metallocene catalyst, but these patents all relate to the Nonmetallocene organic compound that will contain transition metal and (or are called non-metallocene catalyst, or Nonmetallocene title complex) is carried on the carrier after the processing, the non-metallocene catalyst charge capacity is lower, or it combines not really tight with carrier.
Existing olefin polymerization catalysis patent is mostly based on metallocene catalyst, as US4808561, US 5240894, CN 1049439, CN 1136239, CN 1344749, CN1126480, CN 1053673, CN 1307594, CN 1130932, CN 1103069, CN1363537, CN1060179, US574417, EP685494, US4871705 and EP0206794 etc., but these patents also all relate on the carrier after the metallocene catalyst that will contain transition metal is carried on processing.
Patent EP708116 discloses the zirconium tetrachloride that makes gasification earlier and has contacted and load with carrier under 160～450 ℃ of temperature, again the zirconium tetrachloride of load is obtained carried metallocene catalyst with the lithium salts reaction of part, then by cooperate the polymerization that is used for alkene with promotor.The problem that this catalyzer exists is that load process requires high temperature, and high vacuum is not suitable for industrial production.
Patent ZL01131136.3 discloses a kind of method of synthetic carried metallocene catalyst.Silica gel is mixed in solvent with IV B group 4 transition metal halogenide, direct again and part negative ion reaction, thus in a step, realize synthesizing and load of metallocene catalyst.But it is 1:1 that this method requires the transition metal and the mol ratio of part, and needs adding proton donor, and as butyllithium etc., and the part that is adopted is the metallocene part that contains cyclopentadienyl group of bridging type or non-bridging type.
The grade of Xiao Yi is open " novel Ni (acac) in paper 2/ TiCl 4The poly research of/L ligand complex catalyst catalyzed ethylene polymerization for preparing branched " (Zhongshan University's journal: natural science edition, 2003,42 (3): 28), it is with anhydrous MgCl 2, Ni (acac) 2And L, be dissolved in the tetrahydrofuran-ethyl alcohol mixed solvent after, add people's silica gel stirring reaction, add a certain amount of titanium tetrachloride and continue reaction, add a certain amount of Et again 2AlCl reaction, drain catalyzer, having prepared with magnesium chloride-silica gel thus is carrier, the Ni (acac) that modifies with α-diimide ligand L 2/ TiCl 4Composite catalyst. adopt this catalyst list-vinyl polymerization can obtain branched polyethylene, wherein ligand L 2 makes the branched polyethylene that the degree of branching is 4-12 side chain number/1000C.
Though can polymerization obtain the good polymkeric substance of particle form as the carrier of non-metallocene catalyst with silica-gel carrier or with the complex carrier that contains silica gel, and can the controlling polymers size distribution, but the polymerization activity of catalyzer is lower, owing to contain silica gel in the ash, limited the practical use of polymkeric substance.
There is bibliographical information to adopt the chloro aluminium triethyl to handle MgCl 2(THF) 2, and the load bis cyclopentadienyl zirconium dichloride, make carried metallocene catalyst thus.Its process is: magnesium chloride is dissolved in the tetrahydrofuran (THF), handles final load bis cyclopentadienyl zirconium dichloride (EUROPEAN POLYMER JOURNAL, 2005,41,941～947) after the hexane washing of precipitate with the chloro aluminium triethyl.
Sun Min etc. are open in paper, and " in-situ reaction prepares CpTi (dbm) Cl 2/ MgCl 2The research of supported catalyst and catalyzed ethylene polymerization thereof " (the polymer journal, 2004, (1): 138), it adopts the Grignard reagent legal system to be equipped with magnesium chloride support, adds CpTi (dbm) Cl simultaneously 2, prepare CpTi (dbm) Cl with this 2/ MgCl 2Supported catalyst.The alkylation and the loadization of catalyzer were finished in a step, significantly reduced the Preparation of catalysts operation.
Patent CN200510080210.7 discloses original position synthetic supported type vanadium non-metallocene catalyst and preparation method and application; wherein earlier dialkyl magnesium is formed acyl group naphthols magnesium or beta-diketon magnesium compound with acyl group naphthols or beta-diketon reaction; muriate with the tetravalence vanadium reacts again, forms carrier and active catalytic components simultaneously.
Patent CN200610026765.8 discloses a class single active center Z-N olefin polymerization catalysis. this catalyzer with the salicylaldehyde derivatives of the salicylic aldehyde that contains coordinating group or replacement as electron donor, be by in magnesium compound (as magnesium chloride)/tetrahydrofuran solution, adding through pretreated carrier (as silica gel), metallic compound (as titanium tetrachloride) and this electron donor obtain after the processing.
Patent CN200610026766.2 is similar with it, discloses a class and has contained heteroatomic organic compound and the application in Ziegler-Natta catalyst thereof.
Even so, the ubiquitous problem of the load type non-metallocene catalyst that exists in the prior art is that olefin polymerizating activity is low, and in order to improve its activity, just must assist higher promotor consumption.And prior art has been owing to adopted silica gel etc. as load carriers, therefore by containing ash in the polymkeric substance that polymerization obtained, thereby limited the practical use of polymkeric substance.In addition, when adopting the load type non-metallocene catalyst of prior art, polymkeric substance such as resulting polyethylene have lower polymer stacks density.
Therefore, still need a kind of load type non-metallocene catalyst, its preparation method is simple, is fit to suitability for industrialized production, and can overcomes those problems that exist in the prior art load type non-metallocene catalyst.
Summary of the invention
For this reason, the objective of the invention is to provide on the basis of existing technology a kind of magnesium compound load type non-metallocene catalyst, it is by original position load method transistion metal compound directly to be contacted with the magnesium compound that contains the Nonmetallocene part to obtain.In its preparation process, need not the proton donor and electron donor etc., also need not harsh reaction requirement and reaction conditions. therefore, the preparation method of this loaded catalyst is simple, and is very suitable for suitability for industrialized production.
Particularly, the present invention relates to the content of following aspect:
1. the preparation method of a magnesium compound load type non-metallocene catalyst may further comprise the steps:
Magnesium compound is contacted with the Nonmetallocene part, obtain product of contact step and
Handle described product of contact with the chemical processing agent that is selected from IV B family metallic compound, obtain the step of described magnesium compound load type non-metallocene catalyst.
2, according to the preparation method of aspect 1 described magnesium compound load type non-metallocene catalyst, also be included in before described Nonmetallocene part contacts, handle the step of described magnesium compound with the chemical processing agent that helps that is selected from aikyiaiurnirsoxan beta, aluminum alkyls and its mixture.
According to the preparation method of aspect 1 or 2 described magnesium compound load type non-metallocene catalysts, it is characterized in that 3, described magnesium compound is through modification.
4, according to the preparation method of aspect 3 described magnesium compound load type non-metallocene catalysts, it is characterized in that described modification magnesium compound is to make it to precipitate with solvent and obtain by add precipitation in by described magnesium compound and solution that tetrahydrofuran (THF)-pure mixed solvent constitutes.
5, according to the preparation method of aspect each described magnesium compound load type non-metallocene catalyst of 1-4, it is characterized in that, also comprise through filtering and washing, perhaps without filtration and washing, and the step of the load type non-metallocene catalyst that convection drying obtained.
6, according to the preparation method of aspect each described magnesium compound load type non-metallocene catalyst of 1-5, it is characterized in that, also be included in handle with described chemical processing agent before, described product of contact is carried out the exsiccant step.
7. according to the preparation method of aspect each described magnesium compound load type non-metallocene catalyst of 1-6, it is characterized in that described contact procedure is carried out in the presence of the solvent of the described Nonmetallocene part of solubilized.
8. according to the preparation method of aspect 7 described magnesium compound load type non-metallocene catalysts, it is characterized in that the solvent of the described Nonmetallocene part of described solubilized is selected from one or more in alkane, naphthenic hydrocarbon, halogenated alkane, halo naphthenic hydrocarbon, aromatic hydrocarbon and the halogenated aromatic.
9. according to the preparation method of aspect 8 described magnesium compound load type non-metallocene catalysts, it is characterized in that the solvent of the described Nonmetallocene part of described solubilized is selected from one or more in alkane, halogenated alkane and the aromatic hydrocarbon.
10. according to the preparation method of aspect 9 described magnesium compound load type non-metallocene catalysts, it is characterized in that the solvent of the described Nonmetallocene part of described solubilized is selected from one or more in hexane, methylene dichloride and the toluene.
11. preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 1-10, it is characterized in that described magnesium compound is selected from one or more in magnesium halide, alkoxyl group magnesium halide, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and the alkyl alkoxy magnesium.
12. the preparation method according to aspect 11 described magnesium compound load type non-metallocene catalysts is characterized in that, described magnesium compound is selected from magnesium halide.
13. preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 1-12, it is characterized in that described IV B family metallic compound is selected from one or more in halogenide, alkylate and the halogenated alkyl compounds of IV B family metal.
14. the preparation method according to aspect 13 described magnesium compound load type non-metallocene catalysts is characterized in that, described IV B family metallic compound is selected from IV B family metal halide.
15. the preparation method according to aspect 14 described magnesium compound load type non-metallocene catalysts is characterized in that, described IV B family metal halide is selected from titanium tetrachloride and zirconium tetrachloride.
16. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 1-15 is characterized in that, is 1:0.1～1 in the described chemical processing agent of IV B family metallic element and the mol ratio of described Nonmetallocene part.
17. the preparation method according to aspect 16 described magnesium compound load type non-metallocene catalysts is characterized in that, is 1:0.3～0.9 in the described chemical processing agent of IV B family metallic element and the mol ratio of described Nonmetallocene part.
18. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 1-17 is characterized in that, described Nonmetallocene part is 1:1～10 with mol ratio in the described magnesium compound of magnesium elements.
19. the preparation method according to aspect 18 described magnesium compound load type non-metallocene catalysts is characterized in that, described Nonmetallocene part is 1:3～7 with mol ratio in the described magnesium compound of magnesium elements.
20. preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 4-19, it is characterized in that, described alcohol is selected from one or more in Fatty Alcohol(C12-C14 and C12-C18), aromatic alcohol and the alicyclic ring alcohol, and the optional group that is selected from alkyl, halogen atom and alkoxyl group of wherein said alcohol replaces.
21. the preparation method according to aspect 20 described magnesium compound load type non-metallocene catalysts is characterized in that, described alcohol is selected from Fatty Alcohol(C12-C14 and C12-C18).
22. the preparation method according to aspect 21 described magnesium compound load type non-metallocene catalysts is characterized in that, described Fatty Alcohol(C12-C14 and C12-C18) is selected from ethanol, butanols and isooctyl alcohol.
23. preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 4-22, it is characterized in that, in the described magnesium compound of magnesium elements and the mol ratio of tetrahydrofuran (THF) is 1:5～100, is 1:0.5～20 in the described magnesium compound of magnesium elements and the mol ratio of described alcohol.
24, according to the preparation method of aspect 23 described magnesium compound load type non-metallocene catalysts, it is characterized in that, in the described magnesium compound of magnesium elements and the mol ratio of tetrahydrofuran (THF) is 1:10～30, is 1:1～8 in the described magnesium compound of magnesium elements and the mol ratio of described alcohol.
25. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 4-24 is characterized in that, by volume, described precipitation is 1:0.5～6 with the ratio of solvent and tetrahydrofuran (THF).
26. the preparation method according to aspect 25 described magnesium compound load type non-metallocene catalysts is characterized in that, by volume, described precipitation is 1:1～4 with the ratio of solvent and tetrahydrofuran (THF).
27. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 4-26 is characterized in that, described precipitation is selected from alkane, naphthenic hydrocarbon, halogenated alkane and the halo naphthenic hydrocarbon one or more with solvent.
28. the preparation method according to aspect 27 described negative magnesium compound load type non-metallocene catalysts is characterized in that, described precipitation is selected from alkane and the naphthenic hydrocarbon one or more with solvent.
29. the preparation method according to aspect 28 described magnesium compound load type non-metallocene catalysts is characterized in that, described precipitation is selected from hexane and hexanaphthene with solvent.
30. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 2-29 is characterized in that, the described chemical processing agent that helps is selected from methylaluminoxane, isobutyl aluminium alkoxide, triethyl aluminum and the triisobutyl aluminium one or more.
31. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 2-30 is characterized in that, is 1:0.5～4 in the described magnesium compound of magnesium elements with helping the mol ratio of chemical processing agent in aluminium element described.
32. the preparation method according to aspect 31 described magnesium compound load type non-metallocene catalysts is characterized in that, is 1:1～2 in the described magnesium compound of magnesium elements with helping the mol ratio of chemical processing agent in aluminium element described.
33. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 1-32 is characterized in that, described Nonmetallocene part is selected from the compound with following structure:
Figure A200710162667D00171
Wherein:
Q is selected from 0 or 1;
D is selected from 0 or 1;
A be selected from Sauerstoffatom, sulphur atom, selenium atom,
Figure A200710162667D00172
-NR 23R 24,-N (O) R 25R 26, -PR 28R 29,-P (O) R 30OR 31, sulfuryl, sulfoxide group or-Se (O) R 39
B is selected from nitrogen-containing group, phosphorus-containing groups or C 1-C 30Alkyl;
D is selected from Sauerstoffatom, sulphur atom, selenium atom, nitrogenous C 1-C 30Alkyl, phosphorated C 1-C 30Alkyl, sulfuryl, sulfoxide group,
Figure A200710162667D00181
-N (O) R 25R 26,
Figure A200710162667D00182
-P (O) R 32(OR 33), wherein N, O, S, Se, P are respectively ligating atom;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group or phosphorus-containing groups, and wherein N, O, S, Se, P are respectively ligating atom;
G is selected from C 1-C 30The C of alkyl, replacement 1-C 30Alkyl or safing function group;
→ represent singly-bound or two key;
-represent covalent linkage or ionic linkage;
R 1, R 2, R 3, R 22, R 23, R 24, R 25, R 26, R 27, R 28, R 29, R 30, R 31, R 32, R 33And R 39Be selected from hydrogen, C independently of one another 1-C 30The C of alkyl, halogen atom, replacement 1-C 30Alkyl or safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can be each other in key or Cheng Huan.
34. the preparation method according to aspect 33 described magnesium compound load type non-metallocene catalysts is characterized in that,
Described Nonmetallocene part is selected from (A) with following structure and (B) compound:
Figure A200710162667D00183
With
Figure A200710162667D00184
Wherein F is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group or phosphorus-containing groups, and wherein N, O, S, Se, P are respectively ligating atom;
Other are according to aspect 33 described definition.
35. the preparation method according to aspect 34 described magnesium compound load type non-metallocene catalysts is characterized in that,
Described Nonmetallocene part is selected from the compound with following structure A-1 to A-4 and B-1 to B-4:
Figure A200710162667D00191
Figure A200710162667D00201
Wherein:
Y and Z are selected from nitrogen-containing group, oxy radical, sulfur-containing group independently of one another, contain seleno group or phosphorus-containing groups, and wherein N, O, S, Se and P are respectively ligating atom;
R 4, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20And R 21Be selected from hydrogen, C independently of one another 1-C 30The C of alkyl, halogen atom, replacement 1-C 30Alkyl or safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can be each other in key or Cheng Huan;
R 5Be selected from lone-pair electron on the nitrogen, hydrogen, C 1-C 30The C of alkyl, replacement 1-C 30Alkyl, oxy radical, sulfur-containing group, nitrogen-containing group or phosphorus-containing groups, prerequisite are to work as R 5For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group or phosphorus-containing groups, R 5In N, O, S, P, Se be respectively ligating atom;
Other are according to aspect 34 described definition.
36. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 33-35 is characterized in that,
Described halogen is selected from F, Cl, Br, I;
Described safing function group is selected from halogen, oxy radical, nitrogen-containing group, silicon-containing group, germanic group, sulfur-containing group or contains tin group;
Described nitrogen-containing group is selected from
Figure A200710162667D00211
-NR 23R 24,-T-NR 23R 24Or-N (O) R 25R 26
Described phosphorus-containing groups is selected from
Figure A200710162667D00212
-PR 28R 29,-P (O) R 30R 31Or-P (O) R 32(OR 33);
Described oxy radical be selected from hydroxyl ,-OR 34With-T-OR 34
Described sulfur-containing group is selected from-SR 35,-T-SR 35,-S (O) R 36Or-T-SO 2R 37
The described seleno group that contains is selected from-SeR 38,-T-SeR 38,-Se (O) R 39Or-T-Se (O) R 39
Described group T is selected from C 1-C 30The C of alkyl, replacement 1-C 30Alkyl or safing function group;
Described C 1-C 30Alkyl is selected from C 1-C 30Alkyl, C 2-C 30Cyclic alkyl, C 2-C 30Thiazolinyl, C 2-C 30Alkynyl, C 6-C 30Aryl, C 8-C 30Condensed ring radical or C 4-C 30Heterocyclic radical;
The C of described replacement 1-C 30Alkyl is selected from halogenated C 1-C 30Alkyl, halogenated C 6-C 30Aryl, halogenated C 8-C 30Condensed ring radical or halogenated C 4-C 30Heterocyclic radical;
Described silicon-containing group is selected from-SiR 42R 43R 44,-T-SiR 45
Described germanic group is selected from-GeR 46R 47R 48,-T-GeR 49
Describedly contain tin group and be selected from-SnR 50R 51R 52,-T-SnR 53Or-T-Sn (O) R 54
Described R 34, R 35, R 36, R 37, R 38And R 42, R 43, R 44, R 45, R 45, R 46, R 47, R 48, R 49, R 50, R 51, R 52, R 53, R 54Be selected from hydrogen, C independently of one another 1-C 30The C of alkyl, halogen atom, replacement 1-C 30Alkyl or safing function group.
37. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 33-36 is characterized in that,
Described Nonmetallocene part is selected from the compound with following structure:
Figure A200710162667D00221
Figure A200710162667D00222
With
Figure A200710162667D00223
38. the preparation method according to aspect 37 described magnesium compound load type non-metallocene catalysts is characterized in that,
Described Nonmetallocene part is selected from the compound with following structure:
Figure A200710162667D00224
With
Figure A200710162667D00225
39. a magnesium compound load type non-metallocene catalyst comprises carrier and load non-metallocene catalyst thereon, it is characterized in that, it is to make according to the preparation method of aspect 1～38 each described magnesium compound load type non-metallocene catalyst.
40. alkene homopolymerization/copolymerization process, it is characterized in that, being Primary Catalysts according to aspect 39 described magnesium compound load type non-metallocene catalysts, to be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more is promotor, makes alkene homopolymerization or copolymerization.
41., it is characterized in that described promotor is selected from one or more in aikyiaiurnirsoxan beta and the aluminum alkyls according to aspect 40 described alkene homopolymerization/copolymerization process.
42., it is characterized in that described promotor is selected from methylaluminoxane and triethyl aluminum according to aspect 40 or 41 described alkene homopolymerization/copolymerization process.
43., it is characterized in that described alkene is selected from C according to each described alkene homopolymerization/copolymerization process of aspect 40-42 2～C 10Monoolefine, diolefin, cycloolefin and other ethylenically unsaturated compounds.
44., it is characterized in that described C according to aspect 43 described alkene homopolymerization/copolymerization process 2～C 10Monoolefine is selected from ethene, propylene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-hendecene, 1-laurylene, 1-cyclopentenes, norbornylene, norbornadiene and vinylbenzene, described diolefin is selected from 1,4-divinyl, 2,5-pentadiene, 1,6-hexadiene and 1, the 7-octadiene, and described other ethylenically unsaturated compounds are selected from vinyl acetate and (methyl) acrylate.
Preparation method's technology simple possible of magnesium compound load type non-metallocene catalyst of the present invention, and the charge capacity of Nonmetallocene part is adjustable, can improve its charge capacity significantly, improves the polymerization activity of this catalyzer thus significantly.In addition, by adopting different chemical processing agent consumptions or helping the chemical processing agent consumption, can obtain polymerization activity from low to high and adjustable load type non-metallocene catalyst adapts to different olefinic polymerization requirements thus.Therefore, the preparation method of magnesium compound load type non-metallocene catalyst of the present invention also has the active adjustable parameter of polymerization catalyst many, the technology flexible characteristic.
When adopting load type non-metallocene catalyst that the present invention obtained and promotor formation catalyst system to carry out the homopolymerization of alkene/copolymerization, resulting polymkeric substance has high polymer stacks density and low ash, and the variable range of its molecular weight distribution is wide.
Embodiment
At first, the present invention relates to a kind of preparation method of magnesium compound load type non-metallocene catalyst, may further comprise the steps: magnesium compound is contacted with the Nonmetallocene part, obtain the step of product of contact, with handle described product of contact with the chemical processing agent that is selected from IV B family metallic compound, obtain the step of described magnesium compound load type non-metallocene catalyst.
Described magnesium compound is the carrier of this load type non-metallocene catalyst, such as being selected from magnesium halide, alkoxyl group magnesium halide, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium, alkyl alkoxy magnesium or its any one or multiple mixture.
Particularly, magnesium halide is such as being selected from magnesium chloride (MgCl 2), magnesium bromide (MgBr 2), magnesium iodide (MgI 2) and magnesium fluoride (MgF 2) etc., wherein preferred magnesium chloride.
The alkoxyl group magnesium halide is such as being selected from methoxyl group chlorination magnesium (Mg (OCH 3) Cl), oxyethyl group magnesium chloride (Mg (OC 2H 5) Cl), propoxy-magnesium chloride (Mg (OC 3H 7) Cl), n-butoxy magnesium chloride (Mg (OC 4H 9) Cl), isobutoxy magnesium chloride (Mg (i-OC 4H 9) Cl), methoxyl group magnesium bromide (Mg (OCH 3) Br), oxyethyl group magnesium bromide (Mg (OC 2H 5) Br), propoxy-magnesium bromide (Mg (OC 3H 7) Br), n-butoxy magnesium bromide (Mg (OC 4H 9) Br), isobutoxy magnesium bromide (Mg (i-OC 4H 9) Br), methoxyl group magnesium iodide (Mg (OCH 3) I), oxyethyl group magnesium iodide (Mg (OC 2H 5) I), propoxy-magnesium iodide (Mg (OC 3H 7) I), n-butoxy magnesium iodide (Mg (OC 4H 9) I) and isobutoxy magnesium iodide (Mg (i-OC 4H 9) I) etc., wherein preferred methoxyl group chlorination magnesium, oxyethyl group magnesium chloride and isobutoxy magnesium chloride.
Alkoxyl magnesium is such as being selected from magnesium methylate (Mg (OCH 3) 2), magnesium ethylate (Mg (OC 2H 5) 2), propoxy-magnesium (Mg (OC 3H 7) 2), butoxy magnesium (Mg (OC 4H 9) 2), isobutoxy magnesium (Mg (i-OC 4H 9) 2) and 2-ethyl hexyl oxy magnesium (Mg (OCH 2CH (C 2H 5) C 4H) 2) etc., wherein preferred magnesium ethylate and isobutoxy magnesium.
Alkyl magnesium is such as being selected from methyl magnesium (Mg (CH 3) 2), magnesium ethide (Mg (C 2H 5) 2), propyl group magnesium (Mg (C 3H 7) 2), normal-butyl magnesium (Mg (C 4H 9) 2) and isobutyl-magnesium (Mg (i-C 4H 9) 2) etc., wherein preferred magnesium ethide and normal-butyl magnesium.
Alkyl halide magnesium is such as being selected from methylmagnesium-chloride (Mg (CH 3) Cl), ethylmagnesium chloride (Mg (C 2H 5) Cl), propyl group magnesium chloride (Mg (C 3H 7) Cl), normal-butyl chlorination magnesium (Mg (C 4H 9) Cl), isobutyl-chlorination magnesium (Mg (i-C 4H 9) Cl), methyl-magnesium-bromide (Mg (CH 3) Br), ethylmagnesium bromide (Mg (C 2H 5) Br), propyl group magnesium bromide (Mg (C 3H 7) Br), normal-butyl bromination magnesium (Mg (C 4H 9) Br), isobutyl-bromination magnesium (Mg (i-C 4H 9) Br), methyl magnesium iodide (Mg (CH 3) I), ethyl magnesium iodide (Mg (C 2H 5) I), propyl group magnesium iodide (Mg (C 3H 7) I), normal-butyl iodate magnesium (Mg (C 4H 9) I) and isobutyl-iodate magnesium (Mg (i-C 4H 9) I) etc., wherein preferable methyl magnesium chloride, ethylmagnesium chloride and isobutyl-chlorination magnesium.
Alkyl alkoxy magnesium is such as being selected from methyl methoxy base magnesium (Mg (OCH 3) (CH 3)), methyl ethoxy magnesium (Mg (OC 2H 5) (CH 3)), methyl propoxy-magnesium (Mg (OC 3H 7) (CH 3)), methyl n-butoxy magnesium (Mg (OC 4H 9) (CH 3)), methyl isobutoxy magnesium (Mg (i-OC 4H 9) (CH 3)), ethyl magnesium methylate (Mg (OCH 3) (C 2H 5)), ethyl magnesium ethylate (Mg (OC 2H 5) (C 2H 5)), ethyl propoxy-magnesium (Mg (OC 3H 7) (C 2H 5)), ethyl n-butoxy magnesium (Mg (OC 4H 9) (C 2H 5)), ethyl isobutoxy magnesium (Mg (i-OC 4H 9) (C 2H 5)), propyl group magnesium methylate (Mg (OCH 3) (C 3H 7)), propyl group magnesium ethylate (Mg (OC 2H 5) (C 3H 7)), propyl group propoxy-magnesium (Mg (OC 3H 7) (C 3H 7)), propyl group n-butoxy magnesium (Mg (OC 4H 9) (C 3H 7)), propyl group isobutoxy magnesium (Mg (i-OC 4H 9) (C 3H 7)), normal-butyl magnesium methylate (Mg (OCH 3) (C 4H 9)), normal-butyl magnesium ethylate (Mg (OC 2H 5) (C 4H 9)), normal-butyl propoxy-magnesium (Mg (OC 3H 7) (C 4H 9)), normal-butyl n-butoxy magnesium (Mg (OC 4H 9) (C 4H 9)), normal-butyl isobutoxy magnesium (Mg (i-OC 4H 9) (C 4H 9)), isobutyl-magnesium methylate (Mg (OCH 3) (i-C 4H 9)), isobutyl-magnesium ethylate (Mg (OC 2H 5) (i-C 4H 9)), isobutyl-propoxy-magnesium (Mg (OC 3H 7) (i-C 4H 9)), isobutyl-n-butoxy magnesium (Mg (OC 4H 9) (i-C 4H 9)) and isobutyl-isobutoxy magnesium (Mg (i-OC 4H 9) (i-C 4H 9)) etc., wherein preferred butyl magnesium ethylate.
These magnesium compounds can be used alone, and also can multiple mixing use, not special restriction.For example, arbitrarily mol ratio between the two is such as being 0.25～4, and is preferred 0.5～3, more preferably 1～2.
In one embodiment, magnesium compound of the present invention can be its modified form.This modification magnesium compound is such as making it to precipitate with solvent and obtain by adding precipitation in by described magnesium compound and solution that tetrahydrofuran (THF)-pure mixed solvent constitutes.After precipitation,, can obtain this modification magnesium compound thus by solid-liquid separating methods such as filtrations.
Particularly, magnesium compound is joined in the tetrahydrofuran (THF), add alcohol then,, dissolve fully to magnesium compound, obtain magnesium compound solution 20 ℃ of temperature range internal heating stirrings to 5 ℃ of the boiling points that is lower than tetrahydrofuran (THF)-pure mixed solvent.Add precipitation then and make it precipitation, filter at last, wash and dry thus obtained modification magnesium compound with solvent.
There is no particular limitation to the dissolution time in the modification magnesium compound preparation process.Be known that when selecting temperature low, should adopt long dissolution time, and when selecting temperature higher, can adopt short dissolution time.For example, dissolution time was generally 0.5～24 hour.In this preparation process, can utilize to stir to promote dissolving and precipitation solvent the dispersion in magnesium compound solution of magnesium compound in mixed solvent, and help the final precipitation of magnesium compound.This stirring can be adopted any form, and such as stirring rake etc., its rotating speed is generally 10～1000 rev/mins.
In the preparation method of this modification magnesium compound, described alcohol is such as being selected from Fatty Alcohol(C12-C14 and C12-C18), aromatic alcohol and the alicyclic ring alcohol one or more, and described alcohol can be chosen the group that is selected from alkyl, halogen atom and alkoxyl group wantonly and replace, preferred fat alcohol wherein. for example, Fatty Alcohol(C12-C14 and C12-C18) is such as methyl alcohol, ethanol, propyl alcohol, 2-propyl alcohol, butanols, amylalcohol, 2-methyl amyl alcohol, 2-ethylpentanol, 2-hexyl butanols, hexanol and 2-Ethylhexyl Alcohol etc., wherein preferred alcohol, butanols and 2-Ethylhexyl Alcohol; Aromatic alcohol is such as phenylcarbinol, phenylethyl alcohol and methylbenzyl alcohol etc., wherein preferred phenylethyl alcohol; Cyclic alcohol is such as hexalin, cyclopentanol and ring octanol etc., wherein preferred hexalin; The alcohol that alkyl replaces is such as methylcyclopentanol, ethyl cyclopentanol, propyl group cyclopentanol, methyl-cyclohexanol, ethyl cyclohexanol, propyl group hexalin, methyl ring octanol, ethyl ring octanol and propyl group ring octanol etc., wherein preferable methyl hexalin; The alcohol that halogen atom replaces is such as trichlorine methyl alcohol, ethapon and three Mecorals etc., wherein preferred trichlorine methyl alcohol; The alcohol that alkoxyl group replaces is such as glycol-ether, ethylene glycol-n-butyl ether and 1-butoxy-2-propyl alcohol etc., wherein preferred glycol-ether. in these alcohol, and more preferably ethanol and butanols.
These alcohol can be used alone, and also can multiple mixing use.
When the described magnesium compound solution of preparation, be generally 1:5～100 in the described magnesium compound of magnesium elements and the mol ratio of tetrahydrofuran (THF), preferred 1:10～30, and be generally 1:0.5～20 in the described magnesium compound of magnesium elements and the mol ratio of described alcohol, preferred 1:1～8.
When preparing described modification magnesium compound, it is poor solvent for described magnesium compound that described precipitation can be selected for use any with solvent, and is the solvent of good solvent for described tetrahydrofuran (THF)-pure mixed solvent, such as enumerating alkane solvents.
As described alkane solvents, can enumerate pentane, hexane, heptane, octane, nonane and decane etc., wherein preferred hexane, heptane and decane, most preferably hexane.
These precipitations can be used alone with solvent, also can multiple mixing use.
There is no particular limitation with the consumption of solvent to described precipitation, but by volume, and described precipitation is generally 1:0.5～6 with the ratio of solvent and tetrahydrofuran (THF), preferably 1:1～4.
Also there is no particular limitation with the temperature of solvent to described precipitation, but general preferred normal temperature, and this precipitation process is generally also preferably carried out after magnesium compound solution is cooled to normal temperature. in addition, do not limit for filtration, washing and the drying means of described modification magnesium compound (precipitation) are special, can be selected arbitrarily as required.
Magnesium compound of the present invention (comprising the modification magnesium compound) can directly be used for carrying out the contact procedure with the Nonmetallocene part, but one preferred embodiment in, with before the Nonmetallocene part contacts, anticipate described magnesium compound (pre-treatment step) with the chemical processing agent that helps that is selected from aikyiaiurnirsoxan beta, aluminum alkyls and its mixture.
Described aikyiaiurnirsoxan beta can be selected from the line style aikyiaiurnirsoxan beta R shown in the following general formula (I) 2-Al-(Al (R)-O) n-O-AlR 2And the ring-type aikyiaiurnirsoxan beta shown in the following general formula (II)-(Al (R)-O-) N+2
Figure A200710162667D00261
Wherein, the R group can be same to each other or different to each other, and is preferably identical, and is independently from each other C 1-C 8Alkyl, preferable methyl, ethyl and isobutyl-, most preferable; N is the integer of 1-50, preferred 10～30.
Specifically for example, this aikyiaiurnirsoxan beta is preferably selected from methylaluminoxane, ethyl aikyiaiurnirsoxan beta, isobutyl aluminium alkoxide, butyl aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide, wherein most preferable aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide.
These aikyiaiurnirsoxan beta can be used alone, and perhaps are used in combination multiple.
Described aluminum alkyls is for having the compound of following general formula (III):
Al(R) 3 (III)
Wherein the R group can be same to each other or different to each other, and is preferably identical, and is independently from each other C 1-C 8Alkyl, preferable methyl, ethyl and isobutyl-, most preferable.
Particularly, this aluminum alkyls is such as enumerating trimethyl aluminium (Al (CH 3) 3), triethyl aluminum (Al (CH 3CH 2) 3), tri-propyl aluminum (Al (C 3H 7) 3), triisobutyl aluminium (Al (i-C 4H 9) 3), three n-butylaluminum (Al (C 4H 9) 3), triisopentyl aluminium (Al (i-C 5H 11) 3), three n-pentyl aluminium (Al (C 5H 11) 3), three hexyl aluminium (Al (C 6H 13) 3), three isohexyl aluminium (Al (i-C 6H 13) 3), diethylmethyl aluminium (Al (CH 3) (CH 3CH 2) 2) and dimethyl ethyl aluminium (Al (CH 3CH 2) (CH 3) 2) etc., wherein preferred trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, most preferably triethyl aluminum and triisobutyl aluminium.
These aluminum alkylss can be used alone, and perhaps are used in combination multiple.
According to the present invention,, can only adopt aikyiaiurnirsoxan beta as the described chemical processing agent that helps, also can only adopt aluminum alkyls, also can adopt its one or more mixture separately. and there is no particular limitation to each components in proportions in this mixture, can select arbitrarily as required.
When carrying out this pre-treatment given to this invention, be generally 1:0.5～4, preferred 1:1～2 in the described magnesium compound of magnesium elements and the described mol ratio of chemical processing agent that helps in aluminium element.
As the method for carrying out described pre-treatment step, can enumerate following method.At first prepare the described solution that helps chemical processing agent, the described chemical processing agent that helps that adds specified amount then under the temperature below the boiling point of normal temperature solvent to the solution to magnesium compound, react 0.5～6 hour (in case of necessity by stirring), thereby obtaining through this pretreated described magnesium compound. the pre-treatment magnesium compound that is obtained can be by filtering and washing (1～6 time, preferred 1～3 time) mode from mixed solution, separate standby (preferably finally through super-dry), but also can separate and directly be used for carrying out contact procedure with Nonmetallocene part as described below.
Described when helping the chemical treatment agent solution in preparation, there is no particular limitation to employed solvent, as long as it can dissolve this and help chemical processing agent. particularly, can enumerate alkane or the halogenated alkane of C5～C12, C6～C12 aromatic hydrocarbons or halogenated aryl hydrocarbon etc., such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, hexanaphthene, toluene, ethylbenzene, dimethylbenzene, chloro-pentane, chloro-hexane, the chloro heptane, the chloro octane, the chloro nonane, the chloro decane, the chloro undecane, chlorinated dodecane, chlorocyclohexane, chlorotoluene, chloro ethylbenzene and xylene monochloride etc., wherein preferred pentane, hexane, decane, hexanaphthene and toluene, most preferably hexane and toluene.
Should be noted in the discussion above that can not select for use this moment can the dissolved magnesium compound solvent, such as ether solvent, further such as tetrahydrofuran (THF) etc.
These solvents can be used alone, and perhaps are used in combination multiple.
In addition, help the concentration of chemical processing agent in its solution there is no particular limitation, can suitably select as required, as long as can realize described magnesium compound given to this invention and the described molar ratio range that helps chemical processing agent to described.
As previously mentioned, magnesium compound of the present invention (hereinafter, described magnesium compound comprises magnesium compound itself and modification magnesium compound) can directly be used for carrying out the contact procedure with the Nonmetallocene part, but also can be used further to this contact procedure through after the aforesaid pre-treatment step.
According to the present invention, described Nonmetallocene part is selected from the compound with following structure:
At one more specifically in the embodiment, described Nonmetallocene part is selected from (A) with following structure and (B) compound:
Figure A200710162667D00291
With
Figure A200710162667D00292
At one more specifically in the embodiment, described Nonmetallocene part is selected from the compound with following structure A-1 to A-4 and B-1 to B-4:
Figure A200710162667D00293
In above all structural formulas,
Q is selected from 0 or 1;
D is selected from 0 or 1;
A be selected from Sauerstoffatom, sulphur atom, selenium atom,
Figure A200710162667D00302
-NR 23R 24,-N (O) R 25R 26,
Figure A200710162667D00303
-PR 28R 29,-P (O) R 30OR 31, sulfuryl, sulfoxide group or-Se (O) R 39
B is selected from nitrogen-containing group, phosphorus-containing groups or C 1-C 30Alkyl;
D is selected from Sauerstoffatom, sulphur atom, selenium atom, nitrogenous C 1-C 30Alkyl, phosphorated C 1-C 30Alkyl, sulfuryl, sulfoxide group,
Figure A200710162667D00311
-N (O) R 25R 26,
Figure A200710162667D00312
-P (O) R 32(OR 33), wherein N, O, S, Se, P are respectively ligating atom;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group or phosphorus-containing groups, and wherein N, O, S, Se, P are respectively ligating atom;
F is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group or phosphorus-containing groups, and wherein N, O, S, Se, P are respectively ligating atom;
G is selected from C 1-C 30The C of alkyl, replacement 1-C 30Alkyl or safing function group;
Y and Z are selected from nitrogen-containing group, oxy radical, sulfur-containing group independently of one another, contain seleno group or phosphorus-containing groups, such as enumerating-NR 23R 24,-N (O) R 25R 26,-PR 28R 29,-P (O) R 30R 31,-OR 34,-SR 35,-S (O) R 36,-SeR 38With-Se (O) R 39, wherein N, O, S, Se and P are respectively ligating atom;
→ represent singly-bound or two key;
-represent covalent linkage or ionic linkage;
R 1, R 2, R 3, R 4, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21, R 22, R 23, R 24, R 25, R 26, R 27, R 28, R 29, R 30, R 31, R 32, R 33, R 34, R 35, R 36, R 38And R 39Be selected from hydrogen, C independently of one another 1-C 30The C of alkyl, halogen atom, replacement 1-C 30Alkyl (wherein preferred halo alkyl, such as-CH 2Cl and-CH 2CH 2Cl) or the safing function group, above-mentioned group can be the same or different to each other, wherein adjacent group such as R 1With R 2, R 3, R 3With R 4, R 6, R 7, R 8, R 9, and R 23With R 24Or R 25With R 26Deng can be each other in key or Cheng Huan;
R 5Be selected from lone-pair electron on the nitrogen, hydrogen, C 1-C 30The C of alkyl, replacement 1-C 30Alkyl, oxy radical (comprise hydroxyl and alkoxyl group, such as-OR 34With-T-OR 34), sulfur-containing group (comprises-SR 35,-T-SR 35), nitrogen-containing group (comprises-NR 23R 24,-T-NR 23R 24), or phosphorus-containing groups (comprises-PR 28R 29,-T-PR 28R 29,-T-P (O) R 30R 31); Work as R 5For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group or phosphorus-containing groups, R 5In N, O, S, P, Se be respectively ligating atom, and can carry out coordination with IVB family atoms metal; With
According to the present invention, described halogen is selected from F, Cl, Br, I;
Described nitrogen-containing group is selected from
Figure A200710162667D00313
-NR 23R 24,-T-NR 23R 24Or-N (O) R 25R 26
Phosphorus-containing groups is selected from
Figure A200710162667D00321
-PR 28R 29,-P (O) R 30R 31Or-P (O) R 32(OR 33);
Described oxy radical is selected from hydroxyl and alkoxyl group, such as-OR 34With-T-OR 34
Described sulfur-containing group is selected from-SR 35,-T-SR 35,-S (O) R 36Or-T-SO 2R 37
The described seleno group that contains is selected from-SeR 38,-T-SeR 38,-Se (O) R 39Or-T-Se (O) R 39
Described group T is selected from C 1-C 30The C of alkyl, replacement 1-C 30Alkyl or safing function group;
Described R 37Be selected from hydrogen, C 1-C 30The C of alkyl, halogen atom, replacement 1-C 30Alkyl or safing function group.
According to the present invention, described C 1-C 30Alkyl comprises C 1-C 30Alkyl, C 2-C 30Cyclic alkyl, C 2-C 30Thiazolinyl, C 2-C 30Alkynyl, C 6-C 30Aryl, C 8-C 30Condensed ring radical or C 4-C 30Heterocyclic radical;
The C of described replacement 1-C 30Alkyl refers to the alkyl that has one or more inert substituents. and so-called inertia, the coordination process that refers to these substituting groups pair and central metal atom does not have substantial interference. as non-specified otherwise, the C of described replacement 1-C 30Alkyl generally refers to halogenated C 1-C 30Alkyl, halogenated C 6-C 30Aryl, halogenated C 8-C 30Condensed ring radical or halogenated C 4-C 30Heterocyclic radical;
The safing function group refers to other safing function base except that the alkyl of alkyl and replacement.According to the present invention, described safing function group be such as enumerating halogen, oxy radical, nitrogen-containing group, silicon-containing group, germanic group, sulfur-containing group or containing tin group, particularly, and such as enumerating ether (as-OR 34Or-T-OR 35), C 1-C 10Ester group, C 1-C 10Amine, C 1-C 10Alkoxyl group and nitro etc.
Described silicon-containing group is selected from-SiR 42R 43R 44,-T-SiR 45
Described germanic group is selected from-GeR 46R 47R 48,-T-GeR 49
Describedly contain tin group and be selected from-SnR 50R 51R 52,-T-SnR 53Or-T-Sn (O) R 54
Described R 42, R 43, R 44, R 45, R 46, R 47, R 48, R 49, R 50, R 51, R 52, R 53, R 54Be selected from hydrogen, C independently of one another 1-C 30The C of alkyl, halogen atom, replacement 1-C 30Alkyl or safing function group.
According to the present invention, described safing function group will satisfy following condition:
(1) do not disturb coordination process with IV B family atoms metal,
(2) with structural formula in group A, D, E, F, Y and Z all different and
(3) coordination ability with IV B family atoms metal is lower than described A, D, E, F, Y and Z group, and does not replace the coordination of these groups and IV B family atoms metal.
As this Nonmetallocene part, such as enumerating compound with following structure:
Figure A200710162667D00331
Figure A200710162667D00351
Figure A200710162667D00361
Wherein, described Nonmetallocene part is preferably selected from the compound with following structure:
Figure A200710162667D00362
Figure A200710162667D00371
Wherein, described Nonmetallocene part also is preferably selected from the compound with following structure:
Figure A200710162667D00372
Figure A200710162667D00373
With
Figure A200710162667D00374
Described Nonmetallocene part more preferably is selected from the compound with following structure:
With
These Nonmetallocene parts can be used alone, and perhaps are used in combination multiple.
As the method for carrying out described contact procedure, obtain product of contact with contacting of described Nonmetallocene part as long as can realize described magnesium compound (comprising magnesium compound itself, modification magnesium compound and the pretreated magnesium compound of process), not special the qualification, can enumerate following method, but be not limited to this.
The solution that at first prepares described Nonmetallocene part.If what select is that solubleness to described Nonmetallocene part is not very high solvent, the mode that then can select suitably heating is to promote its dissolving; And, then can not adopt type of heating for to the higher solvent of Nonmetallocene part solubleness.Stir if desired, then the rotating speed that should stir is at 10～500 rev/mins.
According to the present invention, the solvent load that dissolving Nonmetallocene part is used does not limit especially, can specifically select Nonmetallocene part dissolving power and the different of solubleness according to solvent, as long as can guarantee to form uniform Nonmetallocene ligand solution, and add that formed slurry system is to get final product uniformly behind the described magnesium compound.Generally speaking, the mass concentration of Nonmetallocene part is 10～250 grams per liters in this solution, preferred 50～160 grams per liters.
Adopting under the situation of convection drying after the contact reacts, the consumption of this solvent then can further reduce.
To this moment used solvent there is no particular limitation, as long as can dissolve described Nonmetallocene part, such as being selected from:
Alkane is such as pentane, hexane, heptane, octane, nonane, decane etc.;
Naphthenic hydrocarbon, such as hexanaphthene, pentamethylene, suberane, cyclodecane, cyclononane etc.;
Halogenated alkane is such as methylene dichloride, dichloro hexane, two chloroheptanes, trichloromethane, trichloroethane, three chlorobutanes, methylene bromide, ethylene dibromide, dibromo-heptane, methenyl bromide, tribromoethane, three n-butyl bromide etc.;
Halo naphthenic hydrocarbon, such as chlorocyclopentane, chlorocyclohexane, chloro suberane, chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromocyclohexane, bromo suberane, bromo cyclooctane, bromo cyclononane, bromo cyclodecane,
Aromatic hydrocarbon is such as toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene etc.; With
Halogenated aromatic is such as chlorotoluene, chloro ethylbenzene, bromo toluene, bromo ethylbenzene etc.
Wherein, preferred alkane, halogenated alkane or aromatic hydrocarbon, most preferably hexane, methylene dichloride and toluene.
Should be noted in the discussion above that can not select for use this moment can the dissolved magnesium compound solvent, such as ether solvent, further such as tetrahydrofuran (THF) etc.
These solvents can be used alone, and perhaps are used in combination multiple.
Then, under evenly stirring, described magnesium compound (comprising magnesium compound itself, modification magnesium compound and the pretreated magnesium compound of process) is being joined in this Nonmetallocene ligand solution under the temperature condition below 35 ℃, so that described Nonmetallocene part is 1:1～10 with mol ratio in the described magnesium compound of magnesium elements, reaction 0.5～24 hour is continued in preferred 1:3～7.Because the long reaction times can make the Nonmetallocene part more tight and firm with combining of magnesium compound, so preferred.
Stirring can be adopted modes such as helical-ribbon type stirring or the stirring of anchor formula, stirs for helical-ribbon type, and stirring velocity is generally 5～50 rev/mins, stirs for the anchor formula, and stirring velocity is generally 5～200 rev/mins.
After the reaction, with reaction mixture through filtering and washing, perhaps through filtration, washing and dry, perhaps without filtration and washing and convection drying obtains product of contact thus.
Described filtration and washing can adopt ordinary method to carry out, and wherein washer solvent can adopt used identical solvent when dissolving the Nonmetallocene part. and this washing is generally carried out 1～8 time, and preferred 2～6 times, most preferably 2～4 times.
Described drying can adopt well-established law to carry out, and such as the rare gas element drying, vacuumize drying, perhaps heating vacuumizes drying, and preferred rare gas element is dry or vacuumize drying.
In addition, also can use obtained in the aforementioned pre-treatment step replace described magnesium compound to carry out this contact procedure without crossing separated mixture. at this moment, owing to had solvent in this mixed solution, can omit the consumption that uses solvent or reduce solvent.
According to the present invention, the product of contact that is obtained can obtain magnesium compound load type non-metallocene catalyst of the present invention by handling with chemical processing agent.
According to the present invention, described chemical processing agent is selected from IV B family metallic compound. as described IV B family metallic compound, can enumerate IV B family metal halide, alkylate and halogenated alkyl compounds.
Particularly, described IV B family metal halide is such as enumerating titanium tetrafluoride (TiF 4), titanium tetrachloride (TiCl 4), titanium tetrabromide (TiBr 4), titanium tetra iodide (TiI 4), zirconium tetrafluoride (ZrF 4), zirconium tetrachloride (ZrCl 4), tetrabormated zirconium (ZrBr 4), zirconium tetraiodide (ZrI 4), tetrafluoride hafnium (HfF 4), hafnium tetrachloride (HfCl 4), hafnium (HfBr 4), tetraiodide hafnium (HfI 4) etc.
Described IV B family metal alkyl compound is such as enumerating tetramethyl titanium (Ti (CH3) 4), tetraethyl titanium (Ti (CH3CH 2) 4), four isobutyl group titanium (Ti (i-C4H 9) 4), tetra-n-butyl titanium (Ti (C4H 9) 4), triethyl group methyltitanium (Ti (CH3)(CH 3CH 2) 3), diethyl-dimethyl titanium (Ti (CH3) 2(CH 3CH 2) 2), trimethyl ethyl titanium (Ti (CH3) 3(CH 3CH 2)), triisobutyl methyltitanium (Ti (CH3)(i-C 4H 9) 3), diisobutyl dimethyl titanium (Ti (CH3) 2(i- C 4H 9) 2), trimethyl isobutyl group titanium (Ti (CH3) 3(i-C 4H 9)), triisobutyl ethyl titanium (Ti (CH3CH 2)(i-C 4H 9) 3), diisobutyl diethyl titanium (Ti (CH3CH 2) 2(i-C 4H 9) 2), triethyl group isobutyl group titanium (Ti (CH3CH 2) 3(i-C 4H 9)), three normal-butyl methyltitanium (Ti (CH3)(C 4H 9) 3), di-n-butyl dimethyl titanium (Ti (CH3) 2(C 4H 9) 2), trimethyl normal-butyl titanium (Ti (CH3) 3(C 4H 9)), three normal-butyl methyltitanium (Ti (CH3CH 2)(C 4H 9) 3), di-n-butyl diethyl titanium (Ti (CH3CH 2) 2(C 4H 9) 2), triethyl group normal-butyl titanium (Ti (CH3CH 2) 3(C 4H 9)), tetramethyl zirconium (Zr (CH3) 4), tetraethyl zirconium (Zr (CH3CH 2) 4), four isobutyl group zirconium (Zr (i-C4H 9) 4), tetra-n-butyl zirconium (Zr (C4H 9) 4), triethyl group methylcyclopentadienyl zirconium (Zr (CH3)(CH 3CH 2) 3), diethyl-dimethyl zirconium (Zr (CH3) 2(CH 3CH 2) 2), trimethyl ethyl zirconium (Zr (CH3) 3(CH 3CH 2)), triisobutyl methylcyclopentadienyl zirconium (Zr (CH3)(i-C 4H 9) 3), diisobutyl zirconium dimethyl (Zr (CH3) 2(i- C 4H 9) 2), trimethyl isobutyl group zirconium (Zr (CH3) 3(i-C 4H 9)), triisobutyl ethyl zirconium (Zr (CH3CH 2)(i-C 4H 9) 3), diisobutyl diethyl zirconium (Zr (CH3CH 2) 2(i-C 4H 9) 2), triethyl group isobutyl group zirconium (Zr (CH3CH 2) 3(i-C 4H 9)), three normal-butyl methylcyclopentadienyl zirconium (Zr (CH3)(C 4H 9) 3), di-n-butyl zirconium dimethyl (Zr (CH3) 2(C 4H 9) 2), trimethyl normal-butyl zirconium (Zr (CH3) 3(C 4H 9)), three normal-butyl methylcyclopentadienyl zirconium (Zr (CH3CH 2)(C 4H 9) 3), di-n-butyl diethyl zirconium (Zr (CH3CH 2) 2(C 4H 9) 2), triethyl group normal-butyl zirconium (Zr (CH3CH 2) 3(C 4H 9)), tetramethyl hafnium (Hf (CH3) 4), tetraethyl hafnium (Hf (CH3CH 2) 4), four isobutyl group hafnium (Hf (i-C4H 9) 4), tetra-n-butyl hafnium (Hf (C4H 9) 4), triethyl group methylcyclopentadienyl hafnium (Hf (CH3)(CH 3CH 2) 3), diethyl-dimethyl hafnium (Hf (CH3) 2(CH 3CH 2) 2), trimethyl ethyl hafnium (Hf (CH3) 3(CH 3CH 2)), triisobutyl methylcyclopentadienyl hafnium (Hf (CH3)(i-C 4H 9) 3), diisobutyl dimethyl hafnium (Hf (CH3) 2(i-C 4H 9) 2), trimethyl isobutyl group hafnium (Hf (CH3) 3(i-C 4H 9)), triisobutyl ethyl hafnium (Hf (CH3CH 2)(i-C 4H 9) 3), diisobutyl diethyl hafnium (Hf (CH3CH 2) 2(i-C 4H 9) 2), triethyl group isobutyl group hafnium (Hf (CH3CH 2) 3(i-C 4H 9)), three normal-butyl methylcyclopentadienyl hafnium (Hf (CH3)(C 4H 9) 3), di-n-butyl dimethyl hafnium (Hf (CH3) 2(C 4H 9) 2), trimethyl normal-butyl hafnium (Hf (CH3) 3(C 4H 9)), three normal-butyl methylcyclopentadienyl hafnium (Hf (CH3CH 2)(C 4H 9) 3), di-n-butyl diethyl hafnium (Hf (CH3CH 2) 2(C 4H 9) 2), triethyl group normal-butyl hafnium (Hf (CH3CH 2) 3(C 4H 9)) etc.
Described IVB family metal haloalkyl compound is such as enumerating trimethyl titanium chloride (TiCl (CH3) 3), triethyl group titanium chloride (TiCl (CH3CH 2) 3), triisobutyl titanium chloride (TiCl (i-C4H 9) 3), three normal-butyl chlorination titanium (TiCl (C4H 9) 3), dimethyl titanium chloride (TiCl2(CH 3) 2), diethyl titanium chloride (TiCl2(CH 3CH 2) 2), diisobutyl titanium chloride (TiCl2(i-C 4H 9) 2), three normal-butyl chlorination titanium (TiCl (C4H 9) 3), methyl titanium trichloride (Ti (CH3)Cl 3), ethyl titanium trichloride (Ti (CH3CH 2)Cl 3), isobutyl group titanium trichloride (Ti (i-C4H 9)Cl 3), normal-butyl titanium trichloride (Ti (C4H 9)Cl 3), trimethyl titanium bromide (TiBr (CH3) 3), triethyl group titanium bromide (TiBr (CH3CH 2) 3), triisobutyl titanium bromide (TiBr (i-C4H 9) 3), three normal-butyl bromination titanium (TiBr (C4H 9) 3), dimethyl dibrominated titanium (TiBr2(CH 3) 2), diethyl dibrominated titanium (TiBr2(CH 3CH 2) 2), diisobutyl dibrominated titanium (TiBr2(i-C 4H 9) 2), three normal-butyl bromination titanium (TiBr (C4H 9) 3), methyl titanium tribromide (Ti (CH3)Br 3), ethyl titanium tribromide (Ti (CH3CH 2)Br 3), isobutyl group titanium tribromide (Ti (i-C4H 9)Br 3), normal-butyl titanium tribromide (Ti (C4H 9)Br 3), trimethyl zirconium chloride (ZrCl (CH3) 3), triethyl group zirconium chloride (ZrCl (CH3CH 2) 3), triisobutyl zirconium chloride (ZrCl (i-C4H 9) 3), three normal-butyl chlorination zirconium (ZrCl (C4H 9) 3), dimethyl zirconium dichloride (ZrCl2(CH 3) 2), diethyl zirconium dichloride (ZrCl2(CH 3CH 2) 2), diisobutyl zirconium dichloride (ZrCl2(i-C 4H 9) 2), three normal-butyl chlorination zirconium (ZrCl (C4H 9) 3), methyl three zirconium chlorides (Zr (CH3)Cl 3), ethyl three zirconium chlorides (Zr (CH3CH 2)Cl 3), isobutyl group three zirconium chlorides (Zr (i-C4H 9)Cl 3), normal-butyl three zirconium chlorides (Zr (C4H 9)Cl 3), trimethyl zirconium bromide (ZrBr (CH3) 3), triethyl group zirconium bromide (ZrBr (CH3CH 2) 3), triisobutyl zirconium bromide (ZrBr (i-C4H 9) 3), three normal-butyl bromination zirconium (ZrBr (C4H 9) 3), dimethyl dibrominated zirconium (ZrBr2(CH 3) 2), diethyl dibrominated zirconium (ZrBr2(CH 3CH 2) 2), diisobutyl dibrominated zirconium (ZrBr2(i-C 4H 9) 2), three normal-butyl bromination zirconium (ZrBr (C4H 9) 3), methyl three zirconium bromides (Zr (CH3)Br 3), ethyl three zirconium bromides (Zr (CH3CH 2)Br 3), isobutyl group three zirconium bromides (Zr (i-C4H 9)Br 3), normal-butyl three zirconium bromides (Zr (C4H 9)Br 3), trimethyl hafnium chloride (HfCl (CH3) 3), triethyl group hafnium chloride (HfCl (CH3CH 2) 3), triisobutyl hafnium chloride (HfCl (i-C4H 9) 3), three normal-butyl chlorination hafnium (HfCl (C4H 9) 3), dimethyl hafnium dichloride (HfCl2(CH 3) 2), diethyl hafnium dichloride (HfCl2(CH 3CH 2) 2), diisobutyl hafnium dichloride (HfCl2(i-C 4H 9) 2), three normal-butyl chlorination hafnium (HfCl (C4H 9) 3), methyl three hafnium chlorides (Hf (CH3)Cl 3), ethyl three hafnium chlorides (Hf (CH3CH 2)Cl 3), isobutyl group three hafnium chlorides (Hf (i-C4H 9)Cl 3), normal-butyl three hafnium chlorides (Hf (C4H 9)Cl 3), trimethyl bromination hafnium (HfBr (CH3) 3), triethyl group bromination hafnium (HfBr (CH3CH 2) 3), triisobutyl bromination hafnium (HfBr (i-C4H 9) 3), three normal-butyl bromination hafnium (HfBr (C4H 9) 3), dimethyl dibrominated hafnium (HfBr2(CH 3) 2), diethyl dibrominated hafnium (HfBr2(CH 3CH 2) 2), diisobutyl dibrominated hafnium (HfBr2(i-C 4H 9) 2), three normal-butyl bromination hafnium (HfBr (C4H 9) 3), methyl three bromination hafnium (Hf (CH3)Br 3), ethyl three bromination hafnium (Hf (CH3CH 2)Br 3), isobutyl group three bromination hafnium (Hf (i-C4H 9)Br 3), normal-butyl three bromination hafnium (Hf (C4H 9)Br 3) etc.
Wherein, as described IVB family metallic compound, preferred IVB family metal halide, more preferably TiCl 4And ZrCl 4
These IV B family metallic compounds can be used alone, and perhaps are used in combination multiple.
According to the present invention, by the product of contact that is obtained in the contact procedure before handling with described IV B family metallic compound, Nonmetallocene part contained in described IV B family's metallic compound and this product of contact is reacted, thereby original position generates Nonmetallocene title complex (original position load reaction), obtains magnesium compound load type non-metallocene catalyst of the present invention thus.
To the mode of carrying out of this original position load reaction without any qualification, as long as can realize this original position load reaction.Particularly, can enumerate following method.
Under the situation that adopts solid chemical processing agent (such as zirconium tetrachloride), at first prepare the solution of described chemical processing agent, under the temperature below 35 ℃, in product of contact, add the described chemical processing agent of (the preferred dropping) specified amount then; Under the situation that adopts liquid chemical treatment agent (such as titanium tetrachloride), can be directly (but also can after being prepared into solution) the described chemical processing agent of specified amount is added (the preferred dropping) in this product of contact, reaction (in case of necessity by stirring) was carried out under the temperature below 35 ℃ 1～12 hour, preferred 2～8 hours, filter then, wash and drying, perhaps directly carry out drying, obtain product of contact thus without filtering and washing.
Described filtration, washing and drying can adopt ordinary method to carry out, and wherein washer solvent can adopt used identical solvent when dissolving solid chemical processing agent. and this washing is generally carried out 1～8 time, and preferred 2～6 times, most preferably 2～4 times.
When carrying out this reaction, be 1:0.1～1 in the described chemical processing agent of IV B family metallic element and the mol ratio of described Nonmetallocene part, preferred 1:0.3～0.9.
When the solution of the described chemical processing agent of preparation, there is no particular limitation to employed solvent, can be suitable for preparation used those when helping the chemical treatment agent solution. and these solvents can be used alone, and perhaps are used in combination multiple.
Should be noted in the discussion above that can not select for use this moment can the dissolved magnesium compound solvent, such as ether solvent, further such as tetrahydrofuran (THF) etc.
There is no particular limitation to the concentration of described chemical processing agent in its solution, can suitably select as required, as long as can realize the molar ratio range of described Nonmetallocene part given to this invention and described chemical processing agent.
It is pointed out that in this treatment step, the use of solvent is not essential. just be or, the reaction of described chemical processing agent and described product of contact can be carried out under the situation that does not have solvent to exist, but this moment, chemical processing agent was necessary for liquid state.
Those skilled in the art knows that above-described various contacts and treating processes are generally all carried out under the anhydrous and oxygen-free condition of strictness, said here anhydrous and oxygen-free condition is meant that the content of water and oxygen in the system continues less than 10ppm.And, load type non-metallocene catalyst of the present invention after the preparation usually under airtight nitrogen envelope pressure-fired preserve standby.
In one embodiment, the invention still further relates to the magnesium compound load type non-metallocene catalyst of making by the preparation method of aforementioned load type non-metallocene catalyst.
The magnesium compound load type non-metallocene catalyst that the present invention makes constitutes catalyst system jointly with promotor, can be used for the homopolymerization/copolymerization of catalyzed alkene.
By being Primary Catalysts with magnesium compound load type non-metallocene catalyst of the present invention, to be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more is promotor, homopolymerization and/or copolymerization that can catalyzed alkene.
There is no particular limitation to the homopolymerization of described alkene and/or copolymerization process, can adopt well known in the art those, such as enumerating slurry process, emulsion method, solution method, substance law and vapor phase process.
Described alkene is selected from C 2～C 10Monoolefine, diolefin, cycloolefin and other ethylenically unsaturated compounds. particularly, described C 2～C 10Monoolefine can be enumerated ethene, propylene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-hendecene, 1-laurylene, 1-cyclopentenes, norbornylene, norbornadiene and vinylbenzene, described diolefin can enumerate 1,4-divinyl, 2,5-pentadiene, 1,6-hexadiene and 1, the 7-octadiene, and described other ethylenically unsaturated compounds can be enumerated vinyl acetate and (methyl) acrylate.Need be pointed out that here that the said homopolymerization of the present invention is meant a kind of polymerization of alkene, and copolymerization is meant the polymerization between the two or more alkene.
As previously mentioned, described promotor can be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt, wherein preferred aikyiaiurnirsoxan beta and aluminum alkyls.
As aikyiaiurnirsoxan beta and aluminum alkyls, those that mentioned when conduct helps chemical processing agent before can adopting, wherein preferable methyl aikyiaiurnirsoxan beta and triethyl aluminum.
Preparation method's technology simple possible of magnesium compound load type non-metallocene catalyst of the present invention, the charge capacity of Nonmetallocene part is adjustable, can improve its charge capacity significantly, improves the polymerization activity of this catalyzer thus significantly.In addition, by adopting different chemical processing agent consumptions or helping the chemical processing agent consumption, can obtain polymerization activity from low to high and adjustable load type non-metallocene catalyst adapts to different olefinic polymerization requirements thus.Therefore, the preparation method of magnesium compound load type non-metallocene catalyst of the present invention also has the active adjustable parameter of polymerization catalyst many, the technology flexible characteristic.
When adopting load type non-metallocene catalyst that the present invention obtained and promotor formation catalyst system to carry out the homopolymerization of alkene/copolymerization, resulting polymkeric substance has high polymer stacks density and low ash, and the variable range of its molecular weight distribution is wide.
Embodiment
Below adopt embodiment that the present invention is described in further detail, but the invention is not restricted to these embodiment.
Polymer stacks density measurement reference standard GB 1636-79 carries out that (unit is g/cm 3).
The content of magnesium and titanium adopts ICP-AES to measure in the magnesium compound load type non-metallocene catalyst.
The polymerization activity of catalyzer calculates in accordance with the following methods: after polyreaction finishes, polymerisate in the reactor is filtered and drying, the quality of this polymerisate of weighing then, with this polymerisate quality divided by the ratio of the quality of used load type non-metallocene catalyst represent catalyzer polymerization activity (unit is a kg polymkeric substance/gCat).
The molecular weight distribution of polymkeric substance adopts the GPC V2000 type gel chromatography analyser of U.S. WATERS company to measure, and is solvent with adjacent trichlorobenzene, and surveying periodic temperature is 150 ℃.
Embodiment 1
Magnesium compound adopts Magnesium Chloride Anhydrous (MgCl 2), chemical processing agent adopts titanium tetrachloride (TiCl 4).
The Nonmetallocene part adopts structural formula to be
Figure A200710162667D00451
Compound.
Take by weighing a certain amount of Nonmetallocene part, add the dissolving of 25ml methylene dichloride, add the 5g Magnesium Chloride Anhydrous again, reaction is 4 hours under 30 ℃ of conditions, filter, and hexane wash 2 times, each 25ml vacuumizes drying then and obtains product of contact.
Measure the 25ml hexane solvent, join in the product of contact, under agitation condition, be added dropwise to chemical processing agent, after 4 hours, filter in reaction under 30 ℃ with 15 minutes, hexane wash 3 times, each 25ml vacuumizes drying at last and obtains load type non-metallocene catalyst.
The mole proportioning of chemical processing agent and Nonmetallocene part is 1:0.5.The mole proportioning of Nonmetallocene part and magnesium compound is 1:5.
This catalyzer is designated as CAT-1.
Embodiment 1-1
Substantially the same manner as Example 1, but following change is arranged:
Magnesium compound is changed into magnesium bromide (MgBr 2), chemical processing agent is changed into zirconium tetrachloride (ZrCl 4). the Nonmetallocene part adopts structural formula to be
Figure A200710162667D00452
Compound.
Adopt toluene solvant dissolving Nonmetallocene part, toluene wash vacuumizes drying.
The mole proportioning of chemical processing agent and Nonmetallocene part is 1:0.3.
The mole proportioning of Nonmetallocene part and magnesium compound is 1:3.
Embodiment 1-2
Substantially the same manner as Example 1, but following change is arranged:
Magnesium compound is changed into oxyethyl group magnesium chloride (MgCl (OC 2H 5)) chemical processing agent changes into tetraethyl-titanium (Ti (CH 3CH 2) 4).
The Nonmetallocene part adopts structural formula to be
Figure A200710162667D00461
Compound.
Adopt hexane solvent dissolving Nonmetallocene part, hexane wash vacuumizes drying.
The mole proportioning of chemical processing agent and Nonmetallocene part is 1:0.9.
The mole proportioning of Nonmetallocene part and magnesium compound is 1:7.
Embodiment 1-3
Substantially the same manner as Example 1, but following change is arranged:
Magnesium compound is changed into butoxy magnesium bromide (MgBr (OC 4H 9)), chemical processing agent is changed into triisobutyl titanium chloride (TiCl (i-C 4H 9) 3).
The Nonmetallocene part adopts structural formula to be
Figure A200710162667D00462
Compound.
Adopt dichloromethane solvent dissolving Nonmetallocene part, directly vacuumize drying, without the filtration washing step.
The mole proportioning of chemical processing agent and Nonmetallocene part is 1:0.7.
Embodiment 1-4
Substantially the same manner as Example 1, but following change is arranged: magnesium compound is changed into magnesium ethylate (Mg (OC 2H 5) 2), the Nonmetallocene part adopts structural formula to be
Figure A200710162667D00463
Compound, adopt chlorotoluene dissolution with solvents Nonmetallocene part.
Embodiment 1-5
Substantially the same manner as Example 1, but following change is arranged:
Magnesium compound is changed into isobutoxy magnesium (Mg (i-OC 4H 9) 2), the Nonmetallocene part adopts structural formula to be
Figure A200710162667D00471
Compound, adopt cyclohexane solvent dissolving Nonmetallocene part.
Embodiment 1-6
Substantially the same manner as Example 1, but following change is arranged:
The Nonmetallocene part adopts structural formula to be
Figure A200710162667D00472
Compound, adopt chlorocyclohexane dissolving Nonmetallocene part.
Embodiment 2
Magnesium compound is a Magnesium Chloride Anhydrous, and chemical processing agent is a titanium tetrachloride.The Nonmetallocene part adopts structural formula to be
Figure A200710162667D00473
Compound.
The 5g Magnesium Chloride Anhydrous is dissolved in tetrahydrofuran (THF) and the alcohol mixed solution, under agitation is heated to 60 ℃, form solution after 1.5 hours, add the 25ml hexane then and make the magnesium compound precipitation, filter then, 25ml hexane wash 1 time, heating under vacuum to 80 ℃ are drained and to be made the modification magnesium compound.
Take by weighing the Nonmetallocene part, add the dissolving of 25ml dichloromethane solvent, add the modification magnesium compound again, reaction is 4 hours under 30 ℃ of conditions, filter, and hexane wash 2 times, each 25ml vacuumizes drying then and obtains product of contact.
Measure the 25ml hexane and join in the product of contact, under agitation condition, be added dropwise to chemical processing agent, after 4 hours, filter in reaction under 30 ℃ with 30 minutes, hexane wash 3 times, each 25ml vacuumizes drying at last and obtains load type non-metallocene catalyst.
The mole proportioning of chemical processing agent and Nonmetallocene part is 1:0.5, and the mole proportioning of Nonmetallocene part and magnesium compound is 1:5.
This catalyzer is designated as CAT-2.
Embodiment 2-1
Substantially the same manner as Example 2, but following change is arranged:
Magnesium compound changes magnesium bromide (MgBr into 2), with the mol ratio of tetrahydrofuran (THF) be 1:20.
Ethanol changes propyl alcohol into, and the mol ratio of magnesium compound and propyl alcohol is 1:3.
Chemical processing agent is changed into zirconium tetrachloride (ZrCl 4). the Nonmetallocene part adopts structural formula to be
Figure A200710162667D00481
Compound.
Adopt toluene solvant dissolving Nonmetallocene part, toluene wash vacuumizes drying.
The mole proportioning of chemical processing agent and Nonmetallocene part is 1:0.3.
The mole proportioning of Nonmetallocene part and magnesium compound is 1:3.
Embodiment 2-2
Substantially the same manner as Example 2, but following change is arranged:
Magnesium compound changes oxyethyl group magnesium chloride (MgCl (OC into 2H 5)), with the mol ratio of tetrahydrofuran (THF) be 1:20.
Ethanol changes butanols into, and the mol ratio of magnesium compound and butanols is 1:6.
The Nonmetallocene part adopts structural formula to be
Figure A200710162667D00491
Compound.
Adopt hexane solvent dissolving Nonmetallocene part, hexane wash vacuumizes drying.
The mole proportioning of chemical processing agent and Nonmetallocene part is 1:0.9.
The mole proportioning of Nonmetallocene part and magnesium compound is 1:7.
Embodiment 2-3
Substantially the same manner as Example 2, but following change is arranged:
Magnesium compound changes butoxy magnesium bromide (MgBr (OC into 4H 9)), ethanol changes hexanol into.
The mol ratio of magnesium compound and tetrahydrofuran (THF) is 1:14, with the mol ratio of hexanol be 1:15,
The Nonmetallocene part adopts structural formula to be
Figure A200710162667D00492
Compound.
Adopt dichloromethane solvent dissolving Nonmetallocene part, directly vacuumize drying, without the filtration washing step.
The mole proportioning of triisobutyl titanium chloride and Nonmetallocene part is 1:0.7.
Embodiment 2-4
Substantially the same manner as Example 2, but following change is arranged:
Magnesium compound changes magnesium ethylate (Mg (OC into 2H 5) 2), the mol ratio of magnesium ethylate and tetrahydrofuran (THF) is 1:10.
Ethanol changes enanthol into, and the mol ratio of butoxy magnesium chloride and enanthol is 1:6.3,
The Nonmetallocene part adopts structural formula to be
Figure A200710162667D00501
Compound, adopt chlorotoluene dissolution with solvents Nonmetallocene part.
Embodiment 2-5
Substantially the same manner as Example 2, but following change is arranged:
Magnesium compound changes isobutoxy magnesium (Mg (i-OC into 4H 9) 2), the mol ratio of isobutoxy magnesium and tetrahydrofuran (THF) is 1:25.
Ethanol changes hexalin into.
The Nonmetallocene part adopts structural formula to be
Figure A200710162667D00502
Compound, adopt cyclohexane solvent dissolving Nonmetallocene part.
Embodiment 2-6
Substantially the same manner as Example 2, but following change is arranged:
The Nonmetallocene part adopts structural formula to be
Figure A200710162667D00503
Compound, adopt chlorocyclohexane dissolution with solvents Nonmetallocene part.
Embodiment 3
Magnesium compound adopts Magnesium Chloride Anhydrous (MgCl 2), chemical processing agent adopts titanium tetrachloride (TiCl 4).
The Nonmetallocene part adopts structural formula to be Compound.
Take by weighing the 5g Magnesium Chloride Anhydrous, add 25ml toluene, agitation condition was added dropwise to methylaluminoxane with 15 minutes down, 2 hours after-filtration of 90 ℃ of reactions, and toluene wash 2 times, each 25ml vacuumizes drying then and obtains through pretreated magnesium compound under 90 ℃ of conditions.Wherein the mole proportioning of magnesium compound and methylaluminoxane is 1:1.
Take by weighing the Nonmetallocene part, add the dissolving of 25ml methylene dichloride, add 5g again through pretreated magnesium compound, reaction is 4 hours under 30 ℃ of conditions, filter, and hexane wash 2 times, each 25ml vacuumizes drying then and obtains product of contact.
Measure the 25ml hexane solvent, join in the product of contact, under agitation condition, be added dropwise to chemical processing agent, after stirring 4 hours under 30 ℃, filter with 30 minutes, hexane wash 3 times, each 25ml vacuumizes drying at last and obtains load type non-metallocene catalyst.
The mole proportioning of chemical processing agent and Nonmetallocene part is 1:0.5.
The mole proportioning of Nonmetallocene part and magnesium compound is 1:5.
This catalyzer is designated as CAT-3.
Embodiment 3-1
Substantially the same manner as Example 3, but following change is arranged:
Magnesium compound is changed into magnesium bromide (MgBr 2), chemical processing agent is changed into zirconium tetrachloride (ZrCl 4).The Nonmetallocene part adopts structural formula to be
Figure A200710162667D00512
Compound.
Take by weighing magnesium compound, add the stupid solvent of second, agitation condition is down with being added dropwise to isobutyl aluminium alkoxide in 15 minutes, 2 hours after-filtration of 100 ℃ of reactions, the ethyl benzene solvent washing vacuumizes drying then and obtains through pretreated magnesium compound under 100 ℃ of conditions. and wherein the mole proportioning of magnesium compound and isobutyl aluminium alkoxide is 1:3.
Adopt toluene solvant dissolving Nonmetallocene part, toluene wash vacuumizes drying.
The mole proportioning of chemical processing agent and Nonmetallocene part is 1:0.3.
The mole proportioning of Nonmetallocene part and magnesium compound is 1:3.
Embodiment 3-2
Substantially the same manner as Example 3, but following change is arranged:
Magnesium compound is changed into oxyethyl group magnesium chloride (MgCl (OC 2H 5)) chemical processing agent changes into tetraethyl-titanium (Ti (CH 3CH 2) 4).
The Nonmetallocene part adopts structural formula to be
Figure A200710162667D00521
Compound.
Take by weighing magnesium compound, add hexane solvent, agitation condition was added dropwise to triethyl aluminum with 15 minutes down, 4 hours after-filtration of 60 ℃ of reactions, and hexane wash vacuumizes drying then and obtains through pretreated magnesium compound under 90 ℃ of conditions.Wherein the mole proportioning of magnesium compound and triethyl aluminum is 1:2.
Adopt hexane solvent dissolving Nonmetallocene part, hexane wash vacuumizes drying.
The mole proportioning of chemical processing agent and Nonmetallocene part is 1:0.9.
The mole proportioning of Nonmetallocene part and magnesium compound is 1:7.
Embodiment 3-3
Substantially the same manner as Example 3, but following change is arranged:
Magnesium compound is changed into butoxy magnesium bromide (MgBr (OC 4H 9)), chemical processing agent is changed into triisobutyl titanium chloride (TiCl (i-C 4H 9) 3).
The Nonmetallocene part adopts structural formula to be Compound.
Take by weighing magnesium compound, add dichloromethane solvent, agitation condition was added dropwise to triisobutyl aluminium with 15 minutes down, and 8 hours after-filtration of 30 ℃ of reactions directly vacuumize drying and obtain through pretreated magnesium compound under 30 ℃ of conditions. and wherein the mole proportioning of magnesium compound and triisobutyl aluminium is 1:4.
Adopt dichloromethane solvent dissolving Nonmetallocene part, directly vacuumize drying, without the filtration washing step.
The mole proportioning of chemical processing agent and Nonmetallocene part is 1:0.7.
Embodiment 3-4
Substantially the same manner as Example 3, but following change is arranged:
Magnesium compound is changed into magnesium ethylate (Mg (OC 2H 5) 2), the Nonmetallocene part adopts structural formula to be Compound.
Take by weighing magnesium compound, add the chlorotoluene solvent, agitation condition was added dropwise to methylaluminoxane and triethyl aluminum with 15 minutes down, 0.5 hour after-filtration of 80 ℃ of reactions, and the chlorotoluene washing vacuumizes drying under 80 ℃ and obtains the pretreated magnesium compound of process.Wherein methylaluminoxane and triethyl aluminum mol ratio are 1:1, and the mole proportioning of magnesium compound and methylaluminoxane is 1:0.5.
Adopt chlorotoluene dissolution with solvents Nonmetallocene part.
Embodiment 3-5
Substantially the same manner as Example 3, but following change is arranged:
Magnesium compound is changed into isobutoxy magnesium (Mg (i-OC 4H 9) 2), the Nonmetallocene part adopts structural formula to be
Figure A200710162667D00541
Compound.
Change into hexanaphthene through pretreated magnesium compound and dissolving Nonmetallocene part with solvent.
Embodiment 3-6
Substantially the same manner as Example 3, but following change is arranged:
The Nonmetallocene part adopts structural formula to be Compound.
Change into chlorocyclohexane through pretreated magnesium compound and dissolving Nonmetallocene part with solvent.
Embodiment 4
Magnesium compound is a Magnesium Chloride Anhydrous, and chemical processing agent is a titanium tetrachloride. the Nonmetallocene part adopts structural formula to be Compound.
The 5g Magnesium Chloride Anhydrous is dissolved in tetrahydrofuran (THF) and the alcohol mixed solution, under agitation is heated to 60 ℃, react and form solution after 1.5 hours, add the 25ml hexane then and make the magnesium compound precipitation, filter then, 25ml hexane wash 1 time, heating under vacuum to 80 ℃ are drained and to be made the modification magnesium compound.
Take by weighing 5g modification magnesium compound, add 25ml toluene, agitation condition was added dropwise to methylaluminoxane with 15 minutes down, 2 hours after-filtration of 90 ℃ of reactions, and toluene wash 2 times, each 25ml vacuumizes drying then and obtains through pretreated magnesium compound under 90 ℃ of conditions.
The mole proportioning of magnesium compound and methylaluminoxane is 1:1.
Take by weighing the Nonmetallocene part, add the dissolving of 25ml dichloromethane solvent, add through pretreated magnesium compound again, reaction is 4 hours under 30 ℃ of conditions, filter, and hexane wash 2 times, each 25ml vacuumizes drying then and obtains product of contact.
Measure the 25ml hexane and join in the product of contact, under agitation condition, be added dropwise to chemical processing agent, after stirring 4 hours under 30 ℃, filter with 30 minutes, hexane wash 3 times, each 25ml vacuumizes drying at last and obtains load type non-metallocene catalyst.
The mole proportioning of chemical processing agent and Nonmetallocene part is 1:0.5.
The mole proportioning of Nonmetallocene part and magnesium compound is 1:5.
This catalyzer is designated as CAT-4.
Embodiment 4-1
Substantially the same manner as Example 4, but following change is arranged:
Magnesium compound changes magnesium bromide (MgBr into 2), with the mol ratio of tetrahydrofuran (THF) be 1:20.
Ethanol changes propyl alcohol into, and the mol ratio of magnesium bromide and propyl alcohol is 1:3.
Chemical processing agent is changed into zirconium tetrachloride (ZrCl 4). the Nonmetallocene part adopts structural formula to be
Figure A200710162667D00551
Compound.
Take by weighing the modification magnesium compound, add ethyl benzene solvent, agitation condition was added dropwise to isobutyl aluminium alkoxide with 15 minutes down, 2 hours after-filtration of 100 ℃ of reactions, and the ethylbenzene washing vacuumizes drying then and obtains through pretreated magnesium compound under 100 ℃ of conditions.Wherein the mole proportioning of magnesium compound and isobutyl aluminium alkoxide is 1:3.
Adopt toluene solvant dissolving Nonmetallocene part, toluene wash vacuumizes drying.
The mole proportioning of chemical processing agent and Nonmetallocene part is 1:0.3.
The mole proportioning of Nonmetallocene part and magnesium compound is 1:3.
Embodiment 4-2
Substantially the same manner as Example 4, but following change is arranged:
Magnesium compound changes oxyethyl group magnesium chloride (MgCl (OC into 2H 5)), with the mol ratio of tetrahydrofuran (THF) be 1:20.
Ethanol changes butanols into, and the mol ratio of oxyethyl group magnesium chloride and butanols is 1:6.
The Nonmetallocene part adopts structural formula to be
Figure A200710162667D00561
Compound.
Take by weighing the modification magnesium compound, add hexane solvent, agitation condition was added dropwise to triethyl aluminum with 15 minutes down, 4 hours after-filtration of 60 ℃ of reactions, and hexane wash vacuumizes drying then and obtains through pretreated magnesium compound under 90 ℃ of conditions.Wherein the mole proportioning of magnesium compound and triethyl aluminum is 1:2.
Adopt hexane solvent dissolving Nonmetallocene part, hexane wash vacuumizes drying.
The mole proportioning of tetraethyl-titanium and Nonmetallocene part is 1:0.9.
The mole proportioning of magnesium is 1:7. in Nonmetallocene part and the oxyethyl group magnesium chloride
Embodiment 4-3
Substantially the same manner as Example 4, but following change is arranged:
Magnesium compound changes butoxy magnesium bromide (MgBr (OC into 4H 9)), ethanol changes hexanol into.
The mol ratio of butoxy magnesium bromide and tetrahydrofuran (THF) is 1:14, with the mol ratio of hexanol be 1:15,
The Nonmetallocene part adopts structural formula to be
Figure A200710162667D00562
Compound.
Take by weighing the modification magnesium compound, add dichloromethane solvent, agitation condition was added dropwise to triisobutyl aluminium with 15 minutes down, and 8 hours after-filtration of 30 ℃ of reactions directly vacuumize drying and obtain through pretreated magnesium compound under 30 ℃ of conditions. and wherein the mole proportioning of magnesium compound and triisobutyl aluminium is 1:4.
Adopt dichloromethane solvent dissolving Nonmetallocene part, directly vacuumize drying, without the filtration washing step.
The mole proportioning of chemical processing agent and Nonmetallocene part is 1:0.7.
Embodiment 4-4
Substantially the same manner as Example 4, but following change is arranged:
Magnesium compound changes magnesium ethylate (Mg (OC into 2H 5) 2), the mol ratio of magnesium ethylate and tetrahydrofuran (THF) is 1:10.
Ethanol changes enanthol into, and the mol ratio of butoxy magnesium chloride and enanthol is 1:6.3,
Take by weighing the modification magnesium compound, add the chlorotoluene solvent, agitation condition was added dropwise to methylaluminoxane and triethyl aluminum with 15 minutes down, 0.5 hour after-filtration of 80 ℃ of reactions, and the chlorotoluene washing vacuumizes drying under 80 ℃ and obtains the pretreated magnesium compound of process.Wherein methylaluminoxane and triethyl aluminum mol ratio are 1:1, and the mole proportioning of magnesium compound and methylaluminoxane is 1:0.5.
The Nonmetallocene part adopts structural formula to be
Figure A200710162667D00571
Compound, adopt chlorotoluene dissolution with solvents Nonmetallocene part.
Embodiment 4-5
Substantially the same manner as Example 4, but following change is arranged:
Magnesium compound changes isobutoxy magnesium (Mg (i-OC into 4H 9) 2), the mol ratio of isobutoxy magnesium and tetrahydrofuran (THF) is 1:25.
Ethanol changes hexalin into.
The Nonmetallocene part adopts structural formula to be
Figure A200710162667D00572
Compound.
Change into hexanaphthene through pretreated magnesium compound and dissolving Nonmetallocene part with solvent.
Embodiment 4-6
Substantially the same manner as Example 4, but following change is arranged:
The Nonmetallocene part adopts structural formula to be
Figure A200710162667D00581
Compound.
Change into chlorocyclohexane through pretreated magnesium compound and dissolving Nonmetallocene part with solvent.
Embodiment 5 (Application Example)
Take by weighing 50mg load type non-metallocene catalyst CAT-1～4 respectively, joining 5 risings jointly with promotor presses in the reactor, add the 1L hexane again, open and stir, rotating speed is 250 rev/mins, be warmed up to 85 ℃ after, feed ethene continuously, control reactor total pressure is 0.8MPa, emptying behind the reaction 2h.Weighing after the taking-up polymkeric substance drying.The concrete outcome data are listed in the table 1.
Embodiment 5-1
Substantially the same manner as Example 5, but following change is arranged:
Before continuously logical ethene in reactor, add the hydrogen of 0.2MPa in advance.
The concrete outcome data are listed in the table 1.
Embodiment 5-2
Substantially the same manner as Example 5, but following change is arranged:
Before in reactor, feeding ethene continuously, add the hydrogen of 0.2MPa in advance, feed ethene continuously after 2 minutes, by the disposable adding 50g1-of comonomer volume pump hexene monomer.
The concrete outcome data are listed in the table 1.
Reference example 1-1
Substantially the same manner as Example 4, but following change is arranged:
The mole proportioning of chemical processing agent and Nonmetallocene part is changed into 1:0.25.
Catalyzer is designated as CAT-A.
Polymerization process is carried out according to embodiment 5-2.
The concrete outcome data are listed in the table 1.
Reference example 1-2
Substantially the same manner as Example 4, but following change is arranged:
The mole proportioning of chemical processing agent and Nonmetallocene part is changed into 1:0.75.
Catalyzer is designated as CAT-B.
Polymerization process is carried out according to embodiment 5-2.
The concrete outcome data are listed in the table 1.
By the obtained effect comparison of sequence number in the table 1 13,16 and 17 as can be known, improve or reduce the mole proportioning of chemical processing agent and Nonmetallocene part, can improve or reduce the catalyzed ethylene polymerization activity of catalyzer, and molecular weight distribution is also widened to some extent or is narrowed down.
This shows, adopt the preparation method of magnesium compound load type non-metallocene catalyst provided by the present invention, can be by changing the consumption of chemical processing agent consumption or Nonmetallocene part, to the polymerization activity of prepared load type non-metallocene catalyst, and the molecular weight distribution that polymerization obtains is regulated flexibly.
Reference example 1-3
Substantially the same manner as Example 4, but following change is arranged:
Wherein the mole proportioning of magnesium compound and methylaluminoxane is changed into and is 1:2.
Catalyzer is designated as CAT-C.
Polymerization process is carried out according to embodiment 5-2.
The concrete outcome data are listed in the table 1.
Reference example 1-4
Substantially the same manner as Example 4, but following change is arranged:
Wherein the mole proportioning of magnesium compound and methylaluminoxane is changed into and is 1:0.5.
Catalyzer is designated as CAT-D.
Polymerization process is carried out according to embodiment 5-2.
The concrete outcome data are listed in the table 1.
By the obtained effect comparison of sequence number in the table 1 13,18 and 19 as can be known,, can improve or reduce the catalyzed ethylene polymerization activity of catalyzer, and molecular weight distribution narrows down to some extent also or widens by improving or reduce the mole proportioning of magnesium compound and aikyiaiurnirsoxan beta.
This shows, adopt the preparation method of magnesium compound load type non-metallocene catalyst provided by the present invention, can help the consumption of chemical processing agent by change, to the olefin polymerizating activity of prepared load type non-metallocene catalyst, and the molecular weight distribution that polymerization obtains is regulated flexibly.
Figure A200710162667D00611

Claims (39)

1. the preparation method of a magnesium compound load type non-metallocene catalyst may further comprise the steps:
Magnesium compound is contacted with the Nonmetallocene part, obtain product of contact step and
Handle described product of contact with the chemical processing agent that is selected from IVB family metallic compound, obtain the step of described magnesium compound load type non-metallocene catalyst.
2. according to the preparation method of the described magnesium compound load type non-metallocene catalyst of claim 1, also be included in before described Nonmetallocene part contacts, handle the step of described magnesium compound with the chemical processing agent that helps that is selected from aikyiaiurnirsoxan beta, aluminum alkyls and its mixture.
3. according to the preparation method of claim 1 or 2 described magnesium compound load type non-metallocene catalysts, it is characterized in that described magnesium compound is through modification.
4. according to the preparation method of the described magnesium compound load type non-metallocene catalyst of claim 3, it is characterized in that described modification magnesium compound is to make it to precipitate with solvent and obtain by add precipitation in by described magnesium compound and solution that tetrahydrofuran (THF)-pure mixed solvent constitutes.
5. according to the preparation method of the described magnesium compound load type non-metallocene catalyst of claim 1, it is characterized in that, also comprise through filtering and washing, perhaps without filtration and washing, and the step of the load type non-metallocene catalyst that convection drying obtained.
6. according to the preparation method of the described magnesium compound load type non-metallocene catalyst of claim 1, it is characterized in that, also be included in handle with described chemical processing agent before, described product of contact is carried out the exsiccant step.
7. according to the preparation method of the described magnesium compound load type non-metallocene catalyst of claim 1, it is characterized in that described contact procedure is carried out in the presence of the solvent of the described Nonmetallocene part of solubilized.
8. according to the preparation method of the described magnesium compound load type non-metallocene catalyst of claim 7, it is characterized in that the solvent of the described Nonmetallocene part of described solubilized is selected from one or more in alkane, naphthenic hydrocarbon, halogenated alkane, halo naphthenic hydrocarbon, aromatic hydrocarbon and the halogenated aromatic.
9. according to the preparation method of the described magnesium compound load type non-metallocene catalyst of claim 8, it is characterized in that the solvent of the described Nonmetallocene part of described solubilized is selected from one or more in alkane, halogenated alkane and the aromatic hydrocarbon.
10. according to the preparation method of the described magnesium compound load type non-metallocene catalyst of claim 9, it is characterized in that the solvent of the described Nonmetallocene part of described solubilized is selected from one or more in hexane, methylene dichloride and the toluene.
11. preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 1, it is characterized in that described magnesium compound is selected from one or more in magnesium halide, alkoxyl group magnesium halide, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and the alkyl alkoxy magnesium.
12. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 11 is characterized in that, described magnesium compound is selected from magnesium halide.
13. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 1 is characterized in that, described IVB family metallic compound is selected from one or more in halogenide, alkylate and the halogenated alkyl compounds of IVB family metal.
14. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 13 is characterized in that, described IVB family metallic compound is selected from IVB family metal halide.
15. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 14 is characterized in that, described IVB family metal halide is selected from titanium tetrachloride and zirconium tetrachloride.
16. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 1 is characterized in that, is 1:0.1～1. in the mol ratio of the described chemical processing agent of IVB family metallic element and described Nonmetallocene part
17. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 16 is characterized in that, is 1:0.3～0.9. in the described chemical processing agent of IVB family metallic element and the mol ratio of described Nonmetallocene part
18. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 1 is characterized in that, described Nonmetallocene part and mol ratio in the described magnesium compound of magnesium elements are 1:1～10.
19. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 18 is characterized in that, described Nonmetallocene part is 1:3～7 with mol ratio in the described magnesium compound of magnesium elements.
20. preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 4, it is characterized in that, described alcohol is selected from one or more in Fatty Alcohol(C12-C14 and C12-C18), aromatic alcohol and the alicyclic ring alcohol, and the optional group that is selected from alkyl, halogen atom and alkoxyl group of wherein said alcohol replaces.
21. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 20 is characterized in that, described alcohol is selected from Fatty Alcohol(C12-C14 and C12-C18).
22. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 21 is characterized in that, described Fatty Alcohol(C12-C14 and C12-C18) is selected from ethanol, butanols and isooctyl alcohol.
23. preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 4, it is characterized in that, in the described magnesium compound of magnesium elements and the mol ratio of tetrahydrofuran (THF) is 1:5～100, is 1:0.5～20 in the described magnesium compound of magnesium elements and the mol ratio of described alcohol.
24. preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 23, it is characterized in that, in the described magnesium compound of magnesium elements and the mol ratio of tetrahydrofuran (THF) is 1:10～30, is 1:1～8 in the described magnesium compound of magnesium elements and the mol ratio of described alcohol.
25. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 4 is characterized in that, by volume, described precipitation is 1:0.5～6 with the ratio of solvent and tetrahydrofuran (THF).
26. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 25 is characterized in that, by volume, described precipitation is 1:1～4. with the ratio of solvent and tetrahydrofuran (THF)
27. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 4 is characterized in that, described precipitation is selected from alkane, naphthenic hydrocarbon, halogenated alkane and the halo naphthenic hydrocarbon one or more with solvent.
28. the preparation method according to the described negative magnesium compound load type non-metallocene catalyst of claim 27 is characterized in that, described precipitation is selected from alkane and the naphthenic hydrocarbon one or more with solvent.
29. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 28 is characterized in that, described precipitation is selected from hexane and hexanaphthene with solvent.
30. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 2 is characterized in that, the described chemical processing agent that helps is selected from methylaluminoxane, isobutyl aluminium alkoxide, triethyl aluminum and the triisobutyl aluminium one or more.
31. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 2 is characterized in that, is 1:0.5～4. in the described magnesium compound of magnesium elements and the mol ratio that helps chemical processing agent in aluminium element described
32. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 31 is characterized in that, is 1:1～2 in the described magnesium compound of magnesium elements with helping the mol ratio of chemical processing agent in aluminium element described.
33. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 1 is characterized in that, described Nonmetallocene part is selected from the compound with following structure:
Figure A200710162667C00051
Wherein:
Q is selected from 0 or 1;
D is selected from 0 or 1;
A be selected from Sauerstoffatom, sulphur atom, selenium atom,
Figure A200710162667C00052
-NR 23R 24,-N (O) R 25R 26,
Figure A200710162667C00053
-PR 28R 29,-P (O) R 30OR 31, sulfuryl, sulfoxide group or-Se (O) R 39
B is selected from nitrogen-containing group, phosphorus-containing groups or C 1-C 30Alkyl;
D is selected from Sauerstoffatom, sulphur atom, selenium atom, nitrogenous C 1-C 30Alkyl, phosphorated C 1-C 30Alkyl, sulfuryl, sulfoxide group,
Figure A200710162667C00054
,-N (O) R 25R 26,
Figure A200710162667C00055
Or-P (O) R 32(OR 33), wherein N, O, S, Se, P are respectively ligating atom;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group or phosphorus-containing groups, and wherein N, O, S, Se, P are respectively ligating atom;
G is selected from C 1-C 30The C of alkyl, replacement 1-C 30Alkyl or safing function group;
→ represent singly-bound or two key;
-represent covalent linkage or ionic linkage;
R 1, R 2, R 3, R 22, R 23, R 24, R 25, R 26, R 27, R 28, R 29, R 30, R 31, R 32, R 33And R 39Be selected from hydrogen, C independently of one another 1-C 30The C of alkyl, halogen atom, replacement 1-C 30Alkyl or safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can be each other in key or Cheng Huan.
34. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 33 is characterized in that,
Described Nonmetallocene part is selected from (A) with following structure and (B) compound:
With
Figure A200710162667C00062
Wherein F is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group or phosphorus-containing groups, and wherein N, O, S, Se, P are respectively ligating atom;
Other are according to the described definition of claim 33.
35. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 34 is characterized in that,
Described Nonmetallocene part is selected from the compound with following structure A-1 to A-4 and B-1 to B-4:
Figure A200710162667C00063
Figure A200710162667C00071
Figure A200710162667C00081
Wherein:
Y and Z are selected from nitrogen-containing group, oxy radical, sulfur-containing group independently of one another, contain seleno group or phosphorus-containing groups, and wherein N, O, S, Se and P are respectively ligating atom;
R 4, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20And R 21Be selected from hydrogen, C independently of one another 1-C 30The C of alkyl, halogen atom, replacement 1-C 30Alkyl or safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can be each other in key or Cheng Huan;
R 5Be selected from lone-pair electron on the nitrogen, hydrogen, C 1-C 30The C of alkyl, replacement 1-C 30Alkyl, oxy radical, sulfur-containing group, nitrogen-containing group or phosphorus-containing groups, prerequisite are to work as R 5For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group or phosphorus-containing groups, R 5In N, O, S, P, Se be respectively ligating atom;
Other are according to the described definition of claim 34.
36. the preparation method according to each described magnesium compound load type non-metallocene catalyst of claim 33-35 is characterized in that,
Described halogen is selected from F, Cl, Br, I;
Described safing function group is selected from halogen, oxy radical, nitrogen-containing group, silicon-containing group, germanic group, sulfur-containing group or contains tin group;
Described nitrogen-containing group is selected from
Figure A200710162667C00082
,-NR 23R 24,-T-NR 23R 24Or-N (o) R 25R 26
Described phosphorus-containing groups is selected from
Figure A200710162667C00083
,-PR 28R 29,-P (O) R 300R 31,-P (O) R 32(OR 33) ,-T-PR 28(OR 29) ,-T-P (O) R 30R 31Or-T-P (O) R 32(OR 33);
Described oxy radical be selected from hydroxyl ,-OR 34With-T-OR 34
Described sulfur-containing group is selected from-SR 35,-T-SR 35,-S (O) R 36Or-T-SO 2R 37
The described seleno group that contains is selected from-SeR 38,-T-SeR 38,-T-Se (O) R 39Or-Se (O) R 39
Described group T is selected from C 1-C 30The C of alkyl, replacement 1-C 30Alkyl or safing function group;
Described C 1-C 30Alkyl is selected from C 1-C 30Alkyl, C 2-C 30Cyclic alkyl, C 2-C 30Thiazolinyl, C 2-C 30Alkynyl, C 6-C 30Aryl, C 8-C 30Condensed ring radical or C 4-C 30Heterocyclic radical;
The C1-C of described replacement 30 alkyl is selected from halogenated C 1-C 30Alkyl, halogenated C 6-C 30Aryl, halogenated C 8-C 30Condensed ring radical or halogenated C 4-C 30Heterocyclic radical;
Described silicon-containing group is selected from-SiR 42R 43R 44,-T-SiR 45
Described germanic group is selected from-GeR 46R 47R 48,-T-GeR 49
Describedly contain tin group and be selected from-SnR 50R 51R 52,-T-SnR 53Or-T-Sn (O) R 54
Described R 34, R 35, R 36, R 37, R 38And R 42, R 43, R 44, R 45, R 46, R 47, R 48, R 49, R 50, R 51, R 52, R 53, R 54Be selected from hydrogen, C independently of one another 1-C 30The C of alkyl, halogen atom, replacement 1-C 30Alkyl or safing function group.
37. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 33 is characterized in that,
Described Nonmetallocene part is selected from the compound with following structure:
Figure A200710162667C00091
Figure A200710162667C00092
With
Figure A200710162667C00093
38. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 37 is characterized in that,
Described Nonmetallocene part is selected from the compound with following structure:
Figure A200710162667C00101
With
Figure A200710162667C00102
39. magnesium compound load type non-metallocene catalyst, comprise carrier and load non-metallocene catalyst thereon, it is characterized in that it is to make according to the preparation method of each described magnesium compound load type non-metallocene catalyst of claim 1～38.
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