CN101412768A - Magnesium compound load type non-metallocene catalyst and preparation thereof - Google Patents
Magnesium compound load type non-metallocene catalyst and preparation thereof Download PDFInfo
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- CN101412768A CN101412768A CN 200710162676 CN200710162676A CN101412768A CN 101412768 A CN101412768 A CN 101412768A CN 200710162676 CN200710162676 CN 200710162676 CN 200710162676 A CN200710162676 A CN 200710162676A CN 101412768 A CN101412768 A CN 101412768A
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- 0 CC(C)(C)c(cc1C(C)(C)C)cc(C=*c2c(C=O)cccc2)c1O Chemical compound CC(C)(C)c(cc1C(C)(C)C)cc(C=*c2c(C=O)cccc2)c1O 0.000 description 6
- XBBZJJMAIFDBBA-UHFFFAOYSA-N CC(C)(C)c(cc1CNc2ccccc2Sc2ccccc2)cc(C(C)(C)C)c1OC Chemical compound CC(C)(C)c(cc1CNc2ccccc2Sc2ccccc2)cc(C(C)(C)C)c1OC XBBZJJMAIFDBBA-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a magnesium compound supported non-metallocene catalyst, which is obtained by directly contacting a non-metallocene ligand and a magnesium compound containing transition metal through an in-situ supporting method. The preparation method for the magnesium compound supported non-metallocene catalyst has simple and feasible process, and the supporting capacity and the polymerization activity of the catalyst have wide adjustable range. When the magnesium compound supported non-metallocene catalyst is combined with a catalyst promoter to catalyze the homopolymerization/copolymerization of olefins, high polymerization activities of the olefins can be obtained only by using small amount of the catalyst promoter.
Description
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 Nonmetallocene part directly to be contacted with the magnesium compound that contains catalytically-active metals to obtain.By with the combination of promotors such as magnesium compound load type non-metallocene catalyst of the present invention and aikyiaiurnirsoxan beta or aluminum alkyls, can be used for the homopolymerization or the 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 the Ziegler that continues, after Ziegler-Natta and the metallocene catalyst the 4th generation olefin polymerization catalysis, such catalyzer has reached on some performance or even has surpassed metallocene catalyst. and non-metallocene catalyst does not contain cyclopentadienyl group, ligating atom is an 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 of formation 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, 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 IVB group 4 transition metal halogenide, direct again and part negative ion reacts, thereby in a step, realize the synthetic and load of metallocene catalyst. but this method requires the mol ratio of transition metal and part is 1:1, and need to add the proton donor, 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
2A1C1 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 the Nonmetallocene part directly to be contacted with the magnesium compound that contains transition metal 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, it may further comprise the steps: magnesium compound is contacted with the chemical processing agent that is selected from IVB family metallic compound, obtain the step of product of contact, with handle described product of contact with the Nonmetallocene part, obtain the step of described 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 chemical processing agent 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 described treatment step carries out in the presence of the solvent of the described Nonmetallocene part of solubilized.
7. according to the preparation method of aspect 6 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.
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, halogenated alkane and the aromatic hydrocarbon.
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 hexane, methylene dichloride and the toluene.
10. according to the preparation method of aspect each described magnesium compound load type non-metallocene catalyst of 1-9, 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.
11. the preparation method according to aspect 10 described magnesium compound load type non-metallocene catalysts is characterized in that, described magnesium compound is selected from magnesium halide, oxyethyl group magnesium halide, magnesium ethylate and butoxy magnesium.
12. preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 1-11, it 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.
13. the preparation method according to aspect 12 described magnesium compound load type non-metallocene catalysts is characterized in that, described IVB family metallic compound is selected from IVB family metal halide.
14. the preparation method according to aspect 13 described magnesium compound load type non-metallocene catalysts is characterized in that, described IVB family metal halide is selected from titanium tetrachloride and zirconium tetrachloride.
15. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 1-14 is characterized in that, is 1:0.1～100. in the described chemical processing agent of IVB family metallic element with mol ratio in the described magnesium compound of magnesium elements
16. the preparation method according to aspect 15 described magnesium compound load type non-metallocene catalysts is characterized in that, is 1:0.5～50. in the described chemical processing agent of IVB family metallic element with mol ratio in the described magnesium compound of magnesium elements
17. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 1-16 is characterized in that, the mass ratio of described Nonmetallocene part and described product of contact is 0.01～0.50:1.
18. the preparation method according to aspect 17 described magnesium compound load type non-metallocene catalysts is characterized in that, the mass ratio of described Nonmetallocene part and described product of contact is 0.10～0.30:1.
19. preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 4-18, 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.
20. the preparation method according to aspect 19 described magnesium compound load type non-metallocene catalysts is characterized in that, described alcohol is selected from Fatty Alcohol(C12-C14 and C12-C18).
21. the preparation method according to aspect 20 described magnesium compound load type non-metallocene catalysts is characterized in that, described Fatty Alcohol(C12-C14 and C12-C18) is selected from ethanol and butanols.
22. preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 4-21, 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
23, according to the preparation method of aspect 22 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.
24. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 4-23 is characterized in that, by volume, described precipitation is 1:0.5～6 with the ratio of solvent and tetrahydrofuran (THF).
25. the preparation method according to aspect 24 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).
26. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 4-25 is characterized in that, described precipitation is selected from alkane with solvent.
27. the preparation method according to aspect 26 described magnesium compound load type non-metallocene catalysts is characterized in that, described precipitation is selected from pentane, hexane, heptane and decane with solvent.
28. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 2-27 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.
29. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 2-27 is characterized in that, is 1:0.5～8. in the described magnesium compound of magnesium elements and the mol ratio that helps chemical processing agent in aluminium element described
30. the preparation method according to aspect 29 described magnesium compound load type non-metallocene catalysts is characterized in that, is 1:1～4. in the described magnesium compound of magnesium elements and the mol ratio that helps chemical processing agent in aluminium element described
31. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 1-30 is characterized in that, described Nonmetallocene part is selected from the compound with following structure:
Wherein:
Q is selected from 0 or 1;
D is selected from 0 or 1;
A be selected from Sauerstoffatom, sulphur atom, selenium atom,
-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,
-N (O) R
25R
26,
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 or become ring each other in key.
32. the preparation method according to aspect 31 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:
With
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 31 described definition.
33. the preparation method according to aspect 32 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:
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 32 described definition.
34. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 31-33 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
-NR
23R
24,-T-NR
23R
24Or-N (O) R
25R
26
Described phosphorus-containing groups is selected from
-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.
35. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 31-34 is characterized in that,
Described Nonmetallocene part is selected from the compound with following structure:
36. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 32-35 is characterized in that,
Described Nonmetallocene part is selected from the compound with following structure:
With
37. 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 1～36 each described magnesium compound load type non-metallocene catalyst.
38. alkene homopolymerization/copolymerization process, it is characterized in that, being Primary Catalysts according to aspect 37 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.
39., it is characterized in that described promotor is selected from one or more in aikyiaiurnirsoxan beta and the aluminum alkyls according to aspect 38 described alkene homopolymerization/copolymerization process.
40., it is characterized in that described promotor is selected from methylaluminoxane and triethyl aluminum according to aspect 39 described alkene homopolymerization/copolymerization process.
41., it is characterized in that described alkene is selected from C according to each described alkene homopolymerization/copolymerization process of aspect 38-40
2～C
10Monoolefine, diolefin, cycloolefin and other ethylenically unsaturated compounds.
42., it is characterized in that described C according to aspect 41 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, can obtain polymerization activity from low to high and adjustable load type non-metallocene catalyst adapts to different olefinic polymerization requirements thus.
When employing load type non-metallocene catalyst that the present invention obtained and promotor constitute catalyst system, only need fewer promotor (such as methylaluminoxane or triethyl aluminum) consumption, just can obtain high olefin polymerizating activity.
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 chemical processing agent that is selected from IVB family metallic compound, obtain the step of product of contact, with handle described product of contact with the Nonmetallocene part, obtain the step of described 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, also can be multiple mixing use not special restriction. for example, mol ratio between the two is such as being 0.25～4 arbitrarily, 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, stir at 20 ℃ of temperature range internal heating to 5 ℃ of the boiling points that is lower than tetrahydrofuran (THF)-pure mixed solvent, dissolve fully to magnesium compound, obtain magnesium compound solution. 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. and 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, 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 chemical processing agent, but one preferred embodiment in, with before chemical processing agent 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.
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 1:0.5～8, preferred 1:1～4 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 chemical processing agent 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 chemical processing agent, but also can be used further to this contact procedure through after the aforesaid pre-treatment step.
According to the present invention, described chemical processing agent is selected from IVB family metallic compound. as described IVB family metallic compound, can enumerate IVB family metal halide, IVB family metal alkyl compound, IVB family metal alkoxide compound, IVB family metal alkyl halides and IVB family metal alkoxide halogenide.
As described IVB family metal halide, alkylate, alkoxy compound, alkyl halide and alkoxy halide, can enumerate the compound of following general formula (IV) structure:
M(OR
1)
mX
nR
2 4-m-n (IV)
Wherein:
M is selected from 0,1,2,3,4;
N is selected from 0,1,2,3,4;
M is an IVB family metal, such as titanium, zirconium, hafnium etc.;
X is a halogen, such as F, Cl, Br, I etc.;
R
1And R
2Be selected from C independently of one another
1-C
30Alkyl is such as methyl, ethyl, propyl group, normal-butyl, isobutyl-etc., R
1And R
2Can be identical, also can be different.
Particularly, described IVB family metal halide can be enumerated 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);
Described IVB family metal alkyl compound can be enumerated tetramethyl-titanium (Ti (CH
3)
4), tetraethyl-titanium (Ti (CH
3CH
2)
4), four isobutyl-titanium (Ti (i-C
4H
9)
4), tetra-n-butyl titanium (Ti (C
4H
9)
4), triethyl methyltitanium (Ti (CH
3) (CH
3CH
2)
3), diethyl-dimethyl titanium (Ti (CH
3)
2(CH
3CH
2)
2), trimethylammonium ethyl titanium (Ti (CH
3)
3(CH
3CH
2)), triisobutyl methyltitanium (Ti (CH
3) (i-C
4H
9)
3), diisobutyl dimethyl titanium (Ti (CH
3)
2(i-C
4H
9)
2), trimethylammonium isobutyl-titanium (Ti (CH
3)
3(i-C
4H
9)), triisobutyl ethyl titanium (Ti (CH
3CH
2) (i-C
4H
9)
3), diisobutyl diethyl titanium (Ti (CH
3CH
2)
2(i-C
4H
9)
2), triethyl isobutyl-titanium (Ti (CH
3CH
2)
3(i-C
4H
9)), three normal-butyl methyltitanium (Ti (CH
3) (C
4H
9)
3), di-n-butyl dimethyl titanium (Ti (CH
3)
2(C
4H
9)
2), trimethylammonium normal-butyl titanium (Ti (CH
3)
3(C
4H
9)), three normal-butyl methyltitanium (Ti (CH
3CH
2) (C
4H
9)
3), di-n-butyl diethyl titanium (Ti (CH
3CH
2)
2(C
4H
9)
2), triethyl normal-butyl titanium (Ti (CH
3CH
2)
3(C
4H
9)) etc.;
Tetramethyl-zirconium (Zr (CH
3)
4), tetraethyl-zirconium (Zr (CH
3CH
2)
4), four isobutyl-zirconium (Zr (i-C
4H
9)
4), tetra-n-butyl zirconium (Zr (C
4H
9)
4), triethyl methylcyclopentadienyl zirconium (Zr (CH
3) (CH
3CH
2)
3), diethyl-dimethyl zirconium (Zr (CH
3)
2(CH
3CH
2)
2), trimethylammonium ethyl zirconium (Zr (CH
3)
3(CH
3CH
2)), triisobutyl methylcyclopentadienyl zirconium (Zr (CH
3) (i-C
4H
9)
3), diisobutyl zirconium dimethyl (Zr (CH
3)
2(i-C
4H
9)
2), trimethylammonium isobutyl-zirconium (Zr (CH
3)
3(i-C
4H
9)), triisobutyl ethyl zirconium (Zr (CH
3CH
2) (i-C
4H
9)
3), diisobutyl diethyl zirconium (Zr (CH
3CH
2)
2(i-C
4H
9)
2), triethyl isobutyl-zirconium (Zr (CH
3CH
2)
3(i-C
4H
9)), three normal-butyl methylcyclopentadienyl zirconium (Zr (CH
3) (C
4H
9)
3), di-n-butyl zirconium dimethyl (Zr (CH
3)
2(C
4H
9)
2), trimethylammonium normal-butyl zirconium (Zr (CH
3)
3(C
4H
9)), three normal-butyl methylcyclopentadienyl zirconium (Zr (CH
3CH
2) (C
4H
9)
3), di-n-butyl diethyl zirconium (Zr (CH
3CH
2)
2(C
4H
9)
2), triethyl normal-butyl zirconium (Zr (CH
3CH
2)
3(C
4H
9)) etc.;
Tetramethyl-hafnium (Hf (CH
3)
4), tetraethyl-hafnium (Hf (CH
3CH
2)
4), four isobutyl-hafnium (Hf (i-C
4H
9)
4), tetra-n-butyl hafnium (Hf (C
4H
9)
4), triethyl methylcyclopentadienyl hafnium (Hf (CH
3) (CH
3CH
2)
3), diethyl-dimethyl hafnium (Hf (CH
3)
2(CH
3CH
2)
2), trimethylammonium ethyl hafnium (Hf (CH
3)
3(CH
3CH
2)), triisobutyl methylcyclopentadienyl hafnium (Hf (CH
3) (i-C
4H
9)
3), diisobutyl dimethyl hafnium (Hf (CH
3)
2(i-C
4H
9)
2), trimethylammonium isobutyl-hafnium (Hf (CH
3)
3(i-C
4H
9)), triisobutyl ethyl hafnium (Hf (CH
3CH
2) (i-C
4H
9)
3), diisobutyl diethyl hafnium (Hf (CH
3CH
2)
2(i-C
4H
9)
2), triethyl isobutyl-hafnium (Hf (CH
3CH
2)
3(i-C
4H
9)), three normal-butyl methylcyclopentadienyl hafnium (Hf (CH
3) (C
4H
9)
3), di-n-butyl dimethyl hafnium (Hf (CH
3)
2(C
4H
9)
2), trimethylammonium normal-butyl hafnium (Hf (CH
3)
3(C
4H
9)), three normal-butyl methylcyclopentadienyl hafnium (Hf (CH
3CH
2) (C
4H
9)
3), di-n-butyl diethyl hafnium (Hf (CH
3CH
2)
2(C
4H
9)
2), triethyl normal-butyl hafnium (Hf (CH
3CH
2)
3(C
4H
9)) etc.;
Described IVB family metal alkoxide compound can be enumerated tetramethoxy titanium (Ti (OCH
3)
4), purity titanium tetraethoxide (Ti (OCH
3CH
2)
4), four isobutoxy titanium (Ti (i-OC
4H
9)
4), four titanium n-butoxide (Ti (OC
4H
9)
4), triethoxy methoxyl group titanium (Ti (OCH
3) (OCH
3CH
2)
3), diethoxy dimethoxy titanium (Ti (OCH
3)
2(OCH
3CH
2)
2), trimethoxy ethanolato-titanium (Ti (OCH
3)
3(OCH
3CH
2)), three isobutoxy methoxyl group titanium (Ti (OCH
3) (i-OC
4H
9)
3), two isobutoxy dimethoxy titanium (Ti (OCH
3)
2(i-OC
4H
9)
2), trimethoxy isobutoxy titanium (Ti (OCH
3)
3(i-OC
4H
9)), three isobutoxy ethanolato-titanium (Ti (OCH
3CH
2) (i-OC
4H
9)
3), two isobutoxy diethoxy titanium (Ti (OCH
3CH
2)
2(i-OC
4H
9)
2), triethoxy isobutoxy titanium (Ti (OCH
3CH
2)
3(i-OC
4H
9)), three n-butoxy methoxyl group titanium (Ti (OCH
3) (OC
4H
9)
3), two n-butoxy dimethoxy titanium (Ti (OCH
3)
2(OC
4H
9)
2), trimethoxy titanium n-butoxide (Ti (OCH
3)
3(OC
4H
9)), three n-butoxy methoxyl group titanium (Ti (OCH
3CH
2) (OC
4H
9)
3), two n-butoxy diethoxy titanium (Ti (OCH
3CH
2)
2(OC
4H
9)
2), triethoxy titanium n-butoxide (Ti (OCH
3CH
2)
3(OC
4H
9)) etc.;
Tetramethoxy zirconium (Zr (OCH
3)
4), tetraethoxy zirconium (Zr (OCH
3CH
2)
4), four isobutoxy zirconium (Zr (i-OC
4H
9)
4), four n-butoxy zirconium (Zr (OC
4H
9)
4), triethoxy methoxyl group zirconium (Zr (OCH
3) (OCH
3CH
2)
3), diethoxy dimethoxy zirconium (Zr (OCH
3)
2(OCH
3CH
2)
2), trimethoxy oxyethyl group zirconium (Zr (OCH
3)
3(OCH
3CH
2)), three isobutoxy methoxyl group zirconium (Zr (OCH
3) (i-OC
4H
9)
3), two isobutoxy dimethoxy zirconium (Zr (OCH
3)
2(i-OC
4H
9)
2), trimethoxy isobutoxy zirconium (Zr (OCH
3)
3(i-C
4H
9)), three isobutoxy oxyethyl group zirconium (Zr (OCH
3CH
2) (i-OC
4H
9)
3), two isobutoxy diethoxy zirconium (Zr (OCH
3CH
2)
2(i-OC
4H
9)
2), triethoxy isobutoxy zirconium (Zr (OCH
3CH
2)
3(i-OC
4H
9)), three n-butoxy methoxyl group zirconium (Zr (OCH
3) (OC
4H
9)
3), two n-butoxy dimethoxy zirconium (Zr (OCH
3)
2(OC
4H
9)
2), trimethoxy n-butoxy zirconium (Zr (OCH
3)
3(OC
4H
9)), three n-butoxy methoxyl group zirconium (Zr (OCH
3CH
2) (OC
4H
9)
3), two n-butoxy diethoxy zirconium (Zr (OCH
3CH
2)
2(OC
4H
9)
2), triethoxy n-butoxy zirconium (Zr (OCH
3CH
2)
3(OC
4H
9)) etc.;
Tetramethoxy hafnium (Hf (OCH
3)
4), tetraethoxy hafnium (Hf (OCH
3CH
2)
4), four isobutoxy hafnium (Hf (i-OC
4H
9)
4), four n-butoxy hafnium (Hf (OC
4H
9)
4), triethoxy methoxyl group hafnium (Hf (OCH
3) (OCH
3CH
2)
3), diethoxy dimethoxy hafnium (Hf (OCH
3)
2(OCH
3CH
2)
2), trimethoxy oxyethyl group hafnium (Hf (OCH
3)
3(OCH
3CH
2)), three isobutoxy methoxyl group hafnium (Hf (OCH
3) (i-OC
4H
9)
3), two isobutoxy dimethoxy hafnium (Hf (OCH
3)
2(i-OC
4H
9)
2), trimethoxy isobutoxy hafnium (Hf (OCH
3)
3(i-OC
4H
9)), three isobutoxy oxyethyl group hafnium (Hf (OCH
3CH
2) (i-OC
4H
9)
3), two isobutoxy diethoxy hafnium (Hf (OCH
3CH
2)
2(i-OC
4H
9)
2), triethoxy isobutoxy hafnium (Hf (OCH
3CH
2)
3(i-C
4H
9)), three n-butoxy methoxyl group hafnium (Hf (OCH
3) (OC
4H
9)
3), two n-butoxy dimethoxy hafnium (Hf (OCH
3)
2(OC
4H
9)
2), trimethoxy n-butoxy hafnium (Hf (OCH
3)
3(OC
4H
9)), three n-butoxy methoxyl group hafnium (Hf (OCH
3CH
2) (OC
4H
9)
3), two n-butoxy diethoxy hafnium (Hf (OCH
3CH
2)
2(OC
4H
9)
2), triethoxy n-butoxy hafnium (Hf (OCH
3CH
2)
3(OC
4H
9)) etc.
Described IVB family metal alkyl halides can be enumerated trimethylammonium titanium chloride (TiCl (CH
3)
3), triethyl titanium chloride (TiCl (CH
3CH
2)
3), triisobutyl titanium chloride (TiCl (i-C
4H
9)
3), three normal-butyl chlorination titanium (TiCl (C
4H
9)
3), dimethyl titanium dichloride (TiCl
2(CH
3)
2), diethyl titanium dichloride (TiCl
2(CH
3CH
2)
2), diisobutyl titanium dichloride (TiCl
2(i-C
4H
9)
2), three normal-butyl chlorination titanium (TiCl (C
4H
9)
3), methyl titanous chloride (Ti (CH
3) Cl
3), ethyl titanous chloride (Ti (CH
3CH
2) Cl
3), isobutyl-titanous chloride (Ti (i-C
4H
9) Cl
3), normal-butyl titanous chloride (Ti (C
4H
9) Cl
3);
Trimethylammonium titanium bromide (TiBr (CH
3)
3), triethyl titanium bromide (TiBr (CH
3CH
2)
3), triisobutyl titanium bromide (TiBr (i-C
4H
9)
3), three normal-butyl bromination titanium (TiBr (C
4H
9)
3), dimethyl dibrominated titanium (TiBr
2(CH
3)
2), diethyl dibrominated titanium (TiBr
2(CH
3CH
2)
2), diisobutyl dibrominated titanium (TiBr
2(i-C
4H
9)
2), three normal-butyl bromination titanium (TiBr (C
4H
9)
3), methyl titanium tribromide (Ti (CH
3) Br
3), ethyl titanium tribromide (Ti (CH
3CH
2) Br
3), isobutyl-titanium tribromide (Ti (i-C
4H
9) Br
3), normal-butyl titanium tribromide (Ti (C
4H
9) Br
3);
Trimethylammonium zirconium chloride (ZrCl (CH
3)
3), triethyl zirconium chloride (ZrCl (CH
3CH
2)
3), triisobutyl zirconium chloride (ZrCl (i-C
4H
9)
3), three normal-butyl chlorination zirconium (ZrCl (C
4H
9)
3), dimethyl zirconium dichloride (ZrCl
2(CH
3)
2), diethyl zirconium dichloride (ZrCl
2(CH
3CH
2)
2), diisobutyl zirconium dichloride (ZrCl
2(i-C
4H
9)
2), three normal-butyl chlorination zirconium (ZrCl (C
4H
9)
3), methyl tri-chlorination zirconium (Zr (CH
3) Cl
3), ethyl tri-chlorination zirconium (Zr (CH
3CH
2) Cl
3), isobutyl-tri-chlorination zirconium (Zr (i-C
4H
9) Cl
3), normal-butyl tri-chlorination zirconium (Zr (C
4H
9) Cl
3);
Trimethylammonium zirconium bromide (ZrBr (CH
3)
3), triethyl zirconium bromide (ZrBr (CH
3CH
2)
3), triisobutyl zirconium bromide (ZrBr (i-C
4H
9)
3), three normal-butyl bromination zirconium (ZrBr (C
4H
9)
3), dimethyl dibrominated zirconium (ZrBr
2(CH
3)
2), diethyl dibrominated zirconium (ZrBr
2(CH
3CH
2)
2), diisobutyl dibrominated zirconium (ZrBr
2(i-C
4H
9)
2), three normal-butyl bromination zirconium (ZrBr (C
4H
9)
3), methyl tribromide zirconium (Zr (CH
3) Br
3), ethyl tribromide zirconium (Zr (CH
3CH
2) Br
3), isobutyl-tribromide zirconium (Zr (i-C
4H
9) Br
3), normal-butyl tribromide zirconium (Zr (C
4H
9) Br
3);
Trimethylammonium hafnium chloride (HfCl (CH
3)
3), triethyl hafnium chloride (HfCl (CH
3CH
2)
3), triisobutyl hafnium chloride (HfCl (i-C
4H
9)
3), three normal-butyl chlorination hafnium (HfCl (C
4H
9)
3), dimethyl hafnium dichloride (HfCl
2(CH
3)
2), diethyl hafnium dichloride (HfCl
2(CH
3CH
2)
2), diisobutyl hafnium dichloride (HfCl
2(i-C
4H
9)
2), three normal-butyl chlorination hafnium (HfCl (C
4H
9)
3), methyl tri-chlorination hafnium (Hf (CH
3) Cl
3), ethyl tri-chlorination hafnium (Hf (CH
3CH
2) Cl
3), isobutyl-tri-chlorination hafnium (Hf (i-C
4H
9) Cl
3), normal-butyl tri-chlorination hafnium (Hf (C
4H
9) Cl
3);
Trimethylammonium bromination hafnium (HfBr (CH
3)
3), triethyl bromination hafnium (HfBr (CH
3CH
2)
3), triisobutyl bromination hafnium (HfBr (i-C
4H
9)
3), three normal-butyl bromination hafnium (HfBr (C
4H
9)
3), dimethyl dibrominated hafnium (HfBr
2(CH
3)
2), diethyl dibrominated hafnium (HfBr
2(CH
3CH
2)
2), diisobutyl dibrominated hafnium (HfBr
2(i-C
4H
9)
2), three normal-butyl bromination hafnium (HfBr (C
4H
9)
3), methyl tribromide hafnium (Hf (CH
3) Br
3), ethyl tribromide hafnium (Hf (CH
3CH
2) Br
3), isobutyl-tribromide hafnium (Hf (i-C
4H
9) Br
3), normal-butyl tribromide hafnium (Hf (C
4H
9) Br
3);
Described IVB family metal alkoxide halogenide can be enumerated trimethoxy titanium chloride (TiCl (OCH
3)
3), triethoxy titanium chloride (TiCl (OCH
3CH
2)
3), three isobutoxy titanium chloride (TiCl (i-OC
4H
9)
3), three n-butoxy titanium chloride (TiCl (OC
4H
9)
3), dimethoxy titanium dichloride (TiCl
2(OCH
3)
2), diethoxy titanium dichloride (TiCl
2(OCH
3CH
2)
2), two isobutoxy titanium dichloride (TiCl
2(i-OC
4H
9)
2), three n-butoxy titanium chloride (TiCl (OC
4H
9)
3), methoxyl group titanous chloride (Ti (OCH
3) Cl
3), oxyethyl group titanous chloride (Ti (OCH
3CH
2) Cl
3), isobutoxy titanous chloride (Ti (i-C
4H
9) Cl
3), n-butoxy titanous chloride (Ti (OC
4H
9) Cl
3);
Trimethoxy titanium bromide (TiBr (OCH
3)
3), triethoxy titanium bromide (TiBr (OCH
3CH
2)
3), three isobutoxy titanium bromide (TiBr (i-OC
4H
9)
3), three n-butoxy titanium bromide (TiBr (OC
4H
9)
3), dimethoxy dibrominated titanium (TiBr
2(OCH
3)
2), diethoxy dibrominated titanium (TiBr
2(OCH
3CH
2)
2), two isobutoxy dibrominated titanium (TiBr
2(i-OC
4H
9)
2), three n-butoxy titanium bromide (TiBr (OC
4H
9)
3), methoxyl group titanium tribromide (Ti (OCH
3) Br
3), oxyethyl group titanium tribromide (Ti (OCH
3CH
2) Br
3), isobutoxy titanium tribromide (Ti (i-C
4H
9) Br
3), n-butoxy titanium tribromide (Ti (OC
4H
9) Br
3);
Trimethoxy zirconium chloride (ZrCl (OCH
3)
3), triethoxy zirconium chloride (ZrCl (OCH
3CH
2)
3), three isobutoxy zirconium chloride (ZrCl (i-OC
4H
9)
3), three n-butoxy zirconium chloride (ZrCl (OC
4H
9)
3), dimethoxy zirconium dichloride (ZrCl
2(OCH
3)
2), diethoxy zirconium dichloride (ZrCl
2(OCH
3CH
2)
2), two isobutoxy zirconium dichloride (ZrCl
2(i-OC
4H
9)
2), three n-butoxy zirconium chloride (ZrCl (OC
4H
9)
3), methoxyl group tri-chlorination zirconium (Zr (OCH
3) Cl
3), oxyethyl group tri-chlorination zirconium (Zr (OCH
3CH
2) Cl
3), isobutoxy tri-chlorination zirconium (Zr (i-C
4H
9) Cl
3), n-butoxy tri-chlorination zirconium (Zr (OC
4H
9) Cl
3);
Trimethoxy zirconium bromide (ZrBr (OCH
3)
3), triethoxy zirconium bromide (ZrBr (OCH
3CH
2)
3), three isobutoxy zirconium bromide (ZrBr (i-OC
4H
9)
3), three n-butoxy zirconium bromide (ZrBr (OC
4H
9)
3), dimethoxy dibrominated zirconium (ZrBr
2(OCH
3)
2), diethoxy dibrominated zirconium (ZrBr
2(OCH
3CH
2)
2), two isobutoxy dibrominated zirconium (ZrBr
2(i-OC
4H
9)
2), three n-butoxy zirconium bromide (ZrBr (OC
4H
9)
3), methoxyl group tribromide zirconium (Zr (OCH
3) Br
3), oxyethyl group tribromide zirconium (Zr (OCH
3CH
2) Br
3), isobutoxy tribromide zirconium (Zr (i-C
4H
9) Br
3), n-butoxy tribromide zirconium (Zr (OC
4H
9) Br
3);
Trimethoxy hafnium chloride (HfCl (OCH
3)
3), triethoxy hafnium chloride (HfCl (OCH
3CH
2)
3), three isobutoxy hafnium chloride (HfCl (i-OC
4H
9)
3), three n-butoxy hafnium chloride (HfCl (OC
4H
9)
3), dimethoxy hafnium dichloride (HfCl
2(OCH
3)
2), diethoxy hafnium dichloride (HfCl
2(OCH
3CH
2)
2), two isobutoxy hafnium dichloride (HfCl
2(i-OC
4H
9)
2), three n-butoxy hafnium chloride (HfCl (OC
4H
9)
3), methoxyl group tri-chlorination hafnium (Hf (OCH
3) Cl
3), oxyethyl group tri-chlorination hafnium (Hf (OCH
3CH
2) Cl
3), isobutoxy tri-chlorination hafnium (Hf (i-C
4H
9) Cl
3), n-butoxy tri-chlorination hafnium (Hf (OC
4H
9) Cl
3);
Trimethoxy bromination hafnium (HfBr (OCH
3)
3), triethoxy bromination hafnium (HfBr (OCH
3CH
2)
3), three isobutoxy bromination hafnium (HfBr (i-OC
4H
9)
3), three n-butoxy bromination hafnium (HfBr (OC
4H
9)
3), dimethoxy dibrominated hafnium (HfBr
2(OCH
3)
2), diethoxy dibrominated hafnium (HfBr
2(OCH
3CH
2)
2), two isobutoxy dibrominated hafnium (HfBr
2(i-OC
4H
9)
2), three n-butoxy bromination hafnium (HfBr (OC
4H
9)
3), methoxyl group tribromide hafnium (Hf (OCH
3) Br
3), oxyethyl group tribromide hafnium (Hf (OCH
3CH
2) Br
3), isobutoxy tribromide hafnium (Hf (i-C
4H
9) Br
3), n-butoxy tribromide hafnium (Hf (OC
4H
9) Br
3).
Wherein, as described IVB family metallic compound, preferred IVB family metal halide, more preferably TiCl
4, TiBr
4, ZrCl
4, ZrBr
4, HfCl
4, HfBr
4, TiCl most preferably
4And ZrCl
4
These IVB family metallic compounds 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 chemical processing agent 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.
Under the situation that adopts solid chemical processing agent (such as zirconium tetrachloride), at first prepare the solution of described chemical processing agent, add the described chemical processing agent of (the preferred dropping) specified amount then to magnesium compound; 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 magnesium compound, contact reacts (in case of necessity by stirring) was carried out 0.5～24 hour, preferred 1～8 hour, more preferably 2～6 hours, filter then and wash, then dry, obtain product of contact thus.
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.This washing is generally carried out 1～8 time, and preferred 2～6 times, most preferably 2～4 times.
When carrying out described contact procedure, be 1:0.1～100 in the described chemical processing agent of IVB family metallic element with mol ratio in the described magnesium compound of magnesium elements, preferred 1:0.5～50.
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 magnesium compound given to this invention and described chemical processing agent.
According to the present invention, also there is no particular limitation to described catalytic temperature.Though select for use higher temperature of reaction to help the reaction of chemical processing agent and magnesium compound carrier, can reduce the reaction times.But because solvent difference, its boiling point also is different. those skilled in the art know, the temperature of reaction of chemical processing agent and carrier should be lower than the boiling point of solvent, such as for hexane, temperature of reaction can be chosen between 20 ℃～65 ℃, can be chosen between 20 ℃～105 ℃ or the like for toluene. therefore, temperature of reaction is different with the difference of solvent, cannot treat different things as the same, be lower than between 5～10 ℃ of the solvent boiling points but be typically chosen in, but the lower limit of temperature is not limited. in addition, this catalytic time is had no particular limits, generally can select for use 0.5～24 hour. under the situation that improves temperature of reaction, the reaction times can be suitably short more.
It is pointed out that in this contact procedure, the use of solvent is not essential.Just be or, the reaction of described chemical processing agent and described magnesium compound 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. the temperature of reaction of this moment and reaction times can suitably be determined as required, generally speaking, temperature of reaction should be lower than 5～10 ℃ of the boiling points of chemical processing agent at least, and the contact reacts time was generally 2～24 hours.For example, the reaction of chemical processing agent and carrier is fierce more, and temperature of reaction just is provided with lowly more, make the reaction times long more thus. such as, when chemical processing agent was titanium tetrachloride, temperature of reaction can be-30 ℃～126 ℃, and the corresponding reaction times is 2～12 hours.
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,, can omit the consumption that uses solvent or reduce solvent owing to had solvent in this mixed solution.
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 the Nonmetallocene part.
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:
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:
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,
-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,
-N (O) R
25R
26,
-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
-NR
23R
24,-T-NR
23R
24Or-N (O) R
25R
26
Phosphorus-containing groups is selected from
-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-TOR
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 IVB family atoms metal,
(2) with structural formula in group A, D, E, F, Y and Z all different and
(3) coordination ability with IVB 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 IVB family atoms metal.
As this Nonmetallocene part, such as enumerating compound with following structure:
Wherein, described Nonmetallocene part is preferably selected from the compound with following structure:
Wherein, described Nonmetallocene part also is preferably selected from the compound with following structure:
Described Nonmetallocene part more preferably is selected from the compound with following structure:
These Nonmetallocene parts 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 Nonmetallocene part, IVB family metal contained in described Nonmetallocene part 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.
If at first prepare the solution of described Nonmetallocene part. what select is that solubleness to described Nonmetallocene part is not very high solvent, and 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 to the regulation of non-metallocene catalyst content in the final load type non-metallocene catalyst, and the solvent that adopts of this stage is to the solvability of this Nonmetallocene part, the mass concentration of this Nonmetallocene part is generally 10～250 grams per liters in the solution, preferred 50～160 grams per liters.
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.
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.
Then, under evenly stirring, described product of contact is joined in this Nonmetallocene ligand solution in the temperature range that is lower than 5 ℃ of solvent boiling points in room temperature, so that the mass ratio of described Nonmetallocene part and described product of contact is 0.01～0.50:1, preferred 0.10～0.30:1, continuing reaction 0.5～24 hour. stirring can be adopted modes such as helical-ribbon type stirring or the stirring of anchor formula, stir for helical-ribbon type, stirring velocity is generally 5～50 rev/mins, stir for the anchor formula, stirring velocity is generally 5～200 rev/mins.
After the reaction, with reaction mixture through filtration, washing and dry, perhaps without filtration and washing and convection drying promptly obtains magnesium compound load type non-metallocene catalyst of the present invention.Generally speaking, for the lower reaction mixture of solid content, a kind of mode before adopting, and, then adopt a kind of mode in back for the higher reaction mixture of solid content.In case of necessity, this washing is generally carried out 1～8 time, preferred 2～6 times, most preferably 2～4 times. described drying can adopt well-established law to carry out, such as the rare gas element drying, vacuumize drying, perhaps heating vacuumizes drying, preferably vacuumize drying. generally speaking, be generally 2～24 hours time of drying, but actual can passing through sampled, and thermal weight loss situation is per sample judged dry terminal point. promptly, thermal weight loss is dry terminal point less than 5% under the temperature that the boiling point of the solvent that adopts being lower than is 5～45 ℃.When selecting lower boiling solvent, can adopt short time of drying, select high boiling solvent then generally to adopt long time of drying. drying temperature generally is lower than 5～45 ℃ of the boiling points of used solvent, such as when adopting tetrahydrofuran (THF) as solvent, drying temperature can be chosen between 23～63 ℃, when selecting toluene as solvent, drying temperature can be chosen between 65～105 ℃, when selecting methylene dichloride as solvent, drying temperature can be chosen between 0～37 ℃ for another example, or the like.
In addition, consider the interaction between described product of contact and the Nonmetallocene part, reacted mixed solution generally carries out 0.5～24 hour airtight wearing out at normal temperatures, to increase the bond strength between carrier and the Nonmetallocene part.
Those skilled in the art knows, above-described various contact and treating processes are generally all carried out under the anhydrous and oxygen-free condition of strictness, here said anhydrous and oxygen-free condition be meant the content of water and oxygen in the system continue 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, 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, can obtain polymerization activity from low to high and adjustable load type non-metallocene catalyst adapts to different olefinic polymerization requirements thus.
When employing load type non-metallocene catalyst that the present invention obtained and promotor constitute catalyst system, only need fewer promotor (such as methylaluminoxane or triethyl aluminum) consumption, just can obtain high olefin polymerizating activity.
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 represents that divided by the ratio of the quality of used load type non-metallocene catalyst (unit is a kg polymkeric substance/gCat) for the polymerization activity of catalyzer with this polymerisate quality.
Embodiment 1
Magnesium compound is Magnesium Chloride Anhydrous (MgCl
2), chemical processing agent is titanium tetrachloride (TiCl
4).
Take by weighing the 5g Magnesium Chloride Anhydrous, preparation makes its dispersion with solvent as product of contact to add the 25ml hexane, then under agitation with being added dropwise to titanium tetrachloride in 30 minutes, react 4 hours after-filtration down at 60 ℃, hexane wash 3 times, each 25ml, vacuum is drained and is obtained product of contact. and titanium tetrachloride and magnesium compound mole proportioning are 1:2.
With structural formula
The Nonmetallocene part be dissolved in (the part mass concentration is 100 grams per liters) in the hexane, under agitation add product of contact then, react 4 hours after-filtration, hexane wash 2 times, each hexane consumption 25ml descended dry 6 hours at 25 ℃ then, obtained magnesium compound load type non-metallocene catalyst.
Wherein part and product of contact quality proportioning are 0.11:1.
This catalyzer is designated as CAT-1, and wherein Mg content is 13.7wt%, and titanium content is 8.4wt%.
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 titanium tetrabromide (TiBr
4), the mole proportioning of itself and magnesium compound is 1:4.5.
The product of contact preparation is changed into decane with solvent.
The Nonmetallocene part is changed into
Be dissolved in the decane, the part mass concentration is 50 grams per liters, and part and product of contact quality proportioning are 0.22:1.
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 is changed into zirconium tetrachloride (ZrCl
4) (toluene solution), the mole proportioning of itself and magnesium compound is 1:1.
The product of contact preparation is changed into toluene with solvent.
The Nonmetallocene part is changed into
Be dissolved in the toluene, the part mass concentration is 170 grams per liters, and part and product of contact quality proportioning are 0.29:1.
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 tetrabormated zirconium (ZrBr
4), the mole proportioning of itself and magnesium compound is 1:30.
The product of contact preparation is changed into pentane with solvent.
The Nonmetallocene part is changed into
Be dissolved in the pentane, the part mass concentration is 90 grams per liters, and part and product of contact quality proportioning are 0.48:1,
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), chemical processing agent is changed into tetraethyl-titanium (Ti (CH
3CH
2)
4), the mole proportioning of itself and magnesium compound is 1:25.
The product of contact preparation is changed into methylene dichloride with solvent.
The Nonmetallocene part is changed into
Be dissolved in the methylene dichloride, the part mass concentration is 214 grams per liters, and part and product of contact quality proportioning are 0.15:1.
React the back without filtration, direct 25 ℃ of following vacuum-dryings.
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), chemical processing agent is changed into tetrabutyl titanium (Ti (C
4H
9)
4), the mole proportioning of itself and magnesium compound is 1:7.5.
The product of contact preparation is changed into dimethylbenzene with solvent.
The Nonmetallocene part is changed into
Be dissolved in the dimethylbenzene.
Embodiment 1-6
Substantially the same manner as Example 1, but following change is arranged:
Magnesium compound is changed into magnesium ethide (Mg (C
2H
5)
2), chemical processing agent is changed into tributyl titanium chloride (TiCl (C
4H
9)
3), the mole proportioning of itself and magnesium compound is 1:20.
The product of contact preparation is changed into hexanaphthene with solvent.
The Nonmetallocene part is changed into
Be dissolved in the hexanaphthene.
Embodiment 1-7
Substantially the same manner as Example 1, but following change is arranged:
Magnesium compound is changed into isobutyl-magnesium (Mg (i-C
4H
9)
2), chemical processing agent is changed into four isobutoxy titanium (Ti (i-C
4H
9)
4).
The product of contact preparation is changed into methylcyclohexane with solvent.
The Nonmetallocene part is changed into
Be dissolved in the methylcyclohexane.
Embodiment 1-8
Substantially the same manner as Example 1, but following change is arranged:
Magnesium compound is changed into ethylmagnesium chloride (Mg (C
2H
5) Cl), chemical processing agent is changed into three isobutoxy ethyl zirconium (Zr (CH
3CH
2) (i-C
4H
9)
3).
The product of contact preparation is changed into chloro-hexane with solvent.
The Nonmetallocene part is changed into
Be dissolved in the chloro-hexane.
Embodiment 1-9
Substantially the same manner as Example 1, but following change is arranged:
Magnesium compound is changed into butylmagnesium chloride (Mg (C
4H
9) Cl), chemical processing agent is changed into diethoxy titanium dichloride (TiCl
2(OCH
3CH
2)
2).
The product of contact preparation is changed into chlorotoluene with solvent.
The Nonmetallocene part is changed into
Be dissolved in the chlorotoluene.
Embodiment 1-10
Substantially the same manner as Example 1, but following change is arranged:
Magnesium compound is changed into butyl magnesium ethylate (Mg (OC
2H
5) (C
4H
9)).
The Nonmetallocene part is changed into
Embodiment 1-11
Substantially the same manner as Example 1, but following change is arranged:
Magnesium compound is changed into magnesium chloride (MgCl
2) and magnesium ethylate (Mg (OC
2H
5)
2) mixture, both mol ratios are 1:2.
The Nonmetallocene part is changed into
Embodiment 1-12
Substantially the same manner as Example 1, but following change is arranged:
Magnesium compound is changed into magnesium ethylate (Mg (OC
2H
5)
2) and dibutyl magnesium (Mg (C
4H
9)
2) mixture, both mol ratios are 0.5:1.
The Nonmetallocene part is changed into
Embodiment 1-13
Substantially the same manner as Example 1, but following change is arranged:
Magnesium compound is changed into magnesium chloride (MgCl
2) and magnesium bromide (MgBr
2) mixture, both mol ratios are 1:4.
The Nonmetallocene part is changed into
Embodiment 1-14
Substantially the same manner as Example 1, but following change is arranged:
Magnesium compound is changed into oxyethyl group magnesium chloride (Mg (OC
2H
5) Cl) and ethyl butoxy magnesium (Mg (C
2H
5) (OC
4H
9)) mixture, both mol ratios are 0.5:1.
The Nonmetallocene part is changed into
Reference example 1-1
Substantially the same manner as Example 1, but following change is arranged:
The quality proportioning of part and product of contact is 0.30:1.
Catalyzer be designated as CAT-A. wherein Mg content be 12.3wt%, titanium content is 7.9wt%.
By this reference example as can be known, the product of contact preparation process is identical, but the content of magnesium and titanium reduces in the load type non-metallocene catalyst. and this phenomenon is because the increase of Nonmetallocene part add-on causes the charge capacity of load type non-metallocene catalyst due to increasing. and the preparation method of magnesium compound load type non-metallocene catalyst of the present invention is adopted in this explanation, can obtain high Nonmetallocene part charge capacity, and its charge capacity is adjustable.
Reference example 1-2
Substantially the same manner as Example 1, but following change is arranged:
The mole proportioning of titanium tetrachloride and magnesium compound is 1:1.
Catalyzer be designated as CAT-B. wherein Mg content be 11.6wt%, titanium content is 9.7wt%.
Under the identical condition of Nonmetallocene part add-on, increase this phenomenon as can be known by titanium content increase in the load type non-metallocene catalyst and Mg content reduction, polymerization activity, adopt the preparation method of magnesium compound load type non-metallocene catalyst of the present invention, can pass through to adopt different chemical processing agent consumptions, and obtain the active high load type non-metallocene catalyst of catalysis in olefine polymerization.
Embodiment 2
Hereinafter, for the event of simplicity of exposition, with chemical processing agent and help the combination of chemical processing agent to be referred to as the composite chemical treatment agent, and be the consumption that benchmark determines to help chemical processing agent with the chemical processing agent, but this with the present invention before specialized range produce contradiction.
Magnesium compound is a Magnesium Chloride Anhydrous, and the composite chemical treatment agent is titanium tetrachloride and triethyl aluminum.
Take by weighing the 5g Magnesium Chloride Anhydrous, adding the 25ml hexane disperses, then under agitation with the hexane solution that was added dropwise to triethyl aluminum in 15 minutes, react 1 hour after-filtration, hexane wash 1 time, obtain prefinished products, to wherein under agitation dripping titanium tetrachloride, react the 2h after-filtration down again, use hexane wash 3 times at 60 ℃ with 30 minutes, each hexane consumption 25ml, 25 ℃ of dryings made product of contact after 6 hours.
Wherein, titanium tetrachloride and magnesium mole proportioning are 1:2, with the triethyl aluminum mol ratio be that 1:1. is with structural formula
The Nonmetallocene part be dissolved in (the part mass concentration is 100 grams per liters) in the hexane, under agitation add product of contact then, react 4 hours after-filtration, hexane wash 2 times, each hexane consumption 25ml, 25 ℃ were descended dry 6 hours then, obtained magnesium compound load type non-metallocene catalyst.
Wherein part and product of contact quality proportioning are 0.11:1.
Catalyzer is designated as CAT-2.
Embodiment 2-1
Substantially the same manner as Example 2, but following change is arranged:
Magnesium compound is changed into magnesium bromide (MgBr
2), the composite chemical treatment agent is titanium tetrachloride-methylaluminoxane, titanium tetrachloride and magnesium compound mol ratio are 1:4.5, with the methylaluminoxane mol ratio be 1:2.
Under agitation with the toluene solution that was added dropwise to methylaluminoxane in 15 minutes, react 2 hours after-filtration earlier, toluene wash 1 time under agitation dripped titanium tetrachloride with 30 minutes again, reacted 0.5h after-filtration, toluene wash 2 times down at 105 ℃.
The Nonmetallocene part is changed into
Be dissolved in the toluene.
The part mass concentration is 50 grams per liters, and part and product of contact quality proportioning are 0.22:1.
Embodiment 2-2
Substantially the same manner as Example 2, but following change is arranged:
Magnesium compound is changed into oxyethyl group magnesium chloride (MgCl (OC
2H
5)), the composite chemical treatment agent is zirconium tetrachloride (ZrCl
4)-triethyl aluminum, zirconium tetrachloride and triethyl aluminum mol ratio are 1:0.5, with the mole proportioning of magnesium compound be 1:1.
Under agitation with the n-heptane solution that was added dropwise to triethyl aluminum in 15 minutes, react 2 hours after-filtration earlier, heptane wash 2 times under agitation with the toluene solution that dripped zirconium tetrachloride in 30 minutes, is reacted 4h after-filtration, heptane wash 1 time down at 100 ℃ again.
The Nonmetallocene part is changed into
Be dissolved in the heptane.
The part mass concentration is 170 grams per liters, and part and product of contact quality proportioning are 0.29:1.
Embodiment 2-3
Substantially the same manner as Example 2, but following change is arranged:
The composite chemical treatment agent is titanium tetrabromide (TiBr
4)-triethyl aluminum, titanium tetrabromide and triethyl aluminum mol ratio are 1:0.25.
Under agitation with the decane solution that was added dropwise to triethyl aluminum in 15 minutes, react after 1 hour earlier,, react the 1h after-filtration down at 110 ℃, decane washing 1 time more under agitation with the decane solution that dripped titanium tetrabromide in 30 minutes.
The Nonmetallocene part is changed into
Be dissolved in the decane.
The part mass concentration is 79 grams per liters, and part and product of contact quality proportioning are 0.48:1.
Embodiment 2-4
Substantially the same manner as Example 2, but following change is arranged:
The composite chemical treatment agent is tetrabormated zirconium (ZrBr4)-triisobutyl aluminium, and tetrabormated zirconium and triisobutyl al mole ratio are 1:2.
Under agitation with the pentane solution that was added dropwise to triisobutyl aluminium in 15 minutes, react after 1 hour earlier,, react the 8h after-filtration down at 30 ℃, the pentane washing more under agitation with the pentane solution that dripped the tetrabormated zirconium in 30 minutes.
The Nonmetallocene part is changed into
Be dissolved in the methylene dichloride.
The part mass concentration is 214 grams per liters, and part and product of contact quality proportioning are that the direct vacuum of 0.15:1. is drained.
Embodiment 2-5
Substantially the same manner as Example 2, but following change is arranged:
Magnesium compound is changed into magnesium ethylate.
The composite chemical treatment agent is titanium tetrachloride-trimethyl aluminium, and titanium tetrachloride and trimethyl aluminium mol ratio are the washing of 1:4. ethylbenzene.
The Nonmetallocene part is changed into
Be dissolved in the ethylbenzene.
Embodiment 2-6
Substantially the same manner as Example 2, but following change is arranged:
Magnesium compound is changed into isobutoxy magnesium (Mg (i-OC
4H
9)
2).
The composite chemical treatment agent is titanium tetrachloride-aluminum ethylate, and titanium tetrachloride and triethoxy al mole ratio are 1:1, with the mole proportioning of magnesium compound be 1:7.5.
The Nonmetallocene part is changed into
Be dissolved in the hexanaphthene.
Embodiment 2-7
Substantially the same manner as Example 2, but following change is arranged:
Magnesium compound is changed into ethylmagnesium chloride (Mg (C
2H
5) Cl).
The composite chemical treatment agent is titanium tetrachloride-triisobutyl alumina alkane, and triisobutyl alumina alkane and titanium tetrachloride mol ratio are 1:1.
The Nonmetallocene part is changed into
Be dissolved in the methylcyclohexane.
Embodiment 2-8
Substantially the same manner as Example 2, but following change is arranged:
Magnesium compound is changed into butyl magnesium ethylate (Mg (OC
2H
5) (C
4H
9)).
The Nonmetallocene part is changed into
Embodiment 2-9
Substantially the same manner as Example 2, but following change is arranged:
Magnesium compound is changed into butylmagnesium chloride (Mg (C
4H
9) Cl).
The Nonmetallocene part is changed into
Embodiment 2-10
Substantially the same manner as Example 2, but following change is arranged:
Magnesium compound is changed into magnesium chloride (MgCl
2) and magnesium ethylate (Mg (OC
2H
5)
2) mixture, both mol ratios are 1:2.
The Nonmetallocene part is changed into
Embodiment 2-11
Substantially the same manner as Example 2, but following change is arranged:
Magnesium compound is changed into magnesium ethylate (Mg (OC
2H
5)
2) and dibutyl magnesium (Mg (C
4H
9)
2) mixture, both mol ratios are 0.5:1.
The Nonmetallocene part is changed into
Embodiment 3
Magnesium compound is a Magnesium Chloride Anhydrous, and chemical processing agent is a titanium tetrachloride.
The 5g Magnesium Chloride Anhydrous is dissolved in tetrahydrofuran (THF) and the alcohol mixed solution, is heated to 60 ℃, stirring reaction formed 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.
Add the 50ml hexane in gained modification magnesium compound, under agitation be added dropwise to titanium tetrachloride with 30 minutes, reacted 4 hours down at 60 ℃, filter, adopt hexane wash 3 times, each hexane consumption 25ml was heated to 90 ℃ of dryings 2 hours then, obtained product of contact.
With structural formula
The Nonmetallocene part be dissolved in the hexane, under agitation add product of contact then, react 4 hours after-filtration, adopt hexane wash 2 times, each hexane consumption 25ml, then 25 ℃ dry 2 hours down, obtain magnesium compound load type non-metallocene catalyst.
Wherein, the mol ratio of Magnesium Chloride Anhydrous and tetrahydrofuran (THF) is 1:12, with the alcoholic acid mol ratio be 1:4, the mole proportioning of magnesium is 1:2 in titanium tetrachloride and the modification magnesium compound, the part mass concentration is 100 grams per liters, part and product of contact quality proportioning are 0.11:1.
This catalyzer is designated as CAT-3.
Embodiment 3-1
Substantially the same manner as Example 3, but following change is arranged:
Magnesium chloride 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 titanium tetrabromide (TiBr
4), with the mole proportioning of magnesium in the modification magnesium compound be 1:4.5.
Adopt decane to make the magnesium compound precipitation, and wash 2 times with decane.
The Nonmetallocene part is changed into
Be dissolved in the decane.
The part mass concentration is 50 grams per liters, and part and product of contact quality proportioning are 0.22:1.
Embodiment 3-2
Substantially the same manner as Example 3, but following change is arranged:
Magnesium chloride 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.
Chemical processing agent is changed into (ZrCl
4), at first being dissolved in the toluene, the mole proportioning of magnesium is 1:1 in zirconium tetrachloride and the modification magnesium compound.
Adopt pentane to make the magnesium compound precipitation, and wash 3 times with pentane.
The Nonmetallocene part is changed into
Be dissolved in the toluene.
The part mass concentration is 170 grams per liters, and part and product of contact quality proportioning are 0.29:1.
Embodiment 3-3
Substantially the same manner as Example 3, but following change is arranged:
Magnesium chloride 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,
Chemical processing agent is changed into tetrabormated zirconium (ZrBr
4), with the mole proportioning of magnesium in the modification magnesium compound be 1:30.
Adopt hexanaphthene to make the magnesium compound precipitation, and wash with hexanaphthene.
The Nonmetallocene part is changed into
Be dissolved in the hexanaphthene.
The part mass concentration is 79 grams per liters, and part and product of contact quality proportioning are 0.48:1.
Embodiment 3-4
Substantially the same manner as Example 3, but following change is arranged:
Magnesium chloride 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,
Chemical processing agent is changed into tetraethyl-titanium (Ti (CH
3CH
2)
4), with the mole proportioning of magnesium in the modification magnesium compound be 1:25.
The product of contact preparation is changed into methylene dichloride with solvent.
The Nonmetallocene part is changed into
Be dissolved in the methylene dichloride.
The part mass concentration is 214 grams per liters, part and product of contact quality proportioning be 0.15:1. without filtration, direct 25 ℃ of following vacuum-dryings.
Embodiment 3-5
Substantially the same manner as Example 3, but following change is arranged:
Magnesium chloride 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.
Chemical processing agent is changed into (Ti (C
4H
9)
4), with the mole proportioning of magnesium in the modification magnesium compound be 1:7.5.
The product of contact preparation is changed into dimethylbenzene with solvent.
The Nonmetallocene part is changed into
Be dissolved in the dimethylbenzene.
Embodiment 3-6
Substantially the same manner as Example 3, but following change is arranged:
Magnesium compound is changed into magnesium ethide (Mg (C
2H
5)
2), ethanol changes the phenyl butanols into;
Chemical processing agent is changed into tributyl titanium chloride (TiCl (C
4H
9)
3), magnesium mole proportioning is 1:20 in tributyl titanium chloride and the modification magnesium compound;
Adopt hexanaphthene to make the magnesium compound precipitation, and wash with hexanaphthene.
The Nonmetallocene part is changed into
The solvent of dissolving Nonmetallocene part is changed into hexanaphthene.
Embodiment 3-7
Substantially the same manner as Example 3, but following change is arranged:
Magnesium compound is changed into isobutyl-magnesium (Mg (i-C
4H
9)
2), chemical processing agent is changed into four isobutoxy titanium (Ti (i-C
4H
9)
4).
The product of contact preparation is changed into methylcyclohexane with solvent.
The Nonmetallocene part is changed into
Be dissolved in the methylcyclohexane.
Embodiment 3-8
Substantially the same manner as Example 3, but following change is arranged:
Magnesium compound is changed into ethylmagnesium chloride (Mg (C
2H
5) Cl), chemical processing agent is changed into three isobutoxy ethyl zirconium (Zr (CH
3CH
2) (i-C
4H
9)
3).
The product of contact preparation is changed into chloro-hexane with solvent.
The Nonmetallocene part is changed into
Be dissolved in the chloro-hexane.
Embodiment 4
Magnesium compound is a Magnesium Chloride Anhydrous, and the composite chemical treatment agent is titanium tetrachloride and triethyl aluminum.
The 5g Magnesium Chloride Anhydrous is added in tetrahydrofuran (THF) and the alcohol mixed solvent, under agitation be 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.
In this modification magnesium compound under agitation with the hexane solution that was added dropwise to triethyl aluminum in 15 minutes (concentration is 0.88mol/L), react after 1 hour, again under agitation with 30 minutes dropping titanium tetrachlorides, react the 2h after-filtration down at 60 ℃, hexane wash 3 times, each hexane consumption 25ml, 25 ℃ of dryings made product of contact in back 6 hours.
With structural formula
The Nonmetallocene part, be dissolved in the hexane, under agitation add above-mentioned product of contact then, reacted 4 hours, filter, hexane wash 2 times, each hexane consumption 25ml, then 25 ℃ dry 6 hours down, obtain magnesium compound load type non-metallocene catalyst.
Wherein, the mol ratio of magnesium chloride and tetrahydrofuran (THF) is 1:12, with the alcoholic acid mol ratio be 1:4, titanium tetrachloride and triethyl aluminum mol ratio are 1:1 in the composite chemical treatment agent, with the mole proportioning of magnesium in the modification magnesium compound be 1:2.
The part mass concentration is 100 grams per liters, and part and product of contact quality proportioning are 0.11:1.
This catalyzer is designated as CAT-4.
Embodiment 4-1
Substantially the same manner as Example 4, but following change is arranged:
Magnesium chloride changes magnesium bromide (MgBr into
2), ethanol changes propyl alcohol into.
Adopt decane to make the magnesium compound precipitation, and wash 2 times with decane.
The composite chemical treatment agent is titanium tetrachloride-methylaluminoxane. earlier under agitation with the toluene solution that was added dropwise to methylaluminoxane in 15 minutes (concentration is 10wt%), react after 4 hours, filter, again under agitation with 30 minutes dropping titanium tetrachlorides, react the 0.5h after-filtration down at 105 ℃, decane washing 2 times.
Wherein, the mol ratio of magnesium bromide and tetrahydrofuran (THF) is 1:20, with the mol ratio of propyl alcohol be 1:3, titanium tetrachloride with the methylaluminoxane mol ratio be 1:2, with the mole proportioning of magnesium in the modification magnesium compound be 1:4.5.
The Nonmetallocene part is changed into
Be dissolved in the decane.
The part mass concentration is 50 grams per liters, and part and product of contact quality proportioning are 0.22:1.
Embodiment 4-2
Substantially the same manner as Example 4, but following change is arranged:
Magnesium chloride changes oxyethyl group magnesium chloride (MgCl (OC into
2H
5)), ethanol changes butanols into.
The mol ratio of oxyethyl group magnesium chloride and tetrahydrofuran (THF) is 1:20, with the mol ratio of butanols be 1:6.
The composite chemical treatment agent is zirconium tetrachloride (ZrCl
4)-triethyl aluminum, zirconium tetrachloride and triethyl aluminum mol ratio are 1:0.5, with the mole proportioning of magnesium in the modification magnesium compound be 1:1.
Wherein, earlier under agitation with the toluene solution that was added dropwise to triethyl aluminum in 15 minutes, react 2 hours after-filtration, toluene wash 1 time under agitation with the toluene solution that dripped zirconium tetrachloride in 30 minutes, is reacted 4h after-filtration, toluene wash down at 100 ℃ again.
The Nonmetallocene part is changed into
Be dissolved in the toluene.
The part mass concentration is 170 grams per liters, and part and product of contact quality proportioning are 0.29:1.
Embodiment 4-3
Substantially the same manner as Example 4, but following change is arranged:
Magnesium chloride 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,
Adopt hexanaphthene to make the magnesium compound precipitation, and wash with hexanaphthene.
The composite chemical treatment agent is titanium tetrabromide (TiBr
4)-triethyl aluminum, titanium tetrabromide and triethyl aluminum mol ratio are 1:0.25, with the mole proportioning of magnesium in the modification magnesium compound be 1:34.
Earlier under agitation with the decane solution that was added dropwise to triethyl aluminum in 15 minutes, react after 1 hour more under agitation with the decane solution that dripped titanium tetrabromide in 30 minutes, under 110 ℃, react the 1h after-filtration, decane washs 4 times.
The Nonmetallocene part is changed into
Be dissolved in the decane.
The part mass concentration is 79 grams per liters, and part and product of contact quality proportioning are 0.48:1.
Embodiment 4-4
Substantially the same manner as Example 4, but following change is arranged:
Magnesium chloride changes magnesium ethylate (Mg (OC into
2H
5)
2), ethanol changes enanthol into.
The mol ratio of magnesium ethylate and tetrahydrofuran (THF) is 1:10, with the mol ratio of enanthol be 1:6.3,
The composite chemical treatment agent is titanium tetrachloride-trimethyl aluminium, and titanium tetrachloride and trimethyl aluminium mol ratio are 1:4.
Under agitation be added dropwise to earlier the pentane solution of triethyl aluminum, react after 1 hour, under agitation with the pentane solution that dripped the tetrabormated zirconium in 30 minutes, react 8h after-filtration, washed with dichloromethane down again at 30 ℃ with 15 clocks.
The Nonmetallocene part is changed into
Be dissolved in the methylene dichloride.
The part mass concentration is 214 grams per liters, part and product of contact quality proportioning be 0.15:1. without filtration, direct 25 ℃ of following vacuum-dryings.
Embodiment 4-5
Substantially the same manner as Example 4, but following change is arranged:
Magnesium chloride changes isobutoxy magnesium (Mg (i-OC into
4H
9)
2), with the mol ratio of tetrahydrofuran (THF) be 1:25.
Ethanol changes hexalin into.
The composite chemical treatment agent is tetrabormated zirconium-triisobutyl aluminium, tetrabormated zirconium and triisobutyl al mole ratio are that 1:4. is earlier under agitation with being added dropwise to triisobutyl aluminium in 15 minutes, react after 1 hour, again under agitation with the xylene solution that dripped the tetrabormated zirconium in 30 minutes, react the 8h after-filtration down at 50 ℃, the dimethylbenzene washing.
The Nonmetallocene part is changed into
Be dissolved in the dimethylbenzene.
Embodiment 4-6
Substantially the same manner as Example 4, but following change is arranged:
Magnesium compound is changed into magnesium ethide (Mg (C
2H
5)
2), ethanol changes the phenyl butanols into;
Adopt hexanaphthene to make the magnesium compound precipitation, and wash with hexanaphthene.
The composite chemical treatment agent is titanium tetrachloride-aluminum ethylate, and titanium tetrachloride and triethyl aluminum mol ratio are 1:1.
The Nonmetallocene part is changed into
Be dissolved in the hexanaphthene.
Embodiment 4-7
Substantially the same manner as Example 4, but following change is arranged:
Magnesium compound is changed into isobutyl-magnesium (Mg (i-C
4H
9)
2).
The composite chemical treatment agent is titanium tetrachloride-triisobutyl alumina alkane, and titanium tetrachloride and triisobutyl alumina alkane mol ratio are 1:1.
The Nonmetallocene part is changed into
Be dissolved in the methylcyclohexane.
Embodiment 4-8
Substantially the same manner as Example 4, but following change is arranged:
Magnesium compound is changed into ethylmagnesium chloride (Mg (C
2H
5) Cl).
The product of contact preparation is changed into chloro-hexane with solvent.
The Nonmetallocene part is changed into
Be dissolved in the chloro-hexane.
Embodiment 5 (Application Example)
With the catalyzer CAT-1 that makes in the embodiment of the invention, CAT-2, CAT-3, CAT-A that makes in CAT-4 and the reference example and CAT-B adopt slurry polymerization processes respectively in 2 liters of polymerization autoclaves, with the hexane is polymer solvent, with methylaluminoxane or triethyl aluminum is promotor, at stagnation pressure 0.8MPa, 85 ℃ of polymerization temperatures, hydrogen partial pressure 0.2MPa and reaction times are to make ethylene homo under 2 hours the condition, research changes promotor consumption (aluminium titanium mol ratio) and plants time-like, to the polymerization activity of catalyzer and the influence of polymer stacks density, the result is as shown in table 1.
The olefinic polyreaction effect of table 1. magnesium compound load type non-metallocene catalyst
| Sequence number | The catalyzer numbering | Promotor | Aluminium titanium mol ratio | Polymerization activity (kgPE/gCat) | Polymer stacks density (g/cm 3) |
| 1 | CAT-1 | Triethyl aluminum | 90 | 4.34 | 0.274 |
| 2 | CAT-1 | Triethyl aluminum | 500 | 4.47 | 0.275 |
| 3 | CAT-1 | Methylaluminoxane | 140 | 4.81 | 0.292 |
| 4 | CAT-1 | Methylaluminoxane | 500 | 4.93 | 0.294 |
| 5 | CAT-A | Triethyl aluminum | 90 | 4.77 | 0.277 |
| 6 | CAT-B | Triethyl aluminum | 90 | 6.42 | 0.313 |
| 7 | CAT-2 | Triethyl aluminum | 90 | 6.79 | 0.334 |
| 8 | CAT-2 | Methylaluminoxane | 140 | 7.21 | 0.342 |
| 9 | CAT-3 | Triethyl aluminum | 90 | 13.40 | 0.365 |
| 10 | CAT-3 | Methylaluminoxane | 140 | 14.16 | 0.350 |
| 11 | CAT-4 | Triethyl aluminum | 90 | 15.93 | 0.352 |
| 12 | CAT-4 | Methylaluminoxane | 140 | 16.83 | 0.333 |
Contrast by sequence number in the table 11 and 2,3 and 4 test-results data as can be known, increase the consumption of promotor triethyl aluminum, when promptly improving aluminium titanium mol ratio, influence active to polymerization catalyst and polymer stacks density is not remarkable. and it can be said that brightly, the magnesium compound load type non-metallocene catalyst that adopts method provided by the invention to prepare only needs fewer promotor consumption just can obtain high olefin polymerizating activity.
The contrast of the test-results data by sequence number in the table 11 and 5 and 6 as can be known, by improving chemical processing agent consumption or Nonmetallocene part add-on, can improve the polymerization activity of the catalyzer of gained, and improve the bulk density of polymkeric substance. it can be said that bright, adopt the magnesium compound load type non-metallocene catalyst of method preparation provided by the invention, its polymerization activity is adjustable flexibly, therefore can be adapted to different olefinic polymerization requirements widely.
In addition, contrast by sequence number in the table 17 and 8,9 and 10,11 and 12 test-results data as can be known, the kind influence active to polymerization catalyst and polymer stacks density that changes promotor is not remarkable. it can be said that bright, adopt the magnesium compound load type non-metallocene catalyst of method preparation provided by the invention, have bigger latitude at the kind time-like of selecting promotor.
Claims (37)
1. the preparation method of a magnesium compound load type non-metallocene catalyst, it may further comprise the steps:
Magnesium compound is contacted with the chemical processing agent that is selected from IV B family metallic compound, obtain product of contact step and
Handle described product of contact with the Nonmetallocene part, obtain the step of described 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 chemical processing agent 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 described treatment step carries out in the presence of the solvent of the described Nonmetallocene part of solubilized.
7. according to the preparation method of the described magnesium compound load type non-metallocene catalyst of claim 6, 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.
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, halogenated alkane and the aromatic hydrocarbon.
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 hexane, methylene dichloride and the toluene.
10. according to the preparation method of 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.
11. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 10 is characterized in that, described magnesium compound is selected from magnesium halide, oxyethyl group magnesium halide, magnesium ethylate and butoxy magnesium.
12. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 1 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.
13. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 12 is characterized in that, described IV B family metallic compound is selected from IV B family metal halide.
14. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 13 is characterized in that, described IV B family metal halide is selected from titanium tetrachloride and zirconium tetrachloride.
15. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 1 is characterized in that, is 1:0.1～100. in the described chemical processing agent of IV B family metallic element with mol ratio in the described magnesium compound of magnesium elements
16. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 15 is characterized in that, is 1:0.5～50. in the described chemical processing agent of IV B family metallic element with mol ratio in the described magnesium compound of magnesium elements
17. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 1 is characterized in that, the mass ratio of described Nonmetallocene part and described product of contact is 0.01～0.50:1.
18. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 17 is characterized in that, the mass ratio of described Nonmetallocene part and described product of contact is 0.10～0.30:1.
19. 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.
20. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 19 is characterized in that, described alcohol is selected from Fatty Alcohol(C12-C14 and C12-C18).
21. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 20 is characterized in that, described Fatty Alcohol(C12-C14 and C12-C18) is selected from ethanol and butanols.
22. 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
23. preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 22, 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.
24. 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).
25. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 24 is characterized in that, by volume, described precipitation is 1:1～4. 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 4 is characterized in that, described precipitation is selected from alkane with solvent.
27. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 26 is characterized in that, described precipitation is selected from pentane, hexane, heptane and decane with solvent.
28. 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.
29. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 2 is characterized in that, is 1:0.5～8. in the described magnesium compound of magnesium elements and the mol ratio that helps chemical processing agent in aluminium element described
30. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 29 is characterized in that, is 1:1～4 in the described magnesium compound of magnesium elements with helping the mol ratio of chemical processing agent in aluminium element described.
31. 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:
Wherein:
Q is selected from 0 or 1;
D is selected from 0 or 1;
A be selected from Sauerstoffatom, sulphur atom, selenium atom,
-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,
-N (O) R
25R
26,
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 or become ring each other in key.
32. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 31 is characterized in that,
Described Nonmetallocene part is selected from (A) with following structure and (B) compound:
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 31.
33. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 32 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:
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 32.
34. the preparation method according to each described magnesium compound load type non-metallocene catalyst of claim 31-33 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
-NR
23R
24,-T-NR
23R
24Or-N (O) R
25R
26
Described phosphorus-containing groups is selected from
-PR
28R
29,-P (O) R
30R
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 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
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.
35. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 31 is characterized in that,
Described Nonmetallocene part is selected from the compound with following structure:
36. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 35 is characterized in that,
Described Nonmetallocene part is selected from the compound with following structure:
37. 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 1～36.
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| CN2007101626760A CN101412768B (en) | 2007-10-16 | 2007-10-16 | Magnesium compound load type non-metallocene catalyst and preparation thereof |
| EP08841802.5A EP2202246B1 (en) | 2007-10-16 | 2008-10-15 | Non-metallocene catalyst supported on magnesium compound and its preparation method |
| KR1020107003494A KR101206940B1 (en) | 2007-10-16 | 2008-10-15 | Non-metallocene catalyst supported on magnesium compound and its preparation method |
| JP2010529215A JP5480148B2 (en) | 2007-10-16 | 2008-10-15 | Magnesium compound-supported nonmetallocene catalyst and production thereof |
| PCT/CN2008/001739 WO2009052701A1 (en) | 2007-10-16 | 2008-10-15 | Non-metallocene catalyst supported on magnesium compound and its preparation method |
| US12/671,654 US8716416B2 (en) | 2007-10-16 | 2008-10-15 | Magnesium-compound supported nonmetallocene catalyst and preparation thereof |
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| US8952113B2 (en) | 2009-11-13 | 2015-02-10 | China Petroleum & Chemical Corp. | Supported nonmetallocene catalyst, preparation and use thereof |
| US8957169B2 (en) | 2009-11-13 | 2015-02-17 | China Petroleum & Chemical Corp. | Supported nonmetallocene catalyst, preparation and use thereof |
| US8981023B2 (en) | 2009-10-26 | 2015-03-17 | China Petroleum & Chemical Corp. | Supported nonmetallocene catalyst, preparation and use thereof |
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| CA2032543A1 (en) * | 1989-12-26 | 1991-06-27 | Robert Olds Hagerty | Dimethylaluminum chloride-activated olefin polymerisation catalyst composition |
| KR100491627B1 (en) * | 2002-12-31 | 2005-05-27 | 삼성토탈 주식회사 | Method for polymerization and copolymerization of ethylene using carbodiimide ligand chelated catalyst |
| CN100569808C (en) * | 2005-03-31 | 2009-12-16 | 中国石油化工股份有限公司 | A kind of load type non-metallocene catalyst and preparation method thereof |
| CN100569734C (en) * | 2006-05-22 | 2009-12-16 | 中国科学院上海有机化学研究所 | One class contains heteroatomic organic compound and the application in Ziegler-Natta catalyst thereof |
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| US8981023B2 (en) | 2009-10-26 | 2015-03-17 | China Petroleum & Chemical Corp. | Supported nonmetallocene catalyst, preparation and use thereof |
| US8952113B2 (en) | 2009-11-13 | 2015-02-10 | China Petroleum & Chemical Corp. | Supported nonmetallocene catalyst, preparation and use thereof |
| US8957169B2 (en) | 2009-11-13 | 2015-02-17 | China Petroleum & Chemical Corp. | Supported nonmetallocene catalyst, preparation and use thereof |
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