CN101412769B - Load type non-metallocene catalyst and preparation thereof - Google Patents
Load type non-metallocene catalyst and preparation thereof Download PDFInfo
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- CN101412769B CN101412769B CN200710162677.5A CN200710162677A CN101412769B CN 101412769 B CN101412769 B CN 101412769B CN 200710162677 A CN200710162677 A CN 200710162677A CN 101412769 B CN101412769 B CN 101412769B
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Abstract
The invention relates to a supported non-metallocene catalyst. The supported non-metallocene catalyst is obtained by a non-metallocene ligand and a transition metal compound which directly react on a carrier through an in-situ supporting method. The preparation method for the 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 supported non-metallocene catalyst is combined with a catalyst promoter to catalyze the homopolymerization/copolymerization of olefins, the high comonomer effect is showed, and high polymerization activities of the olefins can be obtained only by using small amount of the catalyst promoter at the same time. Moreover, the obtained polymers have good particle morphology and high bulk density.
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 load type non-metallocene catalyst, it obtains Nonmetallocene part and transistion metal compound direct reaction on carrier by original position load method.By the promotors such as load type non-metallocene catalyst of the present invention and aikyiaiurnirsoxan beta or aluminum alkyls are combined, can be for the homopolymerization/copolymerization of catalyzed alkene.
Background technology
The non-metallocene catalyst that middle and later periods nineteen nineties occurs, claim again luxuriant rear catalyst, the central atom of Primary Catalysts has comprised nearly all transition metal, at some aspect of performance, reach, even surpass metallocene catalyst, become after Ziegler, Ziegler-Natta and metallocene catalyst the 4th generation olefin polymerization catalysis.By the excellent property of the polyolefin products of such catalyzer manufacturing, and low cost of manufacture.Non-metallocene catalyst ligating atom is oxygen, nitrogen, sulphur and phosphorus, do not contain cyclopentadienyl group or its deriveding group, as indenyl and fluorenyl etc., it is characterized in that central ion has stronger Electron Affinities, and there is cis alkyl or halogen metal division center, easily carry out alkene insertion and σ-key and shift, the easy alkylation of central metal, is conducive to the generation at cation activity center; The title complex forming has the geometric configuration of restriction, stereoselectivity, electronegativity and chirality controllability, and in addition, formed metal-carbon key easily polarizes, and is more conducive to polymerization and the copolymerization of alkene.Therefore, even if also can obtain the olefin polymer of higher molecular weight under higher polymeric reaction temperature.
But homogeneous catalyst has been proved it in olefinic polyreaction has that active duration is short, easily sticky still, high methylaluminoxane consumption, and obtain the too low or too high weak point of polymericular weight, only can, for solution polymerization process or high-pressure polymerization process, seriously limit its industrial applicability.
Patent ZL01126323.7, ZL02151294.9 ZL02110844.7 and WO03/010207 disclose a kind of alkene homopolymerization/catalyst for copolymerization or catalyst system, there is alkene homopolymerization/copolymerization performance widely, but at the disclosed catalyzer of this patent or catalyst system, need higher promotor consumption during in olefinic polymerization, could obtain suitable olefin polymerizating activity, and it is short to exist active duration in polymerization process, the phenomenons such as the sticky still of polymkeric substance.
According to the experience of metallocene catalyst industrial applications, the catalyzer that makes load is very necessary.
By by non-metallocene catalyst load, can avoid the non-metallocene catalyst bimolecular inactivation of homogeneous phase, improve the particle form of polymerization and polymkeric substance.It shows as the initial activity that has suitably reduced to a certain extent catalyzer, the extending catalyst polymerization activity life-span, reduce and even avoided caking or the cruelly poly-phenomenon in polymerization process, improve the form of polymkeric substance, improve the apparent density of polymkeric substance, can make it meet more polymerization technique process, as vapour phase polymerization or slurry polymerization etc.
For patent ZL01126323.7, the disclosed non-metallocene catalyst of ZL02151294.9 ZL02110844.7 and WO03/010207, patent CN1539855A, CN1539856A, CN1789291A, CN1789292A, CN1789290A, WO/2006/063501, 200510119401.x Deng providing various ways to carry out load to obtain load type non-metallocene catalyst, but these patents all relate to the Nonmetallocene organometallic compound that contains transition metal are carried on the carrier after processing, and because the reaction bonded of non-metallocene catalyst and porous support is limited, in the load type non-metallocene catalyst obtaining, Nonmetallocene organic compound is mainly to exist with physical adsorption state, be unfavorable for the control of morphology and the performance of non-metallocene catalyst performance.
Existing olefin polymerization catalysis patent is mostly based on metallocene catalyst, as US4808561, US5240894, CN1049439, CN1136239, CN1344749, CN1126480, CN1053673, CN1307594, CN1130932, CN1103069, CN1363537, CN1060179, US574417, EP685494, US4871705 and EP0206794 etc., but these patents also all relate to the metallocene catalyst that contains transition metal are carried on the carrier after processing.
Patent EP260130 proposes loaded metallocene or non-luxuriant transition-metal catalyst to be carried on the silica supports of methylaluminoxane processing, and the non-luxuriant transition metal here only refers to ZrCl
4, TiCl
4or VOCl
3, this patent think optimum be carrier surface through the mixture of organic-magnesium or magnesium compound and aluminum alkyls, but this process more complicated need to be passed through many preparation processes.
Patent WO03/047752A1 and WO03/047751A1 provide the load method of composite catalyst (Z-N and metallocene catalyst or non-metallocene catalyst and metallocene catalyst) on silicon-dioxide, this patent is thought, the muriate of titanium or vanadium or chlorine oxonium compound are non-metallocene catalyst components, and the catalyzer obtaining is thus bimetallic catalyst.
Patent EP708116 discloses and has first made the zirconium tetrachloride of gasification with carrier, contact and load at 160～450 ℃ of temperature, again the good zirconium tetrachloride of load is obtained to carried metallocene catalyst with the lithium salts reaction of part, then by coordinating with promotor for the polymerization of alkene.The problem that this catalyzer exists is that load process requires high temperature, and high vacuum, is applicable to industrial production.
Patent ZL01131136.3 discloses a kind of method of synthetic carried metallocene catalyst, wherein under normal pressure, makes carrier mix in solvent with IVB group 4 transition metal halogenide, is directly reacting with part negative ion.Thereby the synthetic and load that realizes metallocene catalyst completes in a step.But it is 1: 1 that the method requires transition metal and the mol ratio of part, and need to add proton donor, as butyllithium etc., and the part adopting is the metallocene part that contains cyclopentadienyl group of bridging type or non-bridging type.
Patent CN200510080210.7 discloses synthetic supported type vanadium non-metallocene catalyst and the preparation and application of original position; it first forms acyl group naphthols magnesium or beta-diketon magnesium compound by dialkyl magnesium with acyl group naphthols or beta-diketon reaction; react with the muriate of tetravalence vanadium again, form carrier and active catalytic components simultaneously.
The open Liao Yi class of patent CN200610026765.8 single active center Z-N olefin polymerization catalysis.This catalyzer is usingd the salicylaldehyde derivatives of the salicylic aldehyde that contains coordinating group or replacement as electron donor, by adding after pretreated carrier (as silica gel), metallic compound (as titanium tetrachloride) and this electron donor are processed and obtain in magnesium compound (as magnesium chloride)/tetrahydrofuran solution.
CN200610026766.2 is similar with it, discloses a class containing heteroatomic organic compound and the application in Ziegler-Natta catalyst thereof.
Even so, the ubiquitous problem of load type non-metallocene catalyst existing in prior art is that olefin polymerizating activity is low and be difficult to adjusting, and in order to improve its polymerization activity, must assist higher promotor consumption when carrying out olefinic polymerization.In addition, while adopting the load type non-metallocene catalyst of prior art, the polymkeric substance such as resulting polyethylene have low polymer stacks density and poor polymer morphology.And also there is the unsettled problem of performance in the load type non-metallocene catalyst existing in prior art.
Therefore, still need a kind of load type non-metallocene catalyst, its preparation method is simple, is applicable to suitability for industrialized production, and can overcomes those problems that exist in prior art load type non-metallocene catalyst.
Summary of the invention
For this reason, the object of the invention is to provide on the basis of existing technology a kind of load type non-metallocene catalyst, it obtains Nonmetallocene part and transistion metal compound direct reaction on carrier by original position load method.In its preparation process, need not proton donor and electron donor etc., reaction requirement and reaction conditions that also need not be harsh.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. a preparation method for load type non-metallocene catalyst, comprises the following steps:
Make magnesium compound be dissolved in the mixed solvent being formed by tetrahydrofuran (THF) and alcohol, obtain the step of magnesium compound solution,
Porous support is mixed with described magnesium compound solution, obtains the step of mixed serum,
Dry described mixed serum, the step of acquisition complex carrier,
With a side who is selected from chemical processing agent and Nonmetallocene part, process described complex carrier, obtain the treatment step of modification complex carrier, wherein said chemical processing agent is selected from IVB family metallic compound; With
Described modification complex carrier is contacted with the opposing party in described Nonmetallocene part with being selected from described chemical processing agent, thereby obtain the contact procedure of described load type non-metallocene catalyst.
2. according to the preparation method of the load type non-metallocene catalyst described in aspect 1, also comprise the step of the load type non-metallocene catalyst of dry described acquisition.
3. according to the preparation method of the load type non-metallocene catalyst described in aspect 1 or 2, before being also included in and mixing with described magnesium compound solution, the step of porous support described in thermal activation treatment.
4. according to the preparation method of the load type non-metallocene catalyst described in aspect 1-3 any one, before being also included in described treatment step, with the chemical processing agent that helps that is selected from aikyiaiurnirsoxan beta, aluminum alkyls and composition thereof, process the step of described complex carrier.
5. according to the preparation method of the load type non-metallocene catalyst described in aspect 3 or 4, it is characterized in that, described thermal activation treatment is included under inert atmosphere, processes 0.5～24 hour at 200～800 ℃.
6. according to the preparation method of the load type non-metallocene catalyst described in aspect 5, it is characterized in that, described thermal activation treatment is included under nitrogen or argon gas atmosphere, processes 2～12 hours at 400～700 ℃.
7. according to the preparation method of the load type non-metallocene catalyst described in aspect 6, it is characterized in that, described thermal activation treatment is included at 400～650 ℃ and processes 4～8 hours.
8. according to the preparation method of the load type non-metallocene catalyst described in aspect 1-7 any one, it is characterized in that, described porous support is selected from partial cross-linked and has styrene polymer and the porous inorganic material of surperficial carboxyl, and wherein said porous inorganic material selects the oxide compound that one or more elements of free periodic table of elements HA, III A, IVAHe IVB family metal form, oxide compound, clay, molecular sieve, mica, polynite, wilkinite, diatomite, ZSM-5 and the MCM-41 being generated by pyrohydrolysis by gaseous metal halogenide or gaseous silicon compound.
9. according to the preparation method of the load type non-metallocene catalyst described in aspect 8, it is characterized in that, described porous support is selected from styrene polymer, silicon-dioxide, aluminum oxide, magnesium oxide, titanium dioxide, molecular sieve and polynite.
10. according to the preparation method of the load type non-metallocene catalyst described in aspect 9, it is characterized in that, described porous support is selected from silicon-dioxide.
11. according to the preparation method of the load type non-metallocene catalyst described in aspect 1-10 any one, 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 alkyl alkoxy magnesium
Described alcohol is selected from one or more in fatty alcohol, aromatic alcohol and alicyclic ring alcohol, and the group that wherein said alcohol is optionally selected from alkyl, halogen atom and alkoxyl group replaces.
12. according to the preparation method of the load type non-metallocene catalyst described in aspect 11, it is characterized in that, described magnesium compound is selected from magnesium halide.
13. according to the preparation method of the load type non-metallocene catalyst described in aspect 12, it is characterized in that, described magnesium compound is magnesium chloride.
14. according to the preparation method of the load type non-metallocene catalyst described in aspect 11-13 any one, it is characterized in that, described alcohol is selected from fatty alcohol.
15. according to the preparation method of the load type non-metallocene catalyst described in aspect 14, it is characterized in that, described alcohol is ethanol or butanols.
16. according to the preparation method of the load type non-metallocene catalyst described in aspect 1-15 any one, it is characterized in that, take the described magnesium compound of magnesium elements and the mol ratio of tetrahydrofuran (THF) is 1: 6～40, take the described magnesium compound of magnesium elements and the mol ratio of described alcohol is 1: 1～8, and the mass ratio of described magnesium compound and described porous support is 1: 0.5～4.
17. according to the preparation method of the load type non-metallocene catalyst described in aspect 16, it is characterized in that, take the described magnesium compound of magnesium elements and the mol ratio of tetrahydrofuran (THF) is 1: 8～20, take the described magnesium compound of magnesium elements and the mol ratio of described alcohol is 1: 0.5～4, and the mass ratio of described magnesium compound and described porous support is 1: 1～2.
18. according to the preparation method of the load type non-metallocene catalyst described in aspect 1-17 any one, it is characterized in that, described IVB family metallic compound is selected from one or more in IVB family metal halide, alkylate and alkyl halide.
19. according to the preparation method of the load type non-metallocene catalyst described in aspect 18, it is characterized in that, described IVB family metallic compound is selected from halogenated titanium and zirconium halide.
20. according to the preparation method of the load type non-metallocene catalyst described in aspect 19, it is characterized in that, described IVB family metallic compound is titanium tetrachloride.
21. according to the preparation method of the load type non-metallocene catalyst described in aspect 4-20 any one, it is characterized in that, described aluminum alkyls is selected from triethyl aluminum and trimethyl aluminium, and described aikyiaiurnirsoxan beta is selected from methylaluminoxane and triisobutyl alumina alkane.
22. according to the preparation method of the load type non-metallocene catalyst described in aspect 4-21 any one, it is characterized in that, take Al element described in to help chemical processing agent and the ratio of described complex carrier be 0.25～4 mmole: 1 gram.
23. according to the preparation method of the load type non-metallocene catalyst described in aspect 22, it is characterized in that, take Al element described in to help chemical processing agent and the ratio of described complex carrier be 0.5～2 mmole: 1 gram.
24. according to the preparation method of the load type non-metallocene catalyst described in aspect 1-23 any one, it is characterized in that, by mass, described Nonmetallocene part is 0.05～0.50: 1 with the ratio of complex carrier.
25. according to the preparation method of the load type non-metallocene catalyst described in aspect 24, it is characterized in that, by mass, described Nonmetallocene part is 0.10～0.30: 1 with the ratio of complex carrier.
26. according to the preparation method of the load type non-metallocene catalyst described in aspect 1-25 any one, it is characterized in that, the described chemical processing agent of YiIVB family metallic element meter and the mol ratio of described Nonmetallocene part are 1: 0.1～1.
27. according to the preparation method of the load type non-metallocene catalyst described in aspect 26, it is characterized in that, the described chemical processing agent of YiIVB family metallic element meter and the mol ratio of described Nonmetallocene part are 1: 0.3～0.9.
28. according to the preparation method of the load type non-metallocene catalyst described in aspect 1-27 any one, it 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, phosphorous 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, containing seleno, rolls into a ball 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 independently of one another hydrogen, C
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.
29. the preparation method according to the load type non-metallocene catalyst described in aspect 28, is characterized in that,
Described Nonmetallocene part is selected from has (A) of following structure and (B) compound:
Wherein F is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno, rolls into a ball or phosphorus-containing groups, and wherein N, O, S, Se, P are respectively ligating atom;
Other are according to definition described in aspect 28.
30. the preparation method according to the load type non-metallocene catalyst described in aspect 29, 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 independently of one another nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno, roll into a ball 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 independently of one another hydrogen, C
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 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 is to work as R
5during for oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups, the N in R5, O, S, P, Se are respectively ligating atom;
Other are according to definition described in aspect 29.
31. the preparation method according to the load type non-metallocene catalyst described in aspect 28-30 any one, 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 is selected from hydroxyl ,-OR
34with-T-OR
34;
Be selected from-SR of described sulfur-containing group
35,-T-SR
35,-S (O) R
36or-T-SO
2r
37;
Described containing be selected from-SeR of seleno group
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 the C of halo
1-C
30alkyl, the C of halo
6-C
30aryl, the C of halo
8-C
30condensed ring radical or the C of halo
4-C
30heterocyclic radical;
Be selected from-SiR of described silicon-containing group
42r
43r
44,-T-SiR
45;
Described be selected from-GeR of germanic group
46r
47r
48,-T-GeR
49;
Described containing be selected from-SnR of tin group
50r
51r
52,-T-SnR
53or-T-Sn (O) R
54;
Described R
34, R
35-R
38and R
42-R
54be selected from independently of one another hydrogen, C
1-C
30the C of alkyl, halogen atom, replacement
1-C
30alkyl or safing function group.
32. the preparation method according to the load type non-metallocene catalyst described in aspect 28-31 any one, is characterized in that,
Described Nonmetallocene part is selected from the compound with following structure:
33. the preparation method according to the load type non-metallocene catalyst described in aspect 32, is characterized in that,
Described Nonmetallocene part is selected from the compound with following structure:
34. 1 kinds of load type non-metallocene catalysts, comprise carrier and load non-metallocene catalyst thereon, it is characterized in that, it is to manufacture according to the preparation method of the load type non-metallocene catalyst described in aspect 1～33 any one.
35. 1 kinds of alkene homopolymerization/copolymerization process, it is characterized in that, take according to the load type non-metallocene catalyst described in aspect 34 is Primary Catalysts, take that to be selected from one or more in aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt be promotor, make alkene homopolymerization or copolymerization.
36. according to the alkene homopolymerization/copolymerization process described in aspect 35, it is characterized in that, described promotor is selected from one or more in aikyiaiurnirsoxan beta and aluminum alkyls.
37. according to the alkene homopolymerization/copolymerization process described in aspect 36, it is characterized in that, described promotor is selected from methylaluminoxane and triethyl aluminum.
38. according to the alkene homopolymerization/copolymerization process described in aspect 35-37 any one, it is characterized in that, described alkene is selected from C
2～C
10monoolefine, diolefin, cycloolefin and other ethylenically unsaturated compounds.
39. the alkene homopolymerization/copolymerization process according to described in aspect 38, is characterized in that, described C
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 1,7-octadiene, and described other ethylenically unsaturated compounds are selected from vinyl acetate and (methyl) acrylate.
Preparation method's technique simple possible of load type non-metallocene catalyst of the present invention, and the charge capacity of Nonmetallocene part is adjustable, can improve significantly its charge capacity, improves significantly thus the polymerization activity of this catalyzer.
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.
Adopt method for preparing catalyst provided by the invention, the combination of Nonmetallocene part and porous support is tight, has effectively avoided the impact of free ligand on load type non-metallocene catalyst polymerization, thereby makes the performance of this catalyzer more stable.
When the load type non-metallocene catalyst that employing the present invention obtains and promotor form catalyst system, only need fewer promotor (such as methylaluminoxane or triethyl aluminum) consumption, just can obtain high olefin polymerizating activity.And the polymkeric substance such as resulting polyethylene has good polymer morphology and high polymer bulk density thus.
Embodiment
First, the present invention relates to a kind of preparation method of load type non-metallocene catalyst, comprise the following steps: make magnesium compound be dissolved in the mixed solvent being formed by tetrahydrofuran (THF) and alcohol, obtain the step of magnesium compound solution; Porous support is mixed with described magnesium compound solution, obtain the step of mixed serum; Dry described mixed serum, the step of acquisition complex carrier; With a side who is selected from chemical processing agent and Nonmetallocene part, process described complex carrier, obtain the treatment step of modification complex carrier, wherein said chemical processing agent is selected from IVB family metallic compound; With described modification complex carrier is contacted with the opposing party in described Nonmetallocene part with being selected from described chemical processing agent, thereby obtain the contact procedure of described load type non-metallocene catalyst.
Below first to obtaining the step of magnesium compound solution, describe.
According to one embodiment of the invention, described magnesium compound is 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., preferred magnesium chloride wherein.
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 preferably 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 preferably 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 preferably 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), selenium alkynide (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., preferred butyl magnesium ethylate wherein.
These magnesium compounds can be used separately a kind of, also can multiple mixing use, not special restriction.For example, arbitrarily mol ratio is between the two such as being 0.25～4, preferably 0.5～3, more preferably 1～2.
To the dissolution time in magnesium compound solution preparation process, there is no particular limitation, but be generally 0.5～24 hour.Be known that when selecting temperature lower, should adopt long dissolution time, and when selecting temperature higher, can adopt shorter dissolution time.For example, while dissolving at the temperature lower than 5 ℃ of solvent boiling points, dissolution time is 0.5～4 hour, and while dissolving at 20 ℃, dissolution time is 4～24 hours.In this preparation process, can utilize to stir to promote the dissolving of magnesium compound in mixed solvent.This stirring can adopt any form, and such as stirring rake etc., its rotating speed is generally 10～1000 revs/min.
In the preparation process of this magnesium compound solution, described alcohol is such as being selected from one or more in fatty alcohol, aromatic alcohol and alicyclic ring alcohol, and the group that described alcohol can be optionally selected from alkyl, halogen atom and alkoxyl group replaces, wherein preferred fat alcohol.For example, fatty alcohol 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 separately a kind of, also can multiple mixing use.
When the described magnesium compound solution of preparation, in the described magnesium compound of magnesium elements and the mol ratio of tetrahydrofuran (THF) be generally 1: 6～40, preferably 1: 8～20, and in the described magnesium compound of magnesium elements and the mol ratio of described alcohol be generally 1: 1～8, preferably 1: 0.5～4.
By porous support is mixed with the magnesium compound solution of described acquisition, thereby obtain mixed serum.
The present invention's porous support used can be that surface is with the porosu solid arbitrarily of functional group, such as being selected from one or more in the organic materials that contains surperficial organo-functional group and the inorganic materials that contains surface functional group, the wherein said organic materials that contains surperficial organo-functional group has surperficial organo-functional group (such as being selected from hydroxyl such as being selected from, primary amino, secondary amino group, sulfonic group, carboxyl, amide group, the mono-substituted amide group of N-, sulfoamido, the mono-substituted sulfoamido of N-, sulfydryl, acylimino or hydrazide group) polyethylene, polypropylene, polybutene, polyvinyl alcohol, cyclodextrin and above-mentioned polymkeric substance based on the multipolymer of monomer, polyester, polymeric amide, polyvinyl chloride, polyacrylic ester, polymethacrylate, polystyrene and partial cross-linked polymkeric substance, wherein preferably partial cross-linked and there is the styrene polymer of surperficial carboxyl.The described inorganic materials that contains surface functional group is such as selecting free periodic table of elements IIA, IIIA, the oxide compound that one or more elements of IVAHe IVB family metal form, and halogenide, such as enumerating silicon-dioxide (being called again silicon oxide or silica gel), aluminum oxide, magnesium oxide, titanium oxide, zirconium white, Thorotrast and its oxidation mixture or mixed oxide, and magnesium chloride, wherein its surface functional group can be selected from hydroxyl and carboxyl, the oxide compound being generated by pyrohydrolysis by gaseous metal halogenide or gaseous silicon compound, such as the silica gel being obtained by hydrolyzing silicon tetrachloride, the aluminum oxide being obtained by aluminum chloride hydrolysis etc., or can also enumerate clay, molecular sieve, mica, polynite, wilkinite, diatomite, ZSM-5 and MCM-41 etc.Wherein, preferred surface has the inorganic materials of hydroxyl, such as enumerating silicon-dioxide, aluminum oxide, magnesium oxide, titanium dioxide, molecular sieve and polynite etc., or silicon-dioxide and be selected from HA or the mixed oxide of IIIA family metal oxide, such as silica-magnesia mixed oxide, silica-alumina mixed oxide, silicon-dioxide particularly preferably wherein.
According to the present invention, suitable silicon-dioxide can be manufactured by ordinary method, or can be the commerical prod that can buy arbitrarily, such as enumerating Grace 955, Grace 948, GraceSP9-351, Grace SP9-485, Grace SP9-10046, Davsion Syloid 245, ES70, ES70X, ES70Y, ES70W, ES757, EP10X, EP11, Aerosil812, CS-2133 and MS-3040.
According to the present invention, to the surface-area of this porous support, there is no particular limitation, but be generally 10～1000m
2/ g (BET method mensuration), preferably 100～600m
2/ g; The pore volume of this porous support (determination of nitrogen adsorption) is generally 0.1～4cm
3/ g, preferably 0.2～2cm
3/ g, and its median size (laser particle analyzer mensuration) preferably 1～500 μ m, more preferably 1～100 μ m.
According to the present invention, described porous support can be form arbitrarily, such as granular, spherical, aggregate or other form.
According to the present invention, in a preferred embodiment, before use (before mixing with magnesium compound solution) inorganic porous carrier of the present invention is carried out to thermal activation treatment.This thermal activation treatment can be carried out according to common mode, such as under reduced pressure or under inert atmosphere, porous support being carried out to heat treated.Here said inert atmosphere refers to and in gas, only contains extremely micro-or do not contain the component that can react with porous support, such as enumerating nitrogen and rare gas etc.While carrying out thermal activation, Heating temperature is such as being 200-800 ℃, and preferably 400～700 ℃, most preferably 400～650 ℃, heat-up time is such as being 0.5～24h, preferably 2～12h, most preferably 4～8h.According to the present invention, this reactivation process is preferably carried out under nitrogen or argon gas atmosphere, preferably under nitrogen atmosphere, carries out.Those skilled in the art know, through the carrier of thermal activation, generally will under inert atmosphere, preserve.
According to the present invention, also preferably before use (before mixing with magnesium compound solution) Porous-Organic carrier of the present invention is carried out to thermal activation treatment, the main purpose of wherein this Porous-Organic carrier being carried out to thermal activation is to remove the water of Porous-Organic carrier surface absorption.Due to the poor heat resistance of Porous-Organic carrier, so this thermal activation process can not be destroyed structure and the essentially consist of Porous-Organic carrier itself.This thermal activation treatment can be carried out according to common mode, such as under reduced pressure or under inert atmosphere, porous support being heated.Here said inert atmosphere refers to and in gas, only contains extremely micro-or do not contain the component that can react with porous support, such as enumerating nitrogen and rare gas etc.Usually, the temperature of this thermal activation is 50～400 ℃, and preferably 100～250 ℃, the thermal activation time is 1～24 hour, preferably 2～12h.According to the present invention, this reactivation process is preferably carried out under nitrogen or argon gas atmosphere, preferably under nitrogen atmosphere, carries out.Those skilled in the art know, through the carrier of thermal activation, generally will under inert atmosphere, preserve.
Porous support of the present invention (through thermal activation or without thermal activation, preferably through thermal activation) can adopt usual method to carry out with the mixing process of magnesium compound solution, and there is no particular limitation.Generally speaking, this mixes lasting 0.1～8 hour, and preferably 0.5～4 hour, optimum 1～2 hour, and mixing temperature is the solvent temperature of magnesium compound.In this mixing process, can utilize to stir to promote mixing efficiency.This stirring can adopt any form, and such as stirring rake etc., its rotating speed is generally 10～1000 revs/min.
In this mixing process, the mass ratio of described magnesium compound and described porous support is 1: 0.5～4, preferably 1: 1～2.
By dry described mixed serum, can obtain complex carrier.
Described mixed serum is half-dried not wet system, does not have free liquid, and direct drying after stirring can form the solid materials of good fluidity, can obtain complex carrier of the present invention.Although unessential, in order to ensure the homogeneity of system, this mixed serum dry will be through certain hour as last airtight standing, its time is 2～48 hours, preferably 4～24 hours, most preferably 6～18 hours.
Drying temperature to this mixed serum is not particularly limited, and can suitably select as required.If select the boiling point of alcohol lower in mixed serum, should select lower drying temperature, otherwise select higher drying temperature.Such as for ethanol, drying temperature can be chosen as 40～120 ℃, and for butanols, drying temperature can be chosen as 60～140 ℃.
Complex carrier of the present invention can directly be used for carrying out described treatment step, but one preferred embodiment in, before carrying out described treatment step, with the chemical processing agent that helps that is selected from aikyiaiurnirsoxan beta, aluminum alkyls and its mixture, anticipate described complex carrier (pre-treatment step).
Described aikyiaiurnirsoxan beta can be selected from the line style aikyiaiurnirsoxan beta R shown in following general formula (I)
2-Al-(Al (R)-O) n-O-AlR
2, and the ring-type aikyiaiurnirsoxan beta shown in following general formula (II)-(Al (R)-O-)
n+2.
Wherein, R group can be same to each other or different to each other, 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, preferably 10～30.
Concrete example, this aikyiaiurnirsoxan beta is preferably selected from methylaluminoxane, ethylaluminoxane, 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 separately a kind of, or are used in combination multiple.
Described aluminum alkyls is for having the compound of following general formula (III):
Al(R)
3 (III)
Wherein R group can be same to each other or different to each other, 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 preferably trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, most preferably triethyl aluminum and triisobutyl aluminium.
These aluminum alkylss can be used separately a kind of, or are used in combination multiple.
According to the present invention, as the described chemical processing agent that helps, can only adopt aikyiaiurnirsoxan beta, also can only adopt aluminum alkyls, also can adopt its one or more mixture separately.And to the ratio of each composition in this mixture, there is no particular limitation, can select arbitrarily as required.
When carrying out this pre-treatment given to this invention, take Al element described in to help chemical processing agent and the ratio of described complex carrier be 0.25～4 mmole: 1 gram, preferred 0.5～2 mmole: 1 gram.
As the method for carrying out described pre-treatment step, can enumerate following methods.First described in preparation, help the solution of chemical processing agent, then normal temperature at the temperature below the boiling point of solvent in solution to complex carrier add specified amount described in help chemical processing agent, react 0.5～6 hour (if desired by stirring), thereby obtain through this pretreated described complex carrier.The pre-treatment complex carrier obtaining can be by filtering and wash (1～6 time, preferably 1～3 time) mode from mixed solution, separate standby (preferably finally through super-dry), but also can be separated and be directly used for carrying out the treatment step with chemical processing agent as described below.
When helping chemical treatment agent solution described in preparation, to used solvent, there is no particular limitation, as long as it can dissolve this and help chemical processing agent.Particularly, can enumerate alkane or halogenated alkane, C6～C12 aromatic hydrocarbons or the halogenated aryl hydrocarbon etc. of C5～C12, such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, hexanaphthene, toluene, ethylbenzene, dimethylbenzene, chloro-pentane, chloro-hexane, chloro heptane, chloro octane, chloro nonane, chloro decane, chloro undecane, chlorinated dodecane, chlorocyclohexane, chlorotoluene, chloro ethylbenzene and xylene monochloride etc., wherein preferably pentane, hexane, decane, hexanaphthene and toluene, most preferably hexane and toluene.
It should be noted in the discussion above that because complex carrier of the present invention contains magnesium compound, thus now can not select can dissolved magnesium compound solvent, such as ether solvent, further such as tetrahydrofuran (THF) etc.
These solvents can be used separately a kind of, or are used in combination multiple.
In addition, to described, help the concentration of chemical processing agent in its solution there is no particular limitation, can suitably select as required, if can realize described complex carrier given to this invention with described in help the molar ratio range of chemical processing agent.
As previously mentioned, complex carrier of the present invention can directly be used for carrying out described treatment step, but also can be used further to this treatment step through after aforesaid pre-treatment step.
According to the present invention, when carrying out this treatment step, with a side who is selected from chemical processing agent and Nonmetallocene part, process described complex carrier, to obtain modification complex carrier.
Below first with regard to the situation of using chemical processing agent to process described complex carrier, describe.
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, metal alkyl halides HeIVB family of 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 WeiIVB family metal, such as titanium, zirconium, hafnium etc.;
X is halogen, such as F, Cl, Br, I;
R
1and R
2be selected from independently of one another C
1-C
30alkyl, 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-Butoxyl titanium-chlorides (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-Butoxyl titanium-chlorides (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, preferably 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 separately a kind of, or are used in combination multiple.
When selecting described chemical processing agent to process described complex carrier, as the method for carrying out described treatment step, as long as can realize described complex carrier (hereinafter, described complex carrier comprises complex carrier itself and the pretreated complex carrier of process) obtain modification complex carrier with the processing of described chemical processing agent, be not particularly limited, can enumerate following method, but be not limited to this.
In the situation that adopting solid chemical processing agent (such as zirconium tetrachloride), first prepare the solution of described chemical processing agent, then to complex carrier, add the described chemical processing agent of (preferably dripping) specified amount; In the situation that adopting 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 to (preferably dripping) in complex carrier, contact reacts (if desired by stirring) is carried out 0.5～24 hour, preferably 1～8 hour, more preferably 2～6 hours, most preferably 2～4 times, then filter and wash, then dry, obtain thus modification complex carrier.
Described filtration, washing and dryly can adopt ordinary method to carry out, wherein washer solvent can adopt identical solvent used when dissolving solid chemical processing agent.This washing is generally carried out 1～8 time, and preferably 2～6 times, most preferably 2～4 times.
While carrying out this treatment step, as the consumption of this chemical processing agent, the described chemical processing agent of YiIVB family metallic element meter and the mol ratio of described Nonmetallocene part are 1: 0.1～1, preferably 1: 0.3～0.9.
When the solution of the described chemical processing agent of preparation, to used solvent, there is no particular limitation, can be suitable for preparation used those while helping chemical treatment agent solution.It should be noted in the discussion above that now can not select can dissolved magnesium compound solvent, such as ether solvent, further such as tetrahydrofuran (THF) etc.
These solvents can be used separately a kind of, or are used in combination multiple.
There is no particular limitation for concentration to described chemical processing agent in its solution, can suitably select as required, as long as can reach the chemical processing agent consumption of the present invention's regulation.
According to the present invention, to the temperature of described treatment step now, also there is no particular limitation.Although select higher temperature of reaction to contribute to reacting of chemical processing agent and complex carrier, can reduce the reaction times.But because solvent is different, its boiling point is also different.Those skilled in the art know, the temperature of reaction of chemical processing agent and complex carrier should be lower than the boiling point of solvent, and such as for hexane, temperature of reaction can be chosen between 20 ℃～65 ℃, for toluene, can be chosen between 20 ℃～105 ℃ etc.Therefore, temperature of reaction is different with the difference of solvent, cannot treat different things as the same, but is typically chosen in lower than between 5～10 ℃ of solvent boiling points, but the lower limit of temperature is not limited.In addition, the time of this treating processes is had no particular limits, generally can select 0.5～24 hour.In the situation that improving temperature of reaction, the reaction times can be suitably shorter.
It is pointed out that, in this treatment step, the use of solvent is not essential.That is to say, described chemical processing agent can not carry out with reacting of described complex carrier in the situation that there is no solvent, but now chemical processing agent is necessary for liquid state.Temperature of reaction now and reaction times can be as required suitably determines, generally speaking, temperature of reaction should be at least lower than 5～10 ℃ of the boiling points of chemical processing agent, the contact reacts time is generally 2～24 hours.For example, chemical processing agent is fiercer with reacting of complex carrier, and temperature of reaction just arranges lowlyer, makes thus the reaction times longer.Such as, when chemical processing agent is titanium tetrachloride, temperature of reaction can be-30 ℃～126 ℃, the corresponding reaction times is 2～12 hours.
Then,, with regard to the situation of using Nonmetallocene part to process described complex carrier, describe.
Described Nonmetallocene part is selected from the compound with following structure:
At one more specifically in embodiment, described Nonmetallocene part is selected from has (A) of following structure and (B) compound:
At one, more specifically in 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, phosphorous 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, containing seleno, rolls into a ball 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, containing seleno, rolls into a ball 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 independently of one another nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno, roll into a ball or phosphorus-containing groups, such as can enumerate-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 be respectively coordination former in;
→ 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 independently of one another hydrogen, C
1-C
30the C of alkyl, halogen atom, replacement
1-C
30alkyl (preferred halo alkyl wherein, such as-CH
2cl and-CH
2cH
2cl) or safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group is 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 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
5during for oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups, R
5in N, O, S, P, Se be respectively ligating atom, and can carry out coordination by YuIVB 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;
Be selected from-SR of described sulfur-containing group
35,-T-SR
35,-S (O) R
36or-T-SO
2r
37;
Described containing be selected from-SeR of seleno group
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 with one or more inert substituents.So-called inertia, referring to these substituting groups pair does not have substantial interference with the coordination process of central metal atom.As non-specified otherwise, the C of described replacement
1-C
30alkyl generally refers to the C of halo
1-C
30alkyl, the C of halo
6-C
30aryl, the C of halo
8-C
30condensed ring radical or the C of halo
4-C
30heterocyclic radical;
Safing function group refers to other safing function base except 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.
Be selected from-SiR of described silicon-containing group
42r
43r
44,-T-SiR
45;
Described be selected from-GeR of germanic group
46r
47r
48,-T-GeR
49;
Described containing be selected from-SnR of tin group
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 independently of one another hydrogen, C
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 meet following condition:
(1) do not disturb the coordination process of YuIVB family atoms metal,
(2) all different from group A, D, E, F, Y and Z in structural formula, and
(3) coordination ability of YuIVB family atoms metal is lower than described A, D, E, F, Y and Z group, and do not replace the coordination of these groups YuIVB family atoms metal.
As this Nonmetallocene part, such as enumerating the compound with following structure:
Wherein, described Nonmetallocene part is preferably selected from the compound with following structure:
Wherein, described Nonmetallocene part is also preferably selected from the compound with following structure:
Described Nonmetallocene part is more preferably selected from the compound with following structure:
with
These Nonmetallocene parts can be used separately a kind of, or are used in combination multiple.
When selecting described Nonmetallocene part to process described complex carrier, as the method for carrying out described treatment step, as long as can realize described complex carrier (hereinafter, described complex carrier comprises complex carrier itself and the pretreated complex carrier of process) obtain modification complex carrier with the processing of described Nonmetallocene part, be not particularly limited, can enumerate following method, but be not limited to this.
First the solution of preparing described Nonmetallocene part.If what select is not to be very high solvent to the solubleness of described Nonmetallocene part, can select the mode of suitably heating to promote its dissolving; And for to the higher solvent of Nonmetallocene part solubleness, can not adopt type of heating.If need to stir, the rotating speed of this stirring is at 10～500 revs/min.Regulation according to the present invention to non-metallocene catalyst content in final load type non-metallocene catalyst, and the solvability of the solvent that adopts of this stage to this Nonmetallocene part, in solution, the mass concentration of this Nonmetallocene part is generally 0.02～0.30 grams per milliliter, preferably 0.05～0.15 grams per milliliter.
When carrying out this treatment step, with regard to the consumption of described Nonmetallocene part, by mass, described Nonmetallocene part is 0.05～0.50: 1 with the ratio of complex carrier to general provision, preferably 0.10～0.30: 1.
To solvent now used, there is no particular limitation, as long as can dissolve described Nonmetallocene part, such as being selected from:
Alkane, such as pentane, hexane, heptane, octane, nonane, decane etc.;
Naphthenic hydrocarbon, such as hexanaphthene, pentamethylene, suberane, cyclodecane, cyclononane etc.;
Halogenated alkane, 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, such as toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene etc.; With
Halogenated aromatic, 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.
It should be noted in the discussion above that now can not select can dissolved magnesium compound solvent, such as ether solvent, further such as tetrahydrofuran (THF) etc.
These solvents can be used separately a kind of, or are used in combination multiple.
Then, in room temperature, in the temperature range lower than 5 ℃ of solvent boiling points, under uniform stirring, in this Nonmetallocene ligand solution, add described complex carrier, continue reaction 0.5～24 hour.Stirring can adopt the modes such as helical-ribbon type stirring or the stirring of anchor formula, for helical-ribbon type, stirs, and stirring velocity is generally 5～50 revs/min, for anchor formula, stirs, and stirring velocity is generally 5～200 revs/min.
After reaction, by reaction mixture through filtering, washing and dry, or without filtration and washing and convection drying obtains modification complex carrier of the present invention.Generally speaking, for the lower reaction mixture of solid content, a kind of mode before adopting, and for the higher reaction mixture of solid content, a kind of mode after adopting.If desired, this washing is generally carried out 1～8 time, and preferably 2～6 times, most preferably 2～4 times.Describedly dry can adopt well-established law to carry out, such as rare gas element is dried, vacuumizes dry, or heating vacuumizes dryly, preferably vacuumizes dry.Generally speaking, be generally 2～24 hours time of drying, but actual can be by sampling, and thermal weight loss situation is per sample judged dry terminal.That is, at the temperature of 5～45 ℃ of the boiling points of the solvent lower than adopted, thermal weight loss is less than 5% and is dry terminal.When selecting lower boiling solvent, can adopt shorter time of drying, select high boiling solvent generally to adopt longer time of drying.Drying temperature is generally lower than 5～45 ℃ of the boiling points of solvent used, and when selecting toluene as solvent, drying temperature can be chosen between 65～105 ℃, and when selecting methylene dichloride as solvent, drying temperature can be chosen between 0～37 ℃ for another example, etc.
In addition, no matter select which side in Nonmetallocene part and chemical processing agent to carry out this treatment step, all can replace described complex carrier to carry out this treatment step with the mixed solution without excessively separated obtaining in aforementioned pre-treatment step.Now, owing to there being solvent in this mixed solution, so can omit the consumption that uses solvent or reduce solvent.
After having manufactured modification complex carrier of the present invention, by described modification complex carrier is contacted with the opposing party in described Nonmetallocene part with being selected from described chemical processing agent, thereby can obtain load type non-metallocene catalyst of the present invention.
That is to say, if used chemical processing agent in treatment step, in ensuing contact procedure, just only use Nonmetallocene part; And if in treatment step, used Nonmetallocene part, in ensuing contact procedure, just only use chemical processing agent.
According to the present invention, by described Nonmetallocene part (or described chemical processing agent) is contacted with described modification complex carrier, can make chemical processing agent (or Nonmetallocene part) contained in described Nonmetallocene part (or described chemical processing agent) and this modification complex carrier react, thereby original position generates Nonmetallocene title complex (reaction of original position loadization), obtains thus load type non-metallocene catalyst of the present invention.
To the mode of carrying out of this contact procedure without any restriction, as long as can realize the reaction of this original position loadization.
Particularly, when adopting Nonmetallocene part to carry out this contact procedure, can enumerate and institute's same method that exemplifies (comprising reaction conditions and reagent dosage etc.) when adopting Nonmetallocene part to carry out aforementioned processing step before, nothing but complex carrier is replaced with to modification complex carrier; When adopting chemical processing agent to carry out this contact procedure, can enumerate and institute's same method that exemplifies (comprising reaction conditions and reagent dosage etc.) when adopting chemical processing agent to carry out aforementioned processing step before, nothing but complex carrier is replaced with to modification complex carrier.
In addition, consider the Nonmetallocene part that uses in described modification complex carrier and this contact procedure or the interaction between chemical processing agent, reacted mixed solution generally carries out 0.5～24 hour airtight aging at normal temperatures, to increase the bond strength between the two.
Those skilled in the art knows, above-described various contacts and treating processes are generally all carried out under strict anhydrous and oxygen-free condition, and said anhydrous and oxygen-free condition refers to that in system, the content of water and oxygen continues to be less than 10ppm here.And, load type non-metallocene catalyst of the present invention preparation afterwards conventionally under airtight nitrogen envelope pressure-fired save backup.
In one embodiment, the invention still further relates to the load type non-metallocene catalyst by preparation method's manufacture of aforementioned load type non-metallocene catalyst.
The load type non-metallocene catalyst that the present invention manufactures, forms catalyst system jointly with promotor, can be for the homopolymerization/copolymerization of catalyzed alkene.
By take load type non-metallocene catalyst of the present invention as Primary Catalysts, take, to be selected from one or more in aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt be promotor, homopolymerization and/or copolymerization that can catalyzed alkene.
To the homopolymerization of described alkene and/or copolymerization process, there is no particular limitation, 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 1,7-octadiene, and described other ethylenically unsaturated compounds can be enumerated vinyl acetate and (methyl) acrylate.Need to here be pointed out that, the said homopolymerization of the present invention refers to a kind of polymerization of alkene, and copolymerization refers to the polymerization between 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 mention when conduct helps chemical processing agent before can adopting, wherein preferable methyl aikyiaiurnirsoxan beta and triethyl aluminum.
Preparation method's technique simple possible of load type non-metallocene catalyst of the present invention, and the charge capacity of Nonmetallocene part is adjustable, can improve significantly its charge capacity, improves significantly thus the polymerization activity of this catalyzer.
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.
Adopt method for preparing catalyst provided by the invention, the combination of Nonmetallocene part and porous support is tight, has effectively avoided the impact of free ligand on load type non-metallocene catalyst polymerization, thereby makes the performance of this catalyzer more stable.
When the load type non-metallocene catalyst that employing the present invention obtains and promotor form catalyst system, only need fewer promotor (such as methylaluminoxane or triethyl aluminum) consumption, just can obtain high olefin polymerizating activity.And the polymkeric substance such as resulting polyethylene has good polymer morphology and high polymer bulk density thus.
The present invention finds, by loaded catalyst provided by the invention, shows high comonomer effect, and, under identical polymerizing condition, the Copolymerization activity of catalyzer is active higher than homopolymerization, and under same polymeric condition, the bulk density of multipolymer is higher than homopolymer.
By further polymerization studies, find, by the copolymerization effect of load type non-metallocene catalyst provided by the invention, be mainly derived from the effect of Nonmetallocene part, and activity mainly in load type non-metallocene catalyst active metallic content determine.
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 mensuration of loaded catalyst ZhongIVB family metal content adopts ICP-AES to measure, and part assay adopts elemental analysis method to measure.
The polymerization activity of catalyzer calculates in accordance with the following methods: after polyreaction finishes, polymerisate in reactor is filtered and is dried, then weigh the quality of this polymerisate, with this polymerisate quality, divided by the ratio of the quality of load type non-metallocene catalyst used, represent the polymerization activity (unit is kg polymkeric substance/gCat) of catalyzer.
Embodiment 1
Porous support adopts silica gel (ES757 of Ineos company).This silica gel is continued to roasting 4h and thermal activation under 600 ℃, nitrogen atmosphere.Magnesium compound adopts Magnesium Chloride Anhydrous, and alcohol adopts ethanol, and chemical processing agent adopts titanium tetrachloride.
Take 5g Magnesium Chloride Anhydrous, add tetrahydrofuran (THF) and dehydrated alcohol, be heated to 60 ℃ to dissolving completely, add while hot 10g through the silica gel of thermal activation, stir, after standing 12 hours, vacuum-drying at homogeneous heating to 90 ℃, obtains 19.6g complex carrier.
Take 5g complex carrier, add 50ml hexane, stir and use 30 minutes and be added dropwise to titanium tetrachloride, at 60 ℃, stirring reaction is 4 hours, filters, and adopts hexane washing 3 times, each hexane consumption 25ml, be then heated to 90 ℃ dry 4 hours, obtain modification complex carrier.
By structural formula
nonmetallocene part, be dissolved in hexane, then add modification complex carrier, stirring reaction 4 hours, filters, and adopts hexane washing 2 times, each hexane consumption 25ml, the then dry load type non-metallocene catalyst that obtains for 4 hours at 25 ℃.
Wherein proportioning is, magnesium chloride and tetrahydrofuran (THF) mol ratio are 1: 3.5; Magnesium chloride and ethanol mol ratio are 1: 4.07; The mass ratio of magnesium chloride and porous support is 1: 2; The proportioning of titanium tetrachloride and complex carrier is 9.4 mmoles: 1 gram.Nonmetallocene part mass concentration is 0.05 grams per milliliter, and the quality proportioning of Nonmetallocene part and complex carrier is 0.10: 1.
Load type non-metallocene catalyst is designated as CAT-1, and titanium content is 2.94wt%, and Nonmetallocene part mass content is 0.87%.
Embodiment 1-1
Substantially the same manner as Example 1, but have following change:
Porous support adopts aluminium sesquioxide.Aluminium sesquioxide is continued under 700 ℃, nitrogen atmosphere to roasting 6h.
Magnesium compound is changed into magnesium bromide (MgBr
2), alcohol adopts butanols, and chemical processing agent adopts titanium tetrabromide (TiBr
4).
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into decane.
Wherein proportioning is, magnesium bromide and tetrahydrofuran (THF) mol ratio are 1: 5; Magnesium bromide and butanols mol ratio are 1: 3.5; The mass ratio of magnesium bromide and porous support is 1: 1.4; Titanium tetrabromide and complex carrier proportioning are 7.64 mmoles: 1 gram.Nonmetallocene part mass concentration is 0.11 grams per milliliter, and Nonmetallocene part and complex carrier quality proportioning are 0.22: 1.
Embodiment 1-2
Substantially the same manner as Example 1, but have following change:
Porous support adopts molecular sieve.Molecular sieve is continued under 450 ℃, argon gas atmosphere to roasting 4h.
Magnesium compound is changed into oxyethyl group magnesium chloride (MgCl (OC
2h
5)), alcohol adopts phenylethyl alcohol, and chemical processing agent adopts zirconium tetrachloride (ZrCl
4).
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into methylene dichloride.
Wherein proportioning is, oxyethyl group magnesium chloride and tetrahydrofuran (THF) mol ratio are 1: 4.3; Magnesium bromide and butanols mol ratio are 1: 6; The mass ratio of oxyethyl group magnesium chloride and porous support is 1: 1; Zirconium tetrachloride and complex carrier proportioning are 9.31 mmoles: 1 gram.First zirconium tetrachloride is dissolved in toluene, is made into mass content and is 10% solution, then joins in complex carrier.Nonmetallocene part mass concentration is 0.15 grams per milliliter, and Nonmetallocene part and complex carrier quality proportioning are 0.30: 1.
Embodiment 1-3
Substantially the same manner as Example 1, but have following change:
Porous support adopts titanium dioxide.Titanium dioxide is continued under 550 ℃, argon gas atmosphere to roasting 2h.
Magnesium compound is changed into magnesium ethylate (Mg (OC
2h
5)
2), alcohol adopts ethyl cyclohexanol.Chemical processing agent is changed into tetramethyl-titanium.
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into hexanaphthene.
Wherein proportioning is, magnesium ethylate and tetrahydrofuran (THF) mol ratio are 1: 4.3; Magnesium ethylate and ethyl cyclohexanol mol ratio are 1: 6; The mass ratio of magnesium ethylate and porous support is 1: 4; .Tetramethyl-titanium and complex carrier proportioning are 6.37 mmoles: 1 gram, Nonmetallocene part mass concentration is 0.02 grams per milliliter, and Nonmetallocene part and complex carrier quality proportioning are 0.48: 1.
Embodiment 1-4
Substantially the same manner as Example 1, but have following change:
Porous support adopting montmorillonite.Polynite is continued under 400 ℃, nitrogen atmosphere to roasting 8h.
Magnesium compound is changed into ethylmagnesium chloride (Mg (C
2h
5) Cl), alcohol adopts trichlorine methyl alcohol.
Chemical processing agent is changed into tetramethoxy titanium.
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into toluene.
Wherein proportioning is, ethylmagnesium chloride and tetrahydrofuran (THF) mol ratio are 1: 2.5; Ethylmagnesium chloride and trichlorine methyl alcohol mol ratio are 1: 4.4; The mass ratio of ethylmagnesium chloride and porous support is 1: 1.76; Tetramethoxy titanium and complex carrier proportioning are 2.64 mmoles: 1 gram, Nonmetallocene part mass concentration is 0.28 grams per milliliter, and Nonmetallocene part and complex carrier quality proportioning are 0.01: 1.
Embodiment 1-5
Substantially the same manner as Example 1, but have following change:
Porous support adopts silicon-dioxide-aluminium sesquioxide (dioxide-containing silica is 60 quality %) mixed oxide.Silicon-dioxide-aluminium sesquioxide mixed oxide is continued under 600 ℃, nitrogen atmosphere to roasting 12h.
Magnesium compound is changed into isobutoxy magnesium (Mg (i-OC
4h
9)
2), alcohol adopts glycol-ether.
Chemical processing agent is changed into tetramethoxy zirconium.
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into dimethylbenzene.
Nonmetallocene part mass concentration is 0.05 grams per milliliter, and Nonmetallocene part and complex carrier quality proportioning are 0.10: 1.
Embodiment 1-6
Substantially the same manner as Example 1, but have following change:
Porous support adopts the silica gel being obtained by hydrolyzing silicon tetrachloride.The silica gel being obtained by hydrolyzing silicon tetrachloride is continued under 650 ℃, argon gas atmosphere to roasting 6h.
Magnesium compound is changed into magnesium ethide (Mg (C
2h
5)
2),
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into hexanaphthene.
Embodiment 1-7
Substantially the same manner as Example 1, but have following change:
Porous support adopts spherical polystyrol.This spherical polystyrol is continued under 200 ℃, nitrogen atmosphere to dry 8h.
Magnesium compound is changed into isobutyl-magnesium (Mg (i-C
4h
9)
2),
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into methylcyclohexane.
Reference example 1-1
Substantially the same manner as Example 1, but have following change:
The quality proportioning of Nonmetallocene part and complex carrier is 0.20: 1.
In load type non-metallocene catalyst, titanium mass content is 2.77%, and Nonmetallocene part mass content is 1.52%.
Catalyzer is designated as CAT-A.
From this reference example, other processes are identical, but in load type non-metallocene catalyst, the content of titanium reduces.This phenomenon is because the increase of Nonmetallocene part add-on causes the charge capacity of load type non-metallocene catalyst due to increasing.This explanation adopts the preparation method of load type non-metallocene catalyst of the present invention, 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 have following change:
The quality proportioning of Nonmetallocene part and porous support is 0.05: 1.
In load type non-metallocene catalyst, titanium mass content is 3.00%, and Nonmetallocene part mass content is 0.91%.
Catalyzer is designated as CAT-B.
Under the identical condition of Nonmetallocene part add-on, it is known that in load type non-metallocene catalyst, titanium content increases, polymerization activity increases this phenomenon, adopt the preparation method of load type non-metallocene catalyst of the present invention, can pass through to adopt different chemical processing agent consumptions, and obtain the active different load type non-metallocene catalyst of catalysis in olefine polymerization.
Embodiment 2
The preparation process of complex carrier is with embodiment 1.
Hereinafter, for the event of simplicity of exposition, by chemical processing agent and help the combination of chemical processing agent to be referred to as composite treating agent, and take chemical processing agent and determine the consumption that helps chemical processing agent as benchmark, but this with the present invention before specialized range generation contradiction.
Chemical processing agent adopts titanium tetrachloride and methylaluminoxane composite treating agent.The toluene solution that first adds methylaluminoxane, react after 1.5 hours, filter, 50ml hexane washing 1 time, then with 30 minutes dropping titanium tetrachlorides, at 60 ℃, stirring reaction is 2 hours, filter hexane washing 3 times, each hexane consumption 25ml, then be heated to 90 ℃ of vacuum-dryings 4 hours, obtain modification complex carrier.
By structural formula
nonmetallocene part, be dissolved in hexane, then add modification complex carrier, stirring reaction 4 hours, filters, hexane washing 2 times, each hexane consumption 25ml, the then dry load type non-metallocene catalyst that obtains for 4 hours at 25 ℃.
Wherein proportioning is, the proportioning of titanium tetrachloride and complex carrier is 9.4 mmoles: 1 gram, and methylaluminoxane and titanium tetrachloride mol ratio 1: 1.Nonmetallocene part mass concentration is 0.05 grams per milliliter, and the quality proportioning of Nonmetallocene part and complex carrier is 0.10: 1.
Load type non-metallocene catalyst is designated as CAT-2, and titanium content is 3.08wt%.
Embodiment 2-1
Substantially the same manner as Example 2, but have following change:
The preparation process of complex carrier is with embodiment 1-1.
Nonmetallocene part is changed into
Chemical processing agent adopts titanium tetrachloride and methylaluminoxane composite treating agent.The toluene solution that first adds methylaluminoxane, reacted after 1.5 hours, filters, and pentane washing 1 time, then with 30 minutes dropping titanium tetrachlorides., the solvent that dissolves Nonmetallocene part is changed into hexanaphthene
Wherein proportioning is, titanium tetrachloride and complex carrier proportioning are 6.37 mmoles: 1 gram, and methylaluminoxane and titanium tetrachloride mol ratio 1: 1.Nonmetallocene part mass concentration is 0.02 grams per milliliter, and Nonmetallocene part and complex carrier quality proportioning are 0.48: 1.
Embodiment 2-2
Substantially the same manner as Example 2, but have following change:
The preparation process of complex carrier is with embodiment 1-2.
Chemical processing agent adopts titanium tetrachloride and isobutyl aluminium alkoxide composite treating agent.The toluene solution that first adds isobutyl aluminium alkoxide, reacted after 1.5 hours, filters, and toluene wash 1 time, then drip titanium tetrachloride.
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into toluene.
Wherein proportioning is, titanium tetrachloride and complex carrier proportioning are 2.64 mmoles: 1 gram, and isobutyl aluminium alkoxide and titanium tetrachloride mol ratio 2.7: 1.Nonmetallocene part mass concentration is 0.28 grams per milliliter, and part and complex carrier quality proportioning are 0.01: 1.
Embodiment 2-3
Substantially the same manner as Example 2, but have following change:
The preparation process of complex carrier is with embodiment 1-3.
Chemical processing agent adopts titanium tetrachloride and triethyl aluminum composite treating agent.The hexane solution that first adds triethyl aluminum, reacted after 1.5 hours, filters, and dimethylbenzene washing 1 time, then drip titanium tetrachloride.Titanium tetrachloride and complex carrier proportioning are 7.42 mmoles: 1 gram, and triethyl aluminum and titanium tetrachloride mol ratio 0.54: 1.
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into dimethylbenzene.
Nonmetallocene part mass concentration is 0.05 grams per milliliter, and Nonmetallocene part and complex carrier quality proportioning are 0.10: 1.
Embodiment 2-4
Substantially the same manner as Example 1, but have following change:
The preparation process of complex carrier is with embodiment 1-4.
Chemical processing agent adopts titanium tetrachloride and three second butyl aluminium composite treating agents.The hexane solution that first adds three second butyl aluminium, reacted after 1.5 hours, filters, and chloro-hexane washing 1 time, then drip titanium tetrachloride.Titanium tetrachloride and complex carrier proportioning are 1.92 mmoles: 1 gram, and three second butyl aluminium and titanium tetrachloride mol ratio 1.24: 1.
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into chloro-hexane.
Embodiment 2-5
Substantially the same manner as Example 2, but have following change:
The preparation process of complex carrier is with embodiment 1-5.
Chemical processing agent adopts zirconium tetrachloride and methylaluminoxane composite treating agent.The toluene solution that first adds methylaluminoxane, reacted after 1.5 hours, filtered, and methylcyclohexane washs 1 time, then dripped the toluene solution of zirconium tetrachloride.Zirconium tetrachloride and complex carrier proportioning are 5.54 mmoles: 1 gram, and methylaluminoxane and zirconium tetrachloride mol ratio 1: 1.
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into methylcyclohexane.
Embodiment 2-6
Substantially the same manner as Example 2, but have following change:
The preparation process of complex carrier is with embodiment 1-6.
Chemical processing agent adopts zirconium tetrachloride and triethyl aluminum composite treating agent.The hexane solution that first adds triethyl aluminum, reacted after 1.5 hours, filtered, and chloro-hexane washs 1 time, then dripped the toluene solution of zirconium tetrachloride.Zirconium tetrachloride and complex carrier proportioning are 5.37 mmoles: 1 gram, and triethyl aluminum and titanium tetrachloride mol ratio 0.54: 1.
Nonmetallocene part is changed into
Embodiment 2-7
Substantially the same manner as Example 2, but have following change:
The preparation process of complex carrier is with embodiment 1-7.
Chemical processing agent adopts tetraethyl-titanium and triethyl aluminum composite treating agent.The hexane solution that first adds triethyl aluminum, reacted after 1.5 hours, filtered, and hexanaphthene washs 1 time, then dripped the cyclohexane solution of tetraethyl-titanium.
Nonmetallocene part is changed into
Embodiment 3
The preparation process of complex carrier is with embodiment 1.
To there is structural formula
nonmetallocene part is dissolved in 50ml hexane, then adds 5g complex carrier, and 25 ℃ of stirring reactions filtered after 4 hours, hexane washing 2 times, each hexane consumption 25ml, vacuum-drying 2 hours at 25 ℃ afterwards.Then add 50ml hexane, under agitation condition, with 30 minutes, drip chemical processing agent titanium tetrachloride, at 60 ℃, stirring reaction is 4 hours, filter, hexane washing 3 times, each hexane consumption 25ml, then 25 ℃ of vacuum-dryings obtain load type non-metallocene catalyst for 6 hours.
Wherein proportioning is, Nonmetallocene part mass concentration is 0.05 grams per milliliter, and the quality proportioning of Nonmetallocene part and complex carrier is 0.10: 1, and the proportioning of titanium tetrachloride and complex carrier is 9.4 mmoles: 1 gram,
Load type non-metallocene catalyst is designated as CAT-3, and titanium content is 3.27wt%.
Embodiment 3-1
Substantially the same manner as Example 3, but have following change:
The preparation process of complex carrier is with embodiment 1-1.
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into decane.
Chemical processing agent changes titanium tetrabromide into.
Wherein proportioning is, Nonmetallocene part mass concentration is 0.11 grams per milliliter, and Nonmetallocene part and complex carrier quality proportioning are 0.22: 1, and titanium tetrabromide and complex carrier proportioning are 7.64 mmoles: 1 gram.
Embodiment 3-2
Substantially the same manner as Example 3, but have following change:
The preparation process of complex carrier is with embodiment 1-2.
Chemical processing agent adopts zirconium tetrachloride (ZrCl
4).
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into methylene dichloride.
Wherein proportioning is, Nonmetallocene part mass concentration is 0.15 grams per milliliter, and Nonmetallocene part and complex carrier quality proportioning are 0.30: 1.Zirconium tetrachloride and complex carrier proportioning are 9.31 mmoles: 1 gram.Zirconium tetrachloride need to be dissolved in toluene, is made into mass content and is 10% solution, and then joins in the complex carrier that Nonmetallocene part processes.
Embodiment 3-3
Substantially the same manner as Example 3, but have following change:
The preparation process of complex carrier is with embodiment 1-3.
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into hexanaphthene.
Chemical processing agent is changed into tetramethyl-titanium.
Wherein proportioning is, Nonmetallocene part mass concentration is 0.02 grams per milliliter, and Nonmetallocene part and complex carrier quality proportioning are 0.48: 1.Tetramethyl-titanium and complex carrier proportioning are 6.37 mmoles: 1 gram,
Embodiment 3-4
Substantially the same manner as Example 3, but have following change:
The preparation process of complex carrier is with embodiment 1-4.
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into toluene.
Chemical processing agent is changed into tetramethoxy titanium.
Wherein proportioning is, Nonmetallocene part mass concentration is 0.28 grams per milliliter, and Nonmetallocene part and complex carrier quality proportioning are 0.01: 1.Tetramethoxy titanium and complex carrier proportioning are 2.64 mmoles: 1 gram.
Embodiment 3-5
Substantially the same manner as Example 3, but have following change:
The preparation process of complex carrier is with embodiment 1-5.
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into dimethylbenzene.
Chemical processing agent is changed into tetramethoxy zirconium.
Nonmetallocene part mass concentration is 0.05 grams per milliliter, and Nonmetallocene part and complex carrier quality proportioning are 0.10: 1.
Embodiment 3-6
Substantially the same manner as Example 3, but have following change:
The preparation process of complex carrier is with embodiment 1-6.
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into hexanaphthene.
Embodiment 3-7
Substantially the same manner as Example 3, but have following change:
The preparation process of complex carrier is with embodiment 1-7.
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into methylcyclohexane.
Embodiment 4
The preparation process of complex carrier is with embodiment 1.
Chemical processing agent adopts titanium tetrachloride and methylaluminoxane composite treating agent.
First, to the toluene solution that adds methylaluminoxane in complex carrier 15 minutes, react after 1 hour, filter hexane washing 2 times, 25ml, then adds structural formula to be at every turn
the hexane solution of Nonmetallocene part, stirring reaction 2 hours, filters, hexane washing 2 times, each hexane consumption 25ml, dryly at 25 ℃ adds 50ml hexane after 2 hours, stirs and use 30 minutes to be added dropwise to titanium tetrachloride, at 60 ℃, stirring reaction is 4 hours, filter, adopt hexane washing 3 times, each hexane consumption 25ml, then under normal temperature, be dried 4 hours, obtain load type non-metallocene catalyst.
Wherein proportioning is, the proportioning of titanium tetrachloride and complex carrier is 9.4 mmoles: 1 gram, and methylaluminoxane and titanium tetrachloride mol ratio 1: 1.Nonmetallocene part mass concentration is 0.05 grams per milliliter, and the quality proportioning of Nonmetallocene part and complex carrier is 0.10: 1.
Load type non-metallocene catalyst is designated as CAT-4, and titanium content is 3.23wt%.
Embodiment 4-1
Substantially the same manner as Example 4, but have following change:
The preparation process of complex carrier is with embodiment 1-1.
Chemical processing agent adopts titanium tetrachloride and methylaluminoxane composite treating agent.
The toluene solution that first adds methylaluminoxane, filtration, toluene wash, adds Nonmetallocene part after dry.
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into hexanaphthene.Nonmetallocene part mass concentration is 0.02 grams per milliliter, and Nonmetallocene part and complex carrier quality proportioning are 0.48: 1.
Finally add titanium tetrachloride, titanium tetrachloride and complex carrier proportioning are 6.37 mmoles: 1 gram, and methylaluminoxane and titanium tetrachloride mol ratio 1: 1.
Embodiment 4-2
Substantially the same manner as Example 4, but have following change:
The preparation process of complex carrier is with embodiment 1-2.
Chemical processing agent adopts titanium tetrachloride and isobutyl aluminium alkoxide composite treating agent.The toluene solution that first adds isobutyl aluminium alkoxide.
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into toluene, and Nonmetallocene part mass concentration is 0.28 grams per milliliter, and Nonmetallocene part and complex carrier quality proportioning are 0.01: 1.
Finally add again titanium tetrachloride.Titanium tetrachloride and complex carrier proportioning are 2.64 mmoles: 1 gram, and isobutyl aluminium alkoxide and titanium tetrachloride mol ratio 2.7: 1.
Embodiment 4-3
Substantially the same manner as Example 4, but have following change:
The preparation process of complex carrier is with embodiment 1-3.
Chemical processing agent adopts titanium tetrachloride and triethyl aluminum composite treating agent.The hexane solution that first adds triethyl aluminum.
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into dimethylbenzene.Nonmetallocene part mass concentration is 0.05 grams per milliliter, and Nonmetallocene part and complex carrier quality proportioning are 0.10: 1.
Finally add again titanium tetrachloride.
Embodiment 4-4
Substantially the same manner as Example 4, but have following change:
The preparation process of complex carrier is with embodiment 1-4.
Chemical processing agent adopts titanium tetrachloride and three second butyl aluminium composite treating agents.The hexane solution that first adds three second butyl aluminium.
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into chloro-hexane.
Finally add titanium tetrachloride, titanium tetrachloride and complex carrier proportioning are 1.92 mmoles: 1 gram, and three second butyl aluminium and titanium tetrachloride mol ratio 1.24: 1.
Embodiment 4-5
Substantially the same manner as Example 4, but have following change:
The preparation process of complex carrier is with embodiment 1-5.
Chemical processing agent adopts zirconium tetrachloride and methylaluminoxane composite treating agent.The toluene solution that first adds methylaluminoxane, reacted after 1.5 hours, filters, and methylcyclohexane washing 1 time,
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into methylcyclohexane.
The last toluene solution that drips again zirconium tetrachloride.Zirconium tetrachloride and complex carrier proportioning are 5.54 mmoles: 1 gram, and methylaluminoxane and zirconium tetrachloride mol ratio 1: 1.
Embodiment 4-6
Substantially the same manner as Example 4, but have following change:
The preparation process of complex carrier is with embodiment 1-6.
Chemical processing agent adopts zirconium tetrachloride and triethyl aluminum composite treating agent.The hexane solution that first adds triethyl aluminum, reacted after 1.5 hours, filtered chloro-hexane washing 1 time, vacuum-drying 2 hours.
Nonmetallocene part is changed into
the solvent that dissolves Nonmetallocene part is changed into chloro-hexane.
The last toluene solution that drips again zirconium tetrachloride.Zirconium tetrachloride and complex carrier proportioning are 5.37 mmoles: 1 gram, and triethyl aluminum and titanium tetrachloride mol ratio 0.54: 1.
Embodiment 4-7
Substantially the same manner as Example 4, but have following change:
The preparation process of complex carrier is with embodiment 1-7.
Chemical processing agent adopts tetraethyl-titanium and triethyl aluminum composite treating agent.The hexane solution that first adds triethyl aluminum, reacted after 1.5 hours, filtered hexanaphthene washing 1 time, vacuum-drying 2 hours.
Nonmetallocene part is changed into
The last cyclohexane solution that drips again tetraethyl-titanium.
Embodiment 5 (Application Example)
The CAT-A, the CAT-B that in catalyzer CAT-1, the CAT-2, CAT-3, CAT-4 and the reference example that make in the embodiment of the present invention, make are carried out respectively to the homopolymerization of ethene under the following conditions in accordance with the following methods:
2 liters of polymerization autoclaves, slurry polymerization processes, 1 liter of hexane solvent, polymerization stagnation pressure 0.8MPa, 85 ℃ of polymerization temperatures, hydrogen partial pressure 0.2MPa, 2 hours reaction times.First 1 liter of hexane is joined in polymerization autoclave, open and stir, then add load type non-metallocene catalyst and catalyst mixture, then add hydrogen to 0.2MPa, finally continue to pass into ethene and make polymerization stagnation pressure constant in 0.8MPa.After reaction finishes, by gas reactor emptying, emit still interpolymer, the dry rear quality that weighs.The particular case of this polyreaction and polymerization evaluation result are as shown in table 1.
While carrying out the copolymerization of ethene and other alkene (being comonomer), its condition is on the basis of above ethylene homo, when passing into ethene after 5 minutes, by the disposable comonomer that pumps into of volume pump, its comonomer add-on is: every milligram of load type non-metallocene catalyst adds 1 gram of comonomer.
Table 1. load type non-metallocene catalyst polymerization results table look-up
| Sequence number | Catalyzer numbering | Promotor | Polymeric type | Comonomer kind | Active metal and promotor mol ratio | Polymerization activity (kgPE/gCat) | Polymer stacks density (g/cm 3) |
| 1 | CAT-1 | Triethyl aluminum | Homopolymerization | 140 | 6.44 | 0.33 | |
| 2 | CAT-1 | Triethyl aluminum | Homopolymerization | 500 | 6.53 | 0.33 | |
| 3 | CAT-1 | Triethyl aluminum | Copolymerization | Butene-1 | 140 | 7.73 | 0.35 |
| 4 | CAT-1 | Triethyl aluminum | Copolymerization | Hexene-1 | 140 | 7.51 | 0.36 |
| 5 | CAT-1 | Methylaluminoxane | Homopolymerization | 100 | 7.27 | 0.35 | |
| 6 | CAT-1 | Methylaluminoxane | Homopolymerization | 250 | 7.42 | 0.35 | |
| 7 | CAT-2 | Triethyl aluminum | Homopolymerization | 140 | 6.84 | 0.33 | |
| 8 | CAT-2 | Triethyl aluminum | Copolymerization | Butene-1 | 140 | 8.12 | 0.35 |
| 9 | CAT-2 | Methylaluminoxane | Homopolymerization | 100 | 7.95 | 0.35 | |
| 10 | CAT-3 | Triethyl aluminum | Homopolymerization | 140 | 7.11 | 0.34 | |
| 11 | CAT-3 | Triethyl aluminum | Copolymerization | Butene-1 | 140 | 8.67 | 0.37 |
| 12 | CAT-3 | Methylaluminoxane | Homopolymerization | 100 | 7.85 | 0.37 | |
| 13 | CAT-4 | Triethyl aluminum | Homopolymerization | 140 | 8.31 | 0.36 | |
| 14 | CAT-4 | Triethyl aluminum | Copolymerization | Butene-1 | 140 | 9.27 | 0.39 |
| 15 | CAT-4 | Methylaluminoxane | Homopolymerization | 100 | 8.88 | 0.40 | |
| 16 | CAT-A | Triethyl aluminum | Homopolymerization | 140 | 6.01 | 0.33 | |
| 17 | CAT-A | Triethyl aluminum | Copolymerization | Butene-1 | 140 | 7.04 | 0.35 |
| 18 | CAT-B | Triethyl aluminum | Homopolymerization | 140 | 6.74 | 0.33 | |
| 19 | CAT-B | Triethyl aluminum | Copolymerization | Butene-1 | 140 | 7.26 | 0.34 |
Contrast by sequence number 1 and 2,5 and 6 test-results data in table is known, and the consumption of increase promotor triethyl aluminum or methylaluminoxane is while improving aluminium titanium mol ratio, not remarkable on the impact of polymerization catalyst activity and polymer stacks density.It can be said that brightly, adopt load type non-metallocene catalyst prepared by method provided by the invention only to need fewer promotor consumption just can obtain high olefin polymerizating activity; And the polymkeric substance such as resulting polyethylene has good polymer morphology and high polymer bulk density thus.
By by sequence number 3,4 and 1, or 8 and 7, or 11 and 10, or 17 and 16 or 19 and 18 contrast knownly, and loaded catalyst of the present invention and load type non-metallocene catalyst all show high comonomer effect.Under identical polymerizing condition, the Copolymerization activity of catalyzer is active higher than homopolymerization, and under same polymeric condition, the bulk density of multipolymer is higher than homopolymer.
By sequence number 16,17 and 1,3 or come comparative catalyst CAT-A and CAT-1 by sequence number 18,19 and 1,3, and CAT-B and CAT-1, although can also find that CAT-A homopolymerization activity is lower than CAT-1, but the active amplitude that copolymerization effect increases is higher than the latter, although otherwise CAT-B homopolymerization activity higher than CAT-1, the active amplitude that copolymerization effect increases is lower than the latter.Thus explanation, copolymerization effect is mainly derived from the effect of Nonmetallocene part, and activity mainly in load type non-metallocene catalyst active metallic content determine.
Claims (34)
1. a preparation method for load type non-metallocene catalyst, comprises the following steps:
Make magnesium compound be dissolved in the mixed solvent being formed by tetrahydrofuran (THF) and alcohol, obtain the step of magnesium compound solution,
Porous support is mixed with described magnesium compound solution, obtains the step of mixed serum,
Dry described mixed serum, the step of acquisition complex carrier,
With a side who is selected from chemical processing agent and Nonmetallocene part, process described complex carrier, obtain the treatment step of modification complex carrier, wherein said chemical processing agent is selected from IV B family metallic compound; With
Described modification complex carrier is contacted with the opposing party in described Nonmetallocene part with being selected from described chemical processing agent, thereby obtains the contact procedure of described load type non-metallocene catalyst,
Wherein said 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,
sulfuryl or sulfoxide group;
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, phosphorous C
1-C
30alkyl, sulfuryl, sulfoxide group,
or
wherein N, O, S, Se, P are respectively ligating atom;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno, rolls into a ball 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
2and R
3be selected from independently of one another hydrogen, C
1-C
30the C of alkyl, halogen atom, replacement
1-C
30alkyl or safing function group, R
22and R
27be selected from independently of one another hydrogen, C
1-C
30the C of alkyl, halogen atom or replacement
1-C
30alkyl, 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,
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.
2. a preparation method for load type non-metallocene catalyst, comprises the following steps:
Make magnesium compound be dissolved in the mixed solvent being formed by tetrahydrofuran (THF) and alcohol, obtain the step of magnesium compound solution,
Porous support is mixed with described magnesium compound solution, obtains the step of mixed serum,
Dry described mixed serum, the step of acquisition complex carrier,
With a side who is selected from chemical processing agent and Nonmetallocene part, process described complex carrier, obtain the treatment step of modification complex carrier, wherein said chemical processing agent is selected from IV B family metallic compound; With
Described modification complex carrier is contacted with the opposing party in described Nonmetallocene part with being selected from described chemical processing agent, thereby obtains the contact procedure of described load type non-metallocene catalyst,
Wherein said Nonmetallocene part is selected from has (A) of following structure and (B) compound:
Wherein:
Q is selected from 0 or 1;
D is selected from 0 or 1;
A be selected from Sauerstoffatom, sulphur atom, selenium atom,
sulfuryl or sulfoxide group;
B is selected from nitrogen-containing group, phosphorus-containing groups or C
1-C
30alkyl;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno, rolls into a ball 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 covalent linkage or ionic linkage;
R
1, R
2and R
3be selected from independently of one another hydrogen, C
1-C
30the C of alkyl, halogen atom, replacement
1-C
30alkyl or safing function group, R
22and R
27be selected from independently of one another hydrogen, C
1-C
30the C of alkyl, halogen atom or replacement
1-C
30alkyl, 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,
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,
F is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno, rolls into a ball or phosphorus-containing groups, and wherein N, O, S, Se, P are respectively ligating atom.
3. a preparation method for load type non-metallocene catalyst, comprises the following steps:
Make magnesium compound be dissolved in the mixed solvent being formed by tetrahydrofuran (THF) and alcohol, obtain the step of magnesium compound solution,
Porous support is mixed with described magnesium compound solution, obtains the step of mixed serum,
Dry described mixed serum, the step of acquisition complex carrier,
With a side who is selected from chemical processing agent and Nonmetallocene part, process described complex carrier, obtain the treatment step of modification complex carrier, wherein said chemical processing agent is selected from IVB family metallic compound; With
Described modification complex carrier is contacted with the opposing party in described Nonmetallocene part with being selected from described chemical processing agent, thereby obtains the contact procedure of described load type non-metallocene catalyst,
Wherein said Nonmetallocene part is selected from the compound with following structure A-1 to A-4 and B-1 to B-4:
Wherein:
Q is selected from 0 or 1;
D is selected from 0 or 1;
A be selected from Sauerstoffatom, sulphur atom, selenium atom,
sulfuryl or sulfoxide group;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno, rolls into a ball 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 covalent linkage or ionic linkage;
R
1, R
2and R
3be selected from independently of one another hydrogen, C
1-C
30the C of alkyl, halogen atom, replacement
1-C
30alkyl or safing function group, R
22and R
27be selected from independently of one another hydrogen, C
1-C
30the C of alkyl, halogen atom or replacement
1-C
30alkyl, 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;
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;
F is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno, rolls into a ball or phosphorus-containing groups, and wherein N, O, S, Se, P are respectively ligating atom;
Y and Z are selected from independently of one another nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno, roll into a ball 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 independently of one another hydrogen, C
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 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 is to work as R
5during for oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups, R
5in N, O, S, P, Se be respectively ligating atom.
4. according to the preparation method of the load type non-metallocene catalyst described in claims 1 to 3 any one, also comprise the step of the load type non-metallocene catalyst of dry described acquisition.
5. according to the preparation method of the load type non-metallocene catalyst described in claims 1 to 3 any one, before being also included in and mixing with described magnesium compound solution, the step of porous support described in thermal activation treatment.
6. according to the preparation method of the load type non-metallocene catalyst described in claims 1 to 3 any one, before being also included in described treatment step, with the chemical processing agent that helps that is selected from aikyiaiurnirsoxan beta, aluminum alkyls and composition thereof, process the step of described complex carrier.
7. according to the preparation method of load type non-metallocene catalyst claimed in claim 5, it is characterized in that, described thermal activation treatment is included under inert atmosphere, processes 0.5～24 hour at 200～800 ℃.
8. according to the preparation method of load type non-metallocene catalyst claimed in claim 7, it is characterized in that, described thermal activation treatment is included under nitrogen or argon gas atmosphere, processes 2～12 hours at 400～700 ℃.
9. according to the preparation method of load type non-metallocene catalyst claimed in claim 8, it is characterized in that, described thermal activation treatment is included at 400～650 ℃ and processes 4～8 hours.
10. according to the preparation method of the load type non-metallocene catalyst described in claims 1 to 3 any one, it is characterized in that, described porous support is selected from partial cross-linked and has styrene polymer and a porous inorganic material of surperficial carboxyl, and wherein said porous inorganic material selects free periodic table of elements IIA, I II A, the oxide compound that one or more elements of IVAHe IVB family metal form, the oxide compound being generated by pyrohydrolysis by gaseous metal halogenide or gaseous silicon compound, clay, molecular sieve, mica, polynite, wilkinite, diatomite, ZSM-5 and MCM-41.
11. according to the preparation method of load type non-metallocene catalyst claimed in claim 10, it is characterized in that, described porous support is selected from styrene polymer, silicon-dioxide, aluminum oxide, magnesium oxide, titanium dioxide, molecular sieve and polynite.
12. according to the preparation method of the load type non-metallocene catalyst described in claim 11, it is characterized in that, described porous support is selected from silicon-dioxide.
13. according to the preparation method of the load type non-metallocene catalyst described in claims 1 to 3 any one, 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 alkyl alkoxy magnesium
Described alcohol is selected from one or more in fatty alcohol, aromatic alcohol and alicyclic ring alcohol, and the group that wherein said alcohol is optionally selected from alkyl, halogen atom and alkoxyl group replaces.
14. according to the preparation method of the load type non-metallocene catalyst described in claim 13, it is characterized in that, described magnesium compound is selected from magnesium halide.
15. according to the preparation method of the load type non-metallocene catalyst described in claim 14, it is characterized in that, described magnesium compound is magnesium chloride.
16. according to the preparation method of the load type non-metallocene catalyst described in claim 13, it is characterized in that, described alcohol is selected from fatty alcohol.
17. according to the preparation method of the load type non-metallocene catalyst described in claim 16, it is characterized in that, described alcohol is ethanol or butanols.
18. according to the preparation method of the load type non-metallocene catalyst described in claims 1 to 3 any one, it is characterized in that, take the described magnesium compound of magnesium elements and the mol ratio of tetrahydrofuran (THF) is 1:6～40, take the described magnesium compound of magnesium elements and the mol ratio of described alcohol is 1:1～8, and the mass ratio of described magnesium compound and described porous support is 1:0.5～4.
19. according to the preparation method of the load type non-metallocene catalyst described in claim 18, it is characterized in that, take the described magnesium compound of magnesium elements and the mol ratio of tetrahydrofuran (THF) is 1:8～20, take the described magnesium compound of magnesium elements and the mol ratio of described alcohol is 1:1～4, and the mass ratio of described magnesium compound and described porous support is 1:1～2.
20. according to the preparation method of the load type non-metallocene catalyst described in claims 1 to 3 any one, it is characterized in that, described IVB family metallic compound is selected from one or more in IVB family metal halide, alkylate and alkyl halide.
21. according to the preparation method of the load type non-metallocene catalyst described in claim 20, it is characterized in that, described IVB family metallic compound is selected from halogenated titanium and zirconium halide.
22. according to the preparation method of the load type non-metallocene catalyst described in claim 21, it is characterized in that, described IVB family metallic compound is titanium tetrachloride.
23. according to the preparation method of load type non-metallocene catalyst claimed in claim 6, it is characterized in that, described aluminum alkyls is selected from triethyl aluminum and trimethyl aluminium, and described aikyiaiurnirsoxan beta is selected from methylaluminoxane and triisobutyl alumina alkane.
24. according to the preparation method of load type non-metallocene catalyst claimed in claim 6, it is characterized in that, take Al element described in to help chemical processing agent and the ratio of described complex carrier be 0.25～4 mmole: 1 gram.
25. according to the preparation method of the load type non-metallocene catalyst described in claim 24, it is characterized in that, take Al element described in to help chemical processing agent and the ratio of described complex carrier be 0.5～2 mmole: 1 gram.
26. according to the preparation method of the load type non-metallocene catalyst described in claims 1 to 3 any one, it is characterized in that, by mass, described Nonmetallocene part is 0.05～0.50:1 with the ratio of complex carrier.
27. according to the preparation method of the load type non-metallocene catalyst described in claim 26, it is characterized in that, by mass, described Nonmetallocene part is 0.10～0.30:1 with the ratio of complex carrier.
28. according to the preparation method of the load type non-metallocene catalyst described in claims 1 to 3 any one, it is characterized in that, the described chemical processing agent of YiIVB family metallic element meter and the mol ratio of described Nonmetallocene part are 1:0.1～1a
29. according to the preparation method of the load type non-metallocene catalyst described in claim 28, it is characterized in that, the described chemical processing agent of YiIVB family metallic element meter and the mol ratio of described Nonmetallocene part are 1:0.3～0.9.
30. according to the preparation method of the load type non-metallocene catalyst described in claims 1 to 3 any one, it is characterized in that,
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;
Described 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 ,-OR
34with-T-OR
34;
Be selected from-SR of described sulfur-containing group
35,-T-SR
35,-S (O) R
36or-T-SO
2r
37;
Described containing be selected from-SeR of seleno group
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 or replacement
1-C
30alkyl;
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 the C of halo
1-C
30alkyl, the C of halo
6-C
30aryl, the C of halo
8-C
30condensed ring radical or the C of halo
4-C
30heterocyclic radical;
Be selected from-SiR of described silicon-containing group
42r
43r
44,-T-SiR
45;
Described be selected from-GeR of germanic group
46r
47r
48,-T-GeR
49;
Described containing be selected from-SnR of tin group
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 independently of one another hydrogen, C
1-C
30the C of alkyl, halogen atom or replacement
1-C
30alkyl,
Described R
23, R
24, R
25, R
26, R
28, R
29, R
30, R
31, R
32, R
33and R
39be selected from independently of one another hydrogen, C
1-C
30the C of alkyl, halogen atom or replacement
1-C
30alkyl, 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.
31. according to the preparation method of load type non-metallocene catalyst claimed in claim 1, it is characterized in that,
Described Nonmetallocene part is selected from the compound with following structure:
32. according to the preparation method of the load type non-metallocene catalyst described in claim 31, it is characterized in that,
Described Nonmetallocene part is selected from the compound with following structure:
33. 1 kinds of load type non-metallocene catalysts, comprise carrier and load non-metallocene catalyst thereon, it is characterized in that, it is to manufacture according to the preparation method of the load type non-metallocene catalyst described in claim of right1~32 any one.
The homopolymerization of 34. 1 kinds of alkene and/or copolymerization process, it is characterized in that, the load type non-metallocene catalyst of claim 33 of take is Primary Catalysts, take that to be selected from one or more in aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt be promotor.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710162677.5A CN101412769B (en) | 2007-10-16 | 2007-10-16 | Load type non-metallocene catalyst and preparation thereof |
| JP2010529214A JP5480147B2 (en) | 2007-10-16 | 2008-10-15 | Supported nonmetallocene catalyst and method for producing the same |
| PCT/CN2008/001738 WO2009052700A1 (en) | 2007-10-16 | 2008-10-15 | Supported non-metallocene catalyst and its preparation method |
| KR1020097023956A KR101207294B1 (en) | 2007-10-16 | 2008-10-15 | Supported non-metallocene catalyst and its preparation method |
| US12/669,394 US8193288B2 (en) | 2007-10-16 | 2008-10-15 | Supported nonmetallocene catalyst and preparation thereof |
| EP08842385A EP2202247B1 (en) | 2007-10-16 | 2008-10-15 | Supported non-metallocene catalyst and its preparation method |
Applications Claiming Priority (1)
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| CN102020732B (en) * | 2009-09-10 | 2013-02-06 | 中国石油化工股份有限公司 | Catalyst component preparation method and catalyst for vinyl polymerization |
| WO2011057468A1 (en) | 2009-11-13 | 2011-05-19 | 中国石油化工股份有限公司 | Supported non-metallocene catalyst, preparation method and application thereof |
| CN102399322B (en) * | 2010-09-16 | 2014-02-26 | 中国石油化工股份有限公司 | Load-type non-metallocene catalyst, preparation method thereof, and application thereof |
| CN103304705B (en) * | 2012-03-06 | 2016-01-27 | 中国石油化工股份有限公司 | Load type non-metallocene catalyst, its preparation method and application thereof |
| CN109485761A (en) * | 2017-09-11 | 2019-03-19 | 中国石油化工股份有限公司 | Load type non-metallocene catalyst, preparation method and its application |
| CN109485760A (en) * | 2017-09-11 | 2019-03-19 | 中国石油化工股份有限公司 | Load type non-metallocene catalyst, preparation method and its application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1066274A (en) * | 1991-03-27 | 1992-11-18 | 希蒙特公司 | The component and the catalyzer that are used for olefinic polyreaction |
| CN1789290A (en) * | 2004-12-17 | 2006-06-21 | 扬子石油化工股份有限公司 | Highly active supporting method of non-metallocene catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066274A (en) * | 1991-03-27 | 1992-11-18 | 希蒙特公司 | The component and the catalyzer that are used for olefinic polyreaction |
| CN1789290A (en) * | 2004-12-17 | 2006-06-21 | 扬子石油化工股份有限公司 | Highly active supporting method of non-metallocene catalyst |
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