CN101412764A - Load type non-metallocene catalyst and preparation thereof - Google Patents

Load type non-metallocene catalyst and preparation thereof Download PDF

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Publication number
CN101412764A
CN101412764A CN 200710162672 CN200710162672A CN101412764A CN 101412764 A CN101412764 A CN 101412764A CN 200710162672 CN200710162672 CN 200710162672 CN 200710162672 A CN200710162672 A CN 200710162672A CN 101412764 A CN101412764 A CN 101412764A
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metallocene catalyst
type non
load type
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preparation
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顾越峰
李传峰
马忠林
王亚明
柏基业
陈韶辉
李晓强
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Sinopec Yangzi Petrochemical Co Ltd
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Sinopec Yangzi Petrochemical Co Ltd
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Priority to CN 200710162672 priority Critical patent/CN101412764A/en
Priority to EP08842385A priority patent/EP2202247B1/en
Priority to JP2010529214A priority patent/JP5480147B2/en
Priority to KR1020097023956A priority patent/KR101207294B1/en
Priority to US12/669,394 priority patent/US8193288B2/en
Priority to PCT/CN2008/001738 priority patent/WO2009052700A1/en
Publication of CN101412764A publication Critical patent/CN101412764A/en
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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 has wide adjustable range of the supporting capacity and the polymerization activity of the catalyst. When the supported non-metallocene catalyst is combined with a catalyst promoter to catalyze the homopolymerization/copolymerization of olefins, high polymerization activities of the olefins can be obtained only by the less using amount of the catalyst promoter.

Description

A kind of load type non-metallocene catalyst and preparation method thereof
Technical field
The present invention relates to a kind of for olefines polymerization load type non-metallocene catalyst.Particularly, the present invention relates to a kind of load type non-metallocene catalyst, it obtains Nonmetallocene part and transistion metal compound direct reaction on carrier by original position load method.By with the combination of promotors such as load type non-metallocene catalyst of the present invention and aikyiaiurnirsoxan beta or aluminum alkyls, can be used for the homopolymerization/copolymerization of catalyzed alkene.
Background technology
The non-metallocene catalyst that middle and later periods nineteen nineties occurs, claim luxuriant rear catalyst again, the central atom of Primary Catalysts has comprised nearly all transition metal, reach at some aspect of performance, 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.The 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 have cis alkyl or halogen metal division center, carry out alkene insertion and σ-key easily and shift, the easy alkylation of central metal helps the generation at cation activity center; The title complex that forms has the geometric configuration of qualification, stereoselectivity, electronegativity and chirality controllability, and in addition, formed metal-carbon key polarizes easily, more helps the polymerization and the copolymerization of alkene.Therefore, even under higher polymeric reaction temperature, also can obtain the olefin polymer of higher molecular weight.
But homogeneous catalyst has been proved it in olefinic polyreaction has active duration short, sticking still, high methylaluminoxane consumption easily, and obtain the too low or too high weak point of polymericular weight, only can be used for solution polymerization process or high-pressure polymerization process, seriously limit its industrial applicability.
Patent ZL 01126323.7, ZL 02151294.9 ZL 02110844.7 and WO03/010207 disclose a kind of alkene homopolymerization/catalyst for copolymerization or catalyst system, has alkene homopolymerization/copolymerization performance widely, but need higher promotor consumption during in olefinic polymerization at the disclosed catalyzer of this patent or catalyst system, could obtain suitable olefin polymerizating activity, and it is short to exist active duration in the polymerization process, phenomenons such as the sticking still of polymkeric substance.
According to the experience of metallocene catalyst industrial applications, the catalyzer that makes loadization is very necessary.
By with the non-metallocene catalyst loadization, can avoid homogeneous non-metallocene catalyst bimolecular inactivation, improve the particle form of polymerization and polymkeric substance.It shows as the initial activity that has suitably reduced catalyzer to a certain extent, prolong the polymerization catalyst active lifetime, reduce even avoided caking or the poly-cruelly phenomenon in the polymerization process, improve the form of polymkeric substance, improve the apparent density of polymkeric substance, can make it satisfy more polymerization technique process, as vapour phase polymerization or slurry polymerization etc.
At patent ZL 01126323.7, ZL 02151294.9 ZL 02110844.7 and the disclosed non-metallocene catalyst of WO03/010207, patent CN 1539855A, CN1539856A, CN 1789291A, CN 1789292A, CN 1789290A, WO/2006/063501,200510119401.x carry out load to obtain load type non-metallocene catalyst Deng multiple mode is provided, but these patents all relate on the carrier after the Nonmetallocene organometallic compound that will contain transition metal is carried on processing, and because the reaction bonded of non-metallocene catalyst and carrier is limited, the Nonmetallocene organic compound mainly is to exist with the physical adsorption attitude in the load type non-metallocene catalyst that obtains, and is unfavorable for the control of polymer beads form and the performance of non-metallocene catalyst performance.
Existing olefin polymerization catalysis patent is mostly based on metallocene catalyst, as US4808561, US 5240894, CN 1049439, CN 1136239, CN 1344749, CN1126480, CN1053673, CN 1307594, CN 1130932, CN 1103069, CN1363537, CN 1060179, US 574417, EP 685494, US 4871705 and EP0206794 etc., but these patents also all relate on the carrier after the metallocene catalyst that will contain transition metal is carried on processing.
Patent EP260130 proposes loaded metallocene or non-luxuriant transition-metal catalyst are carried on the silica supports of methylaluminoxane processing, and the non-luxuriant transition metal here only is meant ZrCl 4, TiCl 4Perhaps VOCl 3, what this patent was thought optimum is the mixture of carrier surface through organic-magnesium or magnesium compound and aluminum alkyls, but this process more complicated needs through many preparation processes.
Patent WO03/047752A1 and WO03/047751A1 provide the load method of composite catalyst (Z-N and metallocene catalyst or non-metallocene catalyst and metallocene catalyst) on silicon-dioxide, this patent is thought, the muriate of titanium or vanadium or chlorine oxonium compound are the non-metallocene catalyst components, and the catalyzer that obtains thus is a bimetallic catalyst.
Patent EP708116 discloses the zirconium tetrachloride that makes gasification earlier and has contacted and load with carrier under 160~450 ℃ of temperature, again that load is good zirconium tetrachloride obtains carried metallocene catalyst with the lithium salts reaction of part, then by cooperate the polymerization that is used for alkene with promotor.The problem that this catalyzer exists is that load process requires high temperature, and high vacuum is applicable to industrial production.
Patent ZL01131136.3 discloses a kind of method of synthetic carried metallocene catalyst, and carrier is mixed in solvent with IVB group 4 transition metal halogenide, in direct and part negative ion reaction.Thereby the synthetic and loadization that realizes metallocene catalyst was finished in a step.But it is 1:1 that this method requires the transition metal and the mol ratio of part, and needs adding proton donor, and as butyllithium etc., and the part that is adopted is the metallocene part that contains cyclopentadienyl group of bridging type or non-bridging type.
Patent CN200510080210.7 discloses original position synthetic supported type vanadium non-metallocene catalyst and preparation and has used; it forms acyl group naphthols magnesium or beta-diketon magnesium compound with dialkyl magnesium with acyl group naphthols or beta-diketon reaction earlier; muriate with the tetravalence vanadium reacts again, forms carrier and active catalytic components simultaneously.
Patent CN200610026765.8 discloses a class single active center Z-N olefin polymerization catalysis.This catalyzer, is handled the back through pretreated carrier (as silica gel), metallic compound (as titanium tetrachloride) and this electron donor and is obtained by adding in magnesium compound (as magnesium chloride)/tetrahydrofuran solution as electron donor with the salicylaldehyde derivatives of the salicylic aldehyde that contains coordinating group or replacement.
CN200610026766.2 is similar with it, discloses a class and has contained heteroatomic organic compound and the application in Ziegler-Natta catalyst thereof.
Even so, the ubiquitous problem of the load type non-metallocene catalyst that exists in the prior art is that olefin polymerizating activity is low and be difficult to adjusting, and in order to improve its polymerization activity, must assist higher promotor consumption when carrying out olefinic polymerization.In addition, when adopting the load type non-metallocene catalyst of prior art, polymkeric substance such as resulting polyethylene have the polymer morphology of low polymer stacks density and difference.And also there is the performance problem of unstable in the load type non-metallocene catalyst that exists in the prior art.
Therefore, still need a kind of load type non-metallocene catalyst, its preparation method is simple, is fit to suitability for industrialized production, and can overcomes those problems that exist in the prior art load type non-metallocene catalyst.
Summary of the invention
For this reason, the objective of the invention is to provide on the basis of existing technology a kind of 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 the proton donor and electron donor etc., also need not harsh reaction requirement and reaction conditions.Therefore, the preparation method of this loaded catalyst is simple, and is very suitable for suitability for industrialized production.
Particularly, the present invention relates to the content of following aspect:
1. the preparation method of a load type non-metallocene catalyst may further comprise the steps:
Handle porous support with a side who is selected from chemical processing agent and the Nonmetallocene part, obtain the treatment step of modified porous carrier, wherein said chemical processing agent is selected from IVB family metallic compound; With
Described modified porous carrier is contacted with the opposing party in the 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 aspect 1 described load type non-metallocene catalyst, also comprise the step of the load type non-metallocene catalyst of dry described acquisition.
3,, also be included in before the described treatment step step of the described porous support of thermal activation treatment according to the preparation method of aspect 1 or 2 described load type non-metallocene catalysts.
4. according to the preparation method of aspect each described load type non-metallocene catalyst of 1-3, also be included in before the described treatment step, handle the step of described porous support with the chemical processing agent that helps that is selected from aikyiaiurnirsoxan beta, aluminum alkyls and composition thereof.
According to the preparation method of aspect 3 or 4 described load type non-metallocene catalysts, it is characterized in that 5, described thermal activation treatment is included under the inert atmosphere, handled 0.5~24 hour down at 200~800 ℃.
According to the preparation method of aspect 5 described load type non-metallocene catalysts, it is characterized in that 6, described thermal activation treatment is included under nitrogen or the argon gas atmosphere, handled 2~12 hours down at 400~700 ℃.
According to the preparation method of aspect 6 described load type non-metallocene catalysts, it is characterized in that 7, described thermal activation treatment is included in 400~650 ℃ and handled 4~8 hours down.
8, according to the preparation method of aspect each described load type non-metallocene catalyst of 1-7, it is characterized in that, described porous support is selected from partial cross-linked and has the styrene polymer and the porous inorganic material of surperficial carboxyl, and wherein said the porous inorganic material oxide compound, clay, molecular sieve, mica, polynite, wilkinite, diatomite, ZSM-5 and the MCM-41 that are selected from oxide compound that one or more elements by periodic table of elements IIA, IIIA, IVA and IVB family metal constitute, are generated by pyrohydrolysis by gaseous metal halogenide or gaseous silicon compound.
According to the preparation method of aspect 8 described load type non-metallocene catalysts, it is characterized in that 9, described porous support is selected from styrene polymer, silicon-dioxide, aluminum oxide, magnesium oxide, titanium dioxide, molecular sieve and polynite.
According to the preparation method of aspect 9 described load type non-metallocene catalysts, it is characterized in that 10, described porous support is selected from silicon-dioxide.
According to the preparation method of aspect each described load type non-metallocene catalyst of 1-10, it is characterized in that 11, described IVB family metallic compound is selected from one or more in metal halide, metal alkyl compound and the metal alkyl halides.
According to the preparation method of aspect 11 described load type non-metallocene catalysts, it is characterized in that 12, described IVB family metallic compound is selected from halogenated titanium and zirconium halide.
According to the preparation method of aspect 12 described load type non-metallocene catalysts, it is characterized in that 13, described IVB family metallic compound is a titanium tetrachloride.
According to the preparation method of aspect each described load type non-metallocene catalyst of 4-13, it is characterized in that 14, described aluminum alkyls is selected from triethyl aluminum and trimethyl aluminium, and described aikyiaiurnirsoxan beta is selected from methylaluminoxane and triisobutyl alumina alkane.
According to the preparation method of aspect each described load type non-metallocene catalyst of 4-14, it is characterized in that 15, helping the chemical processing agent and the ratio of described porous support in Al element described is 0.25~4 mmole: 1 gram.
According to the preparation method of aspect 15 described load type non-metallocene catalysts, it is characterized in that 16, helping the chemical processing agent and the ratio of described porous support in Al element described is 0.5~2 mmole: 1 gram.
17, according to the preparation method of aspect each described load type non-metallocene catalyst of 1-16, it is characterized in that, is 1~100 mmole in the ratio of the described chemical processing agent of IVB family metallic element and described porous support: 1 gram.
18, according to the preparation method of aspect 17 described load type non-metallocene catalysts, it is characterized in that, is 5~40 mmoles in the ratio of the described chemical processing agent of IVB family metallic element and described porous support: 1 gram.
According to the preparation method of aspect each described load type non-metallocene catalyst of 1-18, it is characterized in that 19, the proportioning of described Nonmetallocene part and described porous support is: 0.02~1.00 mmole: 1 gram.
According to the preparation method of aspect 19 described load type non-metallocene catalysts, it is characterized in that 20, the proportioning of described Nonmetallocene part and described porous support is: 0.08~0.53 mmole: 1 gram.
21. the preparation method according to aspect each described load type non-metallocene catalyst of 1-20 is characterized in that, described Nonmetallocene part is selected from the compound with following structure:
Figure A200710162672D00151
Wherein:
Q is selected from 0 or 1;
D is selected from 0 or 1;
A be selected from Sauerstoffatom, sulphur atom, selenium atom,
Figure A200710162672D00152
-NR 23R 24,-N (O) R 25R 26,
Figure A200710162672D00153
-PR 28R 29,-P (O) R 30OR 31, sulfuryl, sulfoxide group or-Se (O) R 39
B is selected from nitrogen-containing group, phosphorus-containing groups or C 1-C 30Alkyl;
D is selected from Sauerstoffatom, sulphur atom, selenium atom, nitrogenous C 1-C 30Alkyl, phosphorated C 1-C 30Alkyl, sulfuryl, sulfoxide group,
Figure A200710162672D00154
-N (O) R 25R 26,
Figure A200710162672D00155
-P (O) R 32(OR 33), wherein N, O, S, Se, P are respectively ligating atom;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group or phosphorus-containing groups, and wherein N, O, S, Se, P are respectively ligating atom;
G is selected from C 1-C 30The C of alkyl, replacement 1-C 30Alkyl or safing function group;
→ represent singly-bound or two key;
-represent covalent linkage or ionic linkage;
R 1, R 2, R 3, R 22, R 23, R 24, R 25, R 26, R 27, R 28, R 29, R 30, R 31, R 32, R 33And R 39Be selected from hydrogen, C independently of one another 1-C 30The C of alkyl, halogen atom, replacement 1-C 30Alkyl or safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can be each other in key or Cheng Huan.
22. the preparation method according to aspect 21 described load type non-metallocene catalysts is characterized in that,
Described Nonmetallocene part is selected from (A) with following structure and (B) compound:
Figure A200710162672D00161
With
Figure A200710162672D00162
Wherein F is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group or phosphorus-containing groups, and wherein N, O, S, Se, P are respectively ligating atom;
Other are according to aspect 21 described definition.
23. the preparation method according to aspect 22 described load type non-metallocene catalysts is characterized in that,
Described Nonmetallocene part is selected from the compound with following structure A-1 to A-4 and B-1 to B-4:
Figure A200710162672D00163
Figure A200710162672D00171
Figure A200710162672D00181
Wherein:
Y and Z are selected from nitrogen-containing group, oxy radical, sulfur-containing group independently of one another, contain seleno group or phosphorus-containing groups, and wherein N, O, S, Se and P are respectively ligating atom, as-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 38,-Se (O) R 39,
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 34, R 35, R 36, R 38Be selected from hydrogen, C independently of one another 1-C 30The C of alkyl, halogen atom, replacement 1-C 30Alkyl or safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can be each other in key or Cheng Huan;
R 5Be selected from lone-pair electron on the nitrogen, hydrogen, C 1-C 30The C of alkyl, replacement 1-C 30Alkyl, oxy radical, sulfur-containing group, nitrogen-containing group or phosphorus-containing groups, prerequisite are to work as R 5For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group or phosphorus-containing groups, R 5In N, O, S, P, Se be respectively ligating atom;
Other are according to aspect 22 described definition.
24. the preparation method according to aspect each described load type non-metallocene catalyst of 21-23 is characterized in that,
Described halogen is selected from F, Cl, Br, I;
Described safing function group is selected from halogen, oxy radical, nitrogen-containing group, silicon-containing group, germanic group, sulfur-containing group or contains tin group;
Described nitrogen-containing group is selected from
Figure A200710162672D00191
-NR 23R 24,-T-NR 23R 24Or-N (O) R 25R 26
Described phosphorus-containing groups is selected from
Figure A200710162672D00192
-PR 28R 29,-P (O) R 30R 31Or-P (O) R 32(OR 33);
Described oxy radical be selected from hydroxyl ,-OR 34With-T-OR 34
Described sulfur-containing group is selected from-SR 35,-T-SR 35,-S (O) R 36Or-T-SO 2R 37
The described seleno group that contains is selected from-SeR 38,-T-SeR 38,-Se (O) R 39Or-T-Se (O) R 39
Described group T is selected from C 1-C 30The C of alkyl, replacement 1-C 30Alkyl or safing function group;
Described C 1-C 30Alkyl is selected from C 1-C 30Alkyl, C 2-C 30Cyclic alkyl, C 2-C 30Thiazolinyl, C 2-C 30Alkynyl, C 6-C 30Aryl, C 8-C 30Condensed ring radical or C 4-C 30Heterocyclic radical;
The C of described replacement 1-C 30Alkyl is selected from halogenated C 1-C 30Alkyl, halogenated C 6-C 30Aryl, halogenated C 8-C 30Condensed ring radical or halogenated C 4-C 30Heterocyclic radical;
Described silicon-containing group is selected from-SiR 42R 43R 44,-T-SiR 45
Described germanic group is selected from-GeR 46R 47R 48,-T-GeR 49
Describedly contain tin group and be selected from-SnR 50R 51R 52,-T-SnR 53Or-T-Sn (O) R 54
Described R 34, R 35, R 36, R 37, R 38And R 42, R 43, R 44, R 45, R 45, R 46, R 47, R 48, R 49, R 50, R 51, R 52, R 53, R 54Be selected from hydrogen, C independently of one another 1-C 30The C of alkyl, halogen atom, replacement 1-C 30Alkyl or safing function group.
25. the preparation method according to aspect each described load type non-metallocene catalyst of 21-24 is characterized in that,
Described Nonmetallocene part is selected from the compound with following structure:
Figure A200710162672D00193
Figure A200710162672D00201
With
Figure A200710162672D00202
26. the preparation method according to aspect 25 described load type non-metallocene catalysts is characterized in that,
Described Nonmetallocene part is selected from the compound with following structure:
Figure A200710162672D00203
With
Figure A200710162672D00204
27. a load type non-metallocene catalyst comprises carrier and load non-metallocene catalyst thereon, it is characterized in that, it is to make according to the preparation method of aspect 1~26 each described load type non-metallocene catalyst.
28. alkene homopolymerization/copolymerization process, it is characterized in that, being Primary Catalysts according to aspect 27 described load type non-metallocene catalysts, to be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more is promotor, makes alkene homopolymerization or copolymerization.
29., it is characterized in that described promotor is selected from one or more in aikyiaiurnirsoxan beta and the aluminum alkyls according to aspect 28 described alkene homopolymerization/copolymerization process.
30., it is characterized in that described promotor is selected from methylaluminoxane and triethyl aluminum according to aspect 29 described alkene homopolymerization/copolymerization process.
31., it is characterized in that described alkene is selected from C according to each described alkene homopolymerization/copolymerization process of aspect 28-30 2~C 10Monoolefine, diolefin, cycloolefin and other ethylenically unsaturated compounds.
32., it is characterized in that described C according to aspect 31 described alkene homopolymerization/copolymerization process 2~C 10Monoolefine is selected from ethene, propylene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-hendecene, 1-laurylene, 1-cyclopentenes, norbornylene, norbornadiene and vinylbenzene, described diolefin is selected from 1,4-divinyl, 2,5-pentadiene, 1,6-hexadiene and 1, the 7-octadiene, and described other ethylenically unsaturated compounds are selected from vinyl acetate and (methyl) acrylate.
Preparation method's technology simple possible of load type non-metallocene catalyst of the present invention, and the charge capacity of Nonmetallocene part is adjustable, can improve its charge capacity significantly, improves the polymerization activity of this catalyzer thus significantly.
In addition, by adopting different chemical processing agent consumptions, can obtain polymerization activity from low to high and adjustable load type non-metallocene catalyst adapts to different olefinic polymerization requirements thus.
Adopt method for preparing catalyst provided by the invention, the Nonmetallocene part is tight with combining of carrier, has avoided the influence of free ligand to the load type non-metallocene catalyst polymerization effectively, thereby makes the performance of this catalyzer more stable.
When employing load type non-metallocene catalyst that the present invention obtained and promotor constitute catalyst system, only need fewer promotor (such as methylaluminoxane or triethyl aluminum) consumption, just can obtain high olefin polymerizating activity.And polymkeric substance such as resulting polyethylene has good polymer morphology and high polymer bulk density thus.
Embodiment
At first, the present invention relates to a kind of preparation method of load type non-metallocene catalyst, may further comprise the steps: handle porous support with a side who is selected from chemical processing agent and the Nonmetallocene part, obtain the treatment step of modified porous carrier, wherein said chemical processing agent is selected from IVB family metallic compound; With described modified porous carrier is contacted with the opposing party in the described Nonmetallocene part with being selected from described chemical processing agent, thereby obtain the contact procedure of described load type non-metallocene catalyst.
The used porous support of the present invention can be the porosu solid arbitrarily that the surface has functional group, such as being selected from the organic materials that contains surperficial organo-functional group and containing in the inorganic materials of surface functional group one or more, 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 monomeric multipolymer, polyester, polymeric amide, polyvinyl chloride, polyacrylic ester, polymethacrylate, polystyrene and partial cross-linked polymkeric substance, wherein preferred partial cross-linked and have a styrene polymer of surperficial carboxyl.The described inorganic materials of surface functional group that contains is such as being selected from by periodic table of elements IIA, IIIA, the oxide compound that one or more elements of IVA and IVB family metal constitute, and halogenide, such as enumerating silicon-dioxide (being called silicon oxide or silica gel again), 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 that generates by pyrohydrolysis by gaseous metal halogenide or gaseous silicon compound, such as the silica gel that obtains by the silicon tetrachloride hydrolysis, aluminum oxide that is obtained by the aluminum chloride hydrolysis etc. perhaps can also be enumerated 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., perhaps silicon-dioxide be selected from the mixed oxide of IIA or IIIA family metal oxide, such as silica-magnesia mixed oxide, silica-alumina mixed oxide, wherein preferred especially silicon-dioxide.
According to the present invention, suitable silicon-dioxide can be by the ordinary method manufacturing, it perhaps can be the commerical prod that to buy arbitrarily, such as the Grace 955 that can enumerate Grace company, Grace 948, Grace SP9-351, Grace SP9-485, Grace SP9-10046, DavsionSyloid 245, Aerosil812, CS-2133 of the ES70 of Ineos company, ES70X, ES70Y, ES70W, ES757, EP10X, EP11, Pq Corp. and MS-3040.
According to the present invention, there is no particular limitation to the surface-area of this porous support, but be generally 10~1000m 2/ g (BET method mensuration), preferred 100~600m 2/ g; The pore volume of this porous support (determination of nitrogen adsorption) is generally 0.1~4cm 3/ g, preferred 0.2~2cm 3/ g, and preferred 1~500 μ m of its median size (laser particle analyzer mensuration), more preferably 1~100 μ m.
According to the present invention, described porous support can be a form arbitrarily, such as granular, spherical, aggregate or other form.
According to the present invention, in a preferred embodiment, (before the treatment step) carries out thermal activation treatment to inorganic porous carrier of the present invention before use.This thermal activation treatment can be carried out according to common mode, such as under reduced pressure or under the inert atmosphere porous support being carried out heat treated.Here said inert atmosphere be meant only contain extremely trace in the gas or do not contain can with the component of porous support reaction, such as enumerating nitrogen and rare gas etc.When carrying out thermal activation, Heating temperature is such as being 200-800 ℃, and preferred 400~700 ℃, most preferably 400~650 ℃, heat-up time is such as being 0.5~24h, preferred 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 carries out under nitrogen atmosphere.Those skilled in the art know, generally will preserve under inert atmosphere through the carrier of thermal activation.
According to the present invention, also (before the treatment step) carries out thermal activation treatment to organic porous support of the present invention preferably before use, and wherein the main purpose that this organic porous support is carried out thermal activation is to remove the water of organic porous support surface adsorption.Because the poor heat resistance of organic porous support, so this thermal activation process can not be destroyed the structure and the essentially consist of organic porous support itself.This thermal activation treatment can be carried out according to common mode, such as under reduced pressure or under the inert atmosphere porous support being heated.Here said inert atmosphere be meant only contain extremely trace in the gas or do not contain can with the component of porous support reaction, such as enumerating nitrogen and rare gas etc.Usually, the temperature of this thermal activation is 50~400 ℃, and preferred 100~250 ℃, the thermal activation time is 1~24 hour, preferred 2~12h.According to the present invention, this reactivation process is preferably carried out under nitrogen or argon gas atmosphere, preferably carries out under nitrogen atmosphere.Those skilled in the art know, generally will preserve under inert atmosphere through the carrier of thermal activation.
Porous support of the present invention (preferably through thermal activation) can directly be used for carrying out described treatment step, but one preferred embodiment in, before carrying out this treatment step, anticipate described porous support (pre-treatment step) with the chemical processing agent that helps that is selected from aikyiaiurnirsoxan beta, aluminum alkyls and its mixture.
Described aikyiaiurnirsoxan beta can be selected from the line style aikyiaiurnirsoxan beta R shown in the following general formula (I) 2-Al-(Al (R)-O) n-O-AlR 2And the ring-type aikyiaiurnirsoxan beta shown in the following general formula (II)-(Al (R)-O-) N+2
Figure A200710162672D00231
Wherein, the R group can be same to each other or different to each other, and is preferably identical, and is independently from each other C 1-C 8Alkyl, preferable methyl, ethyl and isobutyl-, most preferable; N is the integer of 1-50, preferred 10~30.
Specifically for example, this aikyiaiurnirsoxan beta is preferably selected from methylaluminoxane, ethyl aikyiaiurnirsoxan beta, isobutyl aluminium alkoxide, butyl aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide, wherein most preferable aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide.
These aikyiaiurnirsoxan beta can be used alone, and perhaps are used in combination multiple.
Described aluminum alkyls is for having the compound of following general formula (III):
Al(R) 3 (III)
Wherein the R group can be same to each other or different to each other, and is preferably identical, and is independently from each other C 1-C 8Alkyl, preferable methyl, ethyl and isobutyl-, most preferable.
Particularly, this aluminum alkyls is such as enumerating trimethyl aluminium (Al (CH 3) 3), triethyl aluminum (Al (CH 3CH 2) 3), tri-propyl aluminum (Al (C 3H 7) 3), triisobutyl aluminium (Al (i-C 4H 9) 3), three n-butylaluminum (Al (C 4H 9) 3), triisopentyl aluminium (Al (i-C 5H 11) 3), three n-pentyl aluminium (Al (C 5H 11) 3), three hexyl aluminium (Al (C 6H 13) 3), three isohexyl aluminium (Al (i-C 6H 13) 3), diethylmethyl aluminium (Al (CH 3) (CH 3CH 2) 2) and dimethyl ethyl aluminium (Al (CH 3CH 2) (CH 3) 2) etc., wherein preferred trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, most preferably triethyl aluminum and triisobutyl aluminium.
These aluminum alkylss can be used alone, and perhaps are used in combination multiple.
According to the present invention, 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 there is no particular limitation to each components in proportions in this mixture, can select arbitrarily as required.
When carrying out this pre-treatment given to this invention, helping the chemical processing agent and the ratio of described porous support in Al element described is 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 method.At first prepare the described solution that helps chemical processing agent, the described chemical processing agent that helps that adds specified amount then under the temperature below the boiling point of normal temperature solvent to the solution to porous support, react 0.5~6 hour (in case of necessity by stirring), thereby obtain through this pretreated described porous support.The pre-treatment porous support that is obtained can be by filtering and washing (1~6 time, preferred 1~3 time) mode from mixed solution, separate standby (preferably finally through super-dry), but also can separate and directly be used for carrying out and treatment step as described below.
Described when helping the chemical treatment agent solution in preparation, there is no particular limitation to employed solvent, as long as it can dissolve this and help chemical processing agent.Particularly, can enumerate alkane or 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 preferred pentane, hexane, decane, hexanaphthene and toluene, most preferably hexane and toluene.
These solvents can be used alone, and perhaps are used in combination multiple.
In addition, help the concentration of chemical processing agent in its solution there is no particular limitation, can suitably select as required, as long as can realize described porous support given to this invention and the described amount ranges that helps chemical processing agent to described.
As previously mentioned, porous support 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 the aforesaid pre-treatment step.
According to the present invention, when carrying out this treatment step, handle described porous support with a side who is selected from chemical processing agent and the Nonmetallocene part, to obtain modified porous carrier.
Below at first describe with regard to the situation of using chemical processing agent to handle described porous support.
According to the present invention, described chemical processing agent is selected from IVB family metallic compound.As described IVB family metallic compound, can enumerate IVB family metal halide, IVB family metal alkyl compound, IVB family metal alkoxide compound, IVB family metal alkyl halides and IVB family metal alkoxide halogenide.
As described IVB family metal halide, alkylate, alkoxy compound, alkyl halide and alkoxy halide, can enumerate the compound of following general formula (IV) structure:
M(OR 1) mX nR 2 4-m-n (IV)
Wherein:
M is selected from 0,1,2,3,4;
N is selected from 0,1,2,3,4;
M is an IVB family metal, such as titanium, zirconium, hafnium etc.;
X is a halogen, such as F, Cl, Br, I etc.;
R 1And R 2Be selected from C independently of one another 1-C 30Alkyl is such as methyl, ethyl, propyl group, normal-butyl, isobutyl-etc., R 1And R 2Can be identical, also can be different.
Particularly, described IVB family metal halide can be enumerated titanium tetrafluoride (TiF 4), titanium tetrachloride (TiCl 4), titanium tetrabromide (TiBr 4), titanium tetra iodide (TiI 4);
Zirconium tetrafluoride (ZrF 4), zirconium tetrachloride (ZrCl 4), tetrabormated zirconium (ZrBr 4), zirconium tetraiodide (ZrI 4);
Tetrafluoride hafnium (HfF 4), hafnium tetrachloride (HfCl 4), hafnium (HfBr 4), tetraiodide hafnium (HfI 4);
Described IVB family metal alkyl compound can be enumerated tetramethyl-titanium (Ti (CH 3) 4), tetraethyl-titanium (Ti (CH 3CH 2) 4), four isobutyl-titanium (Ti (i-C 4H 9) 4), tetra-n-butyl titanium (Ti (C 4H 9) 4), triethyl methyltitanium (Ti (CH 3) (CH 3CH 2) 3), diethyl-dimethyl titanium (Ti (CH 3) 2(CH 3CH 2) 2), trimethylammonium ethyl titanium (Ti (CH 3) 3(CH 3CH 2)), triisobutyl methyltitanium (Ti (CH 3) (i-C 4H 9) 3), diisobutyl dimethyl titanium (Ti (CH 3) 2(i-C 4H 9) 2), trimethylammonium isobutyl-titanium (Ti (CH 3) 3(i-C 4H 9)), triisobutyl ethyl titanium (Ti (CH 3CH 2) (i-C 4H 9) 3), diisobutyl diethyl titanium (Ti (CH 3CH 2) 2(i-C 4H 9) 2), triethyl isobutyl-titanium (Ti (CH 3CH 2) 3(i-C 4H 9)), three normal-butyl methyltitanium (Ti (CH 3) (C 4H 9) 3), di-n-butyl dimethyl titanium (Ti (CH 3) 2(C 4H 9) 2), trimethylammonium normal-butyl titanium (Ti (CH 3) 3(C 4H 9)), three normal-butyl methyltitanium (Ti (CH 3CH 2) (C 4H 9) 3), di-n-butyl diethyl titanium (Ti (CH 3CH 2) 2(C 4H 9) 2), triethyl normal-butyl titanium (Ti (CH 3CH 2) 3(C 4H 9)) etc.;
Tetramethyl-zirconium (Zr (CH 3) 4), tetraethyl-zirconium (Zr (CH 3CH 2) 4), four isobutyl-zirconium (Zr (i-C 4H 9) 4), tetra-n-butyl zirconium (Zr (C 4H 9) 4), triethyl methylcyclopentadienyl zirconium (Zr (CH 3) (CH 3CH 2) 3), diethyl-dimethyl zirconium (Zr (CH 3) 2(CH 3CH 2) 2), trimethylammonium ethyl zirconium (Zr (CH 3) 3(CH 3CH 2)), triisobutyl methylcyclopentadienyl zirconium (Zr (CH 3) (i-C 4H 9) 3), diisobutyl zirconium dimethyl (Zr (CH 3) 2(i-C 4H 9) 2), trimethylammonium isobutyl-zirconium (Zr (CH 3) 3(i-C 4H 9)), triisobutyl ethyl zirconium (Zr (CH 3CH 2) (i-C 4H 9) 3), diisobutyl diethyl zirconium (Zr (CH 3CH 2) 2(i-C 4H 9) 2), triethyl isobutyl-zirconium (Zr (CH 3CH 2) 3(i-C 4H 9)), three normal-butyl methylcyclopentadienyl zirconium (Zr (CH 3) (C 4H 9) 3), di-n-butyl zirconium dimethyl (Zr (CH 3) 2(C 4H 9) 2), trimethylammonium normal-butyl zirconium (Zr (CH 3) 3(C 4H 9)), three normal-butyl methylcyclopentadienyl zirconium (Zr (CH 3CH 2) (C 4H 9) 3), di-n-butyl diethyl zirconium (Zr (CH 3CH 2) 2(C 4H 9) 2), triethyl normal-butyl zirconium (Zr (CH 3CH 2) 3(C 4H 9)) etc.;
Tetramethyl-hafnium (Hf (CH 3) 4), tetraethyl-hafnium (Hf (CH 3CH 2) 4), four isobutyl-hafnium (Hf (i-C 4H 9) 4), tetra-n-butyl hafnium (Hf (C 4H 9) 4), triethyl methylcyclopentadienyl hafnium (Hf (CH 3) (CH 3CH 2) 3), diethyl-dimethyl hafnium (Hf (CH 3) 2(CH 3CH 2) 2), trimethylammonium ethyl hafnium (Hf (CH 3) 3(CH 3CH 2)), triisobutyl methylcyclopentadienyl hafnium (Hf (CH 3) (i-C 4H 9) 3), diisobutyl dimethyl hafnium (Hf (CH 3) 2(i-C 4H 9) 2), trimethylammonium isobutyl-hafnium (Hf (CH 3) 3(i-C 4H 9)), triisobutyl ethyl hafnium (Hf (CH 3CH 2) (i-C 4H 9) 3), diisobutyl diethyl hafnium (Hf (CH 3CH 2) 2(i-C 4H 9) 2), triethyl isobutyl-hafnium (Hf (CH 3CH 2) 3(i-C 4H 9)), three normal-butyl methylcyclopentadienyl hafnium (Hf (CH 3) (C 4H 9) 3), di-n-butyl dimethyl hafnium (Hf (CH 3) 2(C 4H 9) 2), trimethylammonium normal-butyl hafnium (Hf (CH 3) 3(C 4H 9)), three normal-butyl methylcyclopentadienyl hafnium (Hf (CH 3CH 2) (C 4H 9) 3), di-n-butyl diethyl hafnium (Hf (CH 3CH 2) 2(C 4H 9) 2), triethyl normal-butyl hafnium (Hf (CH 3CH 2) 3(C 4H 9)) etc.;
Described IVB family metal alkoxide compound can be enumerated tetramethoxy titanium (Ti (OCH 3) 4), purity titanium tetraethoxide (Ti (OCH 3CH 2) 4), four isobutoxy titanium (Ti (i-OC 4H 9) 4), four titanium n-butoxide (Ti (OC 4H 9) 4), triethoxy methoxyl group titanium (Ti (OCH 3) (OCH 3CH 2) 3), diethoxy dimethoxy titanium (Ti (OCH 3) 2(OCH 3CH 2) 2), trimethoxy ethanolato-titanium (Ti (OCH 3) 3(OCH 3CH 2)), three isobutoxy methoxyl group titanium (Ti (OCH 3) (i-OC 4H 9) 3), two isobutoxy dimethoxy titanium (Ti (OCH 3) 2(i-OC 4H 9) 2), trimethoxy isobutoxy titanium (Ti (OCH 3) 3(i-OC 4H 9)), three isobutoxy ethanolato-titanium (Ti (OCH 3CH 2) (i-OC 4H 9) 3), two isobutoxy diethoxy titanium (Ti (OCH 3CH 2) 2(i-OC 4H 9) 2), triethoxy isobutoxy titanium (Ti (OCH 3CH 2) 3(i-OC 4H 9)), three n-butoxy methoxyl group titanium (Ti (OCH 3) (OC 4H 9) 3), two n-butoxy dimethoxy titanium (Ti (OCH 3) 2(OC 4H 9) 2), trimethoxy titanium n-butoxide (Ti (OCH 3) 3(OC 4H 9)), three n-butoxy methoxyl group titanium (Ti (OCH 3CH 2) (OC 4H 9) 3), two n-butoxy diethoxy titanium (Ti (OCH 3CH 2) 2(OC 4H 9) 2), triethoxy titanium n-butoxide (Ti (OCH 3CH 2) 3(OC 4H 9)) etc.;
Tetramethoxy zirconium (Zr (OCH 3) 4), tetraethoxy zirconium (Zr (OCH 3CH 2) 4), four isobutoxy zirconium (Zr (i-OC 4H 9) 4), four n-butoxy zirconium (Zr (OC 4H 9) 4), triethoxy methoxyl group zirconium (Zr (OCH 3) (OCH 3CH 2) 3), diethoxy dimethoxy zirconium (Zr (OCH 3) 2(OCH 3CH 2) 2), trimethoxy oxyethyl group zirconium (Zr (OCH 3) 3(OCH 3CH 2)), three isobutoxy methoxyl group zirconium (Zr (OCH 3) (i-OC 4H 9) 3), two isobutoxy dimethoxy zirconium (Zr (OCH 3) 2(i-OC 4H 9) 2), trimethoxy isobutoxy zirconium (Zr (OCH 3) 3(i-C 4H 9)), three isobutoxy oxyethyl group zirconium (Zr (OCH 3CH 2) (i-OC 4H 9) 3), two isobutoxy diethoxy zirconium (Zr (OCH 3CH 2) 2(i-OC 4H 9) 2), triethoxy isobutoxy zirconium (Zr (OCH 3CH 2) 3(i-OC 4H 9)), three n-butoxy methoxyl group zirconium (Zr (OCH 3) (OC 4H 9) 3), two n-butoxy dimethoxy zirconium (Zr (OCH 3) 2(OC 4H 9) 2), trimethoxy n-butoxy zirconium (Zr (OCH 3) 3(OC 4H 9)), three n-butoxy methoxyl group zirconium (Zr (OCH 3CH 2) (OC 4H 9) 3), two n-butoxy diethoxy zirconium (Zr (OCH 3CH 2) 2(OC 4H 9) 2), triethoxy n-butoxy zirconium (Zr (OCH 3CH 2) 3(OC 4H 9)) etc.;
Tetramethoxy hafnium (Hf (OCH 3) 4), tetraethoxy hafnium (Hf (OCH 3CH 2) 4), four isobutoxy hafnium (Hf (i-OC 4H 9) 4), four n-butoxy hafnium (Hf (OC 4H 9) 4), triethoxy methoxyl group hafnium (Hf (OCH 3) (OCH 3CH 2) 3), diethoxy dimethoxy hafnium (Hf (OCH 3) 2(OCH 3CH 2) 2), trimethoxy oxyethyl group hafnium (Hf (OCH 3) 3(OCH 3CH 2)), three isobutoxy methoxyl group hafnium (Hf (OCH 3) (i-OC 4H 9) 3), two isobutoxy dimethoxy hafnium (Hf (OCH 3) 2(i-OC 4H 9) 2), trimethoxy isobutoxy hafnium (Hf (OCH 3) 3(i-OC 4H 9)), three isobutoxy oxyethyl group hafnium (Hf (OCH 3CH 2) (i-OC 4H 9) 3), two isobutoxy diethoxy hafnium (Hf (OCH 3CH 2) 2(i-OC 4H 9) 2), triethoxy isobutoxy hafnium (Hf (OCH 3CH 2) 3(i-C 4H 9)), three n-butoxy methoxyl group hafnium (Hf (OCH 3) (OC 4H 9) 3), two n-butoxy dimethoxy hafnium (Hf (OCH 3) 2(OC 4H 9) 2), trimethoxy n-butoxy hafnium (Hf (OCH 3) 3(OC 4H 9)), three n-butoxy methoxyl group hafnium (Hf (OCH 3CH 2) (OC 4H 9) 3), two n-butoxy diethoxy hafnium (Hf (OCH 3CH 2) 2(OC 4H 9) 2), triethoxy n-butoxy hafnium (Hf (OCH 3CH 2) 3(OC 4H 9)) etc.
Described IVB family metal alkyl halides can be enumerated trimethylammonium titanium chloride (TiCl (CH 3) 3), triethyl titanium chloride (TiCl (CH 3CH 2) 3), triisobutyl titanium chloride (TiCl (i-C 4H 9) 3), three normal-butyl chlorination titanium (TiCl (C 4H 9) 3), dimethyl titanium dichloride (TiCl 2(CH 3) 2), diethyl titanium dichloride (TiCl 2(CH 3CH 2) 2), diisobutyl titanium dichloride (TiCl 2(i-C 4H 9) 2), three normal-butyl chlorination titanium (TiCl (C 4H 9) 3), methyl titanous chloride (Ti (CH 3) Cl 3), ethyl titanous chloride (Ti (CH 3CH 2) Cl 3), isobutyl-titanous chloride (Ti (i-C 4H 9) Cl 3), normal-butyl titanous chloride (Ti (C 4H 9) Cl 3);
Trimethylammonium titanium bromide (TiBr (CH 3) 3), triethyl titanium bromide (TiBr (CH 3CH 2) 3), triisobutyl titanium bromide (TiBr (i-C 4H 9) 3), three normal-butyl bromination titanium (TiBr (C 4H 9) 3), dimethyl dibrominated titanium (TiBr 2(CH 3) 2), diethyl dibrominated titanium (TiBr 2(CH 3CH 2) 2), diisobutyl dibrominated titanium (TiBr 2(i-C 4H 9) 2), three normal-butyl bromination titanium (TiBr (C 4H 9) 3), methyl titanium tribromide (Ti (CH 3) Br 3), ethyl titanium tribromide (Ti (CH 3CH 2) Br 3), isobutyl-titanium tribromide (Ti (i-C 4H 9) Br 3), normal-butyl titanium tribromide (Ti (C 4H 9) Br 3);
Trimethylammonium zirconium chloride (ZrCl (CH 3) 3), triethyl zirconium chloride (ZrCl (CH 3CH 2) 3), triisobutyl zirconium chloride (ZrCl (i-C 4H 9) 3), three normal-butyl chlorination zirconium (ZrCl (C 4H 9) 3), dimethyl zirconium dichloride (ZrCl 2(CH 3) 2), diethyl zirconium dichloride (ZrCl 2(CH 3CH 2) 2), diisobutyl zirconium dichloride (ZrCl 2(i-C 4H 9) 2), three normal-butyl chlorination zirconium (ZrCl (C 4H 9) 3), methyl tri-chlorination zirconium (Zr (CH 3) Cl 3), ethyl tri-chlorination zirconium (Zr (CH 3CH 2) Cl 3), isobutyl-tri-chlorination zirconium (Zr (i-C 4H 9) Cl 3), normal-butyl tri-chlorination zirconium (Zr (C 4H 9) Cl 3);
Trimethylammonium zirconium bromide (ZrBr (CH 3) 3), triethyl zirconium bromide (ZrBr (CH 3CH 2) 3), triisobutyl zirconium bromide (ZrBr (i-C 4H 9) 3), three normal-butyl bromination zirconium (ZrBr (C 4H 9) 3), dimethyl dibrominated zirconium (ZrBr 2(CH 3) 2), diethyl dibrominated zirconium (ZrBr 2(CH 3CH 2) 2), diisobutyl dibrominated zirconium (ZrBr 2(i-C 4H 9) 2), three normal-butyl bromination zirconium (ZrBr (C 4H 9) 3), methyl tribromide zirconium (Zr (CH 3) Br 3), ethyl tribromide zirconium (Zr (CH 3CH 2) Br 3), isobutyl-tribromide zirconium (Zr (i-C 4H 9) Br 3), normal-butyl tribromide zirconium (Zr (C 4H 9) Br 3);
Trimethylammonium hafnium chloride (HfCl (CH 3) 3), triethyl hafnium chloride (HfCl (CH 3CH 2) 3), triisobutyl hafnium chloride (HfCl (i-C 4H 9) 3), three normal-butyl chlorination hafnium (HfCl (C 4H 9) 3), dimethyl hafnium dichloride (HfCl 2(CH 3) 2), diethyl hafnium dichloride (HfCl 2(CH 3CH 2) 2), diisobutyl hafnium dichloride (HfCl 2(i-C 4H 9) 2), three normal-butyl chlorination hafnium (HfCl (C 4H 9) 3), methyl tri-chlorination hafnium (Hf (CH 3) Cl 3), ethyl tri-chlorination hafnium (Hf (CH 3CH 2) Cl 3), isobutyl-tri-chlorination hafnium (Hf (i-C 4H 9) Cl 3), normal-butyl tri-chlorination hafnium (Hf (C 4H 9) Cl 3);
Trimethylammonium bromination hafnium (HfBr (CH 3) 3), triethyl bromination hafnium (HfBr (CH 3CH 2) 3), triisobutyl bromination hafnium (HfBr (i-C 4H 9) 3), three normal-butyl bromination hafnium (HfBr (C 4H 9) 3), dimethyl dibrominated hafnium (HfBr 2(CH 3) 2), diethyl dibrominated hafnium (HfBr 2(CH 3CH 2) 2), diisobutyl dibrominated hafnium (HfBr 2(i-C 4H 9) 2), three normal-butyl bromination hafnium (HfBr (C 4H 9) 3), methyl tribromide hafnium (Hf (CH 3) Br 3), ethyl tribromide hafnium (Hf (CH 3CH 2) Br 3), isobutyl-tribromide hafnium (Hf (i-C 4H 9) Br 3), normal-butyl tribromide hafnium (Hf (C 4H 9) Br 3);
Described IVB family metal alkoxide halogenide can be enumerated trimethoxy titanium chloride (TiCl (OCH 3) 3), triethoxy titanium chloride (TiCl (OCH 3CH 2) 3), three isobutoxy titanium chloride (TiCl (i-OC 4H 9) 3), three n-butoxy titanium chloride (TiCl (OC 4H 9) 3), dimethoxy titanium dichloride (TiCl 2(OCH 3) 2), diethoxy titanium dichloride (TiCl 2(OCH 3CH 2) 2), two isobutoxy titanium dichloride (TiCl 2(i-OC 4H 9) 2), three n-butoxy titanium chloride (TiCl (OC 4H 9) 3), methoxyl group titanous chloride (Ti (OCH 3) Cl 3), oxyethyl group titanous chloride (Ti (OCH 3CH 2) Cl 3), isobutoxy titanous chloride (Ti (i-C 4H 9) Cl 3), n-butoxy titanous chloride (Ti (OC 4H 9) Cl 3);
Trimethoxy titanium bromide (TiBr (OCH 3) 3), triethoxy titanium bromide (TiBr (OCH 3CH 2) 3), three isobutoxy titanium bromide (TiBr (i-OC 4H 9) 3), three n-butoxy titanium bromide (TiBr (OC 4H 9) 3), dimethoxy dibrominated titanium (TiBr 2(OCH 3) 2), diethoxy dibrominated titanium (TiBr 2(OCH 3CH 2) 2), two isobutoxy dibrominated titanium (TiBr 2(i-OC 4H 9) 2), three n-butoxy titanium bromide (TiBr (OC 4H 9) 3), methoxyl group titanium tribromide (Ti (OCH 3) Br 3), oxyethyl group titanium tribromide (Ti (OCH 3CH 2) Br 3), isobutoxy titanium tribromide (Ti (i-C 4H 9) Br 3), n-butoxy titanium tribromide (Ti (OC 4H 9) Br 3);
Trimethoxy zirconium chloride (ZrCl (OCH 3) 3), triethoxy zirconium chloride (ZrCl (OCH 3CH 2) 3), three isobutoxy zirconium chloride (ZrCl (i-OC 4H 9) 3), three n-butoxy zirconium chloride (ZrCl (OC 4H 9) 3), dimethoxy zirconium dichloride (ZrCl 2(OCH 3) 2), diethoxy zirconium dichloride (ZrCl 2(OCH 3CH 2) 2), two isobutoxy zirconium dichloride (ZrCl 2(i-OC 4H 9) 2), three n-butoxy zirconium chloride (ZrCl (OC 4H 9) 3), methoxyl group tri-chlorination zirconium (Zr (OCH 3) Cl 3), oxyethyl group tri-chlorination zirconium (Zr (OCH 3CH 2) Cl 3), isobutoxy tri-chlorination zirconium (Zr (i-C 4H 9) Cl 3), n-butoxy tri-chlorination zirconium (Zr (OC 4H 9) Cl 3);
Trimethoxy zirconium bromide (ZrBr (OCH 3) 3), triethoxy zirconium bromide (ZrBr (OCH 3CH 2) 3), three isobutoxy zirconium bromide (ZrBr (i-OC 4H 9) 3), three n-butoxy zirconium bromide (ZrBr (OC 4H 9) 3), dimethoxy dibrominated zirconium (ZrBr 2(OCH 3) 2), diethoxy dibrominated zirconium (ZrBr 2(OCH 3CH 2) 2), two isobutoxy dibrominated zirconium (ZrBr 2(i-OC 4H 9) 2), three n-butoxy zirconium bromide (ZrBr (OC 4H 9) 3), methoxyl group tribromide zirconium (Zr (OCH 3) Br 3), oxyethyl group tribromide zirconium (Zr (OCH 3CH 2) Br 3), isobutoxy tribromide zirconium (Zr (i-C 4H 9) Br 3), n-butoxy tribromide zirconium (Zr (OC 4H 9) Br 3);
Trimethoxy hafnium chloride (HfCl (OCH 3) 3), triethoxy hafnium chloride (HfCl (OCH 3CH 2) 3), three isobutoxy hafnium chloride (HfCl (i-OC 4H 9) 3), three n-butoxy hafnium chloride (HfCl (OC 4H 9) 3), dimethoxy hafnium dichloride (HfCl 2(OCH 3) 2), diethoxy hafnium dichloride (HfCl 2(OCH 3CH 2) 2), two isobutoxy hafnium dichloride (HfCl 2(i-OC 4H 9) 2), three n-butoxy hafnium chloride (HfCl (OC 4H 9) 3), methoxyl group tri-chlorination hafnium (Hf (OCH 3) Cl 3), oxyethyl group tri-chlorination hafnium (Hf (OCH 3CH 2) Cl 3), isobutoxy tri-chlorination hafnium (Hf (i-C 4H 9) Cl 3), n-butoxy tri-chlorination hafnium (Hf (OC 4H 9) Cl 3);
Trimethoxy bromination hafnium (HfBr (OCH 3) 3), triethoxy bromination hafnium (HfBr (OCH 3CH 2) 3), three isobutoxy bromination hafnium (HfBr (i-OC 4H 9) 3), three n-butoxy bromination hafnium (HfBr (OC 4H 9) 3), dimethoxy dibrominated hafnium (HfBr 2(OCH 3) 2), diethoxy dibrominated hafnium (HfBr 2(OCH 3CH 2) 2), two isobutoxy dibrominated hafnium (HfBr 2(i-OC 4H 9) 2), three n-butoxy bromination hafnium (HfBr (OC 4H 9) 3), methoxyl group tribromide hafnium (Hf (OCH 3) Br 3), oxyethyl group tribromide hafnium (Hf (OCH 3CH 2) Br 3), isobutoxy tribromide hafnium (Hf (i-C 4H 9) Br 3), n-butoxy tribromide hafnium (Hf (OC 4H 9) Br 3).
Wherein, as described IVB family metallic compound, preferred IVB family metal halide, more preferably TiCl 4, TiBr 4, ZrCl 4, ZrBr 4, HfCl 4, HfBr 4, TiCl most preferably 4And ZrCl 4
These IVB family metallic compounds can be used alone, and perhaps are used in combination multiple.
As the method for carrying out described treatment step, as long as can realize described porous support (hereinafter, described porous support comprise porous support itself and through pretreated porous support) obtain modified porous carrier with the processing of described chemical processing agent and get final product, not special the qualification, can enumerate following method, but be not limited to this.
Under the situation that adopts solid chemical processing agent (such as zirconium tetrachloride), at first prepare the solution of described chemical processing agent, add the described chemical processing agent of (the preferred dropping) specified amount then to porous support; Under the situation that adopts liquid chemical treatment agent (such as titanium tetrachloride), can be directly (but also can after being prepared into solution) the described chemical processing agent of specified amount is added (the preferred dropping) in porous support, contact reacts (in case of necessity by stirring) was carried out 0.5~24 hour, preferred 1~8 hour, more preferably 2~6 hours, most preferably 2~4 times, filter then and wash, then dry, obtain modified porous carrier thus.
Described filtration, washing and drying can adopt ordinary method to carry out, and wherein washer solvent can adopt used identical solvent when dissolving solid chemical processing agent.This washing is generally carried out 1~8 time, and preferred 2~6 times, most preferably 2~4 times.
When carrying out described treatment step, be 1~100 mmole in the ratio of the described chemical processing agent of IVB family metallic element and described porous support: 1 gram, preferred 5~40 mmoles: 1 gram.
When the solution of the described chemical processing agent of preparation, there is no particular limitation to employed solvent, can be suitable for preparation used those when helping the chemical treatment agent solution.And these solvents can be used alone, and perhaps are used in combination multiple.
There is no particular limitation to the concentration of described chemical processing agent in its solution, can suitably select as required, as long as can realize the amount ranges of described porous support given to this invention and described chemical processing agent.
According to the present invention, also there is no particular limitation to the temperature of described treatment step.Though select for use higher temperature of reaction to help the reaction of chemical processing agent and porous support, can reduce the reaction times.But because the solvent difference, its boiling point also is different.Those skilled in the art know that the temperature of reaction of chemical processing agent and porous support should be lower than the boiling point of solvent, and such as for hexane, temperature of reaction can be chosen between 20 ℃~65 ℃, can be chosen between 20 ℃~105 ℃ or the like for toluene.Therefore, temperature of reaction is different with the difference of solvent, cannot treat different things as the same, and is lower than between 5~10 ℃ of the solvent boiling points but be typically chosen in, but the lower limit of temperature is not limited.In addition, time of this treating processes is had no particular limits, generally can select for use 0.5~24 hour.Under the situation that improves temperature of reaction, the reaction times can be suitably short more.
It is pointed out that in this treating processes, the use of solvent is not essential.That is to say that the reaction of described chemical processing agent and described porous support can be carried out under the situation that does not have solvent to exist, but this moment, chemical processing agent was necessary for liquid state.The temperature of reaction of this moment and reaction times can be as required suitably determines, generally speaking, temperature of reaction should be lower than 5~10 ℃ of the boiling points of chemical processing agent at least, and the contact reacts time was generally 2~24 hours.For example, the reaction of chemical processing agent and porous support is fierce more, and temperature of reaction just is provided with lowly more, makes the reaction times long more thus.Such as, when chemical processing agent was titanium tetrachloride, temperature of reaction can be-30 ℃~126 ℃, the corresponding reaction times is 2~12 hours.
Then, describe with regard to the situation of using the Nonmetallocene part to handle described porous support below.
According to the present invention, described Nonmetallocene part is selected from the compound with following structure:
Figure A200710162672D00321
At one more specifically in the embodiment, described Nonmetallocene part is selected from (A) with following structure and (B) compound:
Figure A200710162672D00322
With
Figure A200710162672D00323
At one more specifically in the embodiment, described Nonmetallocene part is selected from the compound with following structure A-1 to A-4 and B-1 to B-4:
Figure A200710162672D00331
Figure A200710162672D00341
In above all structural formulas,
Q is selected from 0 or 1;
D is selected from 0 or 1;
A be selected from Sauerstoffatom, sulphur atom, selenium atom,
Figure A200710162672D00342
-NR 23R 24,-N (O) R 25R 26,
Figure A200710162672D00343
-PR 28R 29,-P (O) R 30OR 31, sulfuryl, sulfoxide group or-Se (O) R 39
B is selected from nitrogen-containing group, phosphorus-containing groups or C 1-C 30Alkyl;
D is selected from Sauerstoffatom, sulphur atom, selenium atom, nitrogenous C 1-C 30Alkyl, phosphorated C 1-C 30Alkyl, sulfuryl, sulfoxide group,
Figure A200710162672D00351
-N (O) R 25R 26,
Figure A200710162672D00352
-P (O) R 32(OR 33), wherein N, O, S, Se, P are respectively ligating atom;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group or phosphorus-containing groups, and wherein N, O, S, Se, P are respectively ligating atom;
F is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group or phosphorus-containing groups, and wherein N, O, S, Se, P are respectively ligating atom;
G is selected from C 1-C 30The C of alkyl, replacement 1-C 30Alkyl or safing function group;
Y and Z are selected from nitrogen-containing group, oxy radical, sulfur-containing group independently of one another, contain seleno group or phosphorus-containing groups, such as enumerating-NR 23R 24,-N (O) R 25R 26,-PR 28R 29,-P (O) R 30R 31,-OR 34,-SR 35,-S (O) R 36,-SeR 38With-Se (O) R 39, wherein N, O, S, Se and P are respectively ligating atom;
→ represent singly-bound or two key;
-represent covalent linkage or ionic linkage;
R 1, R 2, R 3, R 4, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21, R 22, R 23, R 24, R 25, R 26, R 27, R 28, R 29, R 30, R 31, R 32, R 33, R 34, R 35, R 36, R 38And R 39Be selected from hydrogen, C independently of one another 1-C 30The C of alkyl, halogen atom, replacement 1-C 30Alkyl (wherein preferred halo alkyl, such as-CH 2Cl and-CH 2CH 2Cl) or the safing function group, above-mentioned group can be the same or different to each other, wherein adjacent group such as R 1With R 2, R 3, R 3With R 4, R 6, R 7, R 8, R 9, and R 23With R 24Or R 25With R 26Deng can be each other in key or Cheng Huan;
R 5Be selected from lone-pair electron on the nitrogen, hydrogen, C 1-C 30The C of alkyl, replacement 1-C 30Alkyl, oxy radical (comprise hydroxyl and alkoxyl group, such as-OR 34With-T-OR 34), sulfur-containing group (comprises-SR 35,-T-SR 35), nitrogen-containing group (comprises-NR 23R 24,-T-NR 23R 24), or phosphorus-containing groups (comprises-PR 28R 29,-T-PR 28R 29,-T-P (O) R 30R 31); Work as R 5For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group or phosphorus-containing groups, R 5In N, O, S, P, Se be respectively ligating atom, and can carry out coordination with IVB family atoms metal; With
According to the present invention, described halogen is selected from F, Cl, Br, I;
Described nitrogen-containing group is selected from -NR 23R 24,-T-NR 23R 24Or-N (O) R 25R 26
Phosphorus-containing groups is selected from
Figure A200710162672D00354
-PR 28R 29,-P (O) R 30R 31Or-P (O) R 32(OR 33);
Described oxy radical is selected from hydroxyl and alkoxyl group, such as-OR 34With-T-OR 34
Described sulfur-containing group is selected from-SR 35,-T-SR 35,-S (O) R 36Or-T-SO 2R 37
The described seleno group that contains is selected from-SeR 38,-T-SeR 38,-Se (O) R 39Or-T-Se (O) R 39
Described group T is selected from C 1-C 30The C of alkyl, replacement 1-C 30Alkyl or safing function group;
Described R 37Be selected from hydrogen, C 1-C 30The C of alkyl, halogen atom, replacement 1-C 30Alkyl or safing function group.
According to the present invention, described C 1-C 30Alkyl comprises C 1-C 30Alkyl, C 2-C 30Cyclic alkyl, C 2-C 30Thiazolinyl, C 2-C 30Alkynyl, C 6-C 30Aryl, C 8-C 30Condensed ring radical or C 4-C 30Heterocyclic radical;
The C of described replacement 1-C 30Alkyl refers to the alkyl that has one or more inert substituents.So-called inertia, the coordination process that refers to these substituting groups pair and central metal atom does not have substantial interference.As non-specified otherwise, the C of described replacement 1-C 30Alkyl generally refers to halogenated C 1-C 30Alkyl, halogenated C 6-C 30Aryl, halogenated C 8-C 30Condensed ring radical or halogenated C 4-C 30Heterocyclic radical;
The safing function group refers to other safing function base except that the alkyl of alkyl and replacement.According to the present invention, described safing function group be such as enumerating halogen, oxy radical, nitrogen-containing group, silicon-containing group, germanic group, sulfur-containing group or containing tin group, particularly, and such as enumerating ether (as-OR 34Or-TOR 35), C 1-C 10Ester group, C 1-C 10Amine, C 1-C 10Alkoxyl group and nitro etc.
Described silicon-containing group is selected from-SiR 42R 43R 44,-T-SiR 45
Described germanic group is selected from-GeR 46R 47R 48,-T-GeR 49
Describedly contain tin group and be selected from-SnR 50R 51R 52,-T-SnR 53Or-T-Sn (O) R 54
Described R 42, R 43, R 44, R 45, R 46, R 47, R 48, R 49, R 50, R 51, R 52, R 53, R 54Be selected from hydrogen, C independently of one another 1-C 30The C of alkyl, halogen atom, replacement 1-C 30Alkyl or safing function group.
According to the present invention, described safing function group will satisfy following condition:
(1) do not disturb coordination process with IVB family atoms metal,
(2) with structural formula in group A, D, E, F, Y and Z all different and
(3) coordination ability with IVB family atoms metal is lower than described A, D, E, F, Y and Z group, and does not replace the coordination of these groups and IVB family atoms metal.
As this Nonmetallocene part, such as enumerating compound with following structure:
Figure A200710162672D00371
Figure A200710162672D00391
Figure A200710162672D00401
Wherein, described Nonmetallocene part is preferably selected from the compound with following structure:
Figure A200710162672D00402
Figure A200710162672D00411
Wherein, described Nonmetallocene part also is preferably selected from the compound with following structure:
Figure A200710162672D00412
Figure A200710162672D00421
With
Figure A200710162672D00422
Described Nonmetallocene part more preferably is selected from the compound with following structure:
Figure A200710162672D00423
With
Figure A200710162672D00424
These Nonmetallocene parts can be used alone, and perhaps are used in combination multiple.
When selecting described Nonmetallocene part to handle described porous support, as the method for carrying out described treatment step, as long as can realize described porous support (hereinafter, described porous support comprise porous support itself and through pretreated porous support) obtain modified porous carrier with the processing of described Nonmetallocene part and get final product, not special the qualification, can enumerate following method, but be not limited to this.
The solution that at first prepares described Nonmetallocene part.If what select is that solubleness to described Nonmetallocene part is not very high solvent, the mode that then can select suitably heating is to promote its dissolving; And, then can not adopt type of heating for to the higher solvent of Nonmetallocene part solubleness.Stir if desired, then the rotating speed that should stir is at 10~500 rev/mins.According to the present invention to the regulation of non-metallocene catalyst content in the final load type non-metallocene catalyst, and the solvent that adopts of this stage is to the solvability of this Nonmetallocene part, the mass concentration of this Nonmetallocene part is generally 0.02~0.30 grams per milliliter in the solution, preferred 0.05~0.15 grams per milliliter
To this moment used solvent there is no particular limitation, as long as can dissolve described Nonmetallocene part, such as being selected from:
Alkane is such as pentane, hexane, heptane, octane, nonane, decane etc.;
Naphthenic hydrocarbon, such as hexanaphthene, pentamethylene, suberane, cyclodecane, cyclononane etc.;
Halogenated alkane is such as methylene dichloride, dichloro hexane, two chloroheptanes, trichloromethane, trichloroethane, three chlorobutanes, methylene bromide, ethylene dibromide, dibromo-heptane, methenyl bromide, tribromoethane, three n-butyl bromide etc.;
Halo naphthenic hydrocarbon, such as chlorocyclopentane, chlorocyclohexane, chloro suberane, chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromocyclohexane, bromo suberane, bromo cyclooctane, bromo cyclononane, bromo cyclodecane,
Aromatic hydrocarbon is such as toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene etc.; With
Halogenated aromatic is such as chlorotoluene, chloro ethylbenzene, bromo toluene, bromo ethylbenzene etc.
Wherein, preferred alkane, halogenated alkane or aromatic hydrocarbon, most preferably hexane, methylene dichloride and toluene.
These solvents can be used alone, and perhaps are used in combination multiple.
Then, under evenly stirring, described porous support is joined in this Nonmetallocene ligand solution in the temperature range that is lower than 5 ℃ of solvent boiling points in room temperature, so that the proportioning of described Nonmetallocene part and described porous support is: 0.02~1.00 mmole: 1 gram, preferred 0.08~0.53 mmole: 1 gram, continue reaction 0.5~24 hour.Stirring can be adopted modes such as helical-ribbon type stirring or the stirring of anchor formula, stirs for helical-ribbon type, and stirring velocity is generally 5~50 rev/mins, stirs for the anchor formula, and stirring velocity is generally 5~200 rev/mins.
After the reaction, with reaction mixture through filtration, washing and dry, perhaps without filtration and washing and convection drying promptly obtains modified porous carrier.Generally speaking, for the lower reaction mixture of solid content, a kind of mode before adopting, and, then adopt a kind of mode in back for the higher reaction mixture of solid content.In case of necessity, this washing is generally carried out 1~8 time, and preferred 2~6 times, most preferably 2~4 times.Described drying can adopt well-established law to carry out, and such as the rare gas element drying, vacuumize drying, perhaps heating vacuumizes drying, preferably vacuumizes drying.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 point.That is thermal weight loss is dry terminal point less than 5% under the temperature that the boiling point of the solvent that, adopts being lower than is 5~45 ℃.When selecting lower boiling solvent, can adopt short time of drying, select high boiling solvent then generally to adopt long time of drying.Drying temperature generally is lower than 5~45 ℃ of the boiling points of used solvent, 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, or the like.
In addition, no matter select in Nonmetallocene part and the chemical processing agent which side to carry out this treatment step, all can use obtained in the aforementioned pre-treatment step replace described porous support to carry out this treatment step without crossing separated mixture.At this moment, owing to had solvent in this mixed solution, can omit the consumption that uses solvent or reduce solvent.
After having made modified porous carrier of the present invention, contact with the opposing party in the described Nonmetallocene part with being selected from described chemical processing agent by making described modified porous carrier, thereby can obtain load type non-metallocene catalyst of the present invention.
That is to say,, then in ensuing contact procedure, just only use the Nonmetallocene part if in treatment step, used chemical processing agent; And if in treatment step, used the Nonmetallocene part, then 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 modified porous carrier, chemical processing agent (or Nonmetallocene part) contained in described Nonmetallocene part (or described chemical processing agent) and this modified porous carrier is reacted, thereby original position generates Nonmetallocene title complex (original position load reaction), obtains load type non-metallocene catalyst of the present invention thus.
To the mode of carrying out of this contact procedure without any qualification, as long as can realize this original position load reaction.
Particularly, when adopting the 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 the Nonmetallocene part to carry out the aforementioned processing step before, nothing but porous support is replaced with modified porous 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 the aforementioned processing step before, nothing but porous support is replaced with modified porous carrier.
In addition, consider the Nonmetallocene part that uses in described modified porous carrier and this contact procedure or the interaction between the chemical processing agent, reacted mixed solution generally carries out 0.5~24 hour airtight wearing out at normal temperatures, to increase the bond strength between the two.
Those skilled in the art knows that above-described various contacts and treating processes are generally all carried out under the anhydrous and oxygen-free condition of strictness, said here anhydrous and oxygen-free condition is meant that the content of water and oxygen in the system continues less than 10ppm.And, load type non-metallocene catalyst of the present invention after the preparation usually under airtight nitrogen envelope pressure-fired preserve standby.
In one embodiment, the invention still further relates to the load type non-metallocene catalyst of making by the preparation method of aforementioned load type non-metallocene catalyst.
The load type non-metallocene catalyst that the present invention makes constitutes catalyst system jointly with promotor, can be used for the homopolymerization/copolymerization of catalyzed alkene.
By being Primary Catalysts with load type non-metallocene catalyst of the present invention, be promotor to be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more, homopolymerization and/or copolymerization that can catalyzed alkene.
There is no particular limitation to the homopolymerization of described alkene and/or copolymerization process, can adopt well known in the art those, such as enumerating slurry process, emulsion method, solution method, substance law and vapor phase process.
Described alkene is selected from C 2~C 10Monoolefine, diolefin, cycloolefin and other ethylenically unsaturated compounds.Particularly, described C 2~C 10Monoolefine can be enumerated ethene, propylene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-hendecene, 1-laurylene, 1-cyclopentenes, norbornylene, norbornadiene and vinylbenzene, described diolefin can enumerate 1,4-divinyl, 2,5-pentadiene, 1,6-hexadiene and 1, the 7-octadiene, and described other ethylenically unsaturated compounds can be enumerated vinyl acetate and (methyl) acrylate.Need be pointed out that here that the said homopolymerization of the present invention is meant a kind of polymerization of alkene, and copolymerization is meant the polymerization between the two or more alkene.
As previously mentioned, described promotor can be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt, wherein preferred aikyiaiurnirsoxan beta and aluminum alkyls.
As aikyiaiurnirsoxan beta and aluminum alkyls, those that mentioned when conduct helps chemical processing agent before can adopting, wherein preferable methyl aikyiaiurnirsoxan beta and triethyl aluminum.
Preparation method's technology simple possible of load type non-metallocene catalyst of the present invention, and the charge capacity of Nonmetallocene part is adjustable, can improve its charge capacity significantly, improves the polymerization activity of this catalyzer thus significantly.
In addition, by adopting different chemical processing agent consumptions, can obtain polymerization activity from low to high and adjustable load type non-metallocene catalyst adapts to different olefinic polymerization requirements thus.
Adopt method for preparing catalyst provided by the invention, the Nonmetallocene part is tight with combining of carrier, has avoided the influence of free ligand to the load type non-metallocene catalyst polymerization effectively, thereby makes the performance of this catalyzer more stable.
When employing load type non-metallocene catalyst that the present invention obtained and promotor constitute catalyst system, only need fewer promotor (such as methylaluminoxane or triethyl aluminum) consumption, just can obtain high olefin polymerizating activity.
Embodiment
Below adopt embodiment that the present invention is described in further detail, but the invention is not restricted to these embodiment.
Polymer stacks density measurement reference standard GB 1636-79 carries out that (unit is g/cm 3).
The mensuration of IVB family metal content adopts ICP-AES to measure in the loaded catalyst, and the 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 the reactor is filtered and drying, the quality of this polymerisate of weighing then represents that divided by the ratio of the quality of used load type non-metallocene catalyst (unit is a kg polymkeric substance/gCat) for the polymerization activity of catalyzer with this polymerisate quality.
Embodiment 1
Porous support adopts silica gel, and model is the ES757 of Ineos company, and it is standby after continuing roasting 4h under 600 ℃, N2 atmosphere.
Take by weighing the silica gel after this thermal activation of 5g, add the 50ml hexane, under agitation condition with 30 minutes dropping chemical processing agent titanium tetrachlorides, 60 ℃ of following stirring reactions 4 hours, filter hexane wash 3 times, each hexane consumption 25ml is heated to 60 ℃ of dryings then and obtained modified porous carrier in 2 hours.Wherein, titanium tetrachloride and carrier proportioning are 9.4 mmoles: 1 gram.
To have structural formula
Figure A200710162672D00461
The Nonmetallocene part is dissolved in the hexane, adds modified porous carrier then, 4 hours after-filtration of stirring reaction, and hexane wash 2 times, each hexane consumption 25ml, 25 ℃ obtained load type non-metallocene catalyst down in dry 6 hours then.
The part mass concentration is 0.045 grams per milliliter, and the proportioning of Nonmetallocene part and porous support is: 0.193 mmole: 1 gram.
Catalyzer is designated as CAT-1.
Embodiment 1-1
Substantially the same manner as Example 1, but following change is arranged:
Porous support is selected from aluminium sesquioxide, and the thermal activation condition is 800 ℃, N 2Continue roasting 12h under the atmosphere.
Titanium tetrachloride and carrier proportioning are 14 mmoles: 1 gram, solvent is changed into decane.
The Nonmetallocene part is changed into The part mass concentration is 0.12 grams per milliliter, and the proportioning of Nonmetallocene part and porous support is: 0.386 mmole: 1 gram, the solvent of dissolving Nonmetallocene part is changed into decane.
Embodiment 1-2
Substantially the same manner as Example 1, but following change is arranged:
Porous support is selected from polystyrene, and surface functional group is a carboxyl, and the thermal activation condition is 200 ℃, N 2Continue dry 2h under the atmosphere.
Chemical processing agent is changed into zirconium tetrachloride, at first is dissolved in the toluene, and zirconium tetrachloride and carrier proportioning are 18.7 mmoles: 1 gram, solvent is changed into toluene.
The Nonmetallocene part is changed into
Figure A200710162672D00472
The part mass concentration is 0.16 grams per milliliter, and the proportioning of Nonmetallocene part and porous support is: 0.508 mmole: 1 gram, the solvent of dissolving Nonmetallocene part is changed into toluene.
Embodiment 1-3
Substantially the same manner as Example 1, but following change is arranged:
Porous support is selected from polynite, and surface functional group is a hydroxyl, and the thermal activation condition is 300 ℃, N 2Continue dry 6h under the atmosphere.
Chemical processing agent is changed into titanium tetrabromide, and titanium tetrabromide and carrier proportioning are 5.2 mmoles: 1 gram, solvent is changed into pentane.
The Nonmetallocene part is changed into
Figure A200710162672D00481
Wherein the part mass concentration is 0.02 grams per milliliter, and the proportioning of Nonmetallocene part and porous support is 0.841 mmole: 1 gram, the solvent of dissolving Nonmetallocene part is changed into pentane.
Embodiment 1-4
Substantially the same manner as Example 1, but following change is arranged:
Porous support is selected from polypropylene, and surface functional group is a hydroxyl, and the thermal activation condition is 200 ℃, N 2Continue dry 2h under the atmosphere.
Chemical processing agent is changed into the tetrabormated zirconium, and tetrabormated zirconium and carrier proportioning are 47 mmoles: 1 gram, solvent is changed into methylene dichloride.
The Nonmetallocene part is changed into
Figure A200710162672D00482
Wherein the part mass concentration is 0.28 grams per milliliter, and the proportioning of Nonmetallocene part and porous support is: 0.02 mmole: 1 gram, the solvent of dissolving Nonmetallocene part is changed into methylene dichloride.
Embodiment 1-5
Substantially the same manner as Example 1, but following change is arranged:
Porous support is selected from the silicon-dioxide of silicon tetrachloride through pyrohydrolysis process preparation, and the thermal activation condition is to continue dry 8h under 600 ℃, dry nitrogen atmosphere.
Chemical processing agent is changed into the tetramethyl-titanium, and tetramethyl-titanium and carrier proportioning are 15.1 mmoles: 1 gram, solvent is changed into ethylbenzene.
The Nonmetallocene part is changed into
Figure A200710162672D00491
The solvent of dissolving Nonmetallocene part is changed into ethylbenzene.
Embodiment 1-6
Substantially the same manner as Example 1, but following change is arranged:
Porous support is selected from titanium dioxide, and the thermal activation condition is to continue dry 4h under 400 ℃, dry argon gas atmosphere.
Chemical processing agent is changed into the tetraethyl-titanium, and solvent is changed into hexanaphthene.
The Nonmetallocene part is changed into
Figure A200710162672D00492
The solvent of dissolving Nonmetallocene part is changed into hexanaphthene.
Embodiment 1-7
Substantially the same manner as Example 1, but following change is arranged:
Porous support is selected from the MCM-41 molecular sieve, and the thermal activation condition is 450 ℃, N 2Continue dry 8h under the atmosphere.
Chemical processing agent is changed into the tetramethoxy titanium, and solvent is changed into methylcyclohexane.
The Nonmetallocene part is changed into
Figure A200710162672D00493
The solvent of dissolving Nonmetallocene part is changed into methylcyclohexane.
Embodiment 1-8
Substantially the same manner as Example 1, but following change is arranged:
Porous support is selected from kaolin, and surface functional group is a hydroxyl, and the thermal activation condition is to continue dry 6h under 250 ℃, vacuum.
Chemical processing agent is changed into the tetramethyl-zirconium.
The Nonmetallocene part is changed into
Embodiment 1-9
Substantially the same manner as Example 1, but following change is arranged:
Porous support is selected from diatomite, and surface functional group is a hydroxyl, and the thermal activation condition is 800 ℃, N 2Continue roasting 12h under the atmosphere.
Chemical processing agent is changed into the tetramethoxy zirconium.
The Nonmetallocene part is changed into
Figure A200710162672D00502
Embodiment 2
Porous support adopts silica gel, and model is the ES757 of Ineos company, with it at 600 ℃, N 2Standby behind the lasting roasting 4h under the atmosphere.
In an embodiment, used the composite chemical treatment agent.Hereinafter, for the event of simplicity of exposition, with chemical processing agent and help the combination of chemical processing agent to be referred to as the composite chemical treatment agent, and be the consumption that benchmark determines to help chemical processing agent with the chemical processing agent, but this with the present invention before specialized range produce contradiction.
In the 5g silica-gel carrier, stir, react after 1 hour, again with 30 minutes dropping titanium tetrachlorides with the hexane solution that was added dropwise to triethyl aluminum in 15 minutes, stir the 2h after-filtration down at 60 ℃, hexane wash 3 times, each hexane consumption 30ml, 25 ℃ of dryings made modified porous carrier in back 6 hours.
Wherein, titanium tetrachloride and porous support proportioning are 9.4 mmoles: 1 gram, titanium tetrachloride and triethyl aluminum mol ratio are 1:1 in the composite chemical treatment agent.
To have structural formula
Figure A200710162672D00511
The Nonmetallocene part is dissolved in the hexane, adds above-mentioned modified porous carrier then, and stirring reaction 4 hours filters, hexane wash 2 times, and each hexane consumption 25ml, 25 ℃ obtained load type non-metallocene catalyst down in dry 2 hours then.
The part mass concentration is 0.045 grams per milliliter, and the proportioning of Nonmetallocene part and porous support is: 0.193 mmole: 1 gram.
Catalyzer is designated as CAT-2.Wherein the titanium mass content is 3.29%, and the part mass content is 0.96%.
Embodiment 2-1
Substantially the same manner as Example 2, but following change is arranged:
With the toluene solution that was added dropwise to methylaluminoxane in 15 minutes, react after 4 hours earlier, dripped titanium tetrachloride with 30 minutes again, stir 0.5h after-filtration, toluene wash down at 105 ℃.Wherein, titanium tetrachloride and methylaluminoxane mol ratio are 1:4 in the composite chemical treatment agent.
Embodiment 2-2
Substantially the same manner as Example 2, but following change is arranged:
With the n-heptane solution that was added dropwise to triethyl aluminum in 15 minutes, react after 0.5 hour earlier, again with 30 minutes dropping titanium tetrabromides.Stir 6h after-filtration, heptane wash down at 65 ℃.Wherein, titanium tetrabromide and triethyl aluminum mol ratio are 1:2 in the composite chemical treatment agent.
Embodiment 2-3
Substantially the same manner as Example 2, but following change is arranged:
With the decane solution that was added dropwise to triethyl aluminum in 15 minutes, react after 1 hour earlier, again with the decane solution that dripped zirconium tetrachloride in 30 minutes.Stir the 1h after-filtration down at 110 ℃, the decane washing.Wherein, zirconium tetrachloride and triethyl aluminum mol ratio are 1:0.25 in the composite chemical treatment agent.
Embodiment 2-4
Substantially the same manner as Example 2, but following change is arranged:
With the pentane solution that was added dropwise to triethyl aluminum in 15 minutes, react after 1 hour earlier, again with the pentane solution that dripped the tetrabormated zirconium in 30 minutes.Stir the 8h after-filtration down at 30 ℃, the dimethylbenzene washing.Wherein, tetrabormated zirconium and triethyl aluminum mol ratio are 1:0.5 in the composite chemical treatment agent.
Embodiment 2-5
Substantially the same manner as Example 2, but following change is arranged:
Be added dropwise to triisobutyl aluminium with 15 minutes earlier, react after 1 hour, dripped titanium tetrachloride with 30 minutes again, stir 8h after-filtration, ethylbenzene washing down at 30 ℃.Wherein, titanium tetrachloride and triisobutyl al mole ratio are 1:4 in the composite chemical treatment agent.
Embodiment 2-6
Substantially the same manner as Example 2, but following change is arranged:
Be added dropwise to aluminum ethylate with 15 minutes earlier, react after 1 hour, again with 30 minutes dropping titanium tetrachlorides.Wherein, titanium tetrachloride and triethyl aluminum mol ratio are 1:0.75 in the composite chemical treatment agent.
Embodiment 2-7
Substantially the same manner as Example 2, but following change is arranged:
Be added dropwise to triisobutyl alumina alkane with 15 minutes earlier, react after 1 hour, again with 30 minutes dropping titanium tetrachlorides.Wherein, titanium tetrachloride and triisobutyl alumina alkane mol ratio are 1:1 in the composite chemical treatment agent.
Embodiment 2-8
Substantially the same manner as Example 2, but following change is arranged:
Titanium tetrachloride and carrier proportioning are 5.2 mmoles: 1 gram.
The Nonmetallocene part is changed into
Figure A200710162672D00531
Embodiment 2-9
Substantially the same manner as Example 2, but following change is arranged:
Titanium tetrachloride and carrier proportioning are 15.4 mmoles: 1 gram.
The Nonmetallocene part is changed into
Figure A200710162672D00532
Embodiment 2-10
Substantially the same manner as Example 2, but following change is arranged:
Titanium tetrachloride and carrier proportioning are 20.6 mmoles: 1 gram.
The Nonmetallocene part is changed into
Reference example 2-1
Substantially the same manner as Example 2, but following change is arranged:
The proportioning of Nonmetallocene part and porous support is: 0.386 mmole: 1 gram.
The titanium mass content is 2.87% in the load type non-metallocene catalyst, and the part mass content is 1.81%.
Catalyzer is designated as CAT-A.
By this reference example as can be known, other processes are identical, but the content of titanium reduces in the load type non-metallocene catalyst.This phenomenon is because the increase of Nonmetallocene part add-on causes the charge capacity of load type non-metallocene catalyst due to increasing.The preparation method of load type non-metallocene catalyst of the present invention is adopted in this explanation, can obtain high Nonmetallocene part charge capacity, and its charge capacity is adjustable.
Reference example 2-2
Substantially the same manner as Example 2, but following change is arranged:
The proportioning of Nonmetallocene part and porous support is: 0.064 mmole: 1 gram.
The titanium mass content is 3.64% in the load type non-metallocene catalyst, and the part mass content is 0.45%.
Catalyzer is designated as CAT-B.
Under the identical condition of Nonmetallocene part add-on, increase this phenomenon as can be known by titanium content increase, polymerization activity in the load type non-metallocene catalyst, 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 high load type non-metallocene catalyst of catalysis in olefine polymerization.
Embodiment 3
Porous support adopts silica gel, and model is the ES757 of Ineos company, with it at 600 ℃, N 2Standby behind the lasting roasting 4h under the atmosphere.
To have structural formula
Figure A200710162672D00541
The Nonmetallocene part is dissolved in the 50ml hexane, adds the silica gel after the 5g thermal activation then, 4 hours after-filtration of 25 ℃ of stirring reactions, hexane wash 2 times, each hexane consumption 25ml, 25 ℃ of following vacuum-drying afterwards 2 hours.Add the 50ml hexane then, under agitation condition with dripping the chemical processing agent titanium tetrachloride in 30 minutes, 60 ℃ of following stirring reactions 4 hours, filter, hexane wash 3 times, each hexane consumption 25ml, 25 ℃ of vacuum-dryings obtained load type non-metallocene catalyst in 6 hours then.
Wherein, titanium tetrachloride and carrier proportioning are 9.4 mmoles: 1 gram.
The part mass concentration is 0.045 grams per milliliter, and the proportioning of Nonmetallocene part and porous support is: 0.193 mmole: 1 gram.
Catalyzer is designated as CAT-3.
Embodiment 3-1
Substantially the same manner as Example 3, but following change is arranged:
Porous support is selected from aluminium sesquioxide, and the thermal activation condition is 800 ℃, N 2Continue roasting 12h under the atmosphere.
Titanium tetrachloride and carrier proportioning are 14 mmoles: 1 gram, solvent is changed into decane.
The Nonmetallocene part is changed into
Figure A200710162672D00551
The part mass concentration is 0.12 grams per milliliter, and the proportioning of Nonmetallocene part and porous support is: 0.386 mmole: 1 gram, the solvent of dissolving Nonmetallocene part is changed into decane.
Embodiment 3-2
Substantially the same manner as Example 3, but following change is arranged:
Porous support is selected from polystyrene, and surface functional group is a carboxyl, and the thermal activation condition is 200 ℃, N 2Continue dry 2h under the atmosphere.
Chemical processing agent is changed into zirconium tetrachloride, at first is dissolved in the toluene, and zirconium tetrachloride and carrier proportioning are 18.7 mmoles: 1 gram, solvent is changed into toluene.
The Nonmetallocene part is changed into
Figure A200710162672D00552
The part mass concentration is 0.16 grams per milliliter, and the proportioning of Nonmetallocene part and porous support is: 0.508 mmole: 1 gram, the solvent of dissolving Nonmetallocene part is changed into toluene.
Embodiment 3-3
Substantially the same manner as Example 3, but following change is arranged:
Porous support is selected from polynite, and surface functional group is a hydroxyl, and the thermal activation condition is 300 ℃, N 2Continue dry 6h under the atmosphere.
Chemical processing agent is changed into titanium tetrabromide, and titanium tetrabromide and carrier proportioning are 5.2 mmoles: 1 gram, solvent is changed into pentane.
The Nonmetallocene part is changed into
Figure A200710162672D00561
Wherein the part mass concentration is 0.02 grams per milliliter, and the proportioning of Nonmetallocene part and porous support is 0.841 mmole: 1 gram, the solvent of dissolving Nonmetallocene part is changed into pentane.
Embodiment 3-4
Substantially the same manner as Example 3, but following change is arranged:
Porous support is selected from polypropylene, and surface functional group is a hydroxyl, and the thermal activation condition is 200 ℃, N 2Continue dry 2h under the atmosphere.
Chemical processing agent is changed into the tetrabormated zirconium, and tetrabormated zirconium and carrier proportioning are 47 mmoles: 1 gram, solvent is changed into methylene dichloride.
The Nonmetallocene part is changed into
Figure A200710162672D00562
Wherein the part mass concentration is 0.28 grams per milliliter, and the proportioning of Nonmetallocene part and porous support is: 0.02 mmole: 1 gram, the solvent of dissolving Nonmetallocene part is changed into methylene dichloride.
Embodiment 3-5
Substantially the same manner as Example 3, but following change is arranged:
Porous support is selected from the silicon-dioxide of silicon tetrachloride through pyrohydrolysis process preparation, and the thermal activation condition is to continue dry 8h under 600 ℃, dry nitrogen atmosphere.
Chemical processing agent is changed into the tetramethyl-titanium, and tetramethyl-titanium and carrier proportioning are 15.1 mmoles: 1 gram, solvent is changed into ethylbenzene.
The Nonmetallocene part is changed into
Figure A200710162672D00571
The solvent of dissolving Nonmetallocene part is changed into ethylbenzene.
Embodiment 3-6
Substantially the same manner as Example 3, but following change is arranged:
Porous support is selected from titanium dioxide, and the thermal activation condition is to continue dry 4h under 400 ℃, dry argon gas atmosphere.
Chemical processing agent is changed into the tetraethyl-titanium, and solvent is changed into hexanaphthene.
The Nonmetallocene part is changed into
Figure A200710162672D00572
The solvent of dissolving Nonmetallocene part is changed into hexanaphthene.
Embodiment 3-7
Substantially the same manner as Example 1, but following change is arranged:
Porous support is selected from the MCM-41 molecular sieve, and the thermal activation condition is 450 ℃, N 2Continue dry 8h under the atmosphere.
Chemical processing agent is changed into the tetramethoxy titanium, and solvent is changed into methylcyclohexane.
The Nonmetallocene part is changed into
Figure A200710162672D00581
The solvent of dissolving Nonmetallocene part is changed into methylcyclohexane.
Embodiment 3-8
Substantially the same manner as Example 3, but following change is arranged:
Porous support is selected from kaolin, and surface functional group is a hydroxyl, and the thermal activation condition is to continue dry 6h under 250 ℃, vacuum.
Chemical processing agent is changed into the tetramethyl-zirconium.
The Nonmetallocene part is changed into
Figure A200710162672D00582
Embodiment 3-9
Substantially the same manner as Example 3, but following change is arranged:
Porous support is selected from diatomite, and surface functional group is a hydroxyl, and the thermal activation condition is 800 ℃, N 2Continue roasting 12h under the atmosphere.
Chemical processing agent is changed into the tetramethoxy zirconium.
The Nonmetallocene part is changed into
Figure A200710162672D00583
Embodiment 4
Porous support adopts silica gel, and model is the ES757 of Ineos company, with it at 600 ℃, N 2Standby behind the lasting roasting 4h under the atmosphere.
Stir in the 5g silica-gel carrier and, react after 1 hour with the hexane solution that was added dropwise to triethyl aluminum in 15 minutes, filtration hexane wash 2 times, 25ml at every turn adds structural formula then and is
Figure A200710162672D00591
The hexane solution of Nonmetallocene part, stirring reaction 2 hours filters, hexane wash 2 times, each hexane consumption 25ml, 25 ℃ add the 50ml hexane after dry 2 hours down, stir and with being added dropwise to titanium tetrachloride in 30 minutes, 60 ℃ of following stirring reactions 4 hours, filter, adopt hexane wash 3 times, each hexane consumption 25ml, normal temperature is dry 4 hours down then, obtains load type non-metallocene catalyst.
Wherein, titanium tetrachloride and porous support proportioning are 9.4 mmoles: 1 gram, titanium tetrachloride and triethyl aluminum mol ratio are 1:1.
The part mass concentration is 0.045 grams per milliliter, and the proportioning of Nonmetallocene part and porous support is: 0.193 mmole: 1 gram.
Catalyzer is designated as CAT-4.
Embodiment 4-1
Substantially the same manner as Example 4, but following change is arranged:
With the toluene solution that was added dropwise to methylaluminoxane in 15 minutes, react after 4 hours earlier, dripped titanium tetrachloride with 30 minutes again, stir 0.5h after-filtration, toluene wash down at 105 ℃.Wherein, titanium tetrachloride and methylaluminoxane mol ratio are 1:4.
Embodiment 4-2
Substantially the same manner as Example 4, but following change is arranged:
With the n-heptane solution that was added dropwise to triethyl aluminum in 15 minutes, react after 0.5 hour earlier, again with 30 minutes dropping titanium tetrabromides.Stir 6h after-filtration, heptane wash down at 65 ℃.Wherein, titanium tetrabromide and triethyl aluminum mol ratio are 1:2.
Embodiment 4-3
Substantially the same manner as Example 4, but following change is arranged:
With the decane solution that was added dropwise to triethyl aluminum in 15 minutes, react after 1 hour earlier, again with the decane solution that dripped zirconium tetrachloride in 30 minutes.Stir the 1h after-filtration down at 110 ℃, the decane washing.Wherein, zirconium tetrachloride and triethyl aluminum mol ratio are 1:0.25.
Embodiment 4-4
Substantially the same manner as Example 4, but following change is arranged:
With the pentane solution that was added dropwise to triethyl aluminum in 15 minutes, react after 1 hour earlier, again with the pentane solution that dripped the tetrabormated zirconium in 30 minutes.Stir the 8h after-filtration down at 30 ℃, the dimethylbenzene washing.Wherein, tetrabormated zirconium and triethyl aluminum mol ratio are 1:0.5.
Embodiment 4-5
Substantially the same manner as Example 4, but following change is arranged:
Be added dropwise to triisobutyl aluminium with 15 minutes earlier, react after 1 hour, dripped titanium tetrachloride with 30 minutes again, stir 8h after-filtration, ethylbenzene washing down at 30 ℃.Wherein, titanium tetrachloride and triisobutyl al mole ratio are 1:4.
Embodiment 4-6
Substantially the same manner as Example 4, but following change is arranged:
Be added dropwise to aluminum ethylate with 15 minutes earlier, react after 1 hour, again with 30 minutes dropping titanium tetrachlorides.Wherein, titanium tetrachloride and triethyl aluminum mol ratio are 1:0.75.
Embodiment 4-7
Substantially the same manner as Example 4, but following change is arranged:
Be added dropwise to triisobutyl alumina alkane with 15 minutes earlier, react after 1 hour, again with 30 minutes dropping titanium tetrachlorides.Wherein, titanium tetrachloride and triisobutyl alumina alkane mol ratio are 1:1.
Embodiment 4-8
Substantially the same manner as Example 4, but following change is arranged:
Titanium tetrachloride and carrier proportioning are 5.2 mmoles: 1 gram.
The Nonmetallocene part is changed into
Figure A200710162672D00611
Embodiment 4-9
Substantially the same manner as Example 4, but following change is arranged:
Titanium tetrachloride and carrier proportioning are 15.4 mmoles: 1 gram.
The Nonmetallocene part is changed into
Figure A200710162672D00612
Embodiment 4-10
Substantially the same manner as Example 4, but following change is arranged:
Titanium tetrachloride and carrier proportioning are 20.6 mmoles: 1 gram.
The Nonmetallocene part is changed into
Figure A200710162672D00613
Embodiment 5 (Application Example)
CAT-A, the CAT-B that makes in catalyzer CAT-1, the CAT-2, CAT-3, CAT-4 and the reference example that make in the embodiment of the invention carried out under the following conditions in accordance with the following methods the homopolymerization of ethene respectively:
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.At first 1 liter of hexane is joined in the polymerization autoclave, open and stir, add load type non-metallocene catalyst and catalyst mixture then, add hydrogen again, continue to feed ethene at last and make the polymerization stagnation pressure constant at 0.8MPa to 0.2MPa.Reaction with gas reactor emptying, is emitted the still interpolymer after finishing, dry back weighing quality.The particular case of this polyreaction and polymerization evaluation result are as shown in table 1.
Table 1. load type non-metallocene catalyst is used for olefinic polyreaction effect table look-up
Sequence number Load type non-metallocene alkene catalyst numbering Promotor Aluminium titanium mol ratio Polymerization activity (kgPE/gCat) Polymer stacks density (g/cm 3)
1 CAT-1 Triethyl aluminum 140 1.04 0.20
2 CAT-1 Methylaluminoxane 100 1.62 0.27
3 CAT-2 Triethyl aluminum 140 1.51 0.25
4 CAT-2 Triethyl aluminum 500 1.58 0.25
5 CAT-2 Methylaluminoxane 100 1.94 0.30
6 CAT-2 Methylaluminoxane 250 2.07 0.31
7 CAT-A Triethyl aluminum 140 1.25 0.25
8 CAT-B Triethyl aluminum 140 2.34 0.25
9 CAT-3 Triethyl aluminum 140 2.67 0.28
10 CAT-3 Methylaluminoxane 100 3.41 0.31
11 CAT-4 Triethyl aluminum 140 3.94 0.31
12 CAT-4 Methylaluminoxane 100 5.22 0.33
Contrast by sequence number in the table 13 and 4,5 and 6 test-results data increases the consumption of promotor as can be known, and when promptly improving aluminium titanium mol ratio, influence active to polymerization catalyst and polymer stacks density is not remarkable.It can be said that brightly, adopt the load type non-metallocene catalyst of method provided by the invention preparation only to need fewer promotor consumption just can obtain high olefin polymerizating activity; And polymkeric substance such as resulting polyethylene has good polymer morphology and high polymer bulk density thus.
Contrast by sequence number 9 and 1 in the table 1,11 and 3 test-results data simultaneously in the Preparation of catalysts process, is carried out the chemical processing agent processing earlier and is more helped obtaining highly active load type non-metallocene catalyst as can be known behind the adding Nonmetallocene title complex.
And by the contrast of 1 and 2,3 and 5,9 and 10,11 and 12 test-results data in the table 1 as can be known, help obtaining the polymkeric substance of higher bulk density as promotor with methylaluminoxane.

Claims (28)

1. the preparation method of a load type non-metallocene catalyst may further comprise the steps:
Handle porous support with a side who is selected from chemical processing agent and the Nonmetallocene part, obtain the treatment step of modified porous carrier, wherein said chemical processing agent is selected from IVB family metallic compound; With
Described modified porous carrier is contacted with the opposing party in the 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 described load type non-metallocene catalyst of claim 1, also comprise the step of the load type non-metallocene catalyst of dry described acquisition.
3. according to the preparation method of the described load type non-metallocene catalyst of claim 1, also be included in before the described treatment step step of the described porous support of thermal activation treatment.
4. according to the preparation method of the described load type non-metallocene catalyst of claim 1, also be included in before the described treatment step, handle the step of described porous support with the chemical processing agent that helps that is selected from aikyiaiurnirsoxan beta, aluminum alkyls and composition thereof.
5. according to the preparation method of the described load type non-metallocene catalyst of claim 3, it is characterized in that described thermal activation treatment is included under the inert atmosphere, handled 0.5~24 hour down at 200~800 ℃.
6. according to the preparation method of the described load type non-metallocene catalyst of claim 5, it is characterized in that described thermal activation treatment is included under nitrogen or the argon gas atmosphere, handled 2~12 hours down at 400~700 ℃.
7. according to the preparation method of the described load type non-metallocene catalyst of claim 6, it is characterized in that described thermal activation treatment is included in 400~650 ℃ and handled 4~8 hours down.
8. according to the preparation method of the described load type non-metallocene catalyst of claim 1, it is characterized in that, described porous support is selected from partial cross-linked and has the styrene polymer and the porous inorganic material of surperficial carboxyl, and wherein said the porous inorganic material oxide compound, clay, molecular sieve, mica, polynite, wilkinite, diatomite, ZSM-5 and the MCM-41 that are selected from oxide compound that one or more elements by periodic table of elements IIA, IIIA, IVA and IVB family metal constitute, are generated by pyrohydrolysis by gaseous metal halogenide or gaseous silicon compound.
9. according to the preparation method of the described load type non-metallocene catalyst of claim 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 described load type non-metallocene catalyst of claim 9, it is characterized in that described porous support is selected from silicon-dioxide.
11. the preparation method according to the described load type non-metallocene catalyst of claim 1 is characterized in that, described IVB family metallic compound is selected from one or more in metal halide, metal alkyl compound and the metal alkyl halides.
12. the preparation method according to the described load type non-metallocene catalyst of claim 11 is characterized in that, described IVB family metallic compound is selected from halogenated titanium and zirconium halide.
13. the preparation method according to the described load type non-metallocene catalyst of claim 12 is characterized in that, described IVB family metallic compound is a titanium tetrachloride.
14. the preparation method according to the described load type non-metallocene catalyst of claim 4 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.
15. the preparation method according to the described load type non-metallocene catalyst of claim 4 is characterized in that, helping the chemical processing agent and the ratio of described porous support in Al element described is 0.25~4 mmole: 1 gram.
16. the preparation method according to the described load type non-metallocene catalyst of claim 15 is characterized in that, helping the chemical processing agent and the ratio of described porous support in Al element described is 0.5~2 mmole: 1 gram.
17. the preparation method according to the described load type non-metallocene catalyst of claim 1 is characterized in that, is 1~100 mmole in the ratio of the described chemical processing agent of IVB family metallic element and described porous support: 1 gram.
18. the preparation method according to the described load type non-metallocene catalyst of claim 17 is characterized in that, is 5~40 mmoles in the ratio of the described chemical processing agent of IVB family metallic element and described porous support: 1 gram.
19. the preparation method according to the described load type non-metallocene catalyst of claim 1 is characterized in that, the proportioning of described Nonmetallocene part and described porous support is: 0.02~1.00 mmole: 1 gram.
20. the preparation method according to the described load type non-metallocene catalyst of claim 19 is characterized in that, the proportioning of described Nonmetallocene part and described porous support is: 0.08~0.53 mmole: 1 gram.
21. the preparation method according to the described load type non-metallocene catalyst of claim 1 is characterized in that, described Nonmetallocene part is selected from the compound with following structure:
Figure A200710162672C00041
Wherein:
Q is selected from 0 or 1;
D is selected from 0 or 1;
A be selected from Sauerstoffatom, sulphur atom, selenium atom,
Figure A200710162672C00042
-NR 23R 24,-N (O) R 25R 26, -PR 28R 29,-P (O) R 30OR 31, sulfuryl, sulfoxide group or-Se (O) R 39
B is selected from nitrogen-containing group, phosphorus-containing groups or C 1-C 30Alkyl;
D is selected from Sauerstoffatom, sulphur atom, selenium atom, nitrogenous C 1-C 30Alkyl, phosphorated C 1-C 30Alkyl, sulfuryl, sulfoxide group,
Figure A200710162672C00044
-N (O) R 25R 26,
Figure A200710162672C00045
Or-P (O) R 32(OR 33), wherein N, O, S, Se, P are respectively ligating atom;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group or phosphorus-containing groups, and wherein N, O, S, Se, P are respectively ligating atom;
G is selected from C 1-C 30The C of alkyl, replacement 1-C 30Alkyl or safing function group;
→ represent singly-bound or two key;
-represent covalent linkage or ionic linkage;
R 1, R 2, R 3, R 22, R 23, R 24, R 25, R 26, R 27, R 28, R 29, R 30, R 31, R 32, R 33And R 39Be selected from hydrogen, C independently of one another 1-C 30The C of alkyl, halogen atom, replacement 1-C 30Alkyl or safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can be each other in key or Cheng Huan.
22. the preparation method according to the described load type non-metallocene catalyst of claim 21 is characterized in that,
Described Nonmetallocene part is selected from (A) with following structure and (B) compound:
Figure A200710162672C00051
With
Figure A200710162672C00052
Wherein F is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group or phosphorus-containing groups, and wherein N, O, S, Se, P are respectively ligating atom;
Other are according to the described definition of claim 21.
23. the preparation method according to the described load type non-metallocene catalyst of claim 22 is characterized in that,
Described Nonmetallocene part is selected from the compound with following structure A-1 to A-4 and B-1 to B-4:
Figure A200710162672C00053
Figure A200710162672C00061
Figure A200710162672C00071
Wherein:
Y and Z are selected from nitrogen-containing group, oxy radical, sulfur-containing group independently of one another, contain seleno group or phosphorus-containing groups, and wherein N, O, S, Se and P are respectively ligating atom;
R 4, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20And R 21Be selected from hydrogen, C independently of one another 1-C 30The C of alkyl, halogen atom, replacement 1-C 30Alkyl or safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can be each other in key or Cheng Huan;
R 5Be selected from lone-pair electron on the nitrogen, hydrogen, C 1-C 30The C of alkyl, replacement 1-C 30Alkyl, oxy radical, sulfur-containing group, nitrogen-containing group or phosphorus-containing groups, prerequisite are to work as R 5For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group or phosphorus-containing groups, R 5In N, O, S, P, Se be respectively ligating atom;
Other are according to the described definition of claim 22.
24. the preparation method according to each described load type non-metallocene catalyst of claim 21-23 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
Figure A200710162672C00081
-PR 28R 29,-P (O) R 30R 31,-P (O) R 32(OR 33) ,-T-PR 28(OR 29) ,-T-P (O) R 30R 31Or-T-P (O) R 32(OR 33);
Described oxy radical be selected from hydroxyl ,-OR 34With-T-OR 34
Described sulfur-containing group is selected from-SR 35,-T-SR 35,-S (O) R 36Or-T-SO 2R 37
The described seleno group that contains is selected from-SeR 38,-T-SeR 38,-T-Se (O) R 39Or-Se (O) R 39
Described group T is selected from C 1-C 30The C of alkyl, replacement 1-C 30Alkyl or safing function group;
Described C 1-C 30Alkyl is selected from C 1-C 30Alkyl, C 2-C 30Cyclic alkyl, C 2-C 30Thiazolinyl, C 2-C 30Alkynyl, C 6-C 30Aryl, C 8-C 30Condensed ring radical or C 4-C 30Heterocyclic radical;
The C of described replacement 1-C 30Alkyl is selected from halogenated C 1-C 30Alkyl, halogenated C 6-C 30Aryl, halogenated C 8-C 30Condensed ring radical or halogenated C 4-C 30Heterocyclic radical;
Described silicon-containing group is selected from-SiR 42R 43R 44,-T-SiR 45
Described germanic group is selected from-GeR 46R 47R 48,-T-GeR 49
Describedly contain tin group and be selected from-SnR 50R 51R 52,-T-SnR 53Or-T-Sn (O) R 54
Described R 34, R 35, R 36, R 37, R 38And R 42, R 43, R 44, R 45, R 46, R 47, R 48, R 49, R 50, R 51, R 52, R 53, R 54Be selected from hydrogen, C independently of one another 1-C 30The C of alkyl, halogen atom, replacement 1-C 30Alkyl or safing function group.
25. the preparation method according to the described load type non-metallocene catalyst of claim 21 is characterized in that,
Described Nonmetallocene part is selected from the compound with following structure:
With
Figure A200710162672C00092
26. the preparation method according to the described load type non-metallocene catalyst of claim 25 is characterized in that,
Described Nonmetallocene part is selected from the compound with following structure:
With
Figure A200710162672C00094
27. a load type non-metallocene catalyst comprises carrier and load non-metallocene catalyst thereon, it is characterized in that, it is to make according to the preparation method of each described load type non-metallocene catalyst of claim 1~26.
CN 200710162672 2007-10-16 2007-10-16 Load type non-metallocene catalyst and preparation thereof Pending CN101412764A (en)

Priority Applications (6)

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CN 200710162672 CN101412764A (en) 2007-10-16 2007-10-16 Load type non-metallocene catalyst and preparation thereof
EP08842385A EP2202247B1 (en) 2007-10-16 2008-10-15 Supported non-metallocene catalyst and its preparation method
JP2010529214A JP5480147B2 (en) 2007-10-16 2008-10-15 Supported nonmetallocene catalyst and method for producing the same
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
PCT/CN2008/001738 WO2009052700A1 (en) 2007-10-16 2008-10-15 Supported non-metallocene catalyst and its preparation method

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CN102039188A (en) * 2009-10-26 2011-05-04 中国石油化工股份有限公司 Supported non-metallocene catalyst, its preparation method and uses
CN102039191A (en) * 2009-10-26 2011-05-04 中国石油化工股份有限公司 Load type non-metallocene catalyst, preparation method and application thereof
CN102059148A (en) * 2009-11-13 2011-05-18 中国石油化工股份有限公司 Loaded non-metallocene catalyst and preparation method and application thereof
CN102399331A (en) * 2010-09-16 2012-04-04 中国石油化工股份有限公司 Load-type non-metallocene catalyst, preparation method thereof, and application thereof
CN102964476A (en) * 2011-08-31 2013-03-13 中国石油化工股份有限公司 Supported non-metallocene catalyst, preparation method and application
CN102039190B (en) * 2009-10-26 2013-05-29 中国石油化工股份有限公司 Supported non-metallocene catalyst, preparation method and application thereof
CN103304703A (en) * 2012-03-06 2013-09-18 中国石油化工股份有限公司 Loaded non-metallocene catalyst, its preparation method and application
CN103304694A (en) * 2012-03-06 2013-09-18 中国石油化工股份有限公司 Loaded non-metallocene catalyst, its preparation method and application
CN102059150B (en) * 2009-11-13 2013-11-20 中国石油化工股份有限公司 Loaded non-metallocene catalyst and preparation method and application thereof
US8957169B2 (en) 2009-11-13 2015-02-17 China Petroleum & Chemical Corp. Supported nonmetallocene catalyst, preparation and use thereof
US8981023B2 (en) 2009-10-26 2015-03-17 China Petroleum & Chemical Corp. Supported nonmetallocene catalyst, preparation and use thereof
CN104415788A (en) * 2013-08-23 2015-03-18 中国石油化工股份有限公司 Olefin polymerization catalyst composition and application thereof
CN104415787A (en) * 2013-08-23 2015-03-18 中国石油化工股份有限公司 Olefin polymerization catalyst composition and application method thereof
CN109160966A (en) * 2018-07-06 2019-01-08 杭州师范大学 A kind of tripolite loading metallocene catalyst and the preparation method and application thereof
CN109651547A (en) * 2017-10-10 2019-04-19 中国石油天然气股份有限公司 Atactic copolymerized polypropene and preparation method thereof

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CN102039188A (en) * 2009-10-26 2011-05-04 中国石油化工股份有限公司 Supported non-metallocene catalyst, its preparation method and uses
CN102039191A (en) * 2009-10-26 2011-05-04 中国石油化工股份有限公司 Load type non-metallocene catalyst, preparation method and application thereof
US8981023B2 (en) 2009-10-26 2015-03-17 China Petroleum & Chemical Corp. Supported nonmetallocene catalyst, preparation and use thereof
CN102039191B (en) * 2009-10-26 2013-05-29 中国石油化工股份有限公司 Load type non-metallocene catalyst, preparation method and application thereof
CN102039190B (en) * 2009-10-26 2013-05-29 中国石油化工股份有限公司 Supported non-metallocene catalyst, preparation method and application thereof
CN102039188B (en) * 2009-10-26 2013-07-17 中国石油化工股份有限公司 Supported non-metallocene catalyst, its preparation method and uses
CN102059148A (en) * 2009-11-13 2011-05-18 中国石油化工股份有限公司 Loaded non-metallocene catalyst and preparation method and application thereof
US8957169B2 (en) 2009-11-13 2015-02-17 China Petroleum & Chemical Corp. Supported nonmetallocene catalyst, preparation and use thereof
CN102059148B (en) * 2009-11-13 2013-07-17 中国石油化工股份有限公司 Loaded non-metallocene catalyst and preparation method and application thereof
CN102059150B (en) * 2009-11-13 2013-11-20 中国石油化工股份有限公司 Loaded non-metallocene catalyst and preparation method and application thereof
CN102399331A (en) * 2010-09-16 2012-04-04 中国石油化工股份有限公司 Load-type non-metallocene catalyst, preparation method thereof, and application thereof
CN102964476B (en) * 2011-08-31 2015-11-25 中国石油化工股份有限公司 Load type non-metallocene catalyst, its preparation method and application thereof
CN102964476A (en) * 2011-08-31 2013-03-13 中国石油化工股份有限公司 Supported non-metallocene catalyst, preparation method and application
CN103304694A (en) * 2012-03-06 2013-09-18 中国石油化工股份有限公司 Loaded non-metallocene catalyst, its preparation method and application
CN103304703A (en) * 2012-03-06 2013-09-18 中国石油化工股份有限公司 Loaded non-metallocene catalyst, its preparation method and application
CN103304694B (en) * 2012-03-06 2016-02-24 中国石油化工股份有限公司 Load type non-metallocene catalyst, its preparation method and application thereof
CN103304703B (en) * 2012-03-06 2016-05-25 中国石油化工股份有限公司 Load type non-metallocene catalyst, its preparation method and application thereof
CN104415788A (en) * 2013-08-23 2015-03-18 中国石油化工股份有限公司 Olefin polymerization catalyst composition and application thereof
CN104415787A (en) * 2013-08-23 2015-03-18 中国石油化工股份有限公司 Olefin polymerization catalyst composition and application method thereof
CN104415788B (en) * 2013-08-23 2016-06-29 中国石油化工股份有限公司 Olefin Polymerization catalyst compositions and application thereof
CN104415787B (en) * 2013-08-23 2016-07-06 中国石油化工股份有限公司 A kind of olefin Polymerization catalyst compositions and using method thereof
CN109651547A (en) * 2017-10-10 2019-04-19 中国石油天然气股份有限公司 Atactic copolymerized polypropene and preparation method thereof
CN109160966A (en) * 2018-07-06 2019-01-08 杭州师范大学 A kind of tripolite loading metallocene catalyst and the preparation method and application thereof

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Application publication date: 20090422