CN102964477B - Supported non-metallocene catalyst, preparation method and application - Google Patents

Supported non-metallocene catalyst, preparation method and application Download PDF

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CN102964477B
CN102964477B CN201110259293.1A CN201110259293A CN102964477B CN 102964477 B CN102964477 B CN 102964477B CN 201110259293 A CN201110259293 A CN 201110259293A CN 102964477 B CN102964477 B CN 102964477B
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magnesium
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CN102964477A (en
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李传峰
任鸿平
柏基业
阚林
郭峰
左胜武
梅利
陈韶辉
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China Petroleum and Chemical Corp
Sinopec Yangzi Petrochemical Co Ltd
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Sinopec Yangzi Petrochemical Co Ltd
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Abstract

The invention relates to a supported non-metallocene catalyst and a preparation method. The supported non-metallocene catalyst is prepared by the steps of precipitating a mixed slurry of a magnesium compound and a solvent, loading a non-metallocene complex, treating with an IVB group chemical treating agent and directly drying. The preparation method is simple and feasible, and the load capacity of the non-metallocene ligand is adjustable. The invention also relates to the application of the supported non-metallocene catalyst in olefin homopolymerisation/copolymerization. Compared with the prior art, the supported non-metallocene catalyst has the characteristics of less usage of a cocatalyst for catalyzing polymerization of alkene, high polymerization activity, substantial copolymerization effect, high bulk density of polymer, and high and adjustable viscosity average molecular weight of the prepared ultrahigh molecular weight polyethylene.

Description

Load type non-metallocene catalyst, its preparation method and application thereof
The application based on " (national 11th Five-Year supporting plan problem " in the project of grinding.This project has obtained the great attention of the Ministry of Science and Technology and has supported energetically, its target is to form the polyolefin catalyst technology of new generation with independent intellectual property right, and improve domestic related products unification, improve China's polyolefine kind class, promote its future development to variation, seriation, customizations, high performance.
Technical field
The present invention relates to a kind of non-metallocene catalyst.Particularly, the present invention relates to a kind of load type non-metallocene catalyst, its preparation method and the application in alkene homopolymerization/copolymerization thereof.
Background technology
The non-metallocene catalyst that middle and later periods nineteen nineties occurs, claim again luxuriant rear catalyst, the central atom of Primary Catalysts has comprised nearly all transition metal, reach at some aspect of performance, even exceed metallocene catalyst, become after Ziegler, Ziegler-Natta and metallocene catalyst the 4th generation olefin polymerization catalysis.According to the difference of the central atom of Primary Catalysts, further can divide into again non-metallocene (IIIB family, IVB family, VB family, group vib, VIIB family) catalyzer and non-luxuriant rear transition metal (VIII family) catalyzer.By the excellent property of the polyolefin products of such catalyzer manufacturing, and low cost of manufacture.Non-metallocene catalyst ligating atom is oxygen, nitrogen, sulphur and phosphorus, do not contain cyclopentadienyl group or its deriveding group, as indenyl and fluorenyl etc., it is characterized in that central ion has stronger Electron Affinities, and there is cis alkyl or halogen metal division center, easily carry out alkene insertion and σ-key and shift, the easy alkylation of central metal, is conducive to the generation at cation activity center; The title complex forming has the geometric configuration of restriction, stereoselectivity, electronegativity and chirality controllability, and in addition, the metal-carbon key forming easily polarizes, and is more conducive to polymerization and the copolymerization of alkene.Therefore, even if also can obtain the olefin polymer of higher molecular weight under higher polymeric reaction temperature.
But homogeneous catalyst has been proved it in olefinic polyreaction has that active duration is short, easily sticky still, high methylaluminoxane consumption, and obtain the too low or too high weak point of polymericular weight, only can be used for solution polymerization process or high-pressure polymerization process, seriously limit its industrial applicability.
Patent ZL 01126323.7, ZL 02151294.9ZL 02110844.7 and WO 03/010207 disclose a kind of alkene homopolymerization/catalyst for copolymerization or catalyst system, there is 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 polymerization process, the phenomenons such as the sticky still of polymkeric substance.
Common way be by non-metallocene catalyst by certain load technology, make loaded catalyst, thereby improve the polymerization of alkene and the particle form of resulting polymers.It shows as the initial activity that has suitably reduced to a certain extent catalyzer, the polymerization activity life-span of extending catalyst, reduce and even avoided caking or the cruelly poly-phenomenon in polymerization process, improve the form of polymkeric substance, improve the apparent density of polymkeric substance, can make it meet more polymerization technique process, as vapour phase polymerization or slurry polymerization etc.
Existing olefin polymerization catalysis patent is mostly based on metallocene catalyst, as US 4808561, US 5240894, CN 1344749A, CN 1126480A, ZL94101358.8, CN 1307594A, CN 1103069A, CN1363537A, US6444604, EP0685494, US4871705 and EP0206794 etc., but these patents also all relate to the metallocene catalyst that contains transition metal are carried on carrier after treatment.
For patent ZL 01126323.7, ZL02151294.9ZL 02110844.7 and the disclosed non-metallocene catalyst of WO03/010207, patent CN 1539855A, CN 1539856A, CN 1789291A, CN 1789292A, CN 1789290A, WO/2006/063501, patent ZL200510119401.x etc. provide various ways to carry out load to obtain load type non-metallocene catalyst, but these patents all relate to the Nonmetallocene organic compound that contains transition metal is carried on carrier after treatment.
Chinese patent CN200910180602.9 discloses a kind of preparation method of load type non-metallocene catalyst, and it is that magnesium compound and Nonmetallocene title complex are dissolved in solvent, after being dried, obtains load type non-metallocene catalyst.Patent 200910180605.2 discloses a kind of preparation method of load type non-metallocene catalyst, and it is that magnesium compound and Nonmetallocene title complex are dissolved in solvent, adds precipitation agent precipitation, after filtration washing is dry, obtains load type non-metallocene catalyst.What these two kinds of methods adopted is magnesium compound carrier, and the particle form of catalyzer is difficult to control, and has limited the morphology that polymerization obtains thus.
Chinese patent CN200910180603.3, CN200910180604.8, CN200910210989.8, CN200910210986.4, the disclosed load type non-metallocene catalyst preparation method of CN200910210985.X, CN200910210990.0 and above-mentioned patent are similar, what all use is that magnesium compound is as carrier, still exist the particle form of catalyzer to be difficult to control, limited the morphology that polymerization obtains thus.
Catalyzer taking Magnesium Chloride Anhydrous as carrier demonstrates higher catalytic activity in olefin polymerization process, but this type of catalyzer is highly brittle, easily broken in polymerization reactor, thereby causes polymer morphology bad.Silicon dioxide carried catalyzer has good mobility, can be used for gas fluidised bed polymerisation, but silicon dioxide carried metallocene and non-metallocene catalyst show lower catalytic activity.If therefore magnesium chloride and silicon-dioxide are well organically combined, just may prepare and there is high catalytic activity, the catalyzer of the controlled and good abrasion strength resistance of globule size.
Such as CN1539856A discloses a kind of load method of non-metallocene catalyst of composite carrier load, it is in accordance with the following steps: (1) using as the porous support of carrier under 100-1000 DEG C, inert atmosphere or reduced pressure, dry or roasting 1～24h carries out thermal activation; (2) magnesium compound is dissolved in tetrahydrofuran (THF)-ol mixed system and forms solution, then the porosu solid of thermal activation is joined in this solution, under 0～60 DEG C of agitation condition, fully reaction forms transparent system; Through filtration washing, dry and drain after make complex carrier; Or add non-polar organic solutions to make it precipitation this clear solution and fully separate out, then filtration washing, dry draining make complex carrier; (3) non-metallocene olefin polymerization catalyst is dissolved in solvent, then filtration washing with complex carrier or after modifying complex carrier and contact 12～72 hours, be dried and drain into load type non-metallocene catalyst.This method need to first be prepared complex carrier, then contacts with catalyst solution.
CN1789290A discloses a kind of high activity loading method of load type non-metallocene catalyst, and it comprises the steps:, by carrier and chemical activating agent effect, to obtain modifying carrier; Magnesium compound is dissolved in tetrahydrofuran (THF)-ol mixed system and forms solution, then modification carrier is joined in this solution and reacted, wash after filtration, dry and drain and make complex carrier; Non-metallocene olefin polymerization catalyst is dissolved in solvent, and after then reacting with complex carrier, washing and filtering, dry draining, make load type non-metallocene catalyst.This method is first to prepare modification carrier, then reacts and obtain mixed carrier with magnesium compound, then contacts with catalyst solution.
Patent CN101423574A discloses a kind of supported non-metallocene single site catalysis agent component and preparation method thereof, and the method comprises: the preparation of (1) magnesium chloride/silica-gel carrier; (2) preparation of the preparation of alkylaluminoxane/magnesium chloride/silica-gel carrier and (3) supported non-metallocene single site catalysts component.This method is also first to prepare complex carrier, then reacts with alkylaluminoxane, finally contacts with catalyst solution.
EP260130 proposes loaded metallocene or non-luxuriant transition metal compound loaded on the silica supports of methylaluminoxane processing, and the non-luxuriant transition metal here only refers to ZrCl 4, TiCl 4or 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 need to be passed through many preparation processes.
Patent CN200610026765.8 discloses a class single active center Z-N olefin polymerization catalysis.This catalyzer is using the salicylic alidehyde imine derivative of the salicylic alidehyde imine that contains coordinating group or replacement as electron donor, by adding after pretreated carrier (as silica gel), metallic compound (as titanium tetrachloride) and this electron donor are processed and obtain in magnesium compound (as magnesium chloride)/tetrahydrofuran solution.
Patent CN200610026766.2 is similar with it, discloses a class containing heteroatomic organic compound and the application in Ziegler-Natta catalyst thereof.
Patent CN200910180100.6 and CN200910180607.1 disclose not to be had under alcohol, Nonmetallocene title complex is dissolved in magnesium compound solution, then add porous support, after convection drying or filtration washing are dry through the chemical processing agent processing of IVB family, thereby obtain preparation method and the polymeric applications of load type non-metallocene catalyst, its Nonmetallocene title complex is present among carrier uniformly, but catalyzed ethylene polymerization activity is lower in an embodiment, and similarly patent CN200910180601.4 and the disclosed load type non-metallocene catalyst preparation method of CN200910180606.7 and polymeric applications, its main difference is the chemical processing agent processing without IVB family, thereby cause polymerization catalyst activity lower.
Patent CN200710162666.7 discloses loaded catalyst, load type non-metallocene catalyst and preparation method thereof, it is to have under alcohol existence, magnesium compound is dissolved in tetrahydrofuran solvent, add porous support, after convection drying with titanium tetrachloride reaction, finally load non-metallocene metal complexes again, catalyst activity is higher, and the polymkeric substance that polymerization obtains thus has high bulk density, but preparation process is comparatively complicated, chemical processing agent reacts with carrier and can destroy in type carrier structure, then in polymerization process, produces fine polymer powder.
Even so, the ubiquitous problem of load type non-metallocene catalyst existing in prior art is, load process complexity, generally need to carry out the multistep of carrier and process afterwards load non-metallocene metal complexes again, olefin polymerizating activity low and be difficult to regulate, and in order to improve its polymerization activity, in the time carrying out olefinic polymerization, must assist higher promotor consumption.
Therefore, still need a kind of load type non-metallocene catalyst, its preparation method is simple, is applicable to suitability for industrialized production, and can overcomes to prepare those problems that exist in prior art load type non-metallocene catalyst process.
Summary of the invention
The inventor finds through diligent research on the basis of existing technology, by manufacturing described load type non-metallocene catalyst by a kind of specific preparation method, just can solve foregoing problems, and complete thus the present invention.
In the preparation method of load type non-metallocene catalyst of the present invention, do not add proton donor (such as conventional those that use in this area).In addition, in the preparation method of load type non-metallocene catalyst of the present invention, do not add electron donor (such as in this area for this reason and the compounds such as conventional monoesters class, di-esters, two ethers, diones and the diol-lipid using).Moreover, in the preparation method of load type non-metallocene catalyst of the present invention, reaction requirement and reaction conditions that also need not be harsh.Therefore, the preparation method of this loaded catalyst is simple, and is very suitable for suitability for industrialized production.
Particularly, the present invention relates to the content of following aspect:
1. a preparation method for load type non-metallocene catalyst, comprises the following steps:
Magnesium compound is dissolved in the first solvent, obtains the step of magnesium compound solution;
In described magnesium compound solution, add precipitation agent, obtain the step of modifying carrier;
Described modification carrier is contacted under the existence of the second solvent with Nonmetallocene title complex, obtain the step of mixed serum;
Mixed serum described in convection drying, the step of acquisition modified support; With
The chemical processing agent that is selected from IVB family metallic compound is reacted with described modified support, obtain the step of described load type non-metallocene catalyst.
2. according to the preparation method described in aforementioned either side, it is characterized in that, described magnesium compound is selected from one or more in magnesium halide, alkoxyl group magnesium halide, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and alkyl alkoxy magnesium, be preferably selected from one or more in magnesium halide, more preferably magnesium chloride.
3. according to the preparation method described in aforementioned either side, it is characterized in that, described the first solvent is selected from C 6-12aromatic hydrocarbon, halo C 6-12one or more in aromatic hydrocarbon, ester and ether, are preferably selected from C 6-12one or more in aromatic hydrocarbon and tetrahydrofuran (THF), most preferably tetrahydrofuran (THF), described the second solvent is selected from C 6-12aromatic hydrocarbon, halo C 6-12aromatic hydrocarbon, halo C 1-10one or more in alkane, ester and ether, be preferably selected from one or more in toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromo toluene, bromo ethylbenzene, methylene dichloride, ethylene dichloride, ethyl acetate and tetrahydrofuran (THF), more preferably C 6-12one or more in aromatic hydrocarbon, methylene dichloride and tetrahydrofuran (THF).
4. according to the preparation method described in aforementioned either side, it is characterized in that, described IVB family metallic compound is selected from one or more in 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, be preferably selected from one or more in IVB family metal halide, be more preferably selected from TiCl 4, TiBr 4, ZrCl 4, ZrBr 4, HfCl 4and HfBr 4in one or more, be most preferably selected from TiCl 4and ZrCl 4in one or more.
5. according to the preparation method described in aforementioned either side, it is characterized in that, described Nonmetallocene title complex is selected from one or more in the compound with following chemical structural formula:
Be preferably selected from one or more in compound (A) and the compound (B) with following chemical structural formula:
More preferably be selected from one or more in to compound (A-4) and compound (B-1) to compound (B-4) of the compound (A-1) with following chemical structural formula:
(B-3) (B-4)
In above all chemical structural formulas,
Q is 0 or 1;
D is 0 or 1;
M is 1,2 or 3;
M is selected from periodic table of elements III-th family to XI family atoms metal, preferably IVB family atoms metal, more preferably Ti (IV) and Zr (IV);
N is 1,2,3 or 4, depends on the valence state of described central metal atom M;
X is selected from halogen, hydrogen atom, C 1-C 30the C of alkyl, replacement 1-C 30alkyl, oxy radical, nitrogen-containing group, sulfur-containing group, boron-containing group, containing aluminium base group, phosphorus-containing groups, silicon-containing group, germanic group or containing tin group, multiple X can be identical, also can be different, can also be each other in key or Cheng Huan;
A be selected from Sauerstoffatom, sulphur atom, selenium atom, -NR 23r 24,-N (O) R 25r 26, -PR 28r 29,-P (O) R 30oR 31, sulfuryl, sulfoxide group or-Se (O) R 39, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;
B is selected from nitrogen-atoms, nitrogen-containing group, phosphorus-containing groups or C 1-C 30alkyl;
D is selected from nitrogen-atoms, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, nitrogen-containing group, phosphorus-containing groups, C 1-C 30alkyl, sulfuryl, sulfoxide group, -N (O) R 25r 26, or-P (O) R 32(OR 33), wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;
F is selected from nitrogen-atoms, nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;
G is selected from C 1-C 30the C of alkyl, replacement 1-C 30alkyl or safing function group;
Y is selected from Sauerstoffatom, nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;
Z is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;
→ represent singly-bound or two key;
-represent covalent linkage or ionic linkage;
---represent coordinate bond, covalent linkage or ionic linkage;
R 1to R 4, R 6to R 36, R 38and R 39be selected from independently of one another hydrogen, C 1-C 30the C of alkyl, 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 combine togather into key or Cheng Huan, is preferably formed aromatic ring, and
R 5be selected from lone-pair electron on nitrogen, hydrogen, C 1-C 30the C of alkyl, replacement 1-C 30alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups; Work as R 5during for oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups, R 5in N, O, S, P and Se can be used as coordination atom and described center IVB family atoms metal carries out coordination,
Described safing function group is selected from halogen, oxy radical, nitrogen-containing group, silicon-containing group, germanic group, sulfur-containing group, contains tin group, C 1-C 10ester group or nitro,
Described Nonmetallocene title complex is further preferably selected from one or more in the compound with following chemical structural formula:
Most preferably be selected from one or more in the compound with following chemical structural formula:
6. according to the preparation method described in aforementioned either side, it is characterized in that,
Described halogen is selected from F, Cl, Br or I;
Described nitrogen-containing group is selected from -NR 23r 24,-T-NR 23r 24or-N (O) R 25r 26;
Described phosphorus-containing groups is selected from -PR 28r 29,-P (O) R 30r 31or-P (O) R 32(OR 33);
Described oxy radical is selected from hydroxyl ,-OR 34with-T-OR 34;
Be selected from-SR of described sulfur-containing group 35,-T-SR 35,-S (O) R 36or-T-SO 2r 37;
Described containing be selected from-SeR of seleno group 38,-T-SeR 38,-Se (O) R 39or-T-Se (O) R 39;
Described group T is selected from C 1-C 30the C of alkyl, replacement 1-C 30alkyl or described safing function group;
Described R 37be selected from hydrogen, C 1-C 30the C of alkyl, replacement 1-C 30alkyl or described safing function group;
Described C 1～C 30alkyl is selected from C 1-C 30alkyl, C 7-C 50alkaryl, C 7-C 50aralkyl, C 3-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, wherein said heterocyclic radical contains 1-3 heteroatoms that is selected from nitrogen-atoms, Sauerstoffatom or sulphur atom;
The C of described replacement 1-C 30alkyl is selected from one or more described halogens and/or described C 1-C 30alkyl is as substituent described C 1-C 30alkyl;
Described boron-containing group is selected from BF 4 -, (C 6f 5) 4b -or (R 40bAr 3) -;
Describedly be selected from aluminum alkyls, AlPh containing aluminium base group 4 -, AlF 4 -, AlCl 4 -, AlBr 4 -, AlI 4 -or R 41alAr 3 -;
Be selected from-SiR of described silicon-containing group 42r 43r 44or-T-SiR 45;
Described be selected from-GeR of germanic group 46r 47r 48or-T-GeR 49;
Described containing be selected from-SnR of tin group 50r 51r 52,-T-SnR 53or-T-Sn (O) R 54,
Described Ar represents C 6-C 30aryl, and
R 40to R 54be selected from independently of one another hydrogen, described C 1-C 30the C of alkyl, described replacement 1-C 30alkyl or described safing function group, wherein these groups can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan, and
Described group T defines with aforementioned either side.
7. according to the preparation method described in aforementioned either side, it is characterized in that, taking the described magnesium compound of Mg element and the mol ratio of described Nonmetallocene title complex as 1: 0.01-1, preferably 1: 0.04-0.4, more preferably 1: 0.08-0.2, the ratio of described magnesium compound and described the first solvent is 1mol: 75～400ml, preferably 1mol: 150～300ml, more preferably 1mol: 200～250ml, in the described magnesium compound of Mg element with the mol ratio taking the described chemical processing agent of IVB family metallic element as 1: 0.01-1, preferably 1: 0.01-0.50, more preferably 1: 0.10-0.30, and the volume ratio of described precipitation agent and described the first solvent is 1: 0.2～5, preferably 1: 0.5～2, more preferably 1: 0.8～1.5.
8. according to the preparation method described in aforementioned either side, it is characterized in that, described precipitation agent is selected from C 5-12alkane, C 5-12naphthenic hydrocarbon, halo C 1-10alkane and halo C 5-12one or more in naphthenic hydrocarbon, be preferably selected from pentane, hexane, heptane, octane, nonane, decane, hexanaphthene, pentamethylene, suberane, cyclodecane, cyclononane, methylene dichloride, dichloro hexane, two chloroheptanes, trichloromethane, trichloroethane, three chlorobutanes, methylene bromide, ethylene dibromide, dibromo-heptane, methenyl bromide, tribromoethane, three n-butyl bromide, chlorocyclopentane, chlorocyclohexane, chloro suberane, chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromocyclohexane, bromo suberane, bromo cyclooctane, one or more in bromo cyclononane and bromo cyclodecane, further be preferably selected from hexane, heptane, one or more in decane and hexanaphthene, most preferably hexane.
9. according to the preparation method described in aforementioned either side, be also included in and make before described Nonmetallocene title complex contacts with described modification carrier, by the step of modifying carrier described in chemical processing agent pre-treatment that helps that is selected from aikyiaiurnirsoxan beta, aluminum alkyls or its arbitrary combination.
10. according to the preparation method described in aforementioned either side, it is characterized in that, described aikyiaiurnirsoxan beta is selected from methylaluminoxane, ethylaluminoxane, one or more in isobutyl aluminium alkoxide and normal-butyl alumina alkane, more preferably be selected from one or more in methylaluminoxane and isobutyl aluminium alkoxide, and described aluminum alkyls is selected from trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, triisobutyl aluminium, three n-butylaluminum, triisopentyl aluminium, three n-pentyl aluminium, tri-n-hexyl aluminum, three isohexyl aluminium, one or more in diethylmethyl aluminium and dimethyl ethyl aluminium, be preferably selected from trimethyl aluminium, triethyl aluminum, one or more in tri-n-n-propyl aluminum and triisobutyl aluminium, most preferably be selected from one or more in triethyl aluminum and triisobutyl aluminium.
11. according to the preparation method described in aforementioned either side, it is characterized in that, in the described magnesium compound of Mg element with to help the mol ratio of chemical processing agent as 1 described in Al element: 0-1.0, preferably 1: 0-0.5, more preferably 1: 0.1-0.5.
12. 1 kinds of load type non-metallocene catalysts, it is to be manufactured by the preparation method according to described in aforementioned either side.
13. 1 kinds of alkene homopolymerization/copolymerization process, it is characterized in that, taking the load type non-metallocene catalyst according to described in aspect 12 as Primary Catalysts, to be selected from one or more in aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt as promotor, make alkene homopolymerization or copolymerization.
14. 1 kinds of alkene homopolymerization/copolymerization process, is characterized in that, comprise the following steps:
Manufacture load type non-metallocene catalyst according to the preparation method described in aforementioned either side, and
Taking described load type non-metallocene catalyst as Primary Catalysts, to be selected from one or more in aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt as promotor, make alkene homopolymerization or copolymerization.
Technique effect
Preparation method's technique simple possible of load type non-metallocene catalyst of the present invention, adjustable leeway is large, and the charge capacity of Nonmetallocene title complex is adjustable, can give full play to it and obtain at catalysis in olefine polymerization the performance of polyolefin product.
In addition, by adopting different Nonmetallocene title complexs and chemical processing agent consumption, can obtain the load type non-metallocene catalyst of different catalysis in olefine polymerization activity, and the morphology obtaining is better, bulk density is higher, while preparing ultrahigh molecular weight polyethylene(UHMWPE), polymkeric substance viscosity-average molecular weight is higher, adapts to thus different olefinic polymerization requirements.
Also find simultaneously, when the load type non-metallocene catalyst that employing the present invention obtains and promotor form catalyst system, only need fewer promotor (such as methylaluminoxane or triethyl aluminum) consumption, just can obtain high olefin polymerizating activity, molecular weight distribution is narrow, show significant comonomer effect when copolymerization, under relatively equal condition, Copolymerization activity is higher than homopolymerization activity, and the polymkeric substance such as the polyethylene obtaining by catalyzed alkene homopolymerization or copolymerization has good polymer morphology and high polymer bulk density.
Than the load type non-metallocene catalyst that has the existence of alcohol to obtain in magnesium compound solution, in catalyst preparation process magnesium compound solution of the present invention, there is no the load type non-metallocene catalyst obtaining of alcohol, there is higher catalysis in olefine polymerization activity, polymer stacks density, and narrow molecular weight distribution, and the ultrahigh molecular weight polyethylene(UHMWPE) viscosity-average molecular weight obtaining.
Embodiment
Below the specific embodiment of the present invention is elaborated, but it is pointed out that protection scope of the present invention is not subject to the restriction of these embodiments, but determined by claims of annex.
In the context of the present invention, unless separately there is clearly definition, or this implication has exceeded those skilled in the art's understanding scope, 3 more than carbon atom hydrocarbon or hydrocarbon derivative group (such as propyl group, propoxy-, butyl, butane, butylene, butenyl, hexane etc.) all have implication identical when titled with prefix " just " when not titled with prefix " just ".Such as, propyl group is generally understood as n-propyl, and butyl is generally understood as normal-butyl.
The preparation method who the present invention relates to a kind of load type non-metallocene catalyst, comprises the following steps: magnesium compound is dissolved in the first solvent, obtains the step of magnesium compound solution; In described magnesium compound solution, add precipitation agent, obtain the step of modifying carrier; Described modification carrier is contacted under the existence of the second solvent with Nonmetallocene title complex, obtain the step of mixed serum; Mixed serum described in convection drying, the step of acquisition modified support; With the chemical processing agent that is selected from IVB family metallic compound is reacted with described modified support, obtain the step of described load type non-metallocene catalyst.
Below described magnesium compound is specifically described.
According to the present invention, term " magnesium compound " uses the common concept in this area, refers to the conventional organic or inorganic solid water-free magnesium-containing compound using of carrier as supported olefin polymerization catalyst.
According to the present invention, as described magnesium compound, such as enumerating magnesium halide, alkoxyl group magnesium halide, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and alkyl alkoxy magnesium.
Particularly, as described magnesium halide, such as enumerating magnesium chloride (MgCl 2), magnesium bromide (MgBr 2), magnesium iodide (MgI 2) and magnesium fluoride (MgF 2) etc., wherein preferred magnesium chloride.
As described alkoxyl group magnesium halide, such as enumerating methoxyl group chlorination magnesium (Mg (OCH 3) Cl), oxyethyl group magnesium chloride (Mg (OC 2h 5) Cl), propoxy-magnesium chloride (Mg (OC 3h 7) Cl), n-butoxy magnesium chloride (Mg (OC 4h 9) Cl), isobutoxy magnesium chloride (Mg (i-OC 4h 9) Cl), methoxyl group magnesium bromide (Mg (OCH 3) Br), oxyethyl group magnesium bromide (Mg (OC 2h 5) Br), propoxy-magnesium bromide (Mg (OC 3h 7) Br), n-butoxy magnesium bromide (Mg (OC 4h 9) Br), isobutoxy magnesium bromide (Mg (i-OC 4h 9) Br), methoxyl group magnesium iodide (Mg (OCH 3) I), oxyethyl group magnesium iodide (Mg (OC 2h 5) I), propoxy-magnesium iodide (Mg (OC 3h 7) I), n-butoxy magnesium iodide (Mg (OC 4h 9) I) and isobutoxy magnesium iodide (Mg (i-OC 4h 9) I) etc., wherein preferred methoxyl group chlorination magnesium, oxyethyl group magnesium chloride and isobutoxy magnesium chloride.
As described alkoxyl magnesium, such as enumerating magnesium methylate (Mg (OCH 3) 2), magnesium ethylate (Mg (OC 2h 5) 2), propoxy-magnesium (Mg (OC 3h 7) 2), butoxy magnesium (Mg (OC 4h 9) 2), isobutoxy magnesium (Mg (i-OC 4h 9) 2) and 2-ethyl hexyl oxy magnesium (Mg (OCH 2cH (C 2h 5) C 4h_) 2) etc., wherein preferred magnesium ethylate and isobutoxy magnesium.
As described alkyl magnesium, such as enumerating methyl magnesium (Mg (CH 3) 2), magnesium ethide (Mg (C 2h 5) 2), propyl group magnesium (Mg (C 3h 7) 2), normal-butyl magnesium (Mg (C 4h 9) 2) and isobutyl-magnesium (Mg (i-C 4h 9) 2) etc., wherein preferred magnesium ethide and normal-butyl magnesium.
As described alkyl halide magnesium, such as enumerating methylmagnesium-chloride (Mg (CH 3) Cl), ethylmagnesium chloride (Mg (C 2h 5) Cl), propyl group magnesium chloride (Mg (C 3h 7) Cl), normal-butyl chlorination magnesium (Mg (C 4h 9) Cl), isobutyl-chlorination magnesium (Mg (i-C 4h 9) Cl), methyl-magnesium-bromide (Mg (CH 3) Br), ethylmagnesium bromide (Mg (C 2h 5) Br), propyl group magnesium bromide (Mg (C 3h 7) Br), normal-butyl bromination magnesium (Mg (C 4h 9) Br), selenium alkynide (Mg (i-C 4h 9) Br), methyl magnesium iodide (Mg (CH 3) I), ethyl magnesium iodide (Mg (C 2h 5) I), propyl group magnesium iodide (Mg (C 3h 7) I), normal-butyl iodate magnesium (Mg (C 4h 9) I) and isobutyl-iodate magnesium (Mg (i-C 4h 9) I) etc., wherein preferable methyl magnesium chloride, ethylmagnesium chloride and isobutyl-chlorination magnesium.
As described alkyl alkoxy magnesium, such as enumerating methyl methoxy base magnesium (Mg (OCH 3) (CH 3)), methyl ethoxy magnesium (Mg (OC 2h 5) (CH 3)), methyl propoxy-magnesium (Mg (OC 3h 7) (CH 3)), methyl n-butoxy magnesium (Mg (OC 4h 9) (CH 3)), methyl isobutoxy magnesium (Mg (i-OC 4h 9) (CH 3)), ethyl magnesium methylate (Mg (OCH 3) (C 2h 5)), ethyl magnesium ethylate (Mg (OC 2h 5) (C 2h 5)), ethyl propoxy-magnesium (Mg (OC 3h 7) (C 2h 5)), ethyl n-butoxy magnesium (Mg (OC 4h 9) (C 2h 5)), ethyl isobutoxy magnesium (Mg (i-OC 4h 9) (C 2h 5)), propyl group magnesium methylate (Mg (OCH 3) (C 3h 7)), propyl group magnesium ethylate (Mg (OC 2h 5) (C 3h 7)), propyl group propoxy-magnesium (Mg (OC 3h 7) (C 3h 7)), propyl group n-butoxy magnesium (Mg (OC 4h 9) (C 3h 7)), propyl group isobutoxy magnesium (Mg (i-OC 4h 9) (C 3h 7)), normal-butyl magnesium methylate (Mg (OCH 3) (C 4h 9)), normal-butyl magnesium ethylate (Mg (OC 2h 5) (C 4h 9)), normal-butyl propoxy-magnesium (Mg (OC 3h 7) (C 4h 9)), normal-butyl n-butoxy magnesium (Mg (OC 4h 9) (C 4h 9)), normal-butyl isobutoxy magnesium (Mg (i-OC 4h 9) (C 4h 9)), isobutyl-magnesium methylate (Mg (OCH 3) (i-C 4h 9)), isobutyl-magnesium ethylate (Mg (OC 2h 5) (i-C 4h 9)), isobutyl-propoxy-magnesium (Mg (OC 3h 7) (i-C 4h 9)), isobutyl-n-butoxy magnesium (Mg (OC 4h 9) (i-C 4h 9)) and isobutyl-isobutoxy magnesium (Mg (i-OC 4h 9) (i-C 4h 9)) etc., wherein preferred butyl magnesium ethylate.
These magnesium compounds can use separately one, also can multiple mixing use, not special restriction.
In the time that form with multiple mixing is used, the mol ratio between two kinds of magnesium compounds in described magnesium compound mixture is such as being 0.25～4: 1, preferably 0.5～3: 1, more preferably 1～2: 1.
According to the present invention, magnesium compound is dissolved in first solvent (not comprising alcoholic solvent) of non-alcohols, obtain magnesium compound solution.
Below the step that obtains described magnesium compound solution is specifically described.
Particularly, make described magnesium compound (solid) be dissolved in suitable solvent (being sometimes referred to as below solvent or the first solvent for dissolving described magnesium compound), thereby obtain described magnesium compound solution.
As described the first solvent, such as enumerating C 6-12aromatic hydrocarbon, halo C 6-12aromatic hydrocarbon, ester and ether equal solvent.
As described C 6-12aromatic hydrocarbon, such as enumerating toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene.
As described halo C 6-12aromatic hydrocarbon, such as enumerating chlorotoluene, chloro ethylbenzene, bromo toluene, bromo ethylbenzene etc.
As described ester, such as enumerating methyl-formiate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butylacetate, methyl propionate, ethyl propionate, butyl propionate, butyl butyrate etc.
As described ether, such as enumerating ether, methyl ethyl ether, tetrahydrofuran (THF) etc.
Wherein, preferred C 6-12aromatic hydrocarbon and tetrahydrofuran (THF), most preferably tetrahydrofuran (THF).
According to the present invention, so-called alcoholic solvent refers to any solvent that can be considered alkylol cpd.And the present invention is in preparation when described load type non-metallocene catalyst, in any step, all do not use these alcohols (such as aromatic alcohols such as fatty alcohol, phenylcarbinol such as ethanol etc.).
These first solvents can use separately one, also can use with the multiple mixing of ratio arbitrarily.
In order to prepare described magnesium compound solution, described magnesium compound metering is added in described the first solvent and dissolved.
There is no particular limitation for preparation time (being the dissolution time of described magnesium compound) to described magnesium compound solution, but be generally 0.5～24h, preferably 4～24h.In this preparation process, can utilize and stir the dissolving that promotes described magnesium compound.This stirring can adopt any form, such as stirring rake (rotating speed is generally 10～1000 revs/min) etc.As required, sometimes can promote to dissolve by suitable heating (but top temperature must lower than the boiling point of described solvent).
Then, by be metered into precipitation agent in described magnesium compound solution, solid matter is precipitated out from this solution, obtains thus and modify carrier.
Below described precipitation agent is specifically described.
According to the present invention, term " precipitation agent " uses this area common concept, refers to and can reduce the solubleness of solid substance solute (such as described magnesium compound etc.) in its solution and then unreactiveness liquid that it is separated out with solid form from described solution.
According to the present invention, as described precipitation agent, be poor solvent such as enumerating for solid substance solute (such as magnesium compound) to be precipitated, and be the solvent of good solvent for the described solvent for dissolving described solid substance solute (such as magnesium compound), such as enumerating C 5-12alkane, C 5-12naphthenic hydrocarbon, halo C 1-10alkane and halo C 5-12naphthenic hydrocarbon.
As described C 5-12alkane, such as enumerating pentane, hexane, heptane, octane, nonane and decane etc., wherein preferred hexane, heptane and decane, most preferably hexane.
As described C 5-12naphthenic hydrocarbon, such as enumerating hexanaphthene, pentamethylene, suberane, cyclodecane and cyclononane etc., most preferably hexanaphthene.
As described halo C 1-10alkane, such as enumerating methylene dichloride, dichloro hexane, two chloroheptanes, trichloromethane, trichloroethane, three chlorobutanes, methylene bromide, ethylene dibromide, dibromo-heptane, methenyl bromide, tribromoethane and three n-butyl bromide etc.
As described halo C 5-12naphthenic hydrocarbon, such as enumerating chlorocyclopentane, chlorocyclohexane, chloro suberane, chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromocyclohexane, bromo suberane, bromo cyclooctane, bromo cyclononane and bromo cyclodecane etc.
These precipitation agents can use separately one, also can use with the multiple mixing of ratio arbitrarily.
The mode that adds of precipitation agent can add or drip for disposable, preferably disposable adding.In this precipitation process, can utilize to stir to promote the dispersion of precipitation agent, and be conducive to the final precipitation of solid product.This stirring can adopt any form (such as stirring rake), and rotating speed is generally 10～1000 revs/min etc.
To the consumption of described precipitation agent, there is no particular limitation, but generally by volume, described precipitation agent is 1: 0.2～5 with the ratio of the described solvent for dissolving described magnesium compound, and preferably 1: 0.5～2, more preferably 1: 0.8～1.5.
To the temperature of described precipitation agent, also there is no particular limitation, but general preferred normal temperature is to the temperature lower than the boiling point of used any solvent and precipitation agent (preferably 20-80 DEG C, more preferably 40-60 DEG C), but be sometimes not limited to this.And, general also preferred temperature (the preferably 20-80 DEG C to the boiling point lower than used any solvent and precipitation agent at normal temperature of this precipitation process, more preferably 40-60 DEG C) under carry out 0.3-12 hour, but be sometimes not limited to this, and with solid product substantially completely precipitation be as the criterion.
Completely, after precipitation, obtained solid product filtered, washed and is dried, obtaining and modify carrier.Be not particularly limited for described filtration, washing and dry method, can use as required conventional those that use in this area.
As required, described washing is generally carried out 1～6 time, preferably 3～4 times.Wherein, washer solvent preferably uses the solvent identical with precipitation agent, but also can be different.
Described being dried can adopt ordinary method to carry out, such as heat drying method under rare gas element desiccating method, boulton process or vacuum, and preferably heat drying method, most preferably heat drying method under vacuum under rare gas element desiccating method or vacuum.
Described dry temperature range is generally normal temperature to 140 DEG C.Be generally 2-20 hour time of drying, but also can be according to concrete use different for dissolving the solvent situation of described magnesium compound.Such as, in the time adopting tetrahydrofuran (THF) as solvent for dissolving described magnesium compound, drying temperature is generally 80 DEG C of left and right, under vacuum, be dried 2～12 hours, and in the time adopting toluene as solvent for dissolving described magnesium compound, drying temperature is generally 100 DEG C of left and right, under vacuum, is dried 4～24 hours.
According to the present invention, term " Nonmetallocene title complex " is a kind of single site olefin polymerization catalysts for metallocene catalyst, in structure, do not contain the cyclopentadienyl or derivatives thereofs such as luxuriant ring, fluorenes ring or indenes ring, and when with promotor (such as hereinafter described those) combination, can demonstrate the organometallics (therefore described Nonmetallocene title complex is also sometimes referred to as non-metallocene olefin polymerization title complex) of olefinic polymerization catalysis activity.This compound comprises central metal atom and at least one polydentate ligand of being combined with coordinate bond with described central metal atom (preferably tridentate ligand or more polydentate ligand), and term " Nonmetallocene part " is aforesaid polydentate ligand.
According to the present invention, described Nonmetallocene title complex is selected from the compound with following chemical structural formula:
According to this chemical structural formula, the part that forms coordinate bond with central metal atom M comprises n radicals X and m polydentate ligand (structural formula in bracket).According to the chemical structural formula of described polydentate ligand, group A, D and E (coordination group) form coordinate bond by the contained atom for coordination (such as heteroatomss such as N, O, S, Se and P) of these groups with described central metal atom M.
According to the present invention, all parts (comprising described radicals X and described polydentate ligand) with the absolute value of the negative charge sum absolute value positively charged with described central metal atom M identical.
At one, more specifically in embodiment, described Nonmetallocene title complex is selected from compound (A) and the compound (B) with following chemical structural formula.
At one more specifically in embodiment, described Nonmetallocene title complex is selected from the compound (A-1) with following chemical structural formula to compound (A-4) and compound (B-1) to compound (B-4).
In above all chemical structural formulas,
Q is 0 or 1;
D is 0 or 1;
M is 1,2 or 3;
M is selected from periodic table of elements III-th family to XI family atoms metal, preferably IVB family atoms metal, such as enumerating Ti (IV), Zr (IV), Hf (IV), Cr (III), Fe (III), Ni (II), Pd (II) or Co (II);
N is 1,2,3 or 4, depends on the valence state of described central metal atom M;
X is selected from halogen, hydrogen atom, C 1-C 30the C of alkyl, replacement 1-C 30alkyl, oxy radical, nitrogen-containing group, sulfur-containing group, boron-containing group, containing aluminium base group, phosphorus-containing groups, silicon-containing group, germanic group or containing tin group, multiple X can be identical, also can be different, can also be each other in key or Cheng Huan;
A be selected from Sauerstoffatom, sulphur atom, selenium atom, -NR 23r 24,-N (O) R 25r 26, -PR 28r 29,-P (O) R 30oR 31, sulfuryl, sulfoxide group or-Se (O) R 39, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;
B is selected from nitrogen-atoms, nitrogen-containing group, phosphorus-containing groups or C 1-C 30alkyl;
D is selected from nitrogen-atoms, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, nitrogen-containing group, phosphorus-containing groups, C 1-C 30alkyl, sulfuryl, sulfoxide group, -N (O) R 25r 26, or-P (O) R 32(OR 33), wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group (CN), wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;
F is selected from nitrogen-atoms, nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;
G is selected from C 1-C 30the C of alkyl, replacement 1-C 30alkyl or safing function group;
Y is selected from Sauerstoffatom, nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;
Z is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group, phosphorus-containing groups or cyano group (CN), such as can enumerate-NR 23r 24,-N (O) R 25r 26,-PR 28r 29,-P (O) R 30r 31,-OR 34,-SR 35,-S (O) R 36,-SeR 38or-Se (O) R 39, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;
→ represent singly-bound or two key;
-represent covalent linkage or ionic linkage;
---represent coordinate bond, covalent linkage or ionic linkage.
R 1to R 4, R 6to R 36, R 38and R 39be selected from independently of one another hydrogen, C 1-C 30the C of alkyl, replacement 1-C 30alkyl (wherein preferred halo alkyl, such as-CH 2cl and-CH 2cH 2or safing function group Cl).Above-mentioned group can be the same or different to each other, and wherein adjacent group is such as R 1with R 2, R 6with R 7, R 7with R 8, R 8with R 9, R 13with R 14, R 14with R 15, R 15with R 16, R 18with R 19, R 19with R 20, R 20with R 21, R 23with R 24, or R 25with R 26deng combining togather into key or Cheng Huan, be preferably formed aromatic ring, such as unsubstituted phenyl ring or by 1-4 C 1-C 30the C of alkyl, replacement 1-C 30alkyl (wherein preferred halo alkyl, such as-CH 2cl and-CH 2cH 2cl) or safing function group replace phenyl ring, and
R 5be selected from lone-pair electron on nitrogen, hydrogen, C 1-C 30the C of alkyl, replacement 1-C 30alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups.Work as R 5during for oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups, R 5in N, O, S, P and Se can be used as coordination atom and described center IVB family atoms metal carries out coordination.
According to the present invention, in aforementioned all chemical structural formulas, as the case may be, any adjacent two or more groups, such as R 21with group Z, or R 13with group Y, can combine togather into ring, be preferably formed and comprise the heteroatomic C that comes from described group Z or Y 6-C 30heteroaromatic, such as pyridine ring etc., wherein said heteroaromatic is optionally selected from C by one or more 1-C 30the C of alkyl, replacement 1-C 30the substituting group of alkyl and safing function group replaces.
In the context of the present invention, described halogen is selected from F, Cl, Br or I.Described nitrogen-containing group is selected from -NR 23r 24,-T-NR 23r 24or-N (O) R 25r 26.Described phosphorus-containing groups is selected from -PR 28r 29,-P (O) R 30r 31or-P (O) R 32(OR 33).Described oxy radical is selected from hydroxyl ,-OR 34with-T-OR 34.Be selected from-SR of described sulfur-containing group 35,-T-SR 35,-S (O) R 36or-T-SO 2r 37.Described containing be selected from-SeR of seleno group 38,-T-SeR 38,-Se (O) R 39or-T-Se (O) R 39.Described group T is selected from C 1-C 30the C of alkyl, replacement 1-C 30alkyl or safing function group.Described R 37be selected from hydrogen, C 1-C 30the C of alkyl, replacement 1-C 30alkyl or safing function group.
In the context of the present invention, described C 1-C 30alkyl is selected from C 1-C 30alkyl (preferably C 1-C 6alkyl, such as isobutyl-), C 7-C 50alkaryl (such as tolyl, xylyl, diisobutyl phenyl etc.), C 7-C 50aralkyl (such as benzyl), C 3-C 30cyclic alkyl, C 2-C 30thiazolinyl, C 2-C 30alkynyl, C 6-C 30aryl (such as phenyl, naphthyl, anthryl etc.), C 8-C 30condensed ring radical or C 4-C 30heterocyclic radical, wherein said heterocyclic radical contains 1-3 heteroatoms that is selected from nitrogen-atoms, Sauerstoffatom or sulphur atom, such as pyridyl, pyrryl, furyl or thienyl etc.
According to the present invention, in the context of the present invention, according to the particular case of the relevant group of its combination, described C 1-C 30alkyl refers to C sometimes 1-C 30hydrocarbon two bases (divalent group, or be called C 1-C 30alkylene) or C 1-C 30hydrocarbon three bases (trivalent group), this is obvious to those skilled in the art.
In the context of the present invention, the C of described replacement 1-C 30alkyl refers to the aforementioned C with one or more inert substituents 1-C 30alkyl.So-called inert substituent, refer to these substituting groups to aforementioned for coordination group (refer to aforementioned group A, D, E, F, Y and Z, or also optionally comprise radicals R 5) there is no substantial interference with the coordination process of described central metal atom M; In other words, limit by the chemical structure of polydentate ligand of the present invention, these substituting groups do not have ability or have no chance (such as being subject to the impact of steric hindrance etc.) coordination reaction occurs and form coordinate bond with described central metal atom M.Generally speaking, described inert substituent is such as being selected from aforesaid halogen or C 1-C 30alkyl (preferably C 1-C 6alkyl, such as isobutyl-).
In the context of the present invention, described safing function group does not comprise aforesaid C 1-C 30the C of alkyl and aforesaid replacement 1-C 30alkyl.As described safing function group, be selected from aforementioned halogen, aforementioned oxy radical, aforementioned nitrogen-containing group, silicon-containing group, germanic group, aforementioned sulfur-containing group such as enumerating, contain tin group, C 1-C 10ester group or nitro (NO 2) at least one etc.
In the context of the present invention, limit by the chemical structure of polydentate ligand of the present invention, described safing function group has following characteristics:
(1) do not disturb the coordination process of described group A, D, E, F, Y or Z and described central metal atom M, and
(2) with the coordination ability of described central metal atom M lower than described A, D, E, F, Y and Z group, and do not replace the existing coordination of these groups and described central metal atom M.
In the context of the present invention, described boron-containing group is selected from BF 4 -, (C 6f 5) 4b -or (R 40bAr 3) -; Describedly be selected from aluminum alkyls, AlPh containing aluminium base group 4 -, AlF 4 -, AlCl 4 -, AlBr 4 -, AlI 4 -or R 41alAr 3 -; Be selected from-SiR of described silicon-containing group 42r 43r 44or-T-SiR 45; Described be selected from-GeR of germanic group 46r 47r 48or-T-GeR 49; Described containing be selected from-SnR of tin group 50r 51r 52,-T-SnR 53or-T-Sn (O) R 54, wherein Ar represents C 6-C 30aryl.R 40to R 54be selected from independently of one another hydrogen, aforesaid C 1-C 30the C of alkyl, aforesaid replacement 1-C 30alkyl or aforesaid safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan.Wherein, the definition of group T is the same.
As described Nonmetallocene title complex, such as enumerating following compound:
Described Nonmetallocene title complex is preferably selected from following compound:
Described Nonmetallocene title complex is further preferably selected from following compound:
Described Nonmetallocene title complex is more preferably selected from following compound:
These Nonmetallocene title complexs can use separately one, or are used in combination multiple with ratio arbitrarily.
According to the present invention, the described polydentate ligand in described Nonmetallocene title complex is not as the normally used diether compounds of electronic donor compound capable in this area.
Described Nonmetallocene title complex or described polydentate ligand can be manufactured according to any method well known by persons skilled in the art.About the particular content of its manufacture method, such as can be referring to WO03/010207 and Chinese patent ZL01126323.7 and ZL02110844.7 etc., the full text that this specification sheets is introduced these documents at this point as a reference.
Then, make described modification carrier under the existence of the second solvent, contact (contact reacts) with described Nonmetallocene title complex, obtain mixed serum.
In the time manufacturing described mixed serum, to the way of contact and the engagement sequence etc. of described modification carrier and described Nonmetallocene title complex (and described second solvent), there is no particular limitation, such as enumerating, described modification carrier is first mixed with described Nonmetallocene title complex, and then add wherein the scheme of described the second solvent; Or described Nonmetallocene title complex is dissolved in described the second solvent, manufactures thus Nonmetallocene complex solution, and then make scheme that described modification carrier mixes with described Nonmetallocene complex solution etc., wherein preferred the latter.
In addition, in order to manufacture described mixed serum, such as can be at normal temperature to the temperature lower than the boiling point of used any solvent, described modification carrier and the described Nonmetallocene title complex contact reacts (if desired by stirring) under described the second solvent exists is carried out 0.5～24 hour, preferably 1～8 hour, more preferably 2～6 hours.
Now, the mixed serum obtaining is a kind of system of pulpous state.Although unessential, in order to ensure the homogeneity of system, this mixed serum preferably carries out afterwards the airtight of certain hour (2～48h, preferably 4～24h, most preferably 6～18h) in preparation and leaves standstill.
According to the present invention, in the time manufacturing described mixed serum, to described the second solvent (be sometimes referred to as below and dissolve Nonmetallocene title complex solvent), there is no particular limitation, as long as it can dissolve described Nonmetallocene title complex.As described the second solvent, such as enumerating C 6-12aromatic hydrocarbon, halo C 6-12aromatic hydrocarbon, halo C 1-10one or more in alkane, ester and ether.Specifically such as enumerating toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromo toluene, bromo ethylbenzene, methylene dichloride, ethylene dichloride, ethyl acetate and tetrahydrofuran (THF) etc.Wherein, preferred C 6-12aromatic hydrocarbon, methylene dichloride and tetrahydrofuran (THF).
These solvents can use separately one, or are used in combination multiple with ratio arbitrarily.
In the time manufacturing described mixed serum or described Nonmetallocene complex solution, can use as required stirring (rotating speed of this stirring is generally 10～500 revs/min).
According to the present invention, to the consumption of described the second solvent without any restriction, as long as being enough to realize the amount that described modification carrier fully contacts with described Nonmetallocene title complex.Such as, easily, described Nonmetallocene title complex is generally 0.01～0.25 grams per milliliter with respect to the ratio of described the second solvent, preferably 0.05～0.16 grams per milliliter, but be sometimes not limited to this.
Then,, by described mixed serum convection drying, can obtain a kind of solid product of good fluidity, i.e. described modified support.
Now, described convection drying can adopt ordinary method to carry out, such as heat drying under dry under dry under inert gas atmosphere, vacuum atmosphere or vacuum atmosphere etc., and wherein preferred heat drying under vacuum atmosphere.At the temperature (being generally 30～160 DEG C, preferably 60～130 DEG C) of low 5～15 DEG C of the boiling point of the described dry any solvent generally containing in than described mixed serum, carry out, and be generally 2～24h time of drying, but be sometimes not limited to this.
Below described chemical processing agent is specifically described.
According to the present invention, using IVB family metallic compound as described chemical processing agent.
As described IVB family metallic compound, such as can enumerate be selected from IVB family metal halide, IVB family metal alkyl compound, IVB family metal alkoxide compound, IVB family metal alkyl halides and IVB family metal alkoxide halid at least one.
As described IVB family metal halide, described IVB family metal alkyl compound, described IVB family metal alkoxide compound, described IVB family's metal alkyl halides and described IVB family metal alkoxide halogenide, such as enumerating the compound of following general formula (IV) structure:
M(OR 1) mX nR 2 4-m-n (IV)
Wherein:
M is 0,1,2,3 or 4;
N is 0,1,2,3 or 4;
M is IVB family metal in the periodic table of elements, such as titanium, zirconium and hafnium etc.;
X is halogen, such as F, Cl, Br and I etc.; And
R 1and R 2be selected from independently of one another C 1-10alkyl, such as methyl, ethyl, propyl group, normal-butyl, isobutyl-etc., R 1and R 2can be identical, also can be different.
Particularly, as described IVB family metal halide, such as enumerating titanium tetrafluoride (TiF 4), titanium tetrachloride (TiCl 4), titanium tetrabromide (TiBr 4), titanium tetra iodide (TiI 4);
Zirconium tetrafluoride (ZrF 4), zirconium tetrachloride (ZrCl 4), tetrabormated zirconium (ZrBr 4), zirconium tetraiodide (ZrI 4);
Tetrafluoride hafnium (HfF 4), hafnium tetrachloride (HfCl 4), hafnium (HfBr 4), tetraiodide hafnium (HfI 4).
As described IVB family metal alkyl compound, such as enumerating 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.
As described IVB family metal alkoxide compound, such as enumerating 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.
As described IVB family metal alkyl halides, such as enumerating 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).
As described IVB family metal alkoxide halogenide, such as enumerating trimethoxy titanium chloride (TiCl (OCH 3) 3), triethoxy titanium chloride (TiCl (OCH 3cH 2) 3), three isobutoxy titanium chloride (TiCl (i-OC 4h 9) 3), three n-Butoxyl titanium-chlorides (TiCl (OC 4h 9) 3), dimethoxy titanium dichloride (TiCl 2(OCH 3) 2), diethoxy titanium dichloride (TiCl 2(OCH 3cH 2) 2), two isobutoxy titanium dichloride (TiCl 2(i-OC 4h 9) 2), three n-Butoxyl titanium-chlorides (TiCl (OC 4h 9) 3), methoxyl group titanous chloride (Ti (OCH 3) Cl 3), oxyethyl group titanous chloride (Ti (OCH 3cH 2) Cl 3), isobutoxy titanous chloride (Ti (i-C 4h 9) Cl 3), n-butoxy titanous chloride (Ti (OC 4h 9) Cl 3);
Trimethoxy titanium bromide (TiBr (OCH 3) 3), triethoxy titanium bromide (TiBr (OCH 3cH 2) 3), three isobutoxy titanium bromide (TiBr (i-OC 4h 9) 3), three n-butoxy titanium bromide (TiBr (OC 4h 9) 3), dimethoxy dibrominated titanium (TiBr 2(OCH 3) 2), diethoxy dibrominated titanium (TiBr 2(OCH 3cH 2) 2), two isobutoxy dibrominated titanium (TiBr 2(i-OC 4h 9) 2), three n-butoxy titanium bromide (TiBr (OC 4h 9) 3), methoxyl group titanium tribromide (Ti (OCH 3) Br 3), oxyethyl group titanium tribromide (Ti (OCH 3cH 2) Br 3), isobutoxy titanium tribromide (Ti (i-C 4h 9) Br 3), n-butoxy titanium tribromide (Ti (OC 4h 9) Br 3);
Trimethoxy zirconium chloride (ZrCl (OCH 3) 3), triethoxy zirconium chloride (ZrCl (OCH 3cH 2) 3), three isobutoxy zirconium chloride (ZrCl (i-OC 4h 9) 3), three n-butoxy zirconium chloride (ZrCl (OC 4h 9) 3), dimethoxy zirconium dichloride (ZrCl 2(OCH 3) 2), diethoxy zirconium dichloride (ZrCl 2(OCH 3cH 2) 2), two isobutoxy zirconium dichloride (ZrCl 2(i-OC 4h 9) 2), three n-butoxy zirconium chloride (ZrCl (OC 4h 9) 3), methoxyl group tri-chlorination zirconium (Zr (OCH 3) Cl 3), oxyethyl group tri-chlorination zirconium (Zr (OCH 3cH 2) Cl 3), isobutoxy tri-chlorination zirconium (Zr (i-C 4h 9) Cl 3), n-butoxy tri-chlorination zirconium (Zr (OC 4h 9) Cl 3);
Trimethoxy zirconium bromide (ZrBr (OCH 3) 3), triethoxy zirconium bromide (ZrBr (OCH 3cH 2) 3), three isobutoxy zirconium bromide (ZrBr (i-OC 4h 9) 3), three n-butoxy zirconium bromide (ZrBr (OC 4h 9) 3), dimethoxy dibrominated zirconium (ZrBr 2(OCH 3) 2), diethoxy dibrominated zirconium (ZrBr 2(OCH 3cH 2) 2), two isobutoxy dibrominated zirconium (ZrBr 2(i-OC 4h 9) 2), three n-butoxy zirconium bromide (ZrBr (OC 4h 9) 3), methoxyl group tribromide zirconium (Zr (OCH 3) Br 3), oxyethyl group tribromide zirconium (Zr (OCH 3cH 2) Br 3), isobutoxy tribromide zirconium (Zr (i-C 4h 9) Br 3), n-butoxy tribromide zirconium (Zr (OC 4h 9) Br 3);
Trimethoxy hafnium chloride (HfCl (OCH 3) 3), triethoxy hafnium chloride (HfCl (OCH 3cH 2) 3), three isobutoxy hafnium chloride (HfCl (i-OC 4h 9) 3), three n-butoxy hafnium chloride (HfCl (OC 4h 9) 3), dimethoxy hafnium dichloride (HfCl 2(OCH 3) 2), diethoxy hafnium dichloride (HfCl 2(OCH 3cH 2) 2), two isobutoxy hafnium dichloride (HfCl 2(i-OC 4h 9) 2), three n-butoxy hafnium chloride (HfCl (OC 4h 9) 3), methoxyl group tri-chlorination hafnium (Hf (OCH 3) Cl 3), oxyethyl group tri-chlorination hafnium (Hf (OCH 3cH 2) Cl 3), isobutoxy tri-chlorination hafnium (Hf (i-C 4h 9) Cl 3), n-butoxy tri-chlorination hafnium (Hf (OC 4h 9) Cl 3);
Trimethoxy bromination hafnium (HfBr (OCH 3) 3), triethoxy bromination hafnium (HfBr (OCH 3cH 2) 3), three isobutoxy bromination hafnium (HfBr (i-OC 4h 9) 3), three n-butoxy bromination hafnium (HfBr (OC 4h 9) 3), dimethoxy dibrominated hafnium (HfBr 2(OCH 3) 2), diethoxy dibrominated hafnium (HfBr 2(OCH 3cH 2) 2), two isobutoxy dibrominated hafnium (HfBr 2(i-OC 4h 9) 2), three n-butoxy bromination hafnium (HfBr (OC 4h 9) 3), methoxyl group tribromide hafnium (Hf (OCH 3) Br 3), oxyethyl group tribromide hafnium (Hf (OCH 3cH 2) Br 3), isobutoxy tribromide hafnium (Hf (i-C 4h 9) Br 3), n-butoxy tribromide hafnium (Hf (OC 4h 9) Br 3).
As described IVB family metallic compound, preferred described IVB family metal halide, more preferably TiCl 4, TiBr 4, ZrCl 4, ZrBr 4, HfCl 4and HfBr 4, most preferably TiCl 4and ZrCl 4.
These IVB family metallic compounds can use separately one, or are used in combination multiple with ratio arbitrarily.
According to the present invention, described chemical processing agent is reacted with described modified support, can obtain load type non-metallocene catalyst of the present invention.
When described chemical processing agent is while being liquid at normal temperatures, can be by needing to be utilized the mode that directly drips the described chemical processing agent of predetermined amount in the reaction object (such as aforesaid modified support) of this chemical processing agent processing to use described chemical processing agent.
When described chemical processing agent is while being solid-state at normal temperatures, for measure with easy to operate for the purpose of, preferably use described chemical processing agent with the form of solution.Certainly, in the time that described chemical processing agent is liquid state at normal temperatures, sometimes also can use described chemical processing agent with the form of solution as required, be not particularly limited.
In the time of the solution of the described chemical processing agent of preparation, to the solvent that now used, there is no particular limitation, as long as it can dissolve this chemical processing agent.
Particularly, can enumerate C 5-12alkane, C 5-12naphthenic hydrocarbon, halo C 5-12alkane, halo C 5-12naphthenic hydrocarbon, C 6-12aromatic hydrocarbons or halo C 6-12aromatic hydrocarbons etc., such as enumerating pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, pentamethylene, hexanaphthene, suberane, cyclooctane, 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 use separately one, or are used in combination multiple with ratio arbitrarily.
In addition, there is no particular limitation for the concentration to described chemical processing agent in its solution, can suitably select as required, as long as it can be realized with the described chemical processing agent of predetermined amount and implement described chemical treatment.As previously mentioned, if chemical processing agent is liquid, can directly carries out described processing with chemical processing agent, but use after also can being modulated into chemical treatment agent solution.
Easily, the volumetric molar concentration of described chemical processing agent in its solution is generally set as 0.01～1.0mol/L, but is not limited to this.
As carrying out described chemically treated method, such as enumerating, in the situation that chemical processing agent is solid-state (such as zirconium tetrachloride), first prepare the solution of described chemical processing agent, then to the described solution of the described chemical processing agent that adds in pending reaction object (such as aforesaid modified support) (preferably dripping) to contain predetermined amount, to carry out chemical treatment reaction.In the situation that chemical processing agent is liquid (such as titanium tetrachloride), can directly the described chemical processing agent of predetermined amount be added in (preferably dripping) pending reaction object (such as aforesaid modified support), to carry out chemical treatment reaction, or after this chemical processing agent is prepared into solution, to the described solution of the described chemical processing agent that adds in pending reaction object (such as aforesaid modified support) (preferably dripping) to contain predetermined amount, to carry out chemical treatment reaction.
Generally speaking, under the temperature of reaction of-30～60 DEG C (preferably-20～30 DEG C), make chemical treatment reaction (if desired by stirring) carry out 0.5～24 hour, preferably 1～8 hour, more preferably 2～6 hours.
After chemical treatment reaction finishes, by filtering, wash and being dried, can obtain through chemically treated product, i.e. load type non-metallocene catalyst of the present invention.
According to the present invention, described filtration, washing and dryly can adopt ordinary method to carry out, wherein washer solvent can adopt identical solvent used when dissolving described chemical processing agent.As required, this washing is generally carried out 1～8 time, and preferably 2～6 times, most preferably 2～4 times.
Described being dried can adopt ordinary method to carry out, such as heat drying method under rare gas element desiccating method, boulton process or vacuum, and preferably heat drying method, most preferably heat drying method under vacuum under rare gas element desiccating method or vacuum.Described dry temperature range is generally normal temperature to 140 DEG C, is generally 2-20 hour time of drying, but is not limited to this.
A special embodiment according to the present invention, the preparation method of load type non-metallocene catalyst of the present invention is also included in and makes before described Nonmetallocene title complex contacts with described modification carrier, by the step (pre-treatment step) of modifying carrier described in chemical processing agent pre-treatment that helps that is selected from aikyiaiurnirsoxan beta, aluminum alkyls or its arbitrary combination.
Below the described chemical processing agent that helps is specifically described.
According to the present invention, as the described chemical processing agent that helps, such as enumerating aikyiaiurnirsoxan beta and aluminum alkyls.
As described aikyiaiurnirsoxan beta, such as enumerating the line style aikyiaiurnirsoxan beta shown in following general formula (I): (R) (R) Al-(Al (R)-O) n-O-Al (R) (R), and the ring-type aikyiaiurnirsoxan beta shown in following general formula (II) :-(Al (R)-O-) n+2-.
In aforementioned formula, radicals R is same to each other or different to each other (preferably identical), is selected from independently of one another C 1-C 8alkyl, preferable methyl, ethyl and isobutyl-, most preferable; N is the arbitrary integer within the scope of 1-50, preferably the arbitrary integer in 10～30 scopes.
As described aikyiaiurnirsoxan beta, preferable methyl aikyiaiurnirsoxan beta, ethylaluminoxane, isobutyl aluminium alkoxide and normal-butyl alumina alkane, further preferable methyl aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide.
These aikyiaiurnirsoxan beta can be used separately one, or are used in combination multiple with ratio arbitrarily.
As described aluminum alkyls, such as enumerating the compound shown in following general formula:
Al(R) 3
Wherein, radicals R is same to each other or different to each other (preferably identical), and is selected from independently of one another C 1-C 8alkyl, preferable methyl, ethyl and isobutyl-, most preferable.
Particularly, as described aluminum alkyls, such as enumerating trimethyl aluminium (Al (CH 3) 3), triethyl aluminum (Al (CH 3cH 2) 3), tri-n-n-propyl aluminum (Al (C 3h 7) 3), triisopropylaluminiuand (Al (i-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), tri-n-hexyl aluminum (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 and triisobutyl aluminium, most preferably triethyl aluminum and triisobutyl aluminium.
These aluminum alkylss can use separately one, or are used in combination multiple with ratio arbitrarily.
According to the present invention, as the described chemical processing agent that helps, can only adopt described aikyiaiurnirsoxan beta, also can only adopt described aluminum alkyls, but also can adopt any mixture of described aikyiaiurnirsoxan beta and described aluminum alkyls.And to the ratio of each component in this mixture, there is no particular limitation, can select arbitrarily as required.
According to the present invention, described in to help chemical processing agent be generally to use with the form of solution.In the time helping the solution of chemical processing agent described in preparation, to the solvent that now used, there is no particular limitation, as long as it can dissolve this and help chemical processing agent.
Particularly, can enumerate C 5-12alkane, C 5-12naphthenic hydrocarbon, halo C 5-12alkane, halo C 5-12naphthenic hydrocarbon, C 6-12aromatic hydrocarbons or halo C 6-12aromatic hydrocarbons etc., such as enumerating pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, pentamethylene, hexanaphthene, suberane, cyclooctane, 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 use separately one, or are used in combination multiple with ratio arbitrarily.
It in addition, helps the concentration of chemical processing agent in its solution there is no particular limitation described, can suitably select as required, as long as can realize helping chemical processing agent to carry out described pre-treatment described in predetermined amount.
Through described pre-treatment step, obtain thus through pretreated modification carrier.Then, then according to the pretreated modification carrier of described process is contacted under the existence of the second solvent with aforementioned identical mode with described Nonmetallocene title complex, just described modification carrier is replaced with to the pretreated modification carrier of described process.
That is, according to describe before complete identical mode and carry out described contact reacts, just described modification carrier is replaced with to the pretreated modification carrier of described process, and similarly obtains described mixed serum.
As the method for carrying out described pre-treatment step, such as enumerating, first described in preparing, help the solution of chemical processing agent, then to intend with described in help in the pretreated described modification carrier of chemical processing agent and be metered into and help chemical treatment agent solution (wherein contain predetermined amount described in help chemical processing agent) described in (preferably dripping), or add described modification carrier to the described chemical treatment agent solution amount of falling into a trap that helps, form thus reaction mixture.Now, temperature of reaction is generally-40～60 DEG C, and preferably-30～30 DEG C, the reaction times is generally l～8h, preferably 2～6h, most preferably 3～4h (if desired by stirring).Then,, by filtration, washing and optionally drying, from this reaction mixture, isolate pre-treatment product.
Or, according to circumstances, also can be directly used in follow-up reactions steps with the form of mixed solution without this separation.Now, owing to having contained a certain amount of solvent in described mixed solution, so the solvent load relating in can the described subsequent reactions step of corresponding minimizing.
According to the present invention, described filtration, washing and dryly can adopt ordinary method to carry out, wherein washer solvent can adopt with dissolve described in identical solvent used while helping chemical processing agent.As required, this washing is generally carried out 1～8 time, and preferably 2～6 times, most preferably 2～4 times.Described being dried can adopt ordinary method to carry out, such as heat drying method under rare gas element desiccating method, boulton process or vacuum, and preferably heat drying method, most preferably heat drying method under vacuum under rare gas element desiccating method or vacuum.Described dry temperature range is generally normal temperature to 140 DEG C, is generally 2-20 hour time of drying, but is not limited to this.
According to the present invention, as the consumption of described Nonmetallocene title complex, make to reach 1 in the described magnesium compound (solid) of Mg element and the mol ratio of described Nonmetallocene title complex: 0.01-1, preferably 1: 0.04-0.4, more preferably 1: 0.08-0.2.
According to the present invention, as described for dissolving the solvent of described magnesium compound or the consumption of described the first solvent, make described magnesium compound (solid) and the ratio of described solvent reach 1mol: 75～400ml, preferably 1mol: 150～300ml, more preferably 1mol: 200～250ml.
According to the present invention, as the consumption of described chemical processing agent, make to reach 1 in the described magnesium compound (solid) of Mg element and the mol ratio of the described chemical processing agent in IVB family metal (such as Ti) element: 0.01-1, preferably 1: 0.01-0.50, more preferably 1: 0.10-0.30.
According to the present invention, as the consumption of described precipitation agent, making described precipitation agent and described volume ratio for the solvent that dissolves described magnesium compound is 1: 0.2～5, preferably 1: 0.5～2, more preferably 1: 0.8～1.5.
According to the present invention, as the described consumption that helps chemical processing agent, make in the described magnesium compound (solid) of Mg element with to help the mol ratio of chemical processing agent to reach 1 described in Al element: 0-1.0, preferably 1: 0-0.5, more preferably 1: 0.1-0.5.
Known to those skilled in the art, aforementioned all method stepss all preferably carry out under the condition of anhydrous anaerobic substantially.Here said anhydrous anaerobic substantially refers to the content of water and oxygen in system and continues to be less than 100ppm.And load type non-metallocene catalyst of the present invention needs pressure-fired rare gas element (such as nitrogen, argon gas, helium etc.) in confined conditions to save backup under existing in preparation afterwards conventionally.
In one embodiment, the invention still further relates to the load type non-metallocene catalyst (sometimes also referred to as carry type non-metallocene calalyst for polymerization of olefine) of being manufactured by the preparation method of aforesaid load type non-metallocene catalyst.
In a further embodiment, the present invention relates to a kind of alkene homopolymerization/copolymerization process, wherein using load type non-metallocene catalyst of the present invention as catalyst for olefines polymerizing, make alkene homopolymerization or copolymerization.
With regard to this alkene homopolymerization/copolymerization process involved in the present invention, except the content particularly pointing out below, other contents of not explaining (such as the addition manner of reactor, alkene consumption, catalyzer and alkene for polymerization etc.), can directly be suitable for conventional known those in this area, not special restriction, at this, the description thereof will be omitted.
According to homopolymerization/copolymerization process of the present invention, taking load type non-metallocene catalyst of the present invention as Primary Catalysts, to be selected from one or more in aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt as promotor, make alkene homopolymerization or copolymerization.
Primary Catalysts and promotor can be first to add Primary Catalysts to the mode that adds in polymerization reaction system, and then add promotor, or first add promotor, and then add Primary Catalysts, or both add after first contacting mixing together, or add respectively simultaneously.Primary Catalysts and promotor are added respectively and fashionablely both can in same reinforced pipeline, be added successively, also can in the reinforced pipeline of multichannel, add successively, and both add respectively simultaneously and fashionablely should select the multichannel pipeline that feeds in raw material.For continous way polyreaction, preferably the reinforced pipeline of multichannel adds simultaneously continuously, and for intermittence type polymerization reaction, preferably both add together after first mixing in same reinforced pipeline, or in same reinforced pipeline, first add promotor, and then add Primary Catalysts.
According to the present invention, to the reactive mode of described alkene homopolymerization/copolymerization process, there is no particular limitation, can adopt well known in the art those, such as enumerating slurry process, substance law and vapor phase process etc., wherein preferred slurries method and vapor phase process.
According to the present invention, as described alkene, such as enumerating C 2～C 10monoolefine, diolefin, cyclic olefin and other ethylenically unsaturated compounds.
Particularly, as described C 2～C 12monoolefine, such as enumerating ethene, propylene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-hendecene, 1-laurylene and vinylbenzene etc.; As described cyclic olefin, such as enumerating 1-cyclopentenes and norbornylene etc.; As described diolefin, such as enumerating Isosorbide-5-Nitrae-divinyl, 2,5-pentadiene, 1,6-hexadiene, norbornadiene and 1,7-octadiene etc.; And as described other ethylenically unsaturated compounds, such as enumerating vinyl acetate and (methyl) acrylate etc.Wherein, the homopolymerization of optimal ethylene, or the copolymerization of ethene and propylene, 1-butylene or 1-hexene.
According to the present invention, homopolymerization refers to only a kind of polymerization of described alkene, and copolymerization refers to the polymerization between two or more described alkene.
According to the present invention, described promotor is 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 described aikyiaiurnirsoxan beta, such as enumerating the line style aikyiaiurnirsoxan beta shown in following general formula (I-1): (R) (R) Al-(Al (R)-O) n-O-Al (R) (R), and the ring-type aikyiaiurnirsoxan beta shown in following general formula (II-1) :-(Al (R)-O-) n+2-.
In aforementioned formula, radicals R is same to each other or different to each other (preferably identical), is selected from independently of one another C 1-C 8alkyl, preferable methyl, ethyl and isobutyl-, most preferable.N is the arbitrary integer within the scope of 1-50, preferably the arbitrary integer in 10～30 scopes.
As described aikyiaiurnirsoxan beta, preferable methyl aikyiaiurnirsoxan beta, ethylaluminoxane, isobutyl aluminium alkoxide and normal-butyl alumina alkane, further preferable methyl aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide, and most preferable aikyiaiurnirsoxan beta.
These aikyiaiurnirsoxan beta can be used separately one, or are used in combination multiple with ratio arbitrarily.
As described aluminum alkyls, such as enumerating the compound shown in following general formula (III):
Al(R) 3 (III)
Wherein, radicals R is same to each other or different to each other (preferably identical), and is selected from independently of one another C 1-C 8alkyl, preferable methyl, ethyl and isobutyl-, most preferable.
Particularly, as described aluminum alkyls, such as enumerating trimethyl aluminium (Al (CH 3) 3), triethyl aluminum (Al (CH 3cH 2) 3), tri-n-n-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), tri-n-hexyl aluminum (Al (C 6h 13) 3), three isohexyl aluminium (Al (i-C 6h 13) 3), diethylmethyl aluminium (Al (CH 3) (CH 3cH 2) 2) and dimethyl ethyl aluminium (Al (CH 3cH 2) (CH 3) 2) etc., wherein preferably trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum and triisobutyl aluminium, further preferably triethyl aluminum and triisobutyl aluminium, and triethyl aluminum most preferably.
These aluminum alkylss can use separately one, or are used in combination multiple with ratio arbitrarily.
As described haloalkyl aluminium, such as enumerating the compound shown in following general formula (IV):
Al(R) nX 3-n (IV)
Wherein, radicals R is same to each other or different to each other (preferably identical), and is selected from independently of one another C 1-C 8alkyl, preferable methyl, ethyl and isobutyl-, most preferable.Radicals X is halogen, preferably chlorine.N is 1 or 2.
Particularly, as described haloalkyl aluminium, such as enumerating a Chlorodimethyl aluminium (Al (CH 3) 2cl), dichloromethyl aluminium (Al (CH 3) Cl 2)), aluminium diethyl monochloride (Al (CH 3cH 2) 2cl), ethyl aluminum dichloride (Al (CH 3cH 2) Cl 2), a chlorine dipropyl aluminium (Al (C 3h 7) 2cl), two chloropropyl aluminium (Al (C 3h 7) Cl 2)), a chlorine di-n-butyl aluminium (Al (C 4h 9) 2cl), dichloro n-butylaluminum (Al (C 4h 9) Cl 2), a chloro-di-isobutyl aluminum (Al (i-C 4h 9) 2cl), dichloro aluminium isobutyl (Al (i-C 4h 9) Cl 2), chlorine two n-pentyl aluminium (Al (C 5h 11) 2cl), dichloro n-pentyl aluminium (Al (C 5h 11) Cl 2), a chlorine diisoamyl aluminium (Al (i-C 5h 11) 2cl), dichloro isopentyl aluminium (Al (i-C 5h 11) Cl 2), a chlorine di-n-hexyl aluminium (Al (C 6h 13) 2cl), dichloro n-hexyl aluminium (Al (C 6h 13) Cl 2), chlorine two isohexyl aluminium (Al (i-C 6h 13) 2cl), dichloro isohexyl aluminium (Al (i-C 6h 13) Cl 2),
Chloromethyl aluminium triethyl (Al (CH 3) (CH 3cH 2) Cl), chloromethyl propyl group aluminium (Al (CH 3) (C 3h 7) Cl), chloromethyl n-butylaluminum (Al (CH 3) (C 4h 9) Cl), chloromethyl aluminium isobutyl (Al (CH 3) (i-C 4h 9) Cl), a chloroethyl propyl group aluminium (Al (CH 2cH 3) (C 3h 7) Cl), a chloroethyl n-butylaluminum (AlCH 2cH 3) (C 4h 9) Cl), chloromethyl aluminium isobutyl (AlCH 2cH 3) (i-C 4h 9) Cl) etc., wherein preferred aluminium diethyl monochloride, ethyl aluminum dichloride, a chlorine di-n-butyl aluminium, dichloro n-butylaluminum, a chloro-di-isobutyl aluminum, dichloro aluminium isobutyl, a chlorine di-n-hexyl aluminium, dichloro n-hexyl aluminium, further preferably chlorodiethyl aluminium, ethyl aluminum dichloride and a chlorine di-n-hexyl aluminium, and aluminium diethyl monochloride most preferably.
These haloalkyl aluminium can use separately one, or are used in combination multiple with ratio arbitrarily.
As described boron fluothane, described boron alkyl and described boron alkyl ammonium salt, can directly use conventional those that use in this area, not special restriction.
In addition, according to the present invention, described promotor can use separately one, also can be as required used in combination multiple aforesaid promotor, not special restriction with ratio arbitrarily.
According to the present invention, according to the difference of the reactive mode of described alkene homopolymerization/copolymerization process (such as slurry polymerization), sometimes need to use polymerization solvent.
As described polymerization solvent, can use this area conventional those that use in the time carrying out alkene homopolymerization/copolymerization, not special restriction.
As described polymerization solvent, such as enumerating C 4-10alkane (such as butane, pentane, hexane, heptane, octane, nonane or decane etc.), halo C 1-10alkane (such as methylene dichloride), C 6-12naphthenic hydrocarbon (hexanaphthene, suberane, cyclooctane, cyclononane or cyclodecane), C 6-20aromatic hydrocarbon (such as toluene and dimethylbenzene) etc.Wherein, preferably using pentane, hexane, heptane and cyclohexane give is described polymerization solvent, most preferably hexane.
These polymerizations can be used separately one with solvent, or are used in combination multiple with ratio arbitrarily.
According to the present invention, the polymerization pressure of described alkene homopolymerization/copolymerization process is generally 0.1～10MPa, preferably 0.1～4MPa, and more preferably 0.4～3MPa, but be sometimes not limited to this.According to the present invention, polymeric reaction temperature is generally～and 40 DEG C～200 DEG C, preferably 10 DEG C～100 DEG C, more preferably 40 DEG C～95 DEG C, but be sometimes not limited to this.
In addition, according to the present invention, described alkene homopolymerization/copolymerization process can carry out under the condition that has hydrogen to exist, and also can under the condition that there is no hydrogen, carry out.In the situation that existing, the dividing potential drop of hydrogen can be 0.01%～99% of described polymerization pressure, preferably 0.01%～50%, but be sometimes not limited to this.
According to the present invention, in the time carrying out described alkene homopolymerization/copolymerization process, be generally 1～1000 in the described promotor of aluminium or boron and the mol ratio of the described load type non-metallocene catalyst in described central metal atom: 1, preferably 10～500: 1, more preferably 15～300: 1, but be sometimes not limited to this.
Embodiment
Below adopt embodiment that the present invention is described in further detail, but the present invention is not limited to these embodiment.
(unit is g/cm to polymer stacks density 3) mensuration carry out with reference to CNS GB 1636-79.
In load type non-metallocene catalyst, the content of IVB family metal (such as Ti) and Mg element adopts ICP-AES method to measure, and the content of Nonmetallocene part or title complex adopts analyses.
The polymerization activity of catalyzer calculates in accordance with the following methods: after polyreaction finishes, polymerisate in reactor is filtered and is dried, then weigh the quality of this polymerisate, represent the polymerization activity (unit is kg polymkeric substance/g catalyzer or kg polymkeric substance/gCat) of this catalyzer with this polymerisate quality divided by the ratio of the quality of load type non-metallocene catalyst used.
Molecular weight Mw, the Mn of polymkeric substance and molecular weight distribution (Mw/Mn) adopt the GPC V2000 type gel chromatography analyser of WATERS company of the U.S. to measure, and with 1,2,4-trichlorobenzene, for solvent, temperature when mensuration is 150 DEG C.
The viscosity-average molecular weight of polymkeric substance is calculated in accordance with the following methods: according to standard A STM D4020-00, (capillary inner diameter is 0.44mm to adopt high temperature dilution type Ubbelohde viscometer method, thermostatic bath medium is No. 300 silicone oil, dilution is perhydronaphthalene with solvent, measuring temperature is 135 DEG C) measure the limiting viscosity of described polymkeric substance, then calculate the viscosity-average molecular weight Mv of described polymkeric substance according to following formula.
Mv＝5.37×10 4×[η] 1.37
Wherein, η is limiting viscosity.
Embodiment 1
Magnesium compound adopts Magnesium Chloride Anhydrous, and the first solvent adopts tetrahydrofuran (THF), and precipitation agent adopts hexane, and Nonmetallocene title complex adopts structure to be compound, the second solvent adopts methylene dichloride, the chemical processing agent of IVB family metallic compound adopts titanium tetrachloride, chemical processing agent adopts hexane with solvent.
Take 5g Magnesium Chloride Anhydrous, add after the first solvent and dissolve completely under normal temperature, obtain magnesium compound solution, then add precipitation agent, at 60 DEG C, stirring reaction makes it to precipitate completely for 4 hours, filters, precipitation agent washing 2 times, each precipitation agent consumption is 60ml, vacuumizes dryly at homogeneous heating to 60 DEG C, obtains modifying carrier.
Then add in the solution of Nonmetallocene title complex and the formation of the second solvent modifying carrier, stirring reaction 6 hours at normal temperatures, under normal temperature, vacuum-drying obtains modified support.
Modified support is joined to chemical processing agent with in solvent hexane, normal temperature is added dropwise to chemical processing agent in lower 30 minutes, then homogeneous heating to 60 DEG C isothermal reaction is after 2 hours, filter, chemical processing agent solvent wash 3 times, each 60ml finally vacuumizes dryly at 60 DEG C, obtains load type non-metallocene catalyst.
Wherein proportioning is, magnesium compound and the first solvent burden ratio are 1mol: 210ml; Magnesium compound and Nonmetallocene title complex mol ratio are 1: 0.08; Precipitation agent and the first solvent volume proportioning are 1: 1; Magnesium compound with taking the chemical processing agent mol ratio of IVB family metallic element as 1: 0.15.
Load type non-metallocene catalyst is designated as CAT-1.
Embodiment 1-1
Substantially the same manner as Example 1, but have following change:
The first solvent is changed into toluene, and precipitation agent changes hexanaphthene into, and Nonmetallocene title complex adopts the second solvent is changed into toluene, and the chemical processing agent of IVB family metallic compound is changed into zirconium tetrachloride (ZrCl 4), chemical processing agent is changed into hexanaphthene with solvent.
Wherein proportioning is, magnesium compound and the first solvent burden ratio are 1mol: 150ml; Magnesium compound and Nonmetallocene title complex mol ratio are 1: 0.15; Precipitation agent and the first solvent volume proportioning are 1: 2; Magnesium compound with taking the chemical processing agent mol ratio of IVB family metallic element as 1: 0.20.
Load type non-metallocene catalyst is designated as CAT-1-1.
Embodiment 1-
Substantially the same manner as Example 1, but have following change:
Magnesium compound is changed into anhydrous magnesium bromide (MgBr 2), Nonmetallocene title complex adopts the first solvent is changed into ethylbenzene, and precipitation agent is changed into heptane, and the second solvent adopts tetrahydrofuran (THF), and the chemical processing agent of IVB family metallic compound is changed into titanium tetrabromide (TiBr 4), chemical processing agent is changed into heptane with solvent.
Wherein proportioning is, magnesium compound and the first solvent burden ratio are 1mol: 250ml; Magnesium compound and Nonmetallocene title complex mol ratio are 1: 0.20; Precipitation agent and the first solvent volume proportioning are 1: 0.7; Magnesium compound with taking the chemical processing agent mol ratio of IVB family metallic element as 1: 0.30.
Load type non-metallocene catalyst is designated as CAT-1-2.
Embodiment 1-3
Substantially the same manner as Example 1, but have following change:
Magnesium compound is changed into oxyethyl group magnesium chloride (MgCl (OC 2h 5)), Nonmetallocene title complex adopts the first solvent is changed into dimethylbenzene, and precipitation agent is changed into decane, and the chemical processing agent of IVB family metallic compound is changed into tetraethyl-titanium (Ti (CH 3cH 2) 4), chemical processing agent is changed into decane with solvent.
Wherein proportioning is, magnesium compound and the first solvent burden ratio are 1mol: 300ml; Magnesium compound and Nonmetallocene title complex mol ratio are 1: 0.04; Precipitation agent and the first solvent volume proportioning are 1: 1.5; Magnesium compound with taking the chemical processing agent mol ratio of IVB family metallic element as 1: 0.05.
Load type non-metallocene catalyst is designated as CAT-1-3.
Embodiment 1-4
Substantially the same manner as Example 1, but have following change:
Magnesium compound is changed into magnesium ethylate (Mg (OC 2h 5) 2), Nonmetallocene title complex adopts the first solvent is changed into diethylbenzene, and precipitation agent is changed into pentane, and the chemical processing agent of IVB family metallic compound is changed into tetra-n-butyl titanium (Ti (C 4h 9) 4), chemical processing agent is changed into pentane with solvent.
Wherein proportioning is, magnesium compound and the first solvent burden ratio are 1mol: 400ml; Magnesium compound and Nonmetallocene title complex mol ratio are 1: 0.30; Precipitation agent and the first solvent volume proportioning are 1: 0.5; Magnesium compound with taking the chemical processing agent mol ratio of IVB family metallic element as 1: 0.50.
Load type non-metallocene catalyst is designated as CAT-1-4.
Embodiment 1-5
Substantially the same manner as Example 1, but have following change:
Magnesium compound is changed into methylmagnesium-chloride (Mg (CH 3) Cl), Nonmetallocene title complex adopts the first solvent is changed into chlorotoluene.
Wherein proportioning is, magnesium compound and Nonmetallocene title complex mol ratio are 1: 0.10; Magnesium compound with taking the chemical processing agent mol ratio of IVB family metallic element as 1: 0.10.
Load type non-metallocene catalyst is designated as CAT-1-5.
Embodiment 1-6
Substantially the same manner as Example 1, but have following change:
Magnesium compound is changed into ethylmagnesium chloride (Mg (C 2h 5) Cl), the first solvent is changed into bromo ethylbenzene, and Nonmetallocene title complex adopts precipitation agent is changed into suberane, and the chemical processing agent of IVB family metallic compound is changed into purity titanium tetraethoxide (Ti (OCH 3cH 2) 4), chemical processing agent is changed into suberane with solvent.
Wherein, magnesium compound with taking the chemical processing agent mol ratio of IVB family metallic element as 1: 1.
Load type non-metallocene catalyst is designated as CAT-1-6.
Embodiment 1-7
Substantially the same manner as Example 1, but have following change:
Magnesium compound is changed into magnesium ethide (Mg (C 2h 5) 2), Nonmetallocene title complex adopts the chemical processing agent of IVB family metallic compound is changed into isobutyl-titanous chloride (Ti (i-C 4h 9) Cl 3).
Load type non-metallocene catalyst is designated as CAT-1-7.
Embodiment 1-8
Substantially the same manner as Example 1, but have following change:
Magnesium compound is changed into methyl ethoxy magnesium (Mg (OC 2h 5) (CH 3)), precipitation agent is changed into chlorocyclohexane, and the chemical processing agent of IVB family metallic compound is changed into three isobutoxy titanium chloride (TiCl (i-OC 4h 9) 3), chemical processing agent is changed into chlorocyclohexane with solvent.
Load type non-metallocene catalyst is designated as CAT-1-8.
Embodiment 1-9
Substantially the same manner as Example 1, but have following change:
Magnesium compound is changed into butyl magnesium ethylate (Mg (OC 2h 5) (C 4h 9)), precipitation agent is changed into bromo suberane, and the chemical processing agent of IVB family metallic compound is changed into dimethoxy zirconium dichloride (ZrCl 2(OCH 3) 2).
Load type non-metallocene catalyst is designated as CAT-1-9.
Embodiment 2
Magnesium compound adopts Magnesium Chloride Anhydrous, and the first solvent adopts tetrahydrofuran (THF), and precipitation agent adopts hexane, helps chemical processing agent to adopt triethyl aluminum, and Nonmetallocene title complex adopts structure to be compound, the second solvent adopts methylene dichloride, the chemical processing agent of IVB family metallic compound adopts titanium tetrachloride, chemical processing agent adopts hexane with solvent.
Take 5g Magnesium Chloride Anhydrous, add after the first solvent and dissolve completely under normal temperature, obtain magnesium compound solution, then add precipitation agent, at 60 DEG C, stirring reaction makes it to precipitate completely for 4 hours, filters, precipitation agent washing 2 times, each precipitation agent consumption is 60ml, vacuumizes dryly at homogeneous heating to 60 DEG C, obtains modifying carrier.
Then in obtained modification carrier, add 60ml hexane, under agitation condition, adopt triethyl aluminum (hexane solution that concentration is 15wt%) to help chemical processing agent to process and modify carrier, with 30 minutes dropping triethyl aluminums, at 60 DEG C, stirring reaction is after 4 hours, filter, hexane washing 2 times, each hexane consumption 60ml, under normal temperature, vacuum-drying obtains pretreated modification carrier.
Then, pretreated modification carrier is added in the solution of Nonmetallocene title complex and the formation of the second solvent, stirring reaction 6 hours at normal temperatures, under normal temperature, vacuum-drying obtains modified support.
Modified support is joined to chemical processing agent with in solvent hexane, normal temperature is added dropwise to chemical processing agent in lower 30 minutes, then stirring reaction after 6 hours under normal temperature, filter, chemical processing agent solvent wash 3 times, each 60ml, vacuumizes dryly under last normal temperature, obtain load type non-metallocene catalyst.
Wherein proportioning is, magnesium compound and the first solvent burden ratio are 1mol: 210ml; Magnesium compound and Nonmetallocene title complex mol ratio are 1: 0.08; Precipitation agent and the first solvent volume proportioning are 1: 1; Magnesium compound with help chemical processing agent mol ratio as 1: 0.15 taking Al element; Magnesium compound with taking the chemical processing agent mol ratio of IVB family metallic element as 1: 0.15.
Load type non-metallocene catalyst is designated as CAT-2.
Embodiment 2-1
Substantially the same manner as Example 2, but have following change:
The first solvent is changed into toluene, and precipitation agent changes hexanaphthene into, helps chemical processing agent to change into methylaluminoxane (MAO, the toluene solution of 10wt%), and Nonmetallocene title complex adopts the second solvent is changed into toluene, and the chemical processing agent of IVB family metallic compound is changed into zirconium tetrachloride (ZrCl 4), chemical processing agent is changed into hexanaphthene with solvent.
Wherein proportioning is, magnesium compound and the first solvent burden ratio are 1mol: 150ml; Magnesium compound and Nonmetallocene title complex mol ratio are 1: 0.15; Precipitation agent and the first solvent volume proportioning are 1: 2; Magnesium compound with help chemical processing agent mol ratio as 1: 0.20 taking Al element; Magnesium compound with taking the chemical processing agent mol ratio of IVB family metallic element as 1: 0.20.
Load type non-metallocene catalyst is designated as CAT-2-1.
Embodiment 2-2
Substantially the same manner as Example 2, but have following change:
Magnesium compound is changed into anhydrous magnesium bromide (MgBr 2), Nonmetallocene title complex adopts the first solvent is changed into ethylbenzene, and precipitation agent is changed into heptane, helps chemical processing agent to change into trimethyl aluminium (Al (CH 3) 3), the second solvent is changed into tetrahydrofuran (THF), and the chemical processing agent of IVB family metallic compound is changed into titanium tetrabromide (TiBr 4), chemical processing agent is changed into heptane with solvent.
Wherein proportioning is, magnesium compound and the first solvent burden ratio are 1mol: 250ml; Magnesium compound and Nonmetallocene title complex mol ratio are 1: 0.20; Precipitation agent and the first solvent volume proportioning are 1: 0.7; Magnesium compound with help chemical processing agent mol ratio as 1: 0.30 taking Al element; Magnesium compound with taking the chemical processing agent mol ratio of IVB family metallic element as 1: 0.30.
Load type non-metallocene catalyst is designated as CAT-2-2.
Embodiment 2-3
Substantially the same manner as Example 2, but have following change:
Magnesium compound is changed into oxyethyl group magnesium chloride (MgCl (OC 2h 5)), Nonmetallocene title complex adopts the first solvent is changed into dimethylbenzene, and precipitation agent is changed into decane, helps chemical processing agent to change into triisobutyl aluminium (Al (i-C 4h 9) 3), the chemical processing agent of IVB family metallic compound is changed into tetraethyl-titanium (Ti (CH 3cH 2) 4), chemical processing agent is changed into decane with solvent.
Wherein proportioning is, magnesium compound and the first solvent burden ratio are 1mol: 300ml; Magnesium compound and Nonmetallocene title complex mol ratio are 1: 0.04; Precipitation agent and the first solvent volume proportioning are 1: 1.5; Magnesium compound with help chemical processing agent mol ratio as 1: 0.05 taking Al element; Magnesium compound with taking the chemical processing agent mol ratio of IVB family metallic element as 1: 0.05.
Load type non-metallocene catalyst is designated as CAT-2-3.
Embodiment 2-4
Substantially the same manner as Example 2, but have following change:
Magnesium compound is changed into magnesium ethylate (Mg (OC 2h 5) 2), Nonmetallocene title complex adopts the first solvent is changed into diethylbenzene, and precipitation agent is changed into pentane, helps chemical processing agent to change into isobutyl aluminium alkoxide, and the chemical processing agent of IVB family metallic compound is changed into tetra-n-butyl titanium (Ti (C 4h 9) 4), chemical processing agent is changed into pentane with solvent.
Wherein proportioning is, magnesium compound and the first solvent burden ratio are 1mol: 400ml; Magnesium compound and Nonmetallocene title complex mol ratio are 1: 0.30; Precipitation agent and the first solvent volume proportioning are 1: 0.5; Magnesium compound with help chemical processing agent mol ratio as 1: 0.50 taking Al element; Magnesium compound with taking the chemical processing agent mol ratio of IVB family metallic element as 1: 0.50.
Load type non-metallocene catalyst is designated as CAT-2-4.
Embodiment 2-5
Substantially the same manner as Example 2, but have following change:
Magnesium compound is changed into methylmagnesium-chloride (Mg (CH 3) Cl), Nonmetallocene title complex adopts the first solvent is changed into chlorotoluene.
Wherein proportioning is, magnesium compound and Nonmetallocene title complex mol ratio are 1: 0.10; Magnesium compound with help chemical processing agent mol ratio as 1: 0.40 taking Al element; Magnesium compound with taking the chemical processing agent mol ratio of IVB family metallic element as 1: 0.10.
Load type non-metallocene catalyst is designated as CAT-2-5.
Comparative example A
Substantially the same manner as Example 1, but have following change:
Magnesium compound and Nonmetallocene title complex mol ratio are changed into 1: 0.16;
Catalyzer is designated as CAT-A.
Comparative example B
Substantially the same manner as Example 1, but have following change:
Magnesium compound and Nonmetallocene title complex mol ratio are changed into 1: 0.04;
Catalyzer is designated as CAT-B.
Comparative example C
Substantially the same manner as Example 1, but have following change:
Take 5g Magnesium Chloride Anhydrous, add after butanols and the first solvent and dissolve completely under normal temperature, obtain magnesium compound solution.Wherein mole proportioning of magnesium compound and butanols is 1: 0.5.
Catalyzer is designated as CAT-C.
Comparative example D
Substantially the same manner as Example 1, but have following change:
Modified support is without chemical processing agent processing, directly as load type non-metallocene catalyst.
Catalyzer is designated as CAT-D.
Embodiment 3 (Application Example)
By the catalyzer CAT-1～CAT-2 making in the embodiment of the present invention, CAT-1-1～9, CAT-2-1～5, CAT-A～C, the homopolymerization of carrying out in accordance with the following methods under the following conditions respectively ethene, copolymerization with prepare ultrahigh molecular weight polyethylene(UHMWPE).
Homopolymerization is: 5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 liters of hexane solvents, polymerization stagnation pressure 0.8MPa, 85 DEG C of polymerization temperatures, hydrogen partial pressure 0.2MPa, 2 hours reaction times.First 2.5 liters of hexanes are joined in polymerization autoclave, open and stir, then add 50mg load type non-metallocene catalyst and catalyst mixture, then add hydrogen to 0.2MPa, finally continue to pass into ethene and make polymerization stagnation pressure constant in 0.8MPa.After reaction finishes, by gas reactor emptying, emit still interpolymer, the dry rear quality that weighs.The particular case of this polyreaction and polymerization evaluation result are as shown in table 1.
Copolymerization is: 5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 liters of hexane solvents, polymerization stagnation pressure 0.8MPa, 85 DEG C of polymerization temperatures, hydrogen partial pressure 0.2MPa, 2 hours reaction times.First 2.5 liters of hexanes are joined in polymerization autoclave, open and stir, then add 50mg load type non-metallocene catalyst and catalyst mixture, the disposable hexene-1 comonomer 50g that adds, add again hydrogen to 0.2MPa, finally continue to pass into ethene and make polymerization stagnation pressure constant in 0.8MPa.After reaction finishes, by gas reactor emptying, emit still interpolymer, the dry rear quality that weighs.The particular case of this polyreaction and polymerization evaluation result are as shown in table 1.
Preparing ultrahigh molecular weight polyethylene(UHMWPE) is polymerized to: 5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 liters of hexane solvents, polymerization stagnation pressure 0.5MPa, 70 DEG C of polymerization temperatures, 2 hours reaction times.First 2.5 liters of hexanes are joined in polymerization autoclave, open and stir, then add 50mg load type non-metallocene catalyst and catalyst mixture, promotor is 100 with catalyst activity metal molar ratio, finally continues to pass into ethene and makes polymerization stagnation pressure constant in 0.5MPa.After reaction finishes, by gas reactor emptying, emit still interpolymer, the dry rear quality that weighs.The particular case of this polyreaction and polymerization evaluation result are as shown in table 2.
Test-results data by sequence number in table 13 and 4,16 and 17 are known, increase the consumption of promotor, improve promotor and catalyst activity metal molar than time, impact active on polymerization catalyst and polymer stacks density is not remarkable.It can be said that brightly, adopt load type non-metallocene catalyst prepared by method provided by the invention only to need fewer promotor consumption just can obtain high olefin polymerizating activity; And the polymkeric substance such as the polyethylene that obtained thus has good polymer morphology and high polymer bulk density.
In contrast table 1, the test-results data of sequence number 1 and 3, sequence number 14 and 15 are known, after copolymerization, catalyst activity has increase by a relatively large margin, thereby the load type non-metallocene catalyst that explanation adopts method provided by the invention to prepare has comparatively significant comonomer effect.
And visible by the molecular weight distribution of sequence number 1 to 4,14 to 17 in table 1, narrower by the molecular weight distribution obtaining after catalyst olefinic polymerization provided by the invention.Well known in the art is to adopt the molecular weight distribution prepared of Ziegler-Natta catalyst (active centre is IVB family metal titanium) between 5～8, is that the molecular weight distribution prepared of Ziegler-Natta catalyst is between 8～15 and adopt chromium.
Test-results data by sequence number 1 in contrast table 1 and comparative example sequence number 23～25 are known, increase or reduce the add-on of Nonmetallocene title complex in catalyzer, and its activity increases thereupon or reduce increase.In catalyzer, in preparation process, modified support does not pass through the chemical processing agent processing of IVB family metallic compound, and its activity decreased comparatively significantly adds, but the ultrahigh molecular weight polyethylene(UHMWPE) viscosity-average molecular weight of preparation is higher.Thereby illustrate that Nonmetallocene title complex has the effect that determines catalyst activity and polymer performance, and chemical processing agent plays material impact to catalyst activity.Therefore researcher in this field knows, can obtain the catalyzer of different activities and polymer performance by the proportioning that changes both.
From table 2, adopt catalyzer provided by the present invention, can prepare ultrahigh molecular weight polyethylene(UHMWPE), its bulk density all increases to some extent, and contrast sequence number 1 and 2,3 and 4 visible, employing methylaluminoxane can increase the viscosity-average molecular weight of polymkeric substance as promotor.In contrast table 2, the test-results data of sequence number 1 and comparative example 5～6 are known, increase or reduce Nonmetallocene title complex in catalyzer, and polymkeric substance viscosity-average molecular weight changes and be not obvious.Thereby illustrate that Nonmetallocene title complex also has the effect that determines polymkeric substance viscosity-average molecular weight.
By sequence number in contrast table 11 and 25, and in table 2, the test-results of sequence number 1 and 7 is known, than the load type non-metallocene catalyst that has the existence of alcohol to obtain in magnesium compound solution, in catalyst preparation process magnesium compound solution of the present invention, there is no the load type non-metallocene catalyst obtaining of alcohol, there is higher catalysis in olefine polymerization activity, polymer stacks density, and narrow molecular weight distribution, and the ultrahigh molecular weight polyethylene(UHMWPE) viscosity-average molecular weight obtaining.
Although the specific embodiment of the present invention is had been described in detail above, it is pointed out that protection scope of the present invention is not subject to the restriction of these embodiments, but determined by claims of annex in conjunction with the embodiments.Those skilled in the art can carry out suitable change to these embodiments in the scope that does not depart from technological thought of the present invention and purport, and within these embodiments after changing are obviously also included within protection scope of the present invention.

Claims (17)

1. a preparation method for load type non-metallocene catalyst, comprises the following steps:
Magnesium compound is dissolved in the first solvent, obtains the step of magnesium compound solution;
In described magnesium compound solution, add precipitation agent, obtain the step of modifying carrier;
Described modification carrier is contacted under the existence of the second solvent with Nonmetallocene title complex, obtain the step of mixed serum;
Mixed serum described in convection drying, the step of acquisition modified support; With
The chemical processing agent that is selected from IVB family metallic compound is reacted with described modified support, obtains the step of described load type non-metallocene catalyst,
Wherein said preparation method is optionally also included in and makes before described Nonmetallocene title complex contacts with described modification carrier, by the step of modifying carrier described in chemical processing agent pre-treatment that helps that is selected from aikyiaiurnirsoxan beta, aluminum alkyls or its arbitrary combination.
2. according to preparation method claimed in claim 1, it is characterized in that, described magnesium compound is selected from one or more in magnesium halide, alkoxyl group magnesium halide, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and alkyl alkoxy magnesium.
3. according to preparation method claimed in claim 2, it is characterized in that, described magnesium compound is selected from one or more in magnesium halide.
4. according to preparation method claimed in claim 1, it is characterized in that, described the first solvent is selected from C 6-12aromatic hydrocarbon, halo C 6-12one or more in aromatic hydrocarbon, ester and ether, described the second solvent is selected from C 6-12aromatic hydrocarbon, halo C 6-12aromatic hydrocarbon, halo C 1-10one or more in alkane, ester and ether.
5. according to preparation method claimed in claim 4, it is characterized in that, described the first solvent is selected from C 6-12one or more in aromatic hydrocarbon and tetrahydrofuran (THF), described the second solvent is selected from C 6-12one or more in aromatic hydrocarbon, methylene dichloride and tetrahydrofuran (THF).
6. according to preparation method claimed in claim 1, it is characterized in that, described IVB family metallic compound is selected from one or more in 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.
7. according to preparation method claimed in claim 6, it is characterized in that, described IVB family metallic compound is selected from one or more in IVB family metal halide.
8. according to preparation method claimed in claim 1, it is characterized in that, described Nonmetallocene title complex is selected from one or more in the compound with following chemical structural formula:
In above chemical structural formula,
Q is 0 or 1;
D is 0 or 1;
M is 1,2 or 3;
M is selected from periodic table of elements III-th family to XI family atoms metal;
N is 1,2,3 or 4, depends on the valence state of described M;
X is selected from halogen, hydrogen atom, C 1-C 30the C of alkyl, replacement 1-C 30alkyl, oxy radical, nitrogen-containing group, sulfur-containing group, boron-containing group, containing aluminium base group, phosphorus-containing groups, silicon-containing group, germanic group or containing tin group, multiple X can be identical, also can be different, can also be each other in key or Cheng Huan;
A be selected from Sauerstoffatom, sulphur atom, selenium atom, -NR 23r 24,-N (O) R 25r 26, -PR 28r 29,-P (O) R 30oR 31, sulfuryl, sulfoxide group or-Se (O) R 39, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;
B is selected from nitrogen-atoms, nitrogen-containing group, phosphorus-containing groups or C 1-C 30alkyl;
D is selected from nitrogen-atoms, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, nitrogen-containing group, phosphorus-containing groups, C 1-C 30alkyl, sulfuryl or sulfoxide group, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;
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;
---represent coordinate bond, covalent linkage or ionic linkage;
R 1to R 3be selected from independently of one another hydrogen, C 1-C 30the C of alkyl, replacement 1-C 30alkyl or safing function group, R 22to R 33and R 39be selected from independently of one another hydrogen, C 1-C 30the C of alkyl or replacement 1-C 30alkyl, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan,
Described safing function group is selected from halogen, oxy radical, nitrogen-containing group, silicon-containing group, germanic group, sulfur-containing group, contains tin group, C 1-C 10ester group or nitro,
Described halogen is selected from F, Cl, Br or I;
Described nitrogen-containing group is selected from -NR 23r 24,-T-NR 23r 24or-N (O) R 25r 26;
Described phosphorus-containing groups is selected from -PR 28r 29,-P (O) R 30r 31or-P (O) R 32(OR 33);
Described oxy radical is selected from hydroxyl ,-OR 34with-T-OR 34;
Be selected from-SR of described sulfur-containing group 35,-T-SR 35,-S (O) R 36or-T-SO 2r 37;
Described containing be selected from-SeR of seleno group 38,-T-SeR 38,-Se (O) R 39or-T-Se (O) R 39;
Described group T is selected from C 1-C 30the C of alkyl or replacement 1-C 30alkyl;
Described R 37be selected from hydrogen, C 1-C 30the C of alkyl or replacement 1-C 30alkyl;
Described C 1-C 30alkyl is selected from C 1-C 30alkyl, C 7-C 30alkaryl, C 7-C 30aralkyl, C 3-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, wherein said heterocyclic radical contains 1-3 heteroatoms that is selected from nitrogen-atoms, Sauerstoffatom or sulphur atom;
The C of described replacement 1-C 30alkyl is selected from one or more aforementioned halogens or aforementioned C 1-C 30alkyl is as substituent aforementioned C 1-C 30alkyl;
Wherein, described boron-containing group is selected from BF 4 -, (C 6f 5) 4b -or (R 40bAr 3) -;
Describedly be selected from aluminum alkyls, AlPh containing aluminium base group 4 -, AlF 4 -, AlCl 4 -, AlBr 4 -, AlI 4 -or R 41alAr 3 -;
Be selected from-SiR of described silicon-containing group 42r 43r 44or-T-SiR 45;
Described be selected from-GeR of germanic group 46r 47r 48or-T-GeR 49;
Described containing be selected from-SnR of tin group 50r 51r 52,-T-SnR 53or-T-Sn (O) R 54,
Described Ar represents C 6-C 30aryl, and
R 34to R 36, R 38and R 40to R 54be selected from independently of one another hydrogen, aforementioned C 1-C 30the C of alkyl or aforementioned replacement 1-C 30alkyl, wherein these groups can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan,
And described group T ditto defines.
9. according to preparation method claimed in claim 8, it is characterized in that, described Nonmetallocene title complex is selected from one or more in compound (A) and the compound (B) with following chemical structural formula:
In above all chemical structural formulas,
F is selected from nitrogen-atoms, nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself.
10. according to preparation method claimed in claim 9, it is characterized in that, described Nonmetallocene title complex is selected from one or more in to compound (A-4) and compound (B-1) to compound (B-4) of the compound (A-1) with following chemical structural formula:
In above all chemical structural formulas,
Y is selected from Sauerstoffatom, nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;
Z is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;
R 4, R 6to R 21be selected from independently of one another hydrogen, C 1-C 30the C of alkyl, 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 combine togather into key or Cheng Huan, and
R 5be selected from lone-pair electron on nitrogen, hydrogen, C 1-C 30the C of alkyl, replacement 1-C 30alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups; Work as R 5during for oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups, R 5in N, O, S, P and Se can be used as coordination atom and center IVB family atoms metal carries out coordination.
11. according to preparation method claimed in claim 1, it is characterized in that, described Nonmetallocene title complex is selected from one or more in the compound with following chemical structural formula:
12. according to the preparation method described in claim 11, it is characterized in that, described Nonmetallocene title complex is selected from one or more in the compound with following chemical structural formula:
13. according to preparation method claimed in claim 1, it is characterized in that, taking the described magnesium compound of Mg element and the mol ratio of described Nonmetallocene title complex as 1: 0.01-1, the ratio of described magnesium compound and described the first solvent is 1mol: 75～400ml, in the described magnesium compound of Mg element with the mol ratio taking the described chemical processing agent of IVB family metallic element as 1: 0.01-1, in the described magnesium compound of Mg element and to help the mol ratio of chemical processing agent as 1 described in Al element: 0-1.0, and the volume ratio of described precipitation agent and described the first solvent is 1: 0.2～5.
14. according to preparation method claimed in claim 1, it is characterized in that, described precipitation agent is selected from C 5-12alkane, C 5-12naphthenic hydrocarbon, halo C 1-10alkane and halo C 5-12one or more in naphthenic hydrocarbon.
15. according to the preparation method described in claim 14, it is characterized in that, described precipitation agent is selected from one or more in hexane, heptane, decane and hexanaphthene.
16. 1 kinds of load type non-metallocene catalysts, it is to be manufactured by the preparation method according to described in claim 1-15 any one.
17. 1 kinds of alkene homopolymerization/copolymerization process, it is characterized in that, taking the load type non-metallocene catalyst according to described in claim 16 as Primary Catalysts, to be selected from one or more in aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt as promotor, make alkene homopolymerization or copolymerization.
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CN101412767A (en) * 2007-10-16 2009-04-22 中国石化扬子石油化工有限公司 Load type non-metallocene catalyst and preparation thereof
CN101654492A (en) * 2008-08-21 2010-02-24 中国石化扬子石油化工有限公司 Super-high molecular polyethylene and preparation method and application thereof

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