CN103304699A - Loaded non-metallocene catalyst, its preparation method and application - Google Patents

Loaded non-metallocene catalyst, its preparation method and application Download PDF

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CN103304699A
CN103304699A CN2012100638545A CN201210063854A CN103304699A CN 103304699 A CN103304699 A CN 103304699A CN 2012100638545 A CN2012100638545 A CN 2012100638545A CN 201210063854 A CN201210063854 A CN 201210063854A CN 103304699 A CN103304699 A CN 103304699A
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alkyl
nitrogen
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magnesium
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CN103304699B (en
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任鸿平
李传峰
郭峰
阚林
柏基业
马忠林
陈韶辉
王亚明
杨爱武
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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 loaded non-metallocene catalyst and its preparation method. The loaded non-metallocene catalyst has the characteristics of simple and feasible preparation process, controllable non-metallocene component content, and substantial copolymerization effect, etc. The invention also relates to application of the loaded non-metallocene catalyst in olefin homopolymerization/copolymerization. Compared with the prior art, during application, the loaded non-metallocene catalyst has high olefin polymerization catalytic activity, small size and uniform distribution, and the obtained polymer has a high bulk density.

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 it to the future development of 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, because non cyclopentadienyl catalyst appears on the time after the metallocene catalyst, " after luxuriant " olefin polymerization catalysis therefore is otherwise known as.It has the characteristics similar to metallocene catalyst, can customize as required polymkeric substance, and cost is lower.The central atom of non-metallocene catalyst has comprised nearly all transition metal, reaches at some aspect of performance, even surpasses metallocene catalyst, becomes the olefin polymerization catalysis of new generation after Ziegler-Natta and metallocene catalyst.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.The non-metallocene catalyst ligating atom is oxygen, nitrogen, sulphur and phosphorus, do not contain cyclopentadienyl group or its deriveding group, such as indenyl and fluorenyl etc., it is characterized in that central ion has stronger Electron Affinities, and have cis alkyl or halogen metal division center, 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 that forms has the geometric configuration of restriction, stereoselectivity, electronegativity and chirality controllability, and in addition, formed metal-carbon key easily polarizes, and more is conducive to polymerization and the copolymerization of alkene.Therefore, even under higher polymeric reaction temperature, also can obtain the olefin polymer of higher molecular weight.
But homogeneous catalyst has been proved it in olefinic polyreaction has that active duration is short, easily sticking still, methylaluminoxane consumption are high, 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, has widely alkene homopolymerization/copolymerization performance, but need higher promotor consumption during in olefinic polymerization at the disclosed catalyzer of this patent or catalyst system, could obtain suitable olefin polymerizating activity, and it is short to exist active duration in the polymerization process, the phenomenons such as the sticking still of polymkeric substance.
Common way be with non-metallocene catalyst by certain load technology, make loaded catalyst, thereby improve the polymerization of alkene and the particle form of resulting polymers.It shows as the initial activity that has suitably reduced to a certain extent catalyzer, the polymerization activity life-span of extending catalyst, reduce even avoided caking or the cruelly poly-phenomenon in the polymerization process, improve the form of polymkeric substance, improve the apparent density of polymkeric substance, can make it satisfy more polymerization technique process, such as vapour phase polymerization or slurry polymerization etc.
For patent ZL 01126323.7, ZL 02151294.9ZL 02110844.7 and WO 03/010207 disclosed non-metallocene catalyst, patent CN 1539855A, CN 1539856A, CN 1789291A, CN 1789292A, CN 1789290A, WO/2006/063501, ZL200510119401.x etc. provide various ways to carry out load to obtain load type non-metallocene catalyst, but these patents all relate to the porous oxide medium makes carrier or carrier component, porous oxide can support active ingredient and play the effect that improves polymer morphology in polymerization process, yet can not promote active ingredient performance katalysis, therefore add the performance that porous oxide carrier has limited the non-metallocene catalyst activity.
Patent 200710162667.1,200710162676.0,200910210987.9 and 200910210991.5 disclosed load type non-metallocene catalyst patents provide and have not contained porous oxide, and single Catalysts and its preparation method take magnesium compound as carrier.Because do not have the adding of porous oxide carrier, the catalytic performance of load type non-metallocene catalyst has obtained fully playing, polymerization activity is higher.But this class catalyzer adopts the method for vacuum-drying or solvent deposition in the carrier moulding process, is difficult to control moulding process and the particle form of carrier, so the difficult control of the form of polymkeric substance.
The magnesium halide that generates in the chemical reaction process also can prepare as carrier the olefin polymerization catalysis of load, and can regulate by the control chemical reaction process formation speed of magnesium halide, realizes morphology Control to magnesium halide carrier with this.And studies show that the magnesium halide that is generated by Grignard reagent and halide reaction has higher specific surface, and unordered crystalline structure (Eur Polym J, 2000,19:19), be suitable for preparing loaded catalyst.
Japanese Patent JP1054005A, JP1054006A and JP63186706A provide the method for preparing high activity olefin polymerization catalyst, it is to make Grignard reagent MgRX (R is alkyl, X is halogen) obtain the magnesium compound carrier with halohydrocarbons reaction, then magnesium halide carrier load halogenated titanium is made loaded catalyst, and the activity of this catalyst olefinic polymerization is higher.
Japanese Patent JP1081803A provides a kind of method for preparing olefin polymerization catalysis, it is to make Grignard reagent MgRX (R is alkyl, X is halogen) generate magnesium halide carrier with halogenated compound (such as aluminum chloride) reaction, then magnesium halide carrier load halogenated titanium is made loaded catalyst.
Japanese Patent JP6192329A provides a kind of method for preparing olefin polymerization catalysis, and it is to make Grignard reagent MgRX (R is alkyl, and X is halogen) and halohydrocarbons reaction generate magnesium halide carrier, and then the reaction of carrier and halogenated titanium obtains loaded catalyst.The carrier that the method obtains has narrow size distribution, and the catalyzer of preparation has mobile preferably.
Therefore, present present situation is, still needs a kind of load type non-metallocene catalyst, and its preparation method is simple, is fit to suitability for industrialized production, and can overcomes those problems that exist in the prior art load type non-metallocene catalyst.
Summary of the invention
The inventor finds through diligent research on the basis of existing technology, by making described load type non-metallocene catalyst with a kind of specific preparation method, just can solve foregoing problems, and finish 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 conventional compounds such as monoesters class, di-esters, two ethers, diones and diol-lipid that use).Moreover, in the preparation method of load type non-metallocene catalyst of the present invention, also need not harsh reaction requirement and reaction conditions.Therefore, the preparation method of this loaded catalyst is simple, and is very suitable for suitability for industrialized production.
Particularly, the present invention relates to the content of following aspect:
1. the preparation method of a load type non-metallocene catalyst may further comprise the steps:
Make the reaction of Grignard reagent and halogenating agent, obtain the step of magnesium base carrier;
The Nonmetallocene title complex is contacted in the presence of solvent with described magnesium base carrier, obtain the step of mixed serum; With
The described mixed serum of convection drying obtains the step of described load type non-metallocene catalyst.
2. according to the described preparation method of aforementioned either side, it is characterized in that, described halogenating agent is selected from halo C 1-30In the hydrocarbon one or more are preferably selected from chloro C 1-30Hydrocarbon and bromo C 1-30In the hydrocarbon one or more, wherein said C 1-30Hydrocarbon is C 1-30Alkane, C 2-30Alkene, C 6-30Aromatic hydrocarbons, C 7-30Aralkyl hydrocarbon or C 7-30Alkane aromatic hydrocarbons, described halogenating agent are preferably selected from one or more in monobromethane, monochloroethane, monobromethane, 1-chloro-butane, 1-chloro-hexane, chlorobenzene, bromobenzene and the benzyl chloride.
3. according to the described preparation method of aforementioned either side, it is characterized in that, described Grignard reagent is selected from alkyl magnesium halide that general formula is RMgX and general formula and is in the dialkyl magnesium of (R) (R ') Mg one or more, and wherein radicals R and R ' are same to each other or different to each other, and are C independently of one another 1-C 30Alkyl, preferred C 1-C 30Alkyl, C 2-C 30Thiazolinyl, C 6-C 30Aryl, C 7-C 30Alkaryl or C 7-C 30Aralkyl, further preferable methyl, ethyl, isobutyl-, iso-octyl, cyclohexyl, phenyl or benzyl, most preferable or ethyl, X is halogen, preferred chlorine or bromine, described Grignard reagent is preferably selected from one or more in methylmagnesium-chloride, ethylmagnesium chloride, phenyl-magnesium-chloride, benzylmagnesium chloride, dimethyl magnesium, magnesium ethide and the diphenyl magnesium.
4. according to the described preparation method of aforementioned either side, it is characterized in that, described solvent is selected from C 6-12Aromatic hydrocarbon, halo C 6-12Aromatic hydrocarbon, halo C 1-10In alkane, ester and the ether one or more, be preferably selected from toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromo toluene, bromo ethylbenzene, methylene dichloride, ethylene dichloride, ethyl acetate and the tetrahydrofuran (THF) one or more, more preferably C 6-12In aromatic hydrocarbon, methylene dichloride and the tetrahydrofuran (THF) one or more.
5. according to the described preparation method of 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 compound (A) with following chemical structural formula and in the compound (B) one or more:
Figure BSA00000683115000051
More preferably be selected to compound (A-4) and compound (B-1) to compound (B-4) one or more of compound (A-1) with following chemical structural formula:
Figure BSA00000683115000052
Figure BSA00000683115000061
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, preferred 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, contain aluminium base group, phosphorus-containing groups, silicon-containing group, germanic group or contain tin group, a plurality of X can be identical, also can be different, and 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,
Figure BSA00000683115000063
-PR 28R 29,-P (O) R 30OR 31, sulfuryl, sulfoxide group or-Se (O) R 39, N, O, S, Se and the P coordination atom of respectively doing for oneself wherein;
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,
Figure BSA00000683115000064
-N (O) R 25R 26, Or-P (O) R 32(OR 33), N, O, S, Se and the P coordination atom of respectively doing for oneself wherein;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains 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, contain 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, contain 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, 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 the nitrogen, hydrogen, C 1-C 30The C of alkyl, replacement 1-C 30Alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, contain seleno group or phosphorus-containing groups; Work as R 5For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group or phosphorus-containing groups, R 5In N, O, S, P and Se can be used as coordination and carry out coordination with atom and described center IVB family atoms metal,
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 further is preferably selected from one or more in the compound with following chemical structural formula:
Figure BSA00000683115000071
Most preferably be selected from the compound with following chemical structural formula one or more:
6. according to the described preparation method of 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
Figure BSA00000683115000082
-NR 23R 24,-T-NR 23R 24Or-N (O) R 25R 26
Described phosphorus-containing groups is selected from
Figure BSA00000683115000083
-PR 28R 29,-P (O) R 30R 31Or-P (O) R 32(OR 33);
Described oxy radical be selected from hydroxyl ,-OR 34With-T-OR 34
Described sulfur-containing group is selected from-SR 35,-T-SR 35,-S (O) R 36Or-T-SO 2R 37
The described seleno group that contains is selected from-SeR 38,-T-SeR 38,-Se (O) R 39Or-T-Se (O) R 39
Described group T is selected from C 1-C 30The C of alkyl, replacement 1-C 30Alkyl or 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 contain 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 contain aluminium base group and be selected from aluminum alkyls, AlPh 4 -, AlF 4 -, AlCl 4 -, AlBr 4 -, AlI 4 -Or R 41AlAr 3 -
Described silicon-containing group is selected from-SiR 42R 43R 44Or-T-SiR 45
Described germanic group is selected from-GeR 46R 47R 48Or-T-GeR 49
Describedly contain tin group and be selected from-SnR 50R 51R 52,-T-SnR 53Or-T-Sn (O) R 54,
Described Ar represents C 6-C 30Aryl, and
Described 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
Described R 5Be selected from lone-pair electron on the nitrogen, hydrogen, C 1-C 30The C of alkyl, replacement 1-C 30Alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, contain seleno group or phosphorus-containing groups; Work as R 5For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group or phosphorus-containing groups, R 5In N, O, S, P and Se can be used as coordination and carry out coordination with atom and described center IVB family atoms metal,
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 described preparation method of aforementioned either side, it is characterized in that, the mol ratio of described Grignard reagent and described halogenating agent is 1: 1-100, preferred 1: 1-10, more preferably 1: 1-5, and take the mol ratio of the described Grignard reagent of Mg element and described Nonmetallocene title complex as 1: 0.0001-1, preferred 1: 0.0002-0.4, more preferably 1: 0.0008-0.2.
8. according to the described preparation method of aforementioned either side, also be included in make described Nonmetallocene title complex and described magnesium base carrier contact before, with the step that helps the described magnesium base carrier of chemical processing agent pre-treatment that is selected from aikyiaiurnirsoxan beta, aluminum alkyls or its arbitrary combination.
9. according to the described preparation method of aforementioned either side, it is characterized in that, described aikyiaiurnirsoxan beta is selected from methylaluminoxane, ethylaluminoxane, in isobutyl aluminium alkoxide and the normal-butyl alumina alkane one or more, more preferably be selected from methylaluminoxane and the isobutyl aluminium alkoxide one or more, 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, in diethylmethyl aluminium and the dimethyl ethyl aluminium one or more, be preferably selected from trimethyl aluminium, triethyl aluminum, in tri-n-n-propyl aluminum and the triisobutyl aluminium one or more most preferably are selected from triethyl aluminum and the triisobutyl aluminium one or more.
10. according to the described preparation method of aforementioned either side, it is characterized in that, in the described magnesium compound of Mg element and the mol ratio that helps chemical processing agent take Al element described as 1: 0-1.0, preferred 1: 0-0.5, more preferably 1: 0.1-0.5.
11. a load type non-metallocene catalyst, it is by making according to the described preparation method of aforementioned either side.
12. alkene homopolymerization/copolymerization process, it is characterized in that, take according to aspect 11 described load type non-metallocene catalysts as Primary Catalysts, to be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more as promotor, make alkene homopolymerization or copolymerization.
13. an alkene homopolymerization/copolymerization process is characterized in that, may further comprise the steps:
Described preparation method makes load type non-metallocene catalyst according to aforementioned either side, and
Take described load type non-metallocene catalyst as Primary Catalysts, to be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more 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, and the charge capacity of Nonmetallocene title complex is adjustable, can give full play to the performance that its catalysis in olefine polymerization obtains polyolefin product.
Adopt method for preparing catalyst provided by the invention, because catalyzer is by preparing first the original position magnesium chloride support, then the load non-metallocene metal complexes prepares thereon, the charge capacity of Nonmetallocene title complex is adjustable, only has this single active centre of Nonmetallocene title complex in the catalyzer, and do not have the element of other reactive metal to exist, the polymkeric substance of its preparation is to be obtained by single active centre catalysis fully, the polymkeric substance complete reaction performance of Nonmetallocene title complex.
Method for preparing catalyst provided by the invention can effectively reduce the median size of polymer beads, and easier catalysis obtains the polymkeric substance that particle diameter is less and be evenly distributed; While Nonmetallocene title complex distributes more even in carrier, more is conducive to the performance of Nonmetallocene title complex performance.
Embodiment
The below is elaborated to the specific embodiment of the present invention, but it is pointed out that protection scope of the present invention is not subjected to the restriction of these embodiments, but is determined by claims of appendix.
In the context of the present invention, unless clearly definition is arranged in addition, perhaps this implication has exceeded those skilled in the art's understanding scope, and the hydrocarbon that 3 carbon atoms are above or hydrocarbon derivative group (such as propyl group, propoxy-, butyl, butane, butylene, butenyl, hexane etc.) all have implication identical with titled with prefix " just " time not titled with prefix " just " time.Such as, propyl group is generally understood as n-propyl, and butyl is generally understood as normal-butyl.
The present invention relates to a kind of preparation method of load type non-metallocene catalyst, may further comprise the steps: make the reaction of Grignard reagent and halogenating agent, obtain the step of magnesium base carrier; The Nonmetallocene title complex is contacted in the presence of solvent with described magnesium base carrier, obtain the step of mixed serum; With the described mixed serum of convection drying, obtain the step of described load type non-metallocene catalyst.
According to the present invention, by making the reaction of Grignard reagent and halogenating agent, obtain magnesium base carrier (being also referred to as newborn magnesium halide).
Below described Grignard reagent is carried out specific description.
According to the present invention, as described Grignard reagent, be selected from least a for the dialkyl magnesium of (R) (R ') Mg of alkyl magnesium halide that general formula is RMgX and general formula such as enumerating.
In aforementioned formula, radicals R is same to each other or different to each other with R ' (preferably identical), is selected from independently of one another C 1-C 30Alkyl is such as C 1-C 30Alkyl (straight chain, side chain or ring-type), C 2-C 30Thiazolinyl (straight chain, side chain or ring-type), C 6-C 30Aryl, C 7-C 30Alkaryl or C 7-C 30Aralkyl, wherein preferable methyl, ethyl, isobutyl-, iso-octyl, cyclohexyl, phenyl and benzyl, most preferable and ethyl.X is selected from halogen, preferred chlorine and bromine.
As described alkyl magnesium halide, preferable methyl magnesium chloride, ethylmagnesium chloride, propyl group magnesium chloride, normal-butyl chlorination magnesium, isobutyl-chlorination magnesium, n-hexyl magnesium chloride, isohexyl magnesium chloride, phenyl-magnesium-chloride, benzylmagnesium chloride, methyl-magnesium-bromide, ethylmagnesium bromide, propyl group magnesium bromide, normal-butyl bromination magnesium, selenium alkynide, n-hexyl magnesium bromide, isohexyl bromination magnesium, phenyl-magnesium-bromide and benzyl magnesium bromide, further preferable methyl magnesium chloride, ethylmagnesium chloride, phenyl-magnesium-chloride and benzylmagnesium chloride.
These alkyl magnesium halides can be used alone, and perhaps are used in combination multiple with ratio arbitrarily.
As described dialkyl magnesium, such as enumerating dimethyl magnesium (Mg (CH 3) 2), magnesium ethide (Mg (CH 3CH 2) 2), dipropyl magnesium (Mg (C 3H 7) 2), diisobutyl magnesium (Mg (i-C 4H 9) 2), di-n-butyl magnesium (Mg (C 4H 9) 2), diisoamyl magnesium (Mg (i-C 5H 11) 2), two n-pentyl magnesium (Mg (C 5H 11) 2), dihexyl magnesium (Mg (C 6H 13) 2), two isohexyl magnesium (Mg (i-C 6H 13) 2), methylethyl magnesium (Mg (CH 3CH 2) (CH 3)), diphenyl magnesium (Mg (C 6H 5) 2) and dibenzyl magnesium (Mg[CH 2(C 6H 5)] 2) etc., wherein preferred dimethyl magnesium, magnesium ethide, diisobutyl magnesium, dicyclohexyl magnesium, diphenyl magnesium and dibenzyl magnesium, most preferably dimethyl magnesium, magnesium ethide and diphenyl magnesium.
These dialkyl magnesium can be used alone, and perhaps are used in combination multiple with ratio arbitrarily.
According to the present invention, as described Grignard reagent, can only adopt described alkyl magnesium halide, also can only adopt described dialkyl magnesium, but also can adopt any mixture of described alkyl magnesium halide and described dialkyl magnesium.And there is no particular limitation to the ratio of each component in this mixture, can select arbitrarily as required.
Grignard reagent involved in the present invention can be made according to the method for well known to a person skilled in the art, also can directly use commercially available product, and there is no particular limitation.
According to the present invention, halogenating agent is selected from halo C 1-30At least a in the hydrocarbon, preferred chloro and/or bromo C 1-30At least a in the hydrocarbon.According to the present invention one preferred embodiment, described C 1-30Hydrocarbon is selected from C 1-30Alkane, C 2-30Alkene, C 6-30Aromatic hydrocarbons, C 7-30Aralkyl hydrocarbon and C 7-30Alkane aromatic hydrocarbons.More preferably, described halogenating agent is selected from monobromethane, monochloroethane, monobromethane, 1-chloro-butane, 1-chloro-hexane, chlorobenzene, bromobenzene and benzyl chloride.
These halogenating agents can be used alone, and perhaps are used in combination multiple with ratio arbitrarily.
According to the present invention, the reaction of described Grignard reagent and halogenating agent generally is to carry out in the presence of solvent (below be sometimes referred to as the dissolving Grignard reagent with solvent or the first solvent).To this moment employed solvent there is no particular limitation, as long as it can dissolve this Grignard reagent and this halogenating agent and with them chemical reaction not occur.
As described solvent, such as enumerating C 2-16Chain ether (preferred C 4-12Chain ether) and C 2-16Cyclic ethers (preferred C 4-12Cyclic ethers) one or more in, wherein preferred ether, n-butyl ether, tetrahydrofuran (THF) and Isosorbide-5-Nitrae-dioxane or its make up arbitrarily.
These solvents can be used alone, and perhaps are used in combination multiple with ratio arbitrarily.
According to the present invention, there is no particular limitation with the consumption of solvent to described dissolving Grignard reagent, can suitably select as required, as long as it can realize the aforementioned predetermined reaction of Grignard reagent and halogenating agent.Such as being set as so that the ratio of described Grignard reagent (solid) and described solvent reaches 1mol: 200～3000ml, preferred 1mol: 500～2000ml, more preferably 1mol: 500～1000ml gets final product, but obviously be not limited to this, those skilled in the art can carry out suitable adjustment fully as required.
According to the present invention, there is no particular limitation to the reactive mode of Grignard reagent and halogenating agent.Such as enumerating, (this moment, employed dissolving Grignard reagent can be identical with solvent separately with the solution of described halogenating agent to utilize first aforementioned dissolving Grignard reagent to prepare respectively the solution of described Grignard reagent with solvent, also can be different), then two kinds of solution measures are mixed or a kind of solution measures is wherein added (the preferred dropping) mode in the another kind of solution; Utilize first aforementioned dissolving Grignard reagent to prepare the solution of Grignard reagent (or halogenating agent) with solvent, then add the mode of (the preferred dropping) halogenating agent (or Grignard reagent) to wherein measuring; Perhaps, with described Grignard reagent and described halogenating agent simultaneously or successively metering add described dissolving Grignard reagent to the mode in the solvent etc., but be not limited to this.Wherein, preferably halogenating agent or halogenating agent solution are added drop-wise to mode in the grignard reagent solution.
According to the present invention, in order to make described magnesium base carrier, such as can at normal temperature to the temperature of the boiling point that is lower than employed any solvent, making the reaction of described Grignard reagent and halogenating agent carry out 0.5-48h, preferred 1-24h, optimum 2-8h (in case of necessity by stirring) gets final product.
After reaction finishes, the solid product that obtains is filtered, washs and drying, obtain thus described magnesium base carrier.For described filtration, washing and the dry not special restriction of method, can use as required conventional those that use in this area.
As required, described washing is generally carried out 1～6 time, preferred 3～4 times.Wherein, washer solvent preferably use with described dissolving Grignard reagent with solvent phase with solvent, but also can be different.Described drying can adopt ordinary method to carry out, such as heat drying method under rare gas element desiccating method, boulton process or the vacuum, and heat drying method, most preferably heat drying method under the vacuum under preferred rare gas element desiccating method or the vacuum.The temperature range of described drying is generally 30～160 ℃, preferred 60～130 ℃, is generally 2～24h time of drying, but is not limited to this.
According to the present invention, term " Nonmetallocene title complex " is a kind of single site olefin polymerization catalysts for metallocene catalyst, do not contain the cyclopentadienyl or derivatives thereofs such as luxuriant ring, fluorenes ring or indenes ring in the structure, and with promotor (such as hereinafter described those) combination the time, can demonstrate the organometallics (therefore described Nonmetallocene title complex is also sometimes referred to as the non-metallocene olefin polymerization title complex) of olefinic polymerization catalysis activity.This compound comprises the polydentate ligand (preferably tridentate ligand or more polydentate ligand) that central metal atom and at least one and described central metal atom are combined with coordinate bond, 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 the bracket).According to the chemical structural formula of described polydentate ligand, group A, D and E (coordination group) form coordinate bond with atom (such as heteroatomss such as N, O, S, Se and P) with described central metal atom M by the contained coordination of these groups.
According to the present invention, all parts (comprising described radicals X and described polydentate ligand) with the positively charged absolute value of absolute value and the described central metal atom M of negative charge sum identical.
At one more specifically in the embodiment, described Nonmetallocene title complex is selected from compound (A) and the compound (B) with following chemical structural formula.
Figure BSA00000683115000141
At one more specifically in the embodiment, described Nonmetallocene title complex be selected from compound (A-1) with following chemical structural formula to compound (A-4) and compound (B-1) to compound (B-4).
Figure BSA00000683115000142
Figure BSA00000683115000151
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, preferred IVB family atoms metal is 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, contain aluminium base group, phosphorus-containing groups, silicon-containing group, germanic group or contain tin group, a plurality of X can be identical, also can be different, and can also be each other in key or Cheng Huan;
A be selected from Sauerstoffatom, sulphur atom, selenium atom,
Figure BSA00000683115000152
-NR 23R 24,-N (O) R 25R 26,
Figure BSA00000683115000153
-PR 28R 29,-P (O) R 30OR 31, sulfuryl, sulfoxide group or-Se (O) R 39, N, O, S, Se and the P coordination atom of respectively doing for oneself wherein;
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,
Figure BSA00000683115000154
-N (O) R 25R 26,
Figure BSA00000683115000155
Or-P (O) R 32(OR 33), N, O, S, Se and the P coordination atom of respectively doing for oneself wherein;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group, phosphorus-containing groups or cyano group (CN), N, O, S, Se and the P coordination atom of respectively doing for oneself wherein;
F is selected from nitrogen-atoms, nitrogen-containing group, oxy radical, sulfur-containing group, contain 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, contain 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 enumerating-NR 23R 24,-N (O) R 25R 26,-PR 28R 29,-P (O) R 30R 31,-OR 34,-SR 35,-S (O) R 36,-SeR 38Or-Se (O) R 39, N, O, S, Se and the P coordination atom of respectively doing for oneself wherein;
→ 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 (preferred halo alkyl wherein, such as-CH 2Cl and-CH 2CH 2Cl) or the safing function group.Above-mentioned group can be the same or different to each other, 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, perhaps 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 (preferred halo alkyl wherein, such as-CH 2Cl and-CH 2CH 2Cl) or the phenyl ring that replaces of safing function group, and
R 5Be selected from lone-pair electron on the nitrogen, hydrogen, C 1-C 30The C of alkyl, replacement 1-C 30Alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, contain seleno group or phosphorus-containing groups.Work as R 5For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group or phosphorus-containing groups, R 5In N, O, S, P and Se can be used as coordination and carry out coordination with atom and described center IVB family atoms metal.
According to the present invention, in aforementioned all chemical structural formulas, as the case may be, any adjacent two or more groups are such as R 21With group Z, perhaps 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 optional to be 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
Figure BSA00000683115000161
-NR 23R 24,-T-NR 23R 24Or-N (O) R 25R 26Described phosphorus-containing groups is selected from
Figure BSA00000683115000162
-PR 28R 29,-P (O) R 30R 31Or-P (O) R 32(OR 33).Described oxy radical be selected from hydroxyl ,-OR 34With-T-OR 34Described sulfur-containing group is selected from-SR 35,-T-SR 35,-S (O) R 36Or-T-SO 2R 37The described seleno group that contains is selected from-SeR 38,-T-SeR 38,-Se (O) R 39Or-T-Se (O) R 39Described 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 (preferred C 1-C 6Alkyl is 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 contain 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 30(divalent group perhaps is called C to hydrocarbon two bases 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 refers to these substituting groups aforementioned coordination (is referred to aforementioned group A, D, E, F, Y and Z, perhaps also chooses wantonly and comprise radicals R with group 5) there is not 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 the impact that is subject to 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 (preferred C 1-C 6Alkyl is 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 a 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) coordination ability with described central metal atom M is lower than described A, D, E, F, Y and Z group, and does 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 contain aluminium base group and be selected from aluminum alkyls, AlPh 4 -, AlF 4 -, AlCl 4 -, AlBr 4 -, AlI 4 -Or R 41AlAr 3 -Described silicon-containing group is selected from-SiR 42R 43R 44Or-T-SiR 45Described germanic group is selected from-GeR 46R 47R 48Or-T-GeR 49Describedly contain tin group and be selected from-SnR 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, described 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 described R 5Be selected from lone-pair electron on the nitrogen, hydrogen, C 1-C 30The C of alkyl, replacement 1-C 30Alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, contain seleno group or phosphorus-containing groups; Work as R 5For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group or phosphorus-containing groups, R 5In N, O, S, P and Se can be used as coordination and carry out coordination with atom and described center IVB family atoms metal.
As described Nonmetallocene title complex, such as enumerating following compound:
Figure BSA00000683115000181
Figure BSA00000683115000191
Figure BSA00000683115000201
Described Nonmetallocene title complex is preferably selected from following compound:
Figure BSA00000683115000211
Described Nonmetallocene title complex further is preferably selected from following compound:
Described Nonmetallocene title complex more preferably is selected from following compound:
Figure BSA00000683115000221
These Nonmetallocene title complexs can be used alone, and perhaps are used in combination multiple with ratio arbitrarily.
According to the present invention, the described polydentate ligand in the 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 made 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 magnesium base carrier in the presence of solvent (hereinafter referred to as the second solvent), contact (contact reacts) with described Nonmetallocene title complex, can obtain described mixed serum.
When making described mixed serum, there is no particular limitation to the way of contact of described magnesium base carrier and described Nonmetallocene title complex (and described second solvent) and engagement sequence etc., such as enumerating described magnesium base carrier is mixed first with described Nonmetallocene title complex, and then to the scheme that wherein adds described the second solvent; Described Nonmetallocene title complex is dissolved in described the second solvent, makes thus the Nonmetallocene complex solution, and then make scheme that described magnesium base carrier mixes with described Nonmetallocene complex solution etc., wherein the preferred latter.
In addition, in order to make described mixed serum, such as can be at normal temperature to the temperature of the boiling point that is lower than employed any solvent, described magnesium base carrier and the described Nonmetallocene title complex contact reacts (in case of necessity by stirring) in the presence of described the second solvent was carried out 0.5～24 hour, preferred 1～8 hour, more preferably got final product in 2～6 hours.
At this moment, the mixed serum that obtains is a kind of system of pulpous state.Although unessential, in order to ensure the homogeneity of system, this mixed serum preferably carries out certain hour (2～48h, preferred 4～24h, most preferably 6～18h) airtight leaving standstill afterwards in preparation.
According to the present invention, when making described mixed serum, there is no particular limitation to described the second solvent (below be sometimes referred to as dissolving Nonmetallocene title complex solvent), needs only it and 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 1-10In alkane, ester and the ether one or more.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 be used alone, and perhaps are used in combination multiple with ratio arbitrarily.
When making described mixed serum or described Nonmetallocene complex solution, can use as required stirring (rotating speed of this stirring is generally 10～500 rev/mins).
According to the present invention, to the consumption of described the second solvent without any restriction, get final product with the amount that described Nonmetallocene title complex fully contacts so long as be enough to realize described magnesium base carrier.Such as, being easily, described Nonmetallocene title complex is generally 0.02～0.30 grams per milliliter with respect to the ratio of described the second solvent, preferred 0.05～0.15 grams per milliliter, but sometimes be not limited to this.
Then, by to described mixed serum convection drying, can obtain a kind of solid product of good fluidity, i.e. load type non-metallocene catalyst of the present invention.
At this moment, described convection drying can adopt ordinary method to carry out, such as heat drying under drying under dry under the inert gas atmosphere, the vacuum atmosphere or the vacuum atmosphere etc., and heat drying under the preferred vacuum atmosphere wherein.Carry out under the temperature (being generally 30～160 ℃, preferred 60～130 ℃) that the boiling point of any solvent that described drying generally contains in than described mixed serum is low 5～15 ℃, and be generally 2～24h time of drying, but sometimes be not limited to this.
Special embodiment according to the present invention, before the preparation method of load type non-metallocene catalyst of the present invention also is included in and makes described Nonmetallocene title complex and described magnesium base carrier contacts, with the step that helps the described magnesium base carrier of chemical processing agent pre-treatment (pre-treatment step) that is selected from aikyiaiurnirsoxan beta, aluminum alkyls or its arbitrary combination.
Below the described chemical processing agent that helps is carried out specific description.
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 the following general formula (I): (R) (R) Al-(Al (R)-O) n-O-Al (R) (R), and the ring-type aikyiaiurnirsoxan beta shown in the 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 in the 1-50 scope, the arbitrary integer in preferred 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 alone, and perhaps are used in combination multiple with ratio arbitrarily.
As described aluminum alkyls, such as enumerating the compound shown in the 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 be used alone, and perhaps 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 there is no particular limitation to the ratio of each component in this mixture, can select arbitrarily as required.
According to the present invention, the described chemical processing agent that helps generally is to use with the form of solution.When the described solution that helps chemical processing agent of preparation, to this moment employed solvent 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 be used alone, and perhaps 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 carrying out described pre-treatment with the described chemical processing agent that helps of predetermined amount.
Through described pre-treatment step, obtain through pretreated magnesium base carrier thus.Then, according to contacting with described Nonmetallocene title complex with aforementioned identical mode, just described magnesium base carrier is replaced with the pretreated magnesium base carrier of described process and get final product again.
Namely, by with aforementioned same contact reacts, the pretreated magnesium base carrier of described process is contacted in the presence of described the second solvent with described Nonmetallocene title complex similarly make described mixed serum, and further according to making load type non-metallocene catalyst of the present invention with same before mode.
As the method for carrying out described pre-treatment step, such as enumerating, at first prepare the described solution that helps chemical processing agent, then to intending being metered into (the preferred dropping) described chemical treatment agent solution (the described chemical processing agent that helps that wherein contains predetermined amount) that helps with described helping in the pretreated described magnesium base carrier of chemical processing agent, perhaps add described magnesium base carrier to the described chemical treatment agent solution amount of falling into a trap that helps, form thus reaction mixture.At this moment, temperature of reaction is generally-40～60 ℃, and preferred-30～30 ℃, the reaction times is generally 1～8h, preferred 2～6h, most preferably 3～4h (in case of necessity by stirring).Then, by filtration, washing and optionally drying, from this reaction mixture, isolate the pre-treatment product.
Perhaps, according to circumstances, also can be without this separation and be directly used in follow-up reactions steps with the form of mixed solution.At this moment, owing to contained a certain amount of solvent in the described mixed solution, so the solvent load that relates in can the described subsequent reactions step of corresponding minimizing.
According to the present invention, described filtration, washing and drying can adopt ordinary method to carry out, and wherein washer solvent can adopt and dissolve described used identical solvent when helping chemical processing agent.As required, this washing is generally carried out 1～8 time, and preferred 2～6 times, most preferably 2～4 times.Described drying can adopt ordinary method to carry out, such as heat drying method under rare gas element desiccating method, boulton process or the vacuum, and heat drying method, most preferably heat drying method under the vacuum under preferred rare gas element desiccating method or the vacuum.The temperature range of described drying is generally normal temperature to 140 ℃, is generally 2-20 hour time of drying, but is not limited to this.
According to the present invention, as the consumption of described halogenating agent, so that the mol ratio of described Grignard reagent and described halogenating agent reaches 1: 1-100, preferred 1: 1-10, more preferably 1: 1-5.
According to the present invention, consumption as described Nonmetallocene title complex, so that reach 1 in the mol ratio of the described Grignard reagent (solid) of Mg element and described Nonmetallocene title complex: 0.0001-1, preferred 1: 0.0002-0.4, more preferably 1: 0.0008-0.2.
According to the present invention, as the described consumption that helps chemical processing agent, so that reach 1 in the described Grignard reagent (solid) of Mg element and the described mol ratio of chemical processing agent that helps in the Al element: 0-1.0, preferred 1: 0-0.5, more preferably 1: 0.1-0.5.
Known to those skilled in the artly be that aforementioned all method steps all preferably carries out under the condition of anhydrous anaerobic basically.Here the said basically anhydrous anaerobic content that refers to water and oxygen in the system continues less than 100ppm.And load type non-metallocene catalyst of the present invention needs to save backup in the presence of the pressure-fired rare gas element (such as nitrogen, argon gas, helium etc.) in confined conditions in preparation afterwards usually.
In one embodiment, the invention still further relates to the load type non-metallocene catalyst (sometimes being also referred to as carry type non-metallocene calalyst for polymerization of olefine) of being made 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 with 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 following content that particularly points out, other contents of not explaining (such as polymerization with the addition manner of reactor, alkene consumption, catalyzer and alkene etc.), can directly be suitable for conventional known those in this area, not special restriction, the description thereof will be omitted at this.
According to homopolymerization/copolymerization process of the present invention, take load type non-metallocene catalyst of the present invention as Primary Catalysts, to be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more as promotor, make alkene homopolymerization or copolymerization.
Primary Catalysts and promotor can be to add first Primary Catalysts to the adding mode in the polymerization reaction system, and then the adding promotor, perhaps add first promotor, and then add Primary Catalysts, or both contact first after the mixing and add together, perhaps add simultaneously respectively.Primary Catalysts and promotor added respectively fashionablely both can in same reinforced pipeline, add successively, also can in the reinforced pipeline of multichannel, add successively, and both add simultaneously respectively and fashionablely should select the multichannel pipeline that feeds in raw material.For the continous way polyreaction, the reinforced pipeline of preferred multichannel adds simultaneously continuously, and for the intermittence type polymerization reaction, adds together in same reinforced pipeline after preferably both mix first, perhaps in same reinforced pipeline, add first promotor, and then add Primary Catalysts.
According to the present invention, there is no particular limitation to the reactive mode of described alkene homopolymerization/copolymerization process, 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 is 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, the perhaps 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 the 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 the following general formula (I-1): (R) (R) Al-(Al (R)-O) n-O-Al (R) (R), and the ring-type aikyiaiurnirsoxan beta shown in the following general formula (II-1) :-(Al (R)-O-) N+2-.
Figure BSA00000683115000271
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 in the 1-50 scope, the arbitrary integer in preferred 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 alone, and perhaps are used in combination multiple with ratio arbitrarily.
As described aluminum alkyls, such as enumerating the compound shown in the 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), 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-n-n-propyl aluminum and triisobutyl aluminium, further preferred triethyl aluminum and triisobutyl aluminium, and triethyl aluminum most preferably.
These aluminum alkylss can be used alone, and perhaps are used in combination multiple with ratio arbitrarily.
As described haloalkyl aluminium, such as enumerating the compound shown in the following general formula:
Al(R) nX 3-n
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, preferred 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), a 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), a 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 preferred chlorodiethyl aluminium, ethyl aluminum dichloride and a chlorine di-n-hexyl aluminium, and aluminium diethyl monochloride most preferably.
These haloalkyl aluminium can be used alone, and perhaps 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 be used alone, and also can be as required be used in combination multiple aforesaid promotor, not special restriction with ratio arbitrarily.
According to the present invention, the difference (such as slurry polymerization) according to the reactive mode of described alkene homopolymerization/copolymerization process needs to use the polymerization solvent sometimes.
As described polymerization solvent, can use this area conventional those that use when 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 alone with solvent, perhaps 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, preferred 0.1～4MPa, and more preferably 0.4～3MPa, but sometimes be not limited to this.According to the present invention, polymeric reaction temperature is generally-40 ℃～200 ℃, and preferred 10 ℃～100 ℃, more preferably 40 ℃～95 ℃, but sometimes be 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 carry out under the condition that does not have hydrogen to exist.In the situation that exist, the dividing potential drop of hydrogen can be 0.01%～99% of described polymerization pressure, and is preferred 0.01%～50%, but sometimes is not limited to this.
According to the present invention, when carrying out described alkene homopolymerization/copolymerization process, be generally 1～1000 in the described promotor of aluminium or boron and mol ratio in the described load type non-metallocene catalyst of described central metal atom: 1, preferred 10～500: 1, more preferably 15～300: 1, but sometimes be 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.
The content of IVB family metal (such as Ti) and Mg element adopts the ICP-AES method to measure in the load type non-metallocene catalyst, 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 the reactor is filtered and drying, then the quality of this polymerisate of weighing represents that divided by the ratio of the quality of used load type non-metallocene catalyst (unit is kg polymkeric substance/g catalyzer or kg polymkeric substance/gCat) for the polymerization activity of this catalyzer with this polymerisate quality.
Molecular weight Mw, the Mn of polymkeric substance and molecular weight distribution (Mw/Mn) adopt the GPC V2000 type gel chromatography analyser of U.S. WATERS company to measure, and are solvent with 1,2,4-trichlorobenzene, and the temperature during mensuration is 150 ℃.
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, the thermostatic bath medium is No. 300 silicone oil, dilution is perhydronaphthalene with solvent, measuring temperature is 135 ℃) 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.
The particle diameter of polymkeric substance adopts the LS230 type laser particle analyzer of U.S. Beckman Coulter company to measure, take hexane as dispersion agent.
Embodiment 1
Grignard reagent adopts butylmagnesium chloride (BuMgCl), and the dissolving Grignard reagent adopts tetrahydrofuran (THF) with solvent, and halogenating agent adopts n-propylcarbinyl chloride, and the Nonmetallocene title complex adopts structure to be
Figure BSA00000683115000301
Compound, the second solvent adopts methylene dichloride.
Halogenating agent with 0.1mol under the normal temperature dropwise is added drop-wise to grignard reagent solution, and time for adding is 30 minutes, drips off under the rear normal temperature to stir 2 hours.Filter, with hexane washing 2 times, each hexane consumption 60ml, vacuum-drying obtains the magnesium base carrier under the normal temperature.
Add the second solvent under the normal temperature in the magnesium base carrier, then add the Nonmetallocene title complex, stirred 2 hours under the normal temperature, vacuum-drying obtains load type non-metallocene catalyst under the normal temperature.
Wherein proportioning is, take the described Grignard reagent of Mg element and dissolving Grignard reagent with the proportioning of solvent as 1mol: 500mL, Grignard reagent and halogenating agent mol ratio are 1: 1; Grignard reagent and Nonmetallocene compound mol ratio are 1: 0.05, and the ratio of Nonmetallocene title complex and the second solvent is 0.05 grams per milliliter.
This load type non-metallocene catalyst is designated as CAT-1.
Embodiment 2
Substantially the same manner as Example 1, but following change is arranged:
The Nonmetallocene title complex adopts
Figure BSA00000683115000311
The dissolving Grignard reagent is changed into ether with solvent, and the second solvent is changed into toluene.
Wherein proportioning is, take the described Grignard reagent of Mg element and dissolving Grignard reagent with the proportioning of solvent as 1mol: 1000mL, Grignard reagent and halogenating agent mol ratio are 1: 2; Grignard reagent and Nonmetallocene title complex mol ratio are 1: 0.1, and the ratio of Nonmetallocene title complex and the second solvent is 0.15 grams per milliliter.
Load type non-metallocene catalyst is designated as CAT-2.
Embodiment 3
Substantially the same manner as Example 1, but following change is arranged:
Grignard reagent is changed into ethylmagnesium bromide (EtMgBr), and the dissolving Grignard reagent adopts n-butyl ether with solvent, and the Nonmetallocene title complex adopts
Figure BSA00000683115000321
Halogenating agent adopts monobromethane, and the second solvent adopts ethylbenzene.
Wherein proportioning is, take the described Grignard reagent of Mg element and dissolving Grignard reagent with the proportioning of solvent as 1mol: 667mL; Grignard reagent and halogenating agent mol ratio are 1: 1.5; Grignard reagent and Nonmetallocene title complex mol ratio are 1: 0.2, and the ratio of Nonmetallocene title complex and the second solvent is 0.08 grams per milliliter.
Load type non-metallocene catalyst is designated as CAT-3.
Embodiment 4
Substantially the same manner as Example 1, but following change is arranged:
Grignard reagent is changed into phenyl-magnesium-chloride (C 6H 5MgCl), the Nonmetallocene title complex adopts
Figure BSA00000683115000322
Halogenating agent adopts chlorobenzene, and the second solvent adopts isopropyl benzene.
Wherein proportioning is, take the described Grignard reagent of Mg element and dissolving Grignard reagent with the proportioning of solvent as 1mol: 2000mL; Grignard reagent and halogenating agent mol ratio are 1: 1.1; Grignard reagent and Nonmetallocene title complex mol ratio are 1: 0.04, and the ratio of Nonmetallocene title complex and the second solvent is 0.30 grams per milliliter.
Load type non-metallocene catalyst is designated as CAT-4.
Embodiment 5
Substantially the same manner as Example 1, but following change is arranged:
Grignard reagent is changed into methyl-magnesium-bromide (CH 3MgBr), the dissolving Grignard reagent adopts Isosorbide-5-Nitrae-dioxane with solvent, and the Nonmetallocene title complex adopts
Figure BSA00000683115000331
Halogenating agent adopts bromocyclohexane, and the second solvent adopts dimethylbenzene.
Wherein proportioning is, take the described Grignard reagent of Mg element and dissolving Grignard reagent with the proportioning of solvent as 1mol: 1250mL; Grignard reagent and halogenating agent mol ratio are 1: 1.5; Grignard reagent and Nonmetallocene title complex mol ratio are 1: 0.30, and the ratio of Nonmetallocene title complex and the second solvent is 0.10 grams per milliliter.
Load type non-metallocene catalyst is designated as CAT-5.
Embodiment 6
Substantially the same manner as Example 1, but following change is arranged:
Grignard reagent is changed into benzylmagnesium chloride (Mg (PhCH 2) Cl), the dissolving Grignard reagent adopts the ethyl n-propyl ether with solvent, and the Nonmetallocene title complex adopts
Figure BSA00000683115000332
Halogenating agent adopts Benzyl Chloride.
Wherein proportioning is, take the described Grignard reagent of Mg element and dissolving Grignard reagent with the proportioning of solvent as 1mol: 555mL; Grignard reagent and Nonmetallocene title complex mol ratio are 1: 0.10.
Load type non-metallocene catalyst is designated as CAT-6.
Embodiment 7
Substantially the same manner as Example 1, but following change is arranged:
Grignard reagent is changed into cyclohexyl chlorination magnesium (Mg (C 6H 11) Cl), the dissolving Grignard reagent adopts ether with solvent, and the Nonmetallocene title complex adopts
Figure BSA00000683115000333
Halogenating agent adopts chlorocyclohexane.
Load type non-metallocene catalyst is designated as CAT-7.
Embodiment 8
Substantially the same manner as Example 1, but following change is arranged:
Grignard reagent is changed into magnesium ethide (Mg (C 2H 5) 2), the dissolving Grignard reagent adopts ether with solvent, and the Nonmetallocene title complex adopts
Figure BSA00000683115000341
Halogenating agent adopts the chloro normal hexane.
Load type non-metallocene catalyst is designated as CAT-8.
Embodiment 9
Substantially the same manner as Example 1, but following change is arranged:
Grignard reagent is changed into dihexyl magnesium (Mg (C 6H 13) 2), the dissolving Grignard reagent adopts diethyl ether solution with solvent.
Load type non-metallocene catalyst is designated as CAT-9.
Embodiment 10
Substantially the same manner as Example 1, but following change is arranged:
Add the 60ml hexane to the magnesium base carrier that obtains, under agitation condition, help chemical processing agent triethyl aluminum (0.88mol/L with dropping in 30 minutes at normal temperatures, hexane solution), 60 ℃ of lower stirring reactions 4 hours, filter, hexane washing 2 times, each hexane consumption 60ml, vacuum-drying obtains pretreated magnesium base carrier under the normal temperature.
Replace described magnesium base carrier with this pretreated magnesium base carrier, prepare similarly to Example 1 load type non-metallocene catalyst.
Wherein proportioning is, in the described Grignard reagent of Mg element with take the described mol ratio of chemical processing agent that helps of Al element as 1: 0.3.
Load type non-metallocene catalyst is designated as CAT-10.
Embodiment 11
Substantially the same manner as Example 10, but following change is arranged:
Triethyl aluminum (0.88mol/L, hexane solution) is changed into methylaluminoxane (10wt%, toluene solution).
Wherein proportioning is, in the described Grignard reagent of Mg element with take the described mol ratio of chemical processing agent that helps of Al element as 1: 0.2.
Load type non-metallocene catalyst is designated as CAT-11.
The comparative example A
Substantially the same manner as Example 1, but following change is arranged:
Add the 60ml hexane in catalyzer CAT-1, drip titanium tetrachloride under the normal temperature under agitation condition, time for adding is 30 minutes, then 60 ℃ of lower stirring reactions filtered after 4 hours, hexane washing 2 times, each hexane consumption 60ml, vacuum-drying under the normal temperature obtains loaded catalyst.
The mol ratio of Grignard reagent and chemical processing agent is 1: 0.1.
Loaded catalyst is designated as CAT-A.
Comparative Examples B
Substantially the same manner as Example 1, but following change is arranged:
Grignard reagent and Nonmetallocene title complex mol ratio are changed into 1: 0.10;
Catalyzer is designated as CAT-B.
Comparative Examples C
Substantially the same manner as Example 1, but following change is arranged:
Grignard reagent and Nonmetallocene title complex mol ratio are changed into 1: 0.03;
Catalyzer is designated as CAT-C.
Comparative Examples D
Nonmetallocene title complex with embodiment 1 employing same structure.
Take by weighing the 0.1mol Magnesium Chloride Anhydrous, fully dissolving under the normal temperature is stirred after 2 hours behind the adding tetrahydrofuran solvent under the normal temperature, add the precipitation agent hexane under the normal temperature and make it precipitation, filter, with hexane washing 2 times, each hexane consumption 60ml, vacuum-drying obtains the magnesium compound carrier under the normal temperature.
The Nonmetallocene title complex is dissolved in methylene dichloride, add the magnesium compound carrier under the normal temperature and make the homogeneous system, stir after 2 hours under the normal temperature, vacuum-drying obtains load type non-metallocene catalyst under the normal temperature.
Wherein proportioning is, magnesium chloride and tetrahydrofuran (THF) proportioning are 0.1mol: 150mL; Magnesium chloride and Nonmetallocene title complex mol ratio are 1: 0.05; Precipitation agent and tetrahydrofuran (THF) volume proportion are 1: 1, and the ratio of Nonmetallocene title complex and methylene dichloride is 0.05 grams per milliliter.
Load type non-metallocene catalyst is designated as CAT-D.
Application Example
Homopolymerization, copolymerization and the polymerization of preparation ultrahigh molecular weight polyethylene(UHMWPE) that catalyzer CAT-1～CAT-11 of making in the embodiment of the invention and CAT-A～D are carried out respectively ethene under the following conditions in accordance with the following methods:
Homopolymerization is: 5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 liters of hexane solvents, polymerization stagnation pressure 0.8MPa, 85 ℃ of polymerization temperatures, hydrogen partial pressure 0.2MPa, 2 hours reaction times.At first 2.5 liters of hexanes are joined in the polymerization autoclave, open and stir, then add 50mg load type non-metallocene catalyst and catalyst mixture, add again hydrogen to 0.2MPa, continue at last to pass into ethene and make the polymerization stagnation pressure constant in 0.8MPa.Reaction with gas reactor emptying, is emitted the still interpolymer after finishing, dry rear weighing quality.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 ℃ of polymerization temperatures, hydrogen partial pressure 0.2MPa, 2 hours reaction times.At first 2.5 liters of hexanes are joined in the polymerization autoclave, open and stir, then add 50mg load type non-metallocene catalyst and catalyst mixture, disposable adding hexene-1 comonomer 50g, add again hydrogen to 0.2MPa, continue at last to pass into ethene and make the polymerization stagnation pressure constant in 0.8MPa.Reaction with gas reactor emptying, is emitted the still interpolymer after finishing, dry rear weighing quality.The particular case of this polyreaction and polymerization evaluation result are as shown in table 1.
The preparation 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 ℃ of polymerization temperatures, 6 hours reaction times.At first 2.5 liters of hexanes are joined in the polymerization autoclave, open and stir, then add 50mg load type non-metallocene catalyst and catalyst mixture, promotor and reactive metal mol ratio are 100, continue at last to pass into ethene and make the polymerization stagnation pressure constant in 0.5MPa.Reaction with gas reactor emptying, is emitted the still interpolymer after finishing, dry rear weighing quality.The particular case of this polyreaction and polymerization evaluation result are as shown in table 2.
Figure BSA00000683115000381
Test-results data by sequence number in the table 13 and 4 increase the consumption of promotor as can be known, namely improve promotor and catalyst activity metal molar than the time, impact active on polymerization catalyst and polymer stacks density is not remarkable.It can be said that brightly, adopt the load type non-metallocene catalyst of method provided by the invention preparation only to need fewer promotor consumption just can obtain high olefin polymerizating activity; And the polymkeric substance such as resulting polyethylene has good polymer morphology and high polymer bulk density thus.
In the contrast table 1 sequence number 1 and 3 test-results data as can be known, after the copolymerization, catalyst activity has greatly to be increased, thus explanation adopts the load type non-metallocene catalyst of method preparation provided by the invention to have comparatively significant comonomer effect.
Test-results data by sequence number 1 in the contrast table 1 and Comparative Examples sequence number 16～17 reduce or increase the add-on of Nonmetallocene title complex as can be known in the catalyzer, its activity increases thereupon or reduces, and the molecular weight distribution of polymkeric substance changes hardly.This is because the catalyzer of the present invention's preparation is the catalyzer of single center class, only has a kind of active centre in the catalyst system, and how many catalytic activitys of catalyzer changes with the active centre, but the height of catalytic activity can't change the performance of polymkeric substance.The experimental data of sequence number 1 and Comparative Examples sequence number 15 increases chemical processing agent as can be known in the contrast table 1 in the catalyzer, and its activity increases thereupon, and the molecular weight distribution of polymkeric substance also broadens thereupon.Thereby single-site catalysts can prepare the polymkeric substance of narrow molecular weight distribution.
Test-results data by sequence number 1 in the contrast table 1 and Comparative Examples sequence number 18 as can be known, adopt Grignard reagent and the load type non-metallocene catalyst that the halogenating agent reaction obtains than the load type non-metallocene catalyst that obtains without Grignard reagent higher polymerization activity to be arranged, the polymkeric substance that catalyzed polymerization obtains has narrower molecular weight distribution, higher bulk density, less particle diameter, thereby illustrate and adopt the carrier (magnesium chloride support) of Grignard reagent preparation can make the Nonmetallocene title complex more be evenly distributed in carrier inside, thereby can better bring into play the performance of Nonmetallocene title complex itself.And the carrier that is obtained by the reaction of Grignard reagent and halogenating agent has better crystal habit, and carrier granule is more even and particle diameter is less, polymkeric substance that can easier preparation small particle size, thus reduce cost in the production process.
By as seen 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 is as seen, adopts methylaluminoxane can increase the viscosity-average molecular weight of polymkeric substance as promotor.
By sequence number in the table 11 and 13,14, sequence number 1 and 3 in the table 2,4 test-results data are as can be known, catalyzer is in preparation process, the magnesium base carrier is first through helping chemical processing agent to process, and then the loaded catalyst that obtains with Nonmetallocene title complex contact reacts, and without helping chemical processing agent to process resulting loaded catalyst, have higher polymerization activity, polymer stacks density, viscosity-average molecular weight, and slightly narrow molecular weight distribution.
Although abovely in conjunction with the embodiments the specific embodiment of the present invention is had been described in detail, it is pointed out that protection scope of the present invention is not subjected to the restriction of these embodiments, but determined by claims of appendix.Those skilled in the art can carry out suitable change to these embodiments in the scope that does not break away from technological thought of the present invention and purport, and these embodiments after changing obviously are also included within protection scope of the present invention.
At this, the contriver wishes to carry out following explanation with regard to the difference of Ziegler-Natta catalyst (electron donor that especially wherein relates to), metallocene catalyst and non-metallocene catalyst.
Known in the art is that Ziegler-Natta catalyst, metallocene catalyst and non-metallocene catalyst belong to different catalyst systems.At first, Ziegler-Natta catalyst belongs to the multicenter catalyzer, and non-metallocene catalyst is the same with metallocene catalyst, belongs to single-site catalysts.
Textbook (" Catalysts for Olefin Polymerization and polyolefine ", Xiao Shijing, the remaining tax given birth to work, press of Beijing University of Technology, in December, 2002, this textbook is that China national science and technology scholarly work publishing fund is subsidized " 15 " state key books) at its 7th page metallocene catalyst is defined, namely " metallocene catalyst normally by transition metal (mainly adopt IVB family element ti; Zr; Hf) and at least 1 cyclopentadiene or cyclopentadiene derivant be the complex compound that part forms ", and put down in writing " just because of metallocene catalyst system the characteristic of property different from the Ziegler-Natta catalyst system having been arranged; since the eighties in 20th century, the research of metallocene catalyst and application have obtained huge progress " at its 8th page.Also non-metallocene catalyst is defined at the 8th page, i.e. " so-called non-metallocene catalyst refers to not contain the compound of the non-cyclopentadienyl ligand transition metal of cyclopentadiene group; existing in the promotor methylaluminoxane can catalysis in olefine polymerization ", perhaps " the Nonmetallocene compound mainly is to form the positively charged ion part similar to cyclopentadienyl with the C atom on the heteroatoms substituted-cyclopentadienyl such as B, P, N or other aromatic rings, with IVB family metal (Ti, Zr, Hf) coordination formation Nonmetallocene compound ".
US Patent No. 5244855 discloses a kind of manufacture method of loaded catalyst, this manufacture method comprises that the diether compounds that uses inert polymer carrier, magnesium halide, titanium tetrachloride and following structure is (such as 2-isopentyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, be DMP, use as electron donor) as raw material.
Aforesaid textbook (" Catalysts for Olefin Polymerization and polyolefine ", work is given birth in Xiao Shijing, remaining tax, press of Beijing University of Technology, in December, 2002) be logged into " entering the nineties in 20th century; occurred with 1; 3-two ethers are the synthetic Ziegler-Natta carrier model effective catalyst of new generation of internal electron donor " at its 6th page, " because two ethers electron donor and MgCl 2The carrier coordination ability is very strong, in the catalyzer building-up process, and can be not further and TiCl 4Reaction ... ".This textbook is logged into " MgCl at its 21st page 2Carrier model titanium (Mg-Ti) catalyzer is except carrier (MgCl 2) and active ingredient (Ti compound) outside, also contain internal electron donor compound (Di) ".This textbook is logged into " in the evolution at Ziegler-Natta catalyst, the application of electron donor plays very important effect ", " MgCl at its 72nd page 2After the carried catalyst appearance, the effect of electron donor seems even more important, now become the important component that the Ziegler-Natta catalyst system cannot lack " and " be used as in recent years, the catalyzer MgCl of internal electron donor preparation with 1.3-diether compounds (DE) 2/ TiCl 4/ DE, in the situation that need not external electron donor, " this textbook is in its 100th page of structure that has provided a kind of diether compounds that is used as electron donor, and is roughly the same with the diether compounds that US Patent No. 5244855 is related.This fact shows, the loaded catalyst of US Patent No. 5244855 final manufacturings is Ziegler-Natta carrier model effective catalysts.
Aforesaid textbook also is logged into " because two ethers electron donor and MgCl at its 6th page 2The carrier coordination ability is very strong, in the catalyzer building-up process, and can be not further and TiCl 4Reaction ... ".Therefore, DMP or US Patent No. 5244855 related diether compounds do not react with titanium tetrachloride, so not corresponding to the alleged Nonmetallocene part in this area.

Claims (9)

1. the preparation method of a load type non-metallocene catalyst may further comprise the steps:
Make the reaction of Grignard reagent and halogenating agent, obtain the step of magnesium base carrier;
The Nonmetallocene title complex is contacted in the presence of solvent with described magnesium base carrier, obtain the step of mixed serum; With
The described mixed serum of convection drying obtains the step of described load type non-metallocene catalyst,
Wherein said preparation method is optional also be included in make described Nonmetallocene title complex and described magnesium base carrier contact before, usefulness is selected from the step that helps the described magnesium base carrier of chemical processing agent pre-treatment of aikyiaiurnirsoxan beta, aluminum alkyls or its arbitrary combination.
2. according to preparation method claimed in claim 1, it is characterized in that, described halogenating agent is selected from halo C 1-30In the hydrocarbon one or more are preferably selected from chloro C 1-30Hydrocarbon and bromo C 1-30In the hydrocarbon one or more, wherein said C 1-30Hydrocarbon is C 1-30Alkane, C 2-30Alkene, C 6-30Aromatic hydrocarbons, C 7-30Aralkyl hydrocarbon or C 7-30Alkane aromatic hydrocarbons, described halogenating agent are preferably selected from one or more in monobromethane, monochloroethane, monobromethane, 1-chloro-butane, 1-chloro-hexane, chlorobenzene, bromobenzene and the benzyl chloride.
3. according to preparation method claimed in claim 1, it is characterized in that, described Grignard reagent is selected from alkyl magnesium halide that general formula is RMgX and general formula and is in the dialkyl magnesium of (R) (R ') Mg one or more, and wherein radicals R and R ' are same to each other or different to each other, and are C independently of one another 1-C 30Alkyl, preferred C 1-C 30Alkyl, C 2-C 30Thiazolinyl, C 6-C 30Aryl, C 7-C 30Alkaryl or C 7-C 30Aralkyl, further preferable methyl, ethyl, isobutyl-, iso-octyl, cyclohexyl, phenyl or benzyl, most preferable or ethyl, X is halogen, preferred chlorine or bromine, described Grignard reagent is preferably selected from one or more in methylmagnesium-chloride, ethylmagnesium chloride, phenyl-magnesium-chloride, benzylmagnesium chloride, dimethyl magnesium, magnesium ethide and the diphenyl magnesium.
4. according to preparation method claimed in claim 1, it is characterized in that, described solvent is selected from C 6-12Aromatic hydrocarbon, halo C 6-12Aromatic hydrocarbon, halo C 1-10In alkane, ester and the ether one or more, be preferably selected from toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromo toluene, bromo ethylbenzene, methylene dichloride, ethylene dichloride, ethyl acetate and the tetrahydrofuran (THF) one or more, more preferably C 6-12In aromatic hydrocarbon, methylene dichloride and the tetrahydrofuran (THF) one or more.
5. 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:
Be preferably selected from compound (A) with following chemical structural formula and in the compound (B) one or more:
Figure FSA00000683114900022
More preferably be selected to compound (A-4) and compound (B-1) to compound (B-4) one or more of compound (A-1) with following chemical structural formula:
Figure FSA00000683114900023
Figure FSA00000683114900031
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, preferred 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, contain aluminium base group, phosphorus-containing groups, silicon-containing group, germanic group or contain tin group, a plurality of X can be identical, also can be different, and can also be each other in key or Cheng Huan;
A be selected from Sauerstoffatom, sulphur atom, selenium atom,
Figure FSA00000683114900041
-NR 23R 24,-N (O) R 25R 26,
Figure FSA00000683114900042
-PR 28R 29,-P (O) R 30OR 31, sulfuryl, sulfoxide group or-Se (O) R 39, N, O, S, Se and the P coordination atom of respectively doing for oneself wherein;
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,
Figure FSA00000683114900043
-N (O) R 25R 26,
Figure FSA00000683114900044
Or-P (O) R 32(OR 33), N, O, S, Se and the P coordination atom of respectively doing for oneself wherein;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains 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, contain 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, contain 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, 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 the nitrogen, hydrogen, C 1-C 30The C of alkyl, replacement 1-C 30Alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, contain seleno group or phosphorus-containing groups; Work as R 5For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group or phosphorus-containing groups, R 5In N, O, S, P and Se can be used as coordination and carry out coordination with atom and described center IVB family atoms metal,
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 further is preferably selected from one or more in the compound with following chemical structural formula:
Figure FSA00000683114900051
Most preferably be selected from the compound with following chemical structural formula one or more:
Figure FSA00000683114900052
6. according to preparation method claimed in claim 5, it is characterized in that,
Described halogen is selected from F, Cl, Br or I;
Described nitrogen-containing group is selected from
Figure FSA00000683114900053
-NR 23R 24,-T-NR 23R 24Or-N (O) R 25R 26
Described phosphorus-containing groups is selected from -PR 28R 29,-P (O) R 30R 31Or-P (O) R 32(OR 33);
Described oxy radical be selected from hydroxyl ,-OR 34With-T-OR 34
Described sulfur-containing group is selected from-SR 35,-T-SR 35,-S (O) R 36Or-T-SO 2R 37
The described seleno group that contains is selected from-SeR 38,-T-SeR 38,-Se (O) R 39Or-T-Se (O) R 39
Described group T is selected from C 1-C 30The C of alkyl, replacement 1-C 30Alkyl or 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 contain 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 contain aluminium base group and be selected from aluminum alkyls, AlPh 4 -, AlF 4 -, AlCl 4 -, AlBr 4 -, AlI 4 -Or R 41AlAr 3 -
Described silicon-containing group is selected from-SiR 42R 43R 44Or-T-SiR 45
Described germanic group is selected from-GeR 46R 47R 48Or-T-GeR 49
Describedly contain tin group and be selected from-SnR 50R 51R 52,-T-SnR 53Or-T-Sn (O) R 54,
Described Ar represents C 6-C 30Aryl, and
Described 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
Described R 5Be selected from lone-pair electron on the nitrogen, hydrogen, C 1-C 30The C of alkyl, replacement 1-C 30Alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, contain seleno group or phosphorus-containing groups; Work as R 5For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group or phosphorus-containing groups, R 5In N, O, S, P and Se can be used as coordination and carry out coordination with atom and described center IVB family atoms metal,
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 claim 5.
7. according to preparation method claimed in claim 1, it is characterized in that, the mol ratio of described Grignard reagent and described halogenating agent is 1: 1-100, preferred 1: 1-10, more preferably 1: 1-5, in the described Grignard reagent of Mg element and the mol ratio that helps chemical processing agent take Al element described as 1: 0-1.0, preferred 1: 0-0.5, more preferably 1: 0.1-0.5, and take the mol ratio of the described Grignard reagent of Mg element and described Nonmetallocene title complex as 1: 0.0001-1, preferred 1: 0.0002-0.4, more preferably 1: 0.0008-0.2.
8. load type non-metallocene catalyst, it is by making according to each described preparation method of claim 1-7.
9. alkene homopolymerization/copolymerization process, it is characterized in that, take according to load type non-metallocene catalyst claimed in claim 8 as Primary Catalysts, to be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more as promotor, make alkene homopolymerization or copolymerization.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06192329A (en) * 1992-11-02 1994-07-12 Ube Ind Ltd Carrier for alpha-olefin polymerization catalyst and production
CN102039186A (en) * 2009-10-26 2011-05-04 中国石油化工股份有限公司 Load type non-metallocene catalyst, preparation method and application thereof
CN102039187A (en) * 2009-10-26 2011-05-04 中国石油化工股份有限公司 Load type non-metallocene catalyst as well as preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06192329A (en) * 1992-11-02 1994-07-12 Ube Ind Ltd Carrier for alpha-olefin polymerization catalyst and production
CN102039186A (en) * 2009-10-26 2011-05-04 中国石油化工股份有限公司 Load type non-metallocene catalyst, preparation method and application thereof
CN102039187A (en) * 2009-10-26 2011-05-04 中国石油化工股份有限公司 Load type non-metallocene catalyst as well as preparation method and application thereof

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