CN101376679B - Supported vanadium-based non-ocene polyolefin catalyst, preparation method and application - Google Patents
Supported vanadium-based non-ocene polyolefin catalyst, preparation method and application Download PDFInfo
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Abstract
一种负载型钒系非茂聚烯烃催化剂，包括卤化镁载体和负载在该载体上的通式为LVX2的钒系非茂金属配合物，其中L为式(I)的二胺西佛碱配体去掉OH中H质子后形成的基团，X为卤素，催化剂中镁含量为12～20质量％，钒含量为2～5质量％，所述式(I)中，R′为苯环上的单取代或多取代基，选自氢、C1～C6的烷基、C1～C6的烷氧基或硝基，R为C1～C12的烷基、C4～C8的环烷基或C6～C9的芳基去掉一个氢离子形成的桥连基团。该催化剂具有较高的聚合活性和共聚单体插入率。A supported vanadium-based non-metallocene polyolefin catalyst, comprising a magnesium halide carrier and a vanadium-based non-metallocene complex of the general formula LVX 2 loaded on the carrier, wherein L is a diamine Schiff base of formula (I) The group formed after the ligand removes the H proton in OH, X is a halogen, the content of magnesium in the catalyst is 12-20% by mass, and the content of vanadium is 2-5% by mass,
In the formula (I), R' is a single or multiple substituent on the benzene ring, selected from hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or nitro, and R is A bridging group formed by removing a hydrogen ion from a C 1 -C 12 alkyl group, a C 4 -C 8 cycloalkyl group or a C 6 -C 9 aryl group. The catalyst has high polymerization activity and comonomer insertion rate.
Description
Technical field
The present invention is a kind of supported type vanadium non-metallocene catalyst and preparation method and application, and specifically, the diimine that is a kind of loading type is the vanadium oxide non-metallocene Catalysts and its preparation method of part and the application in olefinic polyreaction.
Background technology
Continuing typical is the transistion metal compound of part with cyclopentadiene and derivative thereof, be that metallocene catalyst successfully is used for after the polyolefin industry production, contain heteroatomic transistion metal compounds such as aerobic, nitrogen in a kind of part, promptly Nonmetallocene polyolefine catalyst has obtained developing rapidly.
In these non cyclopentadienyl catalysts, to being that the research of catalyzer of title complex central atom is more with IVB family and VIII group 4 transition metal, the research of catalyzer that with the VB group 4 transition metal is the center is then less relatively, and the catalytic activity of its vinyl polymerization is lower mostly.
(Chem.Commun., 1998,1673～1674) such as Michael C.W.Chan have reported tertbutylimido half luxuriant vanadium complexes [CpV (N-
tBu) Cl
2] with the amino cinnamic copolymer reaction of vinylbenzene-4-after the loading type imino-vanadium complexes that forms.When this catalyzer was promotor with the aluminium diethyl monochloride, its vinyl polymerization speed was 10～50 times of supported catalyst not, was polyreaction 1 hour under 34,50 ℃, 1.0MPa condition in the Al/V mol ratio, and catalytic activity reaches 7.72 * 10
4GPE (molV)
-1Hr
-1, the gained polyethylene has high molecular (M
w=1.9 * 10
6), molecular weight distribution (Mw/Mn) is 4.9, and branch is few, and branch is less than 1 in 5000 carbon.
Disclosed load typed varadium catalyst mostly is vanadium acetylacetonate (III) that is used for second third copolymerization or the VOCl that is used for olefinic polymerization in the patent
3, VCl
4, VCl
3And with the complex compound of tetrahydrofuran (THF).A kind of second third catalyst for copolymerization is disclosed as CN1079802C, vanadium acetylacetonate loaded on make supported catalyst on the silica gel, this supported catalyst is handled under ethene or ethene and alpha-olefin mixture atmosphere with aluminium diethyl monochloride, aluminium/vanadium mol ratio is controlled at 1.5～3.0: 1, obtain carrying the catalyzer that the vanadium amount is about 0.01 mmole vanadium/gram carrier, with the aluminium diethyl monochloride is promotor, chloride organism (as ethyl trichloroacetate) is an activator, be used for second third copolymerization, can obtain second third elastomerics that degree of crystallinity is low, form is good.
US4579833 discloses a kind of Preparation of catalysts method that is used for vinyl polymerization and copolymerization of load vanadium compound.This catalyzer is supported V Cl on magnesium chloride
4Or VOCl
3Make.Described magnesium chloride support is made as butyl octyl magnesium and tert-butyl chloride reaction, and introduced the electron donor isoamyl ether in reaction process by dialkyl magnesium.Vanadium compound valence state after the load is lower than original tetravalence or pentavalent, promptly exists with the valence state that is reduced.This catalyzer is at aluminum alkyls, and under the acting in conjunction as the tri-n-octylaluminium promotor, but catalyzed ethylene polymerization obtains the uniform polyethylene product of size distribution.
CN1887919A discloses a kind of original position synthetic supported type vanadium non-metallocene catalyst; with acyl-naphthaline amphyl or beta-diketo derivative is part; this catalyzer adopts the preparation of original position synthetic method; earlier acyl-naphthaline amphyl or beta-diketo derivative are dissolved in organic solvent; drip in the alkane solution of dialkyl magnesium at-30～0 ℃; form the complex solution of magnesium, in this solution, splash into VCl at low temperatures again
4Organic solution, make when generating vanadium complex and also generate the carrier magnesium chloride.This catalyzer is equipped with the aluminium diethyl monochloride promotor and is used for ethylene polymerization, has active preferably.
Summary of the invention
The purpose of this invention is to provide a kind of supported type vanadium non-metallocene catalyst and preparation method, this catalyzer has high polymerization activity, the weight of otefi pi polymer height of gained, and comonomer insertion rate is higher during copolymerization.
Another object of the present invention provides the application of above-mentioned catalyzer in olefinic polymerization.
The non-luxuriant polyolefin catalyst of loading type provided by the invention comprises that magnesium halide carrier and the general formula that loads on this carrier are LVX
2The vanadium oxide non-metallocene title complex, L is that the diamines Schiff base ligand of formula (I) removes the group that forms behind the H proton among the OH in the general formula, X is a halogen, Mg content is 12～20 quality % in the catalyzer, content of vanadium is 2～5 quality %,
In the described formula (I), R ' is single the replacement or multi-substituent on the phenyl ring, is selected from hydrogen, C
1～C
6Alkyl, C
1～C
6Alkoxyl group or nitro, R is C
1～C
12Alkyl, C
4～C
8Cycloalkyl or C
6～C
9Aryl remove the bridged group that hydrogen ion forms.
Loaded catalyst provided by the invention is that the vanadium of part is that title complex is an active ingredient with the diimine, adopt in-situ synthesis to prepare loaded catalyst, the preparation method is easy, cost is low, this catalyzer is used for ethylene polymerization and has high polymerization activity, and the gained polyethylene has wider molecular weight distribution.
Embodiment
It is the part of vanadium complex that catalyzer of the present invention adopts diimine, and is carrier with the magnesium halide in active of nascent state, and employing original position synthetic method makes diimine ligand compound and the four halogenation vanadium generation title complex that reacts on carrier, make loaded catalyst.
Formula of the present invention (I) is the diimine ligand compound, and its H ion formation general formula that loses among the two-OH is LVX
2The part of vanadium oxide non-metallocene.In the formula (I), R ' is the substituting group on the phenyl ring, and replacing number is 1～4, the preferred hydrogen of R ', C
1～C
4Alkyl, C
1～C
3Alkoxyl group or nitro, more preferably hydrogen, methyl, ethyl, propyl group, sec.-propyl or nitro.
R is the bridged group of two imido grpups in the linking ligand, preferred C
1～C
4Alkyl, C
5～C
6Cycloalkyl, C
6～C
8Aryl remove the bridged group that hydrogen ion forms, more preferably ethyl, cyclohexyl or phenyl remove the bridged group that a hydrogen ion forms.
General formula LVX
2In the preferred chlorine of X.
The compound that the present invention preferably contains part shown in the formula (I) has: (salicylidene quadrol)-vanadous chloride, (salicylidene 1, the 2-diaminopropanes)-vanadous chloride, (salicylidene 1, the 2-diaminobutane)-vanadous chloride, (salicylidene 1,2-diamino-cyclohexane)-vanadous chloride, (salicylidene O-Phenylene Diamine)-vanadous chloride.
The preferred nascent state magnesium halide of carrier magnesium halide in the catalyzer of the present invention, the nascent state magnesium halide can be made by the sharp refined reagent react of halogenated alkane dative.Preferred magnesium halide is a magnesium chloride.
Preferred 2～4 quality % of content of vanadium in the described catalyzer, preferred 12～18 quality % of Mg content.
Preparation of catalysts method provided by the invention comprises the steps:
(1) the diamines Schiff base ligand of formula (I) be dissolved in form solution in the organic solvent, solution is added in the nascent state magnesium halide, be warming up to the complex solution that 60～120 ℃ of stirring reactions form magnesium,
(2) with VX
4Be dissolved in organic solvent and make solution, in-10～0 ℃ of complex solution that splashes into above-mentioned magnesium, 0～60 ℃ of fully reaction, filter, after the washing with the solids drying, described VX
4Middle X is a halogen.
In the aforesaid method, (1) step expression formula of described nascent state magnesium halide is (RMgX)
p(MgX
2), wherein p is 0.02～0.75, R is selected from C
3～C
12Alkyl, X is a halogen, preferred chlorine.
The preparation method of described nascent state magnesium halide is: in varsol, make the reaction of magnesium powder and halogenated alkane, the mol ratio of described halogenated alkane and magnesium is 1～10: 1, preferred 1.5～6.0: 1.The preferred C of described halogenated alkane
3～C
6Chloroparaffin, as chloro-propane, n-propylcarbinyl chloride, chloro-iso-butane, tert-butyl chloride, chloro iso-pentane or chloro-n-pentane.The preferred C of varsol
5～C
7Alkane or C
6～C
8Aromatic hydrocarbons, as Skellysolve A, iso-pentane, pentamethylene, normal hexane, pentamethylene, normal heptane, benzene or toluene.Add a small amount of iodine and stir together for reaction being accelerated, being preferably in varsol and the magnesium powder, and then add halogenated alkane and react.The mode that the adding mode of halogenated alkane can be taked to drip also can adopt the mode that in batches adds, and temperature of reaction is controlled at 20 ℃～100 ℃, preferred 40 ℃～85 ℃.Reaction times is 0.5～8.0 hour, preferred 1～6 hour.
For further activating the nascent state magnesium halide, improve the activity of loaded catalyst, preferably to nascent state magnesium halide C
1～C
10Fatty alcohol handle, the mol ratio of described alcohol and nascent state magnesium halide is 0.1～1.0: 1.The adding of fatty alcohol can be once to add or drip, and the temperature that alcohol is handled is 10 ℃～100 ℃, preferred 20 ℃～80 ℃, and the treatment time is 0.5～10 hour, preferred 1～5 hour.Described fatty alcohol preferred alcohol, 1-propyl alcohol, 1-butanols, 2-methyl amyl alcohol or isooctyl alcohol.
In the inventive method, preferred 80～110 ℃ of the temperature of reaction of described diamines Schiff base ligand of (1) step and nascent state magnesium halide; Reaction times is 1～6 hour, preferred 2～4 hours.
(2) VX of step adding
4Go on foot preferred 1: 1 of the mol ratio of the structure diamines Schiff base ligand of used formula (I) with (1).Add VX
4After preferred 20 ℃～40 ℃ of temperature of reaction.
The present invention prepares the organic solvent described in the catalyzer method and is selected from C
6～C
10Aromatic hydrocarbons or C
1～C
4Halogenated alkane, preferred toluene.
The synthetic method of the described Schiff base ligand of the inventive method is: in the presence of organic solvent, make the reaction of salicylaldehyde derivatives and diamine, salicylaldehyde derivatives and diamine mol ratio are 1.5～3.5: 1, and temperature of reaction is 40～120 ℃, and preferably adding organic acid during reaction is catalyzer.Make the crystallization of reaction after product, promptly get the Schiff base ligand compound.Described organic solvent can be C
1～C
10Fatty alcohol, as ethanol, propyl alcohol or butanols, also can be C
5～C
10Aliphatic hydrocarbon, benzene, toluene or dimethylbenzene, preferred toluene.Described organic acid is the carboxylic acid that contains 1～10 carbon atom, preferable formic acid or acetate.
Olefine polymerizing process provided by the invention, comprising that with catalyzer of the present invention be Primary Catalysts, is promotor with aluminum alkyls or haloalkyl aluminium, makes olefinic polymerization under polymeric reaction condition, the Al/V mol ratio is 10～1000: 1 during polyreaction, preferred 20～200: 1.
The preferred aluminium diethyl monochloride of described promotor, triethyl aluminum or triisobutyl aluminium.
The preferred C of described alkene
2～C
10Alpha-olefin, more preferably ethene.Polymerization can be a kind of homopolymerization of alpha-olefin, also can be the copolymerization of a kind of alpha-olefin and other alpha-olefin, as the copolymerization of ethene and propylene, butylene or hexene.Polymerization temperature is 0～80 ℃, and pressure is 0.1～3.0MPa.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
Preparation salicylidene quadrol part.
The 2.4mL salicylic aldehyde is mixed the formation light yellow transparent solution with the 11mL dehydrated alcohol, to wherein adding the faint yellow quadrol of 0.6mL, the mol ratio of salicylic aldehyde and quadrol is 2.5: 1.80 ℃ of stirrings that reflux form the orange clear solution.Add several formic acid, produce a large amount of yellow mercury oxides.Reflux and stirred 4 hours, be cooled to 20 ℃, get yellow solid matter.With the 12mL dehydrated alcohol reaction product is transferred to sand core funnel and filters, use 12mL absolute ethanol washing filter cake again, get orange filtrate and yellow filter cake.With filter cake vacuum-drying, get 2.0588g yellow solid powder, be the salicylidene quadrol, yield is 86.41 quality %.
Ultimate analysis measured value (theoretical value), quality %:C, 71.18 (71.62); H, 5.91 (6.01); N, 10.21 (10.44).
Infrared spectroscopy value (KBr, v/cm
-1): 1635 (v
C=N), 1285 (v
C-O), 2600 (v
-OH).
Example 2
Preparation salicylidene 1,2-diamino-cyclohexane part.
With 0.34mL1,2-diamines basic ring hexane and 12mL dehydrated alcohol form light yellow transparent solution, to wherein adding the faint yellow salicylic aldehyde of 0.68mL, and salicylic aldehyde and 1,2-diamino-cyclohexane mol ratio is 2.5: 1.80 ℃ of stirrings that reflux form the green-yellow clear solution.Add several formic acid, reflux and stirred 3 hours.Being cooled to 20 ℃, still is the green-yellow clear solution.After freezing, there is yellow mercury oxide to separate out.Pour out the green-yellow transparent liquid.Add the remaining yellow solid matter of 2mL washing with alcohol, filter, and, get glassy yellow filtrate and yellow filter cake with 12mL normal hexane washing leaching cake.With filter cake vacuum-drying, get 0.5653g yellow solid powder, be salicylidene 1,2-diamino-cyclohexane, yield 70.42 quality %.
Ultimate analysis measured value (theoretical value), quality %:C, 74.16 (74.51); H, 6.91 (6.88); N, 8.56 (8.69).
Infrared spectroscopy value (KBr, v/cm
-1): 1630 (v
C=N), 1280 (v
C-O), 2600 (v
-OH).
Example 3
Preparation salicylidene O-Phenylene Diamine part.
Get 0.2468g O-Phenylene Diamine and 12mL dehydrated alcohol and form the khaki color clear solution, to wherein adding the faint yellow salicylic aldehyde of 0.66mL, salicylic aldehyde and O-Phenylene Diamine mol ratio are 2.5: 1.80 ℃ of stirrings that reflux form the turbid liquid of orange.Add several formic acid, reflux and stirred 2 hours.Be cooled to 20 ℃, filter,, get yellow transparent filtrate and orange filter cake with 30mL normal hexane washing leaching cake.With filter cake vacuum-drying, get 0.5633g orange pressed powder, be the salicylidene O-Phenylene Diamine, yield 73.45 quality %.
Ultimate analysis measured value (theoretical value), quality %:C, 75.67 (75.93); H, 5.09 (5.10); N, 8.76 (8.86).
Infrared spectroscopy value (KBr, v/cm
-1): 1611 (v
C=N); 1275 (v
C-O); 2600 (v
-OH).
Example 4
(1) preparation of active magnesium chloride
Add 12.4mmol magnesium powder and 25ml heptane and 0.02g iodine in the 250ml there-necked flask that nitrogen replacement is crossed, being heated to 75 ℃ stirred 2 hours, drip 62mmol exsiccant n-propylcarbinyl chloride reaction 3 hours, obtain nascent state magnesium chloride suspension, filter, with 25 ℃ of drying under reduced pressure of solids 2.5 hours, expression formula be (BuMgCl)
0.06(MgCl
2) the nascent state magnesium chloride, wherein carbon content is measured by elemental analyser.
(2) non-metallocene catalyst of preparation original position load
Get the nascent state MgCl of (1) step preparation
2Carrier 1.0203g, adding the yellow concentration of 54mL is the toluene solution of the salicylidene quadrol of 0.02mol/L, is heated to 80 ℃ of stirring 2hr that reflux, and gets the turbid liquid of grass green.Cooling places the dry ice bath with reactor, and slowly dripping 27mL dark-brown concentration in reaction system is the VCl of 0.04mol/L
4Toluene solution.After dripping end, slowly be warming up to 25 ℃, continue to stir 8hr, get the turbid liquid of dark-brown.Filter and, be colourless until filtrate with toluene and hexane wash filter cake.With filter cake vacuum-drying, the 1.2641g green powder, at active MgCl
2The catalyst A of load salicylidene quadrol vanadous chloride on the carrier, its ultimate analysis measured value is: C, 10.78 quality %; N, 1.43 quality %; H, 0.83 quality %; V, 2.74 quality %; Mg, 16.71 quality %.
Infrared spectroscopy value (KBr, v/cm
-1): 1616 (v
C=N); 1275 (v
C-O); 609 (v
Cl-Mg-Cl).
By the ultimate analysis data as can be known, as salicylidene quadrol and VCl
4Reinforced mol ratio be 1: 1 o'clock, the mol ratio of part and vanadium illustrates VCl also near 1: 1 in the loaded catalyst
4Only react with part, and not direct and carrier MgCl
2Interact.Each vanadium atom and the coordination of a salicylidene quadrol.
Example 5
Method by example 4 prepares loaded catalyst B, different is with equimolar salicylidene 1, the 2-diamino-cyclohexane replaces the salicylidene quadrol, making active ingredient is salicylidene 1, the catalyst B of 2-diamino-cyclohexane-vanadous chloride, its ultimate analysis measured value is: C, 14.83 quality %; N, 1.65 quality %; H, 1.13 quality %; V, 3.08 quality %; Mg, 15.79 quality %.
Infrared spectroscopy value (KBr, v/cm
-1): 1615 (v
C=N); 1275 (v
C-O); 609 (v
Cl-Mg-Cl).
Example 6
Method by example 4 prepares loaded catalyst C, different is to replace the salicylidene quadrol with equimolar salicylidene O-Phenylene Diamine, making active ingredient is the catalyzer C of salicylidene O-Phenylene Diamine-vanadous chloride, and its ultimate analysis measured value is: C, 15.45 quality %; N, 1.76 quality %; H, 0.923 quality %; V, 3.29 quality %; Mg, 15.56 quality %.
Infrared spectroscopy value (KBr, v/cm
-1): 1595 (v
C=N); 1275 (v
C-O); 609 (v
Cl-Mg-Cl).
Example 7
Get the nascent state MgCl of example 4 (1) step preparation
2Carrier 1.03g is added dropwise to the 6.31mmol propyl carbinol, dropwises the back in 60 ℃ of reactions 1 hour, method by 4 (2) steps of example prepares catalyzer then, obtaining active ingredient is the catalyzer D of salicylidene quadrol-vanadous chloride, and its ultimate analysis measured value is: C, 11.92 quality %; N, 1.31 quality %; H, 0.98 quality %; V, 2.67 quality %; Mg, 16.56 quality %.
Infrared spectroscopy value (KBr, v/cm
-1): 1614 (v
C=N); 1273 (v
C-O); 609 (v
Cl-Mg-Cl).
Example 8
Method by example 7 prepares catalyzer, and different is to change propyl carbinol into the 6.31mmol isooctyl alcohol.Obtain catalyzer E, the active ingredient of catalyzer E is salicylidene quadrol-vanadous chloride, and its ultimate analysis measured value is: C, 13.23 quality %; N, 1.23 quality %; H, 1.18 quality %; V, 2.87 quality %; Mg, 16.12 quality %.
Infrared spectroscopy value (KBr, v/cm
-1): 1613 (v
C=N); 1270 (v
C-O); 608 (v
Cl-Mg-Cl).
Example 9
Get the nascent state MgCl of example 4 (1) step preparation
2Carrier 1.03g, be added dropwise to the 6.31mmol isooctyl alcohol, dropwise the back in 60 ℃ of reactions 1 hour, method by 4 (2) steps of example prepares catalyzer then, and different is that adding 54mL concentration is the salicylidene 1 of 0.02mol/L, and the toluene solution of 2-diamino-cyclohexane reacts, making active ingredient is salicylidene 1, the catalyzer F of 2-diamino-cyclohexane-vanadous chloride, its ultimate analysis measured value is: C, 16.53 quality %; N, 1.45 quality %; H, 1.53 quality %; V, 2.98 quality %; Mg, 15.59 quality %.
Infrared spectroscopy value (KBr, v/cm
-1): 1616 (v
C=N); 1270 (v
C-O); 609 (v
Cl-Mg-Cl).
Example 10
Get the nascent state MgCl of example 4 (1) step preparation
2Carrier 1.03g, be added dropwise to the 6.31mmol isooctyl alcohol, dropwise the back in 60 ℃ of reactions 1 hour, method by 4 (2) steps of example prepares catalyzer then, different is, and to add 54mL concentration be that the toluene solution of the salicylidene O-Phenylene Diamine of 0.02mol/L reacts, making active ingredient is the catalyzer G of salicylidene O-Phenylene Diamine-vanadous chloride, and its ultimate analysis measured value is: C, 17.15 quality %; N, 1.54 quality %; H, 1.32 quality %; V, 3.36 quality %; Mg, 15.26 quality %.
Infrared spectroscopy value (KBr, v/cm
-1): 1593 (v
C=N); 1270 (v
C-O); 607 (v
Cl-Mg-Cl).
Example 11～17
Following example carries out the high-pressure ethylene polyreaction.
With 1 liter of stainless steel cauldron nitrogen replacement three time that agitator is housed, with ethene displacement three times, add 400 milliliters of exsiccant hexanes successively again, concentration is the hexane solution of the aluminium diethyl monochloride of 2.14M, it is 100: 1 that the consumption of promotor should make the Al/V mol ratio, stirs it is uniformly dispersed.With 100 milliliters of hexanes with 5.5 * 10
-5The catalyzer of mole is sent into reactor by filling tube, stirs it is uniformly dispersed.Be warming up to 70 ℃, feed ethene to still and press and be 0.9MPa, 80 ℃ of polyreactions 2 hours obtain polyethylene product.Each example catalyst system therefor, catalyst activity and polymer property see Table 1.
Table 1
Example 18～24
Following example carries out high-pressure ethylene and the 1-hervene copolymer closes reaction.
With 1 liter of stainless steel cauldron nitrogen replacement three time that agitator is housed, again with ethene displacement three times, add 400 milliliters of exsiccant hexanes successively, concentration is the hexane solution of the aluminium diethyl monochloride of 2.14M, it is 100: 1 that the consumption of promotor should make the Al/V mol ratio, stirring is uniformly dispersed it, adds 15 milliliters 1-hexene again.With 100 milliliters of hexanes with 5.5 * 10
-5The catalyzer of mole is sent into reactor by filling tube, stirs it is uniformly dispersed.Feed hydrogen to 0.2MPa, be warming up to 70 ℃, feed ethene to still again and press and be 0.9MPa, 80 ℃ of polyreactions 2 hours obtain polyethylene product.Each example catalyst system therefor, catalyst activity and polymer property see Table 2, melt flow rate (MFR) (MFR in the table 2
2.16) on the XNR-400A melt flow rate (MFR) instrument of Chengde trier limited liability company, measure, FRR is MFR
21.6/ MFR
2.16
Table 2
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| CN1277848C (en) * | 2003-09-17 | 2006-10-04 | 大连理工大学 | Preparation and application of a class of catalysts for ethylene oligomerization of zirconium complexes coordinated by Schiffer bases |
| CN1926081A (en) * | 2004-02-26 | 2007-03-07 | 根特大学 | Metal complexes for use in olefin methathesis and atom or group transfer reactions |
| CN1887919A (en) * | 2005-06-30 | 2007-01-03 | 中国石油化工股份有限公司 | In-situ synthesized supported vanadium non-metallocene polyolefin catalyst and its prepn and application |
| US20070043188A1 (en) * | 2005-08-22 | 2007-02-22 | David Schaubroeck | Multicoordinated metal complexes for use in metathesis reactions |
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