CN104059177A - Supported single metallocene catalyst used for ethylene polymerization - Google Patents
Supported single metallocene catalyst used for ethylene polymerization Download PDFInfo
- Publication number
- CN104059177A CN104059177A CN201310090847.9A CN201310090847A CN104059177A CN 104059177 A CN104059177 A CN 104059177A CN 201310090847 A CN201310090847 A CN 201310090847A CN 104059177 A CN104059177 A CN 104059177A
- Authority
- CN
- China
- Prior art keywords
- metallocene catalyst
- single metallocene
- load single
- preparation
- vinyl polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a supported single metallocene catalyst used for ethylene polymerization and a preparation method thereof. The invention discloses a supported single metallocene catalyst used for ethylene polymerization and a preparation method thereof. The catalyst comprises a single metallocene compound, a chlorinated alkyl silicon modifier, alkyl aluminoxane and a silica gel carrier reaction product; the preparation method comprises the following steps: 1) preparation of a chlorinated alkyl silicon modified silica gel carrier, 2)preparation of an alkyl aluminoxane modified silica gel carrier, and 3)preparation of the modified silica gel supported single metallocene catalyst; and the obtained single metallocene catalyst has high polymerization activity for catalyzing vinyl polymerization or copolymerization. The preparation method of the silica gel carrier is simple, and the obtained supported catalyst particles have good morphology and have adjustable size.
Description
Technical field
The present invention relates to a kind of preparation method of modified silica-gel load single metallocene catalyst, and the application of gained catalyzer aspect olefinic polymerization.
Background technology
The Application and Development of metallocene catalyst is after traditional Ziegler-Natta catalyst, the another important breakthrough, the particularly eighties in olefin polymerization catalysis field, the people such as Kaminsky and Sinn (Angew.Chem., 1980,19,390; Adv.Organoment.Chem., 1980,18,99) develop efficient promotor methylaluminoxane (MAO), make the research of metallocene catalyst enter into a fast-developing stage.In the last few years, in the research of olefin polymerization catalysis, more and more come into one's own with the single metallocene catalyst of giving electronics part, bibliographical information many these classes there is the catalyzer of special performance, as with aryloxy (Organometallics, 1998, 17 (11): 2152-2154), amino (Organometallics, 1996, 15 (14): 3176-3181), amidino groups (J.Am.Chem.Soc., 2000, 122 (5): 958-959), imino-(J.Am.Chem.Soc., 2000, 122 (23): 5499-5509), phosphine amino (Organometallics, 2003, 22 (9): 1937-1947) etc. give the luxuriant titanium of list or single luxuriant zirconium of electronics part.Due to homogeneous phase single metallocene catalyst, will to reach the required MAO consumption of high reactivity large, production cost is high, and the polymkeric substance obtaining is amorphous, cannot in widely used slurry process or gas phase polymerization technique, use, the effective way that overcomes the problems referred to above is exactly solubility single metallocene catalyst load processing.
At present, relevant supported metallocene research report is very many, wherein adopts the catalyzer of spherical magnesium chloride (containing alcohol) load metallocene to have good particle form, as PCT Int.Appl.99/21898; US6,455,647; J.Mol.Catal.A2002,188,123; PCT Int.APP1.2004/078804; CN 101817892; CN 101172988, but in carrier, contain the components such as alcohol, water, alkoxyl group, carrier preparation is complicated; And with Si0
2for the report research of carrier also a lot, as WO2012044063; CN 102286114; CN 1174848; CN 1174849; CN 1356343; US 4,808,561; US 5,026,797; US5,763,543; US 5,661,098, but need to use a large amount of aluminum alkylss in carrier preparation, and the load efficiency of catalyzer is lower, still will introduce a large amount of methylaluminoxane in polymerization process, above drawbacks limit the industrial application of silica gel load single metallocene catalyst.
Also there is document to use the carrier loaded mono-metallocene (PolymerInternational, 2002,51, the 417-423 that contain magnesium chloride, silica gel etc.; US5962360), but activity is very low, and need to add a large amount of MAO in the time of polymerization.
Summary of the invention
One of the object of the invention is to provide a kind of single metallocene catalyst with alkylaluminoxane/chlorination silicon alkyl/silica gel load and preparation method thereof.
Two of the object of the invention is by above-mentioned load single metallocene catalyst, for vinyl polymerization or copolymerization, to have high polymerization activity.
A kind of load single metallocene catalyst for vinyl polymerization of the present invention, this catalyzer comprises the reaction product of following component:
A kind of load single metallocene catalyst for vinyl polymerization of the present invention, this catalyzer comprises the reaction product of following component:
(1) mono-metallocene compound;
(2) chlorination silicon alkyl;
(3) alkylaluminoxane;
(4) silica-gel carrier;
The described mono-metallocene compound of component (1), refers to the mono-metallocene title complex shown in general formula 1,
general formula 1
In general formula 1: M is the transition metal of the 4th family in the periodic table of elements; X
1and X
2be selected from halogen or unsubstituted aliphatics, aromatics or cyclic group, or its combination; X
3to replace or unsubstituted cyclopentadienyl, indenyl or fluorenyl, at X
3on any substituting group be selected from hydrogen atom, replacement or unsubstituted aliphatics, aromatics or cyclic group, or its combination;
X
4for-O-R
a,-NH-R
a,-PH-R
a,-N=R
a,-S-R
a,-O-Si-R
b 3or-O-C-R
b 3, wherein:
R
abe selected from and replace or unsubstituted aliphatics, aromatics, cyclic group or its combination; R
bfor hydrogen atom, replacement or unsubstituted aliphatics, aromatics, cyclic group or its combination;
The described chlorination alkyl of component (2) silica modifier refers to compound: Cl described in following general formula
nsi (R
1)
4-n
Wherein R
1represent C
1-C
20alkyl, n represents the integer of 1-4;
The described alkylaluminoxane general formula of component (3) is:
Wherein R represents C
1-C
12alkyl, a represents the integer of 4-30.
In general formula 1, X
1and X
2preferable methyl, phenyl, benzyl or halogen.
X
3preferably replace or unsubstituted cyclopentadiene X
3on the preferred hydrogen atom of each substituting group, methyl, ethyl, propyl group, normal-butyl, the tertiary butyl or hexyl.
X
4preferably-O-R
aor-N=R
a; And X
4be-O-R
atime, R
athe dibasic aryl of 2,6-, R
athe above substituting group is methyl, ethyl, propyl group, normal-butyl, the tertiary butyl, cyclopentyl, cyclohexyl, methoxyl group, oxyethyl group, propoxy-or butoxy; X
4be-N=R
atime, R
ait is alkyl.
The described chlorination silicon alkyl of component (2) R
1preferable methyl, ethyl, propyl group or phenyl, concrete as trimethylchlorosilane, chlorotriethyl silane, tri isopropyl chlorosilane, dimethyl ethyl chlorosilane, diethyl propyl chloride silane, dipropyl methyl chlorosilane, dichloro-dimethyl silicon, Dichlorodiethyl silicon, dichloro phenylbenzene silicon, dichloromethyl n-propyl silane, dichloromethyl phenyl silane, trichloromethyl silane, trichloroethyl silane, phenyl-trichloro-silicane or silicon tetrachloride etc., preferably trimethylchlorosilane, chlorotriethyl silane, dichloro-dimethyl silicon, Dichlorodiethyl silicon, dichloro phenylbenzene silicon, trichloromethyl silane, trichloroethyl silane and silicon tetrachloride.
For the load single metallocene catalyst of ethylene polymerization, the ratio between each reactant is in every gram of silica-gel carrier, and chloric ether SiClx add-on is 0.01-3mmol; The add-on of mono-metallocene compound is 1-1000 μ mol.
The preferred titanium of central metal M or zirconium.
Described chlorination silicon alkyl, wherein R
1preferable methyl, ethyl, propyl group, n represents the integer of 1-4;
Described alkylaluminoxane is R preferable methyl wherein, and a represents the integer of 10-30; Described alkylaluminoxane preferable methyl aikyiaiurnirsoxan beta (MAO), improved methylaluminoxane (MMAO).
The preparation method of a kind of load single metallocene catalyst for vinyl polymerization of the present invention, comprises the steps:
(1) preparation of the silica-gel carrier of chlorination silicon alkyl modification:, as under nitrogen protection silica-gel carrier is added in reactor at rare gas element, add solvent, be dispersed into suspension, add chlorination alkyl silicon, be warming up to 0-90 DEG C, stirring reaction 3-24 hour; Preferably 30-80 DEG C, stirring reaction 3-6 hour, with 30-60 DEG C of the best.Then with solvent wash for several times, vacuum-drying, obtains the silica supports that contains the modification of chlorination silicon alkyl of good fluidity, described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexanaphthene; Preferably toluene, saturated alkane.
(2) preparation of the silica-gel carrier of alkylaluminoxane: at rare gas element as under nitrogen protection, the silica-gel carrier obtaining in (1) step is added in reactor, add solvent, be dispersed into suspension, add alkylaluminoxane, be warming up to 30-90 DEG C, preferably 40-90 DEG C, stirring reaction 3-24 hour, preferably 3-8 hour, then with solvent wash several, vacuum-drying, obtain the silica-gel carrier that contains alkylaluminoxane of good fluidity, described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexanaphthene; The preferred toluene of solvent.
(3) preparation of modified silica-gel load single metallocene catalyst: at rare gas element as under nitrogen protection, the silica-gel carrier that contains alkylaluminoxane that will prepare in (2) step, join and in solvent, make slurries, the solution of single metallocene catalyst precursor is slowly added drop-wise in these slurries, at 0-80 DEG C, reaction 1-120 minute, obtain load single metallocene catalyst, slurries can be directly used in to polyreaction, or gained reactant is removed to desolventizing, after washing is dry, obtain the solid supported single metallocene catalyst of good fluidity, described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexanaphthene, the preferred toluene of solvent, hexane or both mixtures.
Load single metallocene catalyst for ethylene polymerization of the present invention can be used in different polymerization processs, as vapour phase polymerization and slurry polymerization etc.Can be used for equal polymerization or the copolymerization of alkene, be specially adapted to that ethylene homo closes or the copolymerization of ethene and other alpha-olefin, wherein alpha-olefin adopts propylene, butylene, amylene, hexene, octene, 4-methylpentene-1 etc.
The catalyzer of preparing in load single metallocene catalyst method of the present invention can be directly used in olefinic polymerization, as in gas-phase polymerization process; Also can be used for olefinic polymerization by additional aluminum alkyl catalyst, particularly in slurry process, add aluminum alkyls can remove the impurity in system, improve to a certain extent polymerization activity, and need not add expensive MAO to make promotor.
The solvent that wherein polymerization is used is selected from alkane, aromatic hydrocarbon or halohydrocarbon.Preferably a kind of in hexane, pentane, heptane, benzene, toluene, methylene dichloride, chloroform, ethylene dichloride or their mixture, most preferably is a kind of in hexane, toluene, heptane or their mixture.
The concentration of load single metallocene catalyst in the time of polymerization is 1 × 10
-8mol/L～1 × 10
-3mol/L, preferred concentration range is 1 × 10
-8mol/L～1 × 10
-5mol/L.
Polymerization temperature is-78 DEG C-100 DEG C, preferably 20 DEG C-90 DEG C.
Polymerization pressure is 0.01-10.0MPa, preferably 0.01-2.0MPa.
The present invention compared with prior art has the following advantages:
1, modified silica gel carrier preparation method of the present invention is simple, and the granules of catalyst form obtaining is good, and catalyst particle size is adjustable.
2, the catalyzer of preparing in load single metallocene catalyst method of the present invention has very high vinyl polymerization catalytic activity.
3, the catalyzer of preparing in load single metallocene catalyst method of the present invention has good catalyzed ethylene and the copolymerization of high alpha-olefin, and Copolymerization activity is high.
4, load single metallocene catalyst of the present invention obtains resin powder and has good particle form for olefinic polymerization, and tap density is high, goes for slurry process and vapor phase process polymerization technique.
The analysis and characterization instrument using in the present invention is as follows:
1, ICP (plasma emission spectrum) characterizes: the weight percent of metal in quantitative assay carried catalyst.The P1000 type ICP-AES plasma emission spectrometer that PE company of the instrument selection U.S. produces.
2, the sign of polymericular weight and molecular weight distribution: molecular weight and distribution thereof are measured by gel permeation chromatography (GPC), instrument adopts Waters Alliance GPCV 2000, and solvent is 1; 2; 4-trichlorobenzene, sample concentration is lmg/ml, solvent flow rate is 1.0ml/min; Measuring temperature is 150 DEG C.Each sample measurement secondary.
3, in polymkeric substance, co-monomer content characterizes: in polymkeric substance, hexene monomer content is by nuclear-magnetism
13c-NMR measures, and instrument adopts Bruker AVANCE400, sweep rate l00.6MHz, and temperature is 398K.Sampling time is 5sec, and be 10sec time of lag, scanning times 5000 times.Sample concentration is 10-20mg/ml.
Embodiment
Embodiment 1
(1) preparation of chlorination silicon alkyl/silica-gel carrier
Under nitrogen protection, get 10.0 grams of dry silica-gel carriers and add in glass reactor, add 100 milliliters of dried hexanes, be dispersed into suspension, add 1 milliliter of SiCl
2(n-Bu)
2, start stirring, be warming up to 30 DEG C, to react 4 hours, vacuum-drying, obtains the pressed powder of good fluidity.
(2) preparation of alkylaluminoxane/chlorination silicon alkyl/silica-gel carrier
Under nitrogen protection; get 5.0 grams of modified silica gel carriers obtained above and add in glass reactor, add 60 milliliters of dried toluene, be dispersed into suspension; add MAO (methylaluminoxane) toluene solution of 18 milliliters of 10wt%; be warming up to 50 DEG C, stirring reaction 4 hours, then uses 50 milliliters × 3 toluene wash three times; then wash with hexane; vacuum-drying, obtains the pressed powder of good fluidity, contains the silica-gel carrier of methylaluminoxane.
(3) preparation of load single metallocene catalyst A
Under nitrogen protection, by 2.50 grams of the silica-gel carriers that contains methylaluminoxane obtaining above, join in glass reactor, add 35 milliliters of dried toluene to make slurries, will be dissolved in 0.108 gram of Cp*TiCl in 20 milliliters of toluene
2(O-2,6-
ipr
2c
6h
3) solution be added drop-wise in reactor, 30 DEG C reaction 30 minutes, then use 35 milliliters of toluene wash, vacuum-drying, obtains load single metallocene catalyst A.Characterize through ICP, in catalyst A, Ti weight content is that 0.32%, Al weight content is 10.21%.
Comparing embodiment 1
(1) preparation of alkylaluminoxane/silica-gel carrier
Under nitrogen protection; get the magnesium chloride support that in 7.01 grams of embodiment 1, spraying makes and add in glass reactor, add 90 milliliters of dried toluene, be dispersed into suspension; add the MAO(methylaluminoxane of 40 milliliters of 10wt%) toluene solution; be warming up to 50 DEG C, stirring reaction 4 hours, then uses 50 milliliters × 3 toluene wash three times; then wash with hexane; vacuum-drying, obtains the pressed powder of good fluidity, i.e. alkylaluminoxane/silica-gel carrier.
(2) preparation of load single metallocene catalyst A*
Under nitrogen protection, 2.50 grams of the above-mentioned alkylaluminoxane/silica-gel carriers preparing are joined in glass reactor, add 25 milliliters of dried toluene to make slurries, will be dissolved in 0.108 gram of Cp*TiCl in 20 milliliters of toluene
2(O-2,6-
ipr
2c
6h
3) solution droplets be added in reactor, 30 DEG C reaction 30 minutes, then use 30 milliliters of toluene wash, vacuum-drying, obtains supported non-metallocene single site catalysts A*.Characterize through ICP, in catalyst A *, Ti weight content is that 0.34%, Al weight content is 14.28%.
Embodiment 2
(1) preparation of chlorination silicon alkyl/silica-gel carrier
With embodiment 1 step (1), only by SiCl in embodiment 1
2(n-Bu)
2be changed to SiCl
4.
(2) preparation of alkylaluminoxane/chlorination silicon alkyl/silica-gel carrier
With embodiment 1 step (2).
(3) preparation of supported metallocene catalyst B
With embodiment 1 step (3), obtain load metallocene catalyst B.Characterize through ICP, in catalyst B, Ti weight content is that 0.30%, Al weight content is 11.18%.
Embodiment 3
(1) preparation of chlorination silicon alkyl/silica-gel carrier
With embodiment 1 step (1), only by SiCl in embodiment 1
2(n-Bu)
2be changed to CH
3siCl
3.
(2) preparation of alkylaluminoxane/chlorination silicon alkyl/silica-gel carrier
With embodiment 1 step (2).
(3) preparation of supported metallocene catalyst C
With embodiment 1 step (3), obtain load metallocene catalyst C.Characterize through ICP, in catalyzer C, Ti weight content is that 0.31%, Al weight content is 11.22%.
Embodiment 4
(1), (2) are with (1), (2) preparation method in embodiment 1.
(3) preparation of supported metallocene catalyst D
With embodiment 1 step (3), only by 0.108 gram of Cp*TiCl in embodiment 1
2(O-2,6-
ipr
2c
6h
3) replace with 0..081 gram of CpTiCl
2(N=C
tbu
2), obtain load metallocene catalyst D.Characterize through ICP, in catalyzer D, Ti weight content is that 0.27%, Al weight content is 10.16%.
High-pressure ethylene polymerization experiment
High-pressure ethylene polymerization experiment process is as follows:
In the stainless steel polymermaking autoclave of 2 liters, with the each displacement of nitrogen and ethene three times, then add 1000 milliliters of hexane solvents, along with adding of hexane, the 1-hexene of the triethyl aluminum of 5 milliliter of 1 mol/L (TEA) hexane solution and requirement is added, and the load single metallocene catalyst 50-100 milligram that then adds above-described embodiment to make, is warming up to 60 DEG C, pressure is risen to and maintained 1.0MPa, react 1 hour.Polymerization is anti-
After should finishing, cooling, collects polyethylene particle powder, weighs.
Concrete polymerization result is listed in table 1.
Table 1, load single metallocene catalyst polymerization result
Table 1, load single metallocene catalyst polymerization result
Claims (10)
1. for a load single metallocene catalyst for vinyl polymerization, it is characterized in that, this catalyzer comprises the reaction product of following component:
(1) mono-metallocene compound;
(2) chlorination silicon alkyl;
(3) alkylaluminoxane;
(4) silica-gel carrier;
The described mono-metallocene compound of component (1), refers to the mono-metallocene title complex shown in general formula 1,
general formula 1
In general formula 1: M is the transition metal of the 4th family in the periodic table of elements; X
1and X
2be selected from halogen or unsubstituted aliphatics, aromatics or cyclic group, or its combination; X
3to replace or unsubstituted cyclopentadienyl, indenyl or fluorenyl, at X
3on any substituting group be selected from hydrogen atom, replacement or unsubstituted aliphatics, aromatics or cyclic group, or its combination;
X
4for-O-R
a,-NH-R
a,-PH-R
a,-N=R
a,-S-R
a,-O-Si-R
b 3or-O-C-R
b 3, wherein:
R
abe selected from and replace or unsubstituted aliphatics, aromatics, cyclic group or its combination; R
bfor hydrogen atom, replacement or unsubstituted aliphatics, aromatics, cyclic group or its combination;
The described chlorination alkyl of component (2) silica modifier refers to compound: Cl described in following general formula
nsi (R
1)
4-n
Wherein R
1represent C
1-C
20alkyl, n represents the integer of 1-4;
The described alkylaluminoxane general formula of component (3) is:
Wherein R represents C
1-C
12alkyl, a represents the integer of 4-30.
2. the load single metallocene catalyst for vinyl polymerization according to claim 1, is characterized in that, described mono-metallocene title complex, and central metal M is titanium or zirconium; X
1and X
2be selected from methyl, phenyl, benzyl or halogen; X
3that replace or unsubstituted cyclopentadiene, X
3on each substituting group be selected from hydrogen atom, methyl, ethyl, propyl group, normal-butyl, the tertiary butyl or hexyl.
3. the load single metallocene catalyst for vinyl polymerization according to claim 1, is characterized in that, described mono-metallocene title complex, wherein X
4be-O-R
aor-N=R
a; And X
4be-O-R
atime, R
ait is the dibasic aryl of 2,6-; X
4be-N=R
atime, R
ait is alkyl.
4. the load single metallocene catalyst for vinyl polymerization according to claim 1, is characterized in that R
athe above substituting group is methyl, ethyl, propyl group, normal-butyl, the tertiary butyl, cyclopentyl, cyclohexyl, methoxyl group, oxyethyl group, propoxy-or butoxy.
5. the load single metallocene catalyst for vinyl polymerization according to claim 1, is characterized in that, described chlorination silicon alkyl, wherein R
1for methyl, ethyl, propyl group or phenyl; Described alkylaluminoxane is methylaluminoxane (MAO), improved methylaluminoxane (MMAO).
6. the load single metallocene catalyst for vinyl polymerization according to claim 1, it is characterized in that, ratio between each reactant is in every gram of silica-gel carrier, chloric ether SiClx add-on is 0.01-3mmol, the add-on 0.01-30mmol of alkylaluminoxane, the add-on of mono-metallocene compound is 1-1000 μ mol.
7. the load single metallocene catalyst for vinyl polymerization according to claim 1, is characterized in that, in load single metallocene catalyst, the weight content of aluminium is 1-15%; The weight content of central metal M is 0.05-2%.
8. the preparation method of the load single metallocene catalyst for vinyl polymerization described in claim 1-7, is characterized in that, comprises the following steps:
The first step: under protection of inert gas, silica-gel carrier reacts 3-24 hour with chlorination silicon alkyl at 0-90 DEG C;
Second step: under protection of inert gas, the first step gained chlorination silicon alkyl modified silica-gel is reacted to 3-24 hour with alkylaluminoxane at 0-90 DEG C;
The 3rd step: under protection of inert gas, second step gained alkylaluminoxane modified silica-gel is reacted to 0.5-24 hour with mono-metallocene compound at 0-90 DEG C;
Solvent described in above three steps is toluene, benzene, dimethylbenzene, hexane, heptane or hexanaphthene.
9. the preparation method of the load single metallocene catalyst for vinyl polymerization according to claim 8, is characterized in that, is 30-60 DEG C in the first step temperature of reaction, and dispersion agent used is toluene or saturated alkane; Be 40-90 DEG C in second step temperature of reaction; Dispersion agent used is toluene; Be toluene, hexane or both mixtures at the 3rd step dispersion agent used.
In claim 1-7 the load single metallocene catalyst for vinyl polymerization described in any one in the application of olefinic polymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310090847.9A CN104059177B (en) | 2013-03-21 | 2013-03-21 | A kind of load single metallocene catalyst for vinyl polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310090847.9A CN104059177B (en) | 2013-03-21 | 2013-03-21 | A kind of load single metallocene catalyst for vinyl polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104059177A true CN104059177A (en) | 2014-09-24 |
| CN104059177B CN104059177B (en) | 2016-09-21 |
Family
ID=51547129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310090847.9A Active CN104059177B (en) | 2013-03-21 | 2013-03-21 | A kind of load single metallocene catalyst for vinyl polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104059177B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109843938A (en) * | 2016-10-27 | 2019-06-04 | 尤尼威蒂恩技术有限责任公司 | The method for preparing molecular catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1539855A (en) * | 2003-10-29 | 2004-10-27 | 扬子石油化工股份有限公司 | Loaded method of load type Non-metallocene catalyst-and polymerizing application |
| CN101077879A (en) * | 2006-05-23 | 2007-11-28 | 中国石油天然气股份有限公司 | Monodentate compound containing phenoxy, preparation method and application thereof |
| CN101786019A (en) * | 2010-02-26 | 2010-07-28 | 中国石油天然气股份有限公司 | Transition metal catalyst containing cyclopentadienyl and preparation and application thereof |
| CN102453124A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Supported metallocene catalyst and olefin polymer, and preparation methods thereof |
-
2013
- 2013-03-21 CN CN201310090847.9A patent/CN104059177B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1539855A (en) * | 2003-10-29 | 2004-10-27 | 扬子石油化工股份有限公司 | Loaded method of load type Non-metallocene catalyst-and polymerizing application |
| CN101077879A (en) * | 2006-05-23 | 2007-11-28 | 中国石油天然气股份有限公司 | Monodentate compound containing phenoxy, preparation method and application thereof |
| CN101786019A (en) * | 2010-02-26 | 2010-07-28 | 中国石油天然气股份有限公司 | Transition metal catalyst containing cyclopentadienyl and preparation and application thereof |
| CN102453124A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Supported metallocene catalyst and olefin polymer, and preparation methods thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109843938A (en) * | 2016-10-27 | 2019-06-04 | 尤尼威蒂恩技术有限责任公司 | The method for preparing molecular catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104059177B (en) | 2016-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101423575B (en) | Supported metallocene catalyst component and preparation method thereof and use | |
| JP4689829B2 (en) | Crosslinked metallocenes for olefin copolymerization | |
| CA2387877C (en) | Catalyst systems and their use in a polymerization process | |
| EP1917281B2 (en) | Polymerization catalysts and process for producing bimodal polymers in a single reactor | |
| EP3031832B1 (en) | Method for preparing polyolefin | |
| CN104059179A (en) | Supported single metallocene catalyst for ethylene polymerization | |
| CN101817892B (en) | Method for preparing magnesium chloride loaded metallocene catalyst | |
| CN104059175A (en) | Supported late-transition-metal catalyst used for ethylene polymerization and preparation method thereof and application thereof | |
| US20050003950A1 (en) | Method of making mixed ziegler-natta/metallocece catalysts | |
| US8524627B2 (en) | Activating supports with controlled distribution of OH groups | |
| WO2002046243A2 (en) | Polymerization process | |
| CN104059173A (en) | Supported late-transition-metal catalyst used for ethylene polymerization | |
| CN104059178B (en) | A kind of modified silica-gel load metallocene catalyst and preparation method | |
| CN104059177A (en) | Supported single metallocene catalyst used for ethylene polymerization | |
| CN104059183B (en) | A kind of supported metallocene catalyst for vinyl polymerization, preparation method and application | |
| CN104059171B (en) | A kind of modified silica-gel load metallocene catalyst and preparation method | |
| CN104610481B (en) | Supported metallocene catalyst for ethylene polymerization, preparation method and applications thereof | |
| CN104610479A (en) | Supported metallocene catalyst for ethylene polymerization, preparation method and applications thereof | |
| CN104610480A (en) | Supported metallocene catalyst, preparation method and applications thereof | |
| CN101817891B (en) | Method for preparing magnesium chloride loaded non-metallocene single active site catalyst | |
| CN101148487B (en) | Catalyst and method for preparing ultra-low density polyethylene copolymer by using the same | |
| CN104059174B (en) | A kind of supported single metallocene catalyst for vinyl polymerization | |
| KR20190060317A (en) | A metallocene catalyst system for producing high density polyolefin with a wide molecular weight distribution and a method for producing polyolefin by using the same | |
| CN104059181B (en) | A kind of supported non-metallocene metallic catalyst for vinyl polymerization | |
| CN104059182B (en) | A kind of supported non-metallocene metallic catalyst for vinyl polymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |