CN1253479C - Catalyst for preparing polyethylene with double peak and/or broad peak molecular weight distribution - Google Patents
Catalyst for preparing polyethylene with double peak and/or broad peak molecular weight distribution Download PDFInfo
- Publication number
- CN1253479C CN1253479C CN 03129240 CN03129240A CN1253479C CN 1253479 C CN1253479 C CN 1253479C CN 03129240 CN03129240 CN 03129240 CN 03129240 A CN03129240 A CN 03129240A CN 1253479 C CN1253479 C CN 1253479C
- Authority
- CN
- China
- Prior art keywords
- molecular weight
- tetraalkyl
- catalyst
- weight distribution
- aikyiaiurnirsoxan beta
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention discloses a catalyst for preparing polyethylene with molecular-weight distribution of double peaks and/or broad peaks. The catalyst comprises (a) a transitional metal compound using imine as ligand and (b) one kind of the following substances: (1) a tetraalkyl aluminoxane whose chemical formula is R1(R2)-Al-O-Al-R3(R4) and (2) loaded type tetraalkyl aluminoxane which is formed by loading the tetraalkyl aluminoxane on the surface of an inert solid carrier, wherein R1, R2, R3 and R4 in the chemical formula are hydrocarbyl. The catalyst can be used for catalyzing the polymerization of ethylene; the obtained polymer has molecular-weight distribution of double peaks and/or broad peaks. In the molecular weight distribution of the double peaks, the high molecular weight part of ethene polymers prepared with the catalyst is dominant, and the proportion of the low molecular weight part and the high molecular weight part can be adjusted.
Description
Technical field
The present invention relates to a kind of preparation and have catalyst of polyethylene bimodal and/or the broad peak molecular weight distribution.
Background technology
Poly toughness, intensity and rupture strength are important properties very, and these character can strengthen along with the increase of poly molecular weight.But polymericular weight increases, and its processing characteristics generally will variation.If polymkeric substance has wide or bimodal molecular weight distribution, then both can make polymkeric substance have high mechanical strength, good processing properties, particularly extrudability are arranged again.The method of producing the polyvinyl resin with bimodal molecular weight distribution at present mainly contains three kinds.First kind is that resin with different molecular weight carries out blend under molten state, and this method cost is than higher, and the homogeneity of resin is not good, so that influence the performance of resin.Second method is to carry out stage feeding polymerization by a plurality of reactors, prepares the different polymkeric substance of molecular weight respectively.This method can obtain to form resin comparatively uniformly, the handiness that can regulate is arranged, but on efficient and cost problem is arranged all.The third method is to adopt the polyethylene of single catalyst or mixed catalyst direct production wide molecular weight or bimodal molecular weight distribution in single reaction vessel.In this method, mixed catalyst has more report, discloses a kind of catalyzer of many active centre as Chinese patent CN1342716, and this catalyzer comprises Ti component and V component.
It is title complex part, that contain transition metal with the diimine that U.S. Pat 5955555 discloses multiple, under the activation of aluminum alkyls or aikyiaiurnirsoxan beta, can prepare linear polyethylene.
Summary of the invention
The purpose of this invention is to provide a kind of preparation and have catalyst of polyethylene bimodal and/or the broad peak molecular weight distribution.
Be made up of component a and components b, the ratio between b component and a component with aluminium and transition metal molar ratio computing, is 50～2000, wherein
The a component is a kind of title complex that contains the diimine of transition metal, and its structural formula is:
R in the formula
a, R
b, R
c, R
d, R
eAnd R
fIt respectively is identical or different alkyl; Mt is transition-metal Fe or Co; X is a halogen;
The b component is a kind of in the following material: (1) a kind of tetraalkyl aikyiaiurnirsoxan beta, its structural formula is
R in the formula
1, R
2, R
3, R
4Be identical or different alkyl; Or (2) load on above-mentioned tetraalkyl aikyiaiurnirsoxan beta the loading type tetraalkyl aikyiaiurnirsoxan beta that obtains on the inert solid carrier.
The a component of catalyzer of the present invention is the transistion metal compound reported of patent disclosure.The characteristics of its synthetic method and catalyzed ethylene polymerization are described in detail in the US5955555 patent.
Components b in the described catalyzer prepares by method described below.With alkane or aromatic hydrocarbon is solvent, and one or more aluminum alkyls is reacted with water at low temperatures, remove desolvate after, can obtain components b 1 and be white powder.Also can not remove and desolvate, the solution that contains components b 1 that makes is directly used.
When the components b 1 of preparation catalyzer, the substituting group on the selected aluminum alkyls is selected from C
1-C
20Straight or branched alkane substituting group, as methyl, ethyl, isobutyl-, butyl, hexyl or 2-ethylhexyl etc.
When the components b 1 of preparation catalyzer, can adopt a kind of, two or more aluminum alkyls.When adopting two kinds of aluminum alkylss, the molar ratio of two kinds of aluminum alkylss is 2/1-1/2, is the best with 1/1 wherein.
When the components b 1 of preparation catalyzer, the temperature of water and aluminum alkyls reaction is the best with-78 ℃ to-50 ℃ wherein at-178 ℃ to-20 ℃.Adding the amount of entry and the mol ratio of aluminum alkyls is 1/2.The water that drips above-mentioned amount can be finished in 0.5-2 hour.After being added dropwise to complete, return to room temperature naturally, and at room temperature reacted 1-6 hour, remove then or be not prepared from except that desolvating.
When the components b 2 of preparation catalyzer, be in the toluene solution of 0.02-2M to the concentration that contains b1, add carriers such as an amount of silica gel or laminated clay, at 20-80 ℃, be preferably 30-60 ℃ of reaction 0.5-6 hour, be preferably 1-2 hour, can obtain components b 2 except that after desolvating.The solid weight that adds is the solution of the tetraalkyl aikyiaiurnirsoxan beta of 1 mol in 200 ml aluminium content, is 0.2-4g, and preferred add-on is at 0.4-1g.
When the components b 2 of preparation catalyzer, the silica gel of employing is the inorganic carrier of common load Ziegler-Natta catalyst or metallocene catalyst, and adoptable silica gel model is 952,955 etc.The clay that adopts also can be done the carrier of olefin polymerization catalysis, can be inorganic polynite or through the aliphatic quaternary ammonium salt montmorillonite modified.
With component a and b1 or b2, cooperate according to certain stoichiometry, can in organic solvents such as toluene, carry out the homogeneous phase or the slurry polymerization of ethene.Polyreaction can be to carry out under the 0.1-2.0MPa at 0-60 ℃, ethylene pressure.Preferred polymerization temperature is 20-50 ℃.The molecular weight distribution of prepared polymkeric substance and can be observed significantly bimodally on the graph of molecular weight distribution (GPC figure) of polymkeric substance between 2.5-70, and the area at two peaks can be regulated.
The present invention adopts known transistion metal compound to do Primary Catalysts and tetraalkyl aikyiaiurnirsoxan beta of the present invention is a promotor, in single reaction vessel, come the molecular weight and the molecular weight distribution of controlling polymers by the stoichiometry between two kinds of components of regulating catalyzer, can obtain a series of molecular weight distribution forms from unimodal to bimodal.Particularly, adopt the ethene polymers of Preparation of Catalyst involved in the present invention, in its bimodal molecular weight distribution,, not only the high molecular part can be preponderated, and the ratio of low-molecular-weight part and high molecular part can be regulated.So both poly processing characteristics can be improved, and its mechanical property can be do not reduced again.
Description of drawings
Fig. 1 is the molecular weight of polyethylene distribution plan (GPC figure) among the embodiment 2-4, a) embodiment 2, b among the figure) embodiment 3, c) embodiment 4;
Fig. 2 is the molecular weight of polyethylene distribution plan (GPC figure) among the embodiment 5-7, a) embodiment 5, b among the figure) embodiment 6, c) embodiment 7;
Fig. 3 is the molecular weight of polyethylene distribution plan (GPC figure) among the embodiment 9-11, a) embodiment 9, b among the figure) embodiment 10, c) embodiment 11;
Fig. 4 is the molecular weight of polyethylene distribution plan (GPC figure) among the embodiment 12-14, a) embodiment 12, b among the figure) embodiment 13, c) embodiment 14;
Fig. 5 is the molecular weight of polyethylene distribution plan (GPC figure) among the embodiment 15-17, a) embodiment 15, b among the figure) embodiment 16, c) embodiment 17;
Fig. 6 is the molecular weight of polyethylene distribution plan (GPC figure) among the embodiment 18-21, a) embodiment 18, b among the figure) embodiment 19, c) embodiment 20, d) embodiment 21.
Fig. 7 is the molecular weight of polyethylene distribution plan (GPC figure) among the embodiment 22.
Embodiment
The present invention loads on the components b 2 that obtains on the inert solid carrier with the b1 in the components b and cooperates with component a, can prepare the polyethylene of bimodal and/or wide molecular weight distribution equally.
The present invention illustrates with the following examples, but scope of the present invention is not limited to these embodiment.
All synthetic and polyreactions are to carry out under the reaction conditions of anhydrous and oxygen-free.
The component a that is used for the catalyzer of embodiment is to prepare according to the method described in the US5955555.Concrete method is as follows.In the flask of 200ml, add 50ml methyl alcohol respectively, 2.0 gram 2,6 diacetyl pyridines and 4.32 grams, 2,6 diisopropyl anilines.Add several formic acid again and make catalyzer.Above-mentioned solution at room temperature stirs and spends the night, and has the faint yellow solid precipitation to generate.The solid that obtains after filtration obtains 3.6 gram faint yellow solid, i.e. two (2,6 diisopropyl phenyls)-2,6 diacetyl pyridine imines or { [(ArN=C (Me)) with cold methanol wash several after drying
2C
5H
3N] FeCl
2(Ar=2,6-diisopropyl aniline), productive rate 61%.In 10ml exsiccant tetrahydrofuran (THF), add the anhydrous FeCl of 0.1 gram
2, and dispersed with stirring.Add 0.38 gram, two (2,6 diisopropyl phenyls)-2,6 diacetyl pyridine imines again.The color of solution deepens gradually, and has blue precipitation to generate.Above-mentioned reactant at room temperature stirred 3 days, filtered then.The solid of gained washs after drying with pentane, obtains 0.4 gram blue solid, is { [(ArN=C (Me))
2C
5H
3N] FeCl
2(Ar=2,6-diisopropyl aniline).
Adopt and use the same method, replace 2,6 diisopropyl anilines can prepare the title complex of another kind of part and iron with 2,6 xylidines.The component a that is used for the catalyzer of embodiment, its concrete example is: in following general formula,
Work as R
aAnd R
bBe methyl; R
c, R
d, R
eAnd R
fBe all sec.-propyl; Mt is Fe (II), and when X was Cl, this compound number was Fe-1.Work as R
aAnd R
bBe methyl; R
c, R
d, R
eAnd R
fBe all methyl; Mt is Fe (II), and when X was Cl, this compound number was Fe-2.
The components b 1 that is used for the catalyzer of embodiment is according to following method preparation.In 500 milliliters reaction flask, add 200 milliliters of toluene successively, 0.2 mole of triethyl aluminum.If adopt two kinds of aluminum alkylss, need at room temperature stir 30-60 minute.The solution that obtains is cooled to-78 ℃, under fully stirring, slowly drips 0.1 mole of water.After water adds, return to room temperature naturally, continue reaction 3 hours, obtain the toluene solution of water white tetraalkyl aikyiaiurnirsoxan beta.The concentration of the aluminium of this solution is 1M.Under reduced pressure remove and desolvate, can obtain transparent thick tetraalkyl aikyiaiurnirsoxan beta.Adopt two kinds of aluminum alkylss, under different proportionings, can prepare other various tetraalkyl aikyiaiurnirsoxan beta.Proportioning during the components b 1 of concrete preparation catalyzer sees Table 1.
The components b 2 that is used for the catalyzer of embodiment is according to following method preparation.To 200 ml aluminium concentration is in the toluene solution of tetraalkyl aikyiaiurnirsoxan beta of 1M, adds the silica gel of 0.08g, continues 50 ℃ of reactions after 3 hours, removes by filter solution and through the washing drying under reduced pressure, can obtain the tetraalkyl aikyiaiurnirsoxan beta of white powder.The weight of the silica gel that is added can be between 0.04g-0.8g.Proportioning during the components b 2 of concrete preparation catalyzer sees Table 1.
The slurry polymerization of ethene carries out according to method described below.Polyreaction is to carry out in the polymerization reaction kettle of 500ml.The exsiccant reactor with ethylene gas displacement three times, is added 200ml toluene, components b 1 or b2 then successively.Stirring allows ethene reach capacity in toluene.Add Fe catalyzer initiated polymerization then.The constant pressure that in polymerization process, keeps ethene.After the polymerization 1 hour, with acidifying ethanol termination reaction, polymkeric substance behind washing, suction filtration 60 ℃ of following vacuum-dryings to constant weight, polymerization activity is calculated in weighing.Polyreaction can be carried out at 20-80 ℃, and the pressure of ethene is respectively 0.1 and 0.35MPa during polymerization.The consumption of catalyzer a, b component and other reaction conditions see Table 2 and table 3 during polymerization.
The molecular weight of polymkeric substance and molecular weight distribution are measured on PL GPC-220 gel chromatograph.(with 1,2,4 trichlorobenzene are moving phase, and 150 ℃ of detected temperatures are done pervasive correction with polystyrene standards, K=59.1, α=0.69).
Each embodiment the results are shown in Table 2 and table 3.
Adopt Fe-1 and methylaluminoxane (MAO) to make catalyzer, the result of catalyzed ethylene polymerization, as a comparison case.
Embodiment 2-4
Adopt Fe-1 and by the tetraalkyl aikyiaiurnirsoxan beta of triethyl aluminum preparation in the result of different al/Fe than following catalyzed ethylene polymerization.
Embodiment 5-7
Adopt Fe-1 and by the tetraalkyl aikyiaiurnirsoxan beta of triethyl aluminum/triisobutyl aluminium (1: 1) preparation in the result of different al/Fe than following catalyzed ethylene polymerization.
Embodiment 8
Adopt Fe-1 and by the result of the tetraalkyl aikyiaiurnirsoxan beta catalyzed ethylene polymerization of triisobutyl aluminium preparation.
Embodiment 9-11
Adopt Fe-2 and by the tetraalkyl aikyiaiurnirsoxan beta different al/Fe of triethyl aluminum preparation result than catalyzed ethylene polymerization.
Embodiment 12-14
The tetraalkyl aikyiaiurnirsoxan beta that adopts the preparation of Fe-2 and triethyl aluminum/triisobutyl aluminium (1: 1) is in the result of different al/Fe than following catalyzed ethylene polymerization.
Embodiment 15-17
The loading type tetraalkyl aikyiaiurnirsoxan beta (silica gel) that adopts the preparation of Fe-1 and triethyl aluminum is in the result of different al/Fe than following catalyzed ethylene polymerization.
Embodiment 18-21
The loading type tetraalkyl aikyiaiurnirsoxan beta (silica gel) that adopts the preparation of Fe-2 and triethyl aluminum is in the result of different al/Fe than following catalyzed ethylene polymerization.
Embodiment 22
Adopt the result of the loading type tetraalkyl aikyiaiurnirsoxan beta (polynite) of Fe-1 and triethyl aluminum preparation at catalyzed ethylene polymerization.
Table 1 catalyst component b1 and b2 prepare proportioning
a
| Numbering | Et 3Al/i-Bu 3Al | Carrier consumption gram |
| b1-1 | 1/0 | 0 |
| b1-2 | 0.5/0.5 | 0 |
| b1-3 | 1/0 | 0 |
| b2-1 | 1/0 | 0.02 b |
| b2-2 | 1/0 | 0.10 c |
A) for all building-up reactionss, make solvent with 200ml toluene, keep concentration [Al]=1.0M, Al/H
2O=2/1.
B) carrier was a silica gel 955,400 ℃ of following vacuum-dryings 6 hours.
C) carrier was a sodium-based montmorillonite, 200 ℃ of following vacuum-dryings 6 hours.
Table 2 vinyl polymerization result
a
| Embodiment | Catalyst system | Al/Fe | Polymerization temperature | Ethylene pressure | Polymerization activity | Mw×10 -4b | Mw/Mn c | ||
| Component a | | Mol ratio | ℃ | MPa | 10 7gPE/(MolMt*H*MPa) | Peak 1 | Peak 2 | ||
| 1 | Fe-1 | MAO | 1000 | 30 | 0.1 | 1.5 | 3.63 | 0.25 | 15.8 |
| 2 | Fe-1 | b1-1 | 500 | 30 | 0.1 | 4.3 | 2.92 | 0.60 | 8.8 |
| 3 | Fe-1 | b1-1 | 1000 | 30 | 0.1 | 6.8 | 1.80 | 0.28 | 15.4 |
| 4 | Fe-1 | b1-1 | 2000 | 30 | 0.1 | 11.0 | 0.21 | - | 15.8 |
| 5 | Fe-1 | b1-2 | 500 | 30 | 0.1 | 2.9 | 2.89 | - | 4.3 |
| 6 | Fe-1 | b1-2 | 1000 | 30 | 0.1 | 3.7 | 1.29 | - | 7.3 |
| 7 | Fe-1 | b1-2 | 2000 | 50 | 0.1 | 6.7 | 1.20 | - | 7.5 |
| 8 | Fe-1 | b1-3 | 500 | 30 | 0.1 | 1.1 | 9.42 | - | 5.2 |
| 9 | Fe-2 | b1-1 | 500 | 30 | 0.1 | 2.2 | 3.20 | 0.045 | 16.8 |
| 10 | Fe-2 | b1-1 | 1000 | 30 | 0.1 | 3.1 | 1.98 | 0.046 | 12.1 |
| 11 | Fe-2 | b1-1 | 2000 | 30 | 0.1 | 5.9 | 2.22 | 0.063 | 12.3 |
| 12 | Fe-2 | b1-2 | 500 | 30 | 0.1 | 2.3 | 3.30 | 0.14 | 8.5 |
| 13 | Fe-2 | b1-2 | 1000 | 30 | 0.1 | 2.8 | 1.79 | 0.15 | 7.7 |
| 14 | Fe-2 | b1-2 | 2000 | 30 | 0.1 | 3.3 | 0.088 | - | 3.9 |
A) polymerizing condition: 200ml toluene, [Fe]=1 * 10
-5M, 1 hour;
B) listed data are the molecular weight of each summit in the table;
C) be the molecular weight distributing index of whole polymkeric substance.Relevant graph of molecular weight distribution is seen accompanying drawing.
Table 3 vinyl polymerization result
a
| Embodiment | Catalyst system | Al/Fet | Polymerization temperature | Ethylene pressure | Polymerization activity | Mw×10 -4b | Mw/Mn c | ||
| Component a | | Mol ratio | ℃ | MPa | 10 7gPE/(MolMt*H*M Pa) | | | ||
| 15 | Fe-1 | b2-1 | 200 | 30 | 0.10 | 1.0 | 1.92 | 0.23 | 35 |
| 16 | Fe-1 | b2-1 | 200 | 50 | 0.35 | 2.5 | 5.95 | 0.63 | 47 |
| 17 | Fe-1 | b2-1 | 200 | 60 | 0.35 | 3.0 | 6.84 | 0.89 | 69 |
| 18 | Fe-2 | b2-1 | 200 | 30 | 0.10 | 0.9 | 3.77 | 0.06 | 45 |
| 19 | Fe-2 | b2-1 | 230 | 30 | 0.35 | 3.0 | 1.90 | 0.07 | 22 |
| 20 | Fe-2 | b2-1 | 180 | 50 | 0.35 | 2.4 | 3.63 | 0.14 | 40 |
| 21 | Fe-2 | b2-1 | 150 | 60 | 0.35 | 2.8 | 3.98 | 0.14 | 39 |
| 22 | Fe-1 | b2-2 | 200 | 30 | 0.10 | 2.7 | 7.38 | 0.32 | 51 |
A) polymerizing condition: 200ml toluene, [Fe]=1 * 10
-5M, 1 hour;
B) listed data are the molecular weight of each summit in the table;
C) be the molecular weight distributing index of whole polymkeric substance.Relevant graph of molecular weight distribution is seen accompanying drawing.
Claims (8)
1. one kind prepares and has catalyst of polyethylene bimodal and/or the broad peak molecular weight distribution, it is characterized in that being made up of component a and components b, and the ratio between b component and a component with aluminium and transition metal molar ratio computing, is 50～2000, wherein
The a component is a kind of title complex that contains the diimine of transition metal, and its structural formula is:
R in the formula
a, R
b, R
c, R
d, R
eAnd R
fIt respectively is identical or different alkyl; Mt is transition-metal Fe or Co; X is a halogen;
The b component is a kind of in the following material: (1) a kind of tetraalkyl aikyiaiurnirsoxan beta, its structural formula is
R in the formula
1, R
2, R
3, R
4Be identical or different alkyl; Or (2) load on above-mentioned tetraalkyl aikyiaiurnirsoxan beta the loading type tetraalkyl aikyiaiurnirsoxan beta that obtains on the inert solid carrier.
2. a kind of preparation according to claim 1 has catalyst of polyethylene bimodal and/or the broad peak molecular weight distribution, it is characterized in that, said tetraalkyl aikyiaiurnirsoxan beta consist of R
1R
2-Al-O-Al-R
3R
4, R in the formula
1, R
2, R
3, R
4Be selected from C
1-C
20Straight or branched alkane substituting group.
3. a kind of preparation according to claim 1 and 2 has catalyst of polyethylene bimodal and/or the broad peak molecular weight distribution, it is characterized in that, said tetraalkyl aikyiaiurnirsoxan beta is under the condition of standard anhydrous and oxygen-free, with one or more aluminum alkylss with mix as the alkane of solvent or aromatic hydrocarbon after, slowly drip water down at-178 ℃ to-20 ℃, after being added dropwise to complete, return to room temperature naturally, and at room temperature reacted 1-6 hour, remove then or be not prepared from except that desolvating.
4. a kind of preparation according to claim 3 has catalyst of polyethylene bimodal and/or the broad peak molecular weight distribution, it is characterized in that, the water of said dropping-78 ℃ to-50 ℃, be added dropwise to complete at 0.5-2 hour, the amount that adds entry is relevant with the amount of used aluminum alkyls, H
2The O/Al mol ratio is 1/2.
5. a kind of preparation according to claim 3 has catalyst of polyethylene bimodal and/or the broad peak molecular weight distribution, it is characterized in that, in the preparation process of said tetraalkyl aikyiaiurnirsoxan beta, when using two kinds of different aluminum alkylss, the mol ratio of two kinds of aluminum alkylss is 2/1-1/2.
6. a kind of preparation according to claim 1 has catalyst of polyethylene bimodal and/or the broad peak molecular weight distribution, it is characterized in that, said load tetraalkyl aikyiaiurnirsoxan beta is to prepare by following steps: in the toluene solution of 0.02-2M tetraalkyl aikyiaiurnirsoxan beta, add inert solid carrier, continuation 20-80 ℃ the reaction 0.5-4 hour after, obtain loading type tetraalkyl aikyiaiurnirsoxan beta after removing by filter liquid, drying under reduced pressure can obtain the loading type tetraalkyl aikyiaiurnirsoxan beta of white powder after washing.
7. a kind of preparation according to claim 6 has catalyst of polyethylene bimodal and/or the broad peak molecular weight distribution, it is characterized in that, the add-on of said inert solid carrier is that the solution of the tetraalkyl aikyiaiurnirsoxan beta of 1 mol is counted 0.2-4g with 200 ml aluminium content.
8. a kind of preparation according to claim 7 has catalyst of polyethylene bimodal and/or the broad peak molecular weight distribution, it is characterized in that, said inert solid carrier is porous silica gel, lamellated clay; Clay is inorganic polynite or through the aliphatic quaternary ammonium salt montmorillonite modified.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03129240 CN1253479C (en) | 2003-06-08 | 2003-06-08 | Catalyst for preparing polyethylene with double peak and/or broad peak molecular weight distribution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03129240 CN1253479C (en) | 2003-06-08 | 2003-06-08 | Catalyst for preparing polyethylene with double peak and/or broad peak molecular weight distribution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1470538A CN1470538A (en) | 2004-01-28 |
| CN1253479C true CN1253479C (en) | 2006-04-26 |
Family
ID=34153458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03129240 Expired - Fee Related CN1253479C (en) | 2003-06-08 | 2003-06-08 | Catalyst for preparing polyethylene with double peak and/or broad peak molecular weight distribution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1253479C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024708B (en) * | 2007-02-05 | 2012-07-18 | 中国科学院长春应用化学研究所 | Method for preparing broad-peak polythenel montmorillonite nano composite material using mixed catalyst |
| CN101613425B (en) * | 2009-07-21 | 2011-05-04 | 浙江大学 | Catalyst of polyethylene with double peak and/or broad peak molecular weight distribution |
-
2003
- 2003-06-08 CN CN 03129240 patent/CN1253479C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1470538A (en) | 2004-01-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1138597C (en) | Nickel diimine catalysts with methylalumoxane as cocatalyst, method of polymerization of olefins therewith and polymers produced | |
| CN1301271C (en) | Dual-site olefin polymerisation catalyst composition | |
| CN1727367A (en) | Catalyst system of ethane copolymerization in situ for producing linear polyethylene in low density | |
| CN1303399A (en) | Copolymerization of olefins | |
| CN1809596A (en) | Multi-catalyst system for olefin polymerization | |
| CN1292007C (en) | Bi active component polyolefin catalyst, and its preparing method and use | |
| CN1814627A (en) | Catalyst active constituent and catalyst containing same | |
| CN1253479C (en) | Catalyst for preparing polyethylene with double peak and/or broad peak molecular weight distribution | |
| CN1209387C (en) | Catalyst for preparing polyethylene possessing distribution of molecular weight with doublet and/or broad peak | |
| CN1172969C (en) | Titanium-nickel acetylacetonate composite catalyst for preparing branched polyethylene and its preparation method | |
| CN1966536A (en) | Spherical carrier loaded late transition metal catalyst and its preparing process | |
| CN1850872A (en) | Composite catalytic system for preparing wide/dual-peak distributed high density polyethylene | |
| CN1672793A (en) | Beta-diimide nickel compound/alkyl aluminium catalyst system and its application | |
| CN1288175C (en) | Catalyst for olefin high-temperature polymerization and preparation and use thereof | |
| CN1164625C (en) | High molecular 'after cyclopentadiene' alpha-diimine nickel base olefine polymerization catlayst | |
| CN1271094C (en) | Loading type bifunctional calulyst system and its preparation method and application | |
| CN1342717A (en) | Process for preparing long-chain branched polyethylene elastomer | |
| CN1115348C (en) | Polyolefin catalyst containing azabenzene in ligand and its preparing process and application | |
| CN1421467A (en) | In-situ copolymerization catalyst system for preparing linear low-density polyethylene | |
| CN1119356C (en) | Heat treatment of Ziegler-Natta catalysts | |
| CN102675496B (en) | A kind of method preparing class ball-type double peak weight distributing polyethylene | |
| CN1871263A (en) | Ziegler-natta catalyst for olefin polymerization including aryloxy group and method for polymerization of olefin using the same | |
| CN1871262A (en) | Ethylene polymerization employing bis-imino pyridinyl transition metal catalyst components | |
| CN1194020C (en) | Ti-Ni-SiCl4 composite catalyst for preparing branched polyvinyl and preparation thereof | |
| CN100376604C (en) | Olefin polymerization catalyst and its uses |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060426 |