CN1129614C - Carried post-transition metal catalyst and its prepn. and application - Google Patents
Carried post-transition metal catalyst and its prepn. and application Download PDFInfo
- Publication number
- CN1129614C CN1129614C CN 01118568 CN01118568A CN1129614C CN 1129614 C CN1129614 C CN 1129614C CN 01118568 CN01118568 CN 01118568 CN 01118568 A CN01118568 A CN 01118568A CN 1129614 C CN1129614 C CN 1129614C
- Authority
- CN
- China
- Prior art keywords
- transition metal
- metal catalyst
- inert support
- carried post
- carried
- 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
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention discloses a carried post transition metal catalyst. The present invention is composed of the following components by weight portion: 0.05 to 0.5 of post transition metal olefin polymerization catalyst I, 1.75 to 40 of aluminum alkyl or oxygen-aluminium alkyl alkane, and 100 of inert carrier. The present invention also discloses a preparation method of the carried post transition metal catalyst and the application of the carried post transition metal catalyst on catalyzing ethylene polymerization. The carried catalyst of the present invention and cocatalysts, such as oxygen-aluminium alkyl alkane, aluminum alkyl, etc., form a catalyst system. The catalyst system catalyzes the ethylene polymerization and has high catalytic activity which is generally 10<5>gPE. mol<minus1> Fe. h<minus1>.
Description
The present invention relates to a kind of carried post-transition metal catalyst and preparation method thereof and in catalyzed ethylene polymerization, use.
In recent years, after metallocene catalyst, late transition metal catalyst for olefin polymerization has caused polyolefine scientist's very big interest (J.Am.Chem.Soc., 1995,117:6414～6415; J.Am.Chem.Soc., 1998,120:4049～4050; Chem.Commum., 1998,849～850; Chem.Rev., 2000,100:1169).The same with metallocene catalyst, late transition metal catalyst for olefin polymerization belongs to the catalyst system at single-activity center, its catalytic activity matches in excellence or beauty with metallocene catalyst in many aspects, and kept that polymer architecture in the metallocene catalyst system is controlled, the molecular weight of polymkeric substance and the degree of branching can regulate and advantage such as control, realize the molecule of polymkeric substance is cut out.In addition, a little less than the oxytropism of its catalyzer, help the copolymerization of catalysis polar monomer and alkene, be expected to produce the functional polyolefin material of excellent performance, thereby late transition metal catalyst for olefin polymerization has higher prospects for commercial application.Experience according to the metallocene calalyst for polymerization of olefine industrial applications, very necessary (the Chem Rev of the carrierization of homogeneous catalyst, 2000,100:1347 Chem Rev, 2000,100:1377), supported catalysts helps the form of controlling polymers, suppress sticking still phenomenon, make it be suitable for industrial vapour phase polymerization commonly used and slurry polymerization.In addition, can use a spot of promotor MAO can reach maximum catalytic activity, reduce the cost of catalyst system.At present, the load research to late transition metal catalyst for olefin polymerization still is not reported.
The object of the present invention is to provide a kind of carried post-transition metal catalyst, late transition metal catalyst is carried on SiO
2, MgCl
2, Al
2O
3On inert support.
Another object of the present invention is to provide a kind of method for making of carried post-transition metal catalyst.
The present invention also aims to provide a kind of carried post-transition metal catalyst to use in catalyzed ethylene polymerization, promotors such as supported catalysts of the present invention and alkylaluminoxane, aluminum alkyls are formed catalyst system, catalyzed ethylene polymerization.
A kind of carried post-transition metal catalyst of the present invention, in weight part, form by following component and content:
Late transition metal catalyst for olefin polymerization I 0.05～0.5
Aluminum alkyls or alkylaluminoxane 1.75～40
Inert support 100
Described late transition metal catalyst for olefin polymerization I structure is:
R
1, R
2, R
3, R
4For-H ,-CH
3,-C
2H
5,-CH (CH
3)
2X is-Cl ,-Br
Described alkylaluminoxane or aluminum alkyls are methylaluminoxane (MAO), ethyl aikyiaiurnirsoxan beta (EAO), trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride etc., and the best is a methylaluminoxane.
Described inert support is SiO
2, MgCl
2, Al
2O
3Deng, the best is SiO
2
The preparation of late transition metal catalyst for olefin polymerization I of the present invention is with 2,6-diacetyl pyridine and 2, and the 6-xylidine, 2, the 6-diisopropyl aniline, the 2-isopropyl aniline obtains symmetry or unsymmetrical structure part through a step or two-step reaction; React in tetrahydrofuran (THF) with ferrous salt then and obtain polymerizing catalyst.
The method for making of a kind of carried post-transition metal catalyst of the present invention follows these steps to carry out:
1 with inert support roasting 6～12 hours under 200 ℃～600 ℃ high temperature, vacuumizes 2～4 hours under 110 ℃～200 ℃ then.
2 usefulness alkylaluminoxanes or aluminum alkyls and in the toluene of inert support that step 1 is handled at dehydration and deoxidation, 30～80 ℃ of following stirring reactions 6～12 hours, described alkylaluminoxane or aluminum alkyls/inert support are 4.2～42mmol/g; Toluene/the inert support of described dehydration and deoxidation is preferably 10～50ml/g.
3 with step 2 reaction product with toluene wash for several times, and vacuum is drained, and preserves under noble gas.
The carrierization of 4 catalyzer: with late transition metal catalyst for olefin polymerization I and the inert support of handling through step 3 30～80 ℃ of following stirring reactions 6～12 hours in toluene solution, described toluene/inert support is preferably 10～50ml/g.Then toluene wash for several times, till supernatant liquid becomes colorless.Vacuum is drained, and preserves under noble gas; Described late transition metal catalyst for olefin polymerization I/ inert support is 0.01～1g/g.
A kind of carried post-transition metal catalyst of the present invention is used in catalyzed ethylene polymerization, promotor is alkylaluminoxane or aluminum alkyls, as methylaluminoxane (MAO), ethyl aikyiaiurnirsoxan beta (EAO), trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride etc., the best is methylaluminoxane or triethyl aluminum; Described carried post-transition metal catalyst consumption is 10～400 μ mol/L, and the best is 40～200 μ mol/L; The Al/Fe mol ratio is 50～3000, and the best is 100～2000; Temperature of reaction is-10 ℃～80 ℃, and the best is 20 ℃～60 ℃.
Carried post-transition metal catalyst of the present invention has following characteristics:
1. the iron catalyst for olefine polymerization that catalyzer of the present invention is symmetry or unsymmetrical structure.
2. the catalytic activity height is generally 10
5GPEmol
-1Feh
-1
3. when carried catalyst of the present invention was used for vinyl polymerization, the polymericular weight of generation was 10,000～300,000, and melting range is at 131.5 ℃～135.6 ℃, and the degree of crystallinity scope is 55.1%～78.9%.
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1.1. Preparation of catalysts
In being housed, the 100mLSchlenk bottle that stirs magneton adds 1.0000g (6.13mmol) 2; 6-diacetyl pyridine; under argon shield, the device injection 14.9196g (24.52mmol that stirs magneton is housed with being injected at; 4equiv.) 2; the 6-diisopropyl aniline; 80mL anhydrous methanol and 0.2mL formic acid reacted 48 hours down at 60 ℃.Cooling is filtered, and obtains yellow powder shape product with the cold methanol washing.Dry back to remove single imines by product, obtains pale yellow powder shape part with Virahol extracting 24 hours.
A certain amount of part of weighing (1.05equiv.) places the 20mLSchlenk bottle that magnetic stir bar is housed, and adds FeCl
24H
2O (1.00equiv.).Vacuumize logical argon gas three times, under argon shield, inject 10mL exsiccant tetrahydrofuran (THF), reacted 2 hours down at 25 ℃.After reaction finishes, add the 5mL Skellysolve A, filter then, use Skellysolve A, the anhydrous diethyl ether washing, vacuum-drying at normal temperatures obtains catalyst I a.2. the preparation of supported catalyst
With 1gSiO
2400 ℃ of following roastings 6 hours, then under vacuum 200 ℃ handled 2 hours.Be cooled to room temperature, add 10mLMAO (1.4mol/L toluene solution) and 10mL toluene, 50 ℃ were reacted 12 hours down.With toluene wash for several times, vacuum is drained, and preserves standby under noble gas.0.05g catalyst I a is joined in the above-mentioned system, add 20mL toluene again, stirred 12 hours down at 60 ℃.With toluene wash for several times, till supernatant liquid becomes colorless.Vacuum is drained, and preserves standby under noble gas.3. vinyl polymerization
Exsiccant 250mL three-necked bottle is vacuumized, replaces repeatedly with argon gas, and with the ethene displacement once, the maintenance pressure of the inside of a bottle is 770mmHg.Oil bath is warming up to 50 ℃.
Inject the toluene of 50mL with syringe, start stirring through dehydration and deoxidation.Inject promotor methylaluminoxane 0.71mL with syringe earlier, stir 5min, add the supported catalyst of 2 μ mol then.The AL/Fe ratio is 500.
Polyase 13 0min adds 10% ethanol solution hydrochloride termination reaction, with 95% washing with alcohol polymkeric substance, 60 ℃ of following vacuum-dryings.Operational condition and polymerization property are listed in the table 1.
Embodiment 2.1. Preparation of catalysts
Preparation with embodiment 12. supported catalysts
With 1gSiO
2300 ℃ of following roastings 6 hours, then under vacuum 200 ℃ handled 4 hours.Be cooled to room temperature, add 10mLMAO (1.4mol/L toluene solution) and 10mL toluene, 50 ℃ were reacted 12 hours down.With toluene wash for several times, vacuum is drained, and preserves standby under noble gas.0.05g catalyst I a is joined in the above-mentioned system 40 ℃ of following stirrings 10 hours.With toluene wash for several times, till supernatant liquid becomes colorless.Vacuum is drained, and preserves standby under noble gas.3. vinyl polymerization
Supported catalyst consumption 7.16 μ mol, the Al/Fe ratio is 1250, polymeric reaction temperature is 40 ℃.Other condition is with embodiment 1.Embodiment 3.1. Preparation of catalysts
In being housed, the 100mLSchlenk bottle that stirs magneton adds 1.0000g (6.13mmol) 2; 6-diacetyl pyridine; under argon shield, the device injection 24.3361g (49.04mmol that stirs magneton is housed with being injected at; 8equiv.) 2; the 6-xylidine; 80mL anhydrous methanol and 0.2mL formic acid reacted 48 hours down at 60 ℃.Cooling is filtered, and obtains yellow powder shape product with the cold methanol washing.Dry back to remove the diimine by product, obtains pale yellow powder shape intermediate with Virahol extracting 24 hours.
A certain amount of part of weighing (1.05equiv.) places the 20mLSchlenk bottle that magnetic stir bar is housed, and adds FeCl
24H
2O (1.00equiv.).Vacuumize logical argon gas three times, under argon shield, inject 10mL exsiccant tetrahydrofuran (THF), reacted 2 hours down at 25 ℃.After reaction finishes, add the 5mL Skellysolve A, filter then, use Skellysolve A, the anhydrous diethyl ether washing, vacuum-drying at normal temperatures obtains catalyst I b.2. the preparation of supported catalyst
Catalyzer is Ib.Other condition is with embodiment 13. vinyl polymerizations
Supported catalyst consumption 2 μ mol, the Al/Fe ratio is 100, polymeric reaction temperature is 40 ℃.
Other condition is with embodiment 1.
Embodiment 4.1. Preparation of catalysts
In being housed, the 100mLSchlenk bottle that stirs magneton adds 1.0000g (6.13mmol) 2; 6-diacetyl pyridine; under argon shield, the device injection 1.233g (6.40mmol that stirs magneton is housed with being injected at; 1.05equiv.) 2; the 6-diisopropyl aniline; 80mL anhydrous methanol and 0.2mL formic acid reacted 48 hours down at 60 ℃.Cooling is filtered, and obtains yellow powder shape product with the cold methanol washing.Dry back to remove the diimine by product, obtains pale yellow powder shape intermediate with Virahol extracting 24 hours.
In being housed, the 20mLSchlenk bottle that stirs magneton adds the above-mentioned intermediate of 0.1500g (0.465mmol); under argon shield, inject 0.25g (1.86mmol with syringe; 4equiv) 2-isopropyl aniline, 10mL Virahol and 0.1mL formic acid, reaction is 48 hours under reflux temperature.Reaction system is cooled to room temperature, filters,, filter once more,, obtain yellow powder shape part after the vacuum-drying with cold washed with isopropyl alcohol with the freezing solid that obtains of filtrate.
A certain amount of part of weighing (1.05equiv.) places the 20mLSchlenk bottle that magnetic stir bar is housed, and adds FeCl
24H
2O (1.00equiv.).Vacuumize logical argon gas three times, under argon shield, inject 10mL exsiccant tetrahydrofuran (THF), reacted 2 hours down at 25 ℃.After reaction finishes, add the 5mL Skellysolve A, filter then, use Skellysolve A, the anhydrous diethyl ether washing, vacuum-drying at normal temperatures obtains catalyst I c.2. the preparation of supported catalyst
Catalyst I c.Other condition is with embodiment 1.3. vinyl polymerization supported catalyst consumption 5.29 μ mol, the Al/Fe ratio is 1000, polymeric reaction temperature is 40 ℃.Other condition is with embodiment 1.
Embodiment 5.1. Preparation of catalysts
With embodiment 1.2. the preparation of supported catalyst
With embodiment 2.3. vinyl polymerization
The supported catalyst consumption is 7.16 μ mol, and promotor is AlEt
3, the Al/Fe ratio is 750, polymeric reaction temperature is 40 ℃.Other condition is with embodiment 2.
Embodiment 6.1. Preparation of catalysts
With embodiment 1.2. the preparation of supported catalyst
Carrier is MgCl
2Other condition is with embodiment 1.3. vinyl polymerization
The supported catalyst consumption is 2 μ mol, and the Al/Fe ratio is 500.Other condition is with embodiment 1.
Embodiment 7.1. Preparation of catalysts
With embodiment 3.2. the preparation of supported catalyst
Carrier is Al
2O
3Catalyzer is Ib.Other condition is with embodiment 1.3. vinyl polymerization
The supported catalyst consumption is 2 μ mol, and promotor is AlEt
3, the Al/Fe ratio is 500, polymeric reaction temperature is 40 ℃.Other condition is with embodiment 1.
Embodiment 8.1. Preparation of catalysts
With embodiment 3.2. the preparation of supported catalyst
Use 10mLAlEt
3(1.8mol/L toluene solution) and baked SiO
2Reaction adds 15mL toluene.Catalyzer is Ib.Other condition is with embodiment 1.3. vinyl polymerization
The supported catalyst consumption is 2 μ mol, and promotor is AlEt
3, the Al/Fe ratio is 500, polymeric reaction temperature is 60 ℃.Other condition is with embodiment 1.
Polymerizing condition among table 1. embodiment and aggregated data
Catalyzer and molecular crystal
Help and urge the active * fusing point of Al/Fe temperature embodiment carrier concn to measure
Change agent than (℃) (10
5) (℃)
(μ mol/L) (10
4) (%) embodiment 1 SiO
2Ia, 40 MAO, 500 50 9.34 8.15 135.2 60.8 embodiment, 2 SiO
2Ia, 143.2 MAO, 1,250 40 5.28 6.95 132.2 77.8 embodiment, 3 SiO
2Ib, 40 MAO, 1,000 40 5.06 4.33 133.0 78.9 embodiment, 4 SiO
2Ic, 105.8 MAO, 1,000 40 4.46 3.78 132.5 74.6 embodiment, 5 SiO
2Ia, 143.2 AlEt
3750 40 1.59 1.39 133.4 56.0 embodiment, 6 MgCl
2Ia, 40 MAO, 500 50 2.53 3.22 134.6 55.1 embodiment, 7 Al
2O
3Ib, 40 AlEt
3500 40 2.72 4.56 135.6 64.6 embodiment, 8 SiO
2Ib, 40 AlEt
3500 60 1.06 1.55 131.5 58.3
* activity unit is gPEmol
-1Feh
-1
Claims (10)
1. carried post-transition metal catalyst, in weight part, form by following component and content:
Late transition metal catalyst for olefin polymerization I 0.05～0.5
Aluminum alkyls or alkylaluminoxane 1.75～40
Inert support 100
Described late transition metal catalyst for olefin polymerization I structure is:
R
1, R
2, R
3, R
4For-H ,-CH
3,-C
2H
5,-CH (CH
3)
2X is-Cl ,-Br
2. according to a kind of carried post-transition metal catalyst of claim 1, it is characterized in that: described alkylaluminoxane or aluminum alkyls are methylaluminoxane, ethyl aikyiaiurnirsoxan beta, trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride; Described inert support is SiO
2, MgCl
2, Al
2O
3
3. according to a kind of carried post-transition metal catalyst of claim 1, it is characterized in that: described alkylaluminoxane or aluminum alkyls are methylaluminoxane; Described inert support is SiO
2
4. the method for making of a carried post-transition metal catalyst follows these steps to carry out:
1 with inert support roasting 6～12 hours under 200 ℃～600 ℃ high temperature, vacuumizes 2～4 hours under 110 ℃～200 ℃ then;
2 usefulness alkylaluminoxanes or aluminum alkyls and in the toluene of inert support that step 1 is handled at dehydration and deoxidation, 30～80 ℃ of following stirring reactions 6～12 hours, described alkylaluminoxane or aluminum alkyls/inert support are 4.2～42mmol/g;
3 with step 2 reaction product with toluene wash for several times, and vacuum is drained, and preserves under noble gas;
The carrierization of 4 catalyzer: with late transition metal catalyst for olefin polymerization I and the inert support of handling through step 3 30～80 ℃ of following stirring reactions 6～12 hours in toluene solution; Then toluene wash for several times, till supernatant liquid becomes colorless; Vacuum is drained, and preserves under noble gas; Described late transition metal catalyst for olefin polymerization I/ inert support is 0.01～1g/g; Described late transition metal catalyst for olefin polymerization I structure is:
R
1, R
2, R
3, R
4For-H ,-CH
3,-C
2H
5,-CH (CH
3)
2X is-Cl ,-Br
5. according to the method for making of a kind of carried post-transition metal catalyst of claim 4, it is characterized in that: described alkylaluminoxane or aluminum alkyls are methylaluminoxane, ethyl aikyiaiurnirsoxan beta, trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride; Described inert support is SiO
2, MgCl
2, Al
2O
3
6. according to the method for making of a kind of carried post-transition metal catalyst of claim 4, it is characterized in that: described alkylaluminoxane or aluminum alkyls are methylaluminoxane; Described inert support is SiO
2
7. according to the method for making of claim 4,5, a kind of carried post-transition metal catalyst of 6, it is characterized in that: the toluene/inert support of the described dehydration and deoxidation of step 2 is 10～50ml/g; Toluene/the inert support of the described dehydration and deoxidation of step 4 is 10～50ml/g.
8. a carried post-transition metal catalyst is used in catalyzed ethylene polymerization, it is characterized in that: promotor is alkylaluminoxane or aluminum alkyls; Described carried post-transition metal catalyst consumption is at 10～400 μ mol/L; The Al/Fe mol ratio is 50～3000; Temperature of reaction is-10 ℃～80 ℃.
9. a kind of carried post-transition metal catalyst is according to Claim 8 used in catalyzed ethylene polymerization, it is characterized in that: promotor is methylaluminoxane, ethyl aikyiaiurnirsoxan beta, trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride.
According to Claim 8 or a kind of carried post-transition metal catalyst of 9 in catalyzed ethylene polymerization, use, it is characterized in that: promotor is methylaluminoxane or triethyl aluminum; Described carried post-transition metal catalyst consumption is 40～200 μ mol/L; The Al/Fe mol ratio is 100～2000; Temperature of reaction is 20 ℃～60 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01118568 CN1129614C (en) | 2001-06-04 | 2001-06-04 | Carried post-transition metal catalyst and its prepn. and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01118568 CN1129614C (en) | 2001-06-04 | 2001-06-04 | Carried post-transition metal catalyst and its prepn. and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1389479A CN1389479A (en) | 2003-01-08 |
| CN1129614C true CN1129614C (en) | 2003-12-03 |
Family
ID=4663276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01118568 Expired - Fee Related CN1129614C (en) | 2001-06-04 | 2001-06-04 | Carried post-transition metal catalyst and its prepn. and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1129614C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7175803B2 (en) * | 2019-03-11 | 2022-11-21 | 三井化学株式会社 | Method for producing olefin polymer and catalyst solution for olefin polymer |
-
2001
- 2001-06-04 CN CN 01118568 patent/CN1129614C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1389479A (en) | 2003-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2018503509A (en) | Olefin oligomerization catalyst system and olefin oligomerization method using the same | |
| CN102453154B (en) | Organic chromium catalyst for ethylene polymerization and preparation method thereof | |
| CN113004441A (en) | Iron catalyst and application thereof in preparation of norbornene and ethylidene norbornene copolymer | |
| CN1136242C (en) | Catalyzing system for preparing branched polyolefine | |
| CN111116801B (en) | Preparation method of olefin-unsaturated carboxylic acid copolymer | |
| CN112778350B (en) | [ OONN ] tetradentate fourth subgroup metal complex, preparation method and application | |
| CN1129614C (en) | Carried post-transition metal catalyst and its prepn. and application | |
| CN1259347C (en) | Carried catalyzer for olefinic polymerization and preparation method | |
| CN1172969C (en) | Titanium-nickel acetylacetonate composite catalyst for preparing branched polyethylene and its preparation method | |
| CN111689997B (en) | Metal complex, preparation method and application thereof | |
| CN1273502C (en) | Multinuclear acenaphthene diimine nickle catalyst for synthesis of branched polyethylene | |
| CN1169851C (en) | Ethylene polymerizing titanium-nickel-salicy-alimine composite catalyst and its preparing method | |
| CN1263778C (en) | 4-vinylpyridine homopolymerized and ethylene copolymerized acenaphthenyl diimido nickel catalyst and the prepn process | |
| CN1306013A (en) | Process for preparing unsymmetric 'after-cyclopentadiene' catalyst for polymerization of high-molecular olefine | |
| CN1194020C (en) | Ti-Ni-SiCl4 composite catalyst for preparing branched polyvinyl and preparation thereof | |
| CN1172968C (en) | Branched polyethylene preparing titanium-nickel composite catalyst and its preparing method | |
| CN1560092A (en) | Composite catalist of titanium substitued nickle acenaphthene diimine of synthesizing branched polyvinyl and its preparation process | |
| CN1352203A (en) | High molecular 'after cyclopentadiene' alpha-diimine nickel base olefine polymerization catlayst | |
| CN1197883C (en) | Polor monomer homopolymerization and copolymerization titanium-substituted beta-dione-cobalt acetylacetonate composite catalyst and its preparing method | |
| CN115703849B (en) | Supported double-center catalyst and preparation method and application thereof | |
| CN112745425B (en) | Process for preparing olefin-olefin alcohol copolymers | |
| CN1163524C (en) | Composite Ti-Ni catalyst for oligomerization and copolymerization of ethylene and its preparing process | |
| CN115260356B (en) | Method for preparing olefin-unsaturated carboxylic ester copolymer, olefin-unsaturated carboxylic ester copolymer and application | |
| CN100344656C (en) | Process for preparation of polynorbornene | |
| CN1556118A (en) | Preparation method of composite carrier catalyst used for olefine polymerized lamellar silicate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| 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 | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |