CN1814628A - Improved catalyst system for ethylene polymerization or ethylene and alpha-olefin copolymerization - Google Patents

Improved catalyst system for ethylene polymerization or ethylene and alpha-olefin copolymerization Download PDF

Info

Publication number
CN1814628A
CN1814628A CN 200610049624 CN200610049624A CN1814628A CN 1814628 A CN1814628 A CN 1814628A CN 200610049624 CN200610049624 CN 200610049624 CN 200610049624 A CN200610049624 A CN 200610049624A CN 1814628 A CN1814628 A CN 1814628A
Authority
CN
China
Prior art keywords
catalyst
chromium
loaded catalyst
catalyst system
chromic oxide
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
Application number
CN 200610049624
Other languages
Chinese (zh)
Other versions
CN100400553C (en
Inventor
阳永荣
黄杏冰
王靖岱
蒋斌波
杨宝柱
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Zhejiang University ZJU
Original Assignee
China Petroleum and Chemical Corp
Zhejiang University ZJU
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Zhejiang University ZJU filed Critical China Petroleum and Chemical Corp
Priority to CNB2006100496248A priority Critical patent/CN100400553C/en
Publication of CN1814628A publication Critical patent/CN1814628A/en
Application granted granted Critical
Publication of CN100400553C publication Critical patent/CN100400553C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

This invention discloses an improved catalyst system used in ethene polymerization or copolymerization of ethene with alpha-olefin characterizing that said catalyst system includes: a, Cr loaded catalyst or a mixed system of Cr loaded catalyst and CrO loaded catalyst, b, a dispersing solvent, which may be mineral oil. This invented catalyst can prevent the catalyst from caking due to overheat at the beginning of the reaction and eliminate static of the Cr catalyst.

Description

A kind of improved catalyst system that is used for vinyl polymerization or ethene and alpha-olefin copolymer
Technical field
The present invention relates to a kind of catalyzer, in particular for the improved catalyst system of vinyl polymerization or ethene and alpha-olefin copolymer.
Background technology
United States Patent (USP) 2825721 disclosed chromic oxide (the logical CrO that refers to 3) loaded catalyst, also being referred to as the Phillips catalyzer is the polyethylene field catalyst type of exploitation early.Utilize the aqueous solution or the organic solvent solution impregnated carrier of the compound of chromium such as chromium trioxide, through super-dry, roasting chromium cpd is converted into chromium trioxide, thereby finally forms the chromic oxide loaded catalyst.Chromic oxide loaded catalyst synthetic molecular weight of polyethylene height, molecular weight distribution is wide, and a spot of long-chain branch is arranged on the molecular chain, so resin has good processing properties again when having good physicals.But because the chromic oxide loaded catalyst has a process that is reduced into divalence chromium active centre in polymerization process, the inductive phase that has a very long almost non-activity when making the catalyst vinyl polymerization, make the chromic oxide loaded catalyst drive or trade mark handoff procedure in operational difficulty, even may cause the reactor temperature runaway because having added too much catalyzer.And because the existence of the inductive phase of very long almost non-activity, the chromic oxide loaded catalyst can not shorten the residence time, therefore can not adopt United States Patent (USP) 4543399,4588790 and the condensation mode of 5352749,5405922 gas-phase polyethylenes of announcing and the operating method that supercool coagulates pattern.United States Patent (USP) 3780011,3887494,4806513,4877763 by add other components for example the method for the compound of aluminium, titanium, zinc, boron, phosphorus etc. shorten inductive phase, and improve catalyst performance, but can not eliminate inductive phase by the compound that adds these elements.
Fubini etc. (Fubini B, Ghiotti G, Stradella L, et al.[J] .J.Catal., 1980,66:200~213) find, contain Cr (the VI)/SiO of chromium 1% 2, with after the CO reduction, chromous content is up to 98% under 623K.Chromium-based catalysts after the CO reduction and very fast formation active centre after ethene contacts.McDaniel (McDanie M P.[J] .Adv.Catal., 1985,33:47~98) discovers, through the vinyl polymerization behavior of CO reductive chromium-based catalysts with unreduced be very much similar, and the performance of product is about the same.
United States Patent (USP) 4247421,4735931,4966951,5208309,5274056,5284926,6255413 have announced different divalence chromium loaded catalysts, are used to produce the polymkeric substance of different performance.But this catalyzer initial reaction rate is too fast, and initial activity is too high behind the adding reactor, and reaction is difficult to control.
The investigator utilizes the chromium and the chromic oxide load altogether of other types, and perhaps other chrome catalysts and chromic oxide mix, and reach the purpose of improving kinetics or improving polymer performance.United States Patent (USP) 4325839,4369295 on activatory chromic oxide loaded catalyst basis the luxuriant chromium cpd of load with quick starting characteristic again, United States Patent (USP) 5034364 usefulness silane chromate esters and chromic oxide load on identical carrier together, obtain a kind of mixing chrome catalysts, above-mentioned two patents all are to utilize to mix two kinds of different dynamic characteristic chrome catalysts, reach and improve dynamic (dynamical) purpose.United States Patent (USP) 5198400 and continuity patent 5310834 thereof have been announced a kind of mixed catalyst, a kind of component is a chromic oxide, and contain the compound of aluminium, phosphorus etc., another component is a chromium acetate, United States Patent (USP) 5169816 has been announced a kind of organic chromium mixed catalyst, and above-mentioned three patents all are to utilize the different polymerization properties of two kinds of components to produce high performance polymer.
Too high in order to solve the metallocene catalyst initial activity, reactor is the problem of caking easily, and United States Patent (USP) 5317036 and 5693727 has been announced the not process and the method for the metallocene catalyst introducing polymerization reactor of load.United States Patent (USP) 6069213 has been announced the mixed system that the metallocene catalyst of the metallocene of load and not load is formed.
United States Patent (USP) 6846886 announced a kind of in polymerization process, prepare continuously carried catalyst and not supported catalyst solution composition mixed system introduce the method for polymerization reactor then.
International Application No. WO 2004094489 has been announced two types slurry catalyst, a kind of is single slurry catalyst system of planting supported chrome catalysts (chromic oxide or silane chrome catalysts) and mineral oil composition, and another kind is the slurry catalyst system that chromic oxide loaded catalyst and silane type chrome catalysts are formed dual catalyst and mineral oil composition.In the slurry catalyst system of above-mentioned patent, all do not relate to divalence chromium loading type slurry system, and the slurry system of chromic oxide loading type and divalence chromium loading type mixed catalyst.
Summary of the invention
The present invention is directed to being difficult to that divalence chromium loaded catalyst or chromic oxide and divalence chromium loaded catalyst mixed catalyst exist preserve, static is many, initial activity is high and shortcoming such as easy caking, has developed divalence chromium loaded catalyst or the chromic oxide and the divalence chromium loaded catalyst mixed catalyst slurry system of vinyl polymerization and ethene and a-olefin-copolymerization.
The invention provides the improved catalyst system of vinyl polymerization or ethene and a-olefin-copolymerization, comprise
A) mixed system of divalence chromium loaded catalyst or divalence chromium loaded catalyst and chromic oxide loaded catalyst; B) dispersion solvent.
Described dispersion solvent can be a mineral oil.
Solid content is 0.1~25% in the described catalyst system.
Catalyst system of the present invention can polymerising ethylene, also can be ethene and other a-olefin-copolymerizations, and a-alkene is specially propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, one or several in 1-nonene and the 1-decene.
In the mixed system of described divalence chromium loaded catalyst and chromic oxide loaded catalyst, the chromic oxide loaded catalyst with and divalence chromium loaded catalyst weight ratio be 0.01~10, be preferably 0.02~1.
The chromic oxide loaded catalyst can adopt United States Patent (USP) 2825721 disclosed chromic oxide loaded catalysts, also can adopt United States Patent (USP) 3780011,3887494,4806513,4877763 announce pass through for example chromic oxide loaded catalyst of the compound of aluminium, titanium, zinc, boron, phosphorus, fluorine etc. of other components of interpolation.The weight content that the interpolation element accounts for the chromic oxide loaded catalyst is 0.2~5%.
Divalence chromium loaded catalyst can adopt United States Patent (USP) 4247421,4735931,4966951,5208309,5274056,5284926, the 6255413 various divalence chromium loaded catalysts of being announced.
In the catalyst system, chromic oxide loaded catalyst and divalence chromium loaded catalyst can be same vehicle, also can be different carriers, for example, all are with a kind of silica gel (SiO 2), perhaps different model silica gel, perhaps a kind of is silica gel (SiO 2), a kind of is aluminum phosphate (AlPO 4).
In the catalyst system, the content of chromium is 0.1~5% in the chromic oxide loaded catalyst, and the content of chromium is 0.1~2% in the divalence chromium loaded catalyst.
Catalyst system of the present invention can prevent that the initial reaction stage granules of catalyst from luming because of overheated, and can eliminate the electrostatic problem of chromium loaded catalyst, and can be at United States Patent (USP) 4543399,4588790 and 5352749, the condensation mode of 5405922 gas-phase polyethylenes of announcing and supercool coagulate under the pattern to be operated, and improves the space-time yield of production equipment greatly
Embodiment
Embodiment 1
1. the preparation of divalence chromium supported catalyst
1. the preparation of chromic oxide loaded catalyst:
1) silica gel is predrying.With N 2Be fluidized gas, in activator, Davison957 silica gel (chromium that contains 0.18~0.30wt%) is heated to 150 ℃ predrying, behind 150 ℃ of following constant temperature 4hr, stop heating, continue logical N 2, silica gel transferred to after being cooled to 100 ℃ and blows jar;
2) silica gel titanizing.Deliver to catalyst make up tank after silica gel after predrying accurately weighed, add iso-pentane (6.64L iso-pentane/kg SiO 2), by chuck slurries are heated to 55 ℃ after, with tetraisopropoxy titanium ((C 3H 7O) 4Ti) add Preparation tank, the add-on of tetraisopropoxy titanium is that to make the weight content of Ti be 3.5~4.5%, 55 ℃ stir 2hr after.Heating slurry to 100 ℃, iso-pentane is removed in flash distillation;
3) silica gel activating.Titanizing silica gel is delivered to activator from Preparation tank, and use N 2Make fluidized gas.Heating rate with 50 ℃/hr is heated to 325 ℃ then, behind 325 ℃ of constant temperature 2hr, with fluidized gas from N 2Switch to air, the temperature rise rate with 100 ℃/hr is warmed up to 825 ℃ then, and at 825 ℃ of constant temperature 4hr;
4) CO reduction.Fluidized gas is switched to N from air 2, wait catalyzer to be cooled to 350 ℃, with fluidized gas from N 2Switch to CO and N 2Gas mixture, and at 350 ℃ of constant temperature 2hr;
5) catalyzer cooling.Stop heating, fluidized gas is switched to N from gas mixture 2, be cooled to 100 ℃ always, obtain divalence chromium loaded catalyst.
2. catalyst preparation
Catalyzer dispersion solvent mineral oil, solid content are 4.5%.
3. polymerization
In the gas-phase fluidized-bed reactor of a pilot scale level, produce the multipolymer of ethene and 1-butylene.The reactor controlling level is 2.4m, the heavy 125kg of seed bed, superficial gas velocity 0.65m/s, circulation gas flow 7.0t/hr.The reactor hourly output is 25kg/hr, and the space-time yield of reactor is 74.5kgPE/hrm 3Polymerizing condition and polyethylene product characteristic see Table 1.
Embodiment 2
The preparation of divalence chromium supported catalyst and catalyst formulation are with embodiment 1.
In the gas-phase fluidized-bed reactor of a pilot scale level, under the frozen state pattern, produce the multipolymer of ethene and 1-butylene, reactor device controlling level is 2.4m, the heavy 125kg of seed bed, superficial gas velocity 0.65m/s, circulation gas flow 7.0t/hr.The reactor hourly output is 35kg/hr, and the space-time yield of reactor is 104kg PE/hrm3.
Polymerizing condition and polyethylene product characteristic see Table 1
Embodiment 3
1. the preparation of chromic oxide loaded catalyst:
1) silica gel dipping.Chromium trioxide aqueous solution dip loading Davison955 silica gel, the concentration of chromium make that the weight content of chromium is 0.3% after the load;
2) silica gel is predrying.With N 2Be fluidized gas, the silica gel after in activator, will flooding be heated to 150 ℃ predrying, behind 150 ℃ of following constant temperature 4hr, stop heating, continue logical N 2, silica gel transferred to after being cooled to 100 ℃ and blows jar;
3) silica gel titanizing.Deliver to catalyst make up tank after silica gel after predrying accurately weighed, add iso-pentane (6.64L iso-pentane/kg SiO 2), by chuck slurries are heated to 55 ℃ after, with tetraisopropoxy titanium ((C 3H 7O) 4Ti) add Preparation tank, the add-on of tetraisopropoxy titanium is that to make the weight content of Ti be 3.5~4.5%, 55 ℃ stir 2hr after.Heating slurry to 100 ℃, iso-pentane is removed in flash distillation;
4) silica gel is fluoridized and is activated.Be lower than in the activator temperature under 100 ℃ the situation, titanizing silica gel is delivered to activator from Preparation tank, add hexafluorosilicic acid amine salt ((NH 4) 2SiF 6) (3g hexafluorosilicic acid amine salt/kg SiO 2) to activator, use N 2Make fluidized gas.Heating rate with 50 ℃/hr is heated to 325 ℃, behind 325 ℃ of constant temperature 2hr, with fluidized gas from N 2Switch to air, the temperature rise rate with 100 ℃/hr is warmed up to 825 ℃ then, and at 825 ℃ of constant temperature 4hr;
5) catalyzer cooling.Stop heating, continue blowing air, wait catalyzer to be cooled to 325 ℃, air is switched to N 2, be cooled to 100 ℃ always, obtain the chromic oxide loaded catalyst.
2. the preparation of divalence chromium loaded catalyst
1) silica gel is predrying.With N 2Be fluidized gas, in activator, Davison957 silica gel (chromium that contains 0.18~0.30wt%) is heated to 150 ℃ predrying, behind 150 ℃ of following constant temperature 4hr, stop heating, continue logical N 2, silica gel transferred to after being cooled to 100 ℃ and blows jar.
2) silica gel titanizing.Deliver to catalyst make up tank after silica gel after predrying accurately weighed, add iso-pentane (6.64L iso-pentane/kg SiO 2), by chuck slurries are heated to 55 ℃ after, with tetraisopropoxy titanium ((C 3H 7O) 4Ti) add Preparation tank, the add-on of tetraisopropoxy titanium is that to make the weight content of Ti be 3.5~4.5wt%, 55 ℃ stir 2hr after.Heating slurry to 100 ℃, iso-pentane is removed in flash distillation.
3) silica gel is fluoridized and is activated.Be lower than in the activator temperature under 100 ℃ the situation, titanizing silica gel is delivered to activator from Preparation tank, add hexafluorosilicic acid amine salt ((NH 4) 2SiF 6) (3g hexafluorosilicic acid amine salt/kg SiO 2) to activator, use N 2Make fluidized gas.Heating rate with 50 ℃/hr is heated to 325 ℃, behind 325 ℃ of constant temperature 2hr, with fluidized gas from N 2Switch to air, the temperature rise rate with 100 ℃/hr is warmed up to 825 ℃ then, and at 825 ℃ of constant temperature 4hr.
4) CO reduction.Fluidized gas is switched to N from air 2, wait catalyzer to be cooled to 350 ℃, with fluidized gas from N 2Switch to CO and N 2Gas mixture, and at 350 ℃ of constant temperature 2hr.
5) catalyzer cooling.Stop heating, fluidized gas is switched to N from gas mixture 2, be cooled to 100 ℃ always, obtain divalence chromium loaded catalyst.
3. catalyst preparation
The proportioning of chromic oxide loaded catalyst and divalence chromium loaded catalyst is 1: 2.5.
Catalyzer dispersion solvent mineral oil, solid content are 5.5%.
4. polymerization
In the gas-phase fluidized-bed reactor of a pilot scale level, produce the multipolymer of ethene and 1-hexene.The reactor controlling level is 2.4m, the heavy 125kg of seed bed, superficial gas velocity 0.65m/s, circulation gas flow 7.0t/hr.The reactor hourly output is 25kg/hr, and the space-time yield of reactor is 74.5kg PE/hrm 3Polymerizing condition and polyethylene product performance see Table 1.
Table 1
Embodiment
1 2 3
Operational condition Temperature, ℃ 104 106 92
Pressure, MPa 2.1 2.1 2.1
Ethylene content (mol%) 77 78 78
Isopentane content (mol%) 0 6.56 0
Hydrogen/ethene (mol/mol) 0.09 0.08 0.09
Butylene/ethene (mol/mol) 0.021 0.023 0
Hexene/ethene (mol/mol) 0 0 0.025
Oxygen/ethene (mol/mol ppm) 0.6 0.56 0.12
The polyethylene product performance FI(g/10min) 0.74 0.76 1.05
D(g/cm 3) 0.9435 0.9445 0.9225

Claims (8)

1. improved catalyst system that is used for vinyl polymerization or ethene and alpha-olefin copolymer is characterized in that: described catalyst system comprises the mixed system of a) divalence chromium loaded catalyst or divalence chromium loaded catalyst and chromic oxide loaded catalyst; B) dispersion solvent.
2. according to the described catalyst system of claim 1, it is characterized in that: described dispersion solvent is a mineral oil.
3. according to the described catalyst system of claim 1, it is characterized in that: the solid weight content is 0.1~25% in the described catalyst system.
4. according to the described catalyst system of claim 1, it is characterized in that: the used carrier of divalence chromium loaded catalyst or chromic oxide loaded catalyst can be a silica gel, also can aluminum phosphate.
5. according to the described catalyst system of claim 1, it is characterized in that: in the mixed system of described divalence chromium loaded catalyst and chromic oxide loaded catalyst, the weight ratio of chromic oxide loaded catalyst and divalence chromium loaded catalyst is 0.01~10.
6. according to the described catalyst system of claim 5, it is characterized in that: in the catalyst system, the weight ratio of chromic oxide loaded catalyst and divalence chromium loaded catalyst is 0.02~1.
7. according to claim 1,4,5,6 arbitrary described catalyst systems, it is characterized in that: in the catalyst system, the weight content of chromium is 0.1~5% in the chromic oxide loaded catalyst, and the weight content of chromium is 0.1~2% in the divalence chromium loaded catalyst.
8. according to the described catalyst system of claim 1, it is characterized in that: contain in the catalyst system and add in element aluminum, titanium, zinc, boron, phosphorus, the fluorine one or more, the content that adds element is 0.2~5%.
CNB2006100496248A 2006-02-25 2006-02-25 Improved catalyst system for ethylene polymerization or ethylene and alpha-olefin copolymerization Expired - Fee Related CN100400553C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2006100496248A CN100400553C (en) 2006-02-25 2006-02-25 Improved catalyst system for ethylene polymerization or ethylene and alpha-olefin copolymerization

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2006100496248A CN100400553C (en) 2006-02-25 2006-02-25 Improved catalyst system for ethylene polymerization or ethylene and alpha-olefin copolymerization

Publications (2)

Publication Number Publication Date
CN1814628A true CN1814628A (en) 2006-08-09
CN100400553C CN100400553C (en) 2008-07-09

Family

ID=36907002

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2006100496248A Expired - Fee Related CN100400553C (en) 2006-02-25 2006-02-25 Improved catalyst system for ethylene polymerization or ethylene and alpha-olefin copolymerization

Country Status (1)

Country Link
CN (1) CN100400553C (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012159193A1 (en) * 2011-05-25 2012-11-29 Nova Chemicals (International) S.A. Chromium catalysts for olefin polymerization
CN104817752A (en) * 2015-05-06 2015-08-05 无锡耀汇科技有限公司 Polyethylene thin film and preparation method thereof
CN108976326A (en) * 2017-05-31 2018-12-11 中国石油化工股份有限公司 Metallocene Catalysts for PE and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4820785A (en) * 1986-06-16 1989-04-11 Phillips Petroleum Company In situ comonomer generation in olefin polymerization
US5310834A (en) * 1987-05-20 1994-05-10 Quantum Chemical Corporation Mixed chromium catalysts and polymerizations utilizing same
CN100451039C (en) * 2003-03-28 2009-01-14 联合碳化化学及塑料技术有限责任公司 Chromium-based catalysts in mineral oil for production of polyethylene

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012159193A1 (en) * 2011-05-25 2012-11-29 Nova Chemicals (International) S.A. Chromium catalysts for olefin polymerization
US8846834B2 (en) 2011-05-25 2014-09-30 Nova Chemicals (International) S.A. Chromium catalysts for olefin polymerization
US9593187B2 (en) 2011-05-25 2017-03-14 Nova Chemicals (International) S.A. Chromium catalysts for olefin polymerization
CN104817752A (en) * 2015-05-06 2015-08-05 无锡耀汇科技有限公司 Polyethylene thin film and preparation method thereof
CN108976326A (en) * 2017-05-31 2018-12-11 中国石油化工股份有限公司 Metallocene Catalysts for PE and preparation method thereof
CN108976326B (en) * 2017-05-31 2021-04-13 中国石油化工股份有限公司 Metallocene polyethylene catalyst and preparation method thereof

Also Published As

Publication number Publication date
CN100400553C (en) 2008-07-09

Similar Documents

Publication Publication Date Title
US7563851B2 (en) Production of broad molecular weight polyethylene
CN109535290B (en) Catalyst suitable for producing polyolefin with superfine grain diameter and preparation method and application thereof
CN1391498A (en) Polymerization catalyst systems and processes using alkly lithium compounds as cocatalyst
CN1213082C (en) Catalyst for ethylene polymerization
CN102264772A (en) Method for preparing a titanium catalyst component, titanium catalyst component, method for preparing a titanium catalyst and titanium catalyst
CN1814628A (en) Improved catalyst system for ethylene polymerization or ethylene and alpha-olefin copolymerization
CN1264872C (en) Process for gas-phase (co-)polymerisaton of olefins in fluidised bed reactor
CN104072646B (en) Ethylene gas-phase polymerization or copolymerization catalyst composition, preparation and application thereof
CN1861645A (en) Ball shape catalyst for ethylene polymerization and preparation process thereof
CN1814631A (en) Catalyst system for ethylene polymerization or ethylene and alpha-olefin copolymerization
CN101838351B (en) Catalyst for vinyl polymerization and method for preparing same
CN1233669C (en) Catalyst composition for ethylene polymerization, and preparing method and catalyst thereof
CN1274723C (en) Ethylene slurry ring tube polymerization or copolymerization method
CN104277151B (en) For the catalyst component of olefinic polymerization, its preparation method and application
US20210317236A1 (en) A multi-stage process for producing a c2 to c8 olefin polymer composition
CN102585057A (en) Catalyst for vinyl polymerization reaction
CN109422827A (en) Main catalyst component for solution-process ethylene polymerization, preparation method thereof and catalyst system
CN104277152B (en) For the catalyst component of olefinic polymerization, its preparation method and application
CN1137153C (en) High-efficiency spherical titanium catalyst for olefin polymerization, preparation method thereof and application of catalyst
CN101735366B (en) Complex electron donor for drag reducer polymerization
CN104277155B (en) For the catalyst component of olefinic polymerization, its preparation method and application
US20080153998A1 (en) Modified catalysts for improved polymer properties
CN105111338A (en) Propene polymer and preparation method thereof
CN104277154B (en) For the catalyst component of olefinic polymerization, its preparation method and application
CN103130932A (en) Olefin polymerization method

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: 20080709

Termination date: 20140225